JP3471145B2 - Spinning solution for tin oxide fiber and method for producing tin oxide fiber - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a spinning solution and a method for producing a tin oxide fiber.

[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 scatters. 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 fibers by the conventional solid-phase reaction method. For this reason, JP-A-60-5997, JP-A-60-161337, and JP-A-60-158199 propose methods 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, 3 mm or less in length, the aspect ratio is small, and the cross section is often rectangular. Therefore, when used as a composite material, its function can be sufficiently exhibited. However, there was a problem that its use was limited. Furthermore, since the major axis is too small, it is difficult to produce a paper-like material. Further, in order to improve 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 spun fiber is exposed to a high humidity atmosphere between the spinning and the heat treatment, the fiber shape is not retained and softens. As a result, problems such as collapse of the fibers, adhesion of spun fibers to each other due to softening, and slow drying have occurred. Further, even during spinning, if the humidity is high, the spinning may not be performed stably and the fiber may be cut. 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. The fiber before heat treatment spun from the spinning solution is called gel fiber.

[0007]

As a result, it was found that the moisture resistance of the gel fiber spun from the spinning solution prepared by further dissolving metallic tin in the conventional spinning solution is remarkably increased, and the present invention was completed here. It was

That is, the present invention is a spinning solution in which an alcohol-soluble tin compound and metallic tin are dissolved in alcohol.

Another invention is a spinning solution characterized in that an alcohol-soluble tin compound, metal tin, and an alcohol-soluble group V element compound of the periodic table are dissolved in alcohol.

Yet another invention is a spinning solution, wherein an alcohol-soluble polymer compound is further dissolved in the above spinning solution.

Still another invention is a method for producing tin oxide fiber, characterized in that any one of the above spinning solutions is spun and then heat treated.

Next, the present invention will be described more specifically.

The alcohol used in the present invention is not limited as long as it can dissolve a raw material such as an alcohol-soluble tin compound described later. These alcohols have the general formula ROH
When represented by, 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. Groups, 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 these alcohols 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-propene-1. -Ol, 3-methyl-3-butene-1-ol and the like. In particular, methyl alcohol and ethyl alcohol are preferable because of high solubility of a tin halide compound which is one of alcohol-soluble tin compounds. The above alcohols are usually used alone, but a mixture of two or more kinds of alcohols can be used in order to control the reactivity with the alcohol-soluble tin compound or the solubility of the alcohol-soluble tin compound.

Examples of the alcohol-soluble tin compound (hereinafter referred to as tin compound) used in the present invention include tin halides and organic tin compounds. The halogen in the tin halide compound is Cl, Br, I, F atoms. Among these tin halide compounds, tin chloride and tin bromide are preferable in terms of price and stability. Specifically, Sn
Cl ₂ , SnCl ₂ .2H ₂ 0, SnBr ₂ , SnI ₂ , S
nF _{2 and the} like are mentioned, and in particular SnCl ₂ , SnBr ₂ , S
nCl 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. Examples of the organic tin compound include (CH ₃ ) ₂ Sn, (C ₂ H ₅ ) ₂ Sn, and (C ₃
It can be used or added within a range in which H ₇ ) ₄ Sn and the like are dissolved.

The shape of metallic tin used in the present invention is not particularly limited, and may be plate-like, rod-like, sheet-like, granular, powder-like, sand-like,
Examples thereof include flower-like ones, and from the viewpoint of easy dissolution, granular, powdery, and sandy ones are preferable. Higher purity is preferable, but it is not particularly limited as long as it does not affect the manufacturing method and does not affect the reproducibility of the specific resistance described later.

The proportion of alcohol used is not particularly limited as long as the raw materials such as tin compounds and metallic tin are uniformly dissolved in alcohol. However, if the raw material ratio of the tin compound, metallic tin, etc. is too low, it does not show spinnability, so it needs to be concentrated considerably, and the alcohol is wasted. On the other hand, if the concentration of these raw materials is too high, the raw materials are not completely dissolved and insoluble matters remain, so that a uniform spinning solution cannot be obtained.
Therefore, the use ratio varies depending on the raw material such as tin compound or metallic tin used and the type of alcohol, but in general, the raw material such as tin compound or metallic tin is in a molar ratio of 0. It is preferably used in a ratio of 01 to 0.5. After mixing at this ratio to form a transparent and uniform solution, the alcohol is further evaporated to concentrate the solution to obtain a spinning solution having a desired viscosity. The viscosity of the spinning solution is usually 50 to 30.
It is determined from the range of 000 poise in consideration of spinning conditions such as spinning speed.

In order to obtain a highly conductive tin oxide fiber in the present invention, an alcohol-soluble group V element compound of the periodic table (hereinafter referred to as a group V compound) is optionally contained in the spinning solution. You can This group V compound finally becomes a group V oxide by the heat treatment described below and forms a solid solution in tin oxide. However, when the content is excessive, it does not form a solid solution in tin oxide and becomes a normal oxide. Exists in the form of a mixture as When it forms a solid solution in tin oxide,
Group V elements exist in place of tin atoms in tin oxide. Further, when it is present in the form of a mixture as an oxide without forming a solid solution, the Group V element is mostly an oxide in an atmosphere in which oxygen is present, but it may be present without being partially oxidized.

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 and vanadium alkoxide, and examples of niobium compounds include NbCl ₅ , NbBr ₅ , NbF ₅ , and NbOC.
l ₃ and niobium alkoxide, and TaBr ₅ , TaCl ₅ , and tantalum alkoxide as tantalum compounds, and SbCl ₃ and SbC as antimony compounds.
Examples include l ₅ , SbBr ₃ , antimony oxychloride, or antimony alkoxide, 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% with respect to tin oxide in terms of oxide. If the above ratio is too low, the tin oxide fiber obtained has a low conductivity, and if it is too high, the effect of imparting conductivity is saturated. Incidentally, the amount (mol) of the Group V oxide contained in the tin oxide fiber and the amount (mol) of the Group V compound contained in the spinning solution are usually obtained finally.
Since they match each other, it may be calculated in advance so as to obtain a target ratio and mixed in the spinning solution.

In the present invention, when it is desired to carry out spinning at a high speed, it is effective to add an alcohol-soluble polymer compound to the spinning solution. As such a polymer compound, any polymer compound soluble in alcohol can be used without any limitation. To give a concrete example,
Ethyl cellulose, cellulose acetate, cellulose nitrate,
Examples thereof include celluloses such as cellulose propionate, cellulose triacetate, acetylbutyl cellulose and hydroxylpropyl cellulose, polyvinyl butyral, polymethylene oxide, polyethylene oxide, polypropylene oxide and polyvinyl acetate. By adding these alcohol-soluble polymer compounds, spinning can be performed without being much influenced by the humidity in the atmosphere, and spinning can be performed at a higher speed. That is, for example, when a method of extruding the spinning solution from a nozzle is adopted, in order to spin stably without adding an alcohol-soluble polymer compound, the viscosity of the spinning solution is reduced by evaporating and concentrating the alcohol. It must be 500 or 1000 poise or higher. However, the spinning speed generally tends to decrease as the viscosity of the spinning solution increases. 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 higher speed can be achieved. Further, when the viscosity is low, the pressure applied to the solution is likely to be uniform, so that spinning can be 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. Addition amount of alcohol-soluble polymer is 0.01
If the amount is less than wt%, a sufficient effect cannot be obtained. on the other hand,
If the amount exceeds 20% by weight, not only the effect will be saturated,
When the spun fiber is heat-treated, the amount of carbon and carbon dioxide gas generated increases, making it difficult to remove, and pores are generated in the resulting fiber, which is not preferable.

In the present invention, it is important to dissolve metallic tin in an alcohol solution containing an alcohol-soluble tin compound as a basic component. That is, stable spinning can be performed by spinning from a spinning solution containing metal tin,
In addition, the spun gel fibers are easy to maintain their shape even in a high-humidity atmosphere, the adhesion of gel fibers to each other is prevented, and the gel fibers dry quickly, which makes handling extremely easy.

The amount of metallic tin to be added is not particularly limited as long as it is a range that dissolves in each charging composition. However, if the amount of metallic tin is too large, it may take a long time to dissolve or may remain undissolved. Therefore, the alcohol, the tin compound, the metallic tin, and the alcohol-soluble polymer compound and Group V compound to be blended as necessary. In the solution containing the compound, the ratio of the number of atoms of halogen and tin, that is, X / Sn, is set to 0.60 or more and less than 1.80 when the solution contains no group V compound, and the group V compound is When it is contained, the relationship between the number of atoms of halogen, tin and Group V elements

[0026]

[Equation 1]

It is preferable to adjust and blend so that

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.

That is, the atomic ratio of halogen to tin is X /
When spinning is performed from a spinning solution having Sn, or the relationship X / (Sn + V) of the number of atoms of halogen and tin and a Group V element within the above range, stable spinning can be performed, and the spun gel fiber has a high humidity atmosphere. Even underneath, it is easy to maintain the shape, and the drying becomes faster, making it extremely easy to handle. When the Group V compound is added, the halogen derived from the Group V compound must be taken into consideration as the halogen in addition to the halogen present in the tin halide compound which is the raw material of the tin 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. It is stable, but it takes time to dissolve metallic tin.
The problem arises that metallic tin does not completely dissolve. 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 preferable to control (Sn + V) within the above range.

As the Group V element, not the compound of the Group V element, but the element of the Group V element such as metal antimony is dissolved to dissolve the halogen and the number of atoms of tin and the Group V element X / You may use together the method of controlling (Sn + V).

In the spinning solution of the present invention, the relationship between the number of atoms of halogen and tin in the spinning solution, or the relationship between the number of atoms of halogen and atoms of tin and Group V elements is almost the same as the raw material composition at the time of charging. Therefore, unlike the conventional spinning solution, it is not necessary to repeat the concentration and dissolution operations of the solution, and the spinning solution can be prepared by simply concentrating from a solution adjusted so that the above relationship is established in advance.

When preparing the spinning solution, a tin halide compound such as SnCl ₂ , SnCl ₂ .2H ₂ O, S having a small ratio X / Sn of the number of atoms of halogen and tin is initially prepared.
It is effective to use a compound in which tin is divalent such as nBr ₂ because it can be easily controlled in the above range.

Prior art (Japanese Patent Application No. 06-134046)
In, the atomic ratio X / Sn of halogen and tin is 1.5.
The relation X / (Sn + V) of less than 5 or the number of atoms of halogen and tin and a Group V element is (1.55N _Sn +1.60).
When it was less than Nv), a precipitate was formed in the spinning solution and the solution was unstable. However, when metallic tin is added, even if the relationship between the number of atoms of halogen and tin or the number of atoms of halogen and tin and the Group V element is less than the above range, precipitation does not occur and a uniform spinning solution can be prepared. did it. The present inventors have sufficiently wondered why a spinning solution containing metallic tin is stable even if the relationship between the number of atoms of halogen and tin or the number of atoms of halogen and tin and the Group V element is below the above range. Although it cannot be explained, it is considered that in the conventional method, the spinning solution was repeatedly concentrated and dissolved, so that a large amount of water and the like was mixed to form a precipitate, or the spinning solution was decomposed by repeating the operation.

The method of dissolving the tin compound, the metal tin, and the alcohol-soluble polymer compound or the group V compound, which is blended as necessary, with the alcohol is not particularly limited.
A method in which alcohol is added dropwise to a mixture of a tin compound, metal tin, an alcohol-soluble polymer compound, and a Group V compound with stirring, or a tin compound, metal tin, an alcohol-soluble polymer compound with alcohol is added to alcohol with stirring. A method of dissolving the group V compound simultaneously or sequentially can be used. Further, in order to promote dissolution of metallic tin, it is also effective to reflux alcohol solution to dissolve metallic tin.

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. It is also possible to add a compound for further increasing the spinnability. 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 heat treatment of the obtained gel fiber is carried out at a temperature at which an organic solvent such as alcohol, water or the like is removed from the gel fiber to strengthen the skeleton of the fiber and, in some cases, further crystallization. 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. On the other hand, 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 250 to 1550.
The range of ° C is preferred. More preferably 300 to 1500 ° C
It is preferable to perform heat treatment at the temperature of.

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, it is heated in a reducing atmosphere such as nitrogen, argon, hydrogen, 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 as follows.
It varies greatly depending on the kind of the Group V compound, the addition amount, the firing atmosphere, the firing temperature, etc., but normally 10 ³ to 10 ^-1 Ω.
It can take the value of cm. Further, it is possible to take a value of 10 ⁻⁴ Ω · cm by firing in a reducing atmosphere.

The tin oxide fiber obtained by the present invention may be crystalline or amorphous, but crystalline is preferable from the viewpoint of conductivity.

[0043]

EFFECTS OF THE INVENTION According to the method of the present invention, even if the gel fiber is contacted with a high humidity atmosphere before the heat treatment, the gel fiber is softened and its shape is collapsed, and the adhesion of gel fibers to each other is reduced. It became possible to transition extremely smoothly. As a result, industrially stable operation is possible and productivity is 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 Stannous chloride (SnCl ₂ ) 7.69 g (0.041 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. After that, metal tin 1.
45 g (0.012 mol) was added, and the solution was refluxed and dissolved, and then concentrated to give a relation between the number of atoms of chlorine and tin and antimony. A highly viscous sol with Cl / (Sn + Sb) of 1.60. A spinning solution was obtained. At this time, 0.60N _Sn + 0.65Nv = 0.60,
1.80N _Sn +2.70 Nv = 1.87. This spinning solution is pressed to extrude from the spinning nozzle and the relative humidity is 5
It was continuously wound around a drum at a spinning speed of 6 m / min in an atmosphere of 5%. 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 obtained is 30μ
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 8 × 10 ⁻¹ Ω · cm on average. The gel fiber immediately after spinning was left for 1 hour in an atmosphere of relative humidity of 75%, but the fiber shape was maintained without softening.

Example 2 10.64 g (0.038) of stannous bromide (SnBr ₂ ).
Mol), antimony trichloride (SbCl ₃ ) 1 g (0.0
(04 mol) was dissolved in 100 ml (2.47 mol) of methanol to give a uniform and transparent solution. Then, 1.73 g (0.015 mol) of metallic tin was added, and the solution was refluxed and dissolved, and then concentrated, and the relationship between the numbers of atoms of bromine, chlorine, tin, and antimony [(Br + Cl)] / (S
A spinning solution consisting of a highly viscous sol with n + Sb) of 1.60 was obtained. At this time, 0.60N _Sn + 0.65N
v = 0.60, 1.80N _Sn + 2.70N v =
It is 1.87. The spinning solution was extruded from a nozzle by applying pressure and continuously wound around a drum in an atmosphere having a relative humidity of 55%. After leaving the obtained fiber at room temperature for 1 day,
The temperature is raised to 120 ° C at a rate of 2 ° C / min and the temperature is increased to 3
Hold for 0 minutes. Then 500 at a speed of 10 ° C / min
The temperature was raised to 0 ° C. and the temperature was maintained for 30 minutes for heat treatment. The obtained fiber had an average diameter of 40 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 8 × 10 ⁻¹ Ω · cm on average. Immediately after spinning the gel fiber in an atmosphere of 75% relative humidity 1
After leaving for a while, the fiber shape was maintained without softening.

Example 3 8.94 g (0.047 mol) of stannous chloride (SnCl ₂ ) was used, and 100 parts of ethanol was used instead of methanol.
ml, using 1.13 g of Sb (OC ₂ H ₅ ) ₃ instead of 1 g of SbCl ₃ and 0.67 g of metallic tin
Example 1 except that (0.006 mol) was added, the solution was refluxed to be dissolved and then concentrated, and the relationship Cl / (Sn + Sb) between the numbers of atoms of chlorine, tin and antimony was 1.60. It carried out similarly to. At this time, 0.60N
_Sn + 0.65Nv = 0.60, 1.80N _Sn +
2.70 Nv = 1.87. 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 8 × 10 ^-1 Ω · cm on average.
Met. Further, the gel fiber immediately after spinning was left for 1 hour in an atmosphere having a relative humidity of 75%, but the fiber shape was retained.

Example 4 Example 4 was repeated except that 2-ethoxyethanol was used instead of methanol. 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 8 × 10 ^-1 Ω on average.
・ It was cm. Further, the gel fiber immediately after spinning was left for 1 hour in an atmosphere having a relative humidity of 75%, but the fiber shape was retained.

Example 5 7.41 g (0.039 mol) of stannous chloride (SnCl ₂ ) was used, and TaCl ₅ was used instead of antimony trichloride.
Using 0.945 g (0.0026 mol) and adding 1.62 g (0.014 mol) of metallic tin,
The solution is refluxed to dissolve and then concentrated, and Cl /
The same procedure as in Example 1 was carried out except that a spinning solution of (Sn + Ta) = 1.60 was obtained. At this time, 0.60N _Sn +
0.65Nv = 0.60, 1.80N _Sn +2.7
0Nv = 1.84. As a result of fluorescent X-ray analysis and X-ray diffraction of the obtained fiber, it was confirmed that tantalum was a crystalline tin oxide in which the tantalum was in solid solution according to the charged composition. The specific resistance of the obtained fiber was 8 × 10 ² Ω · cm on average. In addition, the relative humidity of the gel fiber immediately after spinning is 75
%, The fiber shape was retained.

Example 6 7.41 g (0.039 mol) of stannous chloride (SnCl ₂ ) was used, and NbCl ₅ was used instead of antimony trichloride.
Using 0.712 g (0.0026 mol) and adding 1.62 g (0.014 mol) of metallic tin,
The solution is refluxed to dissolve and then concentrated, and Cl /
The same procedure as in Example 1 was carried out except that a spinning solution of (Sn + Nb) = 1.60 was obtained. At this time, 0.60N _Sn +
0.65Nv = 0.60, 1.80N _Sn +2.7
0Nv = 1.84. As a result of analyzing the obtained fiber by fluorescent X-ray analysis and X-ray diffraction, it was confirmed that niobium was crystalline tin oxide which was solid-solved according to the charged composition. The specific resistance of the obtained fiber is 8 × 10 ^{2 on} average.
It was Ω · cm. Further, the gel fiber immediately after spinning was left for 1 hour in an atmosphere having a relative humidity of 75%, but the fiber shape was retained.

Example 7 In Example 1, stannous chloride (SnCl ₂ ) 4.3
4 g (0.023 mol), and metallic tin 3.55 g
(0.030 mol) was used, and the solution was refluxed, dissolved and then concentrated to obtain a spinning solution with Cl / Sn = 1.00. 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 is 8 × on average.
It was 10 ⁻¹ Ω · cm. Further, the gel fiber immediately after spinning was left in an atmosphere having a relative humidity of 75% for 1.5 hours, but the fiber shape was retained.

Example 8 In Example 1, stannous chloride (SnCl ₂ ) 6.0
1 g (0.032 mol) and 2.50 g of tin metal
(0.021 mol) was used, and the solution was refluxed and dissolved, and then concentrated, and the same procedure as in Example 1 was performed except that a spinning solution with Cl / Sn = 1.30 was obtained. 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 ⁻¹ Ω · cm on average. Further, the gel fiber immediately after spinning was left in an atmosphere having a relative humidity of 75% for 1.5 hours, but the fiber shape was retained.

Example 9 In Example 1, stannous chloride (SnCl ₂ ) 7.1
3 g (0.038 mol), and metal tin 1.80 g
(0.015 mol) was used, and the solution was refluxed, dissolved and then concentrated to obtain a spinning solution with Cl / Sn = 1.50. 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 ⁻¹ Ω · cm on average. Further, the gel fiber immediately after spinning was left in an atmosphere having a relative humidity of 75% for 1.5 hours, but the fiber shape was retained.

Example 10 In Example 1, stannous chloride (SnCl ₂ ) 8.8
0 g (0.046 mol), and metallic tin 0.75 g
(0.006 mol) was used, and the solution was refluxed and dissolved, and then concentrated, and the same procedure as in Example 1 was performed except that a spinning solution with Cl / Sn = 1.80 was obtained. 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 ⁻¹ Ω · cm on average. Further, the gel fiber immediately after spinning was left for 1 hour in an atmosphere having a relative humidity of 75%, but the fiber shape was retained.

Example 11 In Example 1, no antimony trichloride was used,
5.15 g (0.027 mol) of stannous chloride (SnCl ₂ ) and 3.03 g (0.026 mol) of metal tin were used to reflux and dissolve the solution, followed by concentration.
The same operation was performed except that a spinning solution of Cl / Sn = 1.00 was obtained. 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 having a relative humidity of 75% for 1.5 hours, but the fiber shape was retained.

Example 12 In Example 1, no antimony trichloride was used,
Using 6.70 g (0.035 mol) of stannous chloride (SnCl ₂ ) and 2.07 g (0.017 mol) of tin metal, the solution was refluxed to be dissolved and then concentrated.
The same operation was carried out except that a spinning solution of Cl / Sn = 1.30 was obtained. 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 having a relative humidity of 75% for 1.5 hours, but the fiber shape was retained.

Example 13 In Example 1, no antimony trichloride was used,
Using stannous chloride (SnCl ₂ ) 7.73 g (0.041 mol) and metallic tin 1.42 g (0.012 mol), the solution was refluxed to dissolve and then concentrated.
The same operation was carried out except that a spinning solution of Cl / Sn = 1.50 was obtained. 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 having a relative humidity of 75% for 1.5 hours, but the fiber shape was retained.

Example 14 In Example 1, no antimony trichloride was used,
Using 9.28 g (0.049 mol) of stannous chloride (SnCl ₂ ) and 0.45 g (0.004 mol) of tin metal, the solution was refluxed to be dissolved and then concentrated.
The same operation was carried out except that a spinning solution of Cl / Sn = 1.80 was obtained. 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 for 1 hour in an atmosphere having a relative humidity of 75%, but the fiber shape was retained.

Example 15 Stannous chloride (SnCl ₂ ) 7.69 g (0.041 mol), antimony trichloride (SbCl ₃ ) 1 g (0.00
4 mol) and 0.06 g of polyethylene oxide having a weight average molecular weight of 2,000,000 are added to 100 ml of methanol (2.47).
To give a uniform and transparent solution. After that, 1.45 g (0.012 mol) of metallic tin was added, and the solution was refluxed and dissolved, and then concentrated, and the relationship Cl / (Sn + Sb) between the number of atoms of chlorine and tin and antimony was 1.60. A spinning solution consisting of a sol having a certain viscosity of 200 poise was prepared. Here, 0.60N _Sn + 0.65N _V =
0.60 and 1.80N _Sn + 2.70N _V = 1.8.
7 When this spinning solution was extruded from the spinning nozzle by applying pressure and continuously wound on a drum, it was possible to continuously spun at a spinning speed of 20 m / min without causing drop of droplets or yarn breakage. It was 1 of the nozzle
It was possible to spin from all 0 holes. The obtained fiber was left at room temperature for 1 day, then heated to 120 ° C. at a rate of 2 ° C./min, and kept at that temperature 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. Also, as a result of X-ray diffraction,
It was confirmed that it had a tin oxide peak and that antimony was in solid solution in tin oxide without any peaks of its oxide or the like. The average specific resistance of the obtained fibers is 8
It was × 10 ^-1 Ω · cm. The gel fiber immediately after spinning was allowed to stand for 1.5 hours in an atmosphere of relative humidity of 85%, but the fiber shape was maintained without softening.

Example 16 Stannous bromide (SnBr ₂ ) 10.64 g (0.038)
Mol), antimony trichloride (SbCl ₃ ) 1 g (0.0
(04 mol) was dissolved in 100 ml (2.47 mol) of methanol to give a uniform and transparent solution. Then, 1.73 g (0.015 mol) of metallic tin was added, and the solution was refluxed and dissolved. Then, weight average molecular weight 50
A uniform solution was obtained by adding a solution prepared by dissolving 0.07 g of polyethylene oxide in 10 ml of methanol.
This solution was concentrated to obtain a relation (Br + Cl) / (Sn + Sb) of the atomic numbers of bromine, chlorine, tin and antimony of 1.60.
A spinning solution consisting of a sol having a viscosity of 200 poise was prepared. Here, 0.60N _Sn + 0.65N _V = 1.00
And 1.80N _Sn + 2.70N _V = 1.87. When this spinning solution was pressed out from a nozzle and continuously wound around a drum, the spinning speed was 20 m / m.
When spinning was performed at a speed of in, spinning could be continuously performed without causing drop of liquid 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 / 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 8 × 10 ⁻¹ Ω · cm on average. The gel fiber immediately after spinning was allowed to stand for 1.5 hours in an atmosphere of relative humidity of 85%, but the fiber shape was maintained without softening.

Example 17 Instead of antimony trichloride, TaCl ₅ 0.945
Example 15 except that g (0.0026 mol) was used, and stannous chloride (SnCl ₂ ) 7.41 g (0.039 mol) and metallic tin 1.62 g (0.014 mol) were used. Similarly, the relationship between the number of atoms of chlorine, tin, and tantalum Cl / (Sn + Ta) is 1.60 and the viscosity is 2
A spinning solution consisting of a sol of 00 poise was prepared. Then 2
When spinning was performed at a speed of 0 m / min, continuous spinning could be performed without causing drop of liquid droplets and breakage of yarn. here,
0.60N _Sn + 0.65N _V = 0.60 and 1.8
0N _{S n} + 2.70N _V = 1.84. It was also possible to spin from all 10 holes of the nozzle. The obtained fiber was analyzed by fluorescent X-ray analysis and X-ray diffraction, and as a result, it was confirmed that tantalum was crystalline tin oxide in solid solution according to the charged composition. The specific resistance of the obtained fiber was 8 × 10 ² Ω · cm on average. Further, the gel fiber immediately after spinning was left for 1.5 hours in an atmosphere of relative humidity 85%, but the fiber shape was retained.

Example 18 Instead of antimony trichloride, NbCl ₅ 0.712
g (0.0026 mol), and stannous chloride (SnCl ₂ ) 7.41 g (0.039 mol) and metal tin 1.62 g (0.014 mol) were used and dissolved. The same procedure as in Example 15 was carried out to prepare a spinning solution composed of a sol having a chlorine / tin / niobium atomic number relationship Cl / (Sn + Nb) of 1.60 and a viscosity of 200 poise. Next, when spinning was performed at a speed of 20 m / min, it was possible to continuously spin the droplets without dropping or breaking the yarn. Here, 0.60N _Sn + 0.65N _V = 0.60,
1.80N is a _{S n} + 2.70N _V = 1.84. 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 analysis and X-ray diffraction, it was confirmed that niobium was crystalline tin oxide which was solid-solved according to the charged composition. The specific resistance of the obtained fiber was 8 × 10 ² Ω · cm on average.
Further, the gel fiber immediately after spinning was left for 1.5 hours in an atmosphere of relative humidity 85%, but the fiber shape was retained.

Example 19 In Example 15, stannous chloride (SnCl ₂ ) 4.
34 g (0.023 mol), 3.55 g of metal tin (0.
030 mol) was added and dissolved to give Cl / (Sn + S
The spinning solution was adjusted in the same manner except that b) was changed to 1.00, and then spinning was performed at a speed of 20 m / min.
Spinning could be performed continuously without dropping liquid droplets or thread breakage. Here, 0.60N _Sn + 0.65N _V = 0.60 and 1.80N _Sn + 2.70N _V = 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. The specific resistance of the obtained fiber was 8 × 10 ⁻¹ Ω · cm on average. Further, the gel fiber immediately after spinning was left for 2 hours in an atmosphere of relative humidity of 85%, but the fiber shape was retained.

Example 20 In Example 15, stannous chloride (SnCl ₂ ) 7.
13 g (0.038 mol), metal tin 1.80 g (0.
(015 mol) except that the sol was dissolved in the same manner to obtain a spinning solution composed of a sol having a viscosity of 200 poise and Cl / Sn = 1.50. Next, when spinning was performed at a speed of 20 m / min, it was possible to continuously spin the droplets without dropping or breaking the yarn. It was also possible to spin from all 10 holes of the nozzle. The obtained fiber X
As a result of line diffraction, it was confirmed to be crystalline tin oxide. The specific resistance of the obtained fiber is 8 × 10 ^-1 Ω on average.
It was cm. Further, the gel fiber immediately after spinning was left for 2 hours in an atmosphere of relative humidity of 85%, but the fiber shape was retained. Example 21 In Example 15, without the addition of antimony trichloride, and 6.70 g of stannous chloride (SnCl ₂ ).
(0.035 mol), metallic tin 2.07 g (0.017 mol)
Mol) and dissolve in the same manner,
A spinning solution consisting of a sol having a viscosity of 200 poise at 1 / Sn = 1.30 was obtained. Next, when spinning was performed at a speed of 20 m / min, it was possible to continuously spin the droplets 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. In addition, the relative humidity of the gel fiber immediately after spinning is 8
It was left in a 5% atmosphere for 2 hours, but the fiber shape was retained.

Example 22 In Example 15, no antimony trichloride was added, and stannous chloride (SnCl ₂ ) 9.28 g
(0.049 mol), 0.45 g of metal tin (0.004
The same procedure as above, except that the
A spinning solution made of a sol having a viscosity of 200 poises was obtained at /Sn=1.80. Next, when spinning was performed at a speed of 20 m / min, it was possible to continuously spin the droplets 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. In addition, the relative humidity of the gel fiber immediately after spinning is 85
%, The fiber shape was retained. Example 23 In Example 1, stannous chloride (SnCl ₂ ) 2.3
8 g (0.013 mol), and metal tin 4.77 g
(0.040 mol) was used, and the solution was refluxed and dissolved, and then concentrated, and the same procedure as in Example 1 was performed except that a spinning solution of Cl / Sn = 0.65 was obtained. 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 ⁻¹ Ω · cm on average. Further, the gel fiber immediately after spinning was left in an atmosphere having a relative humidity of 75% for 1.5 hours, but the fiber shape was retained.

Comparative Example 1 10 g (0.00%) of stannous chloride (SnCl ₂ ) without addition of antimony trichloride (SbCl ₃ ) and metallic tin.
(5 mol), and concentration and addition of methanol were repeated to perform the same procedure as in Example 1 except that the chlorine / tin ratio Cl / Sn in the spinning solution was adjusted to 1.90. 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 is 8 × 1 on average.
It was 0 ⁴ Ω · cm. When the gel fiber immediately after spinning was left in an atmosphere with a relative humidity of 75%, it was softened after 5 minutes and the fiber shape was broken.

Comparative Example 2 The procedure of Comparative Example 1 was repeated except that the concentration of the solution and the addition of methanol were repeated to change the chlorine / tin ratio Cl / Sn in the spinning solution to 1.82. 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 is 8 × 10 ⁴ Ω · c on average.
It was m. When the gel fiber immediately after spinning was left in an atmosphere of 75% relative humidity, it softened after 15 minutes and the shape of the fiber collapsed.

Comparative Example 3 Stannous chloride (SnCl ₂ ) without addition of metallic tin
Using 10 g (0.05 mol), concentration of the solution and addition of methanol were repeated, and the relationship between the numbers of atoms of chlorine, tin and antimony in the spinning solution was changed to Cl / (Sn + Sb) of 1.90. I went the same way. At this time, 0.
60N _Sn + 0.65Nv = 0.60, 1.80N
_Sn + 2.70 Nv = 1.87. 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 8 × 10 ^-1 Ω on average.
It was cm. When the gel fiber immediately after spinning was left in an atmosphere with a relative humidity of 75%, it softened after 10 minutes and the fiber shape collapsed.

Comparative Example 4 Stannous chloride (SnCl ₂ ) without addition of metallic tin
The procedure of Example 21 was repeated, except that 10 g (0.05 mol) was used, concentration and addition of methanol were repeated, and the Cl / Sn relationship between the numbers of chlorine atoms and tin atoms was 1.82. At this time, the spinning speed was 20 m / min, and the droplets dropped,
It was possible to carry out continuous spinning 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, when the gel fiber immediately after spinning was left in an atmosphere of relative humidity of 85%, the fiber shape was maintained for 1 hour, but after that, it softened and the fiber shape collapsed.

Comparative Example 5 Stannous chloride (SnCl ₂ ) 1 without addition of metallic tin
The same procedure as in Example 15 was carried out except that 0 g (0.05 mol) was used, concentration and addition of methanol were repeated, and the relationship Cl / (Sn + Sb) between the numbers of atoms of chlorine and tin and antimony was set to 1.90. Here, 0.60N _Sn +0.
65N _V = 0.60, 1.80N _{S n} + 2.70N _V
= 1.87. At this time, the spinning speed is 20 m / min
Thus, it was possible to continuously spun the liquid without dropping the liquid drop or breaking the yarn. It was also possible to spin from all 10 holes of the nozzle. In the obtained fiber, it was confirmed by fluorescent X-ray analysis 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. 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 is 8 × 10 ⁻¹ Ω on average.
It was cm. Further, when the gel fiber immediately after spinning was left in an atmosphere of relative humidity of 85%, the fiber shape was maintained for 1 hour, but thereafter it softened and the fiber shape collapsed.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) D01F 9/08

Claims (4)

(57) [Claims] 1. A spinning solution for tin oxide fiber, characterized in that an alcohol-soluble tin compound and metallic tin are dissolved in alcohol. 2. A spinning solution comprising an alcohol-soluble tin compound, metal tin, and an alcohol-soluble Group V element compound of the periodic table dissolved in alcohol. 3. The spinning solution for tin oxide fiber according to claim 1, further comprising an alcohol-soluble polymer compound dissolved therein. 4. A method for producing tin oxide fiber, which comprises spinning the tin oxide fiber spinning solution according to claim 1, 2, or 3 and then heat treating the spinning solution.