JPS60246815A - Production of inorganic oxide fiber - Google Patents

Abstract

PURPOSE:To obtain the titled fibers having fire resistance and flexibility, by mixing basic aluminum chloride with an organic acid containing alkoxyl group in the backbone of an aliphatic carboxylic acid to prepare a spinning solution having a specific viscosity, and spinning the resultant spinning solution. CONSTITUTION:A spinning solution containing basic aluminum chloride and further a fiber-consisting material, e.g. a silicic acid ester, convertible into a metal oxide other than alumina by firing oxidation treatment in an electric furnace added thereto is added and mixed with an organic acid containing alkoxyl group in the backbone of an aliphatic monocarboxylic acid, e.g. beta-ethoxypropionic acid, and the resultant mixture solution is then concentrated under heating to prepare a spinning dope having >=1 poise, preferably >=60 poises viscosity at room temperature. The resultant spinning dope is then spun to form precursor fibers, which are then fired and oxidized to afford the aimed fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Industrial Application Field The present invention relates to a method for producing inorganic oxide ram (1), more specifically, a method for producing inorganic oxide fiber using basic aluminum chloride as a spinning raw material. As an improvement, basic aluminum chloride or a fiber constituent material that gives a metal oxide other than alumina by baking oxidation treatment is added to it.
A mixed solution in which an organic acid containing an alkoxyl group is added to the main chain of an aliphatic monocarboxylic acid is heated and concentrated to obtain a spinning stock solution 1=
After that, by firing and oxidizing the precursor fiber obtained by spinning this, it is possible to create a carbon-free fiber that has extremely high mechanical strength and excellent thermal stability at temperatures of 1500°C or higher. The present invention relates to a method for producing quality oxide fibers.

BACKGROUND OF THE INVENTION In recent years, there has been a demand from various industrial fields for the development of reinforcing materials for composite materials having superior mechanical strength such as tensile strength or °ε girlas and heat resistance. Various reinforcing fibers are known as reinforcing fibers for these new composite abrasive materials.

For example, polycrystalline 1N navy blue fibers such as alumino, zirconia, titania, boron nitride fibers, metal fibers such as tungsten, molybdenum, steel, beryllium sun, etc., and polycrystalline fibers such as boron, silicon carbide, boron carbide fibers, etc. Phase fibers and the like are being developed one after another.

Among these, aluminum fibers and navy blue have superior characteristics compared to other fibers. First, alumina fibers have a high melting point (2040°C), so they can be used in ultra-high temperatures, and are stable even in high-temperature oxidizing atmospheres.7. : While carbon fibers and metal fibers can maintain their mechanical properties, they undergo oxidation and become brittle in the above atmosphere, resulting in a significant decrease in mechanical strength.
Although fibers have high tensile strength, they have a low softening point and cannot be used at high temperatures, which is a fatal drawback. Therefore, when used as reinforcing materials for composite materials, short fibers such as various whiskers and lamic fire-resistant fibers are used. Differently, it has characteristics such as a large ratio of fiber length to fiber diameter (aspect ratio), and the ability to orient the fibers in a desired direction, allowing for optimal orientation. Aluminum has such excellent properties that are not found anywhere else.
Various types of fiber-reinforced composite materials, such as alumina fibers mixed with various types of Plus Deck, are available.
Fiber-reinforced plastics or mixed with various metals including aluminum to form aluminum JU and fiber-reinforced metals (starting to be used).

C9 Problems to be Solved by the Invention Various methods have been proposed in the past for producing alumina fibers that have such excellent properties. For example, there is a method of dissolving basic aluminum chloride in water, spinning this solution to make a precursor fiber, and then firing it to make a polycrystalline aluminum fiber. This method involves heating and concentrating the basic aluminum chloride solution. During the spinning process, the viscosity suddenly increases from a certain concentration, making it extremely difficult to maintain a constant viscosity of the spinning solution. This may cause problems such as clogging of the spinneret, so the work can be carried out efficiently. mechanical strength of fibers,
The disadvantage is that the flexibility is not sufficient.

In addition, Tokuto Sho 53-14832 @ publication discloses a method of producing oxide polycrystalline fibers by adding and mixing lactic acid to a basic aluminum chloride solution or a zil'nium compound to prepare a spinning solution, spinning this and then firing it. has been done. In this proposal, the reason for using a limited amount of lactic acid among organic acids is to reduce the viscosity of the spinning solution, and to slow down the rapid increase in viscosity that occurs during the process of heating and concentrating the basic aluminum chloride solution. - There is no mention of the effect of

Furthermore, in JP-A-54-23727, lactic acid is added to a mixture of a basic aluminum chloride solution and 110-id silica, mixed, heated and concentrated to prepare a spinning solution, and the resulting precursor fiber is then spun. A method has been proposed in which polycrystalline oxide fibers are produced through drying and heat treatment.

This method's odor-C lactic acid is produced by Moe's JP-A-Sho! i31483
Basic aluminum chloride is used for different reasons than those stated in Publication No. 2, but basic aluminum chloride is used because the ratio of the raw numbers of aluminum and chlorine in the solution is limited to a relatively narrow range. In addition, the spinning solution used for spinning is kept at room temperature (J
However, there were drawbacks such as the viscosity being limited to a narrow range.

Moreover, in these conventional techniques, the viscosity of the spinning solution actually used for spinning is generally low, ranging from a few voices to high (
The number of strands is narrow, only a few hundred voices, and centrifugal spinning and similar spinning methods are preferred as the spinning method for forming m-threads, so the final oxide fibers obtained are limited to woven strings. , therefore, it has the fatal drawback of being limited in its uses.

Means to Solve 1-0 Problems The present inventors considered these problems and decided to solve the conventional manufacturing method 1-0.
In order to completely eliminate the drawbacks of J-payment, we conducted intensive research and found that, surprisingly, if an organic acid containing an alkyl group in the main chain of an aliphatic monocarboxylic acid is used, aluminum and chlorine atoms can be In addition to being able to utilize a wider range of basic aluminum chloride solutions compared to known methods, the ratio of the numbers of basic aluminum chloride solutions can be increased without precipitation of insoluble salts during the heating and concentration process of the basic aluminum chloride solutions. Moreover, the viscosity of the spinning solution used for spinning at room temperature is more than 1 voice without causing any increase, making it possible to perform stable spinning operations in A3 over a wide range unparalleled by conventional methods. Furthermore, compared to acetic acid used in conventional methods, the organic acid used in the present invention does not generate a bad odor, so there is no need to worry about contaminating the working environment. By reacting with the basic aluminium chloride, the Fulmylam atoms of the basic aluminium chloride change to a 6-coordinated structure, resulting in a stable inorganic borine, and therefore the precursor fiber obtained by spinning can be used even in an indoor environment. The inventors have discovered that inorganic oxide fibers are sufficiently stable and have excellent fire resistance and flexibility by firing and oxidizing the precursor fibers, leading to the completion of the present invention.

In addition, inorganic oxide fibers obtained by spinning a spinning solution prepared from a mixture of organic acids and fiber constituents that provide metal oxides other than alumino through baking oxidation treatment have excellent fire resistance and only a fair amount of heat. It was also found that it has flexibility and does not become brittle at temperatures above 1500°C.

Zunawara The present invention is based on a spinning raw material consisting of J'jiA M-type aluminum chloride, or a spinning raw material to which a fiber constituent material that provides a metal oxide other than alumino through firing oxidation treatment is added with a main chain of an aliphatic monocarboxylic acid. Add and mix an organic acid containing an alni-oxyl group, heat and concentrate to -C18 room temperature to obtain a spinning stock solution with a viscosity of 1 poise or less, and spin by a conventional spinning method to obtain a -C18 precursor fiber. This is a method for producing inorganic oxide fibers, which is characterized by subjecting the fibers to a firing oxidation treatment.

Furthermore, the fibers produced by the present invention are long and have several steps of strength compared to the short fibers produced by the prior art.

1 Action The basic aluminum chloride solution used in the present invention has the general formula, A z (0)-1) s CA ・xHzO(
-'The basic iJ-luminium chloride (II solution) shown is σ
) may be used as is, but aluminum chloride-rum water) 8 liquid l\
) A basic aluminum chloride solution with various surface ratios of aluminum and mulberry is prepared by reacting and dissolving the luminium powder and heating and concentrating it to the desired concentration. It can also be used as a 6J function.

The present invention-゛(゛The hm acid used is excluding formic acid <VF acid,
Various saturated n effects such as 1bionic acid, butyric acid, isobutyric acid, pino\phosphoric acid, octanoic acid, and neuric acid 1]7jIS
The main chain of monocarboxylic acids has an alkoxyl group, -C methoxyl group, -xyl group, nor-n-proboxyl group, isopropoxyl group, n-maltoyacyl group and its isomers, nor-n-ruben. Those containing 1-hexyl group and isomers of 1, norrunulhexanoxyl group and its isomers, etc., specifically methyl-A=cyaacetic acid, 1-xyacetic acid, α-methoxypropionic acid ,β−1,+
-F dipropionic acid, norunlubutoxic 1] [1bi;
Although 4', i acid and the like are well known and preferred, 1 (or β-1-to-1-sibrobiic acid) is particularly preferred.

The addition ratio of the organic acid to the basic aluminum chloride solution is 1.1% of the solid content of the basic aluminum chloride solution.
5...60ffi f for 1 part of 1111100g
fi parts, more preferably 5 to -35 parts by weight.IJ＼Preferably, if the amount of the organic acid added is less than 5 parts by weight, during heating and condensation of the basic aluminum chloride solution, the viscosity may suddenly decrease. This increases the viscosity of the spinning solution and makes it extremely difficult to control the viscosity of the spinning solution.Also, even if 60 parts by weight or more is added, the effect is the same, so it becomes economically meaningless and the amount of the organic acid added is less than 5 parts by weight. When the amount is less than 8 parts, it becomes difficult to obtain inorganic oxide fibers with excellent flexibility.

Further, in the present invention, the organic acids may be used alone or in the form of a mixture of two or more.

Next, the spinning solution in the present invention contains a basic aluminum chloride solution, an organic acid, and fiber constituent substances that can be converted into metal oxides other than alumino by firing oxidation treatment. 40 or less double ends, preferably 25 double knots or less
good. Here, firing oxidation treatment refers to heating, firing, and sintering of the precursor fiber in an electric furnace, Hatake wave furnace, etc., and fiber constituent substances that can be converted into metal oxides other than alumina by this treatment include silicon. As a compound, silica hydrosyl, a silicate ester with a structure of Si (OR)
R is an alkyl group), 1 -S; polyA kanosyl R' which represents the structural unit of -O-
Roxane (R and R2 are the same or different alkyl groups, respectively), polysilicate varnish with the structural unit of ♀R"-18i-0-1 Examples of compounds containing magnesium include magnesium sol and magnezi "Kumual" having the structure Ma(OR)z.
I oxide (R is an alkyl group), magnesium nitrate, F<
11 compounds having the structure of zMg (
Ngnesia hydrate obtained by hydrolyzing [< is an alkyl group] with water, and other compounds other than the above, M
(OR)n (M is a metal, R is an alkyl group, n is an integer of 4 or less), including various metal alkoxides, various metal sols, etc., and one or more of these compounds. Particularly preferred are water-soluble silicon compounds.

The reason for using the fiber constituent material in the present invention is to improve the spinnability of the spinning solution, but intermediate aluminum crystals are produced in the process of converting precursor fibers into oxide fibers by firing and oxidizing them. The soil is used to suppress the growth of the young, and this allows the rice to maintain excellent fire resistance and flexibility even at temperatures above 1500°C.

In order to perform spinning from a spinning solution, a mixture containing basic aluminum chloride, an organic acid, and, if necessary, a fiber constituent material that can be treated with metal oxides other than alumina through firing oxidation treatment, so-called dry spinning is required. is most convenient, but other suitable spinning methods may be followed, such as centrifugal spinning, propellant gas spinning, jet spinning, etc. In addition, the viscosity of the spinning solution at air temperature is 1 poise or more, preferably 60 poise or more.
A suitable value is at least 100 poise, more preferably at least 100 poise. Therefore, the viscosity of the spinning solution is within this range! It is necessary to adjust the cover so that it can be adjusted.

After degassing the spinning solution, the spun and dried precursor fibers usually have 0
．． Although the average diameter is 5μ to 400μ, it is not limited to this range.

The precursor fiber thus obtained is treated under tension at a relatively low temperature, specifically at a temperature of 400°C or less.
．． , After X, the precursor fibers are subjected to firing oxidation treatment at a temperature of 1000°C or higher in an oxidizing atmosphere, or in some cases J, in a reducing atmosphere to remove materials, carbon, etc. in the precursor fibers, and then sintered. This results in pure white, extremely dense, elastic and elastic inorganic oxide fibers. Thus, the inorganic oxide fiber obtained by the present invention can be easily produced in large quantities because it uses basic aluminum chloride 11, which is inexpensive and easily available, as a starting material, and has excellent fire resistance.
Because of its flexibility, it can be mixed with various types of plastic books or metals and used as various fiber-reinforced composite H materials and binding materials.

[Examples] The present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

(Example 1) A basic aluminum chloride solution (AJ!+ (Of-1)s CJ!3゜Δ with a ratio of Af/C atoms of 1.39
,ez Oa = -20,3%) 7007 at 1℃3
β, -, ::c 1-xypropionic acid 60, OmQ while raising the temperature of Nidori Plus to 50℃
was added gradually. After adding all I companies, Noras f1 was heated to 65°C.
3 of the water contained in a basic aluminum chloride solution kept at
1.4% was removed under reduced pressure. Next, this mixed solution was transferred to a pressure-resistant container equipped with a stirring device, and the water content of the mixed solution was reduced to 12.
It will be 9% - C reduction L [The result of continued concentration is AJ! z
A uniform spinning solution with a viscosity of 5,500 voids at room temperature and 03 = 39.4% was obtained. During concentration, no sharp increase in the -C viscosity was observed at all.

After defoaming this spinning solution, the number of holes is 30 in the tension corner of the width fh1'.
Using a spinneret with a hole diameter of 0.08 mm, the fibers were continuously extruded and spun into a spinning tube with a length of 6.5 inches and wound at a speed of 30 m/min. The resulting precursor fibers were transparent and had an average diameter of 40 microns.

Next, the C precursor fibers were placed in an electric furnace and heated to 400°C under tension and in a nitrogen atmosphere, and then the nitrogen gas was removed and the furnace was replaced with air C' at a gastric thirst rate of 1σ of 300°C/llr. 10
For example, alumino fibers with an average diameter of 15/l are fired in air to 00°C. Furthermore, the fibers fired to 1200°C were transparent and strong α-aluminum fibers.

[Example 2] Commercially available industrial basic aluminum chloride rum solution (Abz(O)
-1) sC,f!・2.4)-1zO.

Al103 =23. '5%, the ratio of the number of atoms of Yaju/Hel 2.0) 500- to the Noras used in Example 1, and while warming the Furasuni 1 to 50°C for 4 hours, gradually added 33 ml of added to. After the addition was completed, the fuscisco was rotated in a vacuum chamber to start concentration, and 98 d of water was removed by boiling for 45 minutes. Next, this mixed solution was transferred to the pressure-resistant container used in Example 1 and stirred. While continuing to add silica hydrogen 1] sol so that AfzO3:SiOz = 85:15, the container was heated to 50°C and concentration was continued (
) 229d of water was removed.

During this operation, there was no rapid increase in the viscosity of Oi-C.Next, the water evaporation port was closed, and stirring was continued for an additional 5 hours while keeping the container at 40°C.
03 = 33.3% and a viscosity of 2200 voices at air temperature was obtained. This spinning solution was degassed under vacuum and spun using the same spinning device as used in Example 1 to obtain transparent continuous precursor fibers with an average diameter of 40 μm. The filamentary precursor fibers were placed under tension and under a nitrogen atmosphere for 40 minutes.
The temperature was raised to 0°C and held for 35 minutes. Next, the nitrogen gas was stopped, and the inside of the furnace was replaced with air, and the temperature was increased to 300°/R temperature rate of 1-1r-C to 1200°C (fired in air to obtain a strong nofluminous fiber with a C diameter of 10μ).

[Example; 3] To 500 trfl of the basic aluminum chloride solution with the Ai/C1 atomic ratio of 2.0 used in Example 2, 31 d of organic acidic zo[]boxybutyric acid was added and heated to 65°C. .

Next, condensation is carried out under reduced pressure 1; water ioo#li! was removed. The mixed solution was transferred to the same container as used in Example 1, and while stirring was continued, the prusilicate was added to AJ! z
O,! : SiOz was added in a ratio of 75:25, and the container was maintained at 65° C. and 320 d of water was removed under reduced pressure. The obtained spinning solution is ΔAz03
=33.9%, and the viscosity at room temperature was 3500 Bois.

Example 1 Using the same spinning device as used in Example 1'c, 50 μm precursor fibers were fired in the same manner as in Example 2 to obtain colorless transparent alumina-silica fibers with an average diameter of 15 μm.

[Comparative Example 1] A spinning solution was prepared by exactly the same procedure as in Example 1, except for adding β-cypropanic acid. ! i! -J was attempted, but insoluble salts precipitated in the heated cotton, and a rapid decrease in the upper limit of viscosity was observed, making it impossible to obtain a spinning yarn with the desired viscosity.

(Example 4) /M! /(, 500 IIt of basic aluminum chloride solution with a ratio of the number of atoms of e of 2.5!, 46II of methoxyacetic acid
Add tl and warm the stomach to 50℃ for 10 minutes part ii! After the mixture was maintained at a temperature of 100°C, it was concentrated under reduced pressure to remove 76d of water. Transfer the mixed solution to the container used in Example 1, and while continuing to stir the container,
The temperature was maintained at 5°C, and water was further removed for 120 d under reduced pressure to give Δfz
03 = 28.7%, at room temperature (1 q. A precursor fiber was obtained.Next, the temperature was raised to 500°C in a nitrogen atmosphere and held for 20 minutes, and then the inside of the furnace was replaced with air and heated to 100°C.
Stomach warming was carried out at a rate of 300°C/hr up to 0°C to obtain strong aluminum with an average diameter of 20 μm.

G0 Effects of the Invention According to the present invention, (1) A basic aluminum chloride solution having a wider range of atomic ratios between aluminum and chlorine can be used than in the known h method.

(2) No insoluble salts are precipitated during the heating and concentration process of the basic aluminum chloride solution, and no digastric formation with rapid viscosity occurs.

(33) The viscosity at room temperature of the spinning solution used for spinning is 1
Stable spinning operation is possible over a wide range of poise or higher, which is unparalleled by conventional methods.

(4) The organic acid used in the present invention does not generate a bad odor compared to acetic acid, which is also used in conventional methods. The aluminum atoms of the basic aluminum chloride react with basic nofluminium chloride so that the aluminum atoms of the basic aluminum chloride have a six-coordination structure, resulting in a stable inorganic polymer. The inorganic oxide fibers are sufficiently stable, and the inorganic oxide fibers with excellent fire resistance and flexibility are obtained by oxidizing the precursor fibers with IS. The fibers have excellent fire resistance and flexibility and do not become brittle at temperatures of 1500° C. or higher.

(6) The obtained inorganic oxide single fiber is a long fiber, and has a strength difference of several steps τ compared to the short fiber according to the prior art.

It has extremely excellent effects such as, and has industrial value.

Procedure Nertj, iE (self-motivated) 1. Indication of the case 1982 Patent Application No. 101936 2. Name of the invention Method for manufacturing inorganic oxide fiber 3. Person making the amendment 4. Address of the agent Chiyoda, Tokyo 16 Kanda Kita Jorimono-cho, Ward: 〒i
(Oi Building 3rd floor) Contents of the amendment 1. In the second line of page 4 of the statement box, the statement ``1 nolumina fiber reinforced'' has been corrected to [alumina fiber reinforced 1 etc.

2. Specification letter, page 9, line 1, 1 aluminum solution” and [“
and/or the general formula AJ2+
(OH)s CJ! Add a basic aluminum chloride solution indicated by 3'C.

3. On the 19th line of the same page, [n-butoxychloropianoic acid 1] was corrected to [norn-rutoxyprobionic acid].

4. In the details box, page 11, lines 10 and 13, the words "different" were corrected to "different."

5. Chemical formula at the top of the same page %formula% 6. Chemical formula at the bottom of the same page F OR’ F OR+ 1 -Corrected 3i -0- to -3t -0-.

Il 0R2J ORZ J 7, page 13, line 15 of the specification [-1 in a reducing atmosphere has been corrected to read ``in a reducing atmosphere.''

8. It says Il, 39j on page 14, line 12 of the statement box.
Corrected as lN, 33J.

9. On the first line of page 15 of the statement box, it says N2.9%-1.
115.1%” was corrected.

10. Delete 1 air r J on the 14th line of the same page.

11. From the last line of page 15 of the statement box to the third line of page 16 (1)
CI commercially available T industrial use...50M" and "commercially available industrial basic aluminum chloride (Afz(OH)s C1.
2.4H20) aqueous solution (Afz 03 =23.5
%, ratio of the number of atoms of Af'/(1! 2.0> 500m
"Corrected."

12. On the 4th line of page 16 of the specification, the statement ``1μ = engineering 1-xy'' was corrected to [β-1 toxicity.

13, r229dJ on the 11th line of the same page, r246
dl and correction.

14. On the 14th line of the same page, 1-5HrJ is written as "5 hours".

15. On the second line of page 17 of the specification box, replace "in the air" with "
With air,” he corrected.

16. On the third line of the same page, [1 in the air is excluded.

17. On the 19th line of the same page, the phrase ``colorless and transparent'' is removed from Portrait 11.

18. On page 18, line 5 of the statement box, it says, “L1 stomach decrease.”
Corrected to "rising phenomenon."

19. On the last line of the same page, the text "in the air" was corrected to "in the air."

Claims (1)

[Claims] 1 tll of basic aluminium chloride or a fiber to which a metal oxide other than alumino is applied by baking oxidation treatment
To the fc material, add the T41 component, add and mix an organic acid containing an alkoxyl group in the main chain of an aliphatic monocarboxylic acid, heat and concentrate to obtain a spinning stock solution with a viscosity of 1 poise or more at room temperature, and use the conventional spinning method. 1. A method for producing inorganic oxide fibers, which comprises subjecting a precursor fiber obtained by spinning to a firing oxidation treatment.