JP4803374B2 - Method for producing cellulosic fiber structure - Google Patents

Description

  The present invention relates to a method for producing a cellulosic fiber structure in which a silica-alumina porous body is supported inside a fiber.

Conventionally, many attempts have been made to impart functionality by supporting an inorganic compound such as zeolite or alumino silica gel on a hydrophilic polymer substrate such as a paper or the like. For example, techniques such as internal addition of inorganic compounds such as zeolite and alumino silica gel are known in the coating and papermaking processes, but there are problems that the loading rate is naturally limited, and the functional expression of inorganic compounds is remarkably increased. There are many cases of inhibition. In addition, when zeolite and alumino silica gel are produced and grown in a hydrophilic polymer substrate, it takes a long time and the efficiency is poor.
Furthermore, a large amount of heat energy is required to immerse and impregnate an aqueous solution containing a silicon compound, an aluminum compound and a basic compound for producing zeolite.

  As a technique for solving such a problem, for example, an aqueous solution of either a silicon compound or an aluminum compound, which is a constituent component of zeolite, is impregnated in a hydrophilic polymer base material, and a basic substance and the other aqueous solution are mixed. Further, an inorganic porous crystal monohydrophilic polymer composite in which this is further impregnated and the zeolite is supported inside the cellulose fiber has been proposed (Patent Document 1: JP-A-10-120923, Patent Document 2: JP-A-11-315492).

  However, although the above technique has a wide composition range of solution and is suitable for processing pulp cellulose, it is extremely difficult to uniformly impregnate inorganic raw materials when applied to non-woven fabrics, woven fabrics, and knitted fabrics of cellulosic fibers. . As a result, when the generation of zeolite is uneven, not only will it cause non-uniformity of various performances and poor appearance due to this, but it will also be difficult to fully exhibit antibacterial and deodorizing performances. There was also. In this case, Patent Documents 1 and 2 do not propose a method for producing a silica / alumina porous body by efficiently treating a long woven fabric or nonwoven fabric.

JP-A-10-120923 JP 11-315492 A

  The present invention has been made in view of the above circumstances, and provides a method for producing a cellulosic fiber structure in which a porous silica / alumina is supported inside a cellulosic fiber constituting a long woven or knitted fabric or nonwoven fabric. Objective.

  As a result of intensive studies to achieve the above object, the present inventor impregnates a fiber structure with a silicon compound and a basic substance-containing aqueous solution, and an aluminum compound and a basic substance-containing aqueous solution, and then heats it with moisture and heat. The reaction between the silicon compound and the aluminum compound is promoted inside the cellulosic fiber to form a silica / alumina porous body. In this case, the basic substance concentration of each aqueous solution is adjusted to a range of 15 to 20% by mass. Thus, it has been found that a silicon compound and an aluminum compound can be effectively infiltrated into the cellulosic fiber, and a silica-alumina porous body can be efficiently produced inside the cellulosic fiber. Furthermore, it has been found that a silica / alumina porous body can be similarly produced inside a cellulosic fiber by using an aqueous solution containing a silicon compound, an aluminum compound and a basic substance without using two liquids. .

  In this case, as a method for treating a fiber structure such as a long woven fabric or non-woven fabric, the fiber structure is wound around a roll, and preferably a pair of rolls are arranged so that the fiber structure reciprocates between the rolls. The long fiber structure is efficiently treated by immersing, impregnating, and moist heat heating of the aqueous solution during the reciprocating operation, and the silica / alumina porous body is formed in the cellulose fiber. The inventors have found that it can be generated well and have come to make the present invention.

That is, the present invention
<1> A cellulose fiber structure impregnated with an aqueous solution containing a silicon compound, an aluminum compound and a basic compound is wound around a roll, and the cellulose fiber structure is fed out from the roll.
A method for producing a cellulosic fiber structure, characterized by heating with moist heat to promote a reaction between the silicon compound and the aluminum compound inside the cellulosic fiber to produce a silica / alumina porous body,
<2> A fiber structure wound around a roll is drawn out and introduced into an aqueous solution containing a silicon compound, an aluminum compound, and a basic compound, and an impregnation step of impregnating the aqueous solution is repeated once or a plurality of times, and then in a sealed space The method for producing a cellulosic fiber structure according to <1>, wherein the silica-alumina porous body is produced by heating the material with wet heat and reacting the silicon compound and the aluminum compound inside the cellulosic fiber,
<3> A fiber structure wound around a roll is unwound and guided into a first aqueous solution comprising a silicon compound and a basic compound-containing aqueous solution or an aluminum compound and a basic compound-containing aqueous solution. After impregnating the aqueous solution, aluminum The impregnation step of impregnating the second aqueous solution consisting of the compound and the basic compound or the aqueous solution containing the silicon compound and the basic compound is repeated once or a plurality of times, and then heated in a sealed space with moist heat to form a silicon compound inside the cellulosic fiber. <1> The method for producing a cellulose fiber structure according to <1>, wherein a porous body of silica / alumina is produced by reacting with an aluminum compound;
<4> The apparatus includes a reversible first roll wound around the fiber structure and a reversible second roll wound around the fiber structure, and a silicon compound, an aluminum compound, and a basic compound. Silicon that can introduce and contain the aqueous solution contained in the apparatus and discharge it from the inside of the apparatus, and introduces and accommodates the fiber structure fed from the first roll into the apparatus using a treatment apparatus capable of being heated by moist heat. While the fiber structure is wound around the second roll while being immersed and impregnated in the aqueous solution containing the compound, the aluminum compound and the basic compound, the second roll is reversed and the fiber structure fed out is reversed again with the aqueous solution. After the impregnation step of winding the fiber structure around the first roll while being immersed and impregnated in the inside, the aqueous solution is discharged from the inside of the apparatus after repeating one or more times. <2> The cellulosic fiber structure according to <2>, wherein the cell structure is cured if necessary, and the fiber structure is further subjected to wet heat heating in a sealed space while repeating unwinding and winding between the first roll and the second roll. Manufacturing method,
<5> A reversible first roll in which a fiber structure is wound and a reversible second roll in which the fiber structure is wound, and a silicon compound and basic compound-containing aqueous solution and aluminum. A fiber structure that can be switched between a compound and a basic compound-containing aqueous solution so that it can be switched into and out of the apparatus and discharged from the apparatus, and is fed out from the first roll using a heat-heatable processing apparatus. The fiber structure is wound around a second roll while being immersed and impregnated in a first aqueous solution comprising a silicon compound and a basic compound-containing aqueous solution or an aluminum compound and a basic compound-containing aqueous solution. After that, the fiber structure rolled out by reversing the second roll is switched to the first aqueous solution, and introduced and accommodated in the apparatus. The impregnation step of winding the fiber structure around the first roll while being immersed in a second aqueous solution comprising a compound and a basic compound-containing aqueous solution or a silicon compound and a basic compound-containing aqueous solution is repeated once or a plurality of times. After that, the first and second aqueous solutions are cured as necessary in a state where both the first and second aqueous solutions are discharged from the inside of the apparatus, and further, the feeding and winding between the first roll and the second roll with respect to the fiber structure. <3> the production method according to <3>, wherein the heat and humidity are heated while repeating
<6> The silicon compound is sodium silicate, the aluminum compound is sodium aluminate, the basic compound is caustic soda, and the silica / alumina porous body is zeolite, according to any one of <1> to <5> A method for producing a cellulosic fiber structure,
<7> Any one of <1> to <6>, wherein the wet heat heating heats the fiber structure with water vapor at a temperature of 70 to 85 ° C. in a closed space having a relative humidity of 70% RH or more. A method for producing a cellulosic fiber structure according to claim 1,
<8> The method for producing a cellulosic fiber structure according to any one of <1> to <7>, wherein the fiber structure is a woven fabric, a knitted fabric, or a nonwoven fabric.
I will provide a.

  According to the production method of the present invention, an inorganic raw material can be efficiently and uniformly infiltrated into the fiber using a long cellulose-based fiber structure, and the silica / alumina crystal formation can be promoted. The processing time and process can be shortened and the amount of raw materials used can be reduced, and a uniform silica / alumina porous body can be produced. Moreover, since the fiber structure is heated with steam instead of heating the aqueous solution, the heat energy can be reduced.

  In the method for producing a cellulose fiber structure of the present invention, a cellulosic fiber structure impregnated with an aqueous solution containing a silicon compound, an aluminum compound and a basic compound is wound around a roll, and the cellulose fiber structure is removed from the roll. It is characterized in that a porous silica / alumina is produced by heating and moist heat to promote the reaction between the silicon compound and the aluminum compound inside the cellulosic fiber. In this case, the fiber structure wound around the roll is unwound and led into a first aqueous solution comprising a silicon compound and a basic compound-containing aqueous solution or an aluminum compound and a basic compound-containing aqueous solution. After impregnating the aqueous solution, aluminum The impregnation step of impregnating the second aqueous solution consisting of the compound and the basic compound or the aqueous solution containing the silicon compound and the basic compound is repeated once or a plurality of times, and then heated in a sealed space with moist heat to form a silicon compound inside the cellulosic fiber. It is preferable to react with an aluminum compound to produce a silica / alumina porous body and promote the production.

When the first aqueous solution is an aqueous solution containing a silicon compound and a basic compound, the second aqueous solution is an aqueous solution containing an aluminum compound and a basic compound, and when the first aqueous solution is an aqueous solution containing an aluminum compound and a basic compound, the second aqueous solution is used. The aqueous solution is an aqueous solution containing a silicon compound and a basic compound.
Further, when the aqueous solution is an aqueous solution containing a silicon compound, an aluminum compound, and a basic compound, it is not necessary to switch the aqueous solution, so that the processing time can be shortened.

  Here, examples of the cellulosic fibers include natural cellulose fibers such as cotton and hemp, viscose rayon, copper ammonia rayon (cupra), regenerated cellulose fibers such as tencel, polynosic, and lyocell, and semisynthetic fibers such as acetate. These may be used alone or in combination of two or more. In this case, it is preferable that the cellulosic fiber is usually 35% or more of cotton fiber, more preferably 50% or more, and still more preferably 100% cotton from the viewpoint of excellent hygroscopicity, water absorption, and texture. desirable. It should be noted that other natural fibers such as natural and regenerated cellulose fibers or semi-synthetic fibers, such as synthetic fibers such as nylon, polyester, and polyamide, may be mixed and used within a range not impairing the object of the present invention.

  Examples of the structure composed of the cellulosic fibers include woven fabrics, knitted fabrics, and nonwoven fabrics. Specifically, the cellulosic fibers are twisted by a usual spinning method to form yarns, and the yarns are woven or manufactured. All woven or knitted fabrics such as woven fabrics such as plain weave, twill weave, satin weave, etc., single jerseys such as tengu and kanoko, double jerseys such as milling and smooth, etc. If necessary, treatments such as hair burning, desizing, scouring, bleaching, mercerizing and the like can be performed.

  As the silicon compound, sodium metasilicate, potassium metasilicate, water glass, silica sol and the like can be used. On the other hand, examples of the aluminum compound include sodium aluminate, potassium aluminate, aluminum sulfate, aluminum chloride, and aluminum nitrate.

  For example, when producing zeolite inside a cellulosic fiber, sodium metasilicate can be suitably used as the silicon compound, and sodium aluminate can be suitably used as the aluminum compound.

  As the basic substance, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used. Sodium hydroxide is preferable because it has high solubility in water and a zeolite with high crystallinity can be obtained. is there.

  The silicon compound and basic substance-containing aqueous solution preferably has a silicon compound concentration of 1 to 35% by mass, particularly 2 to 25% by mass. If the concentration of the silicon compound is too low, it may take a long time to produce zeolite, and if it is too high, it may hinder the coating and impregnation of the dough. The aluminum compound and the basic substance-containing aqueous solution preferably have an aluminum compound concentration of 1 to 40% by mass, particularly 2 to 25% by mass. If the concentration of the aluminum compound is too low, it may take a long time to produce zeolite, and if it is too high, it may hinder coating and impregnation of the dough.

  The content of the basic substance in each of the aqueous solutions is preferably 15 to 20% by mass, particularly 16 to 19% by mass. If the content is too low, the production rate or supporting rate of the silica / aluminum porous crystals is low, and if the content is too high, the cellulose fibers are yellowed and the generation rate or supporting rate of the silica / aluminum porous crystals may decrease. is there.

  When an aqueous solution containing a silicon compound, an aluminum compound and a basic compound is used, when the silicon compound is converted into silicon oxide and the aluminum compound is converted into aluminum oxide, the total amount is 0.9 to 2.1. % By weight, especially 1.2-1.9% by weight, is dissolved in the aqueous solution, and the concentration of sodium hydroxide in this aqueous solution is 10-25% by weight, preferably 10-19% by weight, especially 16- It consists of a 19% by weight aqueous sodium hydroxide solution.

  When the cellulose-based fiber structure is impregnated with the above aqueous solution, the fiber structure may be impregnated with each aqueous solution separately, and the order of using the solutions is not particularly limited. That is, the silicon compound-containing aqueous solution may be first impregnated as the first aqueous solution, and then the aluminum compound-containing aqueous solution may be impregnated as the second aqueous solution, or the aluminum compound-containing aqueous solution may be impregnated first as the first aqueous solution, You may impregnate silicon compound containing aqueous solution as 2 aqueous solution. Moreover, you may make it impregnate repeatedly several times.

  In addition, when the aqueous solution is an aqueous solution containing a silicon compound, an aluminum compound, and a basic compound, the aqueous solution need not be switched.

  After impregnating the silicon compound, the aluminum compound and the basic compound, curing is preferably performed at room temperature for 4 to 20 hours, followed by heating with wet heat. The heating conditions are 60 to 100 ° C., particularly 70 to 90 ° C., and 0.5 to 20 hours, particularly 1 to 3 hours are preferable. The wet heat heating can be performed, for example, by a method in which a cellulosic fiber structure impregnated with the above aqueous solution is put into a sealed space and heated to the above temperature. Thereby, a silicon compound and an aluminum compound can be made to react efficiently, and crystal growth can be promoted.

  After completion of the reaction, it is preferable to wash with warm water of 30 to 90 ° C. to wash away the crystals formed on the fiber surface and the sodium hydroxide impregnated inside the fiber, followed by drying.

  In addition, examples of the silica / alumina porous material in the present invention include zeolite, alumino silica gel and the like. Among these, synthetic zeolite (4A type), X and Y types are particularly preferable from the viewpoint of adsorption characteristics and metal ion exchange properties. .

  In the present invention, as shown in FIG. 1, a more preferable method is that a pair of first rolls 4 and a first roll 4 are placed in an apparatus main body 3 in which a reverse cup-shaped cover 2 is detachably attached to a cup-shaped apparatus substrate 1. The two rolls 5 are preferably disposed so as to be able to rotate in the forward and reverse directions, and the long cellulosic fiber structure 6 is preferably reciprocated between the rolls 4 and 5 for processing.

  That is, as described above, the apparatus includes the reversible first roll 4 around which the fiber structure 6 is wound and the reversible second roll 5 around which the fiber structure 6 is wound, and the silicon compound. And an aqueous solution containing a basic compound and an aqueous solution containing an aluminum compound and a basic compound can be switched in and out of the inside of the apparatus and discharged from the inside of the apparatus. While the fiber structure 6 drawn out from one roll 4 is introduced into the apparatus and immersed in the first aqueous solution 7 comprising the silicon compound and the basic compound-containing aqueous solution or the aluminum compound and the basic compound-containing aqueous solution, After winding the fiber structure 6 around the second roll 5, the fiber structure 6 fed out by inverting the second roll is used as the silicon compound and the basic substance. A first aqueous solution comprising a compound-containing aqueous solution or an aluminum compound and a basic compound-containing aqueous solution is switched, and a second aqueous solution comprising an aluminum compound and a basic compound-containing aqueous solution or a silicon compound and a basic compound-containing aqueous solution introduced and contained inside the apparatus. A state in which both the first and second aqueous solutions are discharged from the inside of the apparatus after repeating the impregnation step of winding the fiber structure around the first roll one or more times while being immersed and impregnated in the aqueous solution. Thus, it is preferable that the fiber structure is cured as necessary, and the fiber structure is further subjected to wet heat heating while repeating feeding and winding between the first roll 4 and the second roll 5.

  Here, in FIG. 1, 8 is a guide roll. Reference numeral 9 denotes a first aqueous solution introduction / discharge port, through which the first aqueous solution is introduced into the apparatus main body 3 from a first aqueous solution storage tank (not shown) by operation of a pump (not shown). And returned to the storage tank. Further, reference numeral 10 denotes a second aqueous solution introduction / discharge port, and the second aqueous solution passes through the introduction / discharge port 10 from the second aqueous solution storage tank (not shown) into the apparatus body 3 by the operation of a pump (not shown). It is introduced and returned to the storage tank. 11 is a water inlet, 12 is a water outlet, and 13 is a water vapor inlet. Water can be used for washing and water vapor can be used for wet heat heating as required.

  The first and second rolls 4 and 5 are rotated in the forward and reverse directions by a driving device (not shown) so that the fiber structure can be fed out and taken up. The inside of the apparatus main body 3 can be heated by disposing a heating device.

  In the above operation, the fiber structure drawn out from the first roll 4 is immersed in the first aqueous solution, wound around the second roll 5, and then the first aqueous solution is replaced with the second aqueous solution. The fiber structure is fed out and immersed in the second aqueous solution and wound around the first roll 4. However, after winding the fiber structure with the second roll, the first aqueous solution is not converted into the second aqueous solution. Then, the second roll is reversed and the fiber structure is fed out from the second roll, dipped again in the first aqueous solution and wound around the first roll, and then the first aqueous solution is converted into the second aqueous solution, and the fiber structure is similarly obtained. The first roll is used to immerse and impregnate the fiber structure in the first aqueous solution, such as by reciprocating from the first roll to the second roll and then from the second roll to the first roll and immersing twice in the second aqueous solution. The fiber structure between the second roll After the reciprocating operation of winding and winding is performed one or more times, the fiber structure is immersed and impregnated in the second aqueous solution, and the fiber structure is fed and wound between the first roll and the second roll. It can also be performed by performing a reciprocating operation for taking one or more times, and thereafter, curing and heating with wet heat can be performed. Further, when the aqueous solution is an aqueous solution containing a silicon compound, an aluminum compound, and a basic compound, the reciprocating operation of unwinding and winding between the first roll and the second roll of the fiber structure without switching the aqueous solution. Can be repeated to immerse and impregnate in an aqueous solution.

  According to the production method of the present invention, the silica compound and the aluminum compound can be uniformly permeated into the cellulosic fiber, and the silica / aluminum porous crystal can be uniformly formed.

  Here, the cellulosic fiber structure of the present invention is formed by supporting a porous silica / alumina inside the cellulosic fiber. In the present invention, the cellulosic fiber interior means the skin constituting the cellulosic fiber. It also refers to a portion excluding the surface of the cell wall, pores and lumens (lumen) in the cell wall.

  The cellulosic fiber structure of the present invention is itself excellent in high deodorization (deodorization), cation exchange capacity, moisture absorption / release performance, etc., and has high functionality. Introducing (substitution) one or more metal ions such as copper ion, silver ion, zinc ion, nickel ion, palladium ion, manganese ion, magnesium ion, calcium ion, etc. Various functions such as moldability and virus inactivation can be imparted.

  Since the cellulosic fiber structure of the present invention is extremely excellent in deodorization and antibacterial properties, clothing (food / hygiene-related work clothes, etc.), household items (interior-related products, etc.), sanitary material-related products, environment It can be used for various purposes such as purification materials, agricultural materials (hydroponic cultivation), soil warm beds, automobile-related products, pet-related products, and other industrial materials.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples,% indicates mass%.

[Example 1]
An aqueous solution was prepared according to the following procedure based on the formulation in Table 1.
Mix sodium aluminate and caustic soda with stirring. Also, make an aqueous solution while stirring water and sodium silicate. A mixed solution of sodium aluminate and caustic soda is added to this aqueous solution while stirring, and stirring is continued for about 10 minutes. A combination of sodium silicate and caustic soda, or sodium aluminate and water may be used.

A 100% cotton non-woven fabric having a width of 180 cm and a length of 500 m was processed in the following steps using a jigger processing machine (JEX2180-2000, manufactured by Hanayama Kogyo) shown in FIG.
(1) The first roll 4 wound with the nonwoven fabric 6 is rotated, the nonwoven fabric 6 is fed out, and the nonwoven fabric 6 is immersed in the 40 ° C. aqueous solution 7 and wound on the second roll 5 on the opposite side for 500 m. Took 12 minutes. This immersion was performed three times for a total time of 36 minutes.
(2) The aqueous solution was raised to 65 ° C., the first and second rolls were rotated, and the nonwoven fabric 6 was immersed. This immersion was performed twice for a total of 24 minutes. Thereafter, the aqueous solution is discharged.
(3) The inside of the jigger machine is hermetically sealed, the steam temperature is 65 ° C., the roll is rotated, the nonwoven fabric 6 is fed out, and it takes 35 minutes to feed out 500 m while applying steam to the nonwoven fabric. The relative humidity is 70% RH or higher.
(4) Further, wait for about 10 minutes until the steam temperature reaches 85 ° C., and then rotate the roll and take 70 minutes to feed 500 m while applying the 85 ° C. steam to the nonwoven fabric 6 while feeding the nonwoven fabric 6.
(5) While rotating the roll, the nonwoven fabric 6 was fed out and washed with water. The washing time was 12 minutes to feed 500 m.
(6) While rotating the roll, washing with hot water at 70 ° C. was performed 3 times for 12 minutes per 500 m (36 minutes in total).
(7) Washing with water was performed for 36 minutes while rotating the roll. When pH (PH) reaches 6-7, the water washing is terminated.
The silica / alumina porous body could be uniformly supported inside the cellulose fiber throughout the nonwoven fabric 6.

It is the schematic which shows an example of the processing apparatus used for implementation of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cup-shaped apparatus base | substrate 2 Reverse cup-shaped cover 3 Apparatus main body 4 1st roll 5 2nd roll 6 Nonwoven fabric 7 1st aqueous solution 8 Guide roll 9 1st aqueous solution introduction and discharge port 10 2nd aqueous solution introduction and discharge port 11 Water introduction port 12 Water outlet 13 Steam inlet

Claims (8)

A cellulosic fiber structure impregnated with an aqueous solution containing a silicon compound, an aluminum compound and a basic compound is wound around a roll, and the cellulosic fiber structure is drawn out from the roll.
A method for producing a cellulosic fiber structure, which comprises heating a moist heat to promote a reaction between a silicon compound and an aluminum compound inside a cellulosic fiber to produce a silica / alumina porous body.   The fiber structure wound around a roll is unwound and guided into an aqueous solution containing a silicon compound, an aluminum compound and a basic compound, and the impregnation step of impregnating the aqueous solution is repeated once or a plurality of times, and then heat and humidity are heated in a sealed space The method for producing a cellulosic fiber structure according to claim 1, wherein a silicon compound and an aluminum compound are reacted inside the cellulosic fiber to produce a porous silica / alumina.   The fiber structure wound around a roll is unwound and led into a first aqueous solution comprising a silicon compound and a basic compound-containing aqueous solution or an aluminum compound and a basic compound-containing aqueous solution. After impregnating the aqueous solution, the aluminum compound and the base The impregnation step of impregnating the second aqueous solution composed of the organic compound or the silicon compound and the basic compound-containing aqueous solution is repeated once or a plurality of times, and then heat-heated in a sealed space to heat the silicon compound and the aluminum compound inside the cellulosic fiber. The method for producing a cellulosic fiber structure according to claim 1, wherein a porous body of silica / alumina is produced by reacting the above.   An aqueous solution comprising a reversible first roll around which a fiber structure is wound and a reversible second roll around which the fiber structure is wound, and containing a silicon compound, an aluminum compound and a basic compound. The inside and inside of the apparatus can be discharged and discharged from the inside of the apparatus, and the fiber structure fed from the first roll is introduced into and stored in the inside of the apparatus using a processing apparatus capable of being heated by moist heat, aluminum The fiber structure was wound around the second roll while being immersed and impregnated in the aqueous solution containing the compound and the basic compound, and then the fiber structure rolled out by reversing the second roll was immersed again in the aqueous solution. After the impregnation step of winding the fiber structure around the first roll while being impregnated one or more times, the aqueous solution is discharged from the inside of the apparatus The cellulosic fiber structure according to claim 2, wherein the cellulosic fiber structure is cured as necessary, and further, the fiber structure is subjected to wet heat heating in a sealed space while repeating feeding and winding between the first roll and the second roll. Production method.   A reversible first roll in which a fiber structure is wound and a reversible second roll in which the fiber structure is wound are provided inside the apparatus, and an aqueous solution containing a silicon compound and a basic compound, an aluminum compound, and a base The inside and outside of the apparatus can be switched to and discharged from the inside of the apparatus, and the fiber structure unwound from the first roll can be removed from the first roll using a treatment apparatus capable of being heated by wet heat. The fiber structure was wound around the second roll while being immersed and impregnated in the first aqueous solution comprising the silicon compound and basic compound-containing aqueous solution or the aluminum compound and basic compound-containing aqueous solution introduced and contained in An aluminum compound in which the second roll is turned upside down and the fiber structure is introduced and accommodated inside the apparatus by switching the first aqueous solution. The impregnation step of winding the fiber structure around the first roll was repeated once or a plurality of times while being immersed and impregnated in a second aqueous solution comprising a basic compound-containing aqueous solution or a silicon compound and a basic compound-containing aqueous solution. After that, in a state where both the first and second aqueous solutions are discharged from the inside of the apparatus, they are cured as necessary, and further, the feeding and winding between the first roll and the second roll are performed on the fiber structure. The production method according to claim 3, wherein the heat and humidity are repeated.   The cellulosic fiber according to any one of claims 1 to 5, wherein the silicon compound is sodium silicate, the aluminum compound is sodium aluminate, the basic compound is caustic soda, and the silica-alumina porous body is zeolite. Manufacturing method of structure.   The cellulose according to any one of claims 1 to 6, wherein the wet heat heating heats the fiber structure with water vapor at a temperature of 70 to 85 ° C in a closed space having a relative humidity of 70% RH or more. Method for manufacturing a fiber structure. The said fiber structure is a woven fabric, a knitted fabric, or a nonwoven fabric, The manufacturing method of the cellulosic fiber structure of any one of Claims 1-7.

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