JPS61174499A - Production of alginic acid fiber paper - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel method for producing alginate fiber paper. More specifically, the present invention consists of short fibers mainly composed of alginic acid, water-insoluble alginate, or alginic acid derivatives. The present invention relates to a method for efficiently producing alginate fiber paper having sufficient strength and good texture and feel.

Prior art alginic acid, α-(1,4)-I,-guluronic acid and β
-(1,4)-D-mannuronic acid is a linear polymer that is a type of polysaccharide and widely exists in the natural world as cell membranes and intercellular materials of seaweeds, especially brown algae. This alginic acid is currently used as a relatively cheap industrial raw material.
In the food field, it is used as an ice cream stabilizer, thickener, emulsion stabilizer, beer retention stabilizer, etc. In the textile field, it is used in spinning paste, printing paste, finishing paste, etc. In the paper manufacturing field, it is used as a compensating fiber. It is used. Also, during World War II, it was woven into a cloth called alginate hessian and used as a substitute for burlap in military camouflage nets. Furthermore, it is known that it can be used as a nonwoven fabric made of long fibers or as a knitted fabric. However, in these sheets, alginic acid (
Due to the low single-filament strength of calcium (calcium) fibers, sheets obtained from these fibers have low strength, and the dried fibers are stiff and have no drapability, so their use is extremely limited. Ru.

By the way, paper is a sheet obtained by short fibers composed of cellulose forming inter-fiber bonds through hydrogen bonding, but the number of inter-fiber bonds is an order of magnitude higher than that of woven fabrics and long-fiber non-woven fabrics. Even if the single fiber strength is low, it has enough strength to be used for practical purposes. It is used in fields that require something with so-called "stiffness". Therefore, if paper can be produced from alginate fibers, the above-mentioned drawbacks of the fibers and the woven and nonwoven fabrics obtained therefrom will be eliminated.

There is only one known attempt to make paper from alginate fibers (US Pat. No. 2,600,504).

However, in this attempt, the fibers were treated with an alkali, some of which were treated with a water-soluble alkali salt, and the fibers were fixed together like a binder, because it was not possible to form bonds between the fibers even if the wet paper was formed. Therefore, the paper obtained has a film-like texture and is not satisfactory as paper.

Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to efficiently produce fibers with sufficient strength and good properties from short fibers mainly composed of alginic acid, water-insoluble alginates, or alginic acid derivatives. An object of the present invention is to provide a method for producing alginate fiber paper having a texture and feel.

Means for Solving the Problems As a result of extensive research, the inventors found that the short fibers are
We have discovered that the above object can be achieved by making paper using a wet method using fibers having a specific fiber diameter and fiber length/fiber diameter ratio, and based on this knowledge, we have completed the present invention. .

That is, the present invention provides fibers mainly composed of at least one selected from alginic acid, water-insoluble alginates, and alginic acid derivatives, whose fiber diameter is 0.5H or less, and whose fiber length/stem fiber diameter ratio is 150 or less. The present invention provides a method for producing alginate fiber paper, which comprises dispersing short fibers in water to form the paper, and drying the obtained wet paper.

In the method of the present invention, in order to smoothly perform paper making, the first
As a requirement, it is important to uniformly disperse the short fibers in water without entanglement.

The fibers contain enough water in water and are in a gel-like state, so they are relatively flexible. Therefore, if the ratio of edge fiber length to fiber diameter is not appropriate, when dispersed in water, The fibers are intertwined and entangled with each other, forming bound fibers and no paper layer is formed. This fiber length/fiber diameter ratio is 15
It needs to be 0 or less. When this ratio exceeds 150, even if the concentration is extremely diluted, the short fibers become entangled with each other to form fiber bundles, making it impossible to make paper. In addition, when using short fibers with a relatively large ratio within the above range, a dispersant commonly used in the production of Japanese paper or chemical fiber paper,
For example, paper may be made by adding mucilage obtained from plants such as A. japonica, Noriuchi, and Pinang kaseng, or a synthetic viscosity agent such as polyethylene oxide or polyacrylamide.

On the other hand, the diameter of the short fiber is selected depending on the wet strength of the fiber when spinning by a wet method, and in the present invention, it is selected within the range of Q,5rsx or less. If the fiber diameter exceeds 0.53 ffl, the number of bonds between fibers will be small and paper with good texture and strength will not be formed. Further, short fibers having a fiber diameter of 0.511 m or less have the advantage that they can be sufficiently spun even from those with an extremely low degree of polymerization, or from those containing other polysaccharides of 50 mm or less by weight.

The second requirement is smooth formation of interfiber bonds. In natural rubber made of natural cellulose, hydrogen bonds are easily formed between fibers because cellulose maintains its crystallinity, but in short rayon fibers, which are regenerated cellulose, the arrangement of cellulose molecules is Because the hydrogen bonds between the fibers are disturbed and the hydrogen bonds between the fibers are not sufficient to maintain sufficient strength as paper, Ingu is usually used for the bond between the fibers.

On the other hand, in the short fibers used in the present invention, the constituent α-L-guluronic acid and β-D-mer are bonded with equatorial-equatorial bonds, and α
-The bond between L-guluronic acid and β-D-mannuronic acid is
Because the conformation is axial-f-atorial bonding, even fibers formed simply by wet spinning can be used without a binder if the wet paper is sufficiently pressed and dried. Even without using a method of treating the paper with an alkaline aqueous solution such as salt to make a part of it water-soluble and welding it, dense interfiber hydrogen bonds that can maintain sufficient strength as paper are formed.

The third requirement is to dry the wet paper so that the paper does not wrinkle. The short fibers used in the present invention exhibit a gel-like state when wet, and have a higher water content than cellulose, etc. When drying wet paper, they shrink significantly and dry slowly, with wrinkles. It is desirable to avoid moisture removal by rapid heating.

By making paper so as to satisfy the above requirements, alginate fiber paper with strength and good texture similar to Japanese paper or rayon paper can be obtained.

The short fibers used in the present invention are mainly composed of at least one selected from alginic acid, water-insoluble alginates, and alginic acid derivatives. Examples of water-insoluble alginates include calcium (■), barium (11), iron (II), iron (2), aluminum@), chromium (2), and chromium (inversion) salts of alginic acid. Examples of alginic acid derivatives include alginic acid grafted with alkylene oxide, alginic acid treated with diisocyanate, dialdehyde, etc. to make alginic acid insolubilized or non-shrinkable.0 Method of the present invention In some cases, single fibers composed of these compounds may be slightly hard when dry, and in that case, when wet spinning the fibers, other polysaccharides may be added so as not to interfere with spinnability. It is preferable that the compound be contained within a certain range. Examples of this polysaccharide include acidic heteroglycans such as carrageenan, λ-carrageenan, 1-carrageenan, and xanthan gum; glucurocans such as pectin;
Examples include acidic mucopolysaccharides such as hyaluronic acid and chondroitin sulfate. By adding such polysaccharides, the physical properties of the spun short fibers are improved, and for example, in order to obtain alginate fiber paper with immobilized enzymes and microorganisms, the fibers are dispersed in water and formed. When enclosing enzymes and microorganisms in a gel-like material, their retention, action, growth, etc. can be made suitable.0 Effects of the Invention The alginate fiber paper obtained by the method of the present invention is suitable for practical use. The fiber paper has sufficient strength to be used for various purposes, and its uses include medical gauze that utilizes the physiological activity of the compounds that make up the fiber paper, such as anti-inflammatory properties. Can be mentioned.

Next, the fiber paper has porosity and a specific surface area of beads,
It can be made into a fiber paper that is extremely expensive compared to woven or knitted fabrics, and can also be used as medical test paper by incorporating various diagnostic reagents into the gel fibers.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 Sodium alginate [Kimitsu Chemical ■Crack, Type H] 4
．． Using a pressure filter (manufactured by Toyo Kagaku Sangyo, KST 293-3 ST), a 0 weight (air-dried) aqueous solution (viscosity of 1 weight aqueous solution at 20°C: 650 to 750 cp),
After filtering through filter paper 60 (manufactured by Toyo Kagaku Sangyo), a wet spinning machine was used at a spinning speed of 13.5 ml/
The fibers of calcium alginate were obtained by spinning from a 1,000-hole spindle with a diameter of 0.1 min and using a coagulation bath of a 5% by weight aqueous solution of salt fζ calcium. This fiber was cut into a fiber length of 31 m using a guillotine cutter (manufactured by Onouchi Seisakusho).

The fiber diameter of this product is O, lfl, and the fiber length/fiber diameter ratio is 3
It is 0. Furthermore, the bundled fibers were separated and removed by passing through a 07 rat screen with a slit width of 6/10 Q 0 inches.

When these short fibers were dispersed with a standard disintegrator after adding water to the normal paper-making density, no binding of the fibers was observed. However, when the fiber length is 5, the fiber length/fiber diameter ratio is 50.
In this case, some of the fibers are entangled with each other to form binding fibers,
The fiber length is 15.511 m, and the fiber length is /#! With a fiber diameter ratio of 155, a complete fiber mass was formed.

The short fibers have relatively good dispersibility in water, but if left undisturbed, they will thicken and make it difficult to obtain paper with a uniform texture. Therefore, 0.05% by weight of polyethylene oxide was added to the aqueous solution as a sticky agent. , the short fibers are added to the TAPP
Using an I standard sheet machine, the fibers were dispersed at a fiber concentration such that the basis weight was 60 t/-, and paper-formed. Next, it was sufficiently pressed to remove as much water as possible, and then air-dried under a press to a wrinkle-free basis weight of 68.2 t/rr? Calcium alginate fiber paper was obtained. Regarding the strength of this product, the tear length was 3.56 km, the specific tear strength was 59, and the folding strength was 53. This fiber paper had an extremely good texture similar to rayon paper, and the feel was almost the same as Japanese paper.

For comparison, when the wet paper after pressing was dried at 80° C. without being pressed, the rolled paper showed significant shrinkage and many wrinkles. Further, when dried under a press at 50° C. or lower, no wrinkles were formed at all.

Example 2 The lucium alginate fibers obtained by wet spinning in Example 1 were exchanged for KIO in % hydrochloric acid at room temperature to obtain free alginate fibers. This entire fiber was cut into fibers of 3.0 g in the same manner as in Example 2, and fiber lumps were removed using a flat screen (6/1000 inch). The fiber length/fiber diameter ratio of this short fiber is 30, and even if it is dispersed in water with a standard disintegrator at a fiber concentration of 1.5% by weight,
No occurrence of fiber bundling due to intertwining of fibers was observed.

However, the fiber length is 5. When ON and the fiber length/fiber diameter ratio is 50, some fibers are bundled during dispersion, and the fiber length is 15.5.
mm1 and a fiber length/fiber diameter ratio of 155, the fibers were completely entangled and could not be dispersed.

These free alginate fibers are more dispersible in water than the corresponding calcium salt fibers, but they tend to aggregate, so it is better to make paper by adding 12% by weight of polyethylene oxy as a sticky agent. was even better.

Wet paper shrinks significantly when drying and tends to wrinkle, so
A rolled paper was obtained by drying at room temperature under a press of 97 ml at a pressure of 3.5. By drying under such pressure,
No shrinkage wrinkles occurred.

The obtained alginate fibers have high transparency (opacity 41
．． 0%), and has a high degree of flexibility.As for its strength, the tear length is 3.34kIn1, the tear strength is 44, and the folding strength is 33.
Met. Also, the texture was extremely good.

Examples 3 to 6 According to Examples 1 and 2, two types of sodium alginate with a low degree of polymerization [manufactured by Kimitsu Kagaku ■, Typeni L-2 (20 ° C.
The viscosity of a 1-weight range aqueous solution at 20°C is 30 to 50 cp), Type K3 (the viscosity of a 1-weight range aqueous solution at 20°C is 320 cp)
~380 cp)]. These raw materials have extremely low viscosity, so for convenience of filtration,
A 5.0 weight width (air-dried) aqueous solution was spun all around to form calcium alginate fibers.

As a result, when the fiber length/fiber diameter ratio was 30, no fiber bundling was observed, when it was 50, some fiber bundling occurred, and when the fiber length/fiber diameter ratio was 155, the fibers were entangled and not dispersed at all. Table 1 shows the physical properties of the obtained alginic acid and calcium alginate fiber paper.

Table 1 Example 7 Sodium alginate (manufactured by Kimitsu Kagaku ■, Type H) was used in a 3-weight pot with a diameter of 0.055 in the same manner as in Example 1.
mmf: Spun from a 1000-hole spindle,
Calcium alginate fibers with a fiber diameter of 0.05 m were obtained.

This fiber has a fiber length of 3 tm (fiber length/fiber diameter ratio 60)
, 5 tm (120) and 8w1 (160). The fiber bundles were then removed using a flat screen with a slit width of 671,000 inches.
Using a standard disintegrator, the fiber concentration was 1.5 according to Example 1.
The dispersibility was evaluated by dispersing the samples in a weight range.

The fiber lengths of 3 mm and 5B had extremely good dispersibility, but the fibers of 81 m were intertwined with each other to form fiber clumps.

A paper having a fiber length of 3 fl was made according to Example 1, and a paper which was treated with hydrochloric acid at the fiber stage to form free alginic acid was also made in the same manner. The results are shown in Table 2.

Table 2 Example 8.9 Sodium alginate (type H) was mixed with ragican or pectin at a weight ratio of 371 to sodium alginate/carragican or pectin. Prepare a 3 weight width aqueous solution,
A calcium arginate fiber containing carragican or pectin was obtained by spinning according to Example 1. A portion of the fiber was immersed twice for 10 minutes in ←←←←Imbasic hydrochloric acid to convert it into a free acid form. These were paper-made according to Example 1 to obtain other polysaccharide-containing alginate fiber paper. All of the obtained fiber papers had a good Japanese paper-like appearance. Their physical properties are shown in Table 3.

Table 3 Example 10.11 Example 1 using sodium alginate (type H)
Barium alginate fibers and aluminum alginate fibers were obtained using a coagulation bath of a 5 weight ratio barium chloride aqueous solution and a 5 weight ratio aqueous aluminum chloride solution, respectively. Next, from each short fiber (fiber length 3),
A corresponding fiber paper was prepared. Their physical properties are shown in Table 4.

Table 4 Patent Applicant Director General of the Agency of Industrial Science and Technology Todoroki et al. Office Proceedings Amendment Portion September 3, 1985 Director General of the Japan Patent Office Mr. Michibu Ubuya 2 Title of Invention Process for Manufacturing Alginate Fiber Paper 3 Case of Person Who Makes Amendments Relationship with Patent Applicant: 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (114) Director of the Agency of Industrial Science and Technology 4, Designated Agent Voluntary 7, Detailed explanation of the invention in the specification subject to amendment 8 , The detailed description of the invention column in the description of the amendment will be amended as follows.

(1) Ming 18! Correct the following from lines 7 to 15 on page 4.

``There are two known attempts to make paper from alginate fibers (U.S. Patent No. 2,600,504 II and British Patent No. 1,370,888; No. 35204).

However, in the former method, the fibers are treated with an alkali, some of which are treated with a water-soluble alkali salt, and the fibers are fixed together like a binder, since it is not possible to form bonds between fibers even when a wet paper is formed. The obtained paper has a film-like texture and is not satisfactory as paper.

In the latter, l of gel-like water-insoluble alginate
Since 1lllE is beaten in the same way as normal pulp, IIM is pulverized and treated with water of p) -17 or less,
Even if interfiber bonds are formed without a binder, the wire mesh is often clogged and freeness is low, and mN is too short, making it impossible to form paper with usable strength and texture. It is. ” (2) Same page 8, No. 9
Insert the following sentence between line 10 and line 10.

``However, since the strength of the main fibers is not very high when fine fibers are mixed in, the strength of the paper is significantly reduced, so it is necessary to make the fiber lengths uniform within a range that does not hinder dispersion. The fibers are significantly different from cellulose valves, other compound fibers, or synthetic valves, and beating must be avoided at all costs.

Claims (1)

[Scope of Claims] 1. A fiber mainly composed of at least one selected from alginic acid, water-insoluble alginates, and alginic acid derivatives, with a fiber diameter of 0.5 mm or less and a fiber length/fiber diameter ratio of 1.
A method for producing alginate fiber paper, which comprises dispersing short fibers of 50 or less in water to form a paper, and then drying the obtained wet paper. 2. The production method according to claim 1, wherein the short fibers contain 50% by weight or less of other polysaccharides. 3. The manufacturing method according to claim 1, in which a sticky agent is used in combination when dispersing the short fibers in water. 4. The manufacturing method according to claim 1, wherein the wet paper is dried while applying pressure or tension or both to the wet paper.