JPH01308401A - Structure containing cellulose derivative with excellent liquid absorbing property - Google Patents

Abstract

PURPOSE:To improve liquid absorbing, processing and handling properties, by incorporating a specific CMC(salt) as at least one constituent. CONSTITUTION:CMC(salt), in which (f2)+(f3)+(f6) is 0.10-0.64, (f6)/(f2)+(f3) >=1.5 and the amount of pure water absorption is more than 20 times its own weight at 37 deg.C provided that (f2), (f3) and (f6) are the probabilities of substitution by substituents for OH groups on positions C2, C3 and C6, respectively, on a glucose ring which constitutes cellulose, is prepared by treating cellulose having a polymorph of cellulose II regenerated from alkali cellulose made from natural cellulose with an alkaline solution not having strength to completely convert cellulose into alkali cellulose from the X-ray diffraction viewpoint, and reacting the resulting cellulose with monochloroacetic acid (sodium salt). The obtained CMC(salt) is incorporated, as a constituent, into a sheet-like fabric-like or nonwoven fabric-like structure.

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention is directed to a novel carboxymethyl cellulose (hereinafter referred to as carboxymethyl cellulose rcMc) having excellent liquid absorption properties.
The present invention relates to a CMC structure prepared from J or a salt thereof, which has excellent processability and ease of handling.

(b) Prior art CMC, which is generally used commercially, is obtained from natural cellulose (cellulose, which has a crystalline form) such as linters and pulp, and is obtained from regenerated cellulose (cellulose, which has a crystalline form). CMC obtained using cellulose (having a crystalline form) as a starting material has never been put to practical use.

This is considered to be based on the following two reasons. Firstly,
This is from an economic point of view. CMC is made from natural pulp, links, etc. (it is made by removing impurities from crude raw materials such as wood and cotton, and this process already costs a lot of money).
Since it can be easily produced using cellulose, there is no reason to use cellulose (2), which is produced by further modification of these natural celluloses, as a starting material. Second, there is a delay in understanding the nature of the cellulose industry based on empirical facts and the resulting nature of cellulose chemistry. Although related to what will be discussed later, the technology of mercerizing natural cellulose (alkali cellulose) was already known in the 1870s, the application of mercerization technology was particularly focused on the modification of cotton products. It was not applied to regenerated cellulose fibers that were on the market about 30 years after the establishment of mercerization technology. Also,
This was not necessary because the regenerated cellulose derivative fibers imitated natural silk. Moreover, cellulose ■raw material and cellulose■
It was established about 10 years ago that the structures of alkali cellulose obtained from raw materials were different, and in the cellulose industry, starting from cellulose I and cellulose The academic level has not yet been reached where it is possible to predict the differences in performance of cellulose derivatives obtained in a heterogeneous reaction system via cellulose.

Moreover, most of the commercially used CMCs have a degree of substitution ((F )) in the water-soluble range, and only a small number of CMCs used as ion exchange resins have a degree of substitution in the water-insoluble range. It merely has.

At the research level, there is research on converting textile cellulose into CMC to improve its dyeability, but in this case too, the research is only on cotton, and there is no literature targeting regenerated cellulose.

Methods for producing CMC from natural cellulose can be roughly divided into
Divided into water medium method and solvent method. These methods are characterized in that natural cellulose is converted into alkali cellulose for the purpose of increasing the permeability of the reactant, and then reacted with monochloroacetic acid or monochlorosodium acetate. Furthermore, in order to suppress side reactions of monochloroacetic acid and monochlorosodium acetate as much as possible, mechanical crushing, squeezing,
Means such as shearing and agitation are routinely used, and usually CMC
can only be obtained in powder or fine fiber form. In general, CM
Since C is used in fields that utilize its emulsion stabilizing effect and thickening effect, CMC is generally used in powder form. It has been pointed out that the substitution position in the glucose ring in these commercial CMCs is stochastically often at position 02 [for example, ALAIN PARFONDRY et al.
Carbohydrate Research (Carbohydra)
te Research), 57 (1977) 3
9-49].

Since cellulose has three substitutable OH groups (C, C, C, position) in its constituent glucose rings, the probability of substitution to each of them ( (Nine)
It is clear that the performance differs depending on (k=2, 3, 6)). This (9) naturally differs depending on the synthesis method of the cellulose derivative and the type of raw material cellulose used, and differences in the raw material cellulose used not only cause differences in (9) but also in the internal structure. . Therefore, cellulose derivatives commonly known commercially, such as CMC, methylcellulose, ethylcellulose, cellulose acetate, cellulose acetate butyrate, cellulose nitrate, hydroxypropylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, etc. Induction with novel structures and properties that have not yet been discovered.

It can become a body.

(c) Problems to be Solved by the Invention An object of the present invention is to use cellulose, which has at least one constituent component, CMC or a salt thereof, which has surprisingly large liquid-absorbing properties and is derived from cellulose having a crystalline form (regenerated cellulose). To provide a structure containing as.

(d) Means for Solving the Problems The present invention provides C2+ of glucose rings constituting cellulose.
When the probability of substitution of a substituent to C3+c, position <O)1 group is (f2), (f3), and <16>, respectively, (F ) = (f2) + (fs ) + (
fs ) is 0.10 to 0.64, and <fly>/(
(f2)+(f3)) is 1.5 or more, and a sheet-like, fabric-like, or non-woven structure containing carboxymethylcellulose or a salt thereof derived from cellulose having a cellulose type as at least one component. It is.

Cellulose ■ C derived from cellulose with crystalline form
Even for MC and its salts, when (F) < 0.10,
does not provide a CMC that exhibits the desired liquid absorption properties. Also, (F
)>0.64, it naturally does not have the desired liquid-absorbing properties, and the amount eluted by water increases, making it impractical as an adsorption and liquid-absorbing material.

Regenerated cellulose is generally cellulose having a cellulose crystal type, and can be obtained by converting natural cellulose into alkali cellulose and regenerating it under appropriate conditions, or by dissolving cellulose in a solvent and regenerating it.

From an industrial standpoint, cellulose solutions to be subjected to regeneration are preferably cellulose solution solution 1 (viscose) and cellulose/1i17 ammonia solution, but are of course not limited to these. cellulose/inorganic acid solution,
Cellulose/inorganic salt solutions and cellulose in recently discovered solvents, such as dimethyl sulfoxide/paraformaldehyde, organic solvents/dinitrogen tetroxide, dimethylformamide/chloral, sulfur dioxide/amine, N-
Solutions dissolved in methylmorpholine-N-oxide system, N-ethylpyridium chloride/organic solvent system, N,N-dimethylacetamide/lithium chloride, liquid ammonia/thiocyanate, dimethyl sulfoxide/carbon disulfide/amine system, etc. Also available. In principle, it is also possible to use solutions in which derivatives that can be easily regenerated into cellulose, such as cellulose acetate, are dissolved.

Acids or alkalis are used to regenerate cellulose from the above solutions.

The regenerated cellulose obtained as described above has extremely high purity as cellulose and can be advantageously used for derivatization. CMC tends to maintain the crystalline form of the starting material in terms of X-ray diffraction up to the (F) level of 0.65 (see Figure 2). The CMC of the present invention derived from CMC (hereinafter abbreviated as rCMCIIJ) and the CMC derived from natural cellulose (cellulose having a crystalline system) (hereinafter abbreviated as rcMcIJ) have different structures as described below. This causes a big difference in liquid absorption. In other words, when the amount of moisture absorbed when immersed in pure water at 37°C for 10 minutes is a function of (F), the range of (F) that can absorb 40 times its own weight of pure water is CM
In the case of CI, it is 0.30 to 0.60, whereas in CMCII of the present invention, it is 0.15 to 0.40. In this way, ["MCn is extremely low compared to CMC' I (F)
Since they have the same liquid absorption properties within a range, they also have the practical advantage of being excellent in maintaining stability of the form (generally gel) after liquid absorption. This morphological stability is also related to excellent liquid retention properties after liquid absorption.

CMC II of the present invention can be obtained by a conventional CMC method similar to that known in the art, using cellulose having a cellulose type (regenerated cellulose) as a starting material. That is, cellulose having a cellulose crystal type is treated with an alkali and then reacted with monochloroacetic acid or monochlorosodium acetate. However, the alkali treatment is carried out without completely converting the material into alkali cellulose in terms of X-ray diffraction.

According to this method, raw cellulose having cellulose type I-crystalline type is converted into alkali cellulose I-n, which has an alkali cellulose type different from that made from natural cellulose. Here, the raw material cellulose used is in the form of powder,
It may be in the form of fibers, fabrics, or non-woven fabrics.

Usually, the CMC of the present invention is obtained as a Na salt or a free acid form, but of course it can be easily derived into various salts. For example, it can be derived from alkali metals such as potassium and lithium, alkaline earth metals such as calcium and magnesium, amphoteric metals such as aluminum, transition metals such as titanium, zirconium, chromium and mercury, and salts such as lead. In general, divalent or higher-valent metals reduce the liquid absorption properties of CMC and are therefore undesirable when high liquid absorption properties are desired. has an important meaning.

In addition to liquid absorption properties, each salt may provide unique properties. For example, mercury salts are expected to have a bactericidal effect, and lead salts are expected to have a hemostatic effect.

Since high liquid absorption properties, which are the main objective of the present invention, are those of an aqueous solution, Na salt is most suitable among various salts.

The CMCn of the present invention is particularly excellent in water absorption of physiological saline, and this CMCn has a carboxymethyl group substitution probability at the C, C3, and C positions ((fz), respectively).

(f3), (fg)) sum ((F)= ((f
2) + (f3) + (fs)): l is 0.10 as mentioned above
~0.64, and (fs)>(f2), (
fll)>(f3), that is, the replacement probability to (fg) is maximum, and <fg)/((f2)+(f3)
) is 1.5 or more. Here, (f
, )/((f2)+(f3)) is a value obtained by the following procedure. That is, sample CMC was dissolved in 5 wt% NaOH/[)2[1 at a concentration of about 3 wt%,
0.7M1(z”C-NMR(Pulse-Fowv
er type) at 60°C, 90°Pulse, rep
This is a value calculated from the following length based on data measured under the conditions of etition 2 seconds and 5000 integrations.

In the above formula, S refers to a peak that appears due to the introduction of a substituent to the corresponding position, or a peak that appears due to the introduction of a substituent to any of the C2, C3, and Cs positions,
1) to (3) show the respective peak intensities. . C.O.
indicates the carbonyl carbon peak of the carboxymethyl group. Two peaks appear near C, -S (71 ppm), with CaS on the high magnetic field side and substituent "-" on the low magnetic field side.
A star carbon of CH2C0OH was used. Table 1 shows the estimated values (ppm) of NMR peak positions depending on the type of substitution.

Table 1 Calculated from the chemical shift of CM-glucose.

S indicates substitution.

CH2 as a substituent is expected to be approximately 71.2 ppm.

COONa as a substituent is 178.4 and 178.8
Found in ppm.

In addition, a typical CMC “C-NMR diagram (107,5!
, IHz) are shown in FIG.

CMCI of the present invention (Figure (a)) and comparative example CMCI [
The difference in Figure (b) is obvious. The symbol in the diagram is CM
The positions of carbon atoms forming the glucose ring of C are shown. The symbol S means that the corresponding OH at position 0 is carboxymethylated. From FIG. 1, it is intuitive that C of the present invention
It is recognized that the C, -S peak of MC is large, the CS (unsubstituted) peak is low, and (fg) is high. Also, comparison C
In MC, based on c, -s, c, -s (peak (83
ppm) is clearly observed.

In the CMCn of the present invention that satisfies the above conditions (F) and (9) (k = 2.3.6), the absorption amount of physiological saline (under immersion conditions at 37°C for 10 minutes) is 20 to 20 of its own weight. It is 50 times more. In particular, at CMCI of (F) = 0.25 to 0.64, an absorption amount of 25 times or more is observed.

Such CMCI is obtained by treating regenerated cellulose with an alkali and carboxymethylating it without completely converting it into alkali cellulose according to X-ray diffraction. - This means that the structure of regenerated cellulose is more strongly reflected in #CMC. Here, "without completely converting it into alkali cellulose in terms of X-ray diffraction" means
It refers to a cellulose/alkali mixture that is not completely alkali cellulose in terms of linear diffraction, and does not produce a peak at 2θ = 30°, which is characteristic of alkali cellulose (Figure 3 I (a) and II (see a>). When cellulose ■ is used as a starting material, it refers to a cell in which the appearance of a peak at 2θ = 14° is not observed. Expressed quantitatively, it is a diffraction pattern characteristic of alkali cellulose. When comparing the intensity of peak, 2θ = 9° and 2θ = 14°, +2. (9°)〉■2θ (14°)
Refers to a cellulose/alkali mixture characterized by: Here, I26 (9°) and Ize (14
) are the intensities at 2θ=9° and 14°, respectively.

In order to obtain preferable CMI and its salts that satisfy the above conditions (F) and (9), it is desirable not to mechanically crush, press, or shear the raw cellulose during the CMC reaction. .

Therefore, in this method, the raw material regenerated cellulose can be subjected to the reaction in the form of a sheet, fabric, or nonwoven fabric.
Moreover, it can be said that this method is more advantageous in terms of processability and ease of handling of the final product.

CMCn obtained by this method is not only CMC obtained by the conventional water-based or solvent method using natural cellulose as a starting material, but also CMC obtained by applying a method similar to the above-mentioned method of the present invention to natural cellulose. The chemical structure is uniquely different from that of CMC obtained in 2007, and it has novel properties. These two comparative CMCs have (re)/((I2)+<ra))<1.1, which is different from the CMC of the present invention. This difference clearly reflects the difference in adsorption properties. CMC of the present invention
CMC obtained by applying the same method to natural cellulose has (F) = 0.12 to 0.70, and the amount of physiological saline absorbed at 37°C is 35% of its own weight.
It cannot be more than doubled. On the other hand, CMCII of the present invention always has an absorption capacity of 35 times or more when (F) is in the range of 0.30 to 0.62.

As mentioned above, the first point of the specific manufacturing method of c44cm of the present invention is that regenerated cellulose is treated with an alkaline solution that does not have the ability to completely convert it into alkaline cellulose when viewed from an X-ray diffraction perspective. . Specific examples of such solutions are:
Examples include, but are not limited to, a caustic soda aqueous solution with a concentration of 5 g/dll or less, or an organic solvent system containing water.

In the latter case, the water must be mixed to dissolve the caustic soda and, depending on the organic solvent composition used, to an extent that no precipitation of the caustic soda occurs. As the organic solvent, methanol, ethanol, impropatol, benzene, toluene, etc. are preferably used.

Alkali cellulose formation of regenerated cellulose is a function of temperature and treatment time, and the conditions that do not allow alkaline cellulose formation are generally 60° C. or lower and 30 minutes or less. The amount of caustic soda relative to cellulose is 1 to 1 per glucose residue.
4 moles is enough. The amount of alkaline solution can be selected as appropriate, but is suitably 5 to 20 parts by volume per 1 part by weight of cellulose.

CM is added to the regenerated cellulose/alkaline solution mixture treated as described above with monochloroacetic acid or sodium monochloroacetate either directly or as a solution in a suitable solvent.
All you have to do is convert it to C. The amount of monochloroacetic acid or sodium monochloroacetate can be appropriately determined according to (F) of the final CMC. Water, halogenated hydrocarbons, alcohol, etc. are used as solvents for monochloroacetic acid and monochlorosodium acetate, but if you are looking for manufacturing advantages, it is recommended to dissolve one of the component solvents of the alkaline solution used earlier. desirable. In the method for obtaining CMCII of the present invention, most of the free alkali remains in the alkaline solution at the stage of mixing the reactants (monochloroacetic acid, monochloroacetic acid sodium). Therefore, if we ignore the side reaction of the reactant,
Of course, it is also possible to obtain the CMCI of the present invention by mixing and reacting a solution in which a reactant is directly dissolved in an alkaline solution with regenerated cellulose.

Conditions for the reaction between the reactant and the alkaline solution-treated regenerated cellulose can be determined as appropriate. A common example is 60℃
It takes less than 90 minutes. In this reaction, if an organic solvent is used, 1'! Unlike water-based solvents, the swelling of cellulose is limited, so it is also possible to forcefully circulate the solvent (reaction liquid) to a reaction system in which cellulose is immobilized and use it for reaction. For example, a sheet, fabric, or non-woven cellulose is fixed in the form of a roll to a cylinder with ejection holes distributed around its circumference, immersed in a reaction liquid layer, and the reaction liquid is allowed to flow from the inside of the cylinder to the outside and regenerated. The excess reaction solution that cannot be encapsulated by cellulose can be circulated by returning it to the reaction solution flow droplet. After the reaction is completed, neutralization, washing, and drying may be carried out by conventional methods.

CMC and its salt obtained as described above can be used as an adsorbent or a liquid-absorbing agent by being used as a component of a sheet-like, fabric-like, or non-woven structure. Of course, it is also possible to develop applications that utilize the ion exchange properties of CMC, and it is possible to develop a wide range of applications such as medical materials, sanitary materials, and industrial applications.

When using CMC or its salt as a constituent component,
It can be used in the form of powder, granules, fibers, sheets, fabrics, non-woven fabrics, and other arbitrary forms.

These can be used in any manner as at least one component of a sheet-like, fabric-like, or non-woven structure. An example of this is as follows.

(2) Powdered or granular CMC or its salt is dispersed and contained in a nonwoven fabric structure made of other materials.

■ Mix fibrous CMC or its salt with fibers of other materials and form it into a filter shape.

■ Laminating sheet-like CMC or its salt with sheets of other materials.

In particular, CMC in the form of sheets, fabrics, and non-woven fabrics and its salts have excellent processability and are therefore effective when applied to the structures of the present invention. That is, conventional powdered CMC
In order to process CMC into sanitary products, it is necessary to effectively arrange powdered CMC in a sheet of other materials and then sew it onto the base fabric, which is a complicated process.At the same time, because it is in powder form, it is difficult to demonstrate its original absorption capacity. Although there are drawbacks, if one of the present invention, CMC in the form of a sheet, fabric, or nonwoven fabric, or its salt, is used, it is only necessary to stitch it to the base fabric, and the absorption performance can be maximized.

Example 1 This example clearly shows that the difference in structure of the raw material cellulose used tends to be maintained even after conversion into CMC, and that the CMC of the present invention has excellent liquid absorption properties.

Cellulose fibers regenerated from ammonium solution (cellulose■
type, X-ray diffraction peak = 2θ = 9.5, 12.0°20
, 1 , 21.5, crystallinity 49.8. Degree of polymerization 460)
50 g of an aqueous solution containing 1.34 mol of caustic soda per 10 g of glucose residue was infiltrated at 30°C. 20
After resting for a minute, 6.4 g of isopropyl alcohol containing 0.56 mol of monochloroacetic acid per glucose residue was added.
The mixture was heated to 60° C. and allowed to react for 90 minutes.

After the reaction was completed, the mixture was neutralized and washed with a methanol/hydrochloric acid solution.

The (F) of the obtained long fibrous CMC was 0.34, and (f6
)/'((fz) + (f3)) ltl, there were 8 te. It was found that the X-ray diffraction had a peak at 2θ=9.5.20.1, and that the cellulose type tended to be maintained. After drying this CMC under vacuum, it was left standing in an atmosphere of 60% humidity at 18° C., and its weight was measured. Next, a certain amount was immersed in pure water maintained at 37°C for 10 minutes, and then 2
When excess moisture was removed for 0 minutes and the sample was weighed, it was found that it had absorbed 58 times its own weight of moisture.

Comparative Example: Natural cellulose (cellulose type II, X-ray diffraction peaks = 2θ = 9, 14.7, 16.4).

22.6, crystallinity 50.4, polymerization degree 470),
When CMC was produced under the same conditions as the CMC production conditions of the present invention, (F) was 0.25, and the reaction efficiency of monochloroacetic acid was lower than that of the CMC of the present invention. Therefore, during the above production, monochloroacetic acid was replaced with monochloroacetic acid sodium, and the amount was increased to 0.70 mol per glucose residue, (F) = 0.33° (f, ) / ((fz
)+(f, )) = 1.1 comparative CMC was produced. This CMC also tends to maintain cellulose type I, 37
The amount of pure water absorbed at ℃ was only 45 times its own weight.

Note that the total degree of substitution (F) was measured by neutralization titration. Measurement of crystallinity was performed by L. Segal et al. (Text, Res
, J.

10, 786 (1959)). Further, the X-ray diffraction diagrams of the CMC of the present invention and the comparative CMC are shown in FIG. 2 together with the X-ray diffraction diagrams of the respective raw material celluloses.

In FIG. 2, Ia represents the raw material cellulose type I, [a represents the raw material cellulose type II, Ib represents the CMC obtained from ia, and nb represents the CMC obtained from [[a].

Example 2 This example shows that the CMC of the present invention is (F)=0.10 to 0.
In the range of 64, it is exemplified that the pure water absorbency is 20 times or more than its own weight.

Polymerization degree recycled from viscose: 400, crystallinity: 46%
using regenerated cellulose, (F) = 0.09 to 0.7
Nine types of CMC having different degrees of substitution within the range of 5 were created by the following method. In other words, 10g of regenerated cellulose is
It was immersed in 50 g of aqueous NaOH solution at 25° C., and then a predetermined amount of sodium monochloroacetate dissolved in isopropanol was added to the mixed system, and the mixture was reacted at 60° C. for 90 minutes. After neutralization and drying, the amount of pure water absorbed at 37°C was measured. The results are listed in Table 2.

As a comparative example, various (F ) value was created. Table 2 shows the results of measuring the pure water absorbency of these CMCs.

In addition, the pure water absorption amount was measured by the method described in Example 1, and (
F) was determined by neutralization titration.

As is clear from Table 2, (F) = 0.10 to 0.64
The CMC of the present invention having a large amount of pure water absorption shows a large amount of pure water absorption,
The maximum absorption capacity (F) is around 0.22 to 0.34. This F value is lower (F
) side has certain characteristics. Therefore, the morphological stability in the gel state after absorbing pure water was much better than that of the comparative CMC.

Example 3 In this example, (fs)/((f2)+(fz
)) It is demonstrated that the CMC of the present invention satisfying ≧1.5 surprisingly absorbs physiological saline.

In the CMC of the present invention, 10 g of cellulose regenerated from a cupric ammonia solution of cellulose (the same regenerated cellulose as described in Example 1) was treated with a reaction solution having the composition shown in Table 3. "Reaction liquid a" means 38.2 rnl of isopropanol containing 3.3 g of caustic soda and 22.4 mj of methanol! , 12.8 mg of water, and this mixed solution was used to soak cellulose for 20 minutes at room temperature. Next, the reaction solution was added as it was to obtain a CMC solution. "Reaction solution b" was a 6.6 rnl inpropatol solution containing 2.5 g of monochloroacetic acid, and after adding this solution to the reaction system, it was reacted at 60° C. for 90 minutes. Thereafter, it was neutralized by a conventional method using a methanol/H20 mixture containing acetic acid. Furthermore, it was washed with methanol.

As a comparative example, natural cellulose (DP = 400, crystallinity 50.1) was converted into CMC by the same operation, and its absorbing saline properties were evaluated. However, as described in Example 1, a relatively large amount of monochloroacetic acid was required to produce a comparative CMC having (F) equivalent to that of the CMC of the present invention.

Table 3 *a): Based on neutralization titration.

*b): NaOH has a concentration of 1.0% per glucose residue.
Equivalent to 34 moles.

*C): Monoqual acetic acid has 0 or 1 per glucose residue
Equivalent to 43 moles.

*a): Based on neutralization titration.

*b): Based on NMR.

The reason why the values of (F) obtained by the two measurement methods do not match in the case of a low degree of substitution is considered to be due to the Overhauser effect.

As shown in Table 4, the CMC of the present invention has high (f,);
It is clear that this greatly influences the adsorption and absorbability of the NaCl1 solution.

Furthermore, it was found by X-ray diffraction that the CMC of the present invention was not completely converted into alkali cellulose in the process of manufacturing it. The results are shown in FIG. Each diffraction diagram Ia) in Figure 3
, na), Ib), and IIb) have the following meanings.

Ia): Ce1ll + alkaline solvent Ce11 II [
a): Ce1lII + alkaline solvent Ce1ll
I b): Ce1l I + 18% NaOHNa-C
e1l I t]Ib) :Ce1111+18%N
a0) I Na-Cel I 1 CMC and its salts of the present invention are the X-ray diffraction peak 2 of the starting material cellulose
It can be clearly seen that cellulose treated with an alkaline solution, maintaining θ=10, 20, and 21, is converted into CMC. The peak at 2θ=14°30', which is a characteristic peak of normal alkali cellulose, does not appear. Also,
The above points can also be pointed out when a method similar to the present invention is applied using natural cellulose as a starting material.

Example 4 This example shows good processability from non-woven regenerated cellulose.
It is demonstrated that a CMC structure with good handling is obtained.

Asahi Kasei Kogyo Co., Ltd., recycled copper ammonium rayon long fiber nonwoven fabric, Benliese ■ was cut into 10 cm x 10 cm squares, laminated to a total weight of 10 g, and processed using the method shown in Example 3 to obtain (F) = 0.37, (fa) / ((f,
)+(f,))=1.89 CMC nonwoven fabric was created. This nonwoven fabric absorbs physiological saline approximately 40 times its own weight at 37°C, and absorbs urea/NaC4/Mg5O< /CaC12
/ H2O (=1.94/ 0.8 / 0.11/
0.26/97.09 weight ratio) at 5 times its own weight, NaCj! /Na2CD, /glycerin/CMCNa salt/water (=1.Olo, 4/10.010
．． It had the ability to absorb an artificial blood composition liquid of 46/88.14 (weight ratio) 35.0 times its own weight. This non-woven fabric commercial
C could be easily cut, sewn to other materials, and easily applied to products as a body fluid absorbent.

Example 5 Water was supplied to 10 g of CMC (E) of the present invention obtained in Example 2 to make it highly swell, and 30 g of Manila hemp was added thereto.
After further adding water and dispersing and mixing, the mixture was placed on a paper machine mesh, dehydrated, and methanol was added to process it into a filter shape. This product naturally had superior wet strength and excellent shape retention compared to a product processed into a filter shape using the present invention alone. This material could be used as a body fluid absorbent, ion exchange material, and dehydration material.

[Brief explanation of the drawing]

FIGS. 1(a) and (b) show "C-NMR (107,5 Mtl) of the CMC of the present invention and the comparative CMC, respectively.
z). The symbols in the figure indicate the positions of carbons forming the glucose ring of CMC. The symbol S means that the corresponding OH at position 6 is carboxylmethylated. FIG. 2 is an X-ray diffraction diagram of the following cellulose and CMC. I (a): Raw material cellulose I (comparative example), I
(b): I (a) CMC obtained from cellulose (comparative example), n (a): Raw material cellulose ■ (invention), n (
b): n (a) CMC obtained from cellulose
(Invention) The numbers in the figure indicate the diffraction angle 2θ of the peak indicated by the arrow. FIG. 3 is an X-ray diffraction diagram of the following substance. I (a): Cellulose ■/alkali mixture obtained by the same method as the present invention (comparative example), 1 (b): Alkali cellulose II obtained by a conventional method (comparative example), II (a): Cellulose 1/alkali mixture obtained by the method of the present invention, It (b): Alkaline cellulose I-II obtained by a conventional method (comparative example).

Claims (4)

[Claims] 1. C_2, C of the glucose ring that constitutes cellulose
When the probability of substituting a substituent to the OH group at the _3, C_6, position is 《f_2》, 《f_3》, and 《f_6》, respectively, 《F》=《f_2》+《f_3》+《f_6》
》 is 0.10 to 0.64, and 《f_6》/(《f_2
》+《f_3》) is 1.5 or more, and is characterized by containing carboxymethyl cellulose derived from cellulose having cellulose II crystal type or a salt thereof as at least one component, sheet-like, fabric-like or non-woven fabric. shaped structure. 2. 2. The structure according to claim 1, which contains as a constituent a salt of carboxymethyl cellulose that absorbs pure water at 37° C. at least 20 times its own weight. 3. The structure according to claim 1, which contains as a constituent a salt of carboxymethyl cellulose in which <<F>> is 0.25 to 0.64 and the absorption amount of physiological saline at 37°C is 25 times or more its own weight. body. 4. Claim 1, which is obtained by laminating carboxymethyl cellulose or its salt organized in the form of a sheet, fabric, or nonwoven fabric and another material organized in the form of a sheet, fabric, or nonwoven fabric. Structure.