JPH03121145A - Cellulosic composition with ion exchange capability - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in the water resistance and capable of retaining the ion exchange capability for a long time by mixing a specific regenerated cellulose with a vinyl acetate-maleic acid copolymer in a specified ratio at the molecular level and then solidifying the mixture. CONSTITUTION:The title compsn. is prepd. by mixing 60-99wt.% regenerated cellulose (e.g. viscose rayon) having a polymn. degree of 100-500 with 40-1wt.% vinyl acetate-maleic acid copolymer at the molecular level and then solidifying the mixture.

Description

[Detailed description of the invention] Industrial application field The present invention provides a cellulose composition having an ion exchange function,
More specifically, the present invention relates to a cellulose composition having an ion exchange function, which is a molecular mixture of regenerated cellulose and a specific anionic polymer compound.

Conventional technology As a polymer material with ion exchange function,
Ion exchange resins and chelate resins are known, and by utilizing the ion exchange function of these resins, for example, iron, copper,
Collection of metals such as nickel is being carried out. However, since these resins are synthetic polymers, they have good ion exchange function, water resistance, chemical resistance, etc., but have the disadvantage that they are difficult to dispose of after use.

Although cellulose-based compositions do not have the above-mentioned drawbacks, they have little ion-exchange function by themselves, so they are not widely used as functional materials.

It has been known to introduce anionic polymers to modify cellulose. For example, JP-A-48-98
No. 120 and JP-A No. 48-99416 state that the dyeability, dimensional stability, etc. of viscose rayon are improved by mixing isobutylene-maleic acid polymer into a viscose solution. . Also, JP-A-58-
No. 136351 discloses that polyacrylic acid, cellulose derivatives, cellulose sulfate, chondroitin sulfate, amylose sulfate, amylopectin sulfate, mucopolysaccharide sulfide, polyvinyl alcohol sulfate, cellulose phosphate, or salts thereof are dissolved in a copper ammonia solution of cellulose. It is described that the above-mentioned polymer compound is fixed in a film or fiber to impart hypercoagulability to cellulose.

However, such modified cellulose has the disadvantage that the water resistance of the modified cellulose composition is significantly reduced due to the anionic polymer compound mixed with the cellulose. For this reason, there are disadvantages in that the ion exchange function based on the anionic polymer compound cannot be sufficiently expressed, and the initial ion exchange function deteriorates significantly as the usage time progresses.

Problems to be Solved by the Invention The present invention aims to eliminate the various drawbacks of the conventional cellulose compositions. In other words, it has an excellent ion exchange function equivalent to that of ion exchange resins and chelate resins, has excellent water resistance, maintains excellent ion exchange ability over a long period of time, and is easy to post-process, which is an inherent feature of cellulose. The purpose of the present invention is to provide a novel cellulosic composition capable of retaining the following properties.

A means for solving the problem, that is, the present invention is a mixture of 60 to 99% by weight of regenerated cellulose having a degree of polymerization of 100 to 500 and 40 to 1% by weight of vinyl acetate-maleic acid copolymer. It relates to a cellulose-based composition having an ion exchange function, in which both components are molecularly mixed and solidified.

According to research by the present inventors, the above-mentioned vinyl acetate-maleic anhydride copolymer can provide cellulose with excellent ion exchange ability comparable to that of ion exchange resins and chelate resins, and can be used for long periods of time without deteriorating water resistance. It has been found that it is possible to provide a long-lasting ion exchange ability that can withstand use.

As the regenerated cellulose used in the present invention, wood pulp, cotton linter, etc. used in the production of viscose rayon, cupra, etc. are suitable, and these are recycled into viscose or cuprammonium solution. Since the degree of polymerization of regenerated cellulose affects the mechanical strength of the cellulose composition obtained, in the present invention, the degree of polymerization is 100 to 500.
It is better to use one.

The vinyl acetate-maleic acid copolymer used in the present invention is preferably a substantially equimolar copolymer of both. The molecular weight can vary widely depending on the application, but is usually between 10,000 and 2.
0,000,000, preferably in the range of 100,000 to 500,000. Such a copolymer can be easily obtained by solution polymerizing vinyl acetate and maleic anhydride using a known radical polymerization initiator in the presence of an organic solvent such as benzene, toluene, or acetic acid ester. be able to. Vinyl acetate and maleic anhydride are 0 when obtaining an equimolar copolymer of both.
．． It may be used in a ratio of 9:1.1 to 1.1:0.9.

The polymerization conditions are not particularly limited, and known conditions may be appropriately selected and employed. Polymerization temperature is usually 50 to 120
℃, and the polymerization time is 1 to 6 hours. Examples of radical polymerization initiators include peroxide polymerization initiators such as benzoyl peroxide and acetyl peroxide, and azo polymerization initiators such as azobisisobutyronitrile. The amount is approximately 0.05 to 1.0% by weight based on the body weight. The solvent can be removed from the obtained copolymer solution to obtain a copolymer solid content. Then, if necessary, the copolymer can be made into a water-soluble salt using ammonia, an organic amine, an alkali metal hydroxide, or the like. As the neutralizing agent, alkali metal hydroxides are preferred because they are odorless, and specific examples include sodium hydroxide and potassium hydroxide.

The cellulose-based composition of the present invention is prepared by dissolving and mixing the acetic acid and the nyl-maleic acid copolymer in the presence of a metal-containing alkaline solution such as a viscose solution of cellulose or a cuprammonium solution of cellulose obtained by a known method. After that, the mixture is solidified. From the viewpoint of the yield of the copolymer, it is preferable to use cellulose as a viscose solution. A mixed solution of viscose and copolymer can be solidified into a fibrous material by introducing it through a nozzle into a bath of strong acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid. Sulfuric acid is particularly preferred as the strong acid used as the coagulation bath. Alternatively, a mixed solution of viscose and copolymer may be extruded into hot water through a predetermined rectangular nozzle and washed with dilute hydrochloric acid to form a sponge-like solidified product. Furthermore, the mixed solution may be poured onto a flat plate such as a glass plate or a stainless steel plate, smoothed with a doctor knife, dried, and then washed with dilute sulfuric acid to form a solidified product in the form of a film. In addition, a solidified product in any form such as hollow particles or powder can be obtained by appropriately known methods.

The cellulose-based composition of the present invention thus obtained is a mixture in which regenerated cellulose and vinyl acetate-maleic acid copolymer are molecularly mixed and solidified. The mixing ratio of regenerated cellulose and copolymer is 60 to 99% by weight of the former and 40 to 1% by weight of the latter. If the proportion of regenerated cellulose used is less than 60% by weight, the resulting cellulose-based composition will have a sticky feel on the surface, resulting in disadvantages such as blocking during subsequent processes such as knitting, weaving, and compositing. In addition, if it exceeds 99% by weight, vinyl acetate-
The effect of modifying cellulose by using a maleic acid copolymer becomes insufficient. A particularly preferable mixing ratio of the two may be determined as appropriate depending on the application, but it is usually 90 to 75% regenerated cellulose and 10 to 10% vinyl acetate-maleic acid copolymer.
It is 25%.

The cellulose composition of the present invention can be used as a useful material having various ion exchange functions such as water absorption, deodorizing properties, antibacterial properties, dyeing properties, and metal trapping properties. for example,
The fibrous composition can be processed into absorbent towels, deodorizing towels, medical fibers, etc. Furthermore, by combining the cellulose-based composition of the present invention with other materials such as polyolefin to form a composite material in a desired form, highly hygroscopic materials, ion exchangers, filtration base materials, filter aids, coagulation and sedimentation can be obtained. agent,
Heavy metal ion scavengers, seawater desalination agents, ion exchange agents,
It can be used extremely widely as an antibacterial agent, deodorant, etc.

Effects of the Invention The cellulose-based composition of the present invention has an excellent ion exchange function comparable to that of ion exchange resins and chelate resins, has sufficient water resistance, maintains the ion exchange function for a long period of time, and retains the original cellulose properties. It has the advantage of easy post-processing.

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In each example, all parts and percentages are based on weight unless otherwise specified.

Example 1 Vinyl acetate-maleic anhydride copolymer water-soluble salt (solid content concentration 25%, trade name Tamanoli 5A-25, manufactured by Arayo Kagaku Kogyo ■) was added to a viscose solution of cellulose (cellulose concentration 9%). The copolymer solid content is cellulose solid content 10
They were added in amounts of 3, 5, 10, 20, and 30 parts per 0 part, respectively, and dissolved. Add each mixed solution to 13 sulfuric acid
0g/I! , zinc sulfate 10g/Ω, sulfuric acid sulfur/lium 2
Each sample of the viscose fiber of the present invention was obtained by extruding it through a platinum nozzle into a 50 g/g strong acid bath, desulfurizing it, scouring and bleaching it in a conventional manner. The fineness of each fiber is 3 denier.
The fiber length is 51 mm.

The sample names are TR3 and TR in the order of the amount of tamano solution added.
-5, TR-10, TR-20, and TR-30.

Comparative Example In Example 1, a partially neutralized salt aqueous solution of polyacrylic acid (trade name Tamanoli G-3) was used instead of Tamanori 5A-25.
16, manufactured by Arayo Kagaku Kogyo ■, non-volatile concentration 15.4%, viscosity (20°C) 58000 cps SpH 2,2) or partially neutralized salt aqueous solution of isobutylene-maleic anhydride (trade name Isopan-06, manufactured by Kuraray, non-volatile Min concentration 30.3
%, viscosity (20° C.) 8900 eps, pH 9.8) were each used in a ratio of 10 parts by weight to 100 parts by weight of cellulose, and samples for comparative testing were prepared in the same manner. Each sample is sequentially referred to as GR-10 and IBR-10.

(Performance evaluation and results) (1) Strength and elongation The strength and elongation of each of the above samples and ordinary rayon that does not contain any of the above copolymers for comparison were evaluated using the JI
It was measured according to the method of SL-10157,7.

The results were as follows.

(2) Hygroscopicity ■ Each of the above samples was ring spun to obtain a 20th yarn. Approximately 0.5 g of each sample was dried in a circulating air dryer at 105°C for 3 hours, and the weight (Wl) after drying was accurately weighed.

Further, each sample was left in a circulating air dryer at 60% RH and 25° C. for 5 hours, and then its weight ffi (W2) was precisely weighed. Similarly, after being left in a circulating dryer at 95% RH and 25° C. for 5 hours, the weight (W3) was accurately weighed.

The moisture absorption rate of the sample under each condition was determined using the following formula.

The results are shown in Table 2 below. The table also shows the moisture absorption rate determined in the same manner using ordinary rayon yarn with a count of 20.

Table 2 Next, TR-10, GR-10 and IBR-10 cotton are JI
It was washed 50 times and 100 times using the S K 1004 washing method, and A1 and A2 were determined in the same manner as above. The results are shown in Table 3 below.

Table 3 (3) Water Absorption A water absorption test was conducted as follows using the same TR-10° viscose rayon and 20 count cotton spun yarns used in the hygroscopic test.

Approximately 0.5 g of each sample was dried in a circulating air dryer at 105° C. for 3 hours, and the weight (Wl) after drying was accurately weighed. After pouring 500 cc of deionized water at 20°C into a 1Ω container, the sample is immersed for 3 minutes. Thereafter, the sample was drained on a 42-mesh wire mesh, and the weight (W2) after water absorption was accurately measured.

The water absorption rate of the sample was determined using the following formula.

1 The test was carried out 5 times/1l11 under the same conditions, and the average value was determined.

The results were 9.9 for TR-10 and 4. for viscose rayon.
5. Cotton was 3.9.

(4) 1 g of TR-10 cotton and 5 g each of each malodorous gas (hydrogen sulfide, ammonia, and pyridine) in a deodorizing tetra bag (gas analysis bag made of vinylidene fluoride film, volume 5 Ω)
was sealed and the gas concentration was measured after leaving it for 1 hour. Each gas was decomposed (hydrogen sulfide) adsorbed (ammonia) or neutralized (pyridine) by TR-10, and its concentration was reduced.

Next, 10 g of TR-10, GR-10, and IBR-10 cotton was immersed in an aqueous solution of a metal salt (CuSO4 or ZnCfl2) in which each metal ion was 296 (owf) and left for 10 minutes. . This was then thoroughly washed with distilled water and dried in a dryer at 70°C for 3 hours to obtain TR-10 cotton adsorbed with metal ions. Using this sample, the same malodorous gas removal test as above was conducted.

The results are shown in Table 4.

Table 4 (Gas concentration PI) m) Table 5 (
Gas concentration 111+ff+) JIS K
The sample was washed 50 times using the 1004 washing method, and a malodorous gas removal test was conducted in the same manner as above. The results were as shown in Table 5 below.

(5) Antibacterial properties TR-5, TR-10, and TR-20 cotton samples were tested for antibacterial properties using the shake flask method (accreditation standard for antibacterial and deodorant processed products). The test strain was Staphylococcus 5taph71o coccusaureus as a Gram-negative bacterium.
Klebs as FDA209P and Gram-negative bacteria
iel! apneumoniae ATCC4352
There are two types.

The results (bacterial killing rate) are shown in Table 6.

Table 6 Next, the same TR-10, GR-10 and IBR-10 cotton was washed 50 times and 100 times using the JIS K1004 washing method.
It was washed twice and subjected to the same antibacterial test as above. The results are as follows.

(6) JIS dyeing using TR-10 and regular rayon cotton
The dyeing rate (%) was tested in accordance with L 1015 7.30. The results are as follows.

Table 8 was set and 100 g of water containing metal ions was filtered. The remaining metal ions in the furnace fluid were measured using an atomic absorption spectrometer.

The results are shown in Table 9.

Table 9 (7) Heavy metal ion scavenging properties A thin fibrous web was made by uniformly blending 80% TR-10 cotton with 20% composite fibers of polypropylene core and polyethylene sheath. While heating it, roll it into a roll shape, with an outer diameter of 70 mm, an inner diameter of 30 mm, a length of 250 m, and a density of 0.3.
A cartridge filter of g/cd was created. Next, attach this to the filter cylinder housing, then TR-10, GR-10 and
BR-10 cotton was soaked in Marcel soap aqueous solution (soap concentration 1g/
Ω) according to JIS K 1004 washing method 2
It was washed 5 times and 100 times, and the relationship between the number of washings and the copper ion collection rate was determined. The results are shown in Table 10 below.

The appearance changes in the table are the appearance of samples after washing 100 times.

No. 0 table (Hereafter Up)

Claims (4)

[Claims] (1) Regenerated cellulose with a degree of polymerization of 100 to 500 60 to 9
It is a mixture of 9% by weight and 40-1% by weight of vinyl acetate-maleic acid copolymer, and both components of the mixture are molecularly mixed and solidified to form a cellulose-based composition with an ion exchange function. thing. (2) The cellulose composition according to claim 1, wherein the ion exchange function is water absorption, deodorizing, antibacterial, staining, and/or metal trapping function. (3) The cellulose composition according to claim 1 or 2, wherein the regenerated cellulose is viscose rayon. (4) Claim 1 wherein the vinyl acetate-maleic acid copolymer has a weight average molecular weight of 10,000 to 2,000,000.
, 2 or 3. The cellulose composition according to .