JPH0663179B2 - Deodorizing carrier - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field) The present invention provides a polyacrylic acid / copper complex capable of deodorizing hydrogen sulfide or ammonia odorous substances as a base material for pulp, paper, fibers, etc. in good yield. The present invention relates to a fixed deodorizing carrier and a method for producing the same.

(Prior Art) Conventionally, since a polyacrylic acid / copper complex has a deodorizing ability to easily act on hydrogen sulfide or ammonia to deodorize it, it is fixed on a base material such as pulp, paper or fiber to deodorize it. It has been considered to be used as a material.

(Problems to be Solved by the Invention) However, since a material obtained by simply mixing and fixing a polyacrylic acid / copper complex with pulp, fibers, etc. has a weak affinity between the base material and the complex, depending on the use conditions. Had the drawback of desorbing the complex.

Further, when the complex and ammonia react to form an ammonium complex, they are easily dissolved in water. Therefore, when water comes into contact with the complex fixed on the substrate, the copper complex is said to be eluted. There were also shortcomings.

Because of these drawbacks, it is difficult to apply them to, for example, disposable diapers, deodorizing packaging papers, and deodorizing fibers, and it has been desired to solve these drawbacks.

(Means for Solving Problems) The inventors of the present invention have earnestly studied a method of supporting a copper complex on cellulose, an acrylic fiber, a polyclar fiber, etc. in order to realize the above-mentioned requirements, and as a result, a support for supporting the complex is attempted. A polymer that has a good affinity with the substrate, for example, after depositing chitosan on the surface of the substrate and then fixing the polyacrylic acid / copper complex, the complex will form a complex with chitosan, which is extremely efficient for the substrate. The present invention has been accomplished by finding that it can be firmly fixed. That is, 1. A deodorizing carrier in which chitosan / polyacrylic acid / copper complex is supported on the surface of a supporting substrate.

2. A method for producing a deodorizing carrier in which chitosan is deposited on the surface of a supporting substrate and then a dispersion liquid of a polyacrylic acid / copper metal complex is mixed or brought into contact with it. The deodorizing carrier of the present invention and the method for producing the same will be described below.

First, the base material is immersed in a dilute aqueous solution of chitosan, and then a caustic alkali or the like is added to neutralize the pH to 7 to 10 to form a chitosan layer on the surface of the base material.

Next, a powder of a polyacrylic acid / copper complex or an aqueous dispersion is added to this solution system, and after thoroughly stirring, the substrate is separated, and further washed with water and dried.

Chitosan can be fixed on a substrate by mixing chitosan with a dilute solution of acetic acid, hydrochloric acid, etc. and the substrate, and then neutralizing the solution to a pH of 7.0 to 10.0 with a dilute aqueous solution of sodium or potassium. It deposits on the material with good yield.

The chitosan used is a basic polysaccharide obtained by deacetylating chitin, and may be of a commonly available grade.

Also, polyacrylic acid may be of a commonly available grade.

The polyacrylic acid / copper complex is a known substance that can be easily obtained by adding copper ions to a polyacrylic acid aqueous solution in the form of copper hydroxide or the like.

The amount of chitosan used may be arbitrary depending on the amount of substrate, shape and amount of chitosan / polyacrylic acid / copper to be fixed. 0.001 to 0.5 part of chitosan, preferably 0.005 to 1 part of substrate
~ 0.1 copy is good.

The method for fixing chitosan / polyacrylic acid / copper to a substrate is to fix chitosan, which has affinity with the substrate such as cellulose, polyclar fiber, acrylic fiber, polyester, etc., to the surface layer of the substrate by means such as deposition. This is followed by mixing the polyacrylic acid / copper complex dispersed in a small amount of water.

The composition ratio of polyacrylic acid and copper is preferably 0.1 mol to 1.0 mol of copper per 1 mol of polyacrylic acid. The relationship between the amount of chitosan and polyacrylic acid is polyacrylic acid in the range of 10 to 0.01 parts, preferably 5 parts to 1 part of chitosan.
~ Part 1 is preferred.

(Action and effect) The composition of the produced copper complex is chitosan / polyacrylic acid /
Since it is a complex of copper, even if it comes into contact with ammonia and copper becomes an amine complex, a part that is coordinated with chitosan remains, so the elution of the copper amine complex is suppressed, and the elution of the copper complex is suppressed. It has favorable physical properties for applications that are unwilling.

Also, since the chitosan / polyacrylic acid / copper complex is distributed on the surface layer of the supporting substrate, the surface area of the chitosan / polyacrylic acid / copper complex per unit weight is large, and the entire space occupied by the bulk Therefore, it is preferable when a large surface area of the complex that comes into contact with a malodor is required as in the deodorizing effect.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

The method for quantifying the copper complex used in this example and the evaluation of the deodorizing activity of the carrier were carried out by the following methods.

(I) Quantitative Method for Copper After weighing 1 g of a measurement sample, it was ashed in a crucible, dissolved in nitric acid, and then quantified for copper in the complex by an atomic absorption method.

(II) Odor gas reduction effect measurement method 1.0 g carrier with copper complex fixed on the base material, length 80 mm, inner diameter 15 mm
The glass tube of is almost uniformly filled, and about 5 air containing a predetermined concentration of odorous gas is introduced into the gas introduction port at one end of the glass tube.
The odorous gas concentration of the air discharged from the outlet at the other end was measured, and the difference in odorous gas concentration before and after this treatment was taken as the odorous gas reducing effect.

Example 1 500 g of an aqueous solution containing 1% by weight of chitosan and 1% by weight of acetic acid
Was added to 100 g of well-powdered pulp and kneaded until the system became uniform, then 1% by weight of caustic potash was added to adjust the pH of the system to 7.
Adjusted to 0.

Separately, a solution of 15 g of copper hydroxide dissolved in 60 cc of water and 90 g of a 25% aqueous solution of polyacrylic acid were mixed and the resulting dispersion of polyacrylic acid / copper complex was added to the above pulp kneading system and mixed and stirred for 1 hour. After that, the pulp is separated, dehydrated and washed with water of 1.

After dehydration, it was dried at 60 ° C. for 10 hours to obtain 137.2 g of a pulp carrying a copper / polyacrylic acid / chitosan complex.

When 1 g of this carrier was taken and the amount of copper fixed was measured, it was 7.05.
%Met.

1 g of this pulp was taken and the hydrogen sulfide gas reducing effect and the ammonia gas reducing effect were measured by the odor gas reducing effect measuring method (gas phase method).

The above results are shown in Example 1 of Appendix 1.

Examples 2-7 Aqueous solution containing 0.5-2.0% by weight of chitosan and 1.0% of acetic acid 1
100 g of the various fibers shown in Appendix 1 after 000 g was washed thoroughly with water and defibrated
And kneading until the system becomes uniform, and then adjusting the pH of the system to 6.7 to 7.0 by adding a 1% by weight aqueous solution of caustic soda, and changing the ratio of copper hydroxide / polyacrylic acid as shown in Appendix 1. Except that the copper / acrylic acid complex synthesized in the same manner as in Example I was added, and after mixing and stirring, the fibers were separated and washed with water.
Each was dried to obtain a carrier of copper / polyacrylic acid / chitosan complex.

With respect to each of these carriers, the amount of copper deposited in the copper / polyacrylic acid / chitosan complex and the effect of reducing hydrogen disulfide gas and ammonia gas by them were measured.

These results are shown in Appendix 1.

Example 8 When the aqueous chitosan solution was deposited on the sheet-shaped pulp, the same treatment as in Examples 2 to 7 was repeated except that the impregnation / pressing was repeated 10 times instead of kneading, to prepare a copper / polyacrylic acid / chitosan complex. A carrier was obtained.

The amount of copper adhering to this carrier and the effect of reducing the hydrogen disulfide gas ammonia gas by this carrier were measured, and the results are shown in Appendix 1.

Comparative Example 1 In Example 1, the pulp was treated with polyacrylic acid / copper complex in the same manner as in Example 1 except that the treatment with the chitosan aqueous solution, which is the first treatment step, was not performed.
The pulp was dehydrated and dried, and treated pulp was obtained.

The amount of copper fixed in this pulp was measured and found to be 0.
It was 1% or less, and most of the polyacrylic acid / copper complex was not fixed.

Comparative Example 2 After treating the pulp with a polyacrylic acid / copper complex in the same manner as in Comparative Example 1, the pulp was dehydrated by squeezing without washing with water until the amount of water adhering to 80%, and then dried by a hot air dryer at 80 ° C. Then, a blue pulp having a polyacrylic acid / copper complex attached thereto was obtained.

The amount of copper fixed in this pulp was measured and found to be 2.3.
%, And the adhesion amount was significantly smaller than that in the case of Example 1.

Also, 10 g of this pulp was arranged in a 10 cm × 10 cm quadrilateral, and a 10 cm × 10 cm large wetted gold width was squeezed well, and a 1 kg weight was placed on it with a 10 cm × 10 cm glass plate and left for 3 hours. However, the gold strip was contaminated with the blue color of the polyacrylic acid / copper complex adhering to the pulp.

As described above, if the polyacrylic acid / copper complex was not treated with chitosan before it was attached, it could not be fixed to withstand washing with water, and even if it was intentionally attached gently, it would elute when exposed to water and contact The more it pollutes, the poorer the water resistance.

On the other hand, the fixing body using the chitosan of the present invention does not fall off even if washed with water, and the odorous substance of several thousand ppm is reduced to several hundred ppm, and the odorous gas of several hundred ppm cannot be detected. It has an excellent deodorizing effect as if it were deodorized to some extent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location D21H 19/10 D06M 15/263 7199-3B 11/04 G

Claims (4)

[Claims] 1. A deodorizing carrier in which chitosan / polyacrylic acid / copper complex is carried on the surface of a carrying substrate. 2. A method for producing a deodorizing carrier, which comprises depositing chitosan on the surface of a supporting substrate and then mixing or contacting a dispersion of a polyacrylic acid / copper metal complex. 3. The chitosan is deposited on the surface of the supporting substrate by immersing the supporting substrate in an acidic aqueous solution of chitosan and then making the solution alkaline. A method for producing the deodorizing carrier described. 4. The method for producing a deodorizing carrier according to claim 2, wherein the supporting substrate is a cellulose derivative, a polyvinyl alcohol derivative, or a polyacrylic fiber.