JPH01320059A - Deodorizing material and manufacture of same - Google Patents

Abstract

PURPOSE:To enhance processing easiness and provide applicability to a wide extent of deodorizing fields by attaching Cu(OH)2 in colloidal state to fibers of cellulose type. CONSTITUTION:To fix Cu(OH)2 by attaching it while taking colloidal state, alkali substance for ex. is added to an aqueous solution of water soluble Cu compound in which fibers of cellulose type are dispersed, with the pH adjusted to 4.5-12 to produce Cu(OH)2 colloid, which is attached to the fibers and fixed. The water soluble Cu compound is not defined specifically-anything which is soluble in water-for ex. copper sulfate, copper chloride, copper nitrate, and copper acetate. The alkali substance to generate alkalinity may be any which produces Cu(OH)2 colloid upon reaction with above-mentioned Cu compound-for ex., sodium hydroxide, kalium hydroxide, sodium carbonate, and sodium hydrogencarbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a deodorizing material for removing malodorous components present indoors, in refrigerators, or in various environments.

(Prior Art) Conventionally, deodorizers and the like containing activated carbon as a main component have been used to remove malodorous components from indoors, refrigerators, and the like.

These malodorous components include ammonia, methyl mercaptan, methyl sulfide, methyl disulfide, hydrogen sulfide, trimethylamine, and acetaldehyde.

(Problem to be Solved by the Invention) However, in the deodorizing agent mainly composed of activated carbon, the activated carbon is granular and black, so it must be stored in a container with a good appearance, and it is bulky. Therefore, there were various restrictions when using it. For this reason, deodorizing materials that can be molded into any shape are desired, and deodorizing materials based on cellulose fibers that are easy to dispose of after use and do not pollute the environment are particularly desired. Ta.

Furthermore, there has been a demand for a deodorizing material that effectively acts not only on a single malodorous component but also on a wide range of malodorous components.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have found that CLI(OH)2 can be efficiently attached and immobilized on cellulose fibers under specific manufacturing conditions, and Cu(OH)2 can be efficiently attached and immobilized on cellulose fibers. The present invention was completed based on the discovery that the deodorizing fiber formed by fixing 2 acts effectively against a wide range of malodorous components.

That is, the present invention provides a method for producing deodorizing fibers, which comprises: 1) attaching and immobilizing Cl(OH)2 in a colloidal state to cellulose fibers.

2) Add an alkaline substance to an aqueous solution of a water-soluble copper compound in which cellulose fibers are dispersed to obtain a pi (4°5-12
1. A method for producing deodorizing fibers, which comprises: producing Cu(OH)2 colloid by doing this, and fixing CO(OH)2 by bringing the colloid into contact with cellulose-based 'a' fibers.

3) The method for producing deodorant fibers according to claim 2, wherein the cellulose fibers are acid-treated before being dispersed in an aqueous solution of a water-soluble copper compound.

4) After adding cellulose fibers to an alkaline aqueous solution with a pH of 9.5 or less, add an aqueous solution of a water-soluble copper compound, and further add an alkaline aqueous solution as necessary to reach a pH of 4.
, 5 to 12 to produce a Cu(OH)2 colloid, and the Cu(OH)2 is immobilized by contacting the colloid with a cellulose fiber. Method.

5) A deodorant fiber characterized by being formed by immobilizing Cu(OH)2 on cellulose fiber.

6) The deodorant fiber according to claim 5, wherein the cellulose fiber is a pulp fiber.

7) A deodorizing material containing cellulose fibers with immobilized Cu(OH)2.

8) The deodorizing material according to claim 7, which has a sheet-like shape.

It is related to.

The cellulose fibers used in the present invention include bleached sulfide pulp (NBSP, LBSP, NDSP and L
DSP, etc.) and bleached kraft pulp (NBKP, LBKP, etc.)
etc.), hemp such as Manila hemp and jute, cotton such as absorbent cotton, natural fibers such as cotton linters, paper mulberry and Japanese mulberry, and pulped products thereof, and rayon.

Two or more of these cellulose fibers may be used in combination.

In the present invention, Cu(OH) is added to the above cellulose fiber.
In order to immobilize Cu(OH)2 to make a deodorizing fiber, Cu(OH)2
A colloid is generated, and the colloid is attached to and immobilized on cellulose fibers.

Even if CLI(OH)2 in a solid state other than a colloidal state is attached, it will not be immobilized on the cellulose fibers and will not become a deodorizing fiber.

Examples of methods for attaching and immobilizing Cu(OH)2 in a colloidal state include the following methods.

Production method 1 CL is produced by adding an alkaline substance to an aqueous solution of a water-soluble copper compound in which cellulose fibers are dispersed to adjust the pH to 4°5 to 12, more preferably to pH 6.0 to 9.5.
A J(OH)2 colloid is generated, and the colloid is attached to and immobilized on cellulose fibers. pH4,5-1
If it is not within the range of 2, Cu(OH)2 colloid will not be produced.

In addition, if immobilized at a pH lower than pH 6.0, the amount and rate of immobilization will be low, and if immobilized at a pH higher than pH 9.5, the cellulose fibers tend to become brittle.
The range of 0 to 9.5 is more preferable. When the pH is high, it is more preferable to wash with water after immobilization.

In addition, if cellulose fibers are treated with an acid such as hydrochloric acid, sulfuric acid, sulfurous acid, or nitric acid before dispersing them in an aqueous solution of a water-soluble copper compound, they will be deodorized! Since the color of the I-fiber is brighter, it is more preferable in terms of product appearance.

Manufacturing method 2 After adding cellulose fibers to an alkaline aqueous solution with a pH of 9.5 or less, an aqueous solution of a water-soluble copper compound is added, and if necessary, an alkaline aqueous solution is added to adjust the pH to 4.5.
By adjusting the pH to 12, more preferably 6,0 to 9.5, Cu(OH)2 colloid is generated, and the colloid is fixed by attaching it to the cellulose fiber.

At this time, it is not preferable to add cellulose fibers to an alkaline aqueous solution with a pH exceeding 9.5 because the fibers become brittle. Also,
The pH during immobilization is for the same reason as in the above-mentioned production method 1.

The water-soluble copper compound used in the present invention is not particularly limited as long as it can be dissolved in water, and examples thereof include sulfuric acid steel, chlorinated steel, copper nitrate, copper acetate, and the like.

The alkaline substance that provides alkalinity used in the present invention is Cu(0)-1) which reacts with the copper compound described above.
Any material capable of producing two colloids may be used, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate. Among these, sodium hydroxide and potassium hydroxide are more preferable because they allow pH adjustment.

The deodorizing fiber obtained as described above may be used as a deodorizing material as it is, or it may be further processed into a sheet-like or three-dimensional molded article by a known papermaking method and used as a deodorizing material.

When processing into a molded product, two or more types of cellulose fibers with fixed Cu(OH)2 may be used in combination, and Cu(OH)2 may be fixed within a range that satisfies the necessary deodorizing performance. Unprocessed cellulosic fibers or other types of fibers may be mixed.

Additionally, when processing into a molded product, commonly used papermaking aids such as wet paper strength enhancers and polymer flocculants may be added to the extent that the deodorizing performance of the molded product is not impaired. .

Furthermore, the molded article obtained as described above may be subjected to secondary processing to be used as a deodorizing material.

(Effect of the invention) The production method of the present invention, that is, Cu(OH
)2 in a colloidal state to form Cu(OH
) 2 can be immobilized on cellulose fibers.

CC1 (
OH)2 exhibits deodorizing properties by acting on ammonia, methyl mercaptan, methyl sulfide, methyl disulfide, hydrogen sulfide, trimethylamine, and acetaldehyde, as well as ammonia and hydrogen sulfide in aqueous solutions. Shows particularly excellent deodorizing performance against mercaptans, hydrogen sulfide, etc.

Furthermore, the deodorizing fiber of the present invention on which CLI(OH)2 is immobilized is an excellent deodorizing material as a single fiber, but because of its fibrous form, it has excellent processability and can be used in any form such as a sheet. It can be processed into a shaped molded body and used as a deodorizing material, and can be applied to a wide range of deodorizing fields.

(Examples) The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Incidentally, the sinus values in the examples were measured by the following method.

(1) Copper concentration Measured by atomic absorption spectrophotometry.

(2) Moisture of measurement sample (%) According to JIS P8203.

(3) Deodorizing performance test method 1 Put 1 g of the measurement sample in a 1.5 L plastic bag, and remove the odor gas at the specified concentration.
After filling the sealed bag and sealing it, the concentration of the malodorous gas remaining in the sealed bag is measured using a gas detection tube after a predetermined period of time, and the residual rate (
%) was calculated.

Test method 2 Measurement sample 0.5g was placed in a glass tube (length 13cm, inner diameter 1.
5cm), and inject the foul-smelling gas (N) into the gas inlet at one end.
0.2L of 5L of air containing (initial concentration 11000pp for H3, initial concentration 500ppm for H2S, initial concentration 250ppm for acetaldehyde)
The operation of measuring the malodorous gas concentration of the air discharged from the outlet at the other end with a gas detection tube was repeated, and the residual rate (%) of the malodorous gas concentration from the initial concentration was calculated.

Examples 1-3 NBSPi 00 as cellulose fiber in 2OL of water
After adding 0g and disintegrating it into a slurry in a disintegrator, SO3
Water was added to adjust the pH to 3.3 and acid treatment was performed. Next, a sulfuric acid prepared aqueous solution (CuSOa・5H20 as 20
Copper sulfate was added in an amount of 3 W/W% (calculated as copper) to NBSP. Furthermore, sodium hydroxide aqueous solution (
120g/L) was used to adjust the pH to 5, 0, 6, 0, 9, and 5 respectively to produce Cu(OH)2 colloid, and the colloid was attached to and immobilized on NBSP fibers to obtain deodorizing fibers. Examples 1 to 3 were obtained. Furthermore, each sheet is made into a sheet using a sheet machine and dried to weigh approximately 410g.
/rn2 sheet was obtained.

For each sheet, the '51-equivalent fixation m (W/W%) with respect to Cu(OH)20NBSP was measured, and the fixation rate (%) with respect to the amount of copper added was calculated. The results are summarized in Table-1.

From the results in Table 1, it is clear that the fixation amount and fixation rate are excellent in the range of I)H6°0 or more.

Table-1 Examples 4 to 7 NBSPl 00 as cellulose fiber in 2OL of water
After adding 0g and disintegrating it into a slurry in a disintegrator, SO2
Water was added to adjust the pH to 3.3 and acid treatment was performed. Next, @aqueous solution for acid (CuSOa・5H20 as 20
0g/L) (7) NBSPC: Examples 4 to 7 were prepared by changing the amount added in terms of copper as shown in Table 2.
And so. Next, each sodium hydroxide solution M (120g
/L) was added to adjust the pH to 8 to produce CLJ(OH)2 colloid, and the colloid was attached to and immobilized on NBSP fibers to obtain deodorizing fibers.

Furthermore, each of these was formed into a sheet using a sheet machine and dried to obtain a sheet having a weight of about 410 g/m2.

Next, for each sheet, NB of Cu(OH)2
The fixed ffi (W/W%) in terms of copper with respect to SP was measured, and the fixed rate (%) with respect to the amount of copper added was calculated. The results are summarized in Table-2.

Examples 8 to 11 1000 g of cellulose fiber NBSP was added to 2 OL of an alkaline aqueous solution with pH 9.5 by adding sodium hydroxide.
was added and disintegrated into a slurry using a disintegrator. Furthermore, @aqueous solution for acid (200g/as CuSOa・5H20)
Table 3: Copper sulfate in terms of copper to NBSP using L)
Example 8
~11.

Furthermore, each sodium hydroxide solution YiJ (120g
/L) to produce Cu(OH)2 colloid, and the colloid was adhered to and fixed on NBSP to obtain a deodorizing fiber.

Furthermore, each of these was formed into a sheet using a sheet machine and dried to obtain a sheet having a weight of about 410 g/m2.

Next, for each sheet, N of CLI(OH)2
The fixed ffi (W/W%) in terms of copper with respect to BSP was measured, and the fixed rate (%) with respect to the amount of copper added was calculated. The results are summarized in Table 3.

[Hereinafter, blank Table 2 Table 3 Next, Examples 4 to 11 were tested for deodorizing performance against I-123 gas and NH3 gas using Test Method 1 described above. Tables 4 to 5 summarize the obtained results.
Shown below. Examples 4 to 7 were tested for deodorizing performance against methyl mercaptan gas using the test method 1 described above. The obtained results are summarized in Table 6. Examples 6 and 7 were tested for their deodorizing performance against acetaldehyde gas using Test Method 1 described above. The obtained results are summarized in Table-7.

In addition, for Examples 4 to 7, according to the test method 2 described above,
The deodorizing performance against H2S gas and NH3 gas was tested. The obtained results are summarized in Tables 8 and 9. Examples 6 and 7 were tested for deodorizing performance against acetaldehyde gas using the Nonast method 2 described above. The obtained results are summarized in Table-10.

As mentioned above, from the results in Tables 4 to 10, the deodorizing material of the present invention
It is clear that it acts effectively against each malodorous gas component of S gas, NH3 gas, acetaldehyde gas, and methyl mercaptan gas.

[Below, blank table - 4 Residual character table of H2S gas according to test method 1 - 5 Residual character table of NH3 gas according to test method 1 - 6 Residual ratio table of methyl mercaptan gas according to test method 1 - 7 Acetaldehyde according to test method 1 Gas residual rate table-8 H2S gas residual rate table according to test method 2-9 NH3 gas residual rate table according to test method 2-10 Acetaldehyde gas residual rate table according to test method 2 Comparative examples 1 to 3 Cellulose in 2 OL of water After adding 1000 g of NBSP based fiber and disintegrating it into a slurry using a disintegrator, commercially available Cu(
Weight ratio of 4W/W% dispersion of OH)2 fine powder to pulp in terms of copper: NBSP/Cu = 98/2.
Comparative Example 1 with 96/4 and 94/6 added, respectively
~3. Further, each mixture was mixed for 30 minutes, and then formed into a sheet using a sheet machine and dried to obtain a sheet having a weight of about 410 g/m2.

When either sheet was rubbed by hand, the Cu(OH)2 powder fell off and the Cu(OH)2 was not immobilized.

Examples 12-14 NDSPl 00 as cellulose fiber in 2OL water
After adding 0g and disintegrating it into a slurry in a disintegrator, SO2
Water was added to adjust the pH to 3.3 and acid treatment was performed. Next, Examples 12 to 14 were prepared by adding 2.4.6 W/W% of copper chloride in terms of copper to NDSP using a chloride prepared aqueous solution (CuC1□.2H20). Next, an aqueous sodium hydroxide solution (120 g/L) was added to each to adjust the pH to 8 to produce Cu(OH)2 colloid, and the colloid was attached to NDSP fibers and identified to obtain deodorant fibers.

Furthermore, each of these was formed into a sheet using a sheet machine and dried to obtain a sheet having a weight of about 410 g/m2.

Next, for each sheet, ND of Cu(OH)2
The fixed amount (W/W%) in terms of copper with respect to SP was measured, and the fixed rate (%) with respect to the added amount of copper was calculated. The results are summarized in Table-11.

Next, each sheet was tested for deodorizing performance against H2S gas and NH3 gas using Test Method 1 described above. The obtained results are shown in Table-12 and Table-13.

From the results in Tables 11 to 13, Cu(OH
) It is clear that the object of the present invention can also be achieved by producing colloids.

Table-11 Table-12 Residual rate of H2S gas according to test method 1 Table-13
Residual rate of NH3 gas according to test method 1 Examples 15 to 17 1000 g of absorbent cotton as cellulose fiber in 2 OL of water
After adding and disintegrating into a slurry in a disintegrator, S02 water was added to adjust the pH to 3.3 and acid treatment was performed. Next, a sulfuric acid prepared aqueous solution (200 g/L as CuS04.5H20)
) was added in an amount of 2.4.6 W/W% in terms of copper to absorbent cotton as Examples 15 to 17, respectively. Next, a sodium hydroxide aqueous solution (120 g/L) was added to each p
Adjust to H8 to produce Cu(OH)2 colloid,
The colloid was attached to absorbent cotton and fixed to obtain deodorizing fiber.

Furthermore, each of these was formed into a sheet using a sheet machine and dried to obtain a sheet having a weight of about 410 g/m2.

Next, the fixed ffi (W/W%) of Cu(OH)2 relative to absorbent cotton in terms of steel was measured for each sheet, and the fixed rate (%) with respect to the amount of copper added was calculated.

The results are summarized in Table-1/l.

Next, each sheet was tested with H2S using test method 1.
A deodorizing performance test was conducted for gas and NH3 gas. The results obtained are shown in Tables 15 and 16.

From the results in Tables 14 to 16, it is clear that the object of the present invention can be achieved even if absorbent cotton is used.

[The following is blank space] Table-14 Table-15 Residual rate of H2S gas according to test method 1 Table-16
Residual rate of NH3 gas by test method 1 Examples 18 to 20 Rayon 1000 as cellulose fiber in 2 OL of water
After the slurry was disintegrated into a slurry using a disintegrator, SO2 water was added to adjust the pH to 3.3, followed by acid treatment. Next,
Copper sulfate aqueous solution (Cu SO4.5H20 as 200
g/L, > 2.4.6W in copper equivalent for rayon
/W% were added as Examples 18 to 20, respectively. Next, each sodium hydroxide aqueous solution (120 g/L)
was added to adjust the pH to 8 to produce Cu(OH)2 colloid, and the colloid was adhered to and immobilized on rayon fibers to obtain deodorizing fibers.

Furthermore, each of these was formed into a sheet using a sheet machine and dried to obtain a sheet having a weight of about 410 g/m2.

Next, for each sheet, the amount of Cu(OH)2 fixed in terms of copper (W/W%) with respect to rayon was measured, and the fixation rate (%) with respect to the amount of copper added was calculated. The results are summarized in Table-17.

Next, test method 1 for each sheet:
A deodorizing performance test was conducted for S gas and NH3 gas. The results obtained are shown in Tables 18 and 19.

From the results in Tables 17 to 19, it is clear that the object of the present invention can be achieved even when rayon is used.

[Hereafter, blank space] Table-17 Table-18 Residual rate of H2S gas according to test method 1 Table-19
Residual rate of NH3 gas by test method 1 Examples 21 and 2
2 Using NBKP as cellulose fiber, NBKPlo
After immersing the og in 300 g of water, it was pulverized using a pulverizer.

Next, S02 water was added to adjust the pH to 3, and after further mixing, copper sulfate aqueous solution (CuSO4.5H2) was added to NBKP.
200g/L) was added and mixed at 4W/W% in terms of copper. Next, sodium hydroxide aqueous solution (120g/
L) was added to adjust the pH to 8, and the mixture was further mixed.

Next, it is made into a sheet using a sheet machine and dried to approximately 41 cm.
Example 21 was a sheet having a weight of 0 g/m2.

In addition, a product treated in the same manner as in Example 21 until the pH was adjusted to 8 was dehydrated, then mixed with untreated NBKP disintegrated into a slurry at a ratio of 1=1 in terms of solid content, and then mixed using a sheet machine. Example 22 was formed into a sheet and dried to form a sheet with a weight of about 410 g/m2.

Regarding these, in test method 1 1] 2S scum and NH3
We conducted a gas deodorizing performance test. The results obtained are shown in Tables 20 and 21.

Table-20 Residual character table of H2S gas by test method 1-21
Residual rate of NH3 gas according to test method 1 Example 23 After immersing 5 g of a sheet produced in the same manner as in Example 13 in 50 ml of dilute ammonia aqueous solution (concentration 2000 ppm) and stirring, the ammonia odor of the aqueous solution was left to stand for 1 hour. When I smelled it, I didn't notice any ammonia odor.

Example 24 5 g of a sheet produced in the same manner as in Example 13 was diluted with diluted H2S.
After being immersed in 50 ml of an aqueous solution (concentration 4000 ppm) and stirring, the sample was allowed to stand for 1 hour and then smelled the H2S odor of the aqueous solution, but no H2S odor was detected.

Claims (1)

[Scope of Claims] 1) A method for producing deodorizing fibers, which comprises attaching and immobilizing Cu(OH)_2 in a colloidal state to cellulose fibers. 2) Add an alkaline substance to an aqueous solution of a water-soluble copper compound in which cellulose fibers are dispersed to adjust the pH to 4.5 to 12 to generate Cu(OH)_2 colloid, and bring the colloid and cellulose fibers into contact. A method for producing deodorant fibers, characterized by fixing Cu(OH)_2. 3) The method for producing deodorant fibers according to claim 2, wherein the cellulose fibers are acid-treated before being dispersed in an aqueous solution of a water-soluble copper compound. 4) After adding cellulose fibers to an alkaline aqueous solution with a pH of 9.5 or less, add an aqueous solution of a water-soluble copper compound, and further add an alkaline aqueous solution as necessary to reach a pH of 4.
．． 5 to 12 to produce a Cu(OH)_2 colloid, and the Cu(OH)_2 is immobilized by contacting the colloid with a cellulose fiber. . 5) A deodorizing fiber characterized by being formed by immobilizing Cu(OH)_2 on cellulose fiber. 6) The deodorant fiber according to claim 5, wherein the cellulose fiber is a pulp fiber. 7) A deodorizing material containing cellulose fibers with immobilized Cu(OH)_2. 8) The deodorizing material according to claim 7, which has a sheet-like shape.