KR0175566B1 - Process for preparing deodorizing agent of chitosan component - Google Patents

Abstract

The present invention is to provide a method for producing a chitosan-based deodorant which is a chemical adsorption deodorant widely used in foods, pharmaceuticals, cosmetics, perfumes and physiological products.

The chitosan-based deodorant of the present invention can quickly remove ammonia, mercapto and hydrogen sulfide-based odors as compared with the conventional deodorant.

The method for preparing a chitosan-based deodorant of the present invention comprises reacting an inorganic acid salt solution with a transition metal of the fourth cycle of the periodic table to form a chitosan metal complex solution, and washing and drying the metal complex with a hydrophilic solvent.

Chitosan-based deodorant of the present invention is mainly applied to diapers, sanitary napkins, food and cosmetics because it can quickly remove ammonia, mercapto and hydrogen sulfide-based odor.

Description

Manufacturing Method of Chitosan Deodorant

The present invention relates to a method for producing a chitosan-based deodorant. More specifically, the organic acid salt or inorganic acid salt of chitosan can be prepared by forming a complex with a transition metal to quickly remove odors in nitrogen, mercaptans, and hydrogen sulfides such as ammonia. It relates to a manufacturing method of chitosan-based deodorant that can be widely used in fragrances and sanitary products.

Chitin and chitosan have increased interest in industrial and biochemical applications. And since it is known that chitosan is soluble in organic acids, especially ascorbic acid and salts in water (RA A Muzzareilli et al., Carbohydr. Polym., 4, 137 (1984)), its field of use has increased and have.

Conventionally, activated carbon is typical as a chemisorption deodorant, and the method of using together ferrous sulfide and L-ascorbic acid, and a phthalocyanine chelate compound are known. Activated carbon deodorizers currently in use have an effect on low concentration ranges and various kinds of malodorous substances, but have a disadvantage in that deodorization performance is deteriorated at high concentrations and high temperatures. In addition, the deodorant using a combination of ferrous sulfide and L- ascorbic acid has the disadvantage that the deodorizing performance is poor because the iron sulfide is oxidized in the air. Phthalocyanine-based chelate deodorants have excellent performance on ammonia, but have poor deodorizing performance on hydrogen sulfide systems. All these deodorants have a color according to the transition metal, there are many problems when used in sanitary products, cosmetics and the like.

Accordingly, the present invention is to solve such problems in the prior art, significantly improved deodorization performance than conventional nitrogen-based, mercaptans and hydrogen sulfide-based, powder, bead-type or capsule-type excellent processability and water resistance It is an object to provide a method for producing a chitosan-based deodorant.

Hereinafter, the present invention will be described in detail.

Powdered, beaded, or encapsulated chitosan-based deodorant of the present invention reacts an organic or inorganic acid solution in which chitosan is dissolved with a transition metal of the fourth cycle of the periodic table to form a chitosan metal complex solution and converts the metal shaft end into a hydrophilic solvent. It is characterized by being prepared by washing and drying.

Referring to the present invention in more detail as follows.

The present invention provides a method for producing a powdery, porous bead-type or capsule-type chitosan-based deodorant from a metal complex obtained by reacting an organic acid salt or an inorganic acid salt of chitosan with a transition metal of the fourth cycle of the periodic table. The chitosan-based deodorant prepared according to the present invention can quickly remove ammonia, mercaptones, or hydrogen sulfide-based odors compared to conventional deodorants, and can be widely used in diapers, sanitary napkins, food or cosmetic fields. There is this.

The chitosan used in the present invention is obtained by deacetylating chitin obtained by heating shrimp shell, crab, etc. with caustic soda and treating with hydrochloric acid or the like, and the chitosan suitable for the present invention has a deacetylation degree of 50 to 95%. And the degree of polymerization is about 200 to 25,000.

If the degree of deacetylation of chitosan is less than 50%, the solubility is poor, and if it exceeds 95%, the chitosan having a degree of deacetylation of 50 to 95% is most preferable.

In addition, in the degree of polymerization, chitosan having a degree of polymerization outside the above range is not only difficult to prepare, but also unfavorable in terms of physical properties, and therefore, chitosan having a degree of polymerization within the above range is most suitable.

Meanwhile, according to the method of the present invention, first, 1 part by weight of chitosan as described above is dispersed in 20 to 200 parts by weight of distilled water, and an organic acid or an inorganic acid varies depending on the degree of deacetylation of the chitosan, but is generally the same mole as the amine group of the chitosan. After adding the same amount to about 15 parts by weight or more, the mixture is stirred at a temperature in the range of about 5 to 50 ° C. to completely dissolve the chitosan, thereby preparing a chitosan organic acid salt or an inorganic acid salt.

As the organic acid used in the present invention, acetic acid, tartaric acid, salicylic acid, citric acid, hydroxy acid, acetic acid, ringoic acid, propionic acid, lactic acid, glycerin acid, L-ascorbic acid, xenoic acid, sulfoamine acid or formic acid can be used. Among them, acetic acid, salicylic acid, citric acid or L-ascorbic acid are most preferred, and sulfuric acid, hydrochloric acid or phosphoric acid may be used as the inorganic acid, and sulfuric acid and hydrochloric acid are most preferred.

In the above method, when the temperature of the organic or inorganic acid salt is lower than 5 ° C., the reaction does not occur well. On the contrary, when the temperature exceeds 50 ° C., the organic or inorganic acid is volatilized, as described above. It is good to carry out within the range of ° C.

As described above, after preparing an organic acid salt or an inorganic acid salt of chitosan according to the method of the present invention, it is reacted by adding about 0.1 to 10 parts by weight of transition metal of the fourth period of the periodic table, and reacting with 2 to 15% by weight of caustic. When the pH is adjusted to 3 to 6 with soda, a chitosan metal complex is obtained.

When the chitosan metal complex obtained by the above method is washed with a hydrophilic solvent and dried, a chitosan deodorant according to the present invention is prepared.

Examples of the transition metal of the fourth period of the periodic table used in the present invention include Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, among which Fe, Co, Cu or Zn is most preferred. When they are used in the process of the invention, 0.3 to 2.5 equivalent ratios of amine group content may be added as metal chlorides or metal sulfates.

Moreover, acetone, distilled water, ethanol, methanol, isoflophyl alcohol, propyl alcohol, glycerin, or methyl ethyl keron is mentioned as a hydrophilic solvent used by this invention.

All of the methods according to the present invention as described above are preferably carried out in an inert gas atmosphere such as nitrogen gas, carbon dioxide gas, helium gas or argon gas, because the physical strength of the finally obtained deodorant can be increased. to be

Meanwhile, in order to prepare the chitosan deodorant in powder form by the method according to the present invention, the chitosan metal complex is precipitated in the hydrophilic solvent before being washed with the hydrophilic solvent and then filtered and treated for about 2 hours at about 40 to 70 ° C. Drying in vacuo may produce a powdery chitosan-based deodorant.

In addition, in order to prepare the chitosan deodorant in the form of beads by the method according to the present invention, before forming the chitosan metal complex, an organic or inorganic acid solution of chitosan is added dropwise to an alkaline solution of 2 to 15% by weight of the chitosan organic acid salt beads. After the preparation, the transition metal was immersed in a hydrophilic solvent containing 0.1 to 0% by weight and slowly stirred or treated under a standstill condition at a temperature of about 10 to 50 ° C. for about 30 minutes to 2 hours, and then a bead-type chitosan system. Deodorant can be prepared.

In the above, the alkaline solution serves as a coagulant, and it is preferable to use caustic soda or ammonia solution.

In addition, in order to prepare the chitosan-based deodorant in a capsule form by the method according to the present invention, when the chitosan metal complex is added dropwise to 0.5 to 1% by weight of a polyanionic solution before washing the hydrophilic solvent, the chitosan-based deodorant Can be prepared.

Examples of the polyanion solution used herein include sodium alginate, methoxy pectin, Na-carboxy methyl cellulose sodium (Na-CMC), heparin, condojinsulphurethane, xanthan gum, or gum arabic. Na-carboxy methyl cellulose sodium is most suitable.

As described above, the organic acid salt or inorganic acid salt of chitosan is complexed with the transition metal to prepare a deodorant in powder form, porous bead form, and capsule form from the ammonia and mercaps. Not only can the carbon and hydrogen sulfide odors be removed quickly, but it can be widely used in diapers, sanitary napkins, food and cosmetic fields.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples.

Example 1

1 g of chitosan powder was suspended in 100 g of ion-exchanged water, mixed uniformly in a stream of nitrogen, 1.5 g of L-ascorbic acid was added, stirred and dissolved at 20 ° C to prepare an ascorbate solution of chitosan. 2 g of ferric chloride was added thereto, and a chitosan complex was formed at a pH of 5 to 6 with a caustic soda solution. The solution was added to 300 g of acetone to precipitate, filtered, washed with distilled water, washed with acetone and dried to obtain a powdery chitosan deodorant.

Example 2

1.5 g of chitosan powder was suspended in 100 g of ion-exchanged water, uniformly mixed in a stream of nitrogen, 2 g of L-ascorbic acid was added, stirred and dissolved at 20 ° C. to prepare an ascorbate solution of chitosan, and then caustic soda through a nozzle. Chitosan beads were prepared by dropwise addition to a 2% by weight solution (coagulant), filtered and washed with distilled water and dried. The chitosan beads were then immersed in a methanol solution containing 1 wt% ferrous chloride solution at 20 ° C. for 3 hours to form an iron ion complex, filtered, washed with methanol, and dried to obtain a bead-type chitosan deodorant.

Example 3

1 g of chitosan powder was suspended in 100 g of ion-exchanged water, mixed uniformly in a stream of nitrogen, 1.5 g of acetic acid was added, stirred and dissolved at 20 ° C. to prepare a acetate solution of chitosan. 2 g of ferric chloride was added thereto, and the pH was adjusted to 4 with a caustic soda solution. The solution was added dropwise to a caustic soda solution of 2% by weight through a nozzle to prepare chitosan beads, washed with distilled water and acetone, and dried to form beads. Chitosan type deodorant was obtained.

Example 4

The same procedure was followed as in Example 3 except that the sodium hydroxide concentration of the coagulation solution was changed to 3,5,7,9,10 and 15% by weight.

Example 5

The chitosan powder 1 was suspended in 100 g of ion-exchanged water, mixed uniformly in a nitrogen stream, and 1.5 g of L-ascorbic acid was added, stirred and dissolved at 20 ° C. to prepare an ascorbate solution of chitosan. 2 g of ferric chloride was added thereto, followed by adjusting the pH to 4 with a caustic soda solution, and dropping the solution into a 0.5% Na-carboxymethyl cellulose solution through a nozzle to prepare a capsule of the chitosan complex, distilled water and methanol Washed with and dried to obtain a capsule-type chitosan-based deodorant.

Example 6

In order to activate and deodorize the powdered, beaded, and capsule-type deodorant prepared in Examples 1 to 5, and to give excellent persistence, the sample was left in an ethanol solution containing EDTA 1% as a reducing agent for one hour. It filtered, dried and the chitosan type deodorant was obtained.

Comparative Example 1

The same procedure was followed in Example 1 except that the chitosan ascorbate solution was not complexed with iron salts.

[Test Example 1]

In a fully sealed 5000 ml desiccator, 1.0 g of deodorant samples (Examples 1, 3, 5, Comparative Example 1, and activated carbon) were taken, evenly divided to 50 mm in diameter, and filled with nitrogen gas to remove the atmosphere in the apparatus. .

The concentrations of hydrogen sulfide (H ₂ S) and ammonia (NH ₃ ) were mixed at 100 ppm, respectively, and the inside of the apparatus was filled and sealed, and then measured by gas chromatography every elapsed time (minutes). Deodorization effect was calculated by the residual amount (%) to the initial concentration.

The test results are shown in Table 1.

As shown in Table 1, Comparative Example 1 prepared with chitosan ascorbate was 60 minutes after the residual ratio was 57,4% for HS and 54.4% for NH. The removal rate and removal rate were very high, with the residual amount of 0.6 ~ 4.3%.

Claims (1)

A method for producing a chitosan-based deodorant comprising dissolving chitosan and a transition metal in an organic acid or inorganic acid solution, wherein the chitosan is contained in an amount of about 5 to about 15 times the amount of the molar group as the amine group of the chitosan. Dissolving in a temperature range of 50 ° C., dropping the obtained organic acid salt or inorganic acid salt of chitosan into an alkaline solution through a nozzle to form beads, and immersing the beads in a transition metal solution and adjusting the pH to 3-6. Method for producing a porous bead-type chitosan-based deodorant comprising the step of making a metal complex, and washing and drying the chitosan metal complex with a hydrophilic solvent.