JPH01111067A - Deodorizing fiber and its production - Google Patents

Abstract

PURPOSE: To obtain a deodorizing fiber exhibiting an extremely excellent deodorizing property against stink gases over a long period by carrying a specific amount of a metal porphyrazine compound on a protein fiber. CONSTITUTION: This deodorizing fiber is obtained by carrying a metal porphyrazine compound of the formula (X is H, carboxy, sulfonic acid or their metal salts or amino, provided that at least one of X groups is H or amino; Me is a divalent or trivalent iron ion or cobalt ion) on a fiber in an amount of >=0.3 wt.% (preferably about 2 wt.%) based on the fiber. The deodorizing fiber is obtained by treating the protein fiber in the aqueous solution of the compound of the formula under conditions comprising pH 10 or lower and a temperature of 30-100 deg.C. The protein fiber carrying the metal porphyrazine compound is obtained in a good metal porphyrazine compound-carrying yield, and has an extremely excellent deodorizing property against stink gases over a long period.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a deodorizing fiber that has deodorizing properties and is used for stuffing, carpets, filters, etc., and a method for producing the same.

Conventional Technology Conventionally, commonly used deodorants include those that adsorb odor molecules, such as activated carbon, and those that use other odors to sensuously neutralize or mask them. The main thing was Additionally, devices are also used that use oxidizing agents and reducing agents to cause chemical decomposition and deodorization. The types and effects of these deodorants are summarized as follows.

A. Sensual deodorization■Fragrance? l (ntowor, cinnamic aldehyde, heliotrobin, camphor, bornyl acetate, etc.) ■Masking systems (wood vinegar, baladichlorbenzene, etc.) ■Neutralizing systems (turpentine oil, eucalyptus oil, sandalwood oil, etc.), organic acids etc.) B, chemical odor ■Desulfurization action (removes hydrogen sulfide, etc. with iron sulfate such as ferrous sulfate, iron chloride, etc.) ■Redox action (oxidizing agents such as ozone, chlorine dioxide, hydrogen peroxide, etc.) , reducing agents such as sodium sulfite, etc.) ■Addition/condensation action (addition agents: methacrylic acid ester, maleic acid ester, 8 mixtures: glyoxyzar, etc.) ■Ion exchange action (ampholytic activity of ion exchange resin) Ill cationic agent, anionic agent) C6 Physical/chemical odor ■Drug impregnation adsorption effect (alkaline or acid impregnated activated carbon, mixture of activated carbon and chemical reactant) D, Physical adsorption deodorization■Adsorption effect (neutral activated carbon, fibrous carbon adsorption Adsorption of porous materials such as zeophyte, activated clay, etc.) Absorption action (surface coating with water, organic solvents such as alcohol, hexane, and surfactants) E, biological deodorization Decomposition of deodorizing agents, use of soil bacteria, etc.) ■Preservative and bactericidal effects (chlorine-based such as chloramine T, parabens, phenol-based, Shibagai) The above deodorizing agents and deodorizing methods using them are There are some disadvantages such as poor quality, high running cost, and poor deodorizing effect. For example, activated carbon and air fresheners have poor sustainability, and air fresheners only have a deodorizing effect while the odor of the fragrance is present, and deodorizing equipment that uses redox M- has a long-lasting effect. Running costs are high as chemicals must be constantly replenished, and deodorizers that use surfactants are only effective against mild odors.

On the other hand, metal porphyrin, metal porphyrazine, and their derivatives are known as deodorants that do not have the above-mentioned drawbacks and are safe and easy to use (Japanese Patent Laid-Open No. 56-63355
Publication No.). These metal porphyrins and metal porphyrazines have the property of acting as catalysts to oxidize or reduce malodorous molecules and decompose them, and they permanently function as deodorizers at room temperature and pressure. There is an advantage.

Problems to be solved by the invention By the way, the above-mentioned metal porphyrins and metal porphyrazines have no catalytic activity unless they are in a monomolecular state, but because the molecules have a planar structure, oxodimers are formed through self-association and oxygen molecules. It is easy to remove, and the deodorizing effect is low depending on the amount used.

Therefore, in the above-mentioned Japanese Patent Application Laid-Open No. 56-63355, activated carbon, silica gel, cellulose, polyvinyl, alcohol,
It has been described that when supported on a polymeric substance such as polyacrylic acid, it is several times more effective than using metal porphyrins, metal porphyrins, or /I/fidgins alone.

However, with the above-mentioned polymeric substances, metal porphyrins and metal porphyrazines can only be supported in small amounts or cannot be supported in a sufficiently active state, so that the inherent properties of metal porphyrins and metal porphyrazines are not necessarily supported. has not reached its full potential.

The present invention focuses on metal porphyrazines that are long-lasting and easy to use as deodorants, solves the above-mentioned problems when using metal porphyrazines, and makes metal porphyrazines simple. The object of the present invention is to provide a deodorizing fiber supported in a molecular and active state and a method for producing the same.

Means for Solving the Problems The present invention solves the above problems by adding at least 0% of the metal porphyrazine of the following formula (1) to protein fibers.
．． This is a deodorizing fiber characterized by carrying 3% by weight (based on the fiber) and a method for producing the same.

The following:
It is an e/v group or a metal salt thereof, or a sulfonic acid group or a metal salt thereof, and Me is a divalent or trivalent iron ion or a divalent or trivalent cobalt ion. ) The deodorizing agent used in the present invention is a metal porphyrazine having the structure shown by the above formula (1), where X is hydrogen,
Or Karpoki! multiple μ groups or metal salts thereof, or sulfonic acid groups or metal salts thereof, or amino groups, and at least one is a μ group or a metal salt thereof, or a sulfonic acid group or a metal salt thereof; ,
Further, Me needs to be a derivative of divalent or trivalent iron or divalent or trivalent cobalt. Derivatives other than those mentioned above cannot provide the desired deodorizing effect.

Furthermore, metal porphyrins are compounds similar to the above-mentioned metal porphyrazines, but when applied as deodorant fibers, which is the object of the present invention, they are not preferred from the viewpoint of difficulty in handling and deodorizing effect.

The above metal porphyrazine-carrying fibers include sheep,
Animal hair fibers from animals such as camels and rabbits, silk fibers such as domestic and wild silk fibers, collagen fibers, regenerated fibers, and other protein fibers that have peptide bonds in their molecules are required. Compared to the use of cellulose-based W&fibers such as hemp and rayon, and synthetic fibers such as Esthe μ, nylon, and Acrylic IV, the amount of metal porphyrazine supported, the strength of the deodorizing effect, and its sustainability are significantly higher. Excellent.

The amount of metal porphyrazine supported on protein fiber is
It is necessary that the weight width is at least 0.3 with respect to the fiber, and if the weight width is less than 0.3, the deodorizing effect will be extremely small. In addition, sufficient deodorizing performance can be obtained by supporting metal porphyrazines around 2 weight range, and even if the metal porphyrazine is supported at a larger amount than 2 weight range, the effect will not change much and it is not a good idea from the point of view of cost etc. do not have.

Next, the above deodorizing fiber is obtained by treating the protein fiber in an aqueous solution of a metal porphyrazine represented by the above formula (1) at a temperature of 30° C. to 110° C. below PHIO. It is necessary to perform the treatment at a pH of 10 or less, and a pH of 6 or less is preferable in terms of treatment efficiency (supporting yield). PH is 10
If it is higher than this, the supported amount will be small and the fibers may be damaged, which is not preferable.

Process at a temperature of 30°C to 110°C for 30 to 120 minutes. Although high temperatures can shorten the entire processing time, it is necessary to select a temperature within a range that will not damage the fibers. Deodorant fibers can be obtained by removing the fibers treated under predetermined conditions from the treatment solution and drying them. The supporting yield of metal porphyrazines is 60-704.

When supporting metal porifugins on protein fibers as described above, the supporting yield can be increased by introducing cationic groups into the protein fibers in advance. For example, 3-chloro-2-hydroxypropyl-trimethylammonium chloride [Cl-CH2.CH(OH)
・CH2・N(CH3)5CI], or bis(3-chloro-2-hydroxyprobyl-dimethyammonium)alkyl chlorophyte (CI・CH2・CH(OH)・
CH2N (CH,)2-(CH2), N (CH3)
A cationic group is easily introduced into the protein fiber by reacting a cationizing agent such as 2.CH2-CH (CI()CH2.CI) with the protein fiber under an alkali catalyst. Protein fibers into which such cationic groups have been introduced can support metal porphyrazines by treating them under exactly the same conditions as the above-mentioned treatment of unintroduced fibers with an aqueous solution of metal porphyrazines, The supported yield exceeds 90%.

The deodorizing fiber of the present invention has been found to have about 20 times more deodorizing effect and about 5 times longer durability than when metal porphyrazine is used alone. Approximately three times as effective as when supported on cellulose fibers, and more than 10 times as effective as when mixed and spun on polyester fibers. In addition, when the protein fibers carrying metal porphyrazines have all cationic groups introduced in advance, both the supporting yield and deodorizing performance are 1.5% higher than when no cationic groups are introduced.
More than double the effect was observed.

Function As described above, the deodorizing fiber of the present invention in which the protein fiber carries at least 0.3 weight ratio of the specific metal borohuidine derivative represented by formula (1) exhibits an excellent deodorizing effect;
The reason for this can be roughly inferred as follows.

It is well known that because metal porphyrazines have a planar molecular structure as described above, they tend to dimerize through self-association and form oxodimers in which oxygen is linked to the central metal in a bridging manner. In this state, the central metal is in a low spin state and is not in an active state.
It cannot be used as a decomposition catalyst for malodorous molecules and has no deodorizing effect. Metallic volfusifudines are immobilized on a polymeric support, and the polymer matrix is formed into an inert structure by dimerization as described above. It is also known that prevention increases the proportion of catalytically active species. When a nitrogen atom coordinates to the fifth coordination site of the central metal of the metal bofiruzine, the central metal is excited to a high spin state, and the greater the amount of nitrogen atoms, the more active species of the metal bofiruzine. It has also been reported that.

By the way, protein fiber is a condensation of many types of amino acids through peptide bonds, and has all kinds of atomic groups in its side chains. i.e. proline, arginine,
Its constituent elements are amino acids with side chains containing nitrogen atoms, such as lysine, tryptophan, and histidine.

It is considered that the probability that the nitrogen atom of the side chain is coordinated to the fifth coordination site of the central metal of the metalloporphyrazine incorporated into the protein molecular chain is considered to be quite high. Particularly in water, the degree of freedom of the side chains and the like is high, and it is thought that the metal porphyrazine is adsorbed and at the same time it is easy to form the above-mentioned coordination structure. The metal bofifudins incorporated into the protein fibers exist in a single molecule state and have a high probability that the central metal is in a high spin state due to the coordination of the nitrogen atom. It is thought that an outstanding deodorizing effect and its durability can be obtained compared to when it is carried on the body.

Examples Example 1 Iron (1) phthalosine anine octacarboxylic acid 2g'e1. OI! Dissolve in 09.1 liter of sodium hydroxide aqueous solution and adjust the pH to 3.5 with hydrochloric acid.
After adjusting to 100g of wool fiber, 100g of wool fiber was immersed, mixed uniformly, heated to 80℃, and treated at constant temperature while stirring for 60 minutes.
After that, the fibers are taken out, washed with water, and dried to create a deodorizing fiber.
Obtained 0g. As a result of metal quantitative analysis, 15511
fi [(vs. wool fiber a) iron (1) phthalocyanine octacarboxylic acid was supported.

The deodorizing fiber obtained above is placed in a bag made of polyvinyl fluoride/L/resin, and a certain amount of foul-smelling gas diluted to a predetermined concentration is sealed and the air inside the bag is collected from the bag after a predetermined time. The deodorizing performance was measured by measuring the concentration of malodorous gas. Hydrogen sulfide (H2S) as a malodorous gas, 7:/mo=7 (
NH3) and me)V-1ybutane (cH3SH) were used. The results are shown in Table 1.

As a comparative example, 1.5% of the same iron phrothalocyanine octacarboxylic acid as used in Example 1 above was used.
Heavy J! [The supported polyester fibers and cotton were tested in the same manner as for the deodorant fiber of Example 1 to determine the deodorizing performance t-
Measurement Results shown in Table 1 were obtained.

As shown in Table 1, the deodorizing performance of the deodorant fiber of Example 1 was higher than that of the comparative example Polyester/I/Fj71. Although the amount of fk and (1) phthalocyanine octacarboxylic acid supported is almost the same compared to those using fiber or cotton,
It had significantly superior performance for each gas.

Example λ Wool edge J@toog was mixed with 25 g of bis(3-chloro-2-
pH 8.7 with an aqueous solution of zOl containing 25 g of hydroxypropyldimethylammonium)alkyl chlorophyte.
Processed at 0°C, 1. A cationic group of OX tO-SgVg was introduced. As metal porphyrazine, phthalocyanine octacarboxylic acid (1) 2.6g t
'LOI dissolved in 0.1 aqueous sodium hydroxide solution,
After adjusting the pH to 8 with acetic acid, 100gt of the above cationic group-introduced wool fiber was soaked, mixed uniformly, and
℃ and treated at constant temperature with stirring for 60 minutes, then the fibers were taken out, washed with water, and dried to give about 100g of deodorizing fibers.
I got it. When analyzed by metal quantitative analysis, it was 235 weight 4 (
Iron (1) phthalocyanine octacarboxylic acid (for wool fibers) was supported.

The deodorizing performance of the deodorant fiber obtained above was measured in exactly the same manner as the deodorant fiber of Example 1.

The results are shown in Table 1.

As is clear from the results shown in Table 1, the deodorant fiber of Example 2 has a large amount of fl(1) phthalocyanine octacarboxylic acid supported, and has an even better deodorizing performance than the deodorant fiber of Example 1. It had

Below ##1 Table Example 3 Wool fiber 100gft3-chloro-2-hydroquinepropyltrimethylammonium chloride 20gt2. o
A cationic group of Pf (9, 7, OX to mat/g) was introduced by treatment at 70° C. as a metal porphyrazine. .1 After dissolving in an aqueous sodium hydroxide solution and adjusting to acetic acid 9, it was immersed in the wool fiber t00g' into which the above cationic group had been introduced, mixed uniformly, heated to 80°C, and stirred for 60 minutes. After that, the fibers were taken out, washed with water, and dried to obtain 100gt of deodorizing fibers.When analyzed by metal quantitative analysis, it was found that 4.
Iron (1) phthalocyanine disulfonic acid with a weight range of 52 (# of wool fibers) was supported. This deodorizing fiber exerted an excellent deodorizing effect against various malodorous gases, and its effect was very long-lasting.

Effects of the Invention As mentioned above, the deodorizing fiber of the present invention is easy to manufacture, has a good supporting yield of metal porphyrazines, and has extremely excellent deodorizing performance against various malodorous gases9. It also has a long-term connection and can be used in a wide range of applications such as cotton padding, carpets, filters, and more.

Agent Hiroshi Mori

Claims (1)

[Scope of Claims] 1. A deodorant fiber characterized in that a protein fiber carries at least 0.3% by weight (based on the fiber) of a metal porphyrazine of the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X is hydrogen, a carboxyl group or its metal salt, a sulfonic acid group or its metal salt, or an amino group, and at least one is a carboxyl group or its metal salt. salt or sulfonic acid group or its metal salt, and Me is a divalent or trivalent iron ion or a divalent or trivalent cobalt ion.) 2. Protein fibers are added to an aqueous solution of metal porphyrazine of the following formula. A method for producing deodorizing fibers, characterized in that the treatment is carried out at a pH of 10 or less and a temperature of 30°C to 110°C. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X is hydrogen, a carboxyl group or its metal salt, a sulfonic acid group or its metal salt, or an amino group, and at least one is a carboxyl group or its metal salt. (Me is a divalent or trivalent iron ion, or a divalent or trivalent cobalt ion.) 3. The protein fiber has a cationic group. A method for producing deodorant fibers according to claim 2, characterized in that: