JPH02216266A - Deodorizing acrylic synthetic fiber and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title yarn having deodorizing properties of good washing resistance without damaging characteristics of acrylic synthetic by adding a specific metal porphine and monovalent cation to acrylic synthetic yarn. CONSTITUTION:Acrylic synthetic fiber comprising >=80wt.% acrylonitrile, 1-15wt.% monomer shown by formula I (R1 is H or methyl; n is 2-4; R2 and R3 are methyl or ethyl) such as N,N-dimethylaminoethyl methacrylate and 0-19wt.% another monomer copolymerizable with acrylonitrile is provided with a metal porphine shown by formula II (X is at least one substituent group and H) and a monovalent cation in neutrality or acidity at pH <=7 to give deodorizing acrylic synthetic fiber having excellent washing resistance.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a deodorizing acrylic synthetic fiber having an excellent deodorizing effect and extremely excellent washing resistance, and a method for producing the same. be.

(Prior art) Conventional methods of deodorization include masking malodors with aromatic substances, oxidative decomposition of malodorous substances with oxidizing agents such as potassium permanganate, salts, nitric acid, sodium hydroxide, A method of neutralizing with a neutralizing agent such as sodium carbonate, a method of adsorbing the bad odor with activated carbon, etc. are known.

However, among these methods, the method using a masking agent has the disadvantage of causing discomfort in places where people stay for a long time, and the other methods using oxidative decomposition, neutralization, immobilization, or adsorption have a high selectivity for malodorous substances. There was a drawback.

On the other hand, for textile products, fibers contain antibacterial agents,
Sanitary processing is known that prevents bad odors by preventing the growth of bacteria. However, since this method is an indirect method, it has the disadvantage that it is ineffective against bad odors caused by causes other than bacterial growth. Also, JP-A-59-
Publication No. 66 discloses that a dilute solution of deodorizing active ingredients extracted mainly from the beams of Camellia family plants, particularly tea plants, sakaki flowers, and sasanqua flowers, is added to textile products by infiltration, coating, spraying, etc. According to this method, since the deodorizing component is attached to the surface of the fiber, there is a drawback that the effective deodorizing component is easily removed by washing with water or dry cleaning.

Also, JP-A-55-82519 and JP-A-56-
No. 63355 discloses a deodorant containing metal porphyrin and metal porphyrazine, which are metal complexes having redox ability. When these deodorants are mixed with the spinning material and spun, the spinning properties are poor and the deodorizing effect is insufficient. Furthermore, when mixed with resin and processed with resin, the original texture of the synthetic fiber is damaged and the deodorizing effect cannot be sufficiently developed.

JP-A-52-6985 discloses metal phthalocyanine 0.5 to 20 m! Acrylic fibers with a dye loading of 1% are disclosed. However, even if ordinary acrylic fibers were treated with metal porphyrins such as hematoporphyrin using this loading method, it was not possible to directly apply them to the fibers. In addition, Japanese Patent Application Laid-Open No. 62-7000 discloses msi in which metal phthalocyanine polycarboxylic acid and metal ions are supported. It had the disadvantage that it easily fell off.

The present inventors completed the present invention as a result of intensive research to improve the above-mentioned drawbacks.

(Problems to be Solved by the Invention) The object of the present invention is to have an excellent deodorizing effect and washing resistance,
Another object of the present invention is to provide a deodorizing acrylic synthetic fiber that maintains the fiber performance and texture of the acrylic synthetic fiber, and a method for producing the same.

(Means for Solving the Problems) The deodorizing acrylic synthetic fiber of the present invention contains at least 80% by weight of acrylo, -tolyl, and -Senjin (where R2 is hydrogen or a methyl group, and n is 2 to 4 An acrylic polymer consisting of 1 to 15% by weight of a monomer (where Rz and Rs are methyl or ethyl groups) and 0 to 19% by weight of other monomers copolymerizable with acrylonitrile. The following structural formula (
II) containing metal porphyrin and monovalent copper ions.

Structural formula (■) Fibers of an acrylic polymer consisting of 0 to 19% by weight of acrylonitrile and other copolymerizable monomers are heated in a treatment solution (A) for metal porphyrin having the above structural formula <II). After treatment to contain metal porphyrin, a treatment solution (B) consisting of monovalent copper ions, divalent copper ions, and a reducing agent
The acrylic synthetic fiber is characterized by being heat-treated to contain monovalent copper ions in the acrylic synthetic fiber.

In the present invention, in the general formula 0, X represents at least one substitution method and unsubstituted H] Furthermore, the method for producing the deodorizing acrylic synthetic fiber of the present invention includes:
80% by weight or more of acrylonitrile, 1 to 15% by weight of a monomer represented by -shipman (+), and R8 (wherein, R1 is hydrogen or a methyl group, n is an integer of 2 to 4,
R1, Rs are methyl group or ethyl group) means N, N-
Dimethylamine ethyl methacrylate N, N-diethylaminoethyl methacrylate N, N-dimethylaminopropyl methacrylate.

N,N-diethylaminopropyl methacrylate.

N,N-dimethylaminobutyl methacrylate N,N-
Methacrylic acid 2M 5 bodies such as diethylaminobutyl methacrylate, and N,N-dimethylaminoethyl acrylate, N-diethylaminoethyl acrylate, N,
Examples include acrylic acid derivatives such as N-dimethylaminepropyl acrylate, N,N-diethylaminopropyl acrylate, N,N-dimethylaminobutyl acrylate-i N,N-diethylaminobutyl acrylate.

The monomer in the acrylic polymer not only supports the metal porphyrin (but also has the effect of accelerating the deodorizing reaction of the metal porphyrin). If it is less than 1%, the effect of supporting metal porphyrin will be insufficient, and if it exceeds 15%, the heat resistance of the fiber will decrease and it is not economically preferable.

Other monomers that can be copolymerized with acrylonitrile include:
Any known vinyl monomer copolymerizable with acrylonitrile can be used without particular limitation. For example, methyl acrylate, pentavinyl acetate.

Examples include methyl methacrylate, acrylamide, methacrylamide, styrene, acrylic acid, and methacrylic acid, and the copolymerization ratio thereof can be appropriately selected depending on the purpose.

The acrylic polymer of the present invention contains 80% by weight or more of acrylonitrile, 1 to 15% by weight of the above-mentioned Funato (1) monomer, and 0 to 15% of other monomers copolymerizable with acrylonitrile.
19% by weight of copolymers, but also polyblends of copolymers of acrylonitrile and other monomers with acrylonitrile and monomers of general formula (T), or acrylonitrile and monomers of general formula (T). - such as by polyblends of terpolymers of the monomers of 1) and other monomers, or - polyblends of copolymers of the monomers of sailor (1) and of other monomers, It also includes those that finally have the above composition.

Further, the acrylic polymer may contain resins such as cellulose acetate, polystyrene, acrylonitrile-styrene copolymer, polyvinyl acetate copolymer, and polyvinyl butyral. Particularly preferred is the acrylic polymer containing 2 to 30% by weight of cellulose acetate.

The -X group of the metalloporphyrin of the present invention is a hydrogen group or a substituent. Examples of the substituent include an alkyl group, a substituted alkyl group (eg, chloromethyl group), a halogen group, a nitro group, an amino group, and an azo group.

Thiocyanate group, carboxyl group, carbonyl chloride group, carboxylamide group, nitrile group.

In addition to hydroxyl groups, alkoxyl groups, phenoxydyl groups, sulfonic acid groups, sulfonyl chloride groups, sulfonamide groups, thiol groups, alkyl silicon groups, vinyl groups, alkali salts of carboxyl groups and sulfonic acid groups, etc.
It is not limited to one type of group, and may be substituted with different groups.

For example, 5,10,15.20-tetra(2-nitrophenyl)porphyrin, 5.10.1520-tetra(
3-nitrophenyl)porphyrin, 5.10.15.
20-tetra(4-nitrophenyl)porphyrin, 5
,10,15,20-tetra(4-carboxyphenyl)porphyrin,5.10.15.20-tetra(4
-sulfonatophenyl)porphyrin, 2.3,7.8
Examples include 12.13.17.18-octaethylporphyrin, hematoporphyrin, protoporphyrin, and the like. Further, the central metal M is, for example, Fe, Co, Mn,
These are Ti, V, Ni, Cu, ZnMo, W, Os, or a mixture of Fe and Co.

Particularly preferred are hematoporphyrin, protoporphyrin, and the like represented by the following -Funenin (I[[).

(In the formula, Y and Z may be the same or different, and 4M, which represents -CH(CHs)OH or -CH=CHx, respectively, represents a metal.) In the fiber of the present invention, the metal porphyrin content is It is preferably 0.5 to 10%, more preferably 1 to 5%. 0.5% by weight
If it is below, the deodorizing effect will be poor because the amount of metal porphyrin is small. Further, it is difficult to adhere metal porphyrin exceeding 10% by weight, and since saturation is reached, the performance does not improve in proportion to the amount, which is economically unfavorable.

In particular, a content of 1 to 5% is particularly preferable since it is easy to adhere to fibers and has a good deodorizing effect.

Moreover, the content of monovalent copper ions is preferably 0.1 to 15% by weight, more preferably 0.5 to 8% by weight. 0.
If it is less than 1% by weight, the content of monovalent copper ions is low, resulting in poor deodorizing effect and poor washing resistance. On the other hand, if it exceeds 15% by weight, the fibers will strongly stick together, making it impossible to maintain the performance and feel of acrylic synthetic fibers, and this is not economically preferable. In particular, treatment with a concentration of 0.5 to 5% by weight is easy to implement, has good fiber performance and texture, and has excellent deodorizing properties and washing resistance due to the synergistic effect with metal porphyrin. preferable.

The treatment liquid (A) of the method of the present invention is one in which the metal porphyrin is dissolved in an alkali such as caustic soda, caustic potash, soda carbonate, or potassium carbonate, and the treatment is performed by adjusting the pH with an acid.

Salt or surfactant such as mirabilite, sodium acetate, etc. as necessary,
It is also possible to use additives such as antifouling agents, antistatic agents, and antibacterial agents. The pH of the treatment solution should be neutral or acidic at 8 or less, preferably pH 7 or less to facilitate the application of metal porphyrin to the fibers.

The heat treatment temperature of the present invention is preferably 85° C. or higher, which is around the glass transition point of the acrylic synthetic fiber. 85℃
In the following, it tends to be difficult to apply metal porphyrin to the acrylic polymer fibers. If the treatment temperature exceeds 130°C, the acrylic synthetic fibers will be damaged by the heat and the fiber properties will deteriorate, so it is preferable to perform the treatment at 130°C or lower. In particular, it is preferable to perform the treatment at 90 to 105° C. because the equipment and treatment can be easily carried out.

The treatment time is not particularly limited, but it is preferably 20 to 120 minutes.

In the present invention, the deodorizing effect can be further improved by treating the fibers after heat treatment with the treatment liquid (A) with an aqueous solution of an acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, or acetic acid. Particularly preferred.

Since the treatment liquid (B) of the method of the present invention is a source of monovalent copper ions, monovalent copper salts and complex salts can be used, but usually, secondary copper salts such as divalent copper salts and complex salts are used. The treatment is carried out in an aqueous bath whose main components are a copper compound and a reducing agent capable of reducing divalent copper to monovalent copper, and the pH is adjusted with an acid. If necessary, additives such as surfactants, antifouling agents, electrostatic agents, and antibacterial agents can also be used in combination. Examples of cupric compounds are copper sulfate, cupric chloride, and cupric nitrate.

Examples include cupric acetate. On the other hand, the above-mentioned reducing agents include gold r% copper, hydroxylamine and its salt Hm ferrous, ammonium vanadate, sodium furfural hypophosphite, glycose, sodium bisulfite, sodium thiosulfite, sulfite, sodium disulfite, Examples include sodium dithionate, dithionite, Rongalite, and mixtures of the above. Also, regarding acids, sulfuric acid and hydrochloric acid.

Inorganic acids such as phosphoric acid, organic acids such as citric acid and acetic acid, salts such as disodium hydrogen phosphate, sodium citrate and sodium acetate, and mixtures thereof are added as pH adjusters. 91) of the treatment liquid is not particularly limited, but it is usually neutral or acidic with a pH of 8 or less, preferably 7 or less, in order to incorporate monovalent copper ions into acrylic synthetic fibers. It's easy.

As mentioned above, the post-treatment temperature of the present invention is preferably 85°C or higher, which is around the glass transition point of the acrylic synthetic fiber.If it is 85°C or lower, it takes a long time to adsorb monovalent copper ions. In addition, if the temperature exceeds 130°C, the acrylic synthetic fibers will be damaged by heat and the fiber properties will deteriorate, so it is preferable to process at 130°C or lower. In particular, processing at 90 to 105°C makes it easier to use equipment and process. This is preferable because it can be done. Processing time is not particularly limited, but 20 to 120
Preferably, the treatment time is 1 minute.

(Effects of the Invention) The fiber of the present invention maintains the fiber performance and texture of ordinary acrylic synthetic fibers, and exhibits an excellent deodorizing effect.

The fibers of the present invention can also be used in combination with ordinary acrylic synthetic fibers, polyester, nylon, cotton, rayon, wool fibers, etc., for use in clothing, blankets, car vents, and mats with deodorizing properties. It is extremely meaningful industrially because it can be used for a wide range of purposes such as socks, sheets, futon cotton, etc.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. In the examples, (%) means (% by weight).

[Trimethylamine (ethyl mercaptan) removal rate measurement method]

Place the Ig fiber sample in a 100 ml vial and seal. Furthermore, 1 ml of head space gas (25° C.) of 696 trimethylamine aq (or ethyl mercaptan) is injected into the previously sealed vial using a gas-tight syringe, and after a certain period of time, 1 ml of head space gas is subjected to gas chromatography analysis.

As a control, 1 ml of 6% trimethylamine (or ethyl mercaptan) headspace gas was similarly injected into an empty 100 ml vial and subjected to gas chromatography analysis, and the trimethylamine removal rate (%) was calculated from the reduction rate of the peak area.

Example 1 Fe(m) protoporphyn [the above structural formula (II+
) ) in a 0.5% caustic soda aqueous solution,
1% and further with acetic acid, p t + preparation (p ) 1-5
) to prepare a treatment solution (A). This treatment solution contains acrylonitrile (AN)/methyl acrylate (MA)/dimethylaminoethyl methacrylate (DMAHMA).
= 87.0/7.0/6.0 acrylic synthetic fiber TA fiber Jog was immersed in a bath ratio l: 60) and boiled to 60
Heat treated for minutes. Thereafter, it was cooled, washed with water until neutral, and dried (referred to as treatment A). The treatment solution (B) was sulfuric acid uA4
%, sodium bisulfite 0.5%, and acetic acid 1%. 5 g of the acrylic fibers dyed with the above Fe(III) protoporphyrin were immersed in this solution at a bath ratio of 16.
0), boiled and heat treated for 60 minutes. Thereafter, it was cooled, washed with water until neutral, and dried (referred to as treatment B).

As a comparative example, treatments A and B were performed using ordinary acrylic fibers instead of the acrylic synthetic fibers mentioned above. The trimethylamine (TMA) removal rate and ethyl mercaptan (EMP) removal rate of each sample were measured. The results are shown in Table-1.

NQI ~34. tAN/MA/DMAEMA-87,
Acrylic synthetic fibers with a composition of 0/7.0/6.0 are used (th4 to 6 are AN/MA/SMAS).
(Sodium methallylsulfonate) -90,0/9
．． Acrylic fibers having a composition of 0/1,0 were used.

Regarding size 1.4, each raw cotton was measured.

From Table 1, it was found that the acrylic fibers used in the present invention are sometimes excellent in terms of fiber carriers, and by carrying out treatment B, very excellent deodorizing performance can be imparted. By containing monovalent copper ions, a synergistic effect with Fe (m> protoporphyrin) was exhibited, and the deodorizing performance and washing resistance were significantly improved.
I) Focusing on the amount of protoporphyrin, IItL5
．． 6 acrylic fiber (AN/MA/SMA
S-90.0/9.0/1.0 composition), the acrylic synthetic fiber used in the present invention (AN
/MA/DMAEMA-87, 0/7.0/6.0 composition), it can be seen that the amount of dyeing is high in columns 2 and 3. In addition, the copper content is nearly twice as high.

The content of Fe([+) protoporphyrin and copper in the sample can be obtained by fluorescent X-ray analysis, and the former can be calculated as the amount of Fe(ill) protoporphyrin by quantifying the central metal iron, and the latter can be calculated as the amount of copper. Example 2 Fe(II-protoporphyrin) was dissolved in a 0.5% aqueous solution of caustic soda to a concentration of 1%, and further diluted with acetic acid to pH'
A treatment solution (A) was prepared by using a method manufactured by J. J. Co., Ltd. (pH=5).

In this treatment solution, AN/MA/diethylaminomethacrylate (DEAEMA) = 90.0/8.0/2.0
Soak the acrylic synthetic fibers in a bath ratio of 1:60)
, heat-treated at 100° C. for 30 minutes. Then cool,
After removing the liquid, it was immersed in a 0.5% dilute nitric flI solution for 10 minutes. After treatment, it was washed with water to neutrality and dried. (This is referred to as treatment C.) The treatment liquid (C) is copper sulfate 1%,
Acidic water containing 0.8% hydroxolamide sulfate and 0.04% concentrated sulfuric acid? The acrylic synthetic fibers subjected to Fe(III>protoporphyrin dyeing treatment) were immersed in this liquid (bath ratio 1:80) and heat-treated at 100° C. for 30 minutes.

Thereafter, it was cooled, washed with water until neutral, and dried.

(It will be treated.) Place this fiber in a polyester mesh bag and wash it at home.
5. A deodorization test was conducted after 10 times.

[Washing conditions]

Neutral detergent used in a commercially available small electric washing machine 1 g/l Bath ratio 1:100 Temperature x time 40°C x 5 minutes washing with water 10 minutes drying 80°C x 1 hour Table-2
It can be clearly seen that the treated acrylic synthetic fibers have an extremely fast deodorizing speed and excellent washing resistance (Figures 1 to 3).

Comparative examples of Na 4 to 6 are samples of acrylic synthetic fibers that were only dyed with Fe(m) protoporphyrin and were not treated to contain monovalent steel ions.

The amount of Fe(I[[) protoporphyrin and copper content determined by fluorescent X-rays are shown in Table 2. Both of them are slightly removed by washing, but the inventive examples (-1 to 3) are different from the comparative examples (-3).
Compared to l1m4-5), there is less deterioration, and this tendency is also reflected in the deodorizing effect.

Claims (2)

[Claims] (1) 80% by weight or more of acrylonitrile and general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (However, R_1 is hydrogen or a methyl group, n is an integer from 2 to 4, R_2 and R_3 are methyl groups. or ethyl group) and 0 to 19% by weight of other monomers copolymerizable with acrylonitrile. A deodorizing acrylic synthetic fiber characterized by containing metal porphyrin and monovalent copper ions. Structural formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents at least one substituent and unsubstituted H] (2) 80% by weight or more of acrylonitrile and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 is hydrogen or methyl group, n is an integer from 2 to 4, R_2 and R_3 are methyl group or ethyl group) Fibers of an acrylic polymer consisting of 1 to 15% by weight of the monomer represented by the formula and 0 to 19% by weight of other monomers copolymerizable with acrylonitrile are treated with a metal porphyrin treatment solution having the following structural formula ( After heat treatment in A) to contain metal porphyrin, heat treatment in treatment liquid (B) containing monovalent copper ions, divalent copper ions, and a reducing agent to remove monovalent copper ions from acrylic A method for producing a deodorizing acrylic synthetic fiber, which comprises incorporating the deodorizing acrylic synthetic fiber into the synthetic fiber. Structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents at least one substituent and unsubstituted H]