JPS63175181A - Deodorizing acrylic synthetic fiber and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 a method for producing the same.

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

However, among these methods, the method using a masking agent has the disadvantage of causing discomfort in places where rP8 stays 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, regarding A-fissure products, it is a castle! @1ζ Sanitary processing is known that contains an antibacterial agent to prevent the proliferation of bacteria and thereby prevent bad odors. However, since this method is an indirect method, it has the disadvantage that it is ineffective against odor caused by causes other than bacterial growth. It is disclosed that a diluted solution of deodorizing active ingredients extracted mainly from the leaves of tea plants, sakaki flowers, and sasanqua flowers can be added to textile products by infiltration, coating, spraying, etc. According to this method. However, since the deodorizing component is attached to the surface of the fiber, the deodorizing active component is easily removed by washing with water or dry cleaning.

Also, JP-A-55-82519 and JP-A-56-
No. 68855 discloses a deodorizing agent containing metal porphyrin and metal porphyrazine, which are metal complexes having redox ability. Further, JP-A-61-258077 and JP-A-61-25807811 disclose cellulose fibers and polyamide fibers carrying 0.5 to 20% by weight of phthalocyanine. However, even if fibers are treated with metal porphyrins, metal porphyrazines, and their chemical derivatives, they will adhere to cellulose fibers such as cotton and rayon, and polyamide fibers, but will not directly adhere to synthetic fibers such as acrylic and polyester. It was not possible to apply it, and it was necessary to mix it with resin and process it with resin. For this reason, the original feel of the synthetic fiber is impaired, and the deodorizing effect cannot be sufficiently exerted. Furthermore, when mixed with a spinning dope and spun, the spinnability is poor and the deodorizing effect is insufficient.

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 provide deodorizing acrylic base synthetic fibers that have excellent deodorizing effects and wash resistance, and maintain the fiber performance and texture of acrylic synthetic fibers. and a manufacturing method thereof.

(Means for solving the problem) The m-fiber of the present invention contains 80% by weight or more of acrylonitrile,
General formula (where RI is a methyl group, n is an integer from 2 to 4,
An acrylic polymer fiber consisting of 1 to 15% by weight of a monomer represented by R2 and 8 is a methyl group or an ethyl group, and 0 to 19% by weight of another monomer that can be copolymerized with acrylonitrile, Metal phthalocyanine of the following structural formula 0.5-1
It contains 0ii%.

(In the formula, -X is hydrogen or a substituent, and M is a coordinating metal.) Furthermore, the method of the present invention combines 80% by weight or more of acrylonitrile with the general formula (wherein R1 is hydrogen or a methyl group, and n is 2 to 4 integer, R
2* R8 is 1 fiber of an acrylic polymer consisting of 1 to 15% by weight of a monomer represented by a methyl group or ethyl group and 0 to 19% by weight of another monomer copolymerizable with acrylonitrile. is heat-treated with a treatment solution for metal phthalocyanine having the following structural formula to reduce the metal phthalocyanine to 0.5 to 10
It is characterized by containing % Jujaku.

(In the formula, -X is hydrogen or a substituent, M is a coordination metal R) In the present invention, the general formula (wherein, R1 is hydrogen or a methyl group, n is an integer of 2 to 4,
R2e R8 is a methyl group or an ethyl group) means N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, N,N-diethylaminopropyl methacrylate, N,N-dimethyl Methacrylic acid derivatives such as aminobutyl methacrylate, N,N-diethylaminobutyl methacrylate, and N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, N,N-diethylaminopropyl Acrylate, N.

Examples include acrylic acid derivatives such as N-diethylaminobutyl acrylate and N,N-diethylaminobutyl acrylate.

Pond monomers that can be copolymerized with acrylonitrile include:
Any known vinyl monomer that can be copolymerized with acrylonitrile can be used, and examples thereof include methyl acrylate, vinyl acetate, methyl methacrylate,
Examples include acrylamide, methacrylamide, styrene, etc., and the copolymerization ratio thereof can be appropriately selected depending on the purpose.

The acrylic polymer of the present invention is acrylonitrile 80!
% or more, and 1 to 15% by weight of the monomer of general formula (1) above.
and 0 to 1 other monies copolymerizable with acrylonitrile
Not only a copolymer with an air permeability of 9% or more, but also a polyblend of a copolymer of acrylonitrile and a monomer of general formula (1) with a polymer of acrylonitrile and a monomer of general formula (1), or acrylonitrile and a monomer of general formula (1). By a polyblend of a terpolymer of the Ii-mer of (1) and other monomers, or a polyblend of a copolymer of the monomer of general formula (1) and other monomers, etc. 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. Wait, add 2 to 30 layers of cellulose acetate to the acrylic polymer! Those containing A% are preferred.

The -X group of the metal phthalocyanine of the present invention is a hydrogen group or a substituent. Examples of substituents include alkyl groups, substituted alkyl groups (e.g. chloromethyl group), halogen groups,
Nitro group, amino group, azo group, thiocyanate group, carboxyl group, carbonyl chloride group, carboxylamide group, nitrile M, 71 group, alkoxyl group, phenoxydyl group, sulfone MM, sulfonyl chloride group, sulfonamide group, thiol group, alkyl Examples include silicon groups, vinyl groups, and alkali salts of carboxyl groups and sulfonic acid groups, and not only one type of group may be substituted, but groups on each side may be substituted. Among these, those having 2 to 8 substitutions with carboxyl groups, sulfonic acid groups, alkali salts thereof, halogen groups, amino groups or hydroxyl groups are preferred. Further, the central metal M is, for example, Fe1Co, kite, Ti,
V, Ni%Ou.

Zn, Mo, W, and Os can be used. Preferably, it is Fe or Co, or a mixture of Fe and CO.

In m and m of the present invention, the content of metal phthalocyanine is 0.5 to 10% by weight, preferably 1.5 to 5% by weight. If the air volume is less than 0.5%, the deodorizing effect will be poor since the amount of metal phthalocyanine is small, so it must be avoided. Moreover, if it exceeds 10% by weight, it becomes difficult to apply the metal phthalocyanine, and the deodorizing efficiency decreases, which is economically unfavorable and must be avoided. Particularly preferred is 1.5 to 5 % because it is easy to treat and has good deodorizing efficiency.

The treatment solution used in the method of the present invention is the treatment by dissolving the metal phthalocyanine with an alkali such as caustic soda, caustic potash, soda carbonate, or potassium carbonate, and adjusting the pH with an acid. Depending on the situation, it is also possible to use additives such as inorganic salts such as mirabilite and sodium acetate, or surfactants, antifouling agents, antistatic agents, and antibacterial agents.The pH of the treatment liquid must be neutral or acidic at 8 or less. The pH of the mafco treatment solution is preferably neutral or acidic, preferably 7 or less, to easily impart the metal phthalocyanine to the fibers. That's all,
There is almost no non-uniformity of the liquid, and the stability of the processing liquid is good.

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. 35
At temperatures below .degree. C., it becomes difficult to apply metal phthalocyanine to acrylic polymer fibers. Furthermore, if the treatment temperature exceeds 130°C, the acrylic synthetic fibers will be damaged by the heat and the copper impurity property will decrease, so it is preferable to process at 110"C or less.
It is preferable to process with a trowel because the equipment and process are easy.
When the treatment is carried out under pressure at 1 to taO<0>C, more preferably 105 to 115[deg.]C, the processing time can be shortened and the metal phthalocyanine imparted efficiently. Although the treatment time is not limited to a certain period of time, it is preferable to perform the treatment for 20 to 120 minutes.

In the present invention, the fibers after heat treatment are treated with an aqueous solution of an acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, or acetic acid.
This is particularly preferred since it can further enhance the deodorizing effect.

(Effects of the Invention) According to the present invention, the fiber performance and texture of ordinary acrylic synthetic mul@ are maintained as they are, and at the same time, it exhibits a strong deodorizing effect.

According to the present invention 1ζ, the fibers can also be used in combination with other fibers such as ordinary acrylic synthetic fibers, polyester, nylon, cotton, rayon, wool, etc., and can be used for clothing with deodorizing properties. It is extremely useful in industry as it can be used for a wide range of purposes such as blankets, carpets, mats, socks, sheets, and futon cotton.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. In addition, (%) in the examples means "1%".

[Trimethylamine (edyl mercaptan) removal rate measurement method] Place 1 f of the fiber sample in a 100 ml vial and seal it.
ml was injected into the sealed vial using a gas-tight syringe, and 1 ml of the headspace gas was analyzed by gas chromatography after 800 minutes.

As a control, 1 ml of headspace gas containing 6% trimethylamine (or ethyl mercaptan) was similarly injected into an empty lo o ml vial and subjected to gas chromatography analysis to calculate the reduction rate of the peak direct product (trowel trimethylamine removal rate (%)). .

Example 1 Acrylonitrile (AN)/methyl acrylate (MA
)/diethylaminoethyl methacrylate (DEAEM
A) After applying the iron phthalocyanine octacarboxylic acid shown in Table 1 by changing the processing conditions to the acrylic synthetic fiber consisting of =90.0/4.0/6.0, trimethylamine ('I'MA) The removal rate and ethyl mercaptan removal rate were measured.

As can be seen from Table 1, if it is less than 0.5%, the deodorizing efficiency is insufficient.

Table 1 Example 2 Iron phthalocyanine octacarboxylic acid was decomposed in a 1.0% caustic soda aqueous solution to 2%, and the pH was further adjusted with cold sulfuric acid.
Make adjustments and prepare a processing solution. AN/m for this treatment solution
A/dimethylaminoethyl methacrylate (DMAEM
A)=90.0/7.0. Acrylic synthetic mM 10F (3.0 mm) was immersed in water at a bath ratio of 1:80, boiled, and heat-treated for 60 minutes. Thereafter, it was cooled, washed with water until neutral, and dried.

After cooling, the fibers treated with a treatment solution having a neutral to alkaline pH were immersed in 0.5% dilute sulfuric acid for 10 minutes, washed with water until neutral, and dried. As shown in Table-2,
All showed good deodorizing effects.

Table 2 Example 8 Iron phthalocyanine octacarboxylic acid was diluted with 1.0% caustic soda aqueous solution (compounded to 4%, and further diluted with pfI with acetic acid).
A treatment solution of No. 5 was prepared. AN/MA for this treatment solution
/dimethylaminoethyl acrylate (LAMA to D)
Acrylic synthetic a-fibers having a ratio of 91.5/6.0/2.5 were immersed and heat-treated at a temperature shown in Table 8 for 90 minutes at a bath ratio of 1:20. Thereafter, it was cooled, washed with water until neutral, and dried.

Table 8 Example 4 1G of iron phthalocyanine tetracarboxylic acid was dissolved in a 1.0% caustic soda aqueous solution to prepare an alkaline treatment solution with a concentration of 3%. A N / MA / diethylaminoethyl methacrylate = 89.5, / 7 in this treatment solution
．． Acrylic synthetic fibers consisting of 0/'3.5 were immersed in a bath with a bath ratio of 1:40) and heated for 45 minutes using a 1" trowel. After that, it was cooled and treated with 0.5% dilute nitric acid using 1 trowel. After soaking for a minute, it was washed with water until neutral and dried.

Put this A fiber in a polyester mesh bag and wash it at home.
．． 10.15.A deodorization test was conducted after 20 times.

As shown in Mori-4, it shows a good deodorizing effect even after washing 20 times.

[Washing conditions]

Uses 4 commercially available small electric washers Neutral detergent ly/l Bath ratio L: 100 Temperature x time 40°C x 5 minutes Wash with water for 10 minutes

Claims (8)

[Claims] (1) 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) A metal phthalocyanine having the following structural formula is added to 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.
A deodorizing acrylic synthetic fiber containing 5 to 10% by weight. Structural formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ (In the formula, -X is hydrogen or a substituent, M is a coordinating metal) (2) Content of metal phthalocyanine is 1.5 to 5% by weight
The fiber according to claim 1. (3) 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, R_3 are methyl or ethyl groups) 1 to 15% by weight of a monomer and 0 to 19% by weight of another monomer copolymerizable with acrylonitrile. Metal phthalocyanine is heated to 0.5~
A method for producing deodorizing acrylic synthetic fiber, characterized by containing 10% by weight. Structural formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ (In the formula, -X is hydrogen or a substituent, M is a coordinating metal) (4) The method according to claim 3, wherein the metal phthalocyanine treatment solution has a neutral or acidic pH of 7 or less. (5) The method according to claim 3, wherein the metal phthalocyanine treatment solution has a pH of 8 or more. (6) The method according to claim 3, wherein the treatment temperature is 85 to 130°C. (7) Content of metal phthalocyanine is 1.5 to 5% by weight
The method according to claim 3, wherein: (8) The fiber after heat treatment is treated with sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid,
The method according to claim 3, wherein the acid treatment is performed with acetic acid.