JPS6022928B2 - Acrylic fiber material for cleaning and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an acrylic fiber material suitable for cleaning and a method for producing the same.

More specifically, the present invention relates to a cleaning acrylic fiber material that does not contain phosphate builders and exhibits excellent detergency, and a method for efficiently producing the same. Detergents commonly used in households contain large amounts of phosphate builders, particularly tripolyphosphates.

This is said to combine with the hardness components of tap water and increase the cleaning power of the cleaning active ingredients. However, recently, this phosphate-based builder has been mixed into wastewater and has been found in rivers and rivers.
It has been discovered that these substances leak into the ocean, causing the growth of algae and increased oxygen consumption, and are one of the major causes of destruction of the living environment.The development of detergents that do not contain these substances has become an important social issue. It's coming.

So far, alternatives to phosphate builders include, for example, polysodium salts of nitrilotriacetic acid, nitrogen-containing alloy metal ion scavengers such as ethylenediaminetetraacetic acid, salts of water-soluble polyacrylates, ethylene and maleic acids, etc. Polyanionic compounds such as salts of copolymers of None of these methods can be said to be satisfactory, as they have drawbacks such as foaming in the drainage water.

The present inventors have overcome the drawbacks of these conventional builders and demonstrated cleaning power comparable to conventional cleaning with sufficient phosphate-based builders, even without the addition of phosphate-based builders. Moreover, as a result of intensive research into new cleaning materials that do not cause any environmental pollution,
We discovered that the material obtained by bringing vinyl monomer into contact with acrylic fibers maintained in a wet gel state to polymerize them, adsorbing detergent, and then drying them was suitable for this purpose. Based on this knowledge, the present invention has been made.

That is, the present invention provides an acrylic fiber having an acrylonitrile content of at least 7% by weight, which is spun by a cold method, and a acrylic fiber containing 30 to 20% of the weight of the fiber in the acrylic fiber W. A polymer of vinyl monomers other than acrylonitrile integrally bonded in a proportion of % by weight,
A cleaning alkaline fiber material consisting of a phosphate builder-free detergent and acrylonitrile, which is strongly adsorbed to the fibers in a proportion of 10 to 5% by weight of the total amount of 'CI ingredients (■) and 'B}. An acrylic polymer having a content of at least 7% by weight is green-spun, and the acrylic fiber thus obtained in a wet gel state is brought into contact with a polymerizable vinyl monomer to effect polymerization. The present invention provides a method for producing an acrylic fiber material for cleaning, which is characterized by impregnating the material with a detergent that does not contain a phosphate builder and then drying it. The acrylonitrile fiber used as component (2) of the present invention is obtained by spinning a heavy body containing at least 70% by weight of acrylonitrile units by a wet method. In addition, the vinyl polymer used as component 'B' includes vinyl monomers other than acrylonitrile, such as acrylamide, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, itaconic acid, vinyl acetate, Styrene, alkyl vinyl ether, vinyl pyridine, vinyl pyrrolidone, pinyl carbazole, sodium P-styrene sulfonate,
Examples include homopolymers such as glycidyl methacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate, and sodium arylsulfonate, or copolymers thereof. To integrally bond this vinyl polymer into the fibers of the component, acrylonitrile containing at least 7% by weight of the polymer is wet drawn and maintained in a wet gel state without drying. A radical polymerization catalyst is impregnated inside the fiber, and the fiber is brought into contact with the vinyl monomer to cause polymerization within the fiber. As the radical polymerization catalyst used in this case, any catalyst commonly used in general radical polymerization can be selected.

These polymerization catalysts are dissolved in a suitable solvent, and the wet gel-like fibers before drying are immersed in this solution. After squeezing the liquid, the polymerization catalysts are immediately put into a solution containing the monomer without drying, and the fibers are soaked inside the fibers. Allow polymerization to occur. As a catalyst, a redox catalyst is particularly desirable because polymerization easily occurs at low temperatures and less polymer is produced in a monomer-containing solution.
In this case, one of the components forming the redox catalyst is dissolved in a suitable solvent, and a wet gel-like fiber is immersed in the solution. Next, the other component of the redox catalyst is added to the solution containing the monomer, and the wet gel-like fiber containing the catalyst is introduced into the solution to cause polymerization inside the fiber. The above-mentioned vinyl polymer has a content of 3% per fiber weight, which is a bad component.
It is combined in a proportion of 0 to 20% by weight. This ratio can be determined by measuring the absolute dry weight before and after polymerization within the fiber, and calculating the weight increase rate according to the following formula. Weight increase rate Iron Q: Total dry weight after treatment - Total dry weight after treatment XIO.

The target weight increase rate of absolute dry weight before treatment is 30% to 20% by weight; if the weight increase rate is less than this, the effect as a builder will be lost, and if the weight increase rate is greater than this, the obtained fiber will be The strength of the material decreases, making it impractical.

The wet gel-like fibers polymerized inside the fibers are thoroughly washed with water, and while still in a wet state, are impregnated with a detergent that does not contain a phosphate builder and dried.

The detergent used as component 'C) of the present invention may be any detergent as long as it does not contain phosphate sea-based builders among commonly used detergents. Such detergents are
Usually, the active ingredients are various surfactants and soaps, and ion sequestering agents, bleaching agents, fragrances, enzymes, poppy seeds, photobrighteners, etc. are added to these. Examples of surfactants are , alkylbenzene sulfonates such as sodium n-dodecylbenzene sulfonate, sodium Q-olefin sulfonate, sulfonates of unsaturated aliphatic esters and their salts, ethoxylated or propoxylated aliphatic amides, sulfate esters of alkylphenols, fatty acids. Examples include zwitterionic activators such as group taurides and fatty acid isothionates, alkyl betaines and alkyl sulfobetaisos, and nonionic activators such as ethylene oxide adducts of alkylphenols and ethylene oxide adducts of aliphatic alcohols.

In addition, soaps such as natural or synthetic higher aliphatic alkali metal salts can also be used.

Builders include sodium carbonate, sodium silicate, sodium oxide acetate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, long-chain dicarboxylic acids such as the sodium salts of succinic acid and malonic acid, polycarboxylic acids, hydroxymethylcellulose, methylcellulose, Examples include hydroxyethylcellulose, ethylcellulose, carboxydextrin, and polyvinylpyrrolidone. As a method for impregnating the above-mentioned fibers with a detergent that does not contain phosphate-based pilders, a conventional dipping method, lo-hoo padding method, coating method, or spraying method can be used.

In addition, the amount of detergent component to be impregnated into the wet gel-like fibers polymerized inside the fibers is 1% or more by weight or more than 5% by weight based on the weight of the fibers.
up to % by weight is suitable. As the cleaning agent used in the present invention, commonly used cleaning agents other than those mentioned above may be used.

Although it is outside the scope of the claims, it goes without saying that even if a phosphate builder is blended, the cleaning effect will not be adversely affected. A more detailed explanation will be given below using examples. Example 1 Acrylonitrile 90.2% by weight, methyl acrylate 9
．． % by weight of sodium p-styrene sulfonate. Wet-spun an acrylic polymer consisting of % by weight of the base using nitric acid as a solvent, washed it with water, stretched it approximately 8 times, and never dried a wet gel-like fiber toe in a solution of 0.005 mol of ferrous sulfate. Soak for 10 minutes.

Next, the liquid is sufficiently squeezed using a mangle, and without being dried, it is immersed in a vinyl monomer solution, and the air is replaced by nitrogen gas. The composition of the vinyl monomer solution is acrylic acid 1
parts by weight, 5 parts by weight of acrylamide, 0.0 parts by weight of hydrogen peroxide
05 parts by weight and 35 parts by weight of water. After reacting at 30q○ for 2 hours and reacting with a weight increase rate of 63%, that is, 6% by weight of the vinyl polymer based on the weight ratio of the acrylic fibers,
The fiber tow is thoroughly washed with water and neutralized with a weak alkali,
Next, it was immersed in a detergent solution having the composition shown in Table 1 for 20 minutes, squeezed out so that the detergent solution was 20% by weight based on the total weight of the fiber tow and the vinyl weight body, and dried.

The detergent-impregnated fiber toe was treated with a spray nozzle to form a web, and then needle punched to form a nonwoven fabric.

The cleaning test was carried out using a round-o-meter type tester (1'4'' steel ball 1, fixed capacity, rotation speed 4 min. pm) for 1 night, 40 min.
200 cc of 0.00 warm water and 0.01 cc of detergent were added, and the washing was performed once for 30 minutes, followed by rinsing with warm water for 10 minutes, and then another 10 minutes with warm water.

After cleaning, the samples were dried away from direct sunlight, and the reflectance was measured. The cleaning effects were compared using the following formula. The cleaning effects were determined using hard water and soft water, respectively.

ri = Kaname Migame
value) Rs: Reflectance of contaminated cloth Rw: Reflectance of contaminated cloth after cleaning The results of the cleaning test of the acrylic fiber structure obtained by the method of the present invention are shown in Table 2, and the effect is extremely high. It was something.

Table 1 Table 2 Table H; 150DH hard water S; 30DH soft water Example 2 Acrylonitrile 91. Sword weight%, methyl acrylate 3
．． An acrylic polymer consisting of 5.0% by weight of acrylamide, 0.3% by weight of sodium methallylsulfonate was wet-woven using sodium rhodan as a solvent, washed with water, and stretched approximately 6 times. A wet gel-like fiber tow that does not dry out is immersed for 15 minutes in an aqueous solution of 0.2 mol of ammonium persulfate and 10-4 mol of copper sulfate.

After that, squeeze the liquid thoroughly with a mangle, put it in a monomer solution without drying it, and replace the air with carbon dioxide gas.The composition of the monomer solution is 1 part by weight of methacrylic acid, 5 parts by weight of itaconic acid, 5 parts by weight of pinyl This is a solution consisting of 5 parts by weight of pyrrolidone and 0.1 part by weight of sodium acid sulfite.

At 25qo, the weight increase rate in Table 3, that is, the reaction rate of the vinyl polymer reacted with respect to the weight of the acrylic fiber, is ``0''.
, 23 71,143 27% by weight, the fiber tow was thoroughly washed with water, neutralized with a weak alkali, and then added to a detergent solution having the composition shown in Table 1 B. It was soaked for 15 minutes, squeezed out so that the detergent solution content was 20% based on the total amount of acrylic fiber tow and vinyl polymer, and dried.

The detergent-impregnated fiber tow was treated with a spray nozzle to form a wedge shape, and then further needle punched to form a nonwoven fabric. The results are shown in Table 3. Table 3 Washing water; 15
0 DH hard water As a result of a cleaning test of the acrylic fiber structure obtained by the method of the present invention, the effect was extremely high.

Claims (1)

[Scope of Claims] 1 (A) an acrylic fiber having an acrylonitrile content of at least 70% by weight, which is spun by a wet method, and (B)
A vinyl monomer other than acrylonitrile integrally bonded within the fibers of the acrylic fiber (A) in a proportion of 30 to 200% by weight of the weight of the fiber, and (C) the component (
An acrylic fiber material for cleaning comprising a phosphate builder-free detergent, which is strongly adsorbed onto the fibers in an amount of 10 to 50% by weight of the total amount of A) and component (B). 2 Wet-spinning an acrylic polymer having an acrylonitrile content of at least 70% by weight, and contacting and polymerizing a polymerizable vinyl monomer other than acrylonitrile with the thus obtained acrylic fiber in a wet gel state. , bonded to the acrylic fibers to a proportion of 30 to 200% by weight of the acrylic fibers, and then applied a phosphate-based builder-free detergent to the acrylic fibers and vinyl monomers other than acrylonitrile bonded thereto. A method for producing an acrylic fiber material for cleaning, which comprises impregnating and adsorbing the polymer to a proportion of 10 to 50% by weight of the total amount of the polymer, and then drying the polymer.