JPH0835178A - Antibacterial acrylic fiber - Google Patents

Abstract

(57) [Summary] [Purpose] To provide an antibacterial acrylic fiber with excellent washing durability. [Structure] An antibacterial acrylic fiber obtained by treating an alkylammonium salt type and / or alkyleneammonium salt type antibacterial agent with a urethane compound in combination.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antibacterial acrylic fiber. More specifically, the present invention relates to an antibacterial acrylic fiber having excellent washing durability.

[0002]

2. Description of the Related Art Conventionally, alkylammonium salt type and alkylene ammonium salt type antibacterial agents are known to be excellent antibacterial agents in terms of performance, cost, etc., but unsolved that they have poor washing durability. Due to problems, it has not been used for acrylic fibers.

[0003]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has an object to provide an antibacterial acrylic fiber having excellent washing durability.

[0004]

An object of the present invention is to provide an antibacterial acrylic fiber characterized by being treated by using a combination of an alkylammonium salt type and / or alkyleneammonium salt type antibacterial agent and a urethane compound. To be achieved. The present invention will be described in more detail below.

As the alkylammonium salt type antibacterial agent in the present invention, one or more compounds represented by the following formula (1) are preferably used because they have particularly excellent antibacterial properties.

[0006]

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Here, R _{1 and} R ₂ have 8 to 22 carbon atoms.
Of the above, R _{3 and} R ₄ are alkyl groups having 1 to 5 carbon atoms, and X is a halogen ion. As the alkylene ammonium salt type antibacterial agent, one or more compounds represented by the following formula (2) are particularly preferably used because they have extremely excellent antibacterial properties.

[0008]

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Here, R ₁ is an alkyl or alkenyl group having 8 to 22 carbon atoms, R _{2 and} R ₃ are alkyl groups having 1 to 5 carbon atoms, R'is an alkylene group having 2 to 4 carbon atoms, and m is 1
Alternatively, 2, n is an integer of 1 to 5, and Y is an alkyl phosphate ion. Further, the alkyl phosphate ion in the present invention is preferably one represented by the following formula (3).

[0010]

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Here, R _{4 and} R ₅ have 1 to 12 carbon atoms.
Is an alkyl group. Further, the urethane type compound in the present invention may be a polyether type or a polyester type, but is preferably a polyether type urethane type compound, particularly preferably JP-A 1-2391.
It is the following polyether-based urethane-based compound disclosed in JP-A-73. That is, "a polyether polyol compound obtained by adding an alkylene oxide to a compound having two or more active hydrogens in a molecule is reacted with a polyvalent isocyanate compound to obtain a compound having an unreacted isocyanate group, and then the compound The compound (A) obtained by blocking the unreacted isocyanate group of with an acid sulfite, the same polyether polyol compound used for producing the compound (A) are reacted with epihalohydrin, and then with a polyalkylene polyamine. Compound (B), compound (A) and compound obtained by reacting the obtained reaction product having at least two or more active hydrogens bonded to amino groups in the molecule with epihalohydrin in the presence of water A polyether-based resin comprising a compound (C) obtained by reacting with (B) Particularly preferred sorbitan-based compounds, are effective.

The present invention treats acrylic fibers by using the above-mentioned urethane compound in combination with the alkylammonium salt-type or alkyleneammonium salt-type antibacterial agent. The treatment method is as follows: For example, the treatment in the oiling step) is most effective from the viewpoint of washing durability, but fibers such as tow, loose hair, crepe, cheese, corn, woven and knitted fabrics, and non-woven fabrics and the state of fiber products (even with 100% acrylic fiber) It may be mixed with other fibers such as wool, cotton, hemp, acetate, polyester, polyamide, etc.). As a method for treating the acrylic fiber in the present invention, a conventionally known method such as an Overmeyer or a jet dyeing machine can be used, or a pad-dry cure or the like can be used.

The fiber treatment conditions in the present invention may be selected as desired, but for example, the pH of the treatment liquid is 7
It is desirable that the treatment temperature is 80 ° C. or lower, and preferably 20 to 50 ° C., because the processability and washing durability are excellent. In particular, when treating acrylic fibers during the production of acrylic raw cotton, 8
If the treatment temperature is higher than 0 ° C., the crimp state of the fiber may change, and the spinnability is likely to be affected, which is not preferable.

In the present invention, the adhesion amount of the antibacterial agent and the urethane compound to the acrylic fiber is at least 0.01.
% Owf is sufficient, preferably 0.05 to 0.5
% Owf. A known function-imparting agent such as a known water-absorbing agent, an antibacterial agent, a softening agent, a water-repellent agent or a smoothing agent may be added to the treatment liquid for the acrylic fiber used in the present invention.

The acrylic fiber referred to in the present invention means one containing an acrylonitrile copolymer containing 40% by weight or more of polyacrylonitrile. The single yarn denier of the acrylic fiber in the present invention is 0.5 to 6 denier, preferably 1 to 5.0 denier, and the total denier is 50 to 10.
It is preferably 150 denier.

[0016]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation method in the present invention will be described below. Antibacterial: Based on the test method (manual) for evaluating the processing effect of sanitary processed products (by the Council for Sanitary Processing of Textile Products), the bacterial count method using Staphylococcus aureus is used.

That is, 0.2 ml of a test bacterial suspension containing ⁵ to 30 × 10 ⁵ Staphylococcus aureus prepared in a normal broth medium was uniformly inoculated on a sample of about 0.2 g. . As samples, 6 blank samples and 3 evaluation samples are prepared, and after inoculation, 3 blank samples and 3 evaluation sample samples are immediately statically cultured at 35 to 37 ° C. for 18 hours.

The three non-cultured blank specimens were tested immediately after inoculation, and the three non-cultured blank specimens and three evaluation samples were evaluated.
After completion of the culture, 20 ml of sterilized buffered physiological saline solution was added to the sample and shaken to disperse the viable bacteria in the sample, and a dilution series was made from this dispersed bacterial solution with sterile buffered physiological saline solution. The number of bacteria of "A", "B" and "C" is measured. "A": Blank (3 specimens) dispersed and collected immediately after inoculation "B": Blank (3 specimens) dispersed and collected after 18 hours of culture "C": Evaluation sample (3 specimens) dispersed and collected after 18 hours of culture For each colony, 1 ml of the diluted solution was placed in a Petri dish, about 15 ml of standard agar medium was added to the plate (2 plates were prepared for the same dilution solution), and the plate was cultured at 35 to 37 ° C. for 24 to 48 hours. Count the number and multiply by the dilution factor to calculate the viable cell count in the sample.

The antibacterial property is evaluated by calculating the difference between increased and decreased values according to the following formula. The higher the value, the better the antibacterial property. When the average number of bacteria "A" is a, the average number of bacteria "B" is b, and the average number of bacteria "C" is c, Washing method: Using a household electric washing machine, 40g containing 2g / l of neutral detergent New beads (trade name, manufactured by Kao Corporation)
After washing for 5 minutes in an aqueous solution at 0 ° C., washing with running water for 2 minutes, dehydration, further washing with running water for 2 minutes, dehydration and drying. Wash this 1
It is evaluated as the number of times (HL1), and 10 times of washing (H
L10), 30 washes (HL30), 50 washes (HL)
It was evaluated in 50).

[0020]

Examples 1 and Comparative Examples 1 and 2 As the alkylammonium salt type antibacterial agent, the one represented by the following formula (4) was used.

[0021]

[Chemical 4]

On the other hand, a treatment liquid (PH) containing a 1.2 wt% (pure concentration) aqueous solution of the urethane compound obtained by the following method and a 0.5 wt% (pure concentration) aqueous solution of the above-mentioned antibacterial agent.
7.7) was used to process the acrylic fiber 3d tow in the oiling process at the time of its production (treatment liquid adhesion amount 100% o
wf). The treated tow obtained was biscut into 70 to 127 mm and treated with 10% treated cotton, ordinary acrylic fiber 3d bias cut non-shrinkable cotton 50% and 26% shrinkable cotton 40.
%, A 2/10 Nm high bulky spun yarn was obtained by a worsted method, and after pre-bulky, a loop pile mat (400 g / m ^{2 of} basis weight) was prepared by a sewing machine tuft method, and after dyeing by a conventional method, antibacterial property was evaluated. . <Production Method of Urethane Compound> 200 parts of a polyether polyol compound having an average molecular weight of 3000, which is obtained by adding ethylene oxide to polypropylene glycol having an average molecular weight of 2000, and hexamethylene diisocyanate 2
3 parts were added, and the mixture was reacted under a nitrogen stream at 100 to 110 ° C. for 1 hour to obtain a product containing 2.3% of free isocyanate groups. To the total amount of this product, 65 parts of a 20% sodium bisulfite aqueous solution was added, and the mixture was reacted at room temperature for 1 hour.
44 parts was added to obtain a transparent aqueous solution of the compound (A).

Next, 200 parts of the same polyether polyol compound as used above was added to boron trifluoride etherate 0.
4 parts was added, and 12.3 parts of epichlorohydrin was gradually added while maintaining at 70 to 80 ° C., and 90 to 100 after addition.
React at ℃ for 1 hour, then diethylenetriamine 1
3.9 parts was added and the mixture was reacted at 120 to 130 ° C. for 3 hours. 30 parts of water and 12.3 parts of epichlorosiderin are added to the total amount of the obtained reaction product, and the mixture is reacted at 50 to 60 ° C. for 3 hours, and further 954 parts of water is added to obtain a reddish brown transparent aqueous solution of the compound (B). Got

50 A transparent aqueous solution of the resulting compound (A)
Parts and 50 parts of a reddish brown transparent aqueous solution of the compound (B) are mixed,
An aqueous solution of a urethane compound (concentration 20%, viscosity at 25 ° C., 330 cp, PH6.
3) was obtained. As a comparative example, a mat was prepared by spinning in the same manner as in Example 1 except that the antibacterial agent was treated alone (Comparative Example 1) and the urethane compound was treated alone (Comparative Example 2).
It evaluated after dyeing.

The antibacterial property of the mat obtained in Example 1 is H
L0 = 5.2, HL10 = 5.1, HL30 = 4.3,
HL50 = 3.8, which had excellent antibacterial properties even after washing, but the mats of Comparative Examples 1 and 2 both had HL0 =
1.2 and HL3 = 0.3, and both the antibacterial property before washing and the washing durability were significantly inferior to those of Example 1.

[0026]

Example 2 The same antibacterial properties were evaluated by treating in the same manner as in Example 1 except that the following formula (5) was used as the alkylene ammonium salt type antibacterial agent.

[0027]

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The antibacterial property of Example 2 is HL0 = 5.3, H
L10 = 5.2, HL30 = 4.5, HL50 = 4.0
As in Example 1, it had excellent antibacterial properties even after washing.

[0029]

Example 3 A 2/10 Nm acrylic high bulky yarn was dyed with a jet bulky dyeing machine and then treated with the antibacterial agent and the urethane compound of Example 1 at 40 ° C. for 15 minutes. The adhered amounts of the antibacterial agent and the urethane compound were 0.1% owf and 0.3% owf, respectively.

A loop pile mat (weight per unit area: 400 g / m ² ) was prepared by a sewing machine tuft system using the obtained treated yarn. The antibacterial properties of Example 3 are HL0 = 4.9 and HL10 =
4.6, HL30 = 4.1, HL50 = 3.8,
Similar to Example 1, it had excellent antibacterial properties even after washing.

[0031]

[Examples 4 and 5] A 3 wt% (purity concentration) aqueous solution of a polyester urethane compound (Bondec 1640; manufactured by Dainippon Ink and Chemicals) as a urethane compound (Example 4), a polyether urethane compound (Bondec 1610N)
S: Treated in the same manner as in Example 3 except that a 3% wt% (pure content) aqueous solution (manufactured by Dainippon Ink and Chemicals, Inc.) (Example 5) was used, and the antibacterial property was evaluated.

The antibacterial property of Example 4 is HL0 = 4.8, H
L10 = 4.4, HL30 = 3.9, HL50 = 3.6
As in Example 1, it had excellent antibacterial properties even after washing. In addition, the antibacterial property of Example 5 is HL0 = 4.9, H
L10 = 4.5, HL30 = 4.0, HL50 = 3.7
This mat also had excellent antibacterial properties even after washing, as in Example 1.

[0033]

According to the present invention, an antibacterial acrylic fiber having markedly excellent washing durability can be obtained.

Claims (1)

[Claims] 1. An antibacterial acrylic fiber obtained by treating an alkylammonium salt type and / or alkyleneammonium salt type antibacterial agent with a urethane compound in combination.