JPS636114A - Production of stainproof synthetic yarn - Google Patents

Abstract

PURPOSE:To obtain the titled yarn having improved washing resistance, water repellency and oil repellency in good operation efficiency, by providing undrawn yarn of melt spinning with a specific composition. CONSTITUTION:Yarn of melt spinning is provided with a composition consisting of 40-90wt% polyether compound and 60-10wt% fluorine type stainproofing agent. A random or block copolymer of ethylene oxide and propylene oxide or a derivative thereof obtained by replacing the terminal hydrogen atom of the polymers with <=18C alkyl group or aryl group or alkylaryl group is used as the polyether compound. The copolymerization ratio of ethylene oxide and propylene oxide is preferably 1:9-4:6. A blend of a fluorine-containing urethane compound and a polyacrylic acid fluoroalkyl ester or polymethacrylic acid fluoroalkyl ester is preferable as a fluorine type stainproofing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing stain-resistant synthetic fibers with excellent washing resistance (8 water-based and tθ oil-based) with good operability. .

(Conventional technology) Synthetic fiber products, especially carpets and sportswear.

A commonly used method for imparting antifouling properties such as water repellency and oil repellency to diaper covers and the like is to treat their surfaces with fluorine-based antifouling compounds, but this complicates the process and reduces operability. There have been problems in that this leads to deterioration and cost increase, and the durability of the antifouling performance is poor.

In addition, methods have been proposed in which a fluorine-based antifouling agent compound is introduced into a fiber-forming polymer in the form of a blend or copolymerization and spinning, or a method in which a fluorine-based antifouling agent compound is fixed to the yarn immediately after fiber formation. (For example, JP-A-55-90667, JP-A-58-46123, JP-A-59-94621, etc.).

However, fibers coated with conventional fluorine-based antifouling compounds cannot be used in items such as carpets, which cannot be rinsed thoroughly after washing, or items, such as diaper covers, which cannot be subjected to heat treatment such as ironing after washing.

There was a problem that the antifouling performance after washing was not sufficient.

Even if the amount of antifouling agent applied is increased in anticipation of a decrease in antifouling performance due to washing, the effect is small.

On the contrary, there was a problem in that the operability deteriorated.

(Problems to be Solved by the Invention) The present invention provides excellent water repellency with wash resistance and t
The object of the present invention is to provide a method for producing stain-resistant synthetic fibers having a 8-oil property with good operability.

(Means for solving the problems) The present invention solves the above problems, and the gist thereof is as follows.

When melt-spinning synthetic fibers, a composition consisting of 40 to 90% by weight of a random or block copolymer polyether compound of ethylene oxide and propylene oxide and 60 to 10% by weight of a fluorine-based antifouling agent compound is added to the melt-spun yarn. A method for producing antifouling synthetic fibers, which comprises adding a substance to the stain-resistant synthetic fibers.

The synthetic fibers used in the present invention include polyethylene terephthalate and polybutylene terephthalate.

Poly-p-ethyleneoxybenzoate and polyesters based on these, nylon 6, nylon 12. Nylon 46. Nylon 66, nylon 610 and polyamides based on these, polyethylene, polypropylene and polyolefins based on these, polymers based on polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride and fibers made of polymers based on these, etc. can be mentioned.

9 Polyether compounds in the present invention include random or block copolymers of ethylene oxide and propylene oxide, and their terminal hydrogen atoms substituted with alkyl groups, aryol groups, or alkylaryl groups having 18 or less carbon atoms. Examples include Shitachino. In terms of smoothness and antifouling properties, the polyether compound has a total of 10 ethylene oxide units and propylene oxide units.
A value in the range of 200 to 200 is suitable. This sum is 1
If it is less than 0, the stain resistance and cohesiveness will be poor, and if it exceeds 200, the smoothness will be poor and the stretchability will be poor. Also.

The copolymerization ratio of ethylene oxide and propylene oxide is preferably 1:9 to 4:6 from the viewpoint of antifouling properties, particularly washing and antifouling properties.

The fluorine-based antifouling compound in the present invention includes:

A mixture of a fluorine-containing urethane compound and a polyacrylic acid fluoroalkyl ester or a polymethacrylic acid fluoroalkyl ester is suitable.

Examples of the fluorine-containing urethane compound include compounds represented by the following general formula (al).

RfOOCNH-R'-NHCOOR" (a) Here, Rf is a fluoroalkyl group having 6 to 20 carbon atoms in which some or all of the hydrogen atoms on the carbon atoms are substituted with fluorine atoms (sulfonamide bond, carboxamide bond) bond, ether bond, ester bond, arylene bond, etc.), R1 is an alkylene group, aralkylene group, or arylene group having 2 to 20 carbon atoms, R2 is an organic group having 1 to 20 carbon atoms (fluorine (preferably those containing atoms).

Specific examples of fluorine-containing urethane compounds include 2,4-bis[2-perfluoroalkyl-ethoxycarbonylamino] toluene, 2,4-bis(2-N-alkyl (1 to 5 carbon atoms) perfluoroalkanesulfonyl) Aminoethoxycarbonylaminocotoluene, 2,4-bis[2-N-alkyl (1 to 5 carbon atoms) perfluoroalkane carbonylaminoethoxycarbonylamino]
toluene.

Urethane compounds (perfluoroalkyl group having 6 to 20 carbon atoms) such as 4.4'-bis(2-perfluoroalkylethoxycarbonylamino)diphenylmethane are mentioned.

In addition, polyacrylic acid fluoroalkyl ester or polymethacrylic acid fluoroalkyl ester is a homopolymer of a monomer represented by the secondary general formula (bl or (C1) or a copolymer with other monomers containing no fluorine atom). Examples include polymers.

CHz = CC00Rf Here, Rf is the same as in formula (a), R3 is a hydrogen atom or a methyl group I R' is a hydrocarbon group having 1 to 17 carbon atoms, or a part of the hydrogen atom on the carbon atom or Indicates a group completely substituted with fluorine atoms or chlorine atoms.

The ratio of the fluorine-containing urethane compound and the polyacrylic acid fluoroalkyl ester or the polymethacrylic acid fluoroalkyl ester is 3 near to 9 in terms of washing resistance and stain resistance.
:1 (weight ratio) is preferable.

The method of the present invention is carried out by the so-called spin finish method. That is, a liquid containing a polyether compound and a fluorine-based antifouling agent compound is applied to the undrawn yarn spun from a spinneret, and the drawing of the undrawn yarn and the fixing treatment of the fluorine-based antifouling agent compound are simultaneously or This is a separate method. This method has the advantage of simplifying the process and improving the adhesion between the fluorinated antifoulant compound film and the fibers.

The ratio of the polyether compound and the fluorinated antifouling compound to be applied to the undrawn yarn needs to be 40 to 90% by weight of the polyether compound and 60 to 10% by weight of the fluorinated antifouling compound. If the content of the polyether compound is less than 40% by weight, the stretchability will be poor, and if it exceeds 90% by weight, the stain resistance will be poor. In addition, if the fluorine-based antifouling agent compound exceeds 60% by weight, the fluorine compound may fall off and accumulate in the thread path of the drawing machine, or the smoothness may be insufficient, resulting in poor drawability. The soiling property becomes insufficient.

The amount of the fluorine-based antifouling compound film formed on the fiber surface is 0.05% by weight or more, preferably 0.1 to 0.05% by weight of the fiber.
A suitable amount is 3% by weight.

It is preferable that the cross-sectional shape of the fibers is uneven because the fluorine-based antifouling agent compound-containing liquid can easily adhere to the fibers.

In addition, acrylic resin is added to the treatment solution as a binder to strengthen the film of the fluorine-based antifouling compound on the fibers, and to prevent the dyeability of the fibers from decreasing due to the formation of a film of the fluorine-based antifouling compound. .

It is also preferred to incorporate a surfactant (wetting agent), particularly a fluorine-containing surfactant, into the film.

(Example) Next, the present invention will be explained in more detail with reference to Examples, and the antifouling performance was evaluated by the following method. (“Parts” indicate parts by weight.) +1) 18 Aqueous: Gently place one drop (approximately 0.3 ml) of the isopropyl alcohol/water mixture having the composition shown in Table 1 on nine locations on the test cloth. , the composition of the mixed solution that does not allow more than 5 droplets to penetrate into the test cloth after 3 minutes! The water level was 8 degrees (less than 1 is O).

+2+ 78 Oiliness: AATCC Standard Test Method 1) B -
Based on 1975. Judgment is based on the penetration resistance of each reagent (oil) in Table 2, t8 oil level (less than 1 is O
).

Table 1 Table 2 (3) Washing resistance: Spray 3 ml of washing liquid containing 30 g/l of commercially available foaming detergent for carpets (Rinrei) onto a 100 crA sample, and immediately use a nylon brush to spray 10 Brush back and forth several times and suction under reduced pressure.

Next, apply 20% of a commercially available carpet rinse agent (Rinrei).
g/7! Spray 5 ml of the containing rinse solution, brush back and forth 10 times each in the weft and weft directions with a nylon brush, apply pressure and suction, and dry naturally day and night.
2) test was conducted.

(4) Stretchability: 50 kg of undrawn yarn was stretched and evaluated in three grades based on the amount of antifouling agent that fell off to the roller and the number of yarn breakages.

◯: Good, △: Slightly poor, ×: Bad Example A 13% aqueous emulsion was prepared by dispersing a composition consisting of a polyether compound and a fluorine-based antifouling agent compound shown in Table 3 in water.

In Table 3, 1. In the polyether compound, EO indicates an ethylene oxide unit, PO indicates a propylene oxide unit, and the underlined one is a random copolymer.

Those without underlining indicate block copolymers, and the fluorinated antifouling compounds A and B are represented by the following formula.

Crystal 3 B -(CHz CH)n- C00(C1)□)2-N-SOzCaFttH3 5% of this emulsion was attached to a melt-spun nylon 6 thread (consisting of a single thread with a four-hole hollow square cross section). It was wound up at a speed of 650 m/min.

Next, temperature 130°C 1x magnification 3. S, stretching speed 2000
The yarn was drawn at a speed of m/min and then crimped with an air jet at 260° C. to obtain a crimped yarn of 1225 d/68 f. The obtained crimped yarn had a strength of 3.5 g/d, an elongation of 43%,
The crimp rate was 23%.

After making this crimped yarn into a knitted fabric, acid dyes are used.

Dyeing was carried out at 100° C. for 30 minutes to obtain a pale beige dyed cloth. After drying this dyed cloth, it was heat treated at 135°C for 5 minutes,
Antifouling performance was measured.

The results are shown in Table 4.

3.5 times, WR indicates water repellency, OR indicates oil repellency, and I'lh8.9 is a comparative example.

(Effects of the Invention) According to the present invention, excellent T8 water resistance and 1
8. It becomes possible to produce stain-resistant synthetic fibers with good operability.

Claims (4)

[Claims] (1) When melt-spinning synthetic fibers, 40 to 90% by weight of a random or block copolymer polyether compound of ethylene oxide and propylene oxide is added to the melt-spun yarn.
A method for producing stain-resistant synthetic fibers, which comprises applying a composition comprising: and 60 to 10% by weight of a fluorine-based stain-proofing agent compound. (2) The method according to claim 1, wherein the copolymerization molar ratio of ethylene oxide and propylene oxide in the polyether compound is 1:9 to 4:6. (3) The method according to claim 1, wherein the fluorine-based antifouling agent compound is a mixture of a fluorine-containing urethane compound and a polyacrylic acid fluoroalkyl ester or a polymethacrylic acid fluoroalkyl ester. (4) The method according to claim 3, wherein the weight ratio of the fluorine-containing urethane compound to the fluoroalkyl polyacrylate or fluoroalkyl methacrylate is from 3:7 to 9:1.