JPS62238869A - Antistaining fiber - 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 (Industrial Application Field) The present invention relates to an active fiber having excellent wash resistance, tΩ water resistance, 10 oil resistance and dry fill resistance.

(Prior art) As a method of imparting stain-proofing properties such as T8 water-based and T8 oil-based to textile products, especially carpets, sportswear, diaper covers, etc., it is common to treat the surface with a fluorine-based stain-proofing agent. It has been adopted.

Furthermore, methods have been proposed in which a fluorine compound is introduced into a fiber-forming polymer in the form of a blend or copolymerization and then spun, or a method in which a fluorine compound is fixed to a fiber thread immediately after fiber formation.

Various fluorine-containing compounds are known as fluorine-containing compounds used for this purpose, such as polyacrylic acid type, polymethacrylic acid type, aromatic ester type, and urethane type (for example, Japanese Patent Application Laid-Open No. 1986-1999). No. 90677, 58-
No. 13723, No. 59-94621, No. 59-204
No. 980, No. 61-12969, etc.).

However, conventional fibers coated with fluorine compounds have a problem in that they do not have sufficient antifouling performance after washing. In other words, items treated with certain fluorine-containing compounds have both water repellency and IΩ oil resistance reduced by washing, and items treated with certain fluorine-containing compounds have either oil repellency or T8 water resistance lower than washing Gζ. The decline in antifouling performance due to washing, which has been a problem, is not due to the shedding of the antifouling agent, but is recognized to be due to the residual surfactant during washing, and this tendency is particularly strong in carpets.

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 that the operability deteriorated.

(Problems to be Solved by the Invention) The present invention aims to provide an antifouling fiber having excellent washing resistance, 18 water resistance, oil repellency, and dry fill resistance.

(Means for Solving the Problems) The present invention solves the above problems, and its gist is that the fluorine content is 40% by weight or more and the average molecular weight is 100% by weight or more.
The antifouling fiber is coated with a mixture of an aliphatic fluorine-containing ester compound having a fluoroalkyl group of 0 to 3000 and a fluorine-containing urethane compound having a fluoroalkyl group.

In the present invention, the mixing ratio of the aliphatic fluorine-containing ester compound and the fluorine-containing urethane compound is 20/8 by weight.
0 to 60/40 is desirable. If this ratio is less than 20/80, the oil repellency tends to decrease after washing, and if the ratio is thicker than 60/40, the tank water resistance tends to decrease after washing.

The aliphatic fluorine-containing ester compound in the present invention has a fluorine content of 40% by weight or more and an average molecular weight of 1,000 to 1,000.
It needs to be 3000. Fluorine content is 40
If the molecular weight of 9 is less than 3,000, antifouling performance with sufficient washing resistance will not be exhibited, and if the molecular weight of 9 is less than too much, it will easily fall off when washed, and if the molecular weight of 9 is less than 3000, sufficient antifouling performance will not be exhibited.

Examples of such aliphatic fluorine-containing ester compounds include esters of polyhydric carboxylic acids and perfluoroalkyl alcohols, and esters of perfluoroalkyl carboxylic acids and polyhydric alcohols.

A specific example of polyhydric carboxylic acid is malonic acid.

Succinic acid, glutaric acid, adipic acid, pimelic acid.

Speric acid, azelaic acid, sebacic acid, citric acid, acrylic acid oligomer, meccrylic acid oligomer, maleic acid, fumaric acid, and the like.

Examples of the perfluoroalkyl alcohol include alcohols having a rheoloalkyl 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 5 ether bond) (It may also include.)

Examples of perfluoroalkylcarboxylic acids include carboxylic acids having 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, ether bond). ).

A specific example of polyhydric alcohol is glycerin.

Examples include pentaerythritol and vinyl alcohol oligomers.

Further, examples of the fluorine-containing urethane compound in the present invention include compounds represented by the following general formula.

RfOCONII-R'-NIICOOR2 where, R
f is a fluoroalkyl group having 6 to 20 carbon atoms (sulfonamide bond) in which some or all of the hydrogen atoms on the carbon atoms are replaced with fluorine atoms.

It may contain carbonamide bonds, ether bonds, ester bonds, etc. ), R' is an alkylene group, aralkylene group, or arylene group having 2 to 20 carbon atoms RZ
represents an organic group having 1 to 20 carbon atoms (preferably containing a fluorine atom).

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) aminoethoxyluponylamino] toluene, 2,4-bis[2-N-alkyl (1 to 5 carbon atoms) perfluoroalkane luponylaminoethoxyluponylamino]
toluene.

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

The fibers used in the present invention include polyethylene terephthalate, polybutylene terephthalate, poly-p-ethyleneoxybenzoate, polyesters mainly composed of these, nylon 6, nylon 12. -3-Iron46. 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 polymers based on these Examples include fibers.

The fibers of the present invention are preferably produced by a spin finishing method. That is, a method in which a liquid containing an aliphatic fluorine-containing ester compound and a fluorine-containing compound is applied to undrawn fibers extruded from a spinneret, and the stretching of the fibers and the fixing treatment of the fluorine-containing compound are performed simultaneously or separately. be. This method has the advantage of simplifying the process and improving the adhesion between the fluorine-containing compound film and the fibers.

A liquid containing an aliphatic fluorine-containing ester compound and a fluorine-containing urethane compound is a liquid containing these compounds in bulk form or in the form of an emulsion, suspension, solution, etc. 1 dispersant; j+1 Electric agent, heat resistant agent.

It contains softeners and the like as needed.

Particularly preferred is one in which an aliphatic fluorine-containing ester compound and a fluorine-containing urethane compound are blended with 9 ordinary spinning oils, and by adding this at the time of spinning, the process is simplified.

The stretching of the fibers and the fixing treatment of the fluorine-containing compound are carried out by methods such as (1) applying appropriate heat during stretching, (2) applying heat before stretching and then stretching, and (2) applying heat after stretching.

The amount of the fluorine-containing compound film formed on the fiber surface is suitably 0.05% by weight or more, preferably 0.09 to 0.3% by weight of the fiber.

It is preferable to make the cross-sectional shape of the fibers uneven, since this makes it easier for the fluorine-containing compound-containing liquid to adhere to the fibers.

In addition, in order to prevent recontamination during washing, polyalkylene oxide components are blended or copolymerized into the polymer forming the fibers, and fluorine-containing compounds and network (
It is also preferable to use a polymer-forming polyalkylene oxide compound in combination.

Furthermore, in order to prevent a decrease in the dyeability of fibers due to the formation of a fluorine-containing compound film, it is also preferable to introduce 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.) (1178 aqueous: 1 drop (approximately 0.3 mj) of an isopropyl alcohol/water mixture having the composition shown in Table 1 was gently placed on 9 locations on the test cloth, The water repellency is the composition of the mixed liquid that does not allow 5 or more droplets to penetrate into the test cloth after 5 minutes (less than 1 is O).
And so.

(21ta Oiliness: AATCC Standard Test Method 11B-19
Based on 75. The oil repellency was determined based on the penetration resistance of each reagent (oil) in Table 2 (less than 1 is 0).

Table 1 Table 2 (3) Dry fill resistance: Dry soil with the composition shown in Table 3 and a test piece weighing twice the weight of the dry soil in lQcm x locm were placed in a polyethylene container and mixed and shaken vigorously for 3 minutes. After heating, remove the test piece.

After sucking it up with a vacuum cleaner, measure the brightness.

lη It is expressed as the difference in brightness after dyeing and removal.

Table 3 (4) Washing resistance: 100 cut samples were sprayed with 3 ml of a washing liquid containing 30 g/l of a commercial foaming detergent for carpets (Rinrei), and immediately washed 10 times each in the weft and weft directions with a nylon brush. Perform reciprocating brushing and vacuum suction 9
Next, apply 20% of a commercially available carpet rinse agent (Rinrei).
Spray 5ml of rinse solution containing g/β and use the nylon brush again.

Perform back-and-forth brushing 10 times in each direction.

After suctioning under reduced pressure and natural drying day and night, the tests (1) to (3) above were conducted.

Examples 1 to 5 and Comparative Examples 1 to 5 20 parts of a 20% aqueous dispersion of the fluorine-containing compounds shown in Table 4 mixed in the proportions shown in Table 5 was mixed into an aqueous solution containing an ester oil as the main component and having a concentration of 13%. Spinning oil? & 80 parts.

A melt-spun nylon 6 thread was coated with 6% of this dispersion and wound up at a speed of 700 m/min. Next, the first stage of stretching was carried out at a temperature of 90°C, a ratio of 1.11 hours and 0.1 seconds, and then a temperature of 180°C, a ratio of 3.2° and a time of 0.1 seconds.
．． Second stage stretching for 2 seconds, 1000 d/6
A drawn yarn of 0f was obtained. (No trouble occurred during yarn spinning.) Table 4 Table 5 After making this drawn yarn into a knitted fabric, it was heated to 1100℃ using an acid dye.
The cloth was dyed 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, and its antifouling performance was measured.

Table 6 shows the results for each side.

Table 6 In Table 6, WS-O to 54 shows 0 to 5 times, and WS-O to 54 shows 0 to 5 times, and shows WS-O to WNC Kimika to zoRc award tt1 and DS4 dry fill type men's mouth.

(Effect of the invention) According to the invention, excellent T8 water-based with wash resistance.

An antifouling fiber having oil repellency and dry fill resistance is provided.

Claims (2)

[Claims] (1) Coated with a mixture of an aliphatic fluorine-containing ester compound having a fluoroalkyl group and a fluorine-containing urethane compound having a fluoroalkyl group, with a fluorine content of 40% by weight or more and an average molecular weight of 1000 to 3000. A stain-resistant fiber that is characterized by (2) The mixing ratio of the aliphatic fluorine-containing ester compound and the fluorine-containing urethane compound is 20/80 to 60/4 by weight.
0. The fiber according to claim 1, wherein the fiber is 0.