JPS6359482A - Production of antistaining synthetic fiber - Google Patents

Abstract

(57) [Abstract] 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 method for producing stain-resistant synthetic fibers with excellent water and oil repellency and wash resistance and abrasion resistance with good operability. It is something.

(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 method complicates the process and reduces operability. There were problems in that it led to a decrease in water quality and an increase in cost, and the durability of the antifouling performance was 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, conventional fibers coated with fluorine compounds have a problem in that their antifouling performance decreases due to washing or friction.

Anticipate the deterioration of antifouling performance due to washing and friction.

Even if the amount of antifouling agent applied is increased, the effect is small, and there is a problem that the operability worsens.

(Problems to be Solved by the Invention) The present invention provides excellent water repellency and oil resistance with wash resistance and abrasion resistance by a method of adding a fluorine-based antifouling compound to the yarn during melt spinning. The object of the present invention is to provide a method for manufacturing stain-resistant synthetic fibers 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, random or block copolymer polyether compounds of ethylene oxide and propylene oxide are added to the melt-spun yarns from 40 to 9031! ! ¥%
and 60 to 10% by weight of a fluorine-based antifouling agent compound consisting of the following three types of fluorine-containing compounds.

A: Aliphatic fluorine-containing ester compound having a fluoroalkyl group with a fluorine content of 40% by weight or more and an average molecular weight of 1,000 to 3,000 Day: Fluorine-containing urethane compound having a fluoroalkyl group C: Fluoroalkyl polyacrylate Ester or polymethacrylic acid fluoroalkyl ester The fibers used in the present invention include polyethylene terephthalate, 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.

In addition, examples of the polyether compound in the present invention include random or block copolymers of ethylene oxide and propylene oxide, and those in which the terminal hydrogen atom is substituted with an alkyl group, aryl group, or alkylaryl group having 18 or less carbon atoms. can be mentioned. In terms of smoothness and antifouling properties, polyether compounds have 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 aliphatic fluorine-containing ester compound A in the present invention has a fluorine content of 40% by weight or more and an average molecular weight of 1000%.
~3000 is required. Fluorine content is 4
If it is less than 0%, antifouling performance with sufficient washing resistance will not be exhibited, and if the molecular weight of 9 is less than 1000, it will easily fall off during washing, and if the molecular weight is more 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, methacrylic acid oligomer, maleic acid, fumaric acid, and the like.

Examples of perfluoroalkyl alcohols include alcohols 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 (including sulfonamide bonds, ether bonds, etc.). may be included).

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). (It may also include.)

A specific example of polyhydric alcohol is glycerin.

Examples include pentaerythritol and vinyl alcohol oligomers.

Further, examples of the fluorine-containing urethane compound B in the present invention include compounds represented by the following general formula (1).

RfOCONH-R'-NHCOOR” (1)
Here, Rf 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 substituted with fluorine atoms.

It may contain carbonamide bonds, ether bonds, ester bonds, arylene bonds, etc. ).

R1 represents an alkylene group having 2 to 20 carbon atoms, an aralkylene group, or an arylene group H1 represents an organic group having 1 to 20 carbon atoms (preferably one 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 carbonylaminoethoxycarbonylamino]
toluene.

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

In addition, the polyacrylic acid fluoroalkyl ester or polymethacrylic acid fluoroalkyl ester C in the present invention is a homopolymer of a monomer represented by the following general formula (2) or (3) or other monomers containing no fluorine atoms. Examples include copolymers with monomers.

Hz= CCOORf Here, Rf is the same as formula (1), l R'' is a hydrogen atom or a methyl group I R' is a hydrocarbon group having 1 to 17 carbon atoms, or one of the hydrogen atoms on the carbon atom Indicates a group partially or entirely substituted with a fluorine atom or a chlorine atom.

The ratio of the three types of fluorine-containing compounds A, B, and C is such that A is 20 to
The ratio is preferably 30% by weight, B 40 to 60% by weight, and C 20 to 30% by weight, and the amount of the fluorine-containing compound film formed on the fiber surface is preferably 0.05% by weight or more of the fiber. A suitable content is 0.09 to 0.3% by weight.

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 fluorine-based antifouling 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 polyether compound is less than 40% by weight, the stretchability is poor, and if it exceeds 90% by weight, the antifouling property is 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.

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

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.) ■ta Aqueous: Gently place one drop (approximately 0.3 tsl) of an 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 5 or more droplets to penetrate into the test cloth after 3 minutes is evaluated as water repellency (less than 1 is 0).
).

■Iθ oiliness: AATCC standard test method 1) 8-1975
It was based on The determination was based on the penetration resistance of each reagent (oil) in Table 2, and was determined as ta oil level (less than 1 is 0).

Table 1 Table 2 ■ Washing resistance: Washing liquid 3 containing 30 g/l of commercially available foaming detergent for carpets (Rinrei) in 100eIIi sample
ml was sprayed, immediately brushed back and forth 10 times in each direction with a nylon brush, and suctioned under reduced pressure.

Next, apply 20% of a commercially available carpet rinse agent (Rinrei).
A rinsing solution containing 51 g/l was sprayed, brushed back and forth in the weft and weft directions 10 times each with a nylon brush, vacuum suction was carried out, and after air drying day and night, the above tests 1 to 2 were conducted.

■Abrasion resistance: Dynamic loading method (J
According to IS L 1021-5.1)), using a rubber roll, after 1000 times of friction, the above test (2) was conducted.

(2) 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 breaks.

O: Good, Δ: 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, EO of the polyether compound represents an ethylene oxide unit, PO represents a propylene oxide unit,
The underlined ones are random copolymers.

Those without underlining indicate block copolymers, and the fluorine-based antifouling agent compounds are the compounds shown in Table 4.

Table 4 5% of this emulsion was applied to a melt-spun nylon 6 yarn (consisting of a single yarn with a four-hole square cross section) and the yarn was wound at a speed of 650 m/min.

Next, the temperature is 130°C and the magnification is 3.5. 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 an 8 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 5.

In Table 5, WS-0, 3, and 5 have a washing frequency of O13,
5 times, WR indicates water repellency, OR indicates (θ oil degree, and 2nd floor 9 to 18 are comparative examples.

Table 5 (Effects of the Invention) According to the present invention, it is possible to produce antifouling synthetic fibers having excellent water and oil repellency and wash resistance and abrasion resistance with good operability.

Claims (1)

[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.
and 60 to 10% by weight of a fluorine-based antifouling agent compound consisting of the following three types of fluorine-containing compounds. A: Aliphatic fluorine-containing ester compound having a fluoroalkyl group with a fluorine content of 40% by weight or more and an average molecular weight of 1000 to 3000 B: A fluorine-containing urethane compound having a fluoroalkyl group C: Fluoroalkyl polyacrylate The method according to claim 1, wherein the copolymerization molar ratio of ethylene oxide and propylene oxide in the ester or polymethacrylic acid fluoroalkyl ester (2) polyether compound is 1:9 to 4:6.