JPS61245370A - Antistaining synthetic 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 stain-resistant synthetic fibers with excellent processability and texture.

(Prior art) As a method of imparting antifouling properties such as water repellency, 1B oil resistance, liquid stain resistance, and dry stain resistance to textile products, especially sportswear, raincoats, carpets, etc., the surface thereof is treated with fluorine-based antifouling agents. A method of treatment with a chemical agent is generally adopted. Conventional methods are used to process it.

The method mainly involves post-processing the product, which has the disadvantage of complicating the process, reducing operability, and increasing costs. For this reason, in recent years, methods have been proposed for fixing fluorine compounds to fiber threads immediately after fiber formation, and some of these methods have already reached the stage of practical application.

However, fibers coated with this type of fluorine compound have a problem of high frictional resistance and poor processability. That is, troubles are likely to occur when it comes into contact with pins, rollers, guides, etc. during the yarn manufacturing process or processing process.

In addition, synthetic fibers have a slimy and waxy feel,
This may be undesirable depending on the application.

Conventionally, it has been well known to reduce frictional resistance by incorporating fine inorganic powders such as titanium oxide and silica to form irregularities on the fiber surface, but this method was not effective in removing the slimy and waxy feel. .

(Problems to be Solved by the Invention) The present invention provides an antifouling fabric that has good processability (process passability), does not have a slimy or waxy feel, and has an excellent texture with a crisp feel. The aim is to provide synthetic fibers with high quality.

(Means for Solving the Problems) The present invention solves the above-mentioned problems, and its gist consists of a fiber-forming thermoplastic polymer [A] and a polymer [B] having a higher glass transition temperature than [A]. The stain-resistant synthetic fiber is characterized in that it is formed from a heterogeneous mixture of and has fine protrusions on its surface, and is coated with a fluorine-based stain-proofing agent film.

In the present invention, examples of the dipolymer [A] include polyethylene terephthalate, polybutylene terephthalate, poly-p
- Ethylene oxybenzoate and polyesters based on these, nylon 6° nylon 12. nylon 4
6. Nylon 66, nylon 610, and polyamides mainly composed of these are preferably used. (The glass transition temperature of these polymers is about 20-90°C.)
Examples of the polymer [B] include polyarylate (wholly aromatic polyester), polyetheretherketone, polysulfone, and polyethersulfone.

Although polycarbonate and the like are used, the combination of using polyester as the 9-polymer [A] and polyarylate as the 9-polymer [B] is most preferable in terms of spinnability and the physical properties and texture of the fiber.

As the polyarylate, one obtained from a mixture of a terephthalic acid component and an isophthalic acid component and a bisphenol compound component represented by the following general formula is preferably used.

[X is a direct bond, -CHz, C(CHs)
x -10-, 5Ox- or -CO-. ] From the point of view of versatility and spinnability, the molar ratio of polyarylate is 20/80.
Most preferred are those obtained from a mixture of ~70/30 terephthalic acid and isophthalic acid components and a bisphenol A component.

Polyarylate can be obtained by conventional methods, for example,
It can be obtained by melt polymerization of a mixture of terephthalic acid and isophthalic acid and an acetate ester of a bisphenol compound, or by solution polymerization or interfacial polymerization of a mixture of terephthalic acid chloride and isophthalic acid chloride and a bisphenol compound.

In addition, the polyarylate may contain a small amount of polyester forming components other than those mentioned above.

In addition, it is desirable that the essential viscosity of the polyarylate is 0.5 or more, and if it is less than 0.5, the polyarylate becomes 9 polymer [A]
When polyester is used, it is easy to be finely dispersed in the polyester, and it is difficult to form fibers having fine protrusions on two surfaces.

[The intrinsic viscosity (inherent viscocity) of polyarylate is a value measured at 30° C. using a mixture of phenol and tetrachloroethane in a weight ratio of 6:4 at a concentration of Ig/d It. ] Furthermore, the above polyarylate has a glass transition temperature of 180 to 200°C.

Specific examples of materials other than polyarylate used as the polymer [B] in the present invention include the following. (Tg indicates glass transition temperature) Polyetheretherketone (Tg 144°C) Polycarbonate) (7g 150°C) CH,0 In the present invention, the dipolymer [A] and the polymer [B] are mixed nonuniformly. It is preferable that one polymer [B] is dispersed in a size on the order of tens of micrometers or more, since appropriate protrusions can be formed on the fiber surface.

To obtain such a mixed state, Polymer [A] and Polymer [B] may be appropriately melt-mixed using a dynamic mixer or a static mixer.

In the case of a combination of polyester such as polyethylene terephthalate and polyarylate, for example, phosphoric acid,
It is preferable to include a phosphorus compound having the ability to inhibit transesterification, such as sulfurous acid, phosphonic acid, and esters thereof. If the phosphorus compound is not present, the mixture will be excessively mixed, resulting in a homogeneous mixture, or the polyarylate will be dispersed in streaks, making it difficult to obtain the desired fibers with protrusions on the surface.

The spinning method for obtaining the fiber of the present invention includes (1) melt-spinning the heterogeneous mixture to obtain an undrawn yarn whose glass transition temperature is higher than the glass transition temperature of the dipolymer [A]; (2) A method in which the heterogeneous mixture is melt-spun at a high speed of about 5000 a+/min or more to obtain highly oriented fibers at once.

When yarn is spun using this method, the monopolymer [B] portion is difficult to stretch, so protrusions are formed on the fiber surface.

The size, shape, number, etc. of the protrusions on the fiber surface are 1 polymer [A]
The mixing ratio of and [B] (if the above-mentioned phosphorus compound is present, the mixing ratio of the king containing the phosphorus compound), the mixing conditions (
temperature (9 hours, mixer structure 1, shearing force during mixing, etc.), difference in glass transition temperature between polymers [A] and [B], spinning speed during melt spinning, cooling conditions, temperature during stretching 1 It is adjusted appropriately depending on the magnification, yarn thickness, cross-sectional shape, etc. The height and size of the protrusions on the fiber surface in the fiber axis direction and in the direction perpendicular to the fiber axis are on the order of several hundred micrometers to several micrometers. It is desirable that at least several dozen particles exist per 1 cm of length.

In order to obtain such fibers, the mixing ratio of the bipolymer [A] and the polymer [B] should be set at a weight ratio of 97/3 to 60/40, taking into consideration the fiber physical properties. Preferably 9515-70/3
0, and when the phosphorus compound is present, the content of the phosphorus compound is 0.01 to 1% by weight, preferably 0.0%.
It is desirable that the content be 2 to 0.8% by weight.

In addition, the mixing temperature or spinning temperature is 230 to 320°C.
, preferably 250 to 300°C.

Next, as the fluorine-based antifouling agent used in the present invention, water-repellent among fluorine-containing organic compounds.

The following are the 9 representative ones that have high oil repellency.

(a) A polymer obtained by homopolymerizing or copolymerizing fluorine-containing monomers represented by the following general formulas (1) to (3), or a polymer obtained by copolymerizing these monomers and other monomers not containing fluorine atoms.

cHt =CC00Rf (')RI
Rs (where R8 is a hydrogen atom or a methyl group + R2 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group, an arylene group, or an aralkylene group I R, is a hydrogen atom or an alkyl group having 1 to 1 carbon atoms, cyclo Alkyl group, aryl group or aralkyl group.

Rf represents a fluoroalkyl group having 7 to 3 carbon atoms in which some or all of the hydrogen atoms on the carbon atoms are substituted with fluorine atoms. Further, a fluorine-containing urethane compound represented by the following general formula (4), in which some or all of the hydrogen atoms on the carbon atoms of R** R3 may be substituted with fluorine or chlorine atoms.

Rf OOCN H--Ra N HCOORf
(4) (R4 is a divalent organic group having 2 to 2 o carbon atoms.

0, -3on-, -Coo, -Co.

It may also contain a bond such as N(R3)-.

Rs and Rf represent the groups described above.) A fluorine-containing polyester having a repeating unit represented by the following general formula (5).

Rf 00 CRa COO-R5-(5) (R5 is a trivalent hydrocarbon group having 2 to 10 carbon atoms.

Rn and Rf represent the groups described above.) In the present invention, coating with a fluorine-based antifouling agent film can be performed by applying a known method. That is, this is a method in which a film is formed by treating with a fluorine-based antifouling agent at an arbitrary step after being discharged from a spinning hole.

Particularly preferred is a method in which an appropriate amount of a liquid containing a fluorine-based antifouling agent is applied to an undrawn fiber thread, and then the thread is stretched and the fluorine-based antifouling agent is thermally fixed at the same time or separately. (
The heat fixing treatment may be performed after manufacturing & Im. ) According to this method, in addition to the effect that antifouling fibers can be obtained directly in the fiber forming process, there is also the advantage that the adhesion between the fluorinated antifouling agent film and the fibers is excellent. In addition, it is also possible to use an antifouling agent and a wetting agent (preferably a fluorine-containing agent) together to improve the dyeability of the fibers, which can improve the dyeability without impairing the antifouling performance. It is preferable.

The amount of fluorine-based antifouling agent attached to the fiber is 0.05 to 0.
．． A suitable amount is 5% by weight, preferably 0.1-0.3% by weight.

Note that the fibers of the present invention include not only single-component fibers, but also
It also includes fibers that are composited with other polymer components in the form of bimetallic, sheath-core, seabird-like, etc. In addition, various additives such as a flame retardant, a heat resistant agent, a light resistant agent, a coloring agent, and an antistatic agent may be contained. In particular, it is preferable to introduce a fluorine compound into the fibers, since this improves the adhesion between the fibers and the antifouling coating.

The fibers of the present invention can be used not only for antifouling purposes, but also for so-called breathable and moisture-permeable waterproof fabrics. (In this case, it is preferable to use a yarn with a small single yarn fineness of about 1 d or less.) (Example) The present invention will be explained in more detail with reference to Examples below. Oiliness was evaluated by the following method. (“Parts” indicate parts by weight.) (1) 79 aqueous: 1 of an isopropyl alcohol/water mixture with a volume ratio of 30/70.
A droplet (approximately 0.3 mj) was gently placed on a test cloth, and a case where it did not penetrate after 5 minutes was considered good.

(2) Oil repellency: Based on the AATCC-TMI 1 method.

Example 1 90 parts of polyethylene terephthalate (intrinsic viscosity 0.8°, glass transition temperature 80°C), equimolar mixture of terephthalic acid chloride and isophthalic acid chloride, and bisphenol A
10 parts of polyarylate (intrinsic viscosity 0.7, glass transition temperature 195°C) synthesized by interfacial polymerization method from and bis(
After melt-mixing 0.05 part of n-butyl phosphate at 270°C for 4 minutes using a two-wheel screw mixer,
It was melt spun at 280°C and wound at a speed of 6000 m/llln. .

In this case, 70% by weight of 2-barfluorooctylethyl acrylate, 25% by weight of vinyl chloride, and 3% by weight of 2-chloroethyl vinyl ether were used for the 16 filament threads running down from the spinneret.

4 parts of a copolymer consisting of 2% by weight of 2-hydroxyethyl acrylate and a fluorine-based wetting agent (CsH+, OCNHCzHaN (CT(3))
A solution prepared by dispersing 11 parts in 95 parts by weight of a mineral oil-based oil subliquid was applied to the fibers in an amount of 7% by weight.

The yarn obtained is 75 d/16 f and has a strength of 3.2 g.
/d.

The elongation was 43%, and no thread breakage or winding around the rollers occurred during spinning.

A micrograph (200x magnification) of the obtained yarn is shown in FIG. 1. As is clear from FIG. 1, many fine protrusions were observed on the surface of the fiber.

Also, using the above yarn, warp 110/2.54c+s,
It was woven into taffeta at a density of 100 wefts/2.54 cm, and after scouring, it was dyed at 120° C. for 30 minutes in a dye bath containing a precolor disperse dye.

The resulting fabric is extremely rich in texture.

The water repellency was "good" and the oil resistance of 11 was grade 5.

Comparative Example 1 The same operation as in Example 1 was performed using only the same polyethylene terephthalate as in Example 1.

During spinning, the yarn was taken up by the take-up roller and could not be wound stably, and the fabric had a waxy feel.

Example 2 90 parts of the same polyethylene terephthalate as in Example 1, 10 parts of the same polyarylate as in Example 1, and 0.1 part of triphenyl phosphate were melt-mixed using a two-wheeled screw mixer, and 2 parts of the above polyethylene terephthalate were mixed. The former was melt-spun as a sheath-core type composite yarn at a weight ratio of 40:60 at 280°C, and 6% by weight of the same fluorine-based antifouling agent solution as in Example 1 was applied.
Winding at a speed of m/+sin, temperature: 90°C, magnification: 3.2x.

It was stretched at a speed of Too m/l lin.

The yarn obtained was 75 d/24 f and had a strength of 3.7 g.
/d.

The elongation was 28%, and there were no problems such as thread breakage or fuzz generation during stretching (fuzz generation rate: 0.02 pieces/10'
m).

When dyed taffeta was produced using this yarn in the same manner as in Example 1, the fabric had a very crisp feel and had an I.
The water resistance was "good" and the oil repellency was grade 5.

Comparative Example 2 When the same operation as in Example 2 was performed without using polyarylate, a large number of fluffs appeared during stretching (fuzz generation rate: 3.8 pieces/10'm).

Comparative Example 3 The same operation as in Example 1 was carried out using only the same polyethylene terephthalate as in Example 1 to which 0.1% by weight of titanium oxide having an average particle size of 0.2 μm was added.

The spinning property was good (fuzz generation rate: 0.04 pieces, 710 &
e+), but the obtained fabric had a waxy feel.

(Effects of the Invention) As described above, according to the present invention, there is provided an antifouling synthetic fiber that has good processability (processability) and provides a fabric with a crisp texture.

[Brief explanation of the drawing]

Figure 1 is a micrograph of the fiber of Example 1 (200x magnification)
shows.

Claims (3)

[Claims] (1) A fiber formed from a heterogeneous mixture of a fiber-forming thermoplastic polymer [A] and a polymer [B] having a higher glass transition temperature than [A], and having fine protrusions on the surface, An antifouling synthetic fiber characterized by being coated with a fluorine-based antifouling agent film. (2) The antifouling synthetic fiber according to claim 1, wherein the polymer [A] is polyethylene terephthalate, polybutylene terephthalate, or a polyester mainly composed of these, and the polymer [B] is polyarylate. (3) Polyarylate molar ratio 20/80 to 70/30
The antifouling synthetic fiber according to claim 2, which is obtained from a mixture of a terephthalic acid component and an isophthalic acid component and a bisphenol A component.