JPH0226919A - Fiber excellent in low frictional characteristics and stainproofness - Google Patents

Abstract

PURPOSE:To provide the title novel fiber homogeneously dispersed with fluoropolymer granules, having specified mechanical strength, retaining adequate practical characteristics, good in water repellency and heat resistance, thus suitable for rainwears, etc. CONSTITUTION:The objective fiber homogeneously dispersed with fluoropolymer (pref. polytetrafluoroethylene) granules >=1.5g/de in tenacity. This fiber can preferably be produced by the following process: a raw material monomer constituting fiber-forming host polymer is dispersed, in advance, with fine granules consisting of a fluoropolymer into a slurry, which is then polymerized to prepare chips containing the granules, and these chips are put to spinning. The amount of the fine granules to be used is pref. such as to be 15-30wt.% based on the fiber-forming polymer, in the case of single spinning fiber; while for conjugate spinning fiber, 15-50wt.% based on the sheath or core component polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to fibers that have excellent abrasion resistance and antifouling effects.

[Prior art] Polyethylene terephthalate fibers and nylon fibers, which are general-purpose fiber materials, are easily worn away by mechanical friction, and can even melt when the degree of friction is severe, making it difficult to use fabrics made of these fibers for clothing. It could not be said that the aIirIf1 material had a short lifespan and was sufficient for use as a product.

In particular, when used for sports clothing, it is necessary to make sure that it does not easily become punctured even during extreme exercise such as sliding, and also because of the sweat and fatty secretions that come with exercise. , parts that come into direct contact with the skin, such as hands, feet, collars, etc., easily become dirty, and there are problems in that the stained dirt is difficult to remove.

In order to improve the drawbacks of such general-purpose fiber materials, various improvement methods have been proposed.

For example, clothing fabrics can be post-processed using a silicone-based processing agent to achieve low friction V! Method of making into fabric or JP-A-62-2
As shown in Japanese Patent No. 57419, a method is known in which the abrasion resistance is improved by blending and dispersing organic polysiloxane inside polyester fibers. However, in the former method, the silicone treatment agent is introduced in an instant, so it cannot withstand repeated use and is easily removed, especially during cleaning. Further, even the latter method has a small effect on improving the abrasion resistance, and these conventional methods have limitations. In general, when these silicon-based materials are used, resistance to dirt is extremely weak.

On the other hand, although fibers made solely of polytetrafluoroethylene (hereinafter abbreviated as PTFE) satisfy the above characteristics, it is difficult to color them by means such as dyeing, and there are limits to their use in clothing applications. Met.

Furthermore, in Japanese Patent Application Laid-Open No. 62-238822M, PTF
A mixed spun fiber of a fluorine-based polymer such as E and polyethylene terephthalate (hereinafter abbreviated as PET) is described. The publication states that kneading fine particles such as PTFE to form fibers may cause fiber breakage due to the difficulty of uniformly dispersing the fine particles into the fibers and the low affinity between PTFE and PET. This has been explained as unsuitable and it has been proposed to blend thermoplastic polymers, such as copolymers of PTFE, with PET in the melt to obtain mixed spun fibers. However, in such methods, fluorine-based polymers, even in the form of copolymers, usually have a melting point of about 300°C and an extremely high melt viscosity.
It is difficult to extrude the polymer from the spinneret, and even if the polymer can be extruded, melt fractures occur, and when the spinning temperature is increased to lower the viscosity, PET decomposes significantly, making yarn spinning difficult. , it was difficult to put it into practical use.

[Problems to be Solved by the Invention] In view of the various disadvantages of the prior art as described above, the present invention has been proposed to have excellent abrasion resistance and antifouling properties while maintaining sufficient practical characteristics. The aim is to provide a new fiber material that has two properties.

[Means for Solving the Problems] That is, the fibers of the present invention are as shown in the following first to fourth items.

First, it is a fiber in which one or more types of fluoropolymer particles are substantially uniformly dispersed and has a strength of 1.5 g/d or more.

Second, at least one type of fluoropolymer particles selected from the polymer groups shown in [I] to [VI] below are substantially uniformly dispersed, and the strength is 1.5 g/d or more. It is a fiber.

(R=CF3.0Rf) (Rf is a perfluoroalkyl group) (R=F, CI > (R=F, CI > (R=F, CI > (R=F, CI > It is a fiber having a sheath structure, in which one or more types of fluoropolymer particles are substantially uniformly dispersed in at least the sheath component, and the strength is 2.5 g/
d or more.

Fourthly, it is an m-fiber having a sea-island structure, in which one or more types of fluoropolymer particles are substantially uniformly dispersed in at least the sea component, and the strength is 2.5 g/m.
d or more.

[Function] Hereinafter, the fiber having excellent low friction properties and antifouling properties of the present invention will be explained in more detail.

Since the fiber of the present invention contains fluoropolymer particles,
It exhibits great effects in terms of low friction and antifouling properties.

The present invention achieves low friction properties and antifouling properties by uniformly dispersing fine particles composed of a fluoropolymer in a general-purpose fiber-forming polymer such as polyester polyamide polyacrylonitrile, and achieves practical properties. The purpose is to provide fibers with the following properties. That is, of course, the purpose and structure are different from the precursor fiber in which polytetrafluoroethylene particles are dispersed in a polymer such as sodium alginate as a binder in the manufacturing process of polytetrafluoroethylene fiber. Such precursor fibers are intermediates for obtaining fibers made only of polytetrafluoroethylene by removing the binder polymer component through a firing process, and their strength is at most 0°59/d. .

l of the present invention! In the case of a single spun fiber, the polymer forming the commonly used fluoropolymer particles exists as fine particles uniformly dispersed in the fiber. or,
In the case of composite spun fibers such as core-sheath type fibers or sea-island type fibers, fine particles are uniformly dispersed mainly in the sheath component or sea component, but the fine particles are also contained in the core component or island component. It may be Note that the state in which the particles exist substantially uniformly dispersed herein means, for example, a state in which individual fine particles are dispersed independently without agglomeration, or a state in which there are several to several tens of fine particles. It includes a state in which clustered fine particle groups are uniformly dispersed, or roughly, two of these fine particles and fine particle groups are dispersed.
This also includes situations where people are dispersed.

Such particles may be a mixture of particles having different polymer compositions, or the polymers constituting the particles themselves may be a polymer blend mixture. When a fluoropolymer is present in the fiber as fine particles, the compatibility between the fluoropolymer and the fiber-forming polymer into which it is introduced is low, so that such fine particles are present not only in the fiber but also in a part of it. also appears on the surface and contributes to low friction and antifouling effects.

By forming an uneven pattern on the fiber surface that is continuous or discontinuous in the axial direction of the fiber, the low friction property can be greatly improved. Composite fibers such as sea-island type fibers and core-sheath type fibers, as well as split type fibers such as clover type fibers, have low friction and low friction even when fine particles of the fluoropolymer are introduced into the fibers as a component appearing on the outer surface. Great effect on stain resistance. In particular, by introducing the fluoropolymer fine particles into the fiber, some of the fine particles are also exposed on the surface, and the low friction properties originally possessed by the polymer forming the fine particles are further improved.
This is noticeable due to the reduction in the contact surface area affected by friction.

In addition, since the fluoropolymer fine particles exist near the surface, it is difficult to attract dirt-causing substances, and even if dirt is adsorbed to the fiber surface, the exposed portion of the fluoropolymer fine particles on the surface will peel off. As a result, dirt components are easily removed.

The shapes of the fluoropolymer particles include spheres, ellipsoids, polyhedrons, and other random shapes. The size of one particle is 1μ
The appropriate value is below, preferably 0.7μ or less, more preferably 0.4μ or less. Furthermore, the sizes of the plurality of fluoropolymer particles introduced into the fiber of the present invention may be uniform, or may be distributed and not necessarily uniform in size. When such particles are dispersed in a polymer medium, it is preferable that all the fine particles are uniformly dispersed in the polymer, but a plurality of fine particles may partially aggregate or adhere to each other. The ratio of the fluoropolymer particles to be dispersed to the host polymer, which is a fiber-forming polymer, differs depending on whether the fiber has a single component structure or a composite structure such as a sea-island or core-sheath structure. 5~ for individually spun fibers
5g weight % is good. If it is less than 5% by weight, the proportion of the fluoropolymer particles on the fiber surface will be small, so the effect of improving fiber properties will be small, and if it exceeds 5g% by weight, the tensile properties of the fiber will decrease. Preferably, 10 to 40% by weight, more preferably 15 to 30% by weight is appropriate. In addition, in composite spun fibers, since the island component or sheath component acts as a reinforcing component, it is possible to increase the amount of fine particle additives compared to the above-mentioned single spun fibers. The proportion is preferably 5 to 70% by weight. If it is less than 5% by weight, the effect of improving fiber properties is small;
If it exceeds % by weight, the polymer forming the sea component and the island component tends to be detached, which is not appropriate. Preferably 10 to 60% by weight, more preferably 15 to 5g% by weight is appropriate.

The fiber of the present invention constructed as described above, in which the fluoropolymer is substantially uniformly dispersed in the single spun fiber, has a strength of generally 1.5 g/d or more, and Core-sheath or sea-island structure fibers that are substantially uniformly dispersed in the sheath or sea component have a strength of approximately 2.5.
g/d or more, and has practical strength.

As described above, in the present invention, the amount of particles made of fluoropolymer added is generally 10% by weight or more, and at such a high addition rate of 10% by weight or more, the strength of the single spun fiber is 1.5 g/ d or more, 2.5o/ for composite spun fibers
d or more, which is groundbreaking. In order to maintain high strength despite such a high addition amount, the diameter of the fine particles used in the present invention is desirably as small as 1μ or less, preferably 0.7μ or less, as described above. For example, this is very different from the conventional production of polytetrafluoroethylene fibers, in which the particle diameter was approximately 100 μm, and the above-mentioned fine particles with a diameter of 1 μm or less are used in the textile field. The thing was never done.

The fluoropolymer constituting the particles in the present invention includes:
For example, it means a polymer selected from the following polymer group [F] in which hydrogen atoms are partially or completely replaced with fluorine atoms, but is not limited thereto.

Polymer group [F]: polyamide, polyester, polyimide, polyetherimide, polyamideimide, polyesterimide, polyesteramide, polyether, polyetherester, polyketone, polyetherketone,
Polyacrylic acid, polymethacrylic acid, polyacrylic acid derivatives, polymethacrylic acid derivatives, polyolefins, polyacetylene, polyurethane, polyurea.

These may be aliphatic chain carbon compounds or may have an aliphatic ring or an aromatic ring. In addition, compounds having unsaturated bonds in the carbon chain and compounds having heteroatoms such as oxygen, sulfur, phosphorus, and silicon can also be used as fluorine-based polymer compounds. Examples of fluoropolymers preferably used in the present invention include polytetrafluoroethylene, polytrifluoroethylene, polyvinylidene fluoride, polyfluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, polyhexafluoropropylene, and fluorinated vinyl polymers (polymer group A) such as perfluoroalkyl vinyl ether)
can be mentioned. Alternatively, a copolymer (polymer B group) consisting of a combination of two or more polymers selected from the above polymer group A, or one type of polymer selected from polymer A group and/or polymer B group, or Examples include copolymers (polymer group C) consisting of a combination of a polymer larger than this and an olefin polymer such as polyethylene, polypropylene, polybutadiene, or polyisoprene.

Furthermore, it may be a blended mixture of polymers shown in Groups A to C above. The molecular weight of these polymers is 1
000 or more is appropriate. If it is less than 1000, processability into fibers is poor. Preferably it is about 10,000 to 1,000,000.

Moreover, such a polymer may have a partially crosslinked structure.

The fiber-forming host polymers into which these fluoropolymers are introduced in the form of fine particles include the above-mentioned polymer group [F
In addition to those shown in ], examples include polymers that can be melt molded such as polyphenylene sulfide and polyphenylene oxide, wet moldable polymers such as polyacrylonitrile, cellulose and derivatives thereof, and other polymers that can be molded by a dry method. In this way, a polymer system into which particles made of a fluoropolymer are introduced may be made into fibers alone, or it is possible to form a sea-island type or core-sheath type composite fiber with the polymer system as a sea component or a sheath component. can. At this time, as the corresponding island component or core component polymer, the same or different types of polymers can be selected from the above-mentioned polymers, but systems with relatively similar processing characteristics are preferred. Roughly, the core component and sheath component or
It is appropriate to select polymers with good compatibility so that the adhesion between the sea component and the island component is improved.

Further, as the fluoropolymer constituting the particles used in the present invention, it is preferable to use one selected from the following (I) to (Vl). In addition, the following CI) ~ (I
The composition of the copolymer V) is not particularly limited, but the value of X (molar ratio) is preferably 0.2 or more.

(R=F, CI > (R=F, CI > (R=F, CI > (R=CF 3 , ORf > (Rf is a perfluoroalkyl group) (R=F, CI > the above fluoropolymer When dispersing and turning into fibers,
The powder to be dispersed is preferably a fine powder in consideration of the drawing process in yarn spinning, and the particle size is conveniently on the order of submicrons or smaller. Various particle shapes are used, such as spherical and ellipsoidal. In addition, in order to improve the uniform dispersibility of the fine powder made of the fluoropolymer into the fiber-forming host polymer, a kneading type chip containing the fine particles made of the fluoropolymer is manufactured using a kneading means such as an extruder. After that, it is preferable to subject it to a spinning process. More preferably, fine particles made of the fluoropolymer are preliminarily dispersed in a monomer in the polymerization step to form a slurry, and this is subjected to the polymerization step to produce chips containing the fine particles, which are then spun. A dispersant can also be used in combination to achieve uniform dispersion of the fine particles.

Although a single spinning method in which fine particles made of fluoropolymer are uniformly dispersed in the fiber has practical fiber strength, from the perspective of further increasing the fiber strength, it is necessary to process the fiber into a core-sheath type or sea-island type fiber. I like it a lot. In a fiber having such a core-sheath structure, the core component is used as a reinforcing component of the fiber, and the sheath component has fine particles of a fluoropolymer uniformly dispersed in a host polymer. In addition, in fibers having a sea-island structure, the island component is used as a reinforcing component of the fiber, and the sea component is a polymer system in which fine particles of a fluoropolymer are uniformly dispersed in a host polymer. As mentioned above, the fiber of the present invention, in which the fluoropolymer is substantially uniformly dispersed in the single spun fiber, has a strength of generally 1.5 g/d or more, and has a core-sheath or sea-island structure. Those which are substantially uniformly dispersed in the core or sea component of structural fibers generally have a strength of 2.5 g/d or more.

The fiber of the present invention has high oil repellency and stain resistance,
Particularly effective against oil-based stains.

For this reason, when viewed as a clothing material, it is extremely difficult for stains mainly composed of secretory oil valves from the body to adhere to areas such as collars and sleeves, and deposits such as stains do not remain on clothing. This is convenient for use in luxury goods-oriented clothing. It is also ideal for use as a workwear material for machinery maintenance work where oil tends to adhere. Furthermore, it is much easier to remove dirt that has penetrated into the fiber gaps from clothing by cleaning compared to conventional products. Further, in contrast to the conventional method of applying an antifouling agent through post-treatment, which tends to be easily removed by cleaning, the fibers of the present invention also have excellent cleaning stability. For this reason,
It can be widely used in various clothing applications such as dress shirts and underwear.

Furthermore, the fibers of the present invention exhibit good non-adhesive properties, and therefore are not only resistant to dirt but also have low adhesion of foreign matter. Moreover, it has a high specific gravity and is suitable for use as materials for dropping into the sea. For this reason, it exhibits an anti-algae effect when used in fishing nets, underwater ropes, etc.

Furthermore, the fibers of the present invention have a high degree of water repellency, and are therefore ideal for clothing applications, particularly rain gear.

Furthermore, the fibers of the present invention have higher heat resistance than conventional clothing fibers because a fluoropolymer having a high degree of heat resistance is present near the fiber surface. Furthermore, since the fiber has a low coefficient of friction, less frictional heat is generated, and even when used as a material for athletic clothing, for example, there is less occurrence of holes due to wear or melting.

Furthermore, the fibers of the present invention have higher light resistance than conventional clothing fibers because a fluoropolymer having a high degree of light resistance is present in the fibers, particularly near the fiber surface. In particular, polyamide fiber materials such as nylon have extremely poor UV stability and have limited application to clothing materials. By using polymer particles, it is possible to provide a fiber with high ultraviolet resistance stability while substantially retaining the mechanical properties of nylon fiber. Therefore, the yellowing and coloring of the fibers caused by the deterioration of the polymer due to ultraviolet rays is smaller than that of conventional fibers.

Furthermore, the fiber of the present invention has excellent chemical resistance. For this reason,
It is ideal as a material for use in work clothes for chemical experiments, etc.

l1ivL of the present invention may be a filament,
It may be in the form of a staple, and can also be processed into the form of a tow or sliver. Furthermore, it may have crimps and can be easily processed into felt, wear, etc. using a card machine or the like. Alternatively, it can be processed into fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics.

The fibers of the present invention can be processed into these fabrics alone or in combination with other general-purpose fibers.

The fibers of the present invention can be dyed by conventional methods.

Of course, it is also possible to dye using pigments, for example, by dyeing.

The IIi fiber of the present invention can also be made into an ultrafine fiber with a fineness of 1 denier or less, and can still exhibit the above-mentioned properties such as low friction properties, antifouling properties, and heat resistance.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Polyethylene terephthalate (PET) chips and PT
Fine powder of FE (average particle size approximately 0.3μ) is uniformly mixed using an extruder-type melt-kneading device so that the weight percentage of PET/PTFE is 90/10 to produce spinning chips. did. This chip was used for melt spinning. At this time, the spinning temperature was 290° C. and the spinning speed was 900 m/min. The obtained wound yarn was drawn at 90° C. by 3° twice.

The single yarn fineness of the drawn yarn is 1.9 denier, and the strength is 2°3C.
It was I/d.

Example 2 Polyethylene terephthalate (PET) chips and PT
Fine powder of FE (average particle size approximately 0.3μ) is uniformly mixed using an extruder-type melt-kneading device so that the weight percentage of PET/PTFE is 80/20 to produce spinning chips. did. Using this kneaded polymer as a sheath component and PET as a core component, a core-sheath type $1 [(core/nitrification ratio: 85/15) was manufactured using a composite spinning machine and a core-sheath die. The conditions are spinning temperature: 290'C, spinning speed: 100
It is 0m/min. 4. The obtained wound yarn was heated to 90°C.
It was stretched twice.

The fineness of the drawn yarn was 1.7 denier and the strength was 3.6 g/d.

Example 3 Nylon 6 chips and fine PTFE powder (average particle size of about 0.3μ) were uniformly mixed using an extruder-type melt-kneading device so that the weight percentage of N6/PTFE was 80/20. The mixture was mixed to produce a spinning tip.

Using this kneaded polymer as a sheath component and nylon 6 as a core component, a core-sheath type fiber (core/nitrification ratio: 90/10) was produced using a composite spinning machine and a core-sheath die. The conditions are spinning temperature 2
The temperature was 70°C and the spinning speed was 1000 m/min. 19 The obtained wound yarn was stretched 3.5 times at 5g°C.

The single yarn fineness of the drawn yarn is 2.1 denier and the strength is 4°3CI.
/d.

Example 4 Each fiber of Examples 1 to 3 was analyzed according to the “Synthetic Fiber Handbook Test/Inspection Edition”
The friction properties were evaluated according to the Roder method described in (edited by the Japan Textile Society). The coefficient of friction determined by this method for all the fibers of Example 1.2 was 18% to 34% of that of commercially available polyester fiber yarn (2 denier product). Further, the coefficient of friction of the fiber of Example 3 was 21% of that of commercially available nylon thread (2 denier product).

Example 5 Each of the fibers of Examples 1 to 3 and the commercially available polyester fiber yarn and nylon yarn were subjected to tube knitting processing.

These fabrics were immersed in a contaminated bath having the following composition for 10 minutes, then taken out and air-dried. JIs-1104 these samples
Washing fastness test method shown in No. 5, washing fastness test method, using a round-o-meter, using an aqueous soap solution (0°5%) at 40°C for 30 minutes.
The sample was treated for a minute, then taken out, washed with water, and air-dried.

As a result, each of the fibers of Examples 1 to 3 had better stain resistance than the commercially available polyester fiber threads and nylon threads.

Contaminated bath composition carbon 0.190 sulfur para
0.75g hardened beef tallow 0
．． 25g Refined peanut oil 0.25C) Carbon tetrachloride 400q [Effects of the invention] The fibers of the present invention are particularly excellent in low friction properties and antifouling properties.

Furthermore, it has excellent melt resistance, heat resistance, ultraviolet stability, chemical resistance, and dust resistance, and also has a high degree of oil repellency and stain resistance, making it particularly effective against oil-based stains.

Taking advantage of the above characteristics, the fibers of the present invention can be used not only for general clothing such as dress shirts and outerwear, but also for various sports clothing, special clothing such as laboratory coats and work clothes, shoes, and bags. Footwear, personal belongings, grains, filters, etc.
It can be widely used in various industrial applications such as fishing nets, underwater robes, fishing lines, and fishing rods.

Claims (3)

[Claims] (1) A fiber in which one or more types of fluoropolymer particles are substantially uniformly dispersed and has a strength of 1.5 g/d or more. (2) Fibers selected from the polymer groups shown in [I] to [VI] below, in which at least one type of fluoropolymer particles are substantially uniformly dispersed, and whose strength is 1.5 g/d or more. . ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (R=CF_3, ORf) (Rf is a perfluoroalkyl group) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (R= F, Cl) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[III] (R=F, Cl) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[IV] (R=F, Cl) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[V] (R=F, Cl) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[VI] (3) A fiber having a core-sheath structure, in which one or more types of fluoropolymer particles are substantially uniformly dispersed in at least the sheath component, and the strength is 2.5 g/d or more. . (4) A fiber having a sea-island structure, in which one or more types of fluoropolymer particles are substantially uniformly dispersed in at least the sea component, and the strength is 2.5 g.
/d or more.