JP2018197403A - Water-repellent woven/knitted fabric - Google Patents

Abstract

Provided is a woven or knitted fabric excellent in water repellency or water repellency even when a water repellent composed of a fluorine compound containing a perfluoroalkyl group having 6 or less carbon atoms is used. A water-repellent woven or knitted fabric in which a water-repellent agent made of a fluorine compound containing a perfluoroalkyl group having 6 or less carbon atoms is present on the surface of a woven or knitted fabric containing polyester fibers as constituent fibers. Protrusions and grooves are alternately distributed on the surface of the single fiber of the polyester fiber, and are continuous in the fiber axis direction, and the number and size of the protrusions are in a specific range. JIS L 1092 (spray method) after 10 washings (HL10) in which the contact angle between the water-repellent woven and knitted fabric and water is 140 ° or more and the water droplet rolling angle is 10 ° or less and the JIS L 0217 103 method is used. ) Has a water repellency of 4 or higher. [Selection] Figure 1

Description

  The present invention relates to a water-repellent woven or knitted fabric that is excellent in water repellency while reducing the environmental load due to the fluorine-based water repellent.

  Polyester fibers are excellent in strength, dyeing fastness, and the like, and have high versatility in various processing, and thus are used in a wide range of applications such as clothing and industrial materials. Furthermore, polyester fiber is a very useful material in terms of various functionalities because the polymer blend, cross-sectional shape, or fineness can be easily changed at the spinning stage. Here, in the case where the polyester fiber is used for, for example, sports clothing or casual clothing, higher water repellency is required in addition to various functions.

  As an example of conventional water-repellent processing for polyester fibers, a technique of impregnating a fabric made of polyester fibers with a water-repellent agent and drying the fabric is known. Among water repellents, fluorine-based water repellents are excellent in initial water repellency. In many cases, the fluorine-based water repellent is mainly composed of a water repellent (perfluorooctanoic acid (C8) water repellent) made of a fluorine compound containing a perfluorofluoroalkyl group having 8 carbon atoms. In the C8 water repellent, perfluorooctanoic acid that adversely affects the environment or human body is by-produced. Therefore, as a global trend, a water repellent (perfluorohexanoic acid (C6)) water repellent made of a fluorine compound containing a perfluoroalkyl group having 6 or less carbon atoms is used instead of a C8 fluorine repellent. (See, for example, Patent Documents 1 and 2).

JP 2007-247093 A JP 2014-148775 A

  However, a fabric that has been water-repellent processed using a C6 fluorine-based water repellent does not have sufficient water repellency or water-repellent washing durability as compared to the case of using a C8 fluorine-based water repellent. Therefore, further improvement is required.

  The present inventors diligently studied to solve the above problems. As a result, by using a polyester fiber having a specific cross-sectional shape, even when a water repellent composed of a fluorine compound containing a perfluoroalkyl group having 6 or less carbon atoms is used, water repellency and water repellency are achieved. It was found that a woven or knitted fabric excellent in washing durability was obtained, and the present invention was completed.

That is, the gist of the present invention is the following (1) to (4).
(1) A water repellent woven or knitted fabric in which a water repellent composed of a fluorine compound containing a perfluoroalkyl group having 6 or less carbon atoms is present on the surface of a woven or knitted fabric containing polyester fibers as constituent fibers,
Protrusions and grooves are alternately distributed on the surface of the single fiber of the polyester fiber, and each is continuous in the fiber axis direction, the number and size of the protrusions satisfy the following formulas (I) to (III),
10 ≦ N ≦ 32 (I)
0.3 ≦ W ≦ 3.0 (II)
0.5 ≦ H ≦ 3.0 (III)
(Where N is the number of protrusions, W is the width of the protrusion (μm), and H is the height of the protrusion (μm))
JIS L 1092 (spray method) after 10 washings (HL10) in which the contact angle between the water-repellent woven and knitted fabric and water is 140 ° or more and the water droplet rolling angle is 10 ° or less and the JIS L 0217 103 method is used. The water-repellent knitted or knitted fabric is characterized by having a water repellency at 4) or higher.
(2) The water-repellent woven or knitted fabric according to (1), wherein the polyester fiber has fine pores on the surface of a single fiber.
(3) The number of the micropores is 10 or more in the region of 5 μm × 5 μm size on the surface of the single fiber, and the size of the micropores is 2.0 μm or less for the major axis and 0.5 μm for the minor axis. The water repellent woven or knitted fabric according to (2), wherein the depth is 0.1 to 0.4 μm.
(4) The water-repellent woven or knitted fabric according to any one of (1) to (3), wherein the polyester fiber is contained in 50% by mass or more in all constituent fibers.

  According to the present invention, since the polyester fiber having a specific cross-sectional shape is included as the constituent fiber, the contact area between the water droplet and the surface of the single fiber included in the woven or knitted fabric can be extremely reduced, and the carbon number is 6 or less. Even when a water repellent composed of a fluorine compound containing a perfluoroalkyl group is used, a woven or knitted fabric excellent in water repellency and water repellency and washing durability can be obtained. Furthermore, when micropores are present on the single fiber surface of the polyester fiber, the contact area between the water droplets and the woven or knitted fabric can be further reduced by the synergistic effect with the cross-sectional shape of the single fiber, and the water repellency is remarkable. An improved water-repellent woven or knitted fabric can be obtained.

It is a cross-sectional schematic diagram which shows one Embodiment of the unusual cross section of the single fiber of the polyester fiber which is a constituent fiber of the water-repellent knitted fabric of this invention. It is a partial expansion schematic diagram of the single fiber of a polyester fiber. It is the image which observed the cross-sectional shape of the polyester fiber which comprises the water-repellent woven fabric obtained in Example 1. FIG.

Hereinafter, the present invention will be described in detail.
The water-repellent woven or knitted fabric of the present invention is a water-repellent woven or knitted fabric in which a water-repellent agent composed of a fluorine compound containing a perfluoroalkyl group having 6 or less carbon atoms is present on the surface of a woven or knitted fabric containing polyester fibers as constituent fibers. is there. The polyester fiber has a specific cross-sectional shape, and may be referred to as “water-repellent polyester fiber” in the present specification.

  Of all the constituent fibers of the woven or knitted fabric, the polyester fiber (water repellent polyester fiber) is preferably contained in a proportion of 50% by mass or more, more preferably in a proportion of 65% by mass, and a proportion of 80% by mass or more. More preferably it is included.

  The polyester that is a raw material of the polyester fiber is, for example, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, or polylactic acid. Such polyester is preferably made of a polyester resin in which 80 mol% or more of all structural units is ethylene terephthalate.

  The single fiber of the polyester fiber is a fiber having an irregular cross-sectional shape. Specifically, as shown in FIG. 1, the cross-sectional shape of the polyester fiber 1 is such that the protrusions 2 and the grooves 3 are arranged alternately and uniformly radially on the surface, and the fiber is formed on the surface of the single fiber. A plurality of protrusions (20 in FIG. 1) that are continuous in the axial direction are provided. Between the adjacent protrusions, there are the same number of grooves as the protrusions. Since the polyester fiber having such a configuration is used, in the water-repellent woven or knitted fabric of the present invention, the contact area between the water droplet and the fiber surface can be extremely reduced. As a result, a target contact angle and a low water droplet rolling angle can be achieved, and a water-repellent knitted or knitted fabric that is remarkably excellent in water repellency and water-repellent washing durability can be obtained.

  The cross-sectional shapes of the protrusion and the groove are not particularly limited, but are, for example, rectangular or substantially trapezoidal.

  The number (N) of the protrusions is 10 to 32 on the circumference of the single fiber, and more preferably 16 to 25. By setting the number of protrusions in the above range, the contact area between the water droplet and the fiber surface can be effectively reduced, and as a result, the target contact angle and a low water droplet rolling angle can be achieved. . If the number of protrusions is 10 or more, the grooves are sufficiently present, the contact area between water and the fiber surface can be sufficiently reduced, and excellent water repellency can be imparted to the woven or knitted fabric. . On the other hand, when the number of protrusions is 32 or less, the protrusions are difficult to break, and when the water-repellent woven or knitted fabric of the present invention is used for clothing, for example, it suppresses fibrillation of the polyester fiber during wearing. be able to. As a result, deterioration in quality can be suppressed, and the width between adjacent protrusions does not become excessively small with respect to water droplets, resulting in excellent water repellency.

  The width W and height H of the protrusion will be described below. FIG. 2 is a partially enlarged cross-sectional view of a single fiber of a polyester fiber (an irregular cross-section fiber). In FIG. 2, a straight line connecting the deepest portions of adjacent groove portions is defined as a line segment L, a line segment connecting the line segment L and the topmost portion of the projection portion, and a line segment perpendicular to the line segment L is defined as the height H of the projection portion. . Also, a line segment that intersects the line segment H at the midpoint of the line segment H perpendicularly and connects both side surfaces of a single protrusion is defined as a width W of the protrusion.

In the polyester fiber, the width W (μm) and the height H (μm) of the protrusions satisfy the following formulas (II) and (III).
0.3 ≦ W ≦ 3.0 (II)
0.5 ≦ H ≦ 3.0 (III)

  That is, the width W of the protrusion is in the range of 0.3 to 3.0 μm, preferably 0.4 to 1.8 μm, and more preferably 0.5 to 1.3 μm. When the width W of the protrusion is 0.3 μm or more, fiber fibrillation at the time of wearing or the like is suppressed, and the quality is preferable, and the width between adjacent protrusions is not excessively small with respect to water droplets. Excellent water repellency. Moreover, since the width | variety of a projection part does not become large too much as it is 3.0 micrometers or less, since a groove | channel can fully be ensured, a contact area with a water droplet can be reduced and it will be excellent in water repellency.

  The height H of the protrusion is 0.5 to 3.0 μm, preferably 0.5 to 2.0 μm, and more preferably 0.7 to 1.8 μm. When the height of the protrusion is 0.5 μm or more, the depth of the groove is not too shallow, the surface tension of water is increased, and the water repellency is excellent. Moreover, since a protrusion part does not become large too much as it is 3.0 micrometers or less and fibrillation can be suppressed, the fall of water repellency can be suppressed.

  In the water-repellent woven or knitted fabric of the present invention, the polyester fiber which is a constituent fiber has a specific irregular cross-sectional shape as described above. Therefore, even if a water-repellent agent made of a fluorine-based compound having a perfluoroalkyl group having 6 or less carbon atoms is used for the purpose of reducing environmental load, the water-repellent and water-repellent durability is excellent. . In the present invention, it is preferable to impart water repellency by adhering a water repellant to the surface of the woven or knitted fabric, instead of including a component imparting water repellency inside the water repellent and the polyester fiber. By doing so, troubles such as defective dyeing do not occur, and the workability is improved.

  As the water repellent, a C6 water repellent is used because of concerns such as environmental impact. Specifically, the C6 water repellent is a fluorine water repellent composed of a fluorine compound having a perfluoroalkyl group in the chemical structure, and the perfluoroalkyl group has 6 or less carbon atoms. Say. A perfluoroalkyl group refers to a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. The perfluoroalkyl group may have a straight chain structure or a branched chain structure. When the C6 water repellent is used as the water repellent, it is inferior in water repellency compared to the case of using other fluorine water repellents. By using it, it can be set as the woven / knitted fabric excellent in water repellency.

  As the C6 water repellent, a commercially available product can be suitably used, and examples thereof include “NK guard” series manufactured by Nikka Chemical Co., Ltd., “Asahi guard” series manufactured by Asahi Glass Co., Ltd., and the like. The adhesion concentration of the C6 water repellent is preferably 0.2% owf to 5% owf, more preferably 0.5% owf to 3% owf. If it is 0.2% owf or more, the water repellency is better, and if it is 5% owf or less, it is possible to suppress a decrease in fastness. In the present invention, by making the cross-sectional shape of the fiber specific, a woven or knitted fabric having excellent water repellency and water repellency durability even when the amount of water repellent attached is small. Can do.

  As the water repellent, a copolymer obtained by polymerizing a polymer containing a perfluoroalkyl group as described above and another polymerizable monomer capable of being polymerized by a known polymerization method can be used. Examples of other polymerizable monomers include acrylic acid, methacrylic acid, styrene, and vinyl chloride. Moreover, you may mix suitably an acrylic compound, a vinyl acetate type compound, a melamine type compound, an isocyanate type compound, etc. as needed.

  The polyester fiber preferably has fine pores on the surface of the single fiber. By adopting such a configuration, the synergistic effect of the above-mentioned atypical cross-sectional shape and micropores can further reduce the contact area between water droplets and fibers, and can sufficiently secure an air layer on the fiber surface. An effect that remarkably excellent water repellency (durability of water repellency) is exhibited is obtained. The method of creating the micropores may be a method of generating fine particles at the time of polymerization and dropping them later, or a method of containing particles inactive with respect to polyester (for example, silica fine particles) and dropping them later. It is not limited.

  These micropores are preferably present in a number of 10 or more, more preferably in a number of 20 or more, and in a number of 30 or more in a region of 5 μm × 5 μm size on the surface of a single fiber. More preferably. When there are 10 or more micropores in a 5 μm × 5 μm size region on the surface of a single fiber, the number of micropores is sufficient, so that the contact area between the fibers and water droplets can be further reduced, and the water repellency can be reduced. It can be improved further. The upper limit of the number of fine holes is not particularly limited, but is, for example, about 100, preferably 70 or less, and more preferably 50 or less.

  The length of the long axis of the micropore is preferably 2.0 μm or less, and the length of the short axis is preferably 0.5 μm or less. When the major axis of the micropore is 2.0 μm or less and the minor axis is 0.5 μm or less, water droplets are less likely to enter the groove, and the water repellency is further improved.

  Although the depth of a micropore is not specifically limited, It is preferable that it is 100-400 nm, It is more preferable that it is 150-350 nm, 200-300 nm is further more preferable. When the depth of the fine holes is within the above range, sufficient fine holes can be present at a high density. Further, when the depth of the micropores is 100 nm or more, a sufficient air layer is obtained between the water droplets and the water repellency is further improved. Further, when the depth of the micropores is 400 nm or less, a decrease in fiber strength and fibrillation can be suppressed. In addition, the depth of a micropore is the value measured in the location where the distance from the single fiber surface is the largest.

  The fineness of the polyester fiber is preferably in the range of 0.1 to 10.0 dtex, more preferably in the range of 0.3 to 5.0 dtex, and still more preferably in the range of 0.3 to 3.0 dtex. . When the single yarn fineness is 0.1 dtex or more, the width W of the protrusion is easily 0.3 μm or more, and when it is 10.0 dtex or less, the texture becomes better.

  The total fineness of the polyester fiber is preferably 20 to 300 dtex, and more preferably 25 to 200 dtex. If the total fineness is 20 dtex or more, the strength is more excellent. On the other hand, if it is 300 dtex or less, the texture becomes better.

  In the water-repellent woven or knitted fabric of the present invention, the contact angle with water droplets is 140 ° or more, preferably 145 ° or more, and more preferably 150 ° or more. The upper limit value is not particularly limited, but is about 160 °, for example. The contact angle is an angle formed by the surface of a horizontally stretched fabric (woven or knitted fabric) and a water drop dripped on the surface of the fabric. The larger the contact angle, the better the water repellency. . In the present invention, the contact angle is measured by a θ / 2 method using a single fiber contact angle meter (CA-S Micro 2 type, manufactured by Kyowa Interface Science Co., Ltd.), dropping 4 μL of water droplets on the surface of the fabric. . When the contact angle is less than 140 °, sufficient water droplet rolling property is not achieved, and when rainwater or the like adheres, water droplets are likely to remain on the woven or knitted fabric, resulting in poor water repellency.

  In the water-repellent woven or knitted fabric of the present invention, the water droplet rolling angle is 10 ° or less, preferably 7 ° or less. The water droplet rolling angle is an index for evaluating high water repellency such as the lotus effect (the lotus leaf effect). In this specification, the water droplet rolling angle is measured as follows. That is, a sample (woven or knitted fabric) is mounted on a horizontal plate, and the sample is leveled. 40 μL of water is gently dropped onto this sample, and then the horizontal plate is gently tilted, and the angle at which the water droplet begins to roll is defined as the water droplet rolling angle. This angle indicates the point where the coefficient of static friction is maximum. In the present invention, when the water droplet rolling angle exceeds 10 °, it cannot be said that a sufficiently excellent water repellency is achieved, and water droplets easily remain on the woven or knitted fabric.

  Further, in the water-repellent woven or knitted fabric of the present invention, the water repellency (grade) is 4 or more in JIS L 1092 (spray method) after 10 washings (HL10) according to the JIS L 0217 103 method. In general, the water repellency of a water repellent material decreases as it is washed. In particular, when a C6 water repellent is used as the water repellent, it is compared with the case of using other fluorine water repellents. However, the water-repellent washing durability is inferior, but in the present invention, the specific cross-sectional shape of the fiber can compensate for the decrease in water repellency and maintain excellent water repellency even after washing. I can do it.

  In the present invention, when the woven or knitted fabric is a woven fabric, the woven structure is not particularly limited. Or, there is a satin structure. When the woven or knitted fabric is a knitted fabric, the knitted structure is not particularly limited, and examples thereof include a knitted structure such as a tengu, kanoko, or smooth obtained by a circular knitting machine or a warp knitting machine.

  Moreover, the cover factor, knitting density, etc. of the woven or knitted fabric are not particularly limited, and can be appropriately set in a range not impairing the effects of the present invention, depending on the application.

An example of the method for producing the water-repellent woven or knitted fabric of the present invention will be described below.
A latent water-repellent core-sheath composite polyester fiber is prepared in which a hardly soluble polyester resin composition is disposed in the core and an easily soluble polyester resin is disposed in the sheath. The cross-sectional shape of the core part is substantially the same as the cross-sectional shape of the above-described polyester fiber contained in the water-repellent woven or knitted fabric of the present invention. Then, using this latent water-repellent core-sheath composite polyester fiber, a woven or knitted fabric is obtained, and this woven or knitted fabric is subjected to an alkali weight loss treatment, and then processed with the C6 water repellent as described above, to thereby achieve the water repellency of the present invention. A woven or knitted fabric can be obtained.

  The hardly soluble polyester resin composition comprises a polyester resin that is difficult to elute in an alkali compound (basic compound) solvent (hereinafter referred to as a hardly soluble polyester resin) and particles that are inert to the polyester, or a phosphorus compound and a metal compound. It is preferable to contain derived particles. The easily soluble polyester resin has higher solubility in the solvent of the alkali compound than the hardly soluble polyester resin.

  The easily soluble polyester resin preferably has a dissolution rate of 5 times or more faster in the solvent of the alkali compound than the hardly soluble polyester resin. Therefore, the easily soluble polyester resin is an aromatic dicarboxylic acid component in which 1 to 3 mol% of the dicarboxylic acid component has a sulfonate group, and contains 5 to 15 mass% of a polyalkylene glycol having a number average molecular weight of 1000 to 10,000. It is preferable to do.

  Examples of the aromatic dicarboxylic acid component having a sulfonate group include 5-sodium sulfoisophthalic acid, 5-sodium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 5-potassium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 5- Examples include phosphonium sulfoisophthalic acid. When the aromatic dicarboxylic acid component having a sulfonate group is 1 mol% or more of the dicarboxylic acid component, the dissolution rate in alkali is sufficiently high. When it is 3 mol% or less, the yarn-forming property is better even at high speed, and troubles such as yarn breakage can be suppressed.

  The polyalkylene glycol preferably has a number average molecular weight of 1000 to 10,000. When the number average molecular weight is 1000 or more, the glass transition point of the readily soluble polyester resin does not decrease, and it becomes difficult for fusion to occur in the spinning process. When it is 10,000 or less, the compatibility becomes good and it becomes easy to contain it uniformly.

  When the polyalkylene glycol content is 5% by mass or more, the dissolution rate in alkali is sufficiently high. When the content is 15% by mass or less, the spinning speed is kept sufficiently high while the spinning property is improved, and troubles such as yarn breakage can be suppressed in the spinning process.

  Although it mentions later in detail as a poorly soluble polyester resin, For example, what consists of a terephthalic-acid component and an ethylene glycol component and 80 mol% or more of all the structural units is ethylene terephthalate etc. are mentioned.

Although the method of containing particle | grains in a hardly soluble polyester resin composition is not specifically limited, For example, the following methods (a) or (b) are mentioned.
(A) A method of adding particles to a hardly soluble polyester resin.
(B) A method of generating particles derived from a phosphorus compound and a metal compound during polymerization of a hardly soluble polyester resin.

The method (A) will be described below.
The particles in the method (a) may be either inorganic particles or organic particles as long as they are inert to the polyester, but inorganic particles are preferred from the viewpoint of handleability. Examples of the inorganic particles include silicon oxide, titanium oxide, alumina, barium sulfate, carbon black, and modified products thereof. The shape of the particles, the particle size and the like are not particularly limited, and it is preferable that the above-described size and number of fine pores are formed on the surface of the single fiber after the alkali dropping treatment as described later. Moreover, the hardly soluble polyester resin in the method (a) is obtained by, for example, esterifying a dicarboxylic acid component and a diol component.

The method (b) will be described below.
In the method (b), for example, a dicarboxylic acid component and a diol component are esterified to form a polyester oligomer, a phosphorus compound and a metal compound are added to the polyester oligomer, and then a polycondensation reaction is performed. By carrying out, particles are generated in the polymer to obtain a hardly soluble resin composition containing the hardly soluble polyester resin and the generated particles. Preferable combinations of a phosphorus compound and a metal compound include a phosphorus compound and an alkaline earth metal compound, or a phosphorus compound, an alkali metal compound, and an alkaline earth metal compound. In the present specification, an alkali metal compound and an alkaline earth metal compound may be simply referred to as “metal compound”.

  Although it does not specifically limit as dicarboxylic acid, For example, a terephthalic acid can mainly be used. As long as the effects of the present invention are not impaired, other components may be copolymerized depending on the purpose.

  Although it does not specifically limit as a diol component, For example, ethylene glycol can mainly be used. As long as the effects of the present invention are not impaired, other components may be copolymerized depending on the purpose.

  A polyester oligomer is obtained by esterifying a dicarboxylic acid component (for example, dicarboxylic acid containing terephthalic acid as a main component) and a diol component (for example, diol containing ethylene glycol as a main component). Here, when the dicarboxylic acid component and the diol component are terephthalic acid and ethylene glycol, respectively, the polyester oligomer includes bis (2-hydroxyethyl) terephthalate, and further includes 2 repeating units of ethylene terephthalate in one molecule. In addition, it represents a compound whose intrinsic viscosity, molecular weight, and degree of polymerization have not increased so much that it can be called polyethylene terephthalate, and the terminal is a carboxyl group or a hydroxyethyl group. Until such a polyester oligomer is formed, for example, the esterification reaction can be performed at a temperature of 250 ° C. for 3 to 8 hours. In order to detect the reaction rate of the esterification reaction, the amount of water produced can be measured.

  The polyester oligomer may be copolymerized with other components within a range that achieves the object of the present invention.

  A metal compound and a phosphorus compound are added to the polyester oligomer, and then a polycondensation reaction is performed to obtain a hardly soluble polyester resin composition containing a polyester resin that is hardly soluble in alkali. Here, together with the polycondensation reaction, a reaction between the phosphorus compound and the metal compound occurs, and the above-described particles that are insoluble in the polyester resin are generated. In the present invention, these particles are referred to as “generated particles”.

  Regarding the order of addition of the phosphorus compound and the metal compound, the phosphorus compound may be added first, the phosphorus compound may be added later, or the phosphorus compound and the metal compound may be mixed and added simultaneously.

The addition amount of the metal compound is preferably ¹⁰ × 10 ^-4 ~100 × 10 -4 mol of the acid component 1 mol of constituting the polyester, more preferably 30 × ^{10 -4} ~80 × ¹⁰ -4 Is a mole. When the content is 10 × 10 ⁻⁴ mol or more, it is possible to form generated particles having a size sufficient to improve the water repellency of the polyester fiber, and to improve the water repellency on the surface of the polyester fiber. The above-mentioned number of micropores necessary for the production can be expressed. Since the generation of coarse particles can be suppressed when the amount is 100 × 10 ⁻⁴ mol or less, clogging of the filter for filtering the melted polyester resin composition during spinning does not occur, and the stability of the polyester fiber spinning process Can be kept good.

The addition amount of the phosphorus compound is preferably ¹⁰ × 10 ^-4 ~100 × 10 -4 mol of the acid component 1 mol of constituting the polyester, more preferably 20 × ^{10 -4} ~90 × ¹⁰ -4 Is a mole. When the content is 10 × 10 ⁻⁴ mol or more, it is possible to form generated particles having a size sufficient to improve the water repellency of the polyester fiber, and to improve the water repellency on the surface of the polyester fiber. The above-mentioned number of micropores necessary for the production can be expressed. When the amount is 100 × 10 ⁻⁴ mol or less, generation of coarse generated particles can be suppressed, so that clogging of the filter for filtering the melted polyester resin composition during spinning does not occur, and the polyester fiber spinning process Stability can be kept good. The molar ratio of the metal compound to the phosphorus compound is preferably (metal compound) / (phosphorus compound) = 0.5 to 1.5 in order to be excellent in yarn production stability and latent water repellency.

  Examples of the phosphorus compound include phosphoric acids, phosphonic acids, and phosphinic acids.

  Examples of the alkali metal compound as a preferable metal compound include an alkali metal salt of carboxylic acid.

  Examples of the alkaline earth metal compound as a preferable metal compound include an alkaline earth metal salt of a carboxylic acid.

  Further, a particularly preferred combination of the phosphorus compound and the metal compound is that the average particle diameter of the generated particles is controlled within the above range, and from the viewpoint of obtaining polyester fibers that are remarkably excellent in water repellency, a phosphate ester and a metal salt of acetic acid A combination is preferable, and a combination of triethyl phosphate (triethyl phosphate) and magnesium acetate is more preferable. In addition to these, it is most preferable to use lithium acetate in combination. In addition, when lithium acetate is used alone as the metal compound, the generated particles tend to be too coarse.

  Subsequently, a polycondensation catalyst (for example, ethylene glycol solution) is added and a polycondensation reaction is performed to obtain a polyester resin composition (a hardly soluble polyester resin composition). If necessary, an additive such as a copolymerization monomer or a coloring inhibitor may be added to the polycondensation reaction system as an ethylene glycol solution or a dispersion. In this case, the polycondensation reaction is started by distilling off ethylene glycol (removing ethylene glycol under reduced pressure), and the reaction is continued while distilling off. it can. Here, the production | generation of production | generation particle | grains is started after a polycondensation catalyst is added. And the solubility of a product falls as a solution is distilled off, and this product precipitates as a particle.

  The intrinsic viscosity (intrinsic viscosity) of the hardly soluble polyester resin composition is preferably 0.5 to 1.5 dL / g. When the intrinsic viscosity is within this range, the physical properties of the polyester fiber obtained by spinning the resin composition do not deteriorate, and the polyester resin composition or the polyester fiber can be easily produced.

  As described above, the generated particles are derived from the phosphorus compound and the alkaline earth metal compound, or are derived from the phosphorus compound, the alkali metal compound, and the alkaline earth metal compound. The produced particles are different from the known inert fine particles such as silica fine particles as described above, and the polyester resin composition production stage (synthetic reaction) is individually performed without previously reacting the phosphorus compound and the metal compound. The particles are formed by the reaction between the phosphorus compound and the metal compound.

  The average particle diameter of the generated particles is not particularly limited, but is preferably 0.05 to 0.5 μm, more preferably 0.08 to 0.4 μm.

  Next, the hardly soluble polyester resin composition is placed in the core, and the composite fiber is spun so that the easily soluble polyester resin is placed in the sheath, and the shape of the core in the cross section perpendicular to the fiber longitudinal direction is shown in FIG. Thus, a latent water-repellent core-sheath composite polyester fiber having an irregular cross-sectional shape having protrusions and grooves is obtained. Specifically, a known spinning method (for example, melt spinning method) is adopted, a preferable composite spinning nozzle is selected, the hardly soluble polyester resin composition is arranged in the core portion, and the easily soluble polyester resin is arranged in the sheath portion. By carrying out composite spinning, a latent water-repellent core-sheath composite polyester fiber as a multifilament yarn is obtained.

  In the latent water-repellent core-sheath composite polyester fiber, the shape of the core portion is substantially the same as the cross-sectional shape of the water-repellent polyester fiber described above. This is because the sheath part of the latent water-repellent core-sheath composite polyester fiber is eluted with an alkali compound (basic compound) to express uneven parts, and preferably the core surface is further eluted by further elution with alkali. In this case, the generated particles or the inert fine particles are dropped off to form the water-repellent polyester fibers contained in the woven or knitted fabric of the present invention.

  This may be stretched after being wound as an unstretched yarn by a known method after composite spinning, or may be stretched without being wound once after discharge. Moreover, after winding up at a speed | rate of 3000-9000m / min, you may use for a yarn process or a weaving knitting as it is, without extending | stretching separately.

  The spinning conditions are not particularly limited. For example, an undrawn yarn once wound at a spinning temperature of 270 to 300 ° C., a take-up speed of 1000 to 2000 m / min, and a drawing temperature of 70 to 100 ° C. Examples thereof include an FDY method in which the temperature is 120 to 190 ° C., the drawing speed is 200 to 1000 m / min, and the draw ratio is drawn at about 0.65 to 0.85 times the maximum draw ratio of the undrawn yarn. The maximum draw ratio refers to the ratio at which the undrawn yarn is drawn until it is cut under conditions of a drawing temperature of 80 ° C., a heat setting temperature of 145 ° C., and a drawing speed of 600 m / min.

  As the spinning and stretching methods, for example, POY method (method of winding as a semi-unstretched yarn by high-speed spinning of 2000 m / min or more), HOY method (super-high-speed spinning of 5000 m / min or more, highly oriented unstretched) A method of winding as a yarn) or a spin draw method (a method of spinning at 200 m / min or more and stretching continuously without winding).

  The mass ratio between the readily soluble polyester resin and the hardly soluble polyester resin composition is preferably in the range of (easy soluble polyester resin) :( slightly soluble polyester resin composition) = 5: 95 to 40:60, particularly 10:90 to 30:70 is preferred. When the easily soluble polyester resin is 5% by mass or more, it is easy to obtain a modified cross-sectional shape having protrusions and grooves in the polyester fiber, and when it is 40% by mass or less, the strength is sufficient.

  Next, the obtained latent water-repellent core-sheath composite polyester fiber is woven or knitted to obtain a woven or knitted fabric. The method for forming the knitted or knitted fabric may be performed according to a conventional method, and is not particularly limited. For example, in the case of a woven fabric, an air jet loom, a rapier loom, a fly shuttle loom, a water jet loom, or the like can be used for weaving with a woven structure such as a plain weave structure, a twill structure, or a satin structure. In addition, if it is a knitted fabric, it can be knitted with a knitting structure such as a tengu, kanoko or smooth using a circular knitting machine or a warp knitting machine.

  An alkali weight reduction process (elution) is performed on the woven or knitted fabric using an alkali compound. Before being subjected to the alkali weight loss treatment, if necessary, desizing, scouring, and presetting may be performed according to a conventional method.

  The sheath portion in the latent water-repellent core-sheath composite polyester fiber is eluted and removed by the alkali weight reduction treatment, and the above-mentioned irregular cross-section fiber can be obtained. When elution is further advanced to drop particles contained in the poorly soluble polyester resin in the core part, the fine pores as described above can be formed. In the present invention, the term “latent water repellency” means that the latent water-repellent core-sheath composite polyester fiber as described above is subjected to an alkali weight loss treatment, and the sheath part is eluted to express an uneven sectional shape, and more preferably The water repellency expressed by dropping the core particles and forming fine pores on the surface of the single fiber.

  The alkali weight loss treatment may be performed according to a conventional method, for example, using an aqueous solution of an alkali compound. Examples of the alkali compound used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate and the like. Of these, sodium hydroxide and potassium hydroxide are particularly preferable.

  The concentration of the aqueous solution of the alkali compound varies depending on the type of alkali compound or the treatment conditions, but is usually preferably in the range of 0.1 to 6% by mass, more preferably 1 to 6% by mass, particularly in the range of 2 to 5% by mass. Is preferred. The alkali weight loss treatment temperature is preferably in the range of 40 to 120 ° C, particularly preferably in the range of 60 to 100 ° C. The treatment time is preferably in the range of 1 minute to 4 hours.

  The alkali weight loss rate is within a range in which the cross-sectional shape of the polyester fiber can be set as described above. For example, the mass ratio of the easily soluble polyester resin and the hardly soluble polyester resin, the amount of particles in the method (A), the method It is determined by the addition amount of the metal compound and phosphorus compound in (b).

  Next, the water-repellent finish is applied to the woven or knitted fabric after the alkali weight reduction. The water repellent used in the water repellent process is a C6 water repellent as described above. The method of water repellent finish is not particularly limited, and can be performed using a conventionally known method. For example, a method of impregnating and drying by padding using a bath containing a water repellent can be used.

  The water-repellent woven or knitted fabric of the present invention is suitably used in fields where water repellency is desired, such as sportswear use, inner use, men's clothing use, and women's clothing use.

  Hereinafter, the present invention will be described in detail according to examples. The present invention is not limited to this example. The measurement method or evaluation method in the examples of the present invention is as follows.

(1) Number and size of protrusions (width and height)
One water-repellent polyester fiber was collected from the obtained woven or knitted fabric and cut perpendicularly to the fiber axis direction (longitudinal direction). This cross section was photographed with a scanning electron microscope (SEM) (magnification: 10,000 times) and counted or measured on the photograph.

(2) Number of micropores Ten monofilaments of dark-dyeing polyester fibers were randomly collected from the obtained woven or knitted fabric. The surface of this single fiber was photographed at a magnification of 10,000 using a scanning electron microscope (SEM). An inspection area of 5 μm by 5 μm was set at random in the photographed photo, the number of micropores present in this area was counted, and the average value of 10 was calculated.

(3) Size of micropores In the photograph taken in (2) above, 30 micropores present on the fiber surface were randomly selected. The length in the longitudinal direction of the fiber was taken as the major axis, and the length in the direction perpendicular to the longitudinal direction was taken as the minor axis, and the average value of each was determined.

(4) Depth of fine hole One single fiber of deep dyeable polyester fiber was collected from the woven or knitted fabric and cut perpendicularly to the fiber axis direction (longitudinal direction). This cut surface was photographed at a magnification of 10,000 using a scanning electron microscope (SEM). In this photograph, 30 micropores present on the fiber surface were selected at random, the depth of the micropores was measured, and the average value was obtained. Note that the depth of the micropores was measured at the point where the distance from the single fiber surface was the largest.

(5) Contact angle Using a single fiber contact angle meter (CA-S Micro 2 type, manufactured by Kyowa Interface Science Co., Ltd.), 4 μL of water droplets were dropped on the surface of the fabric and measured by the θ / 2 method. The larger the contact angle, the better the water repellency.

(6) Measurement of rolling angle A sample (woven or knitted fabric) was mounted on a horizontal plate, and the sample was leveled. 40 μL of water was gently dropped onto this sample, and then the horizontal plate was gently tilted, and the angle at which the water droplet began to roll was defined as the water droplet rolling angle.

(7) Water repellency Measured according to the spray method described in JIS L 1092.

(8) Durability of water-repellent washing According to the method 103 described in JIS L 0217, after washing was performed 10 times (HL10), the water repellency was measured according to the spray method described above.

Example 1
An easily soluble polyester resin (polyethylene terephthalate copolymerized with 2.0% by mass of 5-sodium sulfoisophthalic acid and 6.0% by mass of polyethylene glycol) is placed on the sheath, and a hardly soluble polyester resin (polyethylene terephthalate) is placed on the core ( The core-sheath composite polyester fiber (50 dtex / 24f) was obtained. The mass ratio of the core part to the sheath part was core part: sheath part = 80: 20. Using this, a tubular knitted fabric (number of gauges: 28 gauges) was prepared. This tubular knitted fabric is scoured with a surfactant (trade name “Sanmor FL” manufactured by Nikka Chemical Co., Ltd.), and then in a 10 g / l sodium hydroxide aqueous solution at 100 ° C. for 30 minutes, a bath ratio of 1: The weight reduction process was performed at 30, and only the easily soluble polyester resin in the sheath was eluted.

  This stage was set to 0% weight loss rate, and further treated with a sodium hydroxide aqueous solution with a bath ratio of 1:30 and a concentration of 40 g / l at 100 ° C. for 55 minutes to reduce the weight by 16.2% to the core. Then, it was stained by the following method. The dye (manufactured by Dystar, trade name “Dianix Black HG-FS conc.”, Disperse dye) was adjusted to 7.5% оwf and treated at 135 ° C. for 30 minutes at a bath ratio of 1:40. Subsequently, it was reduced and washed at 80 ° C. for 20 minutes with an aqueous solution containing 2 g / l of sodium hydroxide, 2 g / l of hydrosulfite and 1 g / l of Sunmol FL (manufactured by Nikka Chemical Co., Ltd.) at a bath ratio of 1:40.

  Next, a water repellent treatment was performed under the following conditions. C6 water repellent (trade name “NK Guard S-09” manufactured by Nikka Chemical Co., Ltd.) is used as the water repellent, padded at a concentration of 4% оwf, dried at 120 ° C. for 2 minutes, Heat treatment was performed at 160 ° C. for 1 minute to obtain a water-repellent woven or knitted fabric of Example 1, and various evaluations were performed. In addition, FIG. 3 shows the image which observed the cross-sectional shape of the polyester fiber which comprises the water-repellent knitted fabric of Example 1 with the scanning electron microscope (SEM) (magnification 1500 times).

(Example 2)
The following were used as the hardly soluble polyester resin of the core. That is, relative to the acid component 1 mol of constituting the polyester, the phosphorus compound and (triethyl phosphate) 84 × ^{10 -4} mol, magnesium acetate 35 × ^{10 -4} mol and a lithium acetate 35 × ^{10 -4} mol, polyester It added to the oligomer and further polycondensation reaction was performed to use a hardly soluble polyester resin containing the produced particles. Otherwise, spinning was performed in the same manner as in Example 1 to create a tubular knitted fabric. This tubular knitted fabric was subjected to scouring, alkali weight loss, dyeing and reduction washing in the same manner as in Example 1. However, the alkali weight reduction conditions were the same as in Example 1, after elution of only the sheath component (weight loss rate at this stage: 0%), and then in a sodium hydroxide aqueous solution with a concentration of 40 g / l at 100 ° C. for 35 minutes. It processed by ratio 1:30, and also the weight reduction of 20.1% was performed with respect to the core part.

Example 3
In Example 1, only the sheath part was eluted, and thereafter, further reduction was not performed (weight reduction rate of the core part was 0%). The treatment was performed in the same manner as in Example 1, and the contact angle and the rolling angle were measured. It was.

(Comparative Example 1)
Spinning was performed in the same manner as in Example 1 except that a multifilament having a round cross-section made of only the poorly soluble polyester resin of Example 1 was used, thereby producing a 50 ktex / 24f tubular knitted fabric. This tubular knitted fabric was subjected to scouring, alkali weight loss, dyeing and reduction washing in the same manner as in Example 1, and the contact angle and rolling angle were measured. However, the alkali weight reduction conditions were the same as in Example 1, after elution of the sheath component (weight loss rate at 0% at this stage), and then at a bath ratio of 100 ° C. for 90 minutes in a 40 g / l sodium hydroxide aqueous solution. Treatment at 1:30 and a further 18.4% weight loss.

(Comparative Example 2)
A cylindrical knitted fabric was prepared by spinning in the same manner as in Example 2 except that the multifilament having a round cross section formed only of the poorly soluble polyester resin used in Example 2 was used. This tubular knitted fabric was subjected to scouring, alkali weight loss, dyeing and reduction washing in the same manner as in Example 1. However, the alkali weight reduction conditions were as follows: the sheath component was eluted in the same manner as in Example 2 (the weight loss rate at this stage was 0%), and then the bath ratio was 100 ° C. for 50 minutes in a 40 g / l sodium hydroxide aqueous solution. Treatment at 1:30 and a further 17.8% weight loss.

(Comparative Example 3)
Spinning was performed in the same manner as in Example 1 except that the number of protrusions in the cross section of the hardly soluble polyester resin in the core was changed to 8 to create a tubular knitted fabric. This tubular knitted fabric was subjected to scouring, alkali weight loss, dyeing and reduction washing in the same manner as in Example 1. However, the alkali weight reduction conditions were the same as in Example 1, after elution of the sheath component (weight loss rate at this stage: 0%), then in a sodium hydroxide aqueous solution with a concentration of 40 g / l, 100 ° C. × 60 minutes, bath ratio The treatment was carried out at 1:30 and the weight was further reduced by 18.1%.

Table 1 summarizes the evaluation of the water-repellent woven or knitted fabric of the present invention obtained in Examples 1 to 3 and the water-repellent woven or knitted fabric obtained in Comparative Examples 1 to 3.

  In Examples 1 to 3, since the polyester fiber which is a constituent fiber has a specific atypical cross-sectional shape, it was excellent in water repellency and water repellency durability. In particular, in Example 1, since the cross-sectional shape (height and width of the protrusions) of the polyester fiber was more preferable, compared to Example 3, the water repellency was even better. Further, in Example 2, since the fiber surface had micropores, the water repellency was remarkably excellent.

  In Comparative Examples 1 and 2, since the polyester fiber as a constituent fiber had a round cross-sectional shape, it was inferior in water repellency or water repellency durability. In Comparative Example 3, the polyester fiber, which is a constituent fiber, had a cross-sectional shape with an excessively small number of protrusions, so that the water repellency was inferior.

1 Polyester fiber 2 Protrusion 3 Groove

Claims (4)

A water-repellent woven or knitted fabric in which a water repellent composed of a fluorine compound containing a perfluoroalkyl group having 6 or less carbon atoms is present on the surface of a woven or knitted fabric containing polyester fibers as constituent fibers,
Protrusions and grooves are alternately distributed on the surface of the single fiber of the polyester fiber, and each is continuous in the fiber axis direction, the number and size of the protrusions satisfy the following formulas (I) to (III),
10 ≦ N ≦ 32 (I)
0.3 ≦ W ≦ 3.0 (II)
0.5 ≦ H ≦ 3.0 (III)
(Where N is the number of protrusions, W is the width of the protrusion (μm), and H is the height of the protrusion (μm))
JIS L 1092 (spray method) after 10 washings (HL10) in which the contact angle between the water-repellent woven and knitted fabric and water is 140 ° or more and the water droplet rolling angle is 10 ° or less and the JIS L 0217 103 method is used. The water-repellent knitted or knitted fabric is characterized by having a water repellency at 4) or higher.   The water-repellent woven or knitted fabric according to claim 1, wherein the polyester fiber has fine pores on a surface of a single fiber. The number of the fine holes is 10 or more in a region of 5 μm × 5 μm size on the surface of the single fiber,
The water-repellent woven fabric according to claim 2, wherein the size of the micropores is 2.0 μm or less for the major axis, 0.5 μm or less for the minor axis, and 0.1 to 0.4 μm in depth. knitting. The water-repellent woven or knitted fabric according to any one of claims 1 to 3, wherein the polyester fiber is contained in an amount of 50 mass% or more in all constituent fibers.