JP2024007191A - Water-repellent composition, and fiber structure including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent composition that exhibits excellent water repellency, possesses a low water holding capacity to avoid wetting when submerged in water, and demonstrates superior washing durability, and to provide a water-repellent fiber structure and a swimsuit.

SOLUTION: A water-repellent composition includes a fluorinated polymer (I) with a heat absorption peak of lower than 50°C in differential scanning calorimetry, and a fluorinated polymer (II) with a heat absorption peak of 50°C or higher in differential scanning calorimetry. The mass ratio between the fluorinated polymer (I) and the fluorinated polymer (II) is: (I)/(II)=10/90-90/10.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a water-repellent composition, a water-repellent fibrous structure, and a swimsuit. More specifically, the present invention provides excellent water repellency, low water retention that makes it difficult to get wet when immersed in water, and excellent washing properties by immobilizing the fibers on the surface of fibers constituting fiber base materials such as textiles. The present invention relates to a water-repellent composition, a water-repellent fiber structure, and a swimsuit from which a durable water-repellent fiber structure can be obtained.

Textile products that are water and oil repellent and have low water retention without water being impregnated into the fabric are particularly desired for sports and outdoor use. To obtain such products, fluorine-based water and oil repellents are widely used. For example, a method of obtaining low water retention of fabric by fixing a water repellent component made of an acrylate copolymer having a fluoroalkyl group having 6 or less carbon atoms and a cyclic silicone with a melamine resin or an isocyanate compound (Patent Document 1), A known method is to use a water repellent containing a non-fluorine water repellent component to a fluoropolymer of a (meth)acrylic derivative containing a fluoroalkyl group having 6 or less carbon atoms and a fluorinated monomer, and to add a melamine resin or an isocyanate compound to the fluoropolymer. (Patent Document 2). In addition, when a fluorine-based water repellent other than a straight-chain perfluoroalkyl group-containing compound having 6 or less carbon atoms is used in fibers, vinylidene fluoride and tetrafluoroethylene are polymerized with a fluoroalkyl alcohol (meth)acrylic acid derivative. A fluoropolymer has been proposed (Patent Document 3). In addition, (A) a fluorine-containing monomer that is an α-halogen acrylate having a fluoroalkyl group, and (B) a fluorine-containing polymer having a repeating unit derived from a monomer that does not contain a fluorine atom. A surface treatment agent containing the following is known (Patent Document 4).

JP2013-209763A Japanese Patent Application Publication No. 2014-194098 Japanese Patent Application Publication No. 2012-97125 International Publication No. 2004/096939

However, the methods described in Patent Documents 1 and 2 have the following problems. The water-repellent compositions described in these documents use two types of water-repellent components, but since cyclic silicone and non-fluorine water-repellent components have low water-repellency and durability, they are mixed with a fluorine-based water-repellent component. performance may deteriorate in some cases. Therefore, fiber base materials such as textiles to which these water-repellent compositions are applied have a problem in that they cannot achieve both high water repellency, low water retention, and durability.

Furthermore, melamine resin, which is used to impart durability and water repellency, forms a very hard resin coating that can crack due to physical rubbing or abrasion during washing or wearing, and cracks when immersed in water. Therefore, there is a problem that water tends to be impregnated into the inside of the fabric structure, resulting in low water retention.

According to the method described in Patent Document 3, it is difficult to obtain low water retention just by fixing a polymer to fibers. Particularly when applied to a fiber fabric containing polyurethane fibers, the polyurethane fibers have a problem in that the water repellent agent is difficult to adhere to the surface and low water retention cannot be obtained.

According to the method described in Patent Document 4, there is a problem that washing durability is not sufficient.

The present invention has been made in view of such conventional inventions, and provides a water-repellent composition that has excellent water repellency, low water retention that makes it difficult to get wet when immersed in water, and excellent washing durability. The object is to provide a water-repellent fiber structure and a swimsuit.

The water-repellent composition, water-repellent fiber structure, and swimwear of the present invention that solve the above problems mainly include the following configurations.

(1) Contains a fluoropolymer (I) whose heat absorption peak in differential scanning calorimetry is less than 50°C and a fluoropolymer (II) whose heat absorption peak in differential scanning calorimetry is 50°C or higher. A water-repellent composition, wherein the mass ratio of the fluoropolymer (I) to the fluoropolymer (II) is (I)/(II) = 10/90 to 90/10.

According to such a structure, the water-repellent composition is immobilized on the surface of the fibers constituting the fiber base material such as textiles, thereby providing excellent water repellency, low water retention that makes it difficult to get wet when immersed in water, In addition, a water-repellent fiber structure having excellent washing durability can be obtained.

(2) The fluorine-containing polymer (I) and the fluorine-containing polymer (II) have repeating units derived from the fluorine-containing monomer (a1) and repeating units derived from the fluorine-containing monomer (a2). A fluorine-containing polymer having units,
The fluorine-containing monomer (a1) is
Formula: CH ₂ =C(-X1)-C(=O)-Y1-Z1-Rf1
[In the formula, X1 is a halogen atom, Y1 is -O- or -NH-, Z1 is a direct bond or a divalent organic group, and Rf1 is a perfluoroalkyl group having 1 to 6 carbon atoms] . ]
It is a compound represented by
The fluorine-containing monomer (a2) is
Formula: CH ₂ =C(-X2)-C(=O)-Y2-Z2-Rf2
[In the formula, X2 is a monovalent organic group or a hydrogen atom, Y2 is -O- or -NH-, Z2 is a direct bond or a divalent organic group, and Rf2 is a carbon number of 1 to 6 It is a perfluoroalkyl group. ]
The water-repellent composition according to (1), which is a compound represented by:

According to such a configuration, the water-repellent composition is immobilized on the surface of the fibers that constitute the fiber base material such as textiles, thereby achieving excellent water repellency and low water retention that makes it difficult to get wet when immersed in water. have

(3) The fluoropolymer (I) and the fluoropolymer (II) are fluoropolymers having repeating units derived from the halogenated olefin monomer (b), (1) or (2) The water-repellent composition described.

According to such a configuration, the water-repellent composition has excellent washing durability by being immobilized on the surface of the fibers constituting the fiber base material such as textiles.

(4) The water-repellent composition comprises a fiber base material made of synthetic fiber, the water-repellent composition according to any one of (1) to (3), and a water-dispersible polyfunctional isocyanate crosslinking agent. and the water-dispersible polyfunctional isocyanate crosslinking agent are a water-repellent fiber structure immobilized on the surface of the synthetic fiber.

According to such a configuration, in the water-repellent fiber structure, the water-repellent composition can form a film having both flexibility and excellent water repellency on the surface of the synthetic fibers constituting the fiber base material. As a result, the water-repellent fiber structure is difficult for water to penetrate and exhibits excellent low water retention.

(5) The water-repellent fiber structure according to (4), wherein the synthetic fiber has a cross-sectional shape having a plurality of grooves each having a wide portion on the outer periphery.

According to this structure, synthetic fibers have narrow entrances to the grooves, making it difficult for water droplets to enter, and furthermore, the air taken into the grooves acts to push up the water droplets, thereby maintaining an air layer. , the water repellent effect is improved. Furthermore, the water-repellent component attached to the inside of the groove is less susceptible to external forces, and the water-repellent agent is less likely to fall off, providing high durability.

(6) The depth of the groove is 1.0 to 10.0 μm, the width of the entrance of the groove is 0.5 to 5.0 μm, and the number of grooves is 3 to 10. , (5) The water-repellent fibrous structure described in (5).

According to such a configuration, the water-repellent fiber structure can easily exhibit a water-repellent improvement effect due to the lotus effect, and can easily obtain sufficient fiber strength.

(7) The water-repellent fiber structure according to any one of (4) to (6), wherein the synthetic fiber includes polyester fiber or polyamide fiber.

According to such a configuration, the water-repellent fiber structure has excellent adhesiveness between the synthetic fiber and the polyfunctional block isocyanate. As a result, the water-repellent fiber structure has excellent durability and excellent durability when used in water and when washed.

(8) The water-repellent fiber structure according to any one of (4) to (7), which has a water retention rate of 30% by mass or less based on the total mass of the water-repellent fiber structure.

According to such a configuration, the water-repellent fiber structure is suitable for use, for example, in swimwear or outdoors.

(9) A swimsuit using the water-repellent fiber structure according to any one of (4) to (8).

According to such a configuration, the swimsuit has excellent water repellency and low water retention in water, and has excellent durability, and exhibits excellent durability even when used underwater for a long time and when washed.

According to the present invention, it is possible to provide a water-repellent composition, a water-repellent fiber structure, and a swimsuit that have excellent water repellency, low water retention that does not easily get wet when immersed in water, and excellent washing durability. .

<Water repellent composition>
The water-repellent composition of one embodiment of the present invention comprises a fluoropolymer (I) having a heat absorption peak of less than 50°C in differential scanning calorimetry, and a fluoropolymer (I) having a heat absorption peak of 50°C or more in differential scanning calorimetry. fluorine-containing polymer (II). The mass ratio of the fluoropolymer (I) to the fluoropolymer (II) is (I)/(II) = 10/90 to 90/10. The water-repellent composition may further include (1) a liquid medium and (2) a surfactant. Each will be explained below.

The fluorine-containing polymers (fluorine-containing polymer (I) and fluorine-containing polymer (II)) of this embodiment include a repeating unit derived from a fluorine-containing monomer (a1) and a fluorine-containing monomer (a2). It is preferable to have a repeating unit derived from. The fluoropolymer may have only repeating units derived from fluoromonomers. The fluoropolymer may have repeating units derived from the halogenated olefin monomer (b) in addition to repeating units derived from the fluoromonomer.

The fluoropolymer (I) having a heat absorption peak of less than 50°C in differential scanning calorimetry and the fluoropolymer (II) having a heat absorption peak of 50°C or higher in differential scanning calorimetry are It can be prepared by adjusting the quantitative ratio of the fluorine-containing monomer (a1), the second fluorine-containing monomer (a2), and the non-fluorine monomer.

(a) Fluorine-containing monomer The fluorine-containing monomer (a) is composed of a first fluorine-containing monomer (a1) having a fluoroalkyl group and an acrylic acid group having a halogen group at the α-position, a fluoroalkyl group and It is preferable to include a combination with a second fluorine-containing monomer (a2) having an acrylic acid group having a monovalent organic group or a hydrogen atom at the α position.

(a1) First fluorine-containing monomer The first fluorine-containing monomer (a1) is
Formula: CH ₂ =C(-X1)-C(=O)-Y1-Z1-Rf1
[In the formula, X1 is a halogen atom, Y1 is -O- or -NH-, Z1 is a direct bond or a divalent organic group, and Rf1 is a perfluoroalkyl group having 1 to 6 carbon atoms] . ]
This is a compound represented by

In the first fluorine-containing monomer (a1), in the above structure, X1 is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and it is preferable that X1 is a chlorine atom. Y1 is preferably -O-. Z1 is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 18 carbon atoms, formula -R2(R1)N-SO ₂ - or formula -R2(R1)N A group represented by -CO- (wherein R1 is an alkyl group having 1 to 10 carbon atoms, and R2 is a straight chain alkylene group or branched alkylene group having 1 to 10 carbon atoms), or , the formula -CH ₂ CH(OR3)CH ₂ -(Ar-O)p- (wherein, R3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl, etc.), and Ar is a substituted _an arylene group optionally having a substituent; arylene group, q is 0 or 1), -(CH ₂ )m-SO ₂ -(CH ₂ )n- group or -(CH ₂ )m-S-(CH ₂ ) n-group (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, for example 1 or 2 carbon atoms). Aromatic or cycloaliphatic groups may be substituted or unsubstituted. The S group or the SO ₂ group may be bonded directly to the Rf1 group.

(a2) Second fluorine-containing monomer The second fluorine-containing monomer (a2) is
Formula: CH ₂ =C(-X2)-C(=O)-Y2-Z2-Rf2
[In the formula, X2 is a monovalent organic group or a hydrogen atom, Y2 is -O- or -NH-, Z2 is a direct bond or a divalent organic group, and Rf2 is a carbon number of 1 to 6 It is a perfluoroalkyl group. ]
This is a compound represented by

In the second fluorine-containing monomer (a2), in the above structure, X2 is a monovalent organic group or a hydrogen atom, Y2 is -O- or -NH-, and Z2 is a direct bond or Rf2 is preferably a divalent organic group, and is a compound in which Rf2 is a fluoroalkyl group having 1 to 20 carbon atoms. X2 is preferably a linear or branched alkyl group having 2 to 21 carbon atoms or a hydrogen atom. X2 is preferably a methyl group or a hydrogen atom. Y2 is preferably -O-. Examples of Z2 include a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 18 carbon atoms, the formula -R2(R1)N-SO ₂ - or the formula -R2(R1 ) A group represented by N-CO- (wherein R1 is an alkyl group having 1 to 10 carbon atoms, and R2 is a linear alkylene group or branched alkylene group having 1 to 10 carbon atoms.) , or the formula -CH ₂ CH(OR3)CH ₂ -(Ar-O)p- (wherein R3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl), and Ar is , an arylene group having optionally a substituent, p represents 0 or 1), or a group represented by the formula -(CH ₂ )n-Ar-(O)q- (wherein, Ar is a substituent (q is 0 or 1), -(CH ₂ )m-SO ₂ -(CH ₂ )n- group or -(CH ₂ )m-S-(CH ₂ ) n-group (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, for example 1 or 2 carbon atoms). Aromatic or cycloaliphatic groups may be substituted or unsubstituted. The S or _SO2 group may be bonded directly to the Rf2 group.

(b) Non-fluorine monomer The non-fluorine monomer is a halogenated olefin monomer (b) and the like. The halogenated olefin monomer (b) is not particularly limited. In one example, the halogenated olefin monomer (b) is vinyl chloride or vinylidene chloride.

In the water-repellent composition of the present embodiment, the fluorine-containing polymer (I) and the fluorine-containing polymer (II) contain repeating units derived from the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a1). Since it is a fluorine-containing polymer having a repeating unit derived from the monomer (a2), it is immobilized on the surface of the fibers constituting the fiber base material, resulting in excellent water repellency.

In the fluorine-containing polymer (I) and the fluorine-containing polymer (II), a repeating unit derived from the first fluorine-containing monomer (a1) and a repeating unit derived from the second fluorine-containing monomer (a2) The ratio is preferably 10:90 to 90:10, more preferably 25:75 to 90:10. When the ratio of the repeating units derived from the first fluorine-containing monomer (a1) and the repeating units derived from the second fluorine-containing monomer (a2) is within the above range, the water-repellent composition has the following properties: By immobilizing it on the surface of the fibers that make up the fiber base material, the water repellency has excellent washing durability (the water repellency does not easily deteriorate even after repeated washing).

Furthermore, the water-repellent composition of the present embodiment contains repeating units derived from the first fluorine-containing monomer (a1), the second fluorine-containing monomer (a2), and the halogenated olefin monomer (b). By using the fluorine-containing polymer, the water repellent composition is immobilized on the surface of the fibers constituting the fiber base material, resulting in excellent washing durability of water repellency.

In the fluorine-containing polymer (I) and the fluorine-containing polymer (II), a repeating unit derived from the first fluorine-containing monomer (a1), a repeating unit derived from the second fluorine-containing monomer (a2) The proportion of repeating units derived from the halogenated olefin monomer (b) is determined based on the total of the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2). It is preferable that the weight is 0 to 60%, more preferably 10 to 40%. Repeating units derived from the first fluorine-containing monomer (a1), repeating units derived from the second fluorine-containing monomer (a2), and repeating units derived from the halogenated olefin monomer (b). When the ratio is within the above range, the water-repellent composition is immobilized on the surface of the fibers constituting the fiber base material, resulting in excellent water-repellent washing durability.

Furthermore, in the manufacturing process of the water-repellent composition of the present embodiment and the manufacturing process of a water-repellent fiber structure to which the water-repellent composition of the present embodiment is applied, the fluoropolymer is dissolved in an organic solvent. It may exist in the form of an aqueous dispersion, preferably in the form of an aqueous dispersion.

(1) Liquid medium The liquid medium may be an aqueous medium. The liquid medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the organic solvent is preferably 30% by mass or less, more preferably 10% by mass or less, based on the liquid medium. The amount of organic solvent is preferably 0.1% by mass or more based on the liquid medium. Preferably, the liquid medium is water alone. The liquid medium may be only an organic solvent. Here, the liquid medium can be used as follows. That is, the liquid medium can be used in the step of dispersing the water-repellent composition of this embodiment to form a treatment composition and fixing the water-repellent composition on the surface of the synthetic fibers constituting the fiber base material.

(2) Surfactant When the surface treatment agent composition is an aqueous dispersion, it may contain a surfactant. The surfactant includes at least one of a nonionic surfactant, a cationic surfactant, and an anionic surfactant. Additionally, the surfactant may include an amphoteric surfactant. Note that the surface treatment agent composition includes at least the water repellent composition of the present embodiment and a solvent, and may also be referred to as a "water repellent".

In this embodiment, the heat absorption peak temperature of the fluoropolymer measured by differential scanning calorimetry affects the uniformity and flexibility of the film of the water-repellent composition on the fiber base material, and the water repellency and low water retention. , change the durability. When the heat absorption peak temperature is high, a hard film is likely to be formed on the fiber base material. Therefore, the resulting structure has high water repellency and low environmental responsiveness, but has a hard texture and is prone to cracks in the film. As a result, structures tend to be unable to maintain low water retention due to water seeping through the cracks. On the other hand, when the heat absorption peak temperature is low, a relatively soft film is obtained and tends to have high durability.

That is, the water-repellent composition of the present embodiment contains a fluoropolymer (fluoropolymer (II)) with a relatively high heat absorption peak temperature and a fluoropolymer (fluoropolymer (I)) with a relatively low heat absorption peak temperature. ) by mixing them at a predetermined mass ratio, the characteristics of both polymers are compatible, and it has been found that high water repellency, low water retention, and high durability can be achieved.

More specifically, the water-repellent composition of the present embodiment is characterized in that the heat absorption peak temperature for distinguishing both fluoropolymers is bordered at 50°C. This is because a difference in heat absorption peak temperature occurs when a film is formed during heating, and a film having both flexibility and excellent water repellency can be formed.

The heat absorption peak temperature of the fluoropolymer (I) may be less than 50°C, and preferably 45°C or less. On the other hand, the heat absorption peak temperature of the fluoropolymer (II) may be at least 50°C, preferably at least 55°C.

The mass ratio of the fluoropolymer (I) and the fluoropolymer (II) may be (I)/(II) = 10/90 to 90/10, and preferably 20/80 to 80/20. It is more preferable that there be. When the proportion of the fluoropolymer (I) is less than 10% by mass and the proportion of the fluoropolymer (II) exceeds 90% by mass, the water-repellent composition is applied to the surface of the fibers constituting the fiber base material. Water repellency decreases when immobilized. On the other hand, when the proportion of the fluoropolymer (I) is more than 90% by mass and the proportion of the fluoropolymer (II) is less than 10% by mass, the water-repellent composition is difficult to form a film when heated.

As described above, the water repellent composition of this embodiment exhibits excellent water repellency. Furthermore, when a fibrous structure is obtained using a water-repellent composition, the obtained fibrous structure has low water retention that makes it difficult to get wet when immersed in water, and excellent washing durability.

<Water repellent fiber structure>
A water-repellent fiber structure according to an embodiment of the present invention includes a fiber base material made of synthetic fiber, the above-described water-repellent composition, and a water-dispersible polyfunctional isocyanate crosslinking agent. The water-repellent composition and the water-dispersible polyfunctional isocyanate crosslinking agent are fixed on the surface of the synthetic fiber. Each will be explained below.

(fiber base material)
The fiber base material consists of synthetic fibers. The fiber base material may be in the form of fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics, and is not particularly limited.

Synthetic fibers include polyester fibers, polyamide fibers, polyethylene fibers, polypropylene fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyacrylonitrile fibers, and the like. Among these, the synthetic fibers preferably contain a fluorine-containing polymer because of their excellent durability, and preferably contain polyester fibers or polyamide fibers that have good adhesion to polyfunctional blocked isocyanates. As a result, the water-repellent fiber structure has high water repellency and durability.

According to the present embodiment, even when the fabric is stretched, it exhibits excellent water repellency and low water retention, and exhibits particularly excellent effects with fabrics that have a high elongation rate. Normally, when a fabric with a high elongation rate is stretched, the water-repellent coating tends to collapse, making it difficult to maintain high water-repellency. However, the water-repellent fiber structure of the present embodiment has a water-repellent composition containing a fluoropolymer having different absorption peaks in differential scanning calorimetry, and a water-dispersible polyfunctional isocyanate crosslinking agent. By immobilizing it on the surface of synthetic fibers, a resin coating that has both flexibility and durability can be provided on the fiber structure. As a result, the water-repellent fiber structure can exhibit both excellent high water repellency and low water content even in a stretched state.

The water-repellent fiber structure of this embodiment is a knitted fabric, a fabric using yarns mixed or twisted with different shrinkage rates, and polytrimethylene terephthalate or polyurethane material that has elasticity in the fiber itself. It may also be a knitted fabric, a woven fabric, etc. containing elastic fibers. There are no particular limitations on the fibers that can be combined with the stretchable fibers.

The cross-sectional shape of the synthetic fiber is not particularly limited. For example, it is preferable that the synthetic fiber has a special cross-sectional shape having a plurality of groove portions (wide groove portions) on the outer periphery, each having a narrow entrance and widening at the back. Synthetic fibers with such a special cross-sectional shape have narrow entrances to the grooves, making it difficult for water droplets to enter, and furthermore, the air taken into the grooves acts to push up the water droplets, thereby maintaining an air layer. , the water repellent effect is improved. Furthermore, the water-repellent component attached to the inside of the groove is less susceptible to external forces, and the water-repellent agent is less likely to fall off, providing high durability.

The depth of the groove in the cross-sectional shape of the synthetic fiber is preferably 1.0 μm or more. Further, the depth of the groove portion is preferably 10.0 μm or less. When the depth of the groove is within the above range, the water-repellent fiber structure can easily exhibit a water-repellent improvement effect due to the lotus effect, and can easily obtain sufficient fiber strength.

The width of the entrance of the groove is preferably 0.5 μm or more. Moreover, it is preferable that the width of the entrance of the groove is 5.0 μm or less. When the width of the entrance of the groove is within the above range, the water-repellent fiber structure easily exhibits the water-repellent improvement effect due to the lotus effect, and water is difficult to enter into the uneven groove. In this embodiment, the width of the entrance of the groove is determined by the width of the straight line connecting the ends of adjacent protrusions observed when observing the cross section of the fiber polymer in the direction perpendicular to the longitudinal direction of the synthetic fiber. Defined as length.

The number of grooves is preferably three or more. Moreover, it is preferable that the number of groove parts is 10 or less, and it is more preferable that it is 8 or less. When the number of grooves is within the above range, the water-repellent fiber structure tends to have sufficient fiber strength and a water-repellent improvement effect due to the lotus effect.

Synthetic fibers have grooves formed therein, so that the surface of the fibers is uneven. Therefore, the water-repellent fiber structure exhibits high water-repellent performance due to the lotus effect, and the grooves are filled with air in water, and the air film prevents the fiber surface from coming into contact with water, and only part of the solid wall of the convex part is exposed. It will come into contact with water.

In this way, the water-repellent fiber structure of the present embodiment can suppress water friction resistance and shedding of the film on the fiber surface by making the convex portions that come into contact with water as small as possible. In addition, the water-repellent fiber structure can make the air in the grooves act to push up water droplets, so that the water-repellent effect can be improved.

In addition, if the convex part becomes an acute angle, the water-repellent fiber structure (for example, a swimsuit) will become fibrillated due to friction between the fiber surface and various solid surfaces when worn, making it more likely that single filament cracks will occur. , the problem of cracking and whitening of the fiber surface is likely to occur. Therefore, the width of the convex portion is preferably 1.0 μm or more, and preferably 10.0 μm or less. When the width of the convex portion is within the above range, the water-repellent fiber structure easily exhibits a lotus effect and maintains excellent water repellency. Note that in the water-repellent fiber structure, when wearing durability is important, the width of the convex portion may be increased. Thereby, the abrasion durability of the water-repellent fiber structure can be improved.

The shape of the groove is preferably a narrow groove in order to prevent water from penetrating and to prevent fibrillation due to wear during wear. The constricted groove is, for example, a groove that has a wide portion on the outer periphery of a single fiber when a cross section in a direction perpendicular to the length direction of the fiber is observed. It is preferable that there be a plurality of wide portions.

(Water repellent composition)
The water-repellent composition is immobilized on the surface of the synthetic fibers constituting the fiber base material to form a film.

The amount of the water-repellent composition attached to the synthetic fiber is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the entire mass of the fiber base material. Further, the amount of the water-repellent composition attached to the synthetic fiber is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, based on the entire mass of the fiber base material. More preferably, it is 5% by mass or less. By having the amount of adhesion within the above range, the water-repellent fiber structure has excellent water repellency, excellent stability of the processing fluid during processing, and even when a surfactant is added, the water-repellent fiber structure has excellent water repellency. Water quality is less likely to decrease.

(Water-dispersed polyfunctional isocyanate crosslinking agent)
The water-dispersed polyfunctional isocyanate crosslinking agent is immobilized on the surface of the synthetic fiber. Thereby, the water-dispersible polyfunctional isocyanate crosslinking agent can impart a crosslinked structure between the fiber base material and the fluoropolymer, thereby imparting durability.

The water-dispersed polyfunctional isocyanate crosslinking agent is not particularly limited. For example, the water-dispersed polyfunctional isocyanate crosslinking agent may be any organic compound containing two or more isocyanate functional groups in its molecule, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diisocyanate, etc. Examples include phenylmethane diisocyanate, triphenyltriisocyanate, xylene diisocyanate, dichlorohexylmethane diisocyanate, and the like. Among these, water-dispersible polyfunctional isocyanate crosslinking agents include tolylene diisocyanate, trimethylolpropane tolylene diisocyanate adduct, furiselin tolylene diisocyanate adduct, and other blocking compounds (heated to 70 to 200°C together with isocyanate adduct). A multifunctional blocked isocyanate crosslinking agent made by reacting phenol, imine, malonic acid diethyl ester, methyl ethyl ketoxime, sodium bisulfite, hydroxybutane, ε-caprolactam, etc., which is a compound that regenerates isocyanate groups. is preferred.

The amount of the water-dispersible polyfunctional isocyanate crosslinking agent attached to the synthetic fiber is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the entire mass of the fiber base material. Further, the amount of the water-dispersible polyfunctional isocyanate crosslinking agent attached to the synthetic fiber is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on the entire mass of the fiber base material. preferable. When the amount of adhesion is within the above range, the water-repellent fiber structure has excellent water repellency and durability, and even when a surfactant is added, the water repellency does not easily deteriorate.

A dissociation catalyst may be used to improve the rate of thermal separation of the blocked isocyanate or to lower the thermal dissociation temperature. The dissociation catalyst is not particularly limited. For example, the dissociation catalyst is dibutyltindiolate, dibutyltin stearate, stearylzinc, an organic amine compound, or the like.

When a dissociation catalyst is used, the content of the dissociation catalyst is not particularly limited.

Returning to the explanation of the water-repellent fiber structure as a whole, the water-repellent fiber structure of the present embodiment has a structure in which sulfone It is preferable to immobilize via at least one of a group-containing compound or a polyhydric phenol compound. As a result, the resulting water-repellent fiber structure has improved durability, and water repellency and low water retention are easily maintained.

The sulfonic group-containing compound is a salt of an α-olefin sulfonate, a sulfonated product of phenol-formalin resin, a sodium salt of dimethylsulfonate isophthalate, etc., and must be a salt of an α-olefin sulfonate having an average carbon number of 12 to 30. is preferred.

Polyhydric phenol compounds include natural tannins and synthetic tannins represented by sulfonated phenol-formalin resins such as novolac type and resol type.

Sulfonic group-containing compounds and polyhydric phenol compounds are used for polyamide fibers because they have an affinity for amino groups. However, sulfone group-containing compounds and polyhydric phenol compounds can also form films on other synthetic fibers (eg, polyester, polyurethane elastic fibers, polypropylene fibers, etc.). By interposing such a film, the adhesion of the fluoropolymer to the water-repellent fiber structure tends to improve, the fluoropolymer tends to adhere uniformly to the fiber surface, and the water repellency tends to improve.

The method for fixing the sulfonic group-containing compound and the polyhydric phenol compound to the fibers is not particularly limited. For example, a method in which the fibrous structure is immersed in an aqueous solution (hereinafter referred to as pretreatment liquid) containing a sulfone group-containing compound or a polyhydric phenol compound is preferred. The fixed amount of the sulfonic group-containing compound and the polyhydric phenol compound is preferably 1% by mass or more, and preferably 2% by mass or more in terms of solid content, based on the mass of the fiber containing the sulfonic group-containing compound and the polyphenol compound. It is more preferable that Further, the amount of adhesion is preferably 10% by mass or less, more preferably 5% by mass or less. When the amount of adhesion is within the above range, the water-repellent fiber structure does not have an excessively hard feel and tends to exhibit excellent water repellency.

The pH of the pretreatment liquid is preferably adjusted to 2 to 6. To adjust the pH, acids such as acetic acid, maleic acid, hydrochloric acid, sulfuric acid, and formic acid may be used. The bath ratio (mass ratio) between the water-repellent fiber structure and the pretreatment liquid is not particularly limited. The bath ratio of the pretreatment liquid to the water-repellent fiber structure is preferably 10 to 50. The pretreatment temperature is preferably 40 to 100°C, more preferably 50 to 90°C. The pretreatment time is preferably 10 to 60 minutes.

As described above, the water-repellent fiber structure of this embodiment can form a film that has both flexibility and excellent water repellency. As a result, the water-repellent fiber structure is difficult for water to penetrate and exhibits excellent low water retention.

The water retentivity of the water-repellent fiber structure of this embodiment can be measured by the method described in the examples, and from the viewpoint of use for swimwear and outdoors, it is 30% by mass or less of the total mass of the water-repellent fiber structure. The content is preferably 25% or less, particularly when used in competitive swimsuits.

The water-repellent fiber structure of this embodiment is suitably used for swimwear. Water-repellent fiber structures have excellent water repellency, low water retention, and durability when worn as a swimsuit while swimming, and are durable enough to withstand long periods of use underwater and washing. show.

Hereinafter, the present invention will be explained in more detail with reference to Examples. The present invention is not limited to these examples at all. In addition, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

The measurement method and evaluation method are as follows.
(Water repellency)
The fibrous structures were evaluated by the spray method according to the method specified in JIS L 1092 "Waterproofing Test Methods for Textile Products" (1998) and graded. Class determination is between 4th and 5th grade: 4-5th grade, between 3rd and 4th grade: 3-4th grade, between 2nd and 3rd grade: 2nd-3rd grade, 1st grade and 2nd grade The grades were graded 1-2, and the grade was determined on a total of 9 levels from grade 1 to grade 5.
(Water retention rate)
Ten pieces of fiber structures cut into 20×20 cm were prepared, and the mass of each piece was measured and defined as the "mass before treatment." Pour 30L of water into a washing machine (JIS C 9606) (water temperature: 25-29°C), put 10 sheets of the fibrous structure into the water, rotate it for 10 minutes under "strong conditions", and then take it out one by one from the water. The spread state was tilted at about 15 degrees, waited for 10 seconds, water droplets attached to the fiber structure were dropped, and the mass was measured, which was defined as the "mass after treatment", and the water retention rate was measured using the following formula.
Water retention rate (%) = ((mass after treatment - mass before treatment) / mass before treatment) x 100
(Washing method)
The fibrous structure was washed by the method specified in Appendix 1, 103 of JIS L 0217 "Display symbols and display methods for handling textile products" (1995). Specifically, water at 40±2°C was poured into a household electric washing machine equipped with a centrifugal dehydrator as specified in JIS C 9606 at a bath ratio (mass ratio) of 1:30, and a weak alkaline synthetic detergent was added. was added and dissolved, and the fibrous structure was washed under strong conditions for 5 minutes. Next, it was drained and dehydrated, and water was added so that the bath ratio was 1:30, and rinsed for 2 minutes. After draining and dewatering again, water was added so that the bath ratio was 1:30, rinsed for 2 minutes, and drained and dehydrated. This was repeated 30 times, which was defined as 30 home washes. After washing, the fabric was hung to dry indoors under an environment of 20° C. and 65% RH.

(Test base fabric 1)
33 dtex, 10 filament nylon 66 processed yarn covered with 78 dtex polyurethane elastic fiber is used for the warp, and 33 dtex, 10 filament nylon 66 processed yarn covered with 55 dtex polyurethane elastic fiber is used for the warp. A 66% nylon, 34% polyurethane fabric was produced using the weft yarn, and the fabric was made into a fabric with a vertical density of 188 threads/inch x width density of 182 threads/inch by normal scouring and dyeing, which was used as test base fabric 1. . The cross-sectional shape of the test base fabric 1 was a round cross-section.

(Test base fabric 2)
Nylon 66 yarn with 33 decitex, 10 filaments and 8 grooves with wide width parts on the outer periphery is used for the warp, and a nylon 66 yarn covered with 44 decitex polyurethane elastic fiber is used for the warp. A 73% nylon, 27% polyurethane fabric was made using nylon 66 yarn, which has 8 grooves with wide widths on the outer periphery, covered with 44 dtex polyurethane elastic fibers as the weft, and was subjected to normal scouring. The fabric was dyed to have a vertical density of 200 threads/inch and a horizontal density of 196 threads/inch, which was used as the test base fabric 2. The dimensions of each groove were 3 μm deep and 1 μm wide at the entrance. The width of the convex portion was 6 μm.

(fluoropolymer)
Fluorine-containing polymer (I): Unidyne TG-5573 with polymer Tg = 55°C (manufactured by Daikin Industries, Ltd., polymer solid content 25 to 35% by mass)
Fluorine-containing polymer (II): Unidyne TG-5574 with polymer Tg = 36°C (manufactured by Daikin Industries, Ltd., polymer solid content 20 to 30% by mass)

<Example 1>
Using a jet dyeing machine using the test base fabric 1, pre-treatment was performed using a processing solution (Nylon Fix 501 (polyhydric phenol condensate manufactured by Senka Co., Ltd.): 5% OWF) at a bath ratio of 1:20. The temperature was raised from room temperature to 80°C at a rate of 2°C/min, and the mixture was treated in a bath for 30 minutes. Next, the temperature was lowered to 50° C., and then the waste liquid was removed, washed with water, dehydrated, and then dried at 140° C. using a pin tenter to obtain a base fabric 1. Next, using the base fabric 1, it was immersed in a processing liquid 1 prepared using distilled water with each drug at the concentration shown below, squeezed with a mangle to a squeezing rate of 55%, and dried at 130 ° C. It was set at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed fabric before and after washing. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 1)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 40g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 40g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd. Isocyanate crosslinking agent content 36%): 5g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 2>
Using the test base fabric 1, which was pretreated in the same manner as in Example 1, it was immersed in processing liquid 2 prepared using distilled water to contain each chemical at the concentrations shown below, and squeezed. After squeezing with a mangle to a ratio of 55%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 2)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 20g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 60g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd. Isocyanate crosslinking agent content 36%): 5g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 3>
A test fabric 1 was pretreated in the same manner as in Example 1, and was immersed in processing liquid 3 prepared using distilled water to contain each chemical at the concentrations shown below, and squeezed. After squeezing with a mangle to a ratio of 55%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 3)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 60g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 20g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd. Isocyanate crosslinking agent content 36%): 5g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 4>
A test fabric 1 was pretreated in the same manner as in Example 1, and was immersed in a processing liquid 4 prepared using distilled water to contain each chemical at the concentrations shown below, and then squeezed. After squeezing with a mangle to a ratio of 55%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 4)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 40g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 40g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 25g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 5>
A test fabric 1 was pretreated in the same manner as in Example 1, and was immersed in a processing liquid 5 prepared using distilled water to contain each chemical at the concentrations shown below, and then squeezed. After squeezing with a mangle to a ratio of 55%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 5)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 40g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 40g/L
・PHOBOL EXTENDER
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 6>
Using the test base fabric 1, which was pretreated in the same way as in Example 1, it was immersed in a processing liquid 6 prepared using distilled water to contain each chemical at the concentrations shown below, and squeezed. After squeezing with a mangle to a ratio of 55%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 6)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 20g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 60g/L
・Riken Resin MBX-31 (manufactured by Miki Riken Kogyo Co., Ltd., isocyanate crosslinking agent content 45%): 20 g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 7>
Using the test base fabric 1, which was pretreated in the same manner as in Example 1, it was immersed in the processing liquid 7 prepared using distilled water to contain each chemical at the concentration shown below, and then squeezed. After squeezing with a mangle to a ratio of 55%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Processing fluid formulation 7)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 60g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 20g/L
・Meikanate CX (manufactured by Meisei Chemical Industry Co., Ltd., isocyanate crosslinking agent, content not disclosed): 20 g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 8>
A test fabric 1 was pretreated in the same manner as in Example 1, and was immersed in a processing liquid 8 prepared using distilled water to contain each drug at the concentrations shown below, and squeezed. After squeezing with a mangle to a ratio of 55%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 8)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 100g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 100g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 25g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 9>
Using the test base fabric 1, which was pretreated in the same manner as in Example 1, it was immersed in processing liquid 9 prepared using distilled water to contain each chemical at the concentrations shown below, and squeezed. After squeezing with a mangle to a ratio of 55%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 9)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 15g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 45g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 25g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Example 10>
Using a test base fabric 2 that has been pretreated in the same manner as in Example 1, it is immersed in a processing liquid 10 prepared using distilled water to contain each chemical at the concentrations shown below, and then squeezed. After squeezing with a mangle to a yield of 84%, drying at 130°C, and setting at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention of the obtained processed fabric. The resulting processed fabric was a fibrous structure that exhibited high water repellency, low water retention, and excellent water repellency and washing durability.
(Formulation of processing fluid 10)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 20g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 60g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 20g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Comparative example 1>
Using the pretreated base fabric 1 of Example 1, it was immersed in a processing liquid 11 prepared using distilled water to contain each drug at the concentration shown below, and squeezed with a mangle to achieve a squeezing rate of 55%. After drying at 130°C, it was set at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric had low water repellency after 30 home washes and poor washing durability.
(Formulation of processing fluid 11)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 80g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 5g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Comparative example 2>
Using the pretreated base fabric 1 of Example 1, it was immersed in a processing liquid 12 prepared using distilled water to contain each drug at the concentrations shown below, and squeezed with a mangle to achieve a squeezing rate of 55%. After drying at 130°C, it was set at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric had low water repellency after 30 home washes and poor washing durability.
(Formulation of processing fluid 12)
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 80g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 5g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Comparative example 3>
Using the base fabric 1 that was pretreated in Example 1, it was immersed in a processing liquid 13 prepared using distilled water to contain each drug at the concentrations shown below, and squeezed with a mangle to a squeezing rate of 55%. After drying at 130°C, it was set at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric had low water repellency after 30 home washes and poor washing durability.
(Formulation of processing fluid 13)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 76g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 4g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 5g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Comparative example 4>
Using the base fabric 1 that has been pretreated in Example 1, it is immersed in a processing liquid 14 prepared using distilled water to contain each drug at the concentrations shown below, and squeezed with a mangle to achieve a squeezing rate of 55%. After drying at 130°C, it was set at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric had low water repellency after 30 home washes and poor washing durability.
(Formulation of processing fluid 14)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 4g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 76g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 5g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Comparative example 5>
The test base fabric 1 was immersed in a processing liquid 15 prepared using distilled water to contain each drug at the concentration shown below, squeezed with a mangle to a squeezing rate of 55%, dried at 130°C, and then heated at 170°C. Set for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was poor in both washing durability and low water retention.
(Formulation of processing fluid 15)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 40g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 40g/L
・Super Fresh JB-7200 (Kyokinu Kasei Co., Ltd., isocyanate crosslinking agent content 36%): 20g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

<Comparative example 6>
Using the pretreated base fabric 1 of Example 1, it was immersed in a processing liquid 16 prepared using distilled water to contain each drug at the concentrations shown below, and squeezed with a mangle to achieve a squeezing rate of 55%. After drying at 130°C, it was set at 170°C for 1 minute. Table 1 shows the results of measuring the water repellency and water retention rate of the obtained processed cloth. The resulting processed fabric was poor in both washing durability and low water retention.
(Formulation of processing fluid 16)
・Unidyne TG-5573 (water repellent manufactured by Daikin Industries, Ltd.): 25g/L
・Unidyne TG-5574 (water repellent manufactured by Daikin Industries, Ltd.): 75g/L
・Texport BG-290 (penetrating agent manufactured by NICCA Chemical Co., Ltd.): 10g/L

Claims (9)

A fluoropolymer (I) having a heat absorption peak measured by differential scanning calorimetry of less than 50°C, and a fluoropolymer (II) having a heat absorption peak measured by differential scanning calorimetry of 50°C or higher,
A water-repellent composition, wherein the mass ratio of the fluoropolymer (I) to the fluoropolymer (II) is (I)/(II) = 10/90 to 90/10. The fluoropolymer (I) and the fluoropolymer (II) have repeating units derived from the fluoromonomer (a1) and repeating units derived from the fluoromonomer (a2). It is a fluorine-containing polymer,
The fluorine-containing monomer (a1) is
Formula: CH ₂ =C(-X1)-C(=O)-Y1-Z1-Rf1
[In the formula, X1 is a halogen atom, Y1 is -O- or -NH-, Z1 is a direct bond or a divalent organic group, and Rf1 is a perfluoroalkyl group having 1 to 6 carbon atoms] . ]
It is a compound represented by
The fluorine-containing monomer (a2) is
Formula: CH ₂ =C(-X2)-C(=O)-Y2-Z2-Rf2
[In the formula, X2 is a monovalent organic group or a hydrogen atom, Y2 is -O- or -NH-, Z2 is a direct bond or a divalent organic group, and Rf2 is a carbon number of 1 to 6 It is a perfluoroalkyl group. ]
The water-repellent composition according to claim 1, which is a compound represented by: 3. The fluoropolymer (I) and the fluoropolymer (II) according to claim 1 or 2, wherein the fluoropolymer (I) and the fluoropolymer (II) are fluoropolymer having repeating units derived from the halogenated olefin monomer (b). Water repellent composition. It has a fiber base material made of synthetic fiber, the water-repellent composition according to claim 1 or 2, and a water-dispersible polyfunctional isocyanate crosslinking agent,
The water-repellent composition and the water-dispersible polyfunctional isocyanate crosslinking agent are fixed to the surface of the synthetic fiber, and the water-repellent fiber structure is a water-repellent fiber structure. 5. The water-repellent fiber structure according to claim 4, wherein the synthetic fiber has a cross-sectional shape having a plurality of grooves each having a wide portion on the outer periphery. The depth of the groove is 1.0 to 10.0 μm,
The width of the entrance of the groove is 0.5 to 5.0 μm,
The water-repellent fibrous structure according to claim 5, wherein the number of grooves is 3 to 10. The water-repellent fiber structure according to claim 4, wherein the synthetic fibers include polyester fibers or polyamide fibers. The water-repellent fiber structure according to claim 4, having a water retention rate of 30% by mass or less based on the total mass of the water-repellent fiber structure. A swimsuit using the water-repellent fiber structure according to claim 4.