JP2005226190A - Fabric having good color development, deep-colorable property, water repellency and oil repellency, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fabric with a fiber structure having the surface composed of an ultrafine fiber, providing an excellently color-developed and deep-colored black-dyed product, having good water repellency, oil repellency and bulkiness having launderability, and also having excellent nap feeling with warm feeling and suede feeling. <P>SOLUTION: The fabric is produced by treating a fabric composed of a sea-island type conjugate fiber consisting of a water-soluble polyethylene-vinyl alcohol component (A) as the sea component, and a polyester (B) as the island component, with an aqueous solution containing a shrink-promoting compound (C) and a fluorine-containing polymer (D) to shrink the sea component (A), and dissolving and removing the component (A) therefrom. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is composed of ultra-fine fibers, and has excellent surface repellency / deep color, water repellency and oil repellency having washing durability, and is bulky, lightweight and warm to the touch (fluffy feeling, warm feeling) and The present invention relates to a fabric having a suede feeling without fluffing and having good color development and deep color and a method for producing the same.

Conventionally, in a thermoplastic polyester non-fine fiber material, a low-refractive substance is applied to the fiber surface or heated in an emulsified liquid containing the substance to adsorb the substance to the fiber and dyed There are known methods for improving the color development and deep color properties of the water (for example, Japanese Patent Application Laid-Open Nos. 11-269971 and 2000-220074), and water repellency and oil repellency are imparted to the method. Is also known. Further, the polyester fiber containing 0.5 to 10 wt% of silica particles having a particle diameter of 0.1 μm or less and a relatively low refractive index is alkali-treated to form fine irregularities on the fiber surface. It is also known to improve color developability and deep color by utilizing the effect of reducing scattered light intensity due to unevenness (for example, Japanese Examined Patent Publication No. 59-24233).

However, in a method in which a low refractive material is applied to a fiber or a heating treatment is performed in an emulsion containing the component, performances such as water repellency and oil repellency are imparted after the treatment. The current situation is that there is no durability. A polyester fiber containing 0.5 to 10 wt% of silica particles having a particle diameter of 0.1 μm or less and a relatively low refractive index is treated with alkali to form fine irregularities on the fiber surface, thereby providing color development / depth. The method for improving the chromaticity gives the fiber a feeling of stickiness and does not give a satisfactory bulkiness. Furthermore, in particular, in the case of an ultrafine fiber material of 0.1 decitex or less, satisfactory color development and deep color properties are not achieved.

In addition, many similar methods other than those described above have been proposed, all of which have advantages and disadvantages, sufficient color development / deep color, washing durable water repellency, washing durable oil repellency, bulkiness, light weight, warm It is not a method of expressing all feelings.

Japanese Patent Laid-Open No. 11-267971 JP 2000-220074 Japanese Patent Publication No.59-24233

The present invention solves the above-mentioned conventional drawbacks, is excellent in mass production of fabric production and post-processing, excellent in coloration / deep colorability of dyed goods, durable durable water repellency, durable durable oil repellency, etc., and bulky The present invention provides a fabric comprising ultra-fine fibers that are extremely high in weight, light in weight, excellent in warm feeling, and capable of providing a suede feeling without fluffing, and a method for producing the same.

That is, in the present invention, at least a part of the constituent fibers is made of the thermoplastic polymer (B), the single fiber fineness is 0.001 to 0.1 dtex, and the surface has the fluorine-containing polymer (D). It is a fabric that is a fiber and has a L * value of 10 to 18 on the surface of the dyed product when dyed with black of a dye species that is dyeable with respect to the thermoplastic polymer (B). This is a characteristic fabric.
The above-mentioned “L * value of the surface of the dyed product becomes 10 to 18 when dyed with black of a dye species that is dyeable to the thermoplastic polymer (B)” means dyeing described later. It means the L * value obtained when dyeing under conditions and obtaining the L * value on the surface of the dyed product by the measurement method described later.

In addition, as a method for producing such a fabric, a composite fiber comprising a water-soluble ethylene-vinyl alcohol copolymer (A) and another thermoplastic polymer (B), wherein A is at least one of the fiber surfaces. A fabric containing a composite fiber that covers the part and is arranged so that B is an ultrafine fiber is treated with an aqueous solution containing the shrinkage promoting compound (C) and the fluorine-containing polymer (D), and A Is used, and a method for producing an ultrafine fiber fabric in which D is adhered to the fiber surface is used.

Furthermore, in the present invention, preferably, the shrinkage promoting compound (C) is a polyoxyalkylene monoether type compound as described above, and the fluorine-containing polymer (D) is a perfluoroalkyl acrylate copolymer. It is said manufacturing method which is a coalescence or a perfluoroalkyl urethane oligomer. More preferably, in the production method, the polyoxyalkylene monoether type compound is a compound represented by the following formula (1) or the following formula (2).

R ₁ O— (CH ₂ CH ₂ O) _n — (CH ₂ CH (CH ₃ ))) _m —H (1)
(R ₁ in the formula represents an alkyl group having 5 or less carbon atoms, n represents an integer of 10 to 60, and m represents an integer of 10 to 35.)
R ₂ O— (CH ₂ CH ₂ O) _p —H (2)
(R ₂ in the formula represents an alkyl group or an allyl group having an alkyl group, and p represents an integer of 5 to 18)

More preferably, the polyoxyalkylene monoether type compound satisfies the above formula (2) and has an HLB value represented by the following formula (3).
4.5 × 10 ⁻¹ × p + 8.5 ≦ HLB value ≦ 4.5 × 10 ⁻¹ × p + 11.8 (3)
(Wherein P is the same value as P in formula (2))
In the aqueous solution treatment, the heating rate during heating is preferably 2 ° C./min or less.

  The water-soluble ethylene-vinyl alcohol copolymer (A: hereinafter simply abbreviated as PVA) used in the present invention contains 5 to 15 mol% of ethylene units, and the remaining units are substantially contained. Copolymers that are vinyl alcohol units and vinyl acetate units are preferred examples. In view of the spinnability of the composite fiber and the dissolution stability in water, it is particularly desirable to contain 8 to 12 mol% of ethylene units. Moreover, 90-99.99 mol% is preferable, as for the saponification degree of PVA, 92-99.98 mol% is more preferable, 93-99.97 mol% is further more preferable, and 94-99.96 mol% is especially preferable. When the degree of saponification is less than 90 mol%, the thermal stability of PVA is poor and satisfactory melt spinning cannot be performed by thermal decomposition or gelation. On the other hand, PVA having a saponification degree higher than 99.99 mol% cannot be stably produced, and fiberization cannot be stabilized.

  In the composite fiber used in the present invention, the PVA (A) covers at least a part of the fiber surface, that is, the PVA is arranged so that the entire surface of the fiber or a part of the PVA is exposed. is important. As a cross-sectional form of the composite fiber for obtaining the ultrafine fiber referred to in the present invention, it is preferable to have a sea-island structure in which the PVA (A) is a sea component and another thermoplastic polymer (B) is an island component. The island component distribution as seen from the cross-sectional shape of the sea-island structure includes a case where the island component is uniformly distributed and a case where it is randomly distributed non-uniformly. As a composite structure other than the sea-island structure, a concentric core sheath, an eccentric core sheath, a structure in which PVA (A) and another thermoplastic polymer (B) are joined in a bimetallic form, or PVA (A) and other heat Examples thereof include a so-called multilayer laminated structure and a random composite structure in which a layered state is formed by alternately forming layers with the plastic polymer component (B). In order to further exhibit operational stability and the effects of the present invention, a structure having a cross section of a sea-island structure and a substantially uniform distribution of island components is preferable.

When PVA (A) is removed from the composite fiber used in the present invention, an ultrafine fiber composed of B is obtained. The single fiber fineness of the ultrafine fiber is in the range of 0.001 to 0.1 dtex. Is preferred. The fineness is adjusted by adjusting the number of islands of the PVA component (A), the composite ratio, the fineness of the single fiber of the composite fiber, and the shrinkage when removing the PVA component (A) in the composite fiber comprising the above-mentioned preferred sea-island structure. It is determined from the degree of When the fineness of the single ultrafine fiber is lower than 0.001 decitec, the operation stability of the yarn production is small, and the L * value of the black dyed product on the surface of the fabric composed of the ultrafine fiber, which will be described later, is from 18.0. The color becomes large and the color developability and deep color are inferior. Furthermore, the L * value is preferably 15.0 or less from the viewpoint of the operational stability of the coloration / deep color of the dyed product, and the fineness is set to 0.005 to 0.08 so as to be such a value. The decitex range is preferred. Further, when the fineness is smaller than 0.001 dtex, there is a problem that characteristics such as suede-like fluffy feeling, bulkiness, and lightness cannot be obtained. On the contrary, if the fineness is larger than 0.1 dtex, it is not preferable because the appearance of the fabric does not have a suede-like fluffy feeling, lightness, and the like.

  The other thermoplastic polymer (B) constituting the composite fiber used in the present invention is not particularly limited, and examples thereof include polyethylene terephthalate and a polyethylene terephthalate polymer obtained by copolymerizing a third component. Examples of the third component include isophthalic acid, sodium 5-sulfoisophthalate, neopentyl glycol, and the like. In addition, polybutylene terephthalate polymers, polytetramethylene terephthalate polymers, polyesters such as poly (α-hydroxy acid) and copolymers thereof, polyamides such as nylon 6, nylon 66, nylon 6-12, and copolymers thereof. A polymer etc. can be illustrated. Among these thermoplastic polymers, the above-mentioned polyethylene terephthalate-based polyester and nylon 66-based polyamide, which are used for apparel, and the like, particularly polyethylene terephthalate-based polyester, are preferable because the effects of the present invention can be exhibited most significantly. .

The thickness of the single fiber of the composite fiber used in the present invention is generally in the range of 1 to 10 dtex, and in particular, in the range of 1.5 to 5.0 dtex is preferable from the standpoint of yarn production. Furthermore, in the present invention, when the composite fiber is used as a yarn that is a bundled body, the fineness of the yarn is generally in the range of 30 to 200 dtex, and 50 to 100 dtex from the point of yarn production. A range is preferred. Further, the ratio of A and B constituting the composite fiber is generally in the range of 5:95 to 50:50 (weight ratio), and is preferably in the range of 10:90 to 40:60 from the viewpoint of post-processing productivity. . The composite fiber is generally produced by a composite spinning method or a mixed spinning method.

The fabric of the present invention means woven fabrics, knitted fabrics and nonwoven fabrics formed from yarns such as long fiber yarns and spun yarns, and laminates thereof. Of these fabrics, when considering lightness, heat retention, etc., fabrics such as taffeta, decine, georgette, crepe, twill, and satin, or knitted fabrics such as interlock and tricot are particularly preferable.

Further, when the yarn is a spun yarn, it can be a blended yarn with natural fibers such as cotton, wool, silk and the like, including woven fabrics and knitted fabrics using this blended yarn. In addition, in the case of long fiber yarn (multifilament yarn), it is possible to make a fabric composed of 100% of the composite fiber from the viewpoint of handling and handling. It is preferable to interweave into a fabric. As a fabric weight, the range of 50-200 g / m < ² > is preferable. Preferably, 20 to 80% by weight of the total fibers constituting the fabric is the above-described composite fiber. In particular, in the present invention, it is needless to say that the case where the surface of the fabric is substantially covered with the fibers is preferable in terms of the effect.

Furthermore, in the method of the present invention, it is extremely important to treat the fabric containing the composite fiber as described above with an aqueous solution containing the shrinkage promoting compound (C) and the fluorine-containing polymer (D). It is extremely important to remove the constituent A component and to attach the D component to the surface of the ultrafine fiber composed of the B component. By such treatment, the component A constituting the composite fiber is swollen and contracted, and at the same time, the swelling and contracting force of the component A is enhanced by the action of the D component, and the D component adheres to the B component. Will be. By applying such a treatment, the surface of the fiber structure and its cross section have a large number of irregularly shaped loops and curls of ultrafine fibers made of another thermoplastic polymer (B). As a result, high-quality bulkiness, a light feeling, a warm feeling, a suede-like fluff feeling, and the like can be obtained in the fiber structure. And the fabric which was extremely excellent in color development property and deep color property is obtained by the synergistic action of the multiple light absorption derived from these many bulky micro voids and the D component. Furthermore, it becomes possible to obtain a fiber structure having water and oil repellency with good washing resistance.

  In the present invention, when treating with an aqueous solution, it is important that the shrinkage promoting compound (C) and the fluorine-containing polymer (D) are contained in the aqueous solution used for the treatment. The shrinkage-promoting compound (C) is a compound that improves the shrinkage rate of the fabric when it is added to the treatment liquid as compared with the case where it is not added.

Furthermore, when both the shrinkage promoting compound (C) and the fluorine-containing polymer (D) are added to the treatment liquid, compared with the case where only the shrinkage promoting compound (C) is added to the treatment liquid, Although the shrinkage ratio of the fabric is increased, the cause thereof is not necessarily proved, but the fluorine-containing polymer (D) adheres around the fabric-constituting PVA component (A), and as a result, the PVA component (A) It is expected that the rate of dissolution will be slowed, resulting in a higher degree of shrinkage of the PVA during dissolution, resulting in a higher shrinkage of the fabric.

In the present invention, the L * value on the surface of the fabric means that the obtained fabric is subjected to dry heat treatment (preset) with a pin tenter under the following conditions, and the dyed product will be described later. This is a value obtained by measuring the color with a C-2000 type Hitachi color analyzer in accordance with JIS Z8719.
<Dyeing conditions>
Disperse dye Kiwalon Polyester Black SK-489 17% omf
Dispersant Disper TL 1g / l
PH regulator Ultra MT level 1g / l
Bath ratio 1:50
Dyeing temperature x time 130 ° C x 40 minutes
Reduced cleaning hydrosulfite 1g / l
Sodium hydroxide 1g / l
Amiradin D 1g / l
Bath ratio 1:50
Treatment temperature × time 80 ° C. × 20 minutes After carrying out the above reduction cleaning, the heat treatment was carried out at a final set of 170 ° C. and subjected to the above L * value and measurement.

  In the present invention, if the shrinkage of the fabric is small during the treatment with the aqueous solution containing the shrinkage promoting compound (C) and the fluorine-containing polymer (D), the L * value of the dyed product becomes larger than 14.0. The object of the present invention is difficult to achieve because the coloring and deep color properties of the other thermoplastic fibers (B) are insufficient. Specifically, it is preferable to dissolve and remove the PVA component (A) so that the increase in the area shrinkage of the fabric when the fabric is treated is 10 to 50%. When the increase in area shrinkage is less than 10%, the dyed product has good color development and deep color, and it has a fluffy feeling (warm feeling) that feels light and warm, and has a brushed and suede-like appearance. On the other hand, it is difficult to obtain a fabric. On the other hand, if the increase in area shrinkage rate exceeds 50%, a coarse and hard fabric is obtained, which is undesirable. In particular, it is preferable to increase the area shrinkage rate to 20 to 40%. The preferred increase in the area shrinkage is mainly due to the concentration of the fluorine-containing polymer (D) in the treatment bath of the fluorine-containing polymer (D), specifically, the weight percentage of the fluorine-containing polymer (D) to the treated composite fiber ( %). Therefore, it is possible to increase the area shrinkage rate within the preferred range by changing the concentration condition of the fluorine-containing polymer (D).

As the shrinkage-promoting compound (C) used in the present invention, for example, a polyoxyalkylene monoether type compound is suitable, and one or more compounds are selected from the polyoxyalkylene monoether type compound. Is preferred. Particularly preferred is a compound represented by the following formula (1).
R ₁ O— (CH ₂ CH ₂ O) _n — (CH ₂ CH (CH ₃ ))) _m —H (1)
(In the formula, R ₁ represents an alkyl group having 5 or less carbon atoms, n represents an integer of 10 to 60, and m represents an integer of 10 to 35.) In this formula, an ethylene oxide unit and a propylene oxide unit The order may be reversed.

In addition to the compound represented by the above formula (1), a compound represented by the following formula (2) is given as a preferred example.
R ₂ O— (CH ₂ CH ₂ O) _p —H (2)
(R ₂ in the formula represents an alkyl group or an allyl group having an alkyl group, and p represents an integer of 5 to 18)

And as these shrinkage-promoting compounds (C), in the case of the compound of (2) above, it preferably has an HLB value represented by the following formula (3).
4.5 × 10 ⁻¹ × p + 8.5 ≦ HLB value ≦ 4.5 × 10 ⁻¹ × p + 11.8 (3)
(Wherein P is the same value as P in formula (2))

Specific examples of the compound represented by the chemical formula (1) include orioxyethylene (n = 20) polyoxypropylene (m = 28) butyl ether and polyoxyethylene (n = 35) polyoxypropylene (m = 28) butyl ether. And polyoxyethylene (n = 45) polyoxypropylene (m = 33) butyl ether.
Examples of suitable specific compounds of the chemical formula (2) include polyoxyethylene octyl ether (p = 4.7), polyoxyethylene octyl phenyl ether (p = 4, 7), and polyoxyethylene octyl phenyl ether. (P = 6, 10), polyoxyethylene lauryl ether (p = 10) and the like.

  Specific examples of the fluorine-containing polymer (D) used in the present invention include a perfluoroalkyl acrylate low copolymer and a perfluoroalkyl urethane low polymer. The specific molecular weight is in the range of tens of thousands to hundreds of thousands. As a representative example of the product, a trade name: NK guard NDN-7E (manufactured by Nikka Chemical Co., Ltd.) can be mentioned.

  The concentration of the compound or the like in the aqueous solution is preferably 1 g / l to 10 g / l for the shrinkage promoting compound (C), and 3 g in consideration of the running property of the fabric when the aqueous solution treatment is performed in a liquid dyeing machine. A concentration of / l to 5 g / l is more preferred. When the amount is less than 1 g / l, the swelling / shrinking property of the ethylene-vinyl alcohol copolymer constituting the composite fiber becomes small, making it difficult to obtain a bulky fabric, resulting in insufficient coloring and deep color of the dyed product. On the other hand, when the amount exceeds 10 g / l, the texture of the fabric treated with the copolymer hardly dissolved in water becomes rough and the coloring / deep color of the dyed product becomes insufficient. And about fluorine-containing polymer (D), 0.2%-3.0% are preferable with respect to the fabric weight. Considering the effective adsorptivity and the electrostatic property of the treated product, 0.9% to 1.5% is more preferable. If it is less than 0.2%, the deep colorability and darkness of black are insufficient, and the water and oil repellency washing durability is insufficient. On the other hand, if it exceeds 1.5%, the electrostatic property is remarkably lowered, the feeling of sliminess becomes remarkable, the quality of the texture is deteriorated and the practicality is lacking.

The aqueous solution treatment containing these compounds is performed at a temperature below the water dissolution temperature of PVA, and is preferably performed in a temperature range that is 10 ° C. to 30 ° C. lower than the water dissolution temperature. The rate of temperature increase during the treatment with the aqueous solution is preferably slow, specifically 2 ° C. or less / min. In order to adsorb the fluorine-containing polymer to the PVA component and sufficiently swell and shrink it, a temperature rising rate in the range of 0.5 ° C. to 1.0 ° C./min is more preferable. In the present invention, PVA is dissolved and removed by heating to a temperature higher than the water dissolution temperature of PVA. In this case, PVA is not simply dissolved, but by the action of the shrinkage promoting compound (C) and the fluorine-containing polymer (D). In addition to maximizing the shrinkage performance when dissolving, the fluorine-containing polymer (D) is adhered to the surface of the ultrafine fiber (B) after the PVA is dissolved and removed. To express.

Further, the preferable actual condition of the present invention will be explained. In a fabric having a strong binding force between yarns, for example, a woven fabric, a super-fine fiber in a portion with a lot of floating yarns is treated with an emery raising machine to give a peach skin having a higher quality feeling. It is also possible to make a toned fabric. Furthermore, it can be applied to artificial leather.

The fabric obtained by the present invention is composed of ultra-fine fibers, has excellent surface repellency / deep color property, water repellency and oil repellency having washing durability, and is bulky, lightweight and warm to the touch (fluff sensation, warm sensation) Color) and deep color with a suede feeling can be obtained without fluffing, and as a fabric for general clothing and sports clothing, and for non-clothing fields such as interior, bedding and vehicles As a fabric, it can be further used as an artificial leather-finished fabric, and can also be used as a fabric for umbrellas, rain gears, and cold protection devices.

  Hereinafter, the present invention will be specifically described with reference to examples and the like, but the present invention is not limited thereto. In addition, each physical property in an Example was measured with the following method.

[Increase in area shrinkage]
The area shrinkage ratio of the area shrinkage ratio of the fabric when treated under exactly the same conditions except that it contains no compound (C) or (D) and the area shrinkage ratio of the fabric when these compounds are added. We asked for an increase. (When the shrinkage ratio was reduced by adding the compound, the value was shown as a negative value.)
The area shrinkage rate was obtained from the following equation based on dimensional changes in the width direction and length direction of the fabric.
Area shrinkage%) = {1− (1−L _A ) (1−L _B )} × 100
L _A : Shrinkage rate (%) in the width direction of the fabric L _B : Shrinkage rate (%) in the length direction of the fabric

[Color development and deep color]
The black dyed product was measured with a C-2000 type Hitachi color analyzer, and the L ^* value was determined in accordance with JIS Z8719 as follows.
L ^* = 116 (Y / Yn) ^1/3 -16
Here, Yn: Y value of standard light on the perfect diffuse reflection surface. Y: Tristimulus value of black dyeing.
The smaller the L * value, the greater the color development / deep color.

[Water and oil repellency washing durability]
The black dyed product was evaluated for water repellency and oil repellency by the following method on the fabric after repeated washing 10 times according to JIS-L0217 No. 103.
Water repellency: The water repellency was evaluated by a spray test in accordance with JIS-L1092.
Rank of water repellency: Content of water repellency 1: Indicating wetness on the entire surface 2: Indicating wetness on half of the surface, indicating that small individual wetting penetrates the fabric.
3: Indicating wetting on small individual water droplets on the surface.
4: The surface does not wet, but shows adhesion of small water droplets.
5: No wetness or water droplet adhesion on the surface.
The above rank 4 or higher level is recognized as water repellency.
Oil repellency: Using a mixed solution shown in the table below consisting of White Mineral Oil (commonly known as Nujol) and n-Heptanen, several drops are dropped on the fabric surface, and the permeation state after 3 minutes is determined. The oil repellency was evaluated by the ranking shown in the table below.

[Heat retention]
The heat retention rate (%) was measured by a heat retention tester prepared according to ASTM D-1518-57T.

[Increase rate of fabric thickness]
The change in thickness of the dyed product was examined by the following method.
The thickness was measured according to JIS L-1079-76, and the rate of increase in thickness was determined by the following formula.
T = Fb−Fa / Fa
(Fa is the thickness of the fabric before dyeing, Fb is the thickness of the fabric after treatment)

[Texture / bulge]
A sensory test was conducted with 10 panelists, and the number of panelists who felt that the feeling of swelling was excellent was determined as follows. The fabric used here is a 28-gauge knitted fabric.
◎: Nine or more people are judged to be excellent in bulging feeling ○: Seven to eight people are judged to be excellent in bulging feeling Δ: Five to six people are judged to be excellent in bulging feeling ×: Four or fewer people are judged Judged to have excellent bulge

[Suede fluff]
A sensory test was conducted with 10 panelists, and the number of panelists who felt that the suede-like fluff was excellent was judged as follows.
○: 5 or more people are judged to be suede and fluffy ×: 4 or less are judged to be suede and fluffy

Examples 1-3, Comparative Examples 1-4
Polyethylene terephthalate copolymerized with 10 mol% of isophthalic acid as an island component polymer, and a polyethylene-vinyl alcohol copolymer (hereinafter referred to simply as PVA) containing 8.3% ethylene units and a saponification degree of 98.6% as a sea component polymer. Each pellet is melt-discharged from a circular spinning nozzle with a sea-island structure (composite ratio of island component to sea component = 60/40) by a twin-screw extruder, and the number of islands is changed. The oil is inserted into a tube heater (inner wall temperature: 200 ° C) with a length of 1.0m, an inlet diameter of 8mm and an inner diameter of 30mmφ installed at a position 1.2m below the crow's mouth oiling (gear pump oiling) System) and take-up at a take-up speed of 3800 m / min through two take-up rollers, 150 dtex / 7 To give a f each of the multi-filament. There was no problem in spinnability, and a 28-gauge knitting was obtained using the obtained multifilament.

Next, as shown in Table 2, for the tengu edition, as a comparative example, as a comparative example, a single solution containing only a shrinkage promoting compound (polyoxyethylene octyl ether P = 7) at a concentration of 3 g / l, a trade name NK guard NDN as a fluorine-containing polymer. -7E A single solution containing only 6% omf, and, as an example, a concentration of 3 g / l containing the shrinkage-promoting compound and the trade name NK guard NDN-7E (manufactured by Nikka Chemical: Pure 20 %) In a solution such as a combined composition containing 6% omf, the temperature was raised to 100 ° C. at a temperature rising rate from the starting temperature 30 ° C. shown in Table 2, and a treatment at 100 ° C. for 40 minutes was performed. Next, dry heat treatment was performed at 170 ° C. for 1 minute, and the above black staining and reduction cleaning were performed. Table 2 shows the performance of these dry heat preset products at 170 ° C. for 1 minute.

Examples 4-5
The multifilament multifilament used in Example 1 was used as the warp, and 75 dtex / 24 filament made of polyethylene terephthalate was used as the weft to obtain a 3/1 warp twill fabric. This fabric was heated with an aqueous solution containing a treatment concentration of 5 g / l containing a shrinkage promoting compound shown in Table 3 and 6% omf of a fluorine-containing polymer (trade name NK Guard NDN-7E) under the following conditions. It was.
Heating treatment conditions Bath ratio 1:50
Temperature rising rate from 30 ° C. to 100 ° C. 1 ° C./min. 100 ° C. Keep processing time 40 min. This brushed product was dry heat presetted at 170 ° C., black dyed at 130 ° C. and subjected to reduction cleaning treatment at 80 ° C., and then subjected to a dry heat final set at 170 ° C. The single fiber fineness was 0.04 dtex.

Examples 6-7, Comparative Example 5
The multifilament of the composite fiber used in Example 3 is a warp, the weft is a polyethylene terephthalate system, a different type after polymerization is a laminated type of the polymer, and a latent crimped composite fiber of a conjugate having a round cross section is 75 dtex / 24 filaments were used to make a 2/1 oblique twill fabric. This fabric was subjected to a heating treatment under the following conditions with an aqueous solution containing a treatment concentration 5 g / l containing a shrinkage promoting compound shown in Table 4 and 6% omf of a fluorine-containing polymer (trade name NKguard NDN-7E). went.
Heating treatment conditions Bath ratio 1:50
Temperature rising rate from 30 ° C. to 100 ° C. 1 ° C./min 100 ° C. Keep processing time 40 minutes The above-mentioned warm-treated products were subjected to napping treatment on the surface of the fabric with an emery napping machine. This brushed product was dry heat presetted at 170 ° C., black dyed at 130 ° C. and subjected to reduction cleaning treatment at 80 ° C., and then subjected to a dry heat final set at 170 ° C. The single fiber fineness was 0.005 dtex.

The fabric of the present invention can be used as a fabric for general clothing and sports clothing, as a fabric for non-clothing fields such as interiors, beddings, vehicles, etc., and further as an artificial leather preparation fabric. Can be used as a fabric for cold protection.

Claims (9)

A fabric in which at least a part of the constituent fibers is made of a thermoplastic polymer (B), has a single fiber fineness of 0.001 to 0.1 dtex, and has a fluorine-containing polymer (D) on the surface. A fabric having an L * value of 10 to 18 on the surface of the dyed product when the thermoplastic polymer (B) is dyed with a black color of a dyeable dye species. The fabric according to claim 1, wherein the fluorine-containing polymer (D) is a perfluoroalkyl acrylate copolymer or a perfluoroalkyl urethane oligomer. A composite fiber composed of a water-soluble ethylene-vinyl alcohol copolymer (A) and another thermoplastic polymer (B), wherein A covers at least a part of the fiber surface, and B is a microfiber. The fabric containing the composite fibers arranged in such a manner is treated with an aqueous solution containing the shrinkage promoting compound (C) and the fluorine-containing polymer (D) to remove A and attach D to the fiber surface. The manufacturing method of the super extra fine fiber fabric to be made to do. The process according to claim 3, wherein the shrinkage promoting compound (C) is a polyoxyalkylene monoether type compound. The production method according to claim 3, wherein the fluorine-containing polymer (D) is a perfluoroalkyl acrylate copolymer or a perfluoroalkyl urethane oligomer. The production method according to claim 4, wherein the polyoxyalkylene monoether type compound is a compound represented by the following formula (1).
R ₁ O— (CH ₂ CH ₂ O) _n — (CH ₂ CH (CH ₃ )) _m —H (1)
(R ₁ in the formula represents an alkyl group having 5 or less carbon atoms, n represents an integer of 10 to 60, and m represents an integer of 10 to 35.) The production method according to claim 4, wherein the polyoxyalkylene monoether type compound is a compound represented by the following formula (2).
R ₂ O— (CH ₂ CH ₂ O) _p —H (2)
(R ₂ in the formula represents an alkyl group or an allyl group having an alkyl group, and p represents an integer of 5 to 18) The production method according to claim 7, wherein the polyoxyalkylene monoether type compound has an HLB value represented by the formula (3).
4.5 × 10 ⁻¹ × p + 8.5 ≦ HLB value ≦ 4.5 × 10 ⁻¹ × p + 11.8 (3)
(Wherein P is the same value as P in claim 7) The production method according to claim 2, wherein in the aqueous solution treatment, the treatment is performed in the solution being heated, and the heating rate at that time is 2 ° C / min or less.