JPH0364548A - Water repellent durable fabric - Google Patents

Abstract

PURPOSE:To obtain a fabric, capable of exhibiting excellent water repellent durability and suitable for uses of sportswear by weaving yarn of specific single filament size prepared from a modified polyester containing a copolymerized phosphonium salt of sulfonic acid and a quaternary onium salt mixed therein at a specified density. CONSTITUTION:A water repellent fabric, obtained by weaving yarn composed of a modified polyester prepared by copolymerizing 0.5-10mol% phosphonium salt of sulfonic acid (e.g. tetrabutylphosphonium salt of 3,5- dicarboxybenzenesulfonic acid) expressed by the formula (A is aromatic or aliphatic group; X1 is ester-forming functional group; X2 is ester-forming group same as or different from X1 or H; R1 to R4 are groups selected from alkyl and aryl groups; (n) is an optional number) and mixing a quaternary onium salt (e.g. tetramethylammonium hydroxide) in an amount of 0.1-20mol% based on the aforementioned salt in the above-mentioned copolymer and having <=1.2 denier single filament size as warp and weft yarns so as to provide 1400-4600 sum of cover factors in the warp and weft yarn directions and then subjecting the resultant fabric to water repellent finish and excellent in durability in washing.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a water-repellent and durable fabric. The present invention relates to a polyester fiber fabric that is particularly useful for body wear applications.

<Prior Art> Various water-repellent fabrics have been known in the past. For example, ``The sum of the cover factors in the warp and cotton yarn directions is 14.
00 to 3,400 and whose surface is covered with fine irregularities made of water-repellent ultrafine fibers (Japanese Patent Application Laid-Open No. 60-39438 is known, and it is extremely It is known as a highly water-repellent fabric.

However, there are problems with the durability of water repellency with conventional water-repellent fabrics in the shell, and recent fabrics such as W11. The problem of water repellency gradually decreasing due to repeated dry cleaning cannot be avoided. As a result, the application of polyester fibers to the sportswear field has been greatly restricted.

The present invention has been made to solve this problem.

<Problems to be Solved by the Invention> The name of the present invention is that water repellency durability is greatly improved by adding a specific quaternary onium salt to a modified polyester copolymerized with a sulfonic acid phosphonium salt. This was completed after further research.

<Structure of the invention> That is, the present invention is based on the following general formula (I)
0P■RI R2R3R4)n (wherein, A is an aromatic group or aliphatic group, ×1 is an ester-forming functional group, ×2 is X
+ is the same or different ester-forming functional group or hydrogen atom, RIR2, R3 and R4 are the same or different groups selected from alkyl groups and aryl groups, n is a positive integer phosphonium sulfonate Salt is 0.5~
Single yarn 1 containing a composition copolymerized with 10 mol % and a quaternary onium salt mixed with the copolymer at a ratio of 0.1 to 20 mol % based on the sulfonic acid phosphonium salt.
Made of polyester fiber with a degree of 1.2 denier or less, the sum of the cover factors in the warp and kasuri thread directions is 14
00 to 4600, a water-repellent and durable fabric.

The sulfonic acid phosphonium salt used as a copolymerization component in the method of the present invention has the following general formula (J)
...(I)(SO30P■RI
It is represented by R2Ra R4)n. In the formula, A represents an aromatic group or an aliphatic group, and among them, an aromatic group is preferable. ×
1 indicates an ester-forming functional group, and a specific example is (-0
Mouth 2 U-a 011゜0 (=CH2+b+O (C112), 11 +d 0 mouth.

-C+O(0口2)l)+dOH I (However, R' is a lower alkyl group or a phenyl group, 3- a and d are an integer of 1 or more, and b is an integer of 2 or more). . ×2 represents an ester-forming functional group or a hydrogen atom that is the same as or different from X+, and is preferably an ester-forming functional group. R+, R
2+' R3 and R4 represent the same or different groups selected from the group consisting of alkyl groups and aryl groups. n is a positive integer.

Such sulfonic acid phosphonium salts can generally be easily synthesized by reacting the corresponding sulfonic acid with a phosphine or by reacting the corresponding sulfonic acid metal salt with a phosphonium halide.

Preferred specific examples of the sulfonic acid phosphonium salts include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyl 1-heryptylphosphonium salt, 3,5-
Dicarboxybenzenesulfonic acid benzyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt, 34-(β-hydroxyethoxycarbonyl)benzenesulfone Acid tetrabutylphosphonium salt, 3(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetraphenylphosphonium salt, 4hydroxyethyl-1-xybenzenesulfonic acid detrabutylphosphonium salt, 2,6-dicarboxynaphthalene-4-sulfonic acid tetra Examples include butylbosbonium salt, α-tetrabutylphosphonium sulbosuccinic acid, and the like. The above-mentioned sulfonic acid phosphonium salts may be used alone or in combination of two or more.

In order to copolymerize the sulfonic acid phosphonium salt into a polyester, it may be added at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the first stage reaction is completed. The proportion of the sulfonic acid phosphonium salt copolymerized with the polyester is in the range of 0.5 to 10 mol % based on the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester.

If the copolymerization ratio is less than 0.5 mol %, the resulting modified polyl-L-SJ will have insufficient dyeing properties with respect to y-A dyes, and if it exceeds 10% by mole, cationic dyeing properties will no longer be obtained. No significant improvement is shown, and on the contrary, the physical properties of the polyester are deteriorated, making it difficult to achieve the object of the present invention.

In producing such a modified polyester, it is preferable to add a quaternary onium salt. Examples of quaternary onium salts include quaternary ammonium salts and quaternary phosphonium salts. Specifically, quaternary ammonium salts include tetramethylammonium hydroxide, butramethylammonium chloride, and water. De-ammonium oxide, tetraethylammonium chloride, tetraethylammonium bromide.

iodide] - laedyl ammonium, hydroxide - lapropylammonium, chloride - lapropylammonium, tetraisopropylammonium hydroxide.

Tetraisopropylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetraphenylammonium hydroxide.

Examples include tetraphenylammonium chloride.

Quaternary phosphonium salts include: Rubenzyl phosphonium chloride, stearyl ethyl dihydroxyethyl phosphonium 1, nalpha 1, tetrabutyl phosphonium acetate, tetrabutyl phosphonium dodecyl benzene sulfonate.

■Tilttriphenylphosphonium bromide, penzyltriphenylphosphonium chloride, 1 to butylallylphosphonium bromide, ethylene bistris (2
-cyanoethyl)bosbonium bromide, tris-2
Examples include -cyanoethylallylphosphonium chloride, tetrabutyl(hydroxymethyl)phosphonium sulfate, and de-1-rakis(hydroxymethyl)phosphonium chloride.

If the amount of the quaternary onium salt used is too small, the effect of improving heat resistance will be insufficient, and if it is too large, the heat resistance will worsen, and the resulting polyester or molded product will turn yellowish brown. There is a noticeable tendency for coloring to occur. Therefore, the amount of the quaternary onium salt used is preferably in the range of 0.5 to 10 mol % based on the sulfonic acid phosphonium salt.

The addition of the quaternary onium salt at stage 11.1 may be at any stage until the synthesis of the polyester described above is completed,
For example, it may be added to the polyester raw material, during the first stage reaction, or between the end of the first stage reaction and the start of the second stage reaction, or the second stage reaction. It may be added during the reaction.

The quaternary onium salt and the sulfonic acid phosphoric acid salt may be added in any order, and they may be added after being mixed in advance. In addition, when producing a sulfonic acid phosphonium salt, a synthesis method may be adopted in which a quaternary phosphonium salt such as a quaternary phosphonium halide is reacted with a sulfonic acid metal salt, in which case the quaternary phosphonium salt as a raw material is A portion of the reaction product may remain in the sulfonic acid phosphonium salt. In such a case, it is not necessary to use a quaternary phosphonium salt separately, and the remaining quaternary phosphonium salt can be utilized.

=8 By doing this, the intrinsic viscosity is 0.5, which is necessary for high strength.
A modified polyester having an intrinsic viscosity of 8 or more, more preferably 0.64 or more, and excellent whiteness with little yellowing can be obtained.

The modified polyester thus obtained is melt-spun.

In general, melt spinning processes polymers with a melting point J of 30 to 5.
It is melted at a temperature 0°C higher and discharged through a spinneret. The melting point of the sulfonic acid phosbonium salt copolyester polyester mainly containing polyethylene terephthalo-1 is 250 to 255.
℃, and if the above-mentioned normal melt spinning conditions are applied, the spinning temperature will be 285 to 310 ℃, and if melt spinning is performed under such conditions, decomposition will occur during spinning and coloring may occur.
The degree of polymerization may decrease. This is because the spinning temperature is the decomposition temperature of sulfonic acid phosphonium salt (the decomposition humidity of typical tetrabutylphosphonium sulfoisophthalate is 3
05° C.), and even with the above-mentioned stabilization of the polymer, sufficient spinning may not be possible. For this reason, in the case of the above-mentioned modified polyesters, temperatures below 280°C, more preferably 275°C.
It is desirable to spin at temperatures below 0.degree. However, if the spinning temperature is too low, elastic deformation due to tensile stress will lead to brittle fracture, making spinning impossible, so the spinneret temperature should be set at least 5° C. higher than the melting point of the modified polyester.

As mentioned above, the cap temperature should be kept below 280°C, especially 275°C.
By spinning the fibers at temperatures below ℃, in addition to stabilizing the polymer described above, it is possible to greatly reduce deterioration due to thermal decomposition, that is, a decrease in the degree of polymerization and yellowing of the fibers, so that the intrinsic viscosity of the fibers increases. 0.55 or more, preferably 0.60 or more,
Particularly preferably, it is possible for the first time to provide a cationically dyeable modified polyester fiber of 0.63 or more, and this fiber has a silk factor (fiber strength
It can exhibit a high strength of 5 or more, preferably 28 or more.

The single yarn fineness of the fibers constituting the fabric is 1.2 denier or less. As a method for preventing polyester copolymerized with sulfonic acid phosphonium salt from becoming less than 1.2 denier, we have proposed a method of spinning at a take-up speed of 3,000 m/rn or more (Japanese Patent Application No. 1982-41).
No. 532〉.

The polyester IIN of 1.2 denier or less is woven into a fabric, and the sum of cover factors in the warp and weft directions of the obtained fabric is 1400 to 4600. 14
If it is less than 00, [Yo, Shimamitsu + U Ib character's vi nature is 1]
1 (lower). If it exceeds 4600, the surface of the fabric becomes paper-like and the properties as a high-density fabric deteriorate.

Note that the fabric of the present invention is usually used after being subjected to a water-repellent treatment.

The water repellent treatment may be performed by a commonly used known method.

For example, a silicone-based or fluorine-based water repellent may be applied by a spraying method, a padding method, a dipping method, a coating method, or the like. Among these methods, the padding method is the best for uniformly applying water repellent to the fabric.

<Effects of the Invention> The water-repellent and durable fabric of the present invention has moisture permeability and windproof properties (low air permeability)
11- It is a new functional fabric for rear door applications, especially sportswear applications.

Example 3 (Lamination) One-component moisture-permeable polyurethane: Crybon 3314 (manufactured by Dainippon Ink and Chemicals) was applied onto polypropylene paper using a doctor knife so that the solid content was 6 q/-td, and the mixture was heated at 100°C. A two-wave urethane adhesive having the following formulation was applied to the formed skin layer by heating and drying for 2 minutes so that the solid content was 8 g/m, and after heating and drying at 80°C for 1 minute, The surface opposite to the calendered surface of the water-repellent fabric obtained in Example 1 and the above coating were heated at 110°C.
The film was laminated through a heated roll, and after aging for 3 days, the release paper was peeled off. The properties of the thus obtained laminated fabric were as shown in the table.

As in Example 1, the water repellent durability was very excellent.

Comparative Example 1 Ultrafine polyethylene teletor 12 with fresh water shrinkage rate of 8.5%
- A yarn made of a mixture of rate multifilament (total denier: 32 denier, number of filaments: 72) and polyethylene terephthalate multifilament (total denier: 30 denier, number of filaments: 12) with a clean water shrinkage rate of 19% is used for the warp and warp. A high-density plain fabric with a total cover factor of 2071 was woven (warp density 2
50 lines/2.54 cm, latitude density 190 lines/2.5
4 (:m), scouring the fabric according to the usual method,
Relax, dry, Brisera 1~. staining.

It was dried.

However, the staining was carried out under the following conditions.

The conditions for the water repellent treatment at 130° C. for 60 minutes were the same as in Example 1. As shown in the table, the performance of the obtained product was as follows: although the water repellency was initially 100 points, it decreased to 70 points after 10 washes, and the dye transfer property was poor at grade 1.

procedural amendment kick

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, A is an aromatic group or an aliphatic group, X_1 is an ester-forming functional group, X_2 is the same or different ester-forming functional group or hydrogen atom as X_1, R_1, R_2, R
_3 and R_4 are the same or different groups selected from alkyl groups and aryl groups, n is a positive integer) 0.5 to 10 mol% of sulfonic acid phosphonium salts are copolymerized, and consisting of a polyester fiber containing a composition in which an onium salt is mixed with the copolymer at a ratio of 0.1 to 20 mol% relative to the phosphonium sulfonate salt, and having a single fiber fineness of 1.2 denier or less, A water-repellent and durable fabric having a sum of cover factors in the warp and weft directions of 1,400 to 4,600.