JPH09137382A - Water-repelling fiber cloth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide water-repelling fiber cloth excellent in washing resistance and abrasion resistance and suitable for a sport wear by coating fiber cloth with a resin film formed by adding a polyfluoroolefin to a repelling treatment solution consisting of a fluoride water repellent, a triazine compound and a block isocianate compound. SOLUTION: A water repelling treatment solution is prepared in such a manner that it can impart 1.0-6.0wt.% fluoride water repellent consisting of a (meth)acrylate having a perfluoroalkyl group or its copolymer, 0.01-1.0wt.% triazine compound such as trimethylol melamine, 0.01-1.0wt.% block isocyanate compound and 0.1-10wt.% polyfluoroolefin having a constituting unit of the formula [in R1 to R3 , at least one is a fluoride atom and each of the others is H, a halogen or a lower alkyl; (n) is an integer] to cloth. Twill fabric of polyester long filaments dyed in a specified color is dipped into the water repelling treatment solution. The treated fabric is squeezed to remove water by a mangle, dried and subjected to a heat treatment to obtain the objective water repelling cloth.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent fiber cloth having excellent washing durability and abrasion resistance.

[0002]

2. Description of the Related Art Conventionally, a water-repellent treatment has been carried out for the purpose of functionalizing various fiber products irrespective of synthetic fibers and natural fibers. Water-repellent treatment of fabric is usually performed by impregnating an existing fabric with a water-repellent agent such as a fluorine-based water-repellent agent or a silicone water-repellent agent in the final finishing step, and then performing a dry heat treatment. In particular, many water-repellent treatments using a fluorine-based water repellent having excellent washing durability are performed.

[0003] In recent years, the demand for water repellency and washing durability has been further increased by consumers, and especially in the field of sports clothing such as ski wear, windbreaker and mountain wear, such washing durability is improved. For the purpose, it has been attempted to improve the washing durability by a method in which an epoxy resin, an ethylene polymer, a triazine compound, etc. are mixed with a fluorine-based water repellent and applied to a fabric, and then dried and heat treated.

[0004]

However, although the water-repellent processed fabric obtained by the above-mentioned conventional method has good water-repellent washing durability, it deteriorates in water-repellent performance due to abrasion during use. In particular, the decrease in wet wear is large, and ski wear, fishing wear, etc. are easily wet by snow, rain, etc., and there is a strong demand from consumers for improvement. The present invention has been made in view of the above circumstances, and an object thereof is to obtain a fiber cloth having good water repellency with good washing durability and abrasion durability.

[0005]

Means for Solving the Problems As a result of earnest studies for solving the above problems, the inventors of the present invention have excellent washing durability including a fluorine-based water repellent, a triazine compound, and a blocked isocyanate compound. The present inventors have found that the presence of a polyfluoroolefin typified by polytetrafluoroethylene in the water-repellent resin film can provide a water-repellent resin film having both washing durability and abrasion resistance, and have reached the present invention. did.

That is, according to the present invention, a perfluoroalkyl group-containing acrylate or methacrylate or a copolymer with a compound copolymerizable therewith, a triazine compound, a blocked isocyanate compound and a polyolefin has two fluorine atoms in its constituent unit. A water-repellent fiber cloth having excellent durability is characterized in that the constituent fibers of the cloth are covered with a resin film composed of a polymer containing the polyfluoroolefin contained above.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The term “fiber cloth” as used in the present invention means a general synthetic fiber such as a polyamide type, a polyester type, a polyacrylic type or a semi-synthetic fiber of a cellulosic type, a natural fiber such as cotton, silk or wool, or a woven fabric of a mixed fiber thereof, It means a sheet-like fiber structure such as a knitted fabric or a non-woven fabric.

The fiber cloth of the present invention is a copolymer of the constituent fibers of which has a perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable therewith,
It is covered with a resin film composed of a triazine compound, a blocked isocyanate compound, and a polymer composed of one or more polyfluoroolefins having two or more fluorine atoms in the constituent units of the polyolefin.

The term "perfluoroalkyl group-containing acrylate or methacrylate" as used herein is a compound represented by the following general formula (1), which imparts water repellency to fibers.

[0010]

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(Where R ₁ is hydrogen or a lower alkyl group, R _f is C _m F _{2m + 1} (where m is an integer of 2 to 21))
A group having a perfluoroalkyl group represented by the formula and containing at least one group selected from a hydroxyl group, an amino group and an unsaturated group, and n is an integer of 10 to 200. )

The compound copolymerizable with the compound represented by the general formula (1) includes vinyl compounds such as acrylic acid, methacrylic acid, styrene and vinyl chloride.

The amount of the fluorinated acrylate or methacrylate containing a perfluoroalkyl group or the copolymer with the compound copolymerizable therewith is preferably in the range of 1.0 to 6.0% by weight based on the weight of the cloth. . Here, the adhesion amount is 1.0
If it is less than wt%, it is difficult to obtain the durable water repellency targeted by the present invention, which is not preferable. On the other hand, if the amount exceeds 6.0% by weight, not only the durable water repellency intended in the present invention reaches saturation but also the feeling becomes hard, which is not preferable.

The triazine compound used in the present invention is a compound represented by the following general formula (2) of [Chemical Formula 2], and is used in combination with the above-mentioned perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable therewith. It improves the adhesion between the polymer and the fiber.

[0015]

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(However, R _{1 to} R ₆ are all -H,-
_{OH, -CH 2 OCH 3, -CH} 2 OC 2 H 5, -CH
₂ OH, -CH ₂ CH ₂ OH or -CH ₂ CH ₂ CH
₂ OH. )

Of the compounds represented by the above general formula (2), trimethylolmelamine, hexamethylolmelamine and the like are particularly preferably used.

The amount of such triazine compound deposited is
It is preferably in the range of 0.01 to 1.0% by weight based on the weight of the fabric. If the adhesion amount is less than 0.01% by weight, it is difficult to obtain the durability and water repellency intended in the present invention.
If the content exceeds 1.0% by weight, not only durability durable water repellency reaches saturation but also the feeling becomes hard, which is not preferable.

The blocked isocyanate compound used in the present invention may be any compound as long as it is a compound in which an isocyanate group is blocked with acetoxime, phenol, caprolactam, etc., and the block is removed by an appropriate heat treatment to show a free isocyanate group. It is intended to improve the strength of the water-repellent resin film by cross-linking copolymers with a perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable therewith or between the copolymer and a triazine compound.

The amount of the blocked isocyanate compound deposited is 0.01 to 1.0 based on the weight of the cloth.
Preferably it is in the range of weight%. If the amount of adhesion is less than 0.01% by weight, it is difficult to obtain the desired durable water repellency in the present invention. If the amount of adhesion exceeds 1.0% by weight, the durable water repellency not only reaches saturation, , This is not preferable because the hand becomes hard.

A copolymer composed of a polyfluoroolefin in which two or more fluorine atoms are contained in a constituent unit of a polyolefin is one having a general formula (3) represented by the following [Chemical Formula 3] as a constituent unit, and a fiber cloth. It reduces the friction coefficient of the surface of the resin coating that coats, and improves the water-repellent wear durability.

[0022]

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(However, at least one of R _{1 to} R ₃ is a fluorine atom, the others are a hydrogen atom, a halogen atom or a lower alkyl group, and n is an integer.)

The amount of the polymer composed of polyfluoroolefin having two or more fluorine atoms contained in the structural unit of such polyolefin is 0.1 to 1 with respect to the weight of the cloth.
It is preferably in the range of 0% by weight. Here the adhesion amount
If it is less than 0.1% by weight, it is difficult to obtain water repellency with abrasion resistance, and if the amount of adhesion exceeds 10% by weight, not only the coefficient of friction of the fabric surface reaches saturation, but also the water repellent resin It is not preferable because it lowers the strength of the coating and reduces the water-repellent washing durability and abrasion durability.

As a method for imparting these water-repellent resins to the fiber cloth, a copolymer of the above-mentioned perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable therewith, a triazine compound, a catalyst of a triazine compound, A blocked isocyanate compound, a catalyst of a blocked isocyanate compound, a polymer composed of polyfluoroolefin in which two or more fluorine atoms are contained in a constituent unit of polyolefin is used as a mixed treatment liquid such as an emulsion, an organic solvent solution, an aqueous solution, etc. It may be applied to the fiber cloth using a pad method, a spray method, or the like. The present invention has the above configuration.

[0026]

Like the durable water-repellent fiber cloth of the present invention, it has excellent washing durability including a copolymer with a perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable therewith, a triazine compound, and a blocked isocyanate compound. If a polymer made of polyfluoroolefin having two or more fluorine atoms in the polyolefin constitutional unit is present in the water-repellent resin film, the coefficient of friction of the surface of the water-repellent resin film is lowered. As compared to the coating alone, it will wear less during use, and as a result, it will be possible to prevent deterioration of water repellency and to obtain a highly durable water repellent fabric with excellent wash durability and abrasion resistance. I think it will be.

[0027]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples. The performance of fabrics in Examples was measured by the following method. (1) Water repellency JIS L-1092 (spray method) (2) Washing durability Sample before washing and JIS L-1027 (103 method)
The water repellency was measured and evaluated for a sample that was air-dried overnight after being washed 10 times.

(3) Friction coefficient A friction tester was used to attach a 15 cm × 15 cm sample to the inclined plate and a 6.4 cm × 18 cm sample to the sled, and the slant angle θ when the sled slid down to the position of the stopper was measured. The measurement was made in the vertical and horizontal directions of the fabric. The trigonometric function tan θ was calculated from the tilt angle θ.

(4) Abrasion resistance A sample was cut out into a circle with a diameter of 14.5 cm, and two pieces of filter paper of the same size were stacked and fastened at 8 diagonal points with a stapler. Attach it to the holder,
Next, a circular sample with a diameter of 9.8 cm was attached to the sample holder and abraded 700 times under a tensile load of 2.26 kg and a pressing load of 4.54 kg. At this time, 0.3 cc of water was applied to the sample surface on the sample holder side for a total of 7 times at the beginning of wear and every 100 times to wear, and then the sample on the side of the friction element holder was air-dried for 24 hours to evaluate the water repellency. .

Example 1 Polyester filament yarn 105 denier / 216 filaments (50 denier / 48 filaments and 55 denier / 168 filament starcle yarns) were used as warp and weft yarns, with a warp density of 164 yarns / inch and a weft yarn density of 86 yarns / inch. Weaving an inch twill weave, scouring and presetting it using a greige machine by the usual method, ForonNavy S-CT
L (Disperse Dye, manufactured by Sand Co.) was dyed with 4% owf to obtain a navy dyed polyester fiber cloth.

Next, the obtained polyester fiber cloth was dipped in a water repellent treatment solution of the following formulation 1, squeezed with a mangle at a squeezing ratio of 60%, and then dried at a temperature of 110 ° C. for 90 seconds. .

Formulation 1 Asahi Guard LS-317 6% by weight [corresponding to 3.6% by weight with respect to the weight of the fabric] (Meisei Chemical Industry Co., Ltd., organic fluorine-containing compound water and oil repellent) Sumitex Resin M- 3 0.3% by weight [equivalent to 0.18% by weight with respect to the weight of the fabric] (Sumitomo Chemical Co., Ltd., trimethylol melamine) Sumitex Accelerator ACX 0.3% by weight (Sumitomo Chemical Co., Ltd., Trimethylolmelamine catalyst) BP-10M 0.1% by weight [equivalent to 0.06% by weight with respect to the weight of the fabric] (Meisei Chemical Industry Co., Ltd., aliphatic blocked isocyanate) Pass Accel V-2 0.1 % By weight (Meisei Chemical Industry Co., Ltd., catalyst for aliphatic block isocyanate) FLUON AD-1 2.0% by weight [equivalent to 1.2% by weight based on the weight of the fabric] (Asahi ICIF Polytetrafluoroethylene emulsion manufactured by Loropolymers Co., Ltd.) Water 91.2% by weight

Thereafter, dry heat treatment was carried out in a tenter at a temperature of 180 ° C. for a treatment time of 40 seconds to obtain a durable polyester fabric having water repellency according to the present invention.

For comparison with the present invention, the composition of the water repellent treatment liquid in this embodiment is exactly the same as that of this embodiment except that the composition of Asahi Guard LS-317 is 6% by weight and the content of water is 94% by weight. A water repellent fabric for comparison (Comparative Example 1) was obtained by the method. For comparison with the present invention, a water-repellent fabric for comparison (Comparative Example 2) was prepared in the same manner as in this Example except that the addition of Fluon AD-1 to the water-repellent treatment liquid was omitted in this Example. ) Got.

Further, for comparison with the present invention, the concentration of Fluon AD-1 in the water repellent treatment solution in this example was 0.1.
A water repellent fabric for comparison (Comparative Example 3) was obtained by the same method as in this example except that the content was changed to wt% (corresponding to 0.06 wt% based on the fabric weight). In addition to the above comparative example,
Further, in this embodiment, Fluon AD- in the water repellent treatment liquid was used.
A water repellent fabric for comparison (Comparative Example 4) was obtained in the same manner as in this example except that the concentration of 1 was changed to 20% by weight (corresponding to 12% by weight based on the weight of the fabric).

The performances of the present invention and the comparative durable water-repellent fiber cloth obtained as described above were measured, and the results are shown in Table 1 together.

[0037]

[Table 1]

As is clear from Table 1, the durable water-repellent fiber fabric of the present invention was 90 points after 10 washes in the washing durability test, and 100 points after 700 abrasions in the abrasion durability test. It had durable water repellency.
Compared with the durable water repellent fiber fabric of the present invention, Comparative Examples 1 and 4
Was far lower in both washing durability and abrasion durability, and Comparative Examples 2 and 3 were much lower in abrasion durability.

[0039]

The durable water-repellent fiber cloth of the present invention has water repellency excellent in washing durability and abrasion durability. Due to its performance, the durable water-repellent fiber fabric of the present invention can be used for sports clothes such as windbreakers, ski wear, fishing wear, and mountain wear, which require a high degree of durable water repellency. Furthermore, it can also be used for casual clothing such as coats and blousons other than sports clothing.

Claims (1)

[Claims] 1. A perfluoroalkyl group-containing acrylate or methacrylate or a copolymer with a compound copolymerizable therewith, a triazine compound, a blocked isocyanate compound, and a polyolefin containing two or more fluorine atoms in its constituent unit. A water-repellent fiber cloth having excellent durability, characterized in that the constituent fibers of the cloth are coated with a resin film composed of a polymer composed of a fluoroolefin.