JPH0512469B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for imparting durable water repellency to a polyamide fiber structure. [Prior Art] Conventionally, various measures have been proposed for improving the durability of water repellency, especially washing resistance, in water repellent finishing using fluorine-based water repellents. For example, modified amide derivatives, modified imide derivatives,
It is known that an ethylene urea imide adduct or the like is included in a fluorine-based water repellent processing solution and used in combination. Although this method certainly improves durability,
There was a problem that the durability was still insufficient and that it was difficult to obtain a stable product due to variations in durability. Japanese Patent Publication No. 60-36512 states that 50% synthetic fiber
The first step is to apply an emulsion containing a fluorine-based water repellent to the fabric containing the above, dry it, and if necessary heat treat it, followed by a solvent containing a silicone-based water repellent alone or a mixture with a fluorine-based water repellent. A durable water repellent finishing method is described, which is characterized by comprising a second step of applying a solution, drying, and heat-treating. However, even with this method, the durability is still insufficient and has large variations. Also,
The process is complicated because both an aqueous system and a solvent system are used. [Problems to be Solved by the Invention] In view of the problems of the prior art as described above, the present invention provides a fiber structure with water repellency that has a high level of stable durability without variation, and improves the texture. The purpose is to provide a processing method that does not cause damage and is easy to implement. [Means for Solving the Problems] The object of the present invention is to provide a method for water-repelling a fiber structure containing polyamide fibers by applying a treatment liquid containing a fluorine-based water repellent and an aminoplast resin. This is achieved by a method characterized in that a sulfonated phenol formaldehyde low condensate is applied to the fiber structure before the heat treatment. Suitable sulfonated phenol formaldehyde low condensates include, for example, the formula () A-CH ₂ -(B) _o -C () [Here, A and C may be the same or different, and each independently

【formula】

[Formula] and

【formula】 B is a group selected from

【formula】

【formula】

[Formula] and

[Formula], n is a number from 1 to 5, M is H,
NH ₄ , Na or K] or the formula () X-Y-Z () [where X is

【formula】

[Formula] and Y is a group selected from -CH ₂ -,

[Formula] and -SO ₂ -, Z is a group selected from

【formula】

【formula】 as well as

〔Effect of the invention〕

According to the present invention, by applying a sulfonated phenol formaldehyde low condensate to the fibers before treatment with a water repellent, the durability of the water repellent performance is significantly improved. The reason for this is presumed as follows. Synthetic fibers, especially nylon fibers, expand and contract due to repeated water absorption and drying every time they are washed. On the other hand, a thin layer of fluorine-based water repellent does not absorb water and does not expand or contract during washing.
Because of this difference in expansion and contraction behavior, delamination eventually occurs between the nylon fiber surface and the thin layer of water repellent during repeated washing, resulting in loss of water repellency. However, the sulfonated phenol formaldehyde low condensate used in the present invention is thought to act to block the hydrophilic groups of the fibers and make the fibers themselves hydrophobic. When the fiber is polyamide, it is thought that the sulfone group is bound to the amide group or amide group of the polyamide. Regardless of the validity of the above estimation, it is unexpected that the durability of water repellency is significantly improved by the present invention. The invention will be further explained below by means of examples. Examples The test methods used in the examples are as follows. Washing resistance JIS L-0217 103 method Water repellency JIS L-1092 (spray method) The sulfonated phenol formaldehyde low condensates according to the present invention used in the examples are as follows. The above compounds A to D are represented by the formula (),
Compounds F to G are compounds represented by formula (). Examples 1 to 6 and Comparative Example 1 Using 100 parts by weight of each taffeta fabric using nylon filament with warp 75d/400f and weft 140d/36f as a sample, which was scoured, preset, and dyed using a conventional method, the following treatment was performed. I put it in the liquid. Compounds A to F 0.2 parts by weight Water 2000 parts by weight (bath ratio 1:20) After immersing the cloth at 60°C for 30 minutes while moving it, it was washed with water, dehydrated, and dried at 120°C. Each of the fabrics subjected to the above treatment and the fabric not subjected to the above treatment as Comparative Example 1 were soaked in a water repellent solution with the following formulation, squeezed to a squeezing rate of 35%, and dried at 120°C.
Heat treatment was performed at 160°C for 90 seconds. Asahi Guard AG-710 (trademark, water repellent, Asahi Glass Co., Ltd.) 5 parts by weight Bethukamine APM (trademark, melamine-based aminoplast resin, Dainippon Ink Co., Ltd.) 0.3 parts by weight Catalyst cat-376 (the above catalyst) 0.3 parts by weight SK-conc (trademark, water repellent, softening agent,
Dainippon Ink Co., Ltd.) 0.5 parts by weight Catalyst SC-100 (above catalyst) 0.5 parts by weight Each of the obtained fabrics was tested for durability of water repellency. The results are shown in Table 1.

[Table] Examples 7 to 12 and Comparative Example 2 Nylon filament with warp 75d/400f, weft
Taffeta using No. 60/single yarn was scoured and preset using conventional methods, and cotton side dyeing and nylon side dyeing were performed. Using 100 parts by weight of each of the obtained cloths as a sample,
Compounds A to F were treated in the same manner as in Examples 1 to 6. Next, each of the fabrics subjected to the above treatment and the fabric not subjected to the above treatment as Comparative Example 2 were soaked in a water repellent solution with the following formulation, squeezed to a squeezing rate of 45%, dried at 120℃, and then heated to 160℃. Heat treated for 90 seconds. Zircocet CA-15 (trademark, water repellent, Shichifuku Chemical Co., Ltd.) 5 parts by weight Betsukamine APM 0.3 parts by weight Catalyst cat-376 0.3 parts by weight Deck Silicone SK-conc 0.5 parts by weight Catalyst SC-100 0.5 parts by weight The durability of water repellency was tested for each. The results are shown in Table 2.

[Table] From the above test results, it is clear that the durability of water repellency was surprisingly improved by the method of the present invention.

Claims (1)

[Scope of Claims] 1. A method for water-repelling a fiber structure containing polyamide fibers, in which a treatment liquid containing a fluorine-based water repellent and an aminoplast resin is applied and a sulfonated phenol formaldehyde resin is applied before heat treatment. A method characterized in that a condensate is applied to a fibrous structure. 2 The sulfonated phenol formaldehyde low condensate has the formula () A-CH ₂ -(B) _o -C () [Here, A and C may be the same or different, and each independently [Formula] is a group selected from [Formula] and [Formula], B is selected from [Formula] [Formula] [Formula] and [Formula], n is a number from 1 to 5, and M is H ,
NH ₄ , Na or K] or the formula () X-Y-Z () [where X is [Formula] [Formula] and Y is a group selected from -CH ₂ -, [Formula] and -SO ₂ -, Z is a group selected from [Formula] is a group selected from [Formula] and [Formula], and M is H, NH ₄ , Na or K]. 3. In an aqueous bath containing 0.05% by weight or more of a sulfonated phenol formaldehyde low condensate based on the fiber structure, at a bath ratio of 1:20 to 1:50 and at a temperature of 40 to 80°, 10
3. The method of claim 1 or 2, wherein the sulfonated phenol formaldehyde low condensate is applied by treating the fiber structure for ~60 minutes. 4. The method according to any one of claims 1 to 3, wherein the fibrous structure contains polyamide. 5. The method according to any one of claims 1 to 4, wherein the fluorine-based water repellent contains a perfluoroalkyl group or a perfluoroalkylsulfamide group. 6. The method according to any one of claims 1 to 5, wherein the aminoplast resin is a melamine-based, urea-based, or uron-based resin.