JPH08134780A - Method for water and oil repellent processing of wool fiber - Google Patents

Abstract

PURPOSE: To provide a method for water and oil repellent processing of wool fibers capable of imparting water and oil repelenting properties with excellent durabilities to the wool fibers without damaging the touch feeling of the natural wool. CONSTITUTION: This method for water and oil repellent processing of wool fibers comprises applying a polysiloxane-based resin emulsion to felt resistant wool fibers obtained by conducting an oxidation treatment of wool fibers by a chlorine or oxygen oxidation method to increase the adsorptivities of a silicone-based resin by a padding or dipping method, then immersing the fibers into a dispersed solution of a fluorine-based resin to exhaust the resin to the fibers and drying the fibers at approximately 150 deg.C. By this processing the effects are maintained after the repeated laundering and ironing treatments. A dimethylpolysiloxane and an amino-modified polysiloxane as the polysiloxane based resins and a polytetrafluoroethylene resin and a tetrafluoroethylene hexafluoropropylene copoymer resin as the fluorine-based resins can be cited.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a treatment method for imparting water and oil repellency excellent in durability to wool fibers, especially wool fibers having felt resistance.

[0002]

2. Description of the Related Art Conventionally, in order to impart water-repellent and oil-repellent performance to wool fibers and wool fiber products, a fluorine-based water- and oil-repellent agent is treated by a spraying method, a dipping method, a padding method or the like, and then heat treated It has been known. Generally, the above-mentioned fluorine-based water / oil repellent is a copolymer containing a perfluoromonomer as a main component, which is prepared by subjecting a compound having a perfluoroalkyl group and a hydroxyl group to an esterification reaction with acrylic acid, methacrylic acid, or the like. . As the copolymer component, a monomer such as alkyl (meth) acrylate or vinyl chloride or 2-hydroxyethyl methacrylate,
A crosslinkable monomer such as N-methylolacrylamide is used together (hereinafter, such a fluorine-based water / oil repellent agent is referred to as a fluorine-based resin).

However, the adhesion of the fluororesin to the wool fiber is poor, and in the spray method, it is necessary to increase the amount of adhesion in order to eliminate the untreated portion. Therefore,
This may cause processing problems such as perforation during knitting, or impair the original texture of wool.
Further, with the dipping method and the padding method, it is generally difficult to process only a cloth-like material, and there is a risk that processing spots such as dehydration spots occur.

An exhaust method has been proposed as a method for imparting water and oil repellency, but fluororesins generally have poor exhaust properties for wool fibers and their adhesion durability is not good. A method has been proposed in which a specific substance such as an acid or a salt is allowed to coexist with a fluororesin for the purpose of improving exhaustion (JP-A-61-680). Further, a method of utilizing an active isocyanate group or ethyleneimine for the purpose of improving adhesion durability has been proposed (JP-A-63-2).
35577, JP-A-3-220374).

As a method for imparting shrinkage resistance, generally, a chlorine oxidation method utilizing chlorine gas, sodium hypochlorite, sodium dichloroisocyanurate, etc., and oxygen utilizing potassium permanganate, persulfuric acid, potassium persulfate, etc. There is an oxidation method. However, all of these methods are accompanied by oxidative cleavage of the disulfide bond contained in the water-repellent epidermal tissue, and even lose the water repellency inherent in the wool fiber. Therefore, when the wool fiber that has been shrink-proofed by the oxidation method is subjected to the water and oil repellency treatment, not only a large amount of fluororesin is required, but also the durability of the water and oil repellency is low.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a method for imparting water and oil repellency to a wool fiber, particularly a wool fiber having a felt resistance, by using a fluororesin without impairing the original texture. To provide.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a water-repellent and oil-repellent finishing method for wool fibers, which comprises oxidizing a wool fiber, adding a polysiloxane resin, and then adding a fluorine resin. . To add fluorine resin to wool fiber, especially felt-resistant wool fiber to develop water- and oil-repellent performance and to add fluorine resin more uniformly and more durable, It is characterized in that a pretreatment for adding a polysiloxane resin is carried out in advance, and further an oxidation treatment is carried out before the polysiloxane treatment. As a result, it is possible to impart excellent water and oil repellency and its durability to an economical amount of fluororesin, and since the amount of fluororesin attached is small, the original texture of wool is sufficiently achieved. Can be held at.

In order to efficiently and surely apply the polysiloxane resin to the wool fiber, it is necessary to oxidize the wool fiber. Such oxidation treatment may be any of the methods conventionally used as a shrinkage prevention method, for example, chlorine gas, sodium hypochlorite, a chlorine oxidation method utilizing dichloroisocyanuric acid or a salt thereof, or potassium permanganate. An oxygen oxidation method using persulfate, potassium persulfate, or the like is used. The oxidation treatment is more specifically, for example, in the oxidation treatment using dichloroisocyanuric acid,
Dichloroisocyanuric acid or a salt thereof is allowed to act under an acidic condition and post-treated with acidic sodium sulfite. Further, in the oxidation treatment with potassium permanganate, potassium permanganate is allowed to act on the surface in an aqueous solution of a concentrated neutral salt (mainly Glauber's salt), and post-treatment with sodium acid sulfite is performed. . Alternatively, it can be carried out by treating the wool with monopersulfuric acid and also after-treating it with sodium acid sulfite.

The polysiloxane resin can be adsorbed and added to the oxidized wool fiber very well. The addition of the polysiloxane resin to the wool fiber can be performed by immersing the wool fiber in a solution, emulsion, or suspension of the polysiloxane resin by a method such as a padding method, a dipping method, or an exhaust method. As the dipping condition, when the padding method or the dipping method is used, the squeezing ratio and the solid content of the polysiloxane resin may be taken into consideration.
When the exhaust method is used, the polysiloxane solution concentration is 0.1.
It is general to carry out for 10 to 30 minutes under the conditions of 5% owf to 10% owf and temperature of 20 to 60 ° C.

The polysiloxane resin used in the present invention is not particularly limited, and dimethylpolysiloxane, amino-modified polysiloxane, which is commercially available as a softening agent,
Epoxy-modified polysiloxane, reactive polysiloxane, etc. can be used and can be widely selected according to the desired texture and application method. Examples of commercially available products include Silcoat EX-G and Silicon Softener N manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.
X-1, Nikka Silicon AMZ-produced by Nika Kagaku Co., Ltd.
3 or the like can be used. The adhesion amount of the polysiloxane resin is 0.1% owf to 4% owf in terms of solid content, and if it is less than 0.1% owf, the next step Exhaustion of the fluorinated resin is insufficient. By the above pretreatment operation, it becomes possible to efficiently exhaust the fluororesin on the wool fiber surface.

The exhaustion of the fluororesin is carried out by washing the wool fiber with water to remove the unbonded polysiloxane resin adhering to the surface, and then immersing it in a dispersion liquid of the fluororesin to exhaust the fluororesin. Can be made. The amount of the fluorine-based resin to be applied is 0.3% owf to 3% owf in terms of solid content, and below 0.3% owf, water and oil repellency is insufficient. On the other hand, it is meaningless to use 3% owf or more in view of performance and durability. Exhaust conditions are 40-100
When the temperature is 40 ° C. or less, exhaustion may be insufficient, while when the temperature is too high, dye transfer from the dyed product to the bath may occur. Therefore, the preferred exhaust condition is 5
It is 0 to 85 ° C.

The fluorine-based resin is not particularly limited, and means a synthetic polymer containing a fluorine atom in the molecule. Typical structures are polytetrafluoroethylene resin and tetrafluoroethylene- Examples include hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene-ethylene copolymer resin, polytrifluoroethylene chloride resin, polyvinylidene fluoride resin, and the like. Examples of commercially available products include Dickguard F-50 and F-7 manufactured by Dainippon Ink and Chemicals, Inc.
Sumitomo Chemical Co., Ltd. SUMIFLUOIL EM
-21, EM-22 and the like, Zonyl 6700 and Zonyl 7040 manufactured by Tefco Co., Ltd., Asahi Guard AG310, AG710, A manufactured by Asahi Glass Co., Ltd.
G770, AG780, AG800, Maruishi Yuka Kogyo Co., Ltd. Opel FM, KF-7, Tokai Oil Co., Ltd. TS Guard K-317, K-100, Sumitomo 3M Ltd. Made Scotch Guard FC-251,
FX-3582 or the like can be used.

The mechanism of exhaustion is within the speculation, but it is considered that exhaustion is carried out efficiently and uniformly by utilizing the dispersive force generated between the pretreated polysiloxane and the fluororesin. . Therefore, even if the polysiloxane resin and the fluororesin are mixed in advance and the exhaustion treatment is performed, the fluororesin is not exhausted to the wool fiber, and the water / oil repellency of the present invention is not exhibited. Further, the exhaustion of the fluororesin in the present invention is fairly strong, and the dropping out in the water system is extremely unlikely to occur. For example, once exhaustion is completed (even before drying and curing treatment), even if it undergoes a washing step in a dyeing machine (100 ° C.-20 minutes, surfactant concentration 2 g / liter), it is water and water repellent. It has no effect on oil performance.

Next, in order to make the adhesion of the fluororesin stronger, the wool fiber exhausted with the fluororesin is dried and cured at 130 to 180 ° C. for 5 to 30 minutes. However, the fibers turn yellow at high temperatures, so 150 ℃
Good to process at temperatures up to. In addition, the processing method of the present invention can be applied to any of wool raw cotton, top, yarn, and cloth, and the description of the wool fiber in the above description is representative of each of these forms of wool. I am just expressing it.

Hereinafter, the present invention will be described in more detail with reference to examples. Example 1 KROY UNSHRINK
ABLE WOOLSLIMITED TORONTO,
CANADA), a wool top having an average fineness of 21.4μ was continuously chlorinated at a chlorine gas concentration of 2.0% owf to obtain an oxidation-treated wool top. Next, the yarn is spun in the usual way to form a ridge-like knitting yarn (2/44; ply twist S350).
/ Undertwist Z500) was obtained. Next, dyeing was carried out with a dyeing machine to obtain a red dyed yarn. After soaping, 3% owf of polysiloxane resin, Silcoat EX-G (manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., solid content 30%) was added at a bath ratio of 1:10,
The temperature was raised from room temperature at 1 ° C./min and the heating state was maintained at 40 ° C. for 10 minutes. Fluorine resin OPEL F after liquid modification and water washing
5% of M (Maruryo Yuka Kogyo Co., Ltd .; solid content 18%)
owf, and heated from room temperature at 2 ℃ / min to 80 ℃
Was exhausted for 20 minutes. During this treatment, the light milky white bath became completely transparent, and the exhaustion of the fluororesin could be observed. After liquid modification and washing with water, 3% owf of a smoothing agent, Polymax YF (manufactured by Marubishi Yuka Kogyo Co., Ltd.) was added at 50 ° C
For 20 minutes. After finishing the above treatment, the yarn is taken out from the dyeing machine, centrifugally dehydrated, dried at 90 ° C., and then 1
Dry heat treatment was performed at 40 ° C. for 20 minutes.

FIG. 1 shows a scanning electron micrograph of the surface condition of the monofilaments constituting this yarn. It is clear that the surface of the wool fiber is extremely uniformly covered with the resin used, as can be seen by comparing it with the surface state of the untreated wool top monofilament before processing of the present invention (FIG. 2). . Using this thread, a gauge 12 sweater (tenjiku) was knitted. The knitted fabric was evaluated using this sweater.
The water / oil repellency is shown in Table 1, and the shrinkage of the sweater is shown in Table 2. It has better water / oil repellency as compared with the following comparative examples, and it can be seen that there is no problem with respect to shrink resistance.

Comparative Example 1 A wool top of the same type as in Example 1 was subjected to chlorine treatment in the same manner as in Example 1, but a wool treating agent (polyamide resin) WT-570 (Japan PMC Co., Ltd.) was used during the process. 1.5% owf in terms of solid content was applied to obtain a shrink-resistant wool top. Further, from this top, the knit shrink-proof raw yarn (2/44; upper twist S350 / lower twist Z500) was carried out in the same manner as in Example 1.
Was obtained in the form of a strip. Then, a red sweater was obtained by the same steps as in Example 1 except that the exhaust treatment with the polysiloxane resin and the fluorine resin was not performed. Similar to Example 1, this knitted fabric was evaluated for water / oil repellency and shrinkage, and the results are shown in Table 1 and Table 2, respectively.

Comparative Example 2 A red sweater was obtained by the same process as in Example 1 except that the same knitting yarn as in Example 1 was used and no polysiloxane resin was used. Similar to Example 1, this knitted fabric was evaluated for water / oil repellency and shrinkage, and the results are shown in Table 1 and Table 2, respectively. It can be seen that the sweater of Comparative Example 2 does not have a water / oil repellency function, and the shrinkage is larger than that of Example 1.

[0019]

[Table 1]

[0020]

[Table 2]

Comparative Example 3 Processing was carried out in the same manner as in Example 1 except that the oxidation treatment was not carried out, and the water / oil repellency and shrinkage were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2. It can be seen from Table 1 that the oil repellency after 5 washes is slightly lower than that of Example 1. The knitted fabric after 5 times of washing is felt, and the area is about 30.
It was shrinking. Further, it can be seen from the felt shrinkage data in Table 2 that it does not have felt resistance.

Example 2 A white sweater was obtained in the same manner as in Example 1 except that dyeing was not performed in order to confirm the durability of practical stain resistance. After washing and ironing this under various conditions,
The water and oil repellency performance and the practical stain resistance were tested. Table 3 shows the results.

Comparative Example 4 A white sweater was obtained in the same manner as in Comparative Example 1 except that dyeing was not carried out. The results of the practical stain resistance test are shown in Table 4.

[0024]

[Table 3]

[0025]

[Table 4]

The washing-ironing treatment shown in Tables 3 and 4 was carried out according to the following standards. Initial: Untreated HL5: JIS L0217 104 method (use of neutral detergent) Line dry 5 times repeated HL5 A: JIS L0217 104 method (use of neutral detergent) Line dry 5 times repeated JIS L0217 302 method (medium temperature) Ironed HL5 soft : JIS L0217 104 method (using neutral detergent) line drying 5 times, softener (Soflan S) used HL5 soft ： JIS L0217 104 method (neutral detergent) line drying 5 times, softener (Soflan S) Use JIS L0217 302 method (medium temperature) Ironing HL10: JIS L0217 104 method (using neutral detergent) Line drying 10 times repeated HL10 a: JIS L0217 104 method (using neutral detergent) Line drying 10 times JIS L0217 302 method ( Medium temperature) Ironing treatment DC (PA) 5: Commercial dry cleaning (perchlorethylene) repeated 5 times DC (PA) 5A: Commercial dry cleaning (perchlorethylene) repeated 5 times, JIS L0217 302 method (medium temperature) Ironing treatment DC (stone) 5: Commercial dry cleaning (petroleum) Repeat 5 times DC (stone) 5 a: Commercial dry cleaning (petroleum) After repeating 5 times, JIS L0217 302 method (medium temperature) ironing treatment

[0027]

EFFECT OF THE INVENTION The water- and oil-repellent treated wool fiber of the present invention is imparted with a good water- and oil-repellent property, maintains its effect after repeated washing-ironing, and has a natural texture of wool. Was holding.

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph showing the shape of a water- and oil-repellent wool fiber of the present invention.

FIG. 2 is a scanning electron micrograph showing the shape of an untreated wool top before processing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // D06M 101: 12

Claims (3)

[Claims] 1. A water-repellent and oil-repellent finishing method for wool fibers, which comprises adding a polysiloxane resin after oxidizing the wool fibers, and then adding a fluorine resin. 2. The water- and oil-repellent finishing method for wool fibers according to claim 1, wherein the wool fibers are wool fibers having felt resistance. 3. The method for processing water and oil repellency of a wool fiber according to claim 1, wherein the oxidation treatment is a chlorine oxidation method or an oxygen oxidation method.