JPH1060777A - Water and oil repellent animal hair fibrous structure having antistatic and antifouling property and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water and oil repellent animal hair fibrous structure, having a low friction electrostatic charge voltage and antistatic and antifouling properties excellent in durability even in the absence of an antistatic agent by composing a fibrous structure of an animal hair fiber coated with a fluorine-containing resin film. SOLUTION: This water and oil repellent animal hair fibrous structure is obtained by applying a polyfunctional compound such as a polyhydric phenol-formalin condensate to an animal hair fibrous structure such as a plain weave woolen fabric, bonding the polyfunctional compound to the interior and/or the surface of the wool fiber and then coating the outermost surface layer of the wool fiber with a fluorine-containing compound such as a perfluoroalkyl group-containing acrylic copolymer and/or a reactional product of a fluorine-containing compound with an isocyanate cross-linking compound. The resultant antistatic and antifouling water and oil repellent fibrous structure having a withstand voltage T V (JISL1094, 1992 B method) satisfying the relationship of T<=2(700-W)/F W is the METSUKE g/m<2> (mass per unit area), W<=450; F is the content of fluorine % on the surface of the structure [measured by an X-ray photoelectron analysis (ESCA)]} and the >=90 scores water repellency even after pressing after the wearing test (JIS L1096, 1992 E method) of 10,000 friction times.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an animal hair fiber structure having antistatic properties and antifouling properties, and more particularly to antistatic antifouling properties and water repellency against washing and dry cleaning, and furthermore, wear and friction when worn. The present invention relates to a water- and oil-repellent animal hair fiber structure having improved oil-repellency durability.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting a high water-repellent and oil-repellent performance to a fiber structure such as animal hair fiber cloth, a water-repellent and oil-repellent finishing agent made of a fluorine compound is applied to the fiber structure and then heat-treated. A method of attaching a water / oil repellent is generally used.
However, these processing agents are brittle and have poor adhesion to animal hair fibers, so they can be washed and dry-cleaned,
Further, there has been a problem that the processing agent easily falls off from the fibers due to friction or wear between the cloths and the cloth and other objects when worn, and the water / oil repellency is greatly reduced. Further, in general, a fabric subjected to a water / oil repellent treatment has a high charged voltage, generates a large amount of static electricity during a manufacturing process, and becomes difficult to pass through the process. The problem that it becomes easy to carry out has arisen.

[0003] With respect to water repellency, animal hair fibers such as wool have poor adhesion to a water-repellent and oil-repellent agent and do not have sufficient durability. The following proposals have been made to improve this. That is, a method of mixing a blocked isocyanate-based cross-linking agent with a fluorine-based water- and oil-repellent finishing agent containing an active hydrogen group (JP-A-54-133486) to form a base layer of a blocked isocyanate-based compound on the fiber surface To improve the adhesiveness of a fluorine-based water- and oil-repellent finishing agent (Japanese Patent Application Laid-Open No. 54-139641). A method of treating with a processing agent (JP-A-60-151380), a method of copolymerizing a fluorine-containing acrylic monomer on the fiber surface (JP-B-63-14117), and the like can be mentioned. However, any of these methods is insufficient in water repellency durability. In particular, washing of a fiber structure containing animal hair fibers such as wool is basically performed by dry cleaning, but the performance is remarkably deteriorated by repeated dry cleaning, and the dry cleaning durability is poor.

With respect to the antistatic property, a method of mixing an antistatic agent such as an ionic surfactant into a processing bath has been used. However, this antistatic agent easily falls off during a step such as washing. It is temporary and not durable. Further, if a surfactant such as an antistatic agent remains on the fiber surface, the water / oil repellency is impaired.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of such circumstances, and has high durability and control over animal hair fibers such as wool, which cannot be obtained by the prior art. An object of the present invention is to provide a water-repellent and oil-repellent fiber structure having electric conductivity and antifouling property.

The inventors of the present invention have conducted intensive studies on the causes of a decrease in water repellency due to dry cleaning, washing and friction of animal hair fiber cloth such as wool which has been subjected to a water repellent treatment with a fluorine-based water / oil repellent. The water- and oil-repellent finishing agent is difficult to coat the fiber surface evenly on animal hair fibers such as wool, and the binding between animal hair fiber such as wool and the water- and oil-repellent finishing agent is weak, so dry cleaning, washing and wearing The main cause was that the water-repellent agent dropped off due to abrasion and friction in the medium.

[0007] From the above, the present inventors have found that in order to dramatically improve the water and oil repellency durability of animal hair fiber structures such as wool, it is possible to uniformly coat animal hair fibers and dry clean them. The present invention was deemed necessary to have flexibility enough to withstand rubbing, washing, abrasion, and friction, and to improve the bonding strength with animal hair fibers.

In general, a cloth subjected to a water / oil repellent treatment has a high charged voltage, easily generates static electricity during the manufacturing process, and causes trouble during the manufacturing process. In addition, when it becomes a product, dust easily adheres due to static electricity,
The value as a product decreases. As a countermeasure, a method of adding an antistatic agent such as an ionic surfactant to a processing bath to impart the antistatic agent has been performed. It easily falls off in the process of washing, etc., and has no durability. On the other hand, when an antistatic agent coexists, it is difficult to exhibit a high degree of water / oil repellency, and it is desired to achieve both antistatic properties and water / oil repellency.

[0009]

That is, the present invention relates to an animal hair fiber structure having animal hair fibers in which at least the surface of the animal hair fibers is coated with a fluorine-containing film, wherein the animal hair fibers have no antistatic agent. In JIS L1094-1992 B
Voltage T (volt) in a 20 ° C., 40% RH environment according to the method satisfies the relationship of the following formula (1), and JIS L1
Water-repellent and oil-repellent animal hair fiber structure having antistatic and antifouling properties, wherein the water repellency after 10,000 times of abrasion by E method (Martindale method) of 096-1992 shows 90 points or more after pressing. Stuff. T ≦ 2 (700−W) / F (1) W: Textile weight of fiber structure (g / m ² ), W ≦ 450 F: Carbon on animal hair fiber structure surface by X-ray photoelectron analyzer (ESCA) The amount of fluorine (%) when analyzing fluorine, oxygen, nitrogen and sulfur, and the inside or / and the surface of the animal hair fiber of the fiber structure containing the animal hair fiber, chemically or physically After bonding a polyfunctional compound having two or more bondable functional groups, the outermost layer surface of the animal hair fiber is mainly treated with a fluorine-containing compound or / and a reactant with a crosslinkable compound capable of reacting with the fluorine-containing compound. A method for producing a water / oil repellent fibrous structure having antistatic and antifouling properties, characterized by being coated.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The animal hair fiber in the present invention means a natural keratinous fiber obtained from animals such as wool, camel, goat, rabbit and the like, and also includes a descaled one thereof. The animal hair fiber structure means a woven fabric, a knitted fabric, a nonwoven fabric, a thread, or the like obtained by using animal hair fibers alone or by mixing animal hair fibers with other fibers. Other fibers other than animal hair fibers used here mixed include synthetic fibers such as polyester, acrylic, nylon, aramid, vinyl chloride, silk, cotton,
Natural fibers such as hemp and regenerated fibers such as rayon. In order to further exert the effects of the present invention, the mixing ratio of animal hair fibers is preferably 20% or more, and in order to exhibit the properties of animal hair fibers, it is 40% or more, and more preferably 50% or more.

The fluorine-containing film in the present invention is a film formed of a fluorine-containing compound, a fluorine-containing compound and a crosslinkable compound, and a polyfunctional compound having a functional group binding to animal hair fibers. The film is chemically or physically bonded to animal hair fibers.

The thickness of the film containing fluorine is not particularly limited, but is preferably 0.01 to 10 μm from the viewpoint of durability and feeling.
Is preferably, and more preferably 0.1 to 3 μm.

In the present invention, the film containing fluorine is:
Usually, it covers the surface of animal hair monofilament with a scale, and it is characterized by embedding especially the gaps and grooves of the scale.However, the component constituting the film containing fluorine is the animal hair fiber. There is no problem even if it gets inside,
In this case, the durability may be further improved by the anchor effect.

In addition to the fluorine-containing compound, the fluorine-containing film may be a cross-linkable compound capable of reacting with both the fluorine-containing compound and the animal hair fiber. Examples include polyfunctional compounds having a functional group to be bonded, in which a film is formed by a fluorine-containing compound and a reaction product of these compounds, and the film is chemically or physically strongly bonded to animal hair fibers. .

As the fluorine-containing compound, a general fluorine-based water / oil repellent such as an acrylic copolymer containing a perfluoroalkyl group can be used. Among these, those having a functional group such as a hydroxyl group, a carboxyl group, or a glycidyl group that reacts with the crosslinkable compound are preferable because durability is further improved.

The crosslinkable compound is a compound having two or more functional groups capable of reacting with animal hair fiber and a fluorine-containing compound, and specific examples thereof include isocyanate compounds, epoxy compounds, and aminoformaldehyde resins. However, isocyanate compounds are preferred because they can easily exhibit durability and do not impair the feeling.

The polyfunctional compound having a functional group that chemically or physically binds to animal hair fibers is a compound having a functional group such as a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, a halogen group, and a vinyl group. Specific examples thereof include a polyhydric phenol compound and a formaldehyde condensate thereof.

In the present invention, in order to further improve durability, it is preferable to use a penetrant in combination. The penetrant may be any penetrant that can well wet the animal hair fiber surface, but is preferably a compound having an ether group, an ester group or a hydroxyl group in the molecule, such as a monoalkyl etherified product of alkylene glycol or monoalkyl ether. Alkyl ester compounds and the like can be mentioned.

The method for forming the fluorine-containing film or reactant according to the present invention on the surface of animal hair fibers or in the gaps between the scales is not particularly limited, and a general method of processing animal hair fibers may be employed. For example, a method in which an aqueous processing liquid containing the above-mentioned components is padded on animal hair fibers, dried and cured can be employed. In the present invention, it is preferable from the viewpoint of durability to pre-treat animal hair fibers with a polyfunctional compound that physically or chemically binds to the animal hair fibers.

The animal hair fibrous structure coated with a fluorine-containing film according to the present invention is free from an antistatic agent and is coated with a hydrophobic film mainly composed of a fluorine compound. Regardless, the charged voltage due to friction does not increase, but rather the charged voltage can be made lower than that of unprocessed animal hair fiber, thereby exhibiting antistatic properties. This is based on the method B of JIS L1094-1992.
It is apparent from the fact that the charged voltage T (volt) under an environment of 40 ° C. and 40% RH satisfies the relationship of the following equation (1). T ≦ 2 (700−W) / F (1) W: Animal hair fiber structure weight (g / m ² ), provided that W ≦ 45
0F: The amount of fluorine (%) when carbon, fluorine, oxygen, nitrogen, and sulfur on the surface of the animal hair fiber structure were analyzed by an X-ray photoelectron analyzer (ESCA).

The animal hair fiber structure of the present invention is
Even after the abrasion test by the E method (Mandale method) of IS L1096-1992, there is almost no decrease in water repellency, and even if the number of wears is 10,000 or more, the water repellency shows 90 points or more by press treatment. 20,000 wear
It has durability enough to show 90 points or more even after 0 times.

The pressing is performed according to JIS L1042-19.
Press treatment by the H-4 method of No. 92 is preferable, but it is possible to develop substantially the same water repellency even under the condition of ironing wool with a household iron.

The reason why the animal hair fiber structure of the present invention exhibits durable antistatic properties and water / oil repellency is that the fluorine-containing film causes an excessive reaction between the fluorine-containing compound and the crosslinkable compound. Therefore, it is considered that the compound retains flexibility and efficiently participates in the bond between the animal hair fiber and the fluorine-containing compound. It is also considered that the reactant forming the film enters the gaps between the animal hair fibers and more effectively covers the scale, which contributes to the durability.

Since the film has flexibility, the film is prevented from falling off even by abrasion test or washing, and even if it comes off by washing or the like, the film is re-attached (bonded) to the animal hair fiber by pressing, so that the film is durable. It is considered that the antistatic antifouling property, water repellency and oil repellency can be maintained.

【Example】

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. Processing agents of Examples 1 and 2 (A) Fluorine-containing compound Perfluorooctyl ethyl acrylate component: 75 parts by weight, stearyl acrylate component: 10% by weight, n-methylol acrylamide component: 8% by weight, glycidyl methacrylate component: 7% by weight A fluoroalkyl group-containing copolymer (active ingredient 18%, hereinafter abbreviated as FWP1).

(B) Crosslinking Agent A blocked isocyanate crosslinking agent obtained by adding 3 mol of diphenylmethane diisocyanate to trimethylolpropane, and then dispersing in water water a blocked dosocyanate compound in which the remaining 3 mol of isocyanate groups are blocked with methyl ethyl ketoxime. (Active ingredient 30%, dispersed particle size 0.5 μm, hereinafter abbreviated as BNCO). (C) Penetrant propylene glycol monomethyl ether (abbreviated as PME).

Examples 1 and 2 Wool fabrics of plain weave (2/60 × 2/60, unit weight of 234 g / m ² ) and twill weave (2/60 × / 60, unit weight of 358 g / m ² ) are shown below. Fluorine-containing compounds and crosslinking agents,
Pad treatment with a processing agent bath composed of a penetrant (squeezing rate: 60
%), Dried at 110 ° C. for 2 minutes, and cured at 160 ° C. for 2 minutes. (Example 1 processing agent formulation) FWP1: 7 parts BNCO: 2 parts PGE: 4 parts Deionized water: 87 parts

Example 2 The same wool fabric as in Example 1 was used at 60 ° C. and 2 g / l of a sulfonate of polyhydric phenol / formalin polycondensate.
After pretreatment for 0 minutes, washing with water, drying, and pad treatment (squeezing rate: 60%) with a processing agent bath comprising the same fluorine-containing compound, cross-linking agent and penetrating agent as in Example 1, then 110
After drying at ℃ for 2 minutes, a curing treatment was performed at 160 ° C for 2 minutes.

Processing agent of comparative example (D) Fluorinated water / oil repellent processing agent Perfluorooctyl ethyl acrylate 80% by weight, 2
-Ethylhexyl methacrylate 8% by weight, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid 7
Perfluoroalkyl group-containing copolymer (hereinafter abbreviated as FWP2) consisting of 5% by weight of methyl methacrylate and 5% by weight of methyl methacrylate.

(E) Crosslinking Agent (E-1) Crosslinking Agent 1 Crosslinking Agent BNCO (E-2) Crosslinking Agent 2 Trimethylolmelamine: Sumitex Resin M-3 (hereinafter TMM) manufactured by Sumitomo Chemical Co., Ltd. Abbreviated).

(F) Catalyst Organic amine hydrochloride: Sumitex Accelerator ACX (hereinafter abbreviated as SA) manufactured by Sumitomo Chemical Co., Ltd.

(G) Penetrant isopropyl alcohol (hereinafter abbreviated as IPA) (H) Antistatic agent Derektor LKM-3 (cationic compound manufactured by Meisei Chemical Industry Co., Ltd .; hereinafter abbreviated as AS). (I) Epoxy resin glycerol polyglycidyl ether; Denacol EX313 (hereinafter abbreviated as GPE) manufactured by Nagase Kasei Kogyo Co., Ltd.

COMPARATIVE EXAMPLE The same wool fabric as in Examples 1 and 2 was subjected to pad treatment (squeezing rate: 60%) using the following water- and oil-repellent treatment formula, dried at 110 ° C. for 2 minutes, and then dried at 160 ° C. A curing treatment was performed for 2 minutes.

Comparative Example 1 (Processing agent formulation of Comparative Example 1) FWP2: 6 parts BNCO: 1 part IPA: 3 parts Ion-exchanged water: 90 parts

Comparative Example 2 (Processing agent formulation of Comparative Example 2) FWP2: 6 parts BNCO: 1 part IPA: 3 parts AS: 2 parts Ion-exchanged water: 88 parts

Comparative Example 3 (Processing agent formulation of Comparative Example 3) FWP2: 6 parts BNCO: 1 part TMM: 1 part SA: 0.4 part IPA: 3 parts AS: 2 parts Ion-exchanged water: 86.6 parts

Comparative Example 4 As a pretreatment, a wool fabric was padded with a 5% GPE solution (squeezing rate: 60%), and dried at 110 ° C. for 2 minutes.
Curing treatment is performed at 160 ° C. for 2 minutes, followed by pad treatment (squeezing rate: 60%) using the following water- and oil-repellent treatment formula, followed by drying at 110 ° C. for 2 minutes and curing treatment at 160 ° C. for 2 minutes. Was. (Processing agent formulation of Comparative Example 4) FWP2: 6 parts BNCO: 1 part IPA: 3 parts AS: 2 parts Ion-exchanged water: 88 parts

JIS Dry Cleaning Test Method After the dry cleaning process is repeated three times in accordance with the dry cleaning process of JIS L1092-1992, tumble drying is performed at 60 ° C. for 30 minutes, and JDC3
And What was repeated 6 times was designated as JDC6.

Commercial dry cleaning test method A normal dry cleaning was requested at a commercial dry cleaning shop in the market, and a commercial dry cleaning test was performed.
The treatment conditions are as follows:
Then, for main washing, treatment was performed for 5 minutes in a 25 ° C. perclene solution containing 0.3% by volume of a cationic soaping agent, followed by dewatering, followed by tumble drying at 60 ° C. for 15 minutes. This was defined as one cycle, and SDC3 was repeated three times, and SDC6 was repeated six times.

Evaluation method for water repellency: A spray test according to JIS L1092-1992
Initial and JDC 3 and 6 and S of work cloths of Examples and Comparative Examples
The water repellency of DCs 3 and 6 was evaluated. The evaluation of water repellency was performed based on Table 1.

[0041]

[Table 1]

Oil repellency evaluation method The oil repellency of Examples 1-2 and Comparative Examples 1-4 was compared by the AATCC-118 method.

Test Method for Film Flexibility of Fluorine-Containing Compound The working fluids of Examples 1-2 and Comparative Examples 1-4 were applied on a polyethylene film, dried at 110 ° C. for 2 minutes, and then cured at 160 ° C. for 2 minutes. Then, a film of a fluorine-containing compound having a thickness of about 0.1 mm was formed, and the flexibility was compared.
In addition, each processing liquid used the mixed liquid except pure water from the processing prescription.

Evaluation method of antistatic property According to the method B of JIS L1094-1992, at 20 ° C.
Under a 40% RH environment, the initial charged voltages of the unprocessed cloth, the working cloths of Examples 1 and 2, and the comparative examples 1 to 4 were measured and compared.

Abrasion and friction durability evaluation method The processed cloth after water / oil repellency processing of Examples and Comparative Examples was evaluated according to the E method (Martindale method) of JIS L1096-1992. 000, 2
After 000 times of wear, the water repellency was evaluated, and the wear and friction durability were compared. Furthermore, JIS L after wear
Press treatment was performed according to the H-4 method of 1042-1992 to evaluate water repellency.

Tables 2 and 3 show the water repellency of Examples 1 and 2 and Comparative Examples 1 to 4 at the beginning and after dry cleaning. Thus, it can be seen that the water repellent durability of Examples 1 and 2 of the present invention is significantly improved in both JIS dry cleaning and commercial dry cleaning as compared with Comparative Examples 1 to 4.

[0047]

[Table 2]

[0048]

[Table 3]

Table 4 shows Examples 1 and 2 and Comparative Examples 1 to
4 shows oil repellency. As a result, those according to Examples 1 and 2 of the present invention show excellent durability and oil repellency as compared with the comparative example.

[0050]

[Table 4]

Table 5 shows Examples 1 and 2 and Comparative Examples 1 to
4 shows a film forming property. This indicates that the films according to Examples 1 and 2 of the present invention are superior to the comparative example in the flexibility of the formed film.

The film-forming properties of the fluorine-containing compound were evaluated by observing the state of the formed film, and evaluated by ○: a film having flexibility and smoothness, ×: a film having a hard and cracked film.

[Table 5]

Table 6 shows Examples 1 and 2 and Comparative Examples 1 to
4 shows a charged voltage of 4. As a result, it can be seen that in Examples 1 and 2 of the present invention, the charged voltage after processing was suppressed to be lower than that in the comparative example, and was lower than that of the cloth before processing.

[0054]

[Table 6]

Table 7 shows the ESCA of Examples 1 and 2.
(X-ray photoelectron analyzer ESCA-850 manufactured by Shimadzu Corporation
The amount of fluorine (%) on the surface of the animal hair fiber was determined by using the formula (1), and the relationship with the charged voltage was examined by the above equation (1). Here, the fluorine amount (%) is the fluorine content (%) when carbon, fluorine, oxygen, nitrogen, and sulfur on the surface of the processed fabric are analyzed by ESCA. As a result, in the case of Comparative Examples 1 to 4, while Expression (1) was not satisfied and the charged voltage was high,
In the case of Examples 1 and 2, it can be seen that Expression (1) is satisfied.

[0056]

[Table 7]

Tables 8 and 9 show the wear and friction durability of Examples 1 and 2 and Comparative Examples 1 to 4. Thus, it can be seen that the samples according to Examples 1 and 2 of the present invention have much better wear and friction durability than the comparative example. In particular, in Examples 1 and 2, even after 20,000 wears, 100 points are obtained after the press treatment.

[0058]

[Table 8]

[0059]

[Table 9]

[0060]

According to the animal hair fiber structure of the present invention, since each of the single fibers of animal hair fibers is coated with a film containing fluorine, it can be controlled without using a normal antistatic agent. Both electrical and water / oil repellency can be achieved, and the durability against dry cleaning, washing, wear and abrasion, etc. is remarkably superior to conventional water repellent and oil repellent fiber structures of animal hair fibers. .

Claims (2)

[Claims] 1. An animal hair fiber structure having animal hair fibers coated with a film containing fluorine at least on the surface of the animal hair fibers, and in the absence of an antistatic agent, JIS L
The charged voltage T (volts) in an environment of 20 ° C. and 40% RH according to the B method of 1094-1992 satisfies the relationship of the following formula (1), and according to the E method (Martindale method) of JIS L1096-1992. A water repellent and oil repellent animal hair fiber structure having antistatic and antifouling properties, wherein the water repellency after 10,000 times of wear shows 90 points or more after pressing. T ≦ 2 (700−W) / F (1) W: Textile weight of fiber structure (g / m ² ), W ≦ 450 F: Carbon on animal hair fiber structure surface by X-ray photoelectron analyzer (ESCA) Fluorine amount (%) when analyzing, fluorine, oxygen, nitrogen and sulfur 2. A polyfunctional compound having two or more functional groups that chemically or physically bind to animal hair fibers is bonded to the inside or / and the surface of the animal hair fibers of the fiber structure containing animal hair fibers. After that, the outermost layer surface of the animal hair fiber is coated with a fluorine-containing compound or / and a reactant with a crosslinkable compound capable of reacting with the fluorine-containing compound. A method for producing an oil-repellent fiber structure.