JPS6021969A - Water and oil repelling process of fine fiber raised fabric - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water- and oil-repellent processing method for ultrafine fiber napped fabrics.

Conventionally, high-grade suede is obtained by adding an elastic polymer such as polyurethane to a raised fabric such as a nonwoven fabric, a woven fabric, or a knitted fabric, which has raised naps made of ultrafine fibers. , tailored blanket fabrics are known, but these raised fabrics using ultrafine fibers have a high degree of napping, are impregnated with an elastic polymer such as polyurethane, and have a large surface area. Due to this, it has high water absorption, and therefore,
Even when water- and oil-repellent finishing is carried out using a conventional method, not only is a sufficient effect not obtained, but the durability is also insufficient.

The inventors of the present invention have conducted extensive research in order to develop ultrafine fiber napkin fabrics that have an elegant appearance similar to natural leather, excellent rebound elasticity, and are also durable and have excellent water and oil repellency. As a result, we have arrived at the present invention.

A water- and oil-repellent ultrafine fiber napkin fabric characterized in that it is irradiated with high-frequency waves in the presence of the body, treated with a gas that generates low-temperature plasma, and then treated with a water- and oil-repellent finishing agent containing a fluoroalkyl group. A water-repellent fabric made of ultrafine fibers, which is characterized by using a water- and oil-repellent finishing agent mainly containing a fluoroalkyl group-containing compound and an acidic solution containing salts as a water- and oil-repellent finishing agent. It is related to oil repellent finishing.

The present invention will be explained in detail below.

The ultrafine fibers used in the present invention are ultrafine fibers with a single fiber denier of 08 deniers or less, and include, for example, ultrafine fibers obtained by ordinary super draw or high speed spinning methods, and ultrafine fibers made of two different polymers. Sea-island type or mixed-spun type board fibers, which are ultrafine fibers obtained by dissolving and removing the sea component after fabric formation, or multilayer bonded fibers made of two different polymers. There are ultrafine fibers etc. which can be obtained by dividing and exfoliating each polymer component by mechanical action after forming a fabric, or by dissolving and removing one of the polymer components.

As polymers forming ultrafine fibers, polyesters such as polyethylene terephthalate, polyamides such as nylon 6 and nylon 66, or synthetic polymers such as polyacrylonitrile are particularly light and heavy.The single fiber denier of the ultrafine fibers is 0.8 denier or less. It is effective in terms of the characteristics of the raised fabric, preferably 001 to 0.
．． It is 3 denier.

When the single fiber denier of the ultra-fine fiber is greater than 08, the texture of the raised fabric made from the ultra-fine fiber becomes rough and hard.
There are some facial orientations in which it is not possible to obtain a raised fabric with the desired soft and supple texture.

In the present invention, the napped fabric means a fabric having napped fabrics made of ultrafine fibers on the surface of the fabric, and either a nonwoven fabric type or a knitted fabric type can be used. There are also no particular limitations on the constituent fibers of the sheet structure that constitutes the raised blanket.

These raised fabrics are generally dyed or printed by a conventional method, and if necessary, raised by shearing and brushing. The dyed and printed raised fabric is then preferably treated with an elastomeric polymer.

The elastic polymer used here is acrylonitrile.
There are elastomeric polymers such as butadiene copolymer, polychloroprene, styrene-butashev copolymer, polyurethane, and polyacrylate, but polyurethane is more suitable in terms of performance and feel of the fabric from which it is obtained.

Fabrics may be treated with these elastic polymers so that the solid content is 2 to 30% owf.

Conventionally, the raised fabrics produced in this way have been made water and oil repellent by applying a water and oil repellent finishing agent using a padding method and then performing heat treatment. The napped fabric has a high density of naps, a large surface area, and is impregnated with a large amount of elastic polymer such as polyurethane, so it has very high water absorption and also has a large drop in performance due to abrasion. Not only was the water and oil repellent property not sufficiently effective, but its durability was also insufficient.

As an improvement measure, the method of the present invention completes the process of performing water and oil repellent treatment after pretreatment with plasma, and the durability of the product is significantly improved by plasma pretreatment. In the plasma treatment used in the present invention, oxygen or a mixed gas of oxygen and another gas such as an inert gas such as helium argon, nitrogen, water vapor, or carbon dioxide gas can be used as the gas. The pressure of the processing machine during the treatment is suitable under conditions where low-temperature plasma is generated and the temperature of the atmosphere does not damage the raised fabric, that is, 20 to 0.1 Torr, more preferably 10 to 0.5 Torr. Also, the frequency of the high frequency used to generate plasma is 1 to 3,
It can be used in the range of 000 MI-IZ, but in practice it is 13.56 MI-IZ, 27.12 MI-IZ, 40
．． 68MI-IZ, 915M1. I'Z, 2450
Use either MIIZ.

When oxygen or an oxygen-containing mixed gas under reduced pressure is irradiated with high frequency waves, that is, when high frequency energy is applied, oxygen molecules are depleted and low-temperature plasma is generated. Accordingly, in the present invention, the ultrafine napped fabric is treated in this plasma atmosphere.

The processing time varies depending on the basis weight, density, and required performance of the ultra-fine napped fabric, but it is usually within the range of several seconds to 30 minutes.

The thus pretreated ultra-fine napped fabric is then treated with a fluoroalkyl group-containing water- and oil-repellent finishing agent.

As a treatment method, a method of applying a finishing agent to the raised fabric by padding and then heat-treating it may be used, but in order to further improve the water and oil repellency of the raised fabric, the fluoroalkyl group-containing water and oil repellent finishing agent and A preferred method is to immerse the fabric in a solution containing salts with a pH of 2 to 5 for at least 5 minutes and then dry it.

Various compounds can be used as the fluoroalkyl group-containing compounds used as water and oil repellents in the present invention, and one of the main ones is CF3(CF2)-(CI'
-12) 110COCH=CH2゜CF3(CF2),
CH20COC(CH3)=CH2゜(CH3)2CP
(CF2), o(CH2)30COCI-1=CH2゜(CF3)CIi”(CF2) 6CH2CH(OCO
CH3)OCOC(C1-13)-CII; Examples include a combination or a copolymer of such unsaturated esters and one or more kinds of other polymerizable compounds not containing fluoroalkyls. In this case, examples of polymerizable compounds that do not contain fluoroalkyl groups include ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, hao'y"7 hinyritene, acrylonitrile, styrene, α-methylstyrene, p-methyl Examples include styrene, acrylic acid and its alkyl esters, methacrylic acid and its alkyl esters, acrylamide, methacrylamide, diacetate/acrylamide, and the like.

The reason why it is more preferable to treat the fabric in a bath in carrying out the present invention is that the ultrafine fiber napped fabric has a high density;
Therefore, with mere padding, it is difficult for the processing agent to penetrate deep into the tissue, and the desired performance of the resulting fabric may not be sufficient. However, with the bath treatment method, the processing agent can be efficiently absorbed into the fabric. This is because it can be exhausted. Further, in a simple exhaustion treatment, these fluoroalkyl group-containing compounds may not be selectively exhausted onto the fibers.

In such a case, in the present invention, an inorganic salt is added to the processing solution and the pH value of the processing solution is adjusted to a range of 2 to 5 to efficiently apply the water and oil repellent agent to the surface of the fibers. I succeeded in adsorbing it and it's 7. When this condition is met, water and oil repellency can be applied much more efficiently than when treatment is performed using only a water and oil repellent treatment agent.
It is possible.

As the inorganic salts used here, those exhibiting the characteristics of electrolytes generally used for dyeing etc., such as sodium sulfate, tuthorium chloride, aluminum sulfate, magnesium chloride, calcium chloride, etc. can be used.

It is effective to use the salt in an amount of about 0.5 to 5% oWf. In addition, this treatment solution contains JR of the fabric obtained.
It is also possible to use a cationic softener, a cationic antistatic agent, etc. in combination for the purpose of improving the bonding properties. In addition, these cationic surfactants have fluoroalkyl group-containing water repellency, ↑
It also has the property of promoting the adsorption of serum oil agents onto fabrics.

However, depending on the type and amount of these softeners 1 and antistatic agents, water and oil repellency may be reduced, so it is necessary to use an appropriate amount of a pre-selected auxiliary agent. It is most important to keep the Pl of the treatment bath within the range of acidic P.

As the pH of the processing agents increases, the adsorption of these processing agents to the fabric decreases, especially as the bath temperature increases.
Furthermore, there is a phenomenon where this tendency is exacerbated.0 The appropriate pH range is 2 to 5, especially when P
The most stable processing is possible in the range of H2 to H4.

, H adjustment is not particularly limited, and acetic acid, sulfuric acid, formic acid,
Any acid may be used, such as oxalic acid, ur-tralinic acid, and sulfuric acid.

The effect of improving the adsorption effect of processing agents by adding inorganic salts and adjusting the pH is similar to the effect of salts and pH as dyeing aids in general dyeing systems. Conceivable.

The adhesion rate of the treatment agent to the fibers requires a total concentration in terms of solid content of about 0.2% or more by weight of the fibers.

If this concentration is too low in K, satisfactory performance cannot be obtained. On the other hand, if the concentration is extremely high, rough hardening of the texture will occur, so a range of 03 to 06% is appropriate.

In order to carry out the above treatment, the present invention is preferably immersed in a treatment solution at 40 to 8oC' under appropriate conditions within the range of bath ratio 1:1o to 5o, and treated for at least 5 minutes. .

The reason for this is to increase the adsorption of the treatment agent to the fibers that make up the fabric, and it is more advantageous to raise the temperature of the treatment bath and take a longer treatment time than to immerse it in a low-temperature bath for a short time. It is.

Since the emulsification stability of the processing agent decreases when the temperature of the shikajia kneading reaches high temperatures, the most preferable industrial conditions are processing at 40 to 80°C for about 20 minutes. Stirring 1: etc. is performed forcibly using a pump or the like.

The treated fabric is dehydrated and then dried at 100-150'C and heat treated to obtain a water- and oil-repellent fabric having the level of performance aimed at by the present invention. If the heat treatment temperature is low, a long time treatment is required, and if the temperature is high, there are problems such as yellowing, so heat treatment at 100 to 150° C. for 3 to 10 minutes is usually required.

The napped fabric made of ultrafine fibers obtained in this way has excellent water and oil repellency, and is also very durable, which is an excellent feature not found in conventional ultrafine fiber napped fabrics. It can be made into a product with performance.

The present invention will be explained below with reference to Examples.

In addition, in the examples, product performance was evaluated by the following method.

1) Water repellency...pu p (+r+ is water repellency) Based on performance measurement conditions.

(Good) Grade 5 to Grade 1 (Poor) 2) Oil repellency: Conforms to AATCC method oil repellency performance measurement conditions.

(Good) Grade 7 to Grade 1 (Poor) Example 1 A copolymer of 93% by weight of acrylonitrile and 7% by weight of vinyl acetate was dissolved in dimethylacetamide and subjected to wet spinning.

Next, it was stretched in boiling water to obtain an ultrafine fiber tow having an average dyeing degree of 0.01 denier and a total fineness of 4.20.0 denier.

This tow was canted to 3 mm and poured into water to prepare a dispersion.

On the other hand, acrylic fiber filament 180d as fiber fabric
/60f woolly processed yarn has a basis weight of 120g/rr?
A knitted fabric was prepared, and the ultrafine field fiber dispersion was extracted from this fabric to obtain a composite in which one acrylic ultrafine short fiber web was laminated on the acrylic filament-processed yarn knitted fabric.

Place this complex on a 200-mesh wire mesh at 2 m/min.
The water jet treatment was performed from the side of the acrylic microfiber web while moving at a speed of /min.

Water jet treatment has a hole diameter of 0.15'mm and a distance between holes of 1 rn.
2CrI from the web using an rn liquid jet nozzle.
From distance L to 25! ? /c++! A water stream was sprayed at a pressure of G.

Next, this web was guided onto a metal roll with a diameter of 20 crIL, and using a similar nozzle, a water stream was sprayed at a pressure of 30 kg/crl G from a distance of 2 cril from the web to dry it. A composite sort-like structure was obtained.

The sheet material thus obtained was dyed using a conventional dyeing method, dried, and then fluffed using a planning device. This sheet was immersed in an 8% aqueous polyurethane dispersion and squeezed with a mangle. Subsequently, a 3% aqueous solution of sodium alginate was applied to the fluffed surface using a roll coater while the sheet was still undried. It was dried in a hot air dryer at 140°C. The amount of sodium alginate applied is 4%.
The amount of polyurethane deposited was 72% relative to the weight of the fabric.

Next, add 0.5j of soda ash at 80°C! The sample was washed in hot water containing 1/1 to extract sodium alginate, and then dried.

After that, under reduced pressure of oxygen 0.5 Torr, frequency 13, 56
Low-temperature plasma was generated at MHZ with a power of 300 W, and the raised fabric was treated in this atmosphere for 5 minutes, and then further processed using a water and oil repellent agent containing a fluoroalkyl group-containing compound under the following processing conditions. went. As a control, plasma-treated sample No. 7 was also treated in the same manner.

(1) Standard conditions for dipping treatment (2) Conditions for padding method treatment The treated sheet was dehydrated using a mangle to a squeezing rate of 90%, and then heat treated at 130° C. for 5 minutes.

The obtained results are as shown in Table 1.O As seen in the above results, the samples treated under the conditions of Flat 4 and Flat 5, which are examples of the present invention, had poor initial water repellency, oil repellency, and durability. It was excellent.

The conventional treatment (Ban 1) with padding has excellent initial performance, but the performance deteriorates greatly due to dry cleaning, and the treatment with immersion treatment without plasma treatment (A2
, 3) had slightly improved durability compared to the treatment method 1, but was still insufficiently durable.

On the other hand, even under the treatment bath conditions of the present invention, when the pH was as high as 6, the performance was slightly inferior, and when the pH was in the range of 3 to 4, very excellent results were obtained.

Example 2 The composite sheet prepared in Example 1 was subjected to dyeing, polyurethane treatment, and plasma treatment in the same manner as in Example 1, and then water and oil repellent treatment was performed under the following conditions.

(1) Processing conditions for padding method and spray method Both the padding method and the streaking method were processed so that the amount of big amp was 80% of the weight of the fabric.

The treated sheet was squeezed using a mangle to achieve a squeezing rate of 80%.

The sheet processed with (]), f2) is then 130
'cXs heat treatment has been carried out. The results obtained are shown in Table 2.

As can be seen from the above results, flat 4.0 is an example of the present invention. The material treated under the following conditions had excellent initial performance and rigidity.

Although the initial performance of conventional treatments using the spray method and the padding method was fair, there was a tendency for the performance to deteriorate somewhat after dry cleaning. However, in the example
The durability was improved compared to No. 1 without plasma treatment, and the improvement in durability due to plasma treatment was clearly recognized.

On the other hand, although the initial performance of the A3 immersion method without adding mirabilite is acceptable, its durability is slightly inferior to that of the treatment with mirabilite added, and it is recognized that the adsorption effect of mirabilite is large. It was done.

Example 3 Five sheets of satin were woven using polyester 50d/72F as the weft and polyester processed yarn 150d/48f as the warp.

After scouring, relaxing and drying this gray fabric, it was softened and one surface was raised using a raising machine. Then, it was dyed using a jet dyeing machine. After drying and heat setting the raised fabric, it was immersed in an emulsion type 5% polyurethane solution and squeezed with a mangle. After drying in a hot air dryer at 140°C, the surface was sanded using a sanding machine.

Next, a gas in which low-temperature plasma was generated under the treatment conditions shown below was led out of the plasma atmosphere, and the raised fabric was treated with this gas.

The plasma-treated raised fabric was subjected to water- and oil-repellent treatment under the conditions described in 1.

In addition, as a control, a sample without plasma treatment was also treated at the same time.

Water and oil repellent treatment conditions After the water and oil repellent treatment, heat treatment was carried out at 120°C for 4 minutes → 150°Q for 4 minutes. The results obtained are shown in Table 3.

As seen in the above results, A7°8.
Those treated under 9 conditions were excellent in both initial performance and durability.

Although the initial performance of the specimens processed without plasma treatment was fair, their durability was considerably inferior to that of the specimens processed with plasma treatment.

Even for items treated by the treatment method of the present invention, the Pl (at the time of water- and oil-repellent processing) is as high as 7, and the effect tends to decrease as the treatment temperature increases, so the PH during water- and oil-repellent processing is important. It was recognized that

Patent applicant: Mitsubishi Rayon Co., Ltd. Agent Patent Attorney 1) Taketoshi Mura

Claims (1)

[Scope of Claims] A method for making water and oil repellent ultrafine fiber napkin fabric, which comprises treating it with a water and oil repellent finishing agent mainly containing a fluoroalkyl group-containing compound. 2) The method according to claim 1, wherein an acidic solution containing a water- and oil-repellent agent mainly composed of a fluoroalkyl group-containing compound and a salt is used as the water- and oil-repellent agent.