JPS60209070A - Modification of fiber structure - 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 (Technical Field of the Invention) The present invention relates to a method for modifying a fibrous structure with excellent durability and a high degree of modification.

(Problems with Prior Art) Kraft polymerization has been known as a method for modifying the surface of durable fibers. This method uses radiation, electron beams, ultraviolet rays, low-temperature plasma, or chemical polymerization initiators to form radicals that serve as starting points for graft polymerization on the surface or inside of the fibers, and then generates radical-polymerizable seven polymers. This allows graft polymerization to occur. On this occasion,
When oxygen is present, it reacts with the generated radicals and has the effect of stopping the polymerization reaction, so it is necessary to completely remove oxygen throughout the entire treatment process. ``This means that regardless of whether the reaction is carried out in a gas phase, solution, or emulsion system, operations such as high-level vacuum equipment or replacing the system with an inert gas such as nitrogen are essential, and equipment Not only is the cost extremely high, but! It is extremely difficult to degas oxygen from structures with a large surface area, such as structures, and these factors make graft polymerization difficult. The biggest drawback was that it was difficult to use as a rough processing technology.

(Object of the Invention) The present invention is capable of imparting highly durable modification performance to fiber structures, particularly synthetic fiber structures, very simply and rationally.

Further, according to the present invention, the most important feature is that fibers can be modified with high efficiency and that a degassing step, which was essential in the prior art, is not required.

(Invention 6) The fiber structure of the present invention is characterized in that the fiber structure is subjected to high-frequency heat treatment after imparting a radically polymerizable compound to the fiber structure. (Description of structure) The fiber structure of the present invention is made of polyamide, Synthetic 111i such as polyester and polyacrylic, natural fibers such as wool, silk, cotton, linen, semi-synthetic such as acetate and rayon! l
Contains woven fibers. Among these fibers, synthetic #A
l11 is particularly effective.

4IIIi structures made of such fibers include all forms such as cotton, tow, sliver, yarn, fabric, and felt.

In the present invention, in addition to such a fiber structure, a polymeric elastomer resin such as a urethane resin, an acrylic resin,
Materials impregnated or coated with silicone resins, fluorine resins, etc. can also be used, and these materials may also contain dyes, pigments, antioxidants, etc. in advance.

The radically polymerizable compound as used in the present invention is a compound that exhibits radical polymerizability, and is polymerizable by a known method in advance.
! Radicals are roughly generated, or at the same time, a radical polymerization initiator is contained.

Such a compound may be any compound having a polymerizable unsaturated bond in its molecule, and is appropriately selected depending on the purpose of surface modification.

For example, if the purpose is to impart hydrophilic properties such as water absorption, SR properties, and III conductivity, use hydrophilic acid such as acrylic acid, methacrylic acid, polyethylene oxide dimethacrylate, 2-hydroxyethyl methacrylate, and acrylamide. -1 In addition, for the purpose of imparting water repellency, examples include fluorine-containing unsaturated compounds such as bentadefluorooctyl acrylate, trifluorochloroethylene, and trifluoroethyl methacrylate; There is no need to limit it, and any material having a polymerizable unsaturated group can be applied.

In the present invention, such compounds can be applied not only singly but also as a mixture of two or more, and if necessary, a wider variety of compounds can be mixed and applied to simultaneously impart five types of modification performance.

There are no limitations to the manner in which such compounds may be applied to tiatIi. For example, the usual bubble ink method, dipping method,
A textile printing method, a =1-ting method, etc. can be applied.

The method of the present invention is a popular method for graft polymerization, but it is essential to form radicals on the fibers in order to initiate radical polymerization before that, and the method uses radiation, electron beams, ultraviolet rays, low temperature Although any method using plasma irradiation or chemical initiator can be employed, among them, low temperature plasma irradiation method gives good results to the present invention.

The low-temperature plasma irradiation treatment suitably used in the present invention is as follows:
This is a 111 rough exposure process to plasma discharge generated by applying a high voltage. Such discharges include spark discharges,
There are various types of discharge such as corona discharge and glow discharge, and any type of discharge may be used as long as it does not cause 1Ω damage to the fibers, but glow discharge is particularly preferred because it is uniform in discharge and has an excellent radical forming effect.

Glow discharge number J 50 torr or less, even 20
jOrr or less, particularly preferably 0.01 to 1Q tor
It is generated by applying a high voltage in a gas atmosphere under reduced pressure.The treatment time is selected depending on the type of fiber and the treatment location, but it is usually from several seconds to several minutes, preferably 1
The duration is about 5 seconds to 5 minutes.

Examples of the gas that provides the radical forming effect of the present invention include Ar, N2, l-1e% CO2, Co10
Examples include 2, l-120, and air. Especially Ar.

1e, N2, Go, etc. are preferable because they form radicals efficiently.

Radical formation using a chemical initiator has many advantages, such as not requiring any special Iff for treatment. It takes n
Initiators include common initiators, such as peroxides such as methyl isobutyl ketone, cumene hydroperoxide, and benzoyl peroxide; At the same time, a method is applied in which the compound is applied to the fibers and then decomposed by high-frequency heating to form radicals in the fibers.

The present invention provides i
After applying the polymer to t<, radical polymerization is initiated by high-frequency heating.

Such high frequency heating means a frequency of 300 MHz to 1
This is a heat treatment method that utilizes the fact that a dielectric material such as water selectively absorbs this energy and generates heat in electromagnetic waves of 0.000 Ml-1z.

In this method, electromagnetic waves and dielectric materials are the main players, but this t[
The first wave has extremely excellent permeability, and has the characteristic of uniformly heating even when 41 sheets are rolled up, as long as a dielectric material is present.

In the present invention, improving thermal efficiency in this process is related to grafting efficiency, especially! ! ! It is essential. In this sense, it is preferable to select a medium with high thermal efficiency, such as water, as a medium for imparting a radically polymerizable compound.Furthermore, if a spreadable fabric is immersed in this medium and then rolled up as it is, it will not roll up. The presence of media throughout the fabric, including between the layers, results in the fabric having no air gaps, but instead the presence of media.

The high frequency may be applied either while the fabric is being rolled up or after it has been rolled up.

When performing such high-frequency heat treatment, it is preferable to fill the atmosphere with saturated steam as the medium used, such as water vapor, or to cover and seal the periphery of the fabric to be treated with a film, etc., from the viewpoint of preventing drying due to heating and sustaining energy absorption. .

Treatment conditions vary depending on the applied process and the type of radically polymerizable compound, but a temperature condition of at least the polymerization initiation temperature, that is, usually at least 50°C, preferably at least 80°C, is employed. Generally, if the temperature is high, a short processing time is sufficient;
Usually, a treatment time of 30 seconds or more, preferably 1 minute or more is used, but for example, it may be left at 50°C all day and night, or left at 95°C.
Various conditions such as 30 seconds are applied. However, this processing time cannot be set unambiguously because the time required to raise the temperature by high frequency varies greatly depending on the type of medium used. For example, water is 20℃/sec, acetone is 9℃/sec,
The rate varies depending on the type of medium, such as 31°C/sec for ethylene glycol, 32°C/sec for methyl alcohol, and 1.5°C/sec for toluene. Therefore, it is necessary to set the processing time depending on the medium used.

(Effect of R-light) The modified product according to the present invention has a property of highly durable modification performance, and has the characteristic that the texture is almost unchanged from that before treatment. The present invention has the advantage that such processed products can be provided extremely simply and stably.

In particular, if a method is adopted in which the step of applying a radically polymerizable compound to the treated fabric is carried out by low-temperature plasma treatment, it is possible to impart uniform modification performance with extremely little change in texture, and it is also extremely effective. Modified products can be provided on a continuous basis.

The present invention will be described in more detail below with reference to Examples.

Example 1 A textured yarn fabric (75 denier, 36 filaments) made of 100% polyester was treated with a non-iron resistant agent 2 g/Q1
/-4 ash 19/fir 98°C x 3 (1) Scoured, thoroughly washed with water and dried.

This fabric was treated by exposing it to low temperature plasma obtained under the following conditions.

(Low temperature plasma treatment conditions) Gas +Ar: 30 CC/min Decompression degree: 0.6 torr Applied voltage: 3 KV Processing speed: 20 cn+/min Next, this treated fabric was treated with acrylic Ell (50 parts) and methacrylic 12 (50 parts). After immersing it in a treatment solution consisting of 200g/α of the mixed solution, applying 60% of the treatment solution to the weight of the fabric using a mangle, it was rolled up and placed in a high-frequency heater [Tokyo Niura Electric Co., Ltd. ER- 678C], processed for 5 minutes, washed with water, and dried.

The weight increase rate of the obtained modified fabric was 2.2% by weight, and the flexibility was unchanged from that of the untreated fabric.

Next, the washing resistance for SR property was measured according to the following procedure, and the SR property (restaining rate) was 7.3% after washing WO times (immediately after finishing), and the SR property (restaining rate) after 130 washings.
7.3%, and 7.6% after 30 washes. The SR properties were excellent in both performance and durability. The SR property of the unprocessed fabric (after scouring) is 36.0% and 37.0% after 30 washes.
It was 8%.

[Laundry] Zabu” [Anionic detergent manufactured by Kao Soap Co., Ltd.] 2Q
After raising the temperature of the aqueous solution of /Q to 45°C, loading it with the sample into a household washing machine, washing for 5 minutes, washing with water for 2 minutes, and drying for 10 minutes, each cycle was repeated 3 times.
Repeat 0 times.

[SR properties] For samples subjected to the following contamination treatment, Macbeth MS-2
The reflectance before and after the contamination treatment was measured using a 000 model spectrophotometer, and the recontamination rate was calculated from the following formula.

FT t'j 'A rate (%) - (Ro -R8/Ro
) XI 00RO: Reflectance before contamination treatment R8: Reflectance after contamination treatment (contamination treatment) 12.5 parts each of stearic acid, oleic acid, hydrogenated oil, and olive oil, 8.5 parts of cetyl alcohol, and 21.5 parts of solid paraffin. 5 parts of cholesterol, 5.0 parts of carbon black, and 15.0 parts of carbon black;
and diluted with water to 0.075% by weight. This diluted solution is heated to 40° C., the sample is immersed in it for 20 minutes, and then the contaminated sample is washed in running water for 1 minute and dried.

Example 2 The sample after scouring in Example 1 was mixed with benzoyl peroxide (polymerization initiator) 2a/! 1 monochlorobenzene carrier (carrier T-40; Ipposha) 1011/fl,
Emulsifier (/Iken EX-160; Sanyo Chemical) 5Q /(
The treatment was carried out at 80°C for 30 minutes at a bath ratio of 1:50. Next, high-frequency heat treatment was carried out in the same manner as in Example 1 using 25 u/(1) of the same mixture. After thorough washing with water, 11
It was dried at 0°C.

The weight increase rate of the obtained modified product was 1.6%, and it had a soft texture similar to Example 1. Although this material was extremely hydrophilic and exhibited excellent SR properties, a decrease in strong electric current was observed in the fabric.

Example 3 Using the low-temperature plasma-treated fabric of Example 1, the radically polymerizable compound to be applied was changed to 2-hydroxyethyl methacrylate, and this was made into an aqueous solution of 50 g/a.
The fabric was immersed in this, reduced to an adhesion ff of 160% (based on the weight of the fabric), and subjected to high frequency heat treatment in the same manner as in Example 1.

This compound had extremely high grafting efficiency, and the treated product had a weight ant addition of 5.6%, and although it felt a little harder than Example 1, the texture of the modified product was extremely good. It was also excellent in durability, with an SR property of 6.3% and an SR property of 6.5% after 30 washes.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] A method for modifying a fibrous structure, which comprises applying a radically polymerizable compound to the fibrous structure and then subjecting the fibrous structure to high-frequency heat treatment.