JPH0465573A - Method for carrying out surface modification of synthetic fiber fabric - Google Patents

Abstract

PURPOSE:To obtain an antistatic and sweat-absorbing synthetic fiber fabric having excellent resistance to washing by applying a specific polyether ester polymer to the surface of synthetic fiber fabric and then applying an inorganic gas low temperature plasma treatment thereto. CONSTITUTION:A polyether ester polymer expressed by formula I or formula II (m+n is 10-100; R1 and R2 are 1-20C alkyl; R3 is H, methyl, ethyl or methoxymethyl; X is formic acid, acetic acid, oxalic acid, glycolic acid, citric acid or p-toluenesulfonic acid) is applied to the surface of woven or knit fabric consisting of a synthetic fiber, especially polyester based fiber and the coated fabric is dried and heat-treated and then subjected to an inorganic gas low- temperature plasma treatment to provide excellent resistance to washing as well as antistatic performance and water absorbing performance to the fabric. Furthermore, a mixture of polyethylene glycol and acrylic polymer of PVA can be used in place of the polyether ester polymer as the surface treating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for surface modification of fibrous structures made of synthetic fibers. More specifically, it relates to a modification method that imparts antistatic properties and water absorption properties.

(Prior art) The antistatic property imparting or water absorbing property imparting technology in post-processing of synthetic fiber structures mainly involves forming a film of a wood-loving substance on the surface of fibers or textile products using a resin treatment method or a grafting method. It has been known. However, the methods developed so far still have the problem of insufficient washing durability for general clothing, and the finished texture is rough and hard. For example, JP-A-60-134071 describes that an antistatic effect can be obtained by applying block-type quaternary 7-minopolyalkylene glycol etherified polyester to polyester synthetic fibers, followed by drying and heat treatment. Washing durability is insufficient from a practical point of view.

On the other hand, methods for imparting electrostatic properties through low-temperature plasma treatment have been developed in recent years.
No. 9 proposes a method in which a hydrophilic substance is applied, followed by steam treatment and then low-temperature plasma treatment. Moreover, in JP-A-63-152461, a hydrophilic substance is added,
A method has been proposed in which polyester fibers are subjected to low-temperature plasma treatment while being maintained at a temperature equal to or higher than the secondary transition point.

(Problems to be Solved by the Invention) However, the method described in JP-A-62-162079 requires M heat treatment before low-temperature plasma treatment, requiring yl and H operations, and furthermore, the hydrophilic substance is It requires something with a polymerizable double bond, is expensive, and is technically difficult to produce with high reproducibility.

Furthermore, the method described in JP-A-63-152461 has the disadvantage that special equipment such as a roller is required to pass a heating medium through the plasma atmosphere in order to control the temperature of polyester fibers during low-temperature plasma treatment. have.

As described above, the conventional technology has problems in washing durability and production technology, and a solution has been desired.

The present invention is intended to solve the above-mentioned problems, and its purpose is to create a synthetic fiber structure that maintains durable antistatic performance and water absorption performance without impairing the physical properties and texture of synthetic fibers. On offer.

Another object of the present invention is to provide a method for manufacturing such a structure industrially easily and inexpensively.

(Means for Solving the Problems) The present invention provides a method of applying a polyether ester polymer represented by the following general formula (1) or (II) to at least the surface and then treating it in a low-temperature plasma atmosphere of an inorganic gas. It is characterized by:

General formula (1) General formula (II) (However, m and n are positive integers and rl+n=10 to 100
, R, and R8 are the same or different alkyl groups having 1 to 2 carbon atoms, R1 is hydrogen, methyl, ethyl or methoxymethyl group, X is formic acid, acetic acid, oxalic acid, glycolic acid, citric acid, p-toluene Sulfone #) Also, in the above invention, in place of the polyether ester polymer, the polyether ester polymer,
It is characterized by using a mixture of polyethylene glycol polymer and acrylic copolymer or polyvinyl alcohol.

The synthetic fiber structure referred to in the present invention refers to synthetic fibers such as polyester, polyamide, polyacrylic, and yarns containing such fibers, I! This refers to knitted fabrics, non-woven fabrics, etc., and in particular, remarkable effects can be obtained when the present invention is applied to woven and knitted fabrics made of polyester.

The polyetherester polymer of the present invention contains nitrogen and has the specific polymer terminal groups described above. A quaternized product as described in JP-A No. 60-134071 is water-soluble but has poor durability and cannot be used in the present invention.

The polyethylene glycol used in the second aspect of the invention preferably has an average molecular weight of 400 to 2,000, more preferably 600 to 1,000. By mixing such a polyethylene glycol polymer with the polyether ester polymer, antistatic sweat absorbing performance and hand feel can be improved. Of course, polyethylene glycol according to the invention of claim 1 may also be used in combination.

Examples of the acrylic copolymer used in the invention of claim 2 include copolymers containing comonomers of general formula (m), general formula (■), and general formula (V) as essential components, and 60 weight%
Preferably, the emulsion has a Brookfield LVF viscosity of 100 to 1000 cp at 25°C. Alkyl acrylate is represented by general formula (III), dialkylaminoethyl acrylate is represented by general formula (TV), and dialkylaminopropyl acrylate is represented by general formula (V).

General formula (II [) R1 / CH, = C \ CO - R6 General formula (II /) R1 / \ R1 General formula (V) R2 / \ R 宕 (However, R1 is hydrogen or methyl group, R1 is carbon number 1~1
2 long-chain alkyl groups, R1 and R8 are the same or different alkyl groups such as methyl, ethyl, hydroxyethyl, etc.) The average degree of polymerization of the polyvinyl alcohol used in the invention of claim 2 is 300 to 1700, and the degree of saponification is 80-95 is preferable.

In the second aspect of the invention, a mixture consisting of the polyether ester polymer, polyethylene glycol polymer, and acrylic copolymer or polyvinyl alcohol is used. The mixing ratio of the polyether ester polymer and the polyethylene glycol polymer is 9:1 to 1:9, and even 7
:3 to 3 near is preferable. Further, the acrylic copolymer or polyvinyl alcohol is preferably mixed with the polyether ester and polyethylene glycol mixture in a ratio of 1:9 to 4:6, more preferably 2:8 to 4:6.

The low-temperature plasma treatment of the present invention refers to exposing the fibrous structure to a glow discharge generated by applying high frequency waves in an inorganic gas atmosphere under a reduced pressure of about 0.01 to 5 torr. The inorganic gas may be oxygen, nitrogen, argon, air, etc., but argon is more preferred.

The present invention first applies a method such as a dipping method, a banding method, a printing method, etc. to a synthetic fiber structure by applying a polyether ester polymer in the invention of claim 1, and applying the mixture to the synthetic fiber structure in the invention of claim 2. Generally, the polymer is applied at least to its surface.Then, the polymer is dried and heat-treated using a tenter or the like to solidify it, and then the low-temperature plasma treatment described above is performed.

In the present invention, the amount of the polyether ester polymer or the mixture applied is 0.5 to 10% by weight based on the fiber structure.
, preferably 2 to 6% by weight.

The film-forming property obtained only by dry heat treatment after application of the polyether ester polymer is significantly reduced when a polyethylene glycol polymer is added and mixed.

Such a decrease in film-forming properties becomes an obstacle to maintaining uniform performance from the initial roll to the final roll, especially during industrial production. However, in the invention of claim 2, the film forming property is improved by adding the acrylic copolymer or polyvinyl alcohol,
The degree of this is even greater than when polyether ester polymer is used alone.

(Example) Performance evaluation according to the present invention is performed by the following method.

Washing durability Based on JIS L 0217 103 method, bath ratio 1:30 Washing New Beads (manufactured by Kao Corporation) 2 g/l Washing 5 minutes, rinsing 2 minutes, spin drying 1 minute, rinsing 2 minutes, spin drying 1 minute It was repeated once and 30 times.

Frictional charging voltage JIS t, 1094 B method half
Decrease period JIS L 1094 A
Injection dyeing water-based JIS L 1096.
Method A Example 1 A dispersion of block type N,N diptylaminopolyethylene glycol etherified polyester acetate as a nitrogen-containing polyether ester polymer was applied to a polyester processed yarn fabric in an amount of 3% by weight (based on the fiber) by a padding method, 120 ℃×
After drying for 3 minutes and heat treatment at 160° C. for 3 minutes, low-temperature plasma treatment was performed under the conditions shown above.

Electricity 2. 5 kW vacuum degree
0.5 tall gas type! ! Oxygen, nitrogen, argon, air gas flow rate
500cc/min Processing speed: 20cm/min After low-temperature plasma treatment, the sample was washed with hot water at 40-50℃ for 10 minutes
Performance of Surface Modified Polyester Processed Yarn Fabric From the results shown in Table 1, the surface modification method of the present invention provided good washing durability.

Example 2 A block type N,N dibutylamine oxide type polyethylene glycol etherified polyester and a polyethylene glycol polymer having an average molecular weight of 400 to 20,000 were mixed as a nitrogen-containing polyether ester polymer in a polyester processed yarn fabric at a mixing ratio of 6:4 (1) % (based on fiber). After application, it was dried at 120°C for 3 minutes, heat treated at 160°C for 3 minutes, and subjected to low-temperature plasma treatment under the following conditions.

Power: 2.5 kW Degree of vacuum: 0.5 Tall Gas type: Nitrogen gas flow rate: 700 cc/min Processing speed: 30 cm/min After low-temperature plasma treatment, the sample was washed with hot water at 40 to 50°C for 10 minutes.
The surface-modified polyester processed yarn fabric had a texture similar to that of natural fibers. The performance is shown in Table 2.

Example 3 The same nitrogen-containing polyether ester polymer and polyethylene glycol polymer having an average molecular weight of 800 were applied to a polyester textured yarn fabric by the padding method in the same manner as in Example 1, with varying mixing ratios. The amount applied is 3% by weight (based on the fiber). After application, it was dried at 120°C for 3 minutes, heat treated at 160°C for 3 minutes, and subjected to low-temperature plasma treatment under the following conditions.

Electricity 2. 5 kW vacuum degree
Gas type: Nitrogen gas flow rate: 1000 cc/min Processing speed: 30 cm/min After low temperature plasma treatment, the sample was washed with hot water at 40 to 50°C for 10 minutes.
As can be seen from the results of the surface-modified polyester textured yarn fabric, improvements in performance and hand can be achieved by selecting the mixing ratio of the nitrogen-containing polyetherester polymer and the polyethylene glycol polymer.

Example 4 A half tricot knitted fabric of nylon 6 filament yarn or a knitted fabric of polyacrylic yarn was mixed with the same nitrogen-containing polyether ester and polyethylene glycol polymer having an average molecular weight of 600 as in Example 1 at a solid content mixing ratio of 4:6 to 3% by weight. (For fibers) After application, it was dried at 120°C for 3 minutes, heat treated at 160°C for 3 minutes, and subjected to low-temperature plasma treatment under the following conditions.

Power: 2 kW Vacuum degree: 0.7 Tall Gas type: Argon gas flow rate: 700 Cc/min Processing speed: 30 cm/min After low temperature plasma treatment, it was washed with hot water for 10 minutes at 40 to 50°C 8
Performance of surface-modified nylon knitted fabrics and acrylic knitted fabrics
Shown in the table.

The results shown in Table 4 indicate that the nylon or acrylic fiber structure has good washing durability.

Example 5 Dimethylaminoethyl methacrylate (30 mol) was added to the same polyester fabric as in Example 1 to a mixture of the nitrogen-containing polyether ester polymer and the polyethylene glycol polymer having an average molecular weight of 800 in a solid content ratio of 4:6. %),
An acrylic copolymer with a composition of ethyl methacrylate (30 mol%) and acrylic 92 ethylhexyl (40 mol%) and a Brookfield LVF viscosity of 250 cp at 25°C of a 60% by weight copolymer emulsion was used in a ratio of 7=3. 4% by weight (based on the fiber) was applied by the banding method. After application, drying at 120°C and heat treatment at 160°C, Example 4
Low-temperature plasma treatment was performed under the same conditions. After the low-temperature plasma treatment, it was washed with hot water at 40 to 50°C for 10 minutes.

Incidentally, when the puffing liquid was placed in a petri dish and water was removed at 105° C., a good film was formed.

Example 6 Dimethylaminoethyl methacrylate (30 mol %) was added to the same polyester fabric as in Example 1, with the mixture ratio of nitrogen-containing polyether ester polymer and polyethylene glycol polymer having an average molecular weight of 600 being 4:6. Butyl acrylate (20 mol%) Acrylic 92 ethyl hequinyl (
2 of the 60 wt% copolymer emulsion with a composition of 50 mol%).
Brookfield LVF viscosity at 5°C is 150c
The acrylic copolymer P was mixed at a ratio of 7:3 and applied in an amount of 4% by weight (based on the fiber) using a padding method.

After application, dry at 120°C and heat treatment at 160°C, Example 4
Low-temperature plasma treatment was performed under the same conditions.

After the low-temperature plasma treatment, it was washed with hot water at 40 to 50°C for 10 minutes.

When the banding solution was placed in a petri dish and water was removed at 105° C., a good film was formed.

Example 7 A polyester fabric was mixed with the same nitrogen-containing polyetherester polymer as in Example 1 and a polyethylene glycol polymer with an average molecular weight of 600 at a mixing ratio of 4:6, with an average degree of polymerization of 50o and a degree of saponification of 88.0±1. .5 polyvinyl alcohol was mixed at a ratio of 7:3 and applied to the fiber by a banding method at a concentration of 4% by weight (based on the fiber). After application, it was dried at 120° C. for 3 minutes, heat treated at 160° C. for 3 minutes, and subjected to low-temperature plasma treatment under the same conditions as in Example 4. 40~50℃ after low temperature plasma treatment
Washed with hot water for 10 minutes.

When the banding solution was placed in a petri dish and water was removed at 105° C., a good film was formed.

Comparative Example 2 Block type N, NN dibutylethylaminopolyethylene glycol etherified polyester quaternary ammonium salt and polyethylene glyco-J having an average molecular weight of 600 were added to a polyester processed yarn fabric at a mixing ratio of 6:4 to 3% by weight (by weight). Line W) After application, drying and heat treatment were carried out in the same way as in Example 2. As a result of the low temperature braz or higher, Comparative Example 2 had insufficient washing durability performance.

(Effects of the Invention) According to the present invention, it is possible to obtain an antistatic, sweat-absorbing synthetic fiber structure that is uniform from the initial roll to the final roll and has excellent washing resistance.
The present invention can be said to be an industrially useful production technology.

Procedural amendment 1, Indication of the case 1990 Patent Application No. 171893 2, Name of the invention Method for surface modification of synthetic fiber structures 3, Person making the amendment Relationship to the case Patent applicant address Sumida Go, Sumida-ku, Tokyo No. 17-4, 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka City, Osaka 534 Patent Department, Kanebo Co., Ltd. 6゜7゜ Contents of the amendment in the "Detailed Description of the Invention" section of the specification subject to the amendment (1) "Processing speed 20C1/min J" on page 1), line 9 of the specification is corrected to "processing time 4 minutes".

(2) Same book, page 13, line 16, page 15, line 13, 1
"Processing speed 30cm 1 minute" on page 7, line 17 is corrected to "processing time 4 minutesj."

that's all

Claims (2)

[Claims] (1) After applying a polyether ester polymer represented by the following general formula (I) or (II) to at least the surface,
A method for surface modification of synthetic fiber structures characterized by treatment in a low-temperature plasma atmosphere of inorganic gas. General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, m and n are positive integers, m + n = 10 to 100, R
_1 and R_2 are the same or different alkyl groups having 1 to 20 carbon atoms, R_3 is hydrogen, methyl, ethyl or methoxymethyl group, X is formic acid, acetic acid, oxalic acid, glycolic acid, citric acid, P-toluenesulfonic acid) (2) In the method according to claim 1, in place of the polyetherester polymer, the polyetherester polymer,
A method for surface modification of synthetic fiber structures using a mixture of a polyethylene glycol polymer and an acrylic copolymer or polyvinyl alcohol.