JPS584872A - Treatment of synthetic fiber - 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 method for imparting superior and durable antistatic properties and hydrophilic properties to 8 synthetic fibers.

Synthetic fibers have excellent physical and chemical properties.

It is widely used for clothing, industrial materials, etc.

On the other hand, it has drawbacks such as the adhesion of dust due to static electricity, the occurrence of electric shock, and the sticky feeling caused by sweating.

In order to solve these drawbacks, a method was proposed in which a polyethylene glycol compound having a polymerizable vinyl group in one molecule was added to fibers, and the compound was polymerized on the fibers to obtain antistatic properties and water absorption properties. 54-40680, etc.), a method of treatment with a mixture of a polyethylene glycol compound and a metal salt of an organic acid monomer (Japanese Patent Publication No. 50-6599, etc.)
and so on.

However, the processing methods in both methods are not compatible with the compound, and compared to the conventional method of simply attaching a finishing agent to the fibers after antistatic and sweat absorption, they are more or less durable. However, the durability is insufficient, such as the antistatic property being lost after repeated washing, and many products have the disadvantage that their washing resistance and weather resistance are inferior, and they also have a significantly poor texture. There are many things to do.

In contrast, a method has recently been proposed in which fibers are modified by graft polymerization in which acrylic acid or methacrylic acid coexists with a polyethylene glycol compound having a vinyl group (Japanese Unexamined Patent Publication No. 52-25894). However, although this known example indicates the use of graft processing, it does not clarify the specific means for obtaining a product that is rational and has good quality and performance.

The inventors of the present invention have focused on this point, and as a result of intensive study, have come to provide a method for obtaining a practically valuable, highly durable, antistatic and water-absorbing synthetic fiber. The present invention has the following configuration to achieve the above object.

That is, 1 the present invention involves immersing a synthetic fiber in a treatment bath containing a compound represented by the general formula % and an organic acid monomer having an unsaturated double bond, and then heating the bath to treat the compound. is polymerized and fixed on the fiber surface and inside the fiber. .

The present invention employs such a technical configuration.

The adhesion state (9) of a copolymer of a compound of the general formula (hereinafter referred to as a polyethylene glycol compound) and an organic acid monomer to the fibers is significantly improved, and the polymerization state is improved to provide good and durable antistatic properties and hydrophilic properties. At the same time, synthetic fibers can be produced.

What is important for the compound represented by the general formula of the present invention is that it has water solubility. Examples include diacrylate, bisphenol F-polyethylene glycol dimethacrylate, bisphenol s-polyethylene glycol diacrylate, and bisphenol S-polyethylene glycol dimethacrylate. In the general formula, when n=5 or less, the solubility of the monomer in water is insufficient;

If n=60, it is difficult to produce the monomer, so it is limited to a range of 5 to 30. Furthermore, X represents an H9-alkyl group or an alkoxy group.Next, the organic acid monomer having an unsaturated double bond used in the present invention is one that is compatible with the above polyethylene glycol compound and is water-soluble. is selected. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid.

Aliphatic organic acid monomers such as butenetricarboxylic acid, acrylamide, methacrylamide, and their alkali metal salts can be applied, but the latter metal salts are less effective. These organic acid monomers may be used alone or in combination of two or more.

What is important is that by selecting such aliphatic organic acid monomers, organic bonding with the polyethylene glycol compounds and synthetic fibers is successfully achieved, which not only improves antistatic properties and hydrophilic properties, but also improves the antistatic properties and hydrophilic properties. This is because we were able to add even more durability to the properties.

In the present invention, among the above-mentioned organic acid monomers, monomers selected from acrylic acid, itaconic acid, and methacrylic acid are particularly preferable because they are excellent in the above-mentioned characteristics.

In the present invention, the mixing ratio of the polyethylene glycol compound and the organic acid monomer is 2 to 50 parts by weight of the organic acid monomer per 10 parts of the polyethylene glycol compound.
parts, preferably 5 to 20 parts to 10 parts of the former.

After dissolving the above mixture in a solvent, for example water.

Synthetic fibers are immersed in the aqueous solution and heated in that state,
It is polymerized and fixed on the surface and inside of the synthetic fiber.

At this time, the amount of the polyethylene glycol compound and the organic acid motumer attached is 0.000% in terms of solid content based on the weight of the fiber.
1 to 10% by weight, preferably 0.5 to 5% by weight.

That is, when the amount of adhesion is 0.1% or less, the antistatic effect aimed at by the present invention cannot be obtained.

If the weight exceeds 10, it becomes impractical in terms of texture, roughness and cost. Any desired amount of adhesion can be easily obtained by appropriately adjusting the concentration of the mixed aqueous solution.

The object to be treated is immersed in an aqueous solution of a polyethylene glycol compound and an organic acid monomer at a bath ratio of 1:5 to 1:200,
It is appropriate to carry out the heat treatment at a temperature of 50 to 135°C for 20 to 90 minutes. The bath ratio with the treated material is generally 30 (to 50).

From the viewpoint of polymerization efficiency of polyethylene glycol compounds and organic acid monomers, the smaller the bath ratio, the better (,1
: It is preferable to process at 20 or less.

As the solvent used in such a bath, industrially applicable organic solvents such as methanol, ethanol, methyl ethyl ketone, trichlene, perchlorene, tetrahydrofuran, acetone, etc., and water can be used. is preferred.

In the present invention, a copolymer consisting of a polyethylene glycol compound and the organic acid monomer is fixed to synthetic fibers by such heat treatment in a bath. Because it has the property of rationing.

It is thought that a process is carried out in which migration of the monomer first proceeds in the treatment bath, and then copolymerization reaction proceeds by heating in the bath. That is, the fixation of the present invention is achieved through such a process, and is characterized in that it includes copolymerization with the organic acid monomer that has entered the interior of the fiber.

Such treatment may be carried out either before dyeing the treated product or after simultaneous dyeing and dyeing, but in post-treatment after dyeing, dyes may fall off at high temperatures (LVF of 100°C or higher), so dyeing may be difficult. It is common to process them before or at the same time. If post-treatment is necessary, it is desirable to use a radical initiator or the like and perform the treatment at the lowest possible temperature.

Generally, an initiator does not need to be present in the treatment bath, but a radical polymerization initiator or a radical polymerization initiator and a reducing substance may be added as necessary.

Alternatively, the material may be pretreated with the radical polymerization initiator and then treated. The initiator promotes polymerization on the surface and inside of the fiber, shortens the time required to lower the processing temperature, and at the same time
It also contributes to improving durability and is highly effective.

Examples of such radical polymerization initiators include organic peroxides such as benzoyl peroxide and hydroperoxide, azobisbutyronitrile ammonium persulfate,
Examples include potassium persulfate, while hydrogen iodide is a reducing substance.

These include hydrogen sulfide, sodium sulfite, and the reaction product of sodium hydrosulfide sulfoxylate and formalin.

When added to the treatment bath, 1/10 to 1/1 of the amount of polyethylene glycol compound and organic acid monomer used.
When adding 0.00 to 0.00 and performing pretreatment, it is appropriate to add 0.1 to 3 weight based on the weight of the fiber.

Additionally, a compound having a swelling effect that causes structural relaxation of synthetic fibers may be added to the treatment solution.

This is one effective means from the viewpoint of promoting internal polymerization. For example, benzoic acid, benzoic acid derivatives.

It may be a salicylic acid derivative, a chlorobenzene compound, a phenylphenol compound, etc., as long as it can swell the fibers.

The treated synthetic fiber thus obtained has durable antistatic properties and hydrophilic properties, but it can be further improved by treating it in an aqueous alkali metal salt solution and replacing the organic acid monomer with the metal salt. Trainable.

Synthetic fibers used in the present invention include polyethylene terephthalate fibers, polyethylene fibers, Nylon, acrylic fibers and fiber structures containing them,
Its form is thread, cotton.

It may be any fabric, sewn product, non-woven fabric, etc.

In addition, these synthetic fibers are available in undyed and dyed products.

Almost the same effect can be obtained in either case.

To restate the effects of the present invention, a copolymerization reaction between the vinyl-terminated polyethylene glycol compound and the organic acid salt occurs, and graft polymerization also progresses inside the fibers of the synthetic fiber. Conceivable. Not only does it form a film on the fiber surface.

Due in part to the anchoring effect of the polymer formed inside the fibers, the durability of the polymer film is significantly improved.On the other hand, the resulting polymer has very strong hydrophilicity, so
It can impart permanent antistatic properties, water absorption properties, and sweat absorption properties to the treated object.

Furthermore, by using a vinyl group-modified polyethylene glycol compound and an organic acid monomer in combination, it is not only economical because the amount used is smaller than when treating them alone, but also prevents the formation of unnecessary homopolymers and changes in texture. It has become possible to easily and stably produce treated products with excellent homogeneity and texture.

The present invention will be specifically explained below with reference to examples. In the examples, the antistatic properties, water absorption properties, and washing durability were evaluated as follows.

[Antistatic property: measurement of static electricity generation]

Measuring device: Rotary static tester (manufactured by Toa Shokai) Friction target cloth: 2-cotton (50 count broad) Friction speed: 4
00 rpm Temperature: 20°C ± 1°C Humidity = 30% ± 1% All measurement samples were left in a measurement chamber adjusted to the above temperature and humidity for at least 20 hours, and then the measurement was stopped under the above conditions.

The measured value is an average value of n=5, and the unit is volt (Vl).

[Water absorption: water absorption rate]

Hold a 1'5 x 15 an inch sample in a wooden frame so that it does not sag, and use a burette to drop 0.03 ce/inch water droplets onto the horizontally stretched sample. Measure the time it takes for the water droplets to be completely absorbed by the sample. Measure.

[Sample washing conditions]

Kao Soap Products "Zabu" 0.2% at 40℃, bath ratio 1:50
The clothes were washed for 10 minutes using an electric washing machine (Galaxy) manufactured by Toshiba ■, and then dried using a gas home dryer manufactured by Osaka Gas ■. This was repeated 30 times as one wash, and then used as a sample for measuring the amount of static electricity generated and water absorption rate.

Example 1 A twill fabric (280 g/m
)made. After desizing, scouring, and drying by the usual method, 1
Heat setting was performed at 80° C. for 60 seconds. The sample was added to an aqueous solution of X% bisphenol A polyethylene glycol dimethacrylate (15 moles each of oxyethylene glycol repeating units) and Y% organic acid monomer (X, Y, and monomer types are shown in Table 1) at a bath ratio of 1:20. Soak.

The temperature was raised to 130°C over 45 minutes, and the mixture was treated at 130°C for 60 minutes. Then, it was washed with hot water and dried. The amount of static electricity generated and the water absorption rate of this processed product were measured, and the results are summarized in Table 9-1.

Comparative Example 1 An aqueous solution of bisphenol A polyethylene glycol dimethacrylate and an organic acid monomer alone was prepared using the same sample as in Example 1, and treated under the same conditions as in Example 1.
The amount of static electricity generated and the rate of water absorption were measured. The results are summarized in Table-1.

From the results shown in Table 1, by using a polyethylene glycol compound and an organic acid monomer in combination, excellent antistatic properties and water absorption properties are obtained, and durability is also significantly improved.

In addition, the treated product is treated with a cationic dye, 0athilonB.
lu193BLHi, o%owf, acetic acid 0.5g/l
! As a result of dyeing at 95°C for 60 minutes at a bath ratio of 1:50, the dyeing treated with polyethylene glycol compound and organic acid monomer alone resulted in uneven dyeing, whereas the dyeing treated with the combination showed no uneven dyeing and uniform dyeing. It was proven that the dyeing was done uniformly.

Example 2 Nylon filament 40D-10 filament yarn was used to knit into tricot. As usual.

After scouring and heat setting, acid dye Sumino1
Milling Red Re (resident chemistry) 1.5
%owf l Score Roll 4400 (Kako Atlas) 1.0%owf.

Dyeing was carried out at 98° C. for 60 minutes at a bath ratio of 1:15. After staining, bisphenol A polyethylene glycol dimethacrylate (oxyethylene glycol repeating unit 15 moles each) was applied for 2 days 01. and acrylic acid 1,5% 8o1. An aqueous solution consisting of 0.2% ammonium persulfate, 801° sodium formaldehyde sulfoxylate 0.0-3% sol was immersed in the prepared solution at a bath ratio of 1:15, and the temperature was raised from room temperature to 700°C.

It was treated at 70°C for 30 minutes. After treatment, wash with water, dry,
The amount of static electricity generated and the rate of water absorption were measured. The results are shown in Table-2.

Table 2 As shown in the above table, even when dyed products were treated with the method of the present invention, durable treated products with excellent antistatic properties and water absorption properties were obtained.

Example 6 The same sample as in Example 1 was treated with benzoyl peroxide 2
10 parts of monochlorobenzene, and 5 parts of Triton 102 (Sanyo Boeki) dispersed in 1000 parts of water, with a bath ratio of 1:
20 at 80℃ for 30 minutes.

Soaked. The sample was treated in the same manner as in Example 1, with bath ratios of 1:10, 1:20, 1:30°1:so,
It was treated at a ratio of 1:100. Amount of static electricity generated after washing and drying,
e. The water velocity was measured and the results are summarized in Table 6.

- As shown in the table above, those pretreated with a radical polymerization initiator had even better antistatic properties and better durability. In addition, the smaller the processing bath ratio, the better.
At 1:5, there was a large variation in the measured values, probably because there was a lot of processing. From a practical standpoint, the optimum range is 1:io to 1:20.

Example 4 Sample and treatment method of Example 1 (however, bisphenol A
(1) Ionet TD-208 (Sanyo Kasei M) (2% polyethylene glycol dimethacrylate, 2% itaconic acid) was used in the treatment bath.
) IF carrier n-20 (one-sided oil and fat ■) (3) Polyniscar DS (ash paint ■) were added in an amount of 1.5 inches each. The results are summarized in Table 4.

As shown in the table above, those using a swelling agent are much improved and have excellent durability compared to those that do not use a swelling agent.

Example 5 The sample treated in Example 2 was mixed with 2 g/l of soda ash.

The treatment was carried out at 70° C. for 20 minutes at a bath ratio of 1:100. The results are summarized in Table-5.

Table 5 As shown in the results in the above table, the antistatic effect was even better when sodium was subjected to metal/ring substitution treatment.

Claims (6)

[Claims] (1) Synthetic fibers are immersed in a treatment bath containing a compound represented by the general formula and an organic acid monomer having an unsaturated double bond, and then the temperature of the bath is raised to remove the compound and monomer from the synthetic fibers. A method for treating synthetic fibers, characterized by fixing a copolymer. (2) The method for treating synthetic fibers according to claim (1), wherein the synthetic fibers are pretreated with at least one of a radical polymerization initiator and a swelling agent for the fibers. (3) The method for treating synthetic fibers according to claim (1), characterized in that at least one of a radical polymerization initiator and a swelling agent for the synthetic fibers is coexisting in the treatment bath. (4) The method for treating synthetic fibers according to claim (1), wherein the temperature of the treatment bath is raised to a range of 50 to 155°C. (5) The method for treating synthetic fibers according to claim (1), wherein the bath ratio of the treatment bath is 1:20 or less. (6) Claim (1) characterized in that the temperature is raised in a treatment bath, the treatment is performed, and then the treatment is performed with an alkaline aqueous solution.
Method for treating synthetic fibers as described in section.