JPS5846589B2 - Modification treatment method for fiber materials - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for modifying fibrous materials.

Synthetic fibers have many excellent mechanical and chemical properties, especially polyester fibers due to their heat setting properties.
It has many excellent practical properties, but on the other hand, it has the disadvantages of not being hygroscopic or absorbing water, and being easily charged.
Depending on the application, it may not be used alone in many cases.

Conventionally, many attempts have been made to impart sweat absorption and antistatic properties to synthetic fibers such as polyester by radically polymerizing polyethylene glycol dimethacrylate or the like on the surface thereof.

For example, JP-A-47-16798, JP-A-48-270
66°48-35199.53-130396, etc.

However, with this method, the film obtained is brittle and hydrophilic, so it does not have sufficient durability, and although the initial water absorption is sufficient, the antistatic effect is not sufficient, and furthermore, it has a strong slimy feeling when exposed to air. There were disadvantages such as undesirable results.

In addition, an attempt was made to form a coating on the surface of synthetic fibers using a hydrophilic polyester polymer having polyethylene oxide segments by an impregnation-heating method or an exhaustion method to make the surface of synthetic fibers hydrophilic.
-6399.5346960 etc., but the performance and durability are unsatisfactory.

Furthermore, a compound having a polymerizable vinyl group at one end or side chain of the polyoxyalkylene segment is mixed with a polyfunctional vinyl monomer having two or more vinyl groups to form a coating on the surface of the synthetic fiber. It has also been proposed to form monomers (Japanese Patent Laid-Open No. 48-91398), but the polyfunctional monomer is hydrophobic, resulting in decreased water absorption and antistatic performance, and poor solubility in water, making it difficult to handle. However, the durability is only slightly improved.

Further, a common drawback of these modification methods is that the antistatic properties are insufficient under low humidity.

The present inventors have carried out extensive research in order to improve the drawbacks found in conventional synthetic fiber modification processing methods, and as a result, they have arrived at the present invention.

According to the present invention, there is provided a method for modifying fiber materials, which comprises the following components: (1) an acidic monomer having an unsaturated double bond; (2) an unsaturated double bond; A basic monomer having a bond, (3) N-methylolacrylamide, N-methylolmethacrylamide or N-N'-methylenebisacrylamide, and (4) a bifunctional monomer represented by the following general formula, - CnH
2n- (where n represents an integer from 1 to 6), 2 represents H or -CH3, and a and b are a + b
represents a positive integer such that x is from 5 to 50, and X and y represent O or a positive integer such that x+y is from 0 to 30.

provided that a+b+x+y is 10 or more] is applied to the fiber material, and the monomers are polymerized on the fiber material.

According to this method of the present invention, the monomer forms an insoluble cross-linked film on the surface and/or inside of the fiber through radical polymerization, so that the monomer can withstand dozens of home washings and dry cleanings. This makes it possible to process fiber materials to make them hydrophilic, thereby eliminating the drawbacks of synthetic fibers, such as being easily charged, having poor water absorption, and being difficult to remove dirt.

The acidic monomer (1) includes acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, itaconic acid, crotonic acid, vinyl sulfonic acid,
Examples include 2-allyloxy-2-hydroxypropanesulfonic acid and 2-acrylamido-2methylpropanesulfonic acid.

As the basic monomer (2), 4-vinylpyridine, 2-vinylpyridine, 2vinyl-
6-methylpyridine, dimethylamino※※ethyl methacrylate, diethylaminoethyl methacrylate, 2-
Methyl-5-vinylpyridine, 2-vinyl-5-ethylpyridine, 4-(4-propenylbutynyl)pyridine,
Examples include dimethylaminonelopyl methacrylamide.

Specific examples of the bifunctional monomer (4) include, but are not limited to, and monomers with similar structures having two or more vinyl groups can also be used.

There is no problem in using two or more types of each of the monomers (1) to (4).

By using the acidic monomers and basic monomers (1) and (2) together, ionic bonds are created before and after polymerization,
The antistatic effect is improved by providing a more hydrophilic surface.
Even under low humidity conditions of about 0%, the electrostatic voltage is several hundred V or less, and the effect of improving water absorption is also significant.

(3) N-methylol acrylamide and N-methylol methacrylamide are heated to produce (1), (2), (
Not only does it copolymerize with the monomer (4), but the methylol groups in the side chains undergo dehydration crosslinking, creating three-dimensional bonds and exhibiting surprising durability.

N-N'methylenebisacrylamide is also effective for crosslinking.

It is also possible to use a reactive resin such as melamine or glyoxal in combination for the purpose of promoting the crosslinking reaction of methylol groups, and it can also be used for the purpose of controlling the texture.

In the present invention, potassium persulfate, ammonium persulfate, and hydrogen peroxide can be used as common water-soluble polymerization initiators.

Further, as a water-insoluble polymerization initiator, benzoyl peroxide, azobisisobutyronitrile, tertiary-butyl peroxide, etc. can be dissolved in a hydrophobic organic solvent and emulsified with an anionic or nonionic surfactant.

Also, commercially available carriers may be used in place of these organic solvents.

Although there are no particular limitations on the mixing ratio and usage amount of the monomers (1) to (4), the texture of the obtained woven or knitted fabric varies depending on the composition and concentration, and the usage ratio is determined depending on the purpose of treatment.

The amount of each of the monomers (1) to (4) used is preferably 0.1 to 5.0 parts per 100 parts of the monomer mixed aqueous solution.

Control of the pH value of the monomer mixed aqueous solution or dispersion is important.

This is because N-methylolacrylamide (3) causes dehydration condensation on the acidic side and crosslinks, and the pH is 2.5.
Adjustment to a range of ~5.5 gives good results.

This can be achieved by increasing the molar ratio of the acidic monomer (1) and the basic monomer (2) to 1:1 or more.

Furthermore, the pH may be adjusted using acetic acid, formic acid, phosphoric acid, or the like.

If the above monomer mixture is not easily soluble in water, nonionic,
Surfactants such as anions may also be added.

The amount of the polymerized crosslinked product attached to the fiber material is 0.0 on a weight basis.
The range of 2 to 6% is preferable, and if it is less than 0.2%, the modification effect is small and the durability is not sufficient.

The effect obtained is sufficient with a coating amount of up to 6%; if it exceeds that amount, the texture becomes hard and the water absorption performance deteriorates, giving undesirable results.

The present invention is characterized in that the monomer mixture shown in (1) to (4) is applied to fibers, and then radical polymerization and crosslinking are performed, but any commonly used polymerization method can be used. Dry heat, wet heat, radiation, microwave heating, ultraviolet rays, exhaustion method, pad batch method, etc. can be applied.

Specifically, for example, it is a method in which a fiber material is impregnated with an aqueous solution of a monomer mixture and polymerized by drying or wet heat, at a temperature of 90 to 190°C and a time of 30 seconds to 10 minutes.

There are also methods of immersing a fiber material in an aqueous solution of a monomer mixture and heating and polymerizing it in the presence of a hydrophobic organic solvent and a water-insoluble polymerization initiator. These methods include leaving the material under heating, irradiating it with an electron beam at room temperature after impregnation, and rapidly heating it from the inside using microwaves.

The fiber materials targeted by the present invention are polyester-based, polyamide-based, acrylic-based, cellulose-based, protein-based, etc., and also include blends and blends thereof.

The fibers may be in any form such as staples, filaments, or knitted fabrics.

Next, a method for measuring the effects obtained by the present invention will be described.

1. Charge voltage using a Kyoto University Kaken type rotary static tester, 2.
0°C, 65% R, H, or 20°C x 30% R, H,
The charged voltage was measured by rubbing it against cotton cloth in an atmosphere (JIS
1094-1980B method).

Note that unless otherwise specified, the values are shown at 20° C. and 65% R and H.

2. Place a water-absorbing sample horizontally and drop one drop (0.03 CC) of distilled water from a billet from a height of 5 Cr/L onto the sample until the water is completely absorbed and no longer shows any unique reflected light. The time is expressed in seconds.

3. Suction length Measured by JIS-10798 method (Bayrak method).

4. Removal of oil stains Drop one drop of heavy oil B onto the center of a sample of approximately 15 crrL x 15 crrL and allow it to be completely absorbed, then leave it for 2 hours.

Then, JIS L-0217-103 home washing was repeated three times, and after air drying, judgment was made on the contamination gray scale.

5. Washing restainability A contaminated mother liquor having the following composition was prepared.

Carbon black (Mitsubishi Channel 1 part black #
100) Beef tallow hydrogenated fatty acids (m, p, 51℃) 15 parts soap (
JIS K3302-U) 10 parts distilled water
75 parts This contaminated mother liquor was diluted 100 times, two test pieces of 1Qcm x 5m were placed per 100CC, and the mixture was heated at 40° using a Launder-o-meter.
Rotate at C for 30 minutes.

Next, add room temperature water, wash twice (1 minute + 2 minutes), and air dry.

The degree of recontamination was determined by comparing it with the sample before contamination using the contamination gray scale.

Hereinafter, the configuration and effects of the present invention will be specifically explained using examples.

Example 1 A processing solution having the following composition was prepared.

A polyester Amundsen fabric is dipped in this material, and the content is reduced to 100%.The fabric is wound around a glass rod, and a neoflon film (product of Daikin Industries, Ltd.) is placed on top of it.
Wrap and seal both ends.

*Next, it was left in a dryer at 110° for 10 hours.

After the reaction, the sample was washed with hot water, dried, and heat set, and the weight increase rate was confirmed to be 4.2%.

The performance of this product is shown in Table 1.

It can be seen that the treated fabric has excellent antistatic properties, water absorption properties, and oil stain prevention properties.

It was also found that the performance was maintained even after washing.

■■Example 2 A processing fluid having the following composition was prepared.

This material was impregnated into a polyester pallet and squeezed with a mangle to an impregnation rate of 70%, followed by steam heat treatment at 110° C. for 5 minutes, followed by hot water washing and setting.

The treated fabric showed a weight increase of 3.1% compared to before treatment.

When the stain removability of heavy oil B was judged on the stain gray scale, the untreated cloth was ranked 1st class, while the treated cloth was ranked 4.5.
grade, and a significant improvement effect was seen.

In addition, when we evaluated the restaining property during washing, we found that unprocessed fabric was 1
．． It was found that the treated fabric was grade 3, while it was grade 5, and that it had antifouling properties.

Furthermore, in order to examine durability, the products were washed at home up to 80 times and evaluated for electrostatic voltage and water absorption.

The results are shown in Table 2. Example 3 A polyester stretch pongee was impregnated with the treatment solution used in Example 2 and squeezed to an impregnation rate of 80%, and then the woven fabric was wrapped around a glass rod, and a Mylar film was wrapped over the rod and sealed.

Then output 200W of 2450 MHz microwave.
It was irradiated for 4 minutes.

The obtained sample was heated at 80°C with 0.5% sodium carbonate solution.
After washing with water for 10 minutes, washing with running water was performed for 10 minutes.

Furthermore, after air-drying this product, it was heat-set at 190° C. for 30 seconds.

The treated fabric showed a weight gain of 3.6%.

In order to check the antistatic effect of the treated cloth, the charging voltage was measured using a rotary static tester at 30% R1H, and the result was 130V.

That of the untreated cloth was 3800V, and a significant difference was observed.

In addition, the electrostatic voltage after washing the processed cloth 20 times is 260■,
After 10 dry cleanings (JIS LO860), the voltage was 290V, which revealed a durable and excellent antistatic effect that is effective even at low humidity.

Example 4 The treatment solution used in Example 2 was impregnated into a polyester Woolly Pussin fabric, squeezed with a mangle to 100% impregnation, and 1.5M was applied using a Vandegraaf electrostatic accelerator in a nitrogen atmosphere.
An electron beam of eV and 50 μA was irradiated at 3 Mrad.

Next, wash in hot water at 70°C for 1 minute, dry, and then heat at 190°C for 3 minutes.
It was set for 0 seconds and the weight increase rate was determined to be 4.1%.

The charging voltage of this product was 185V, and the time required for water absorption was 0.5 seconds.

On the other hand, the unprocessed cloth had a voltage of 2900V and 195 seconds, which was a significant improvement.

Example 5 A processing solution having the following composition was prepared.

*Benzoyl peroxide 0.1% Nonionic/anionic surfactant 0.1% 4 parts of polyester pongee fabric was immersed in 200 parts of this, heated while stirring, and kept at 80°C for 30 minutes. ,
The temperature was further raised to 100°C and maintained for 20 minutes to complete the reaction.

This product was washed with hot water, dried, and heat set, and the weight increase rate was confirmed to be 3.2%.

The charging voltage of this product at 20℃, 30% R, H is 260
v, and that of the unprocessed product was 3500 V, and the antistatic effect was sufficient under low humidity conditions.

Example 6 A fabric was impregnated in the same manner as in Example 2, except that it was heat treated at 110°C for 5 minutes in a nitrogen stream. .

The charged voltage of the treated cloth was 290V, and after 40 washes it was 350V, showing excellent durability.

Example 7 An impregnation liquid having the following composition was prepared.

Then, the fibers shown in Table 3 were impregnated, and the impregnation rate was reduced to 80 to 100% using a mangle.

Then, it was treated in saturated steam at 110° C. for 5 minutes, heated at 70° C. for 5 minutes, and heated three times, then air-dried and heat-treated at 180° C. for 30 seconds.

The performance of the treated fabric is shown in Table 3 in comparison to the untreated fabric.

From this, it is clear that the treated cloth has excellent antistatic effect and water absorption performance, and maintains its performance even after washing 20 times.

※※Comparative example 1 A processing solution having the following composition was prepared.

Using this treatment liquid, the treatment was carried out in exactly the same manner as in Example 1 of the present invention.

The weight increase rate of the polyester Amundsen fabric is 2.1%, and the charged voltage of the treated fabric before washing is 160V, and the water absorption is 0.
．． It was found that the durability of Example 1 of the present invention was low, as the oil stain removal property was 900 V and 13 seconds and 2nd grade after 40 washes, respectively, while it was 3.5 grade for 5 seconds and oil stain removal.

Comparative example 2 A process with the following composition was prepared.

In comparison, polyester pulses were impregnated with this liquid, and the impregnation rate was reduced to 70% using a mangle, followed by steam heat treatment, groove light, and setting.

The weight increase rate of the processed fabric was 1.8%.

When we measured the charged voltage of this item, it was 200V before washing, but after washing 20, 40, 60, and 80 times, it was 360V, 800V, 100OV11200V, respectively*
*, and it was found that the durability was inferior compared to Example 2 of the present invention.

Comparative example 3 Three types of monomer aqueous solutions A, B, and C below were prepared.

A: Three processed polyester yarn fabrics were prepared, each impregnated with the above-mentioned processing liquid, and squeezed with a mangle to an impregnation rate of 100%.

Then, the polymer was polymerized by heating at 110° C. for 5 minutes in saturated steam, and then washed with hot water at 80° C. for 10 minutes.

After the sample was air-dried, it was heat-treated at 180° C. for 30 seconds.

Weight increase rate of treated fabric, weight increase rate for equivalent suspension rate (X100), and initial and 20 Monomer concentration The electrostatic voltage was measured after washing twice.

These are shown in Table 4.

When treatment liquid A is used, since the copolymerizability of sodium acrylate is low, the weight increase is small and the initial antistatic property is excellent, but the performance deteriorates greatly due to washing.

In the case of B, although the polymerizability is good, it has a drawback that the electrostatic voltage after washing is high.

When the treatment liquid of C according to the present invention is used, the weight increase is large and the monomer utilization efficiency is also high.

Furthermore, the electrostatic voltage is low both at the initial stage and after washing 20 times, and has excellent durability.

Comparative example 4 The following monomer solution was prepared.

For comparison with Example 2, a polyester palace fabric was immersed in this material, the impregnation rate was reduced to 70%, and then heated and polymerized in saturated steam at 110° C. for 5 minutes.

The sample was washed with hot water at 80° C. for 10 minutes, washed with water, and then air-dried.

Heat treatment was performed at 180° C. for 30 seconds, and the weight increase rate was determined to be 2.3%.

When we investigated the water absorption and charging voltage of this item at the initial stage and after washing 20 times, the water absorption was 1.8 seconds and 2.6 seconds at the initial stage and after washing 20 times, respectively, and the charging voltage was 66
0V and 1500V, and the durability was insufficient.

Claims (1)

[Claims] 1 The following components: (1) an acidic monomer having an unsaturated double bond, (2) a basic monomer having an unsaturated double bond, (3) N-methylolacrylamide, N-methylolmethacrylamide or N-N'-methylenebisacrylamide, and (4) a bifunctional monomer represented by the following general formula, CnH2
o- (where n represents an integer from 1 to 6),
2 represents H or -CH3, and a and b are a+b of 5 to
Represents a positive integer such as 50, where X and y are x+y
represents O or a positive integer such that 0 to 30. provided that a+b+x+y is 10 or more] is applied to the fiber material, and the monomers are polymerized on the fiber material. Modification treatment method.