JPS6040548B2 - Modification processing method for synthetic fiber materials - Google Patents

Description

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

In the past, modification processing methods using graft polymerization of synthetic fiber materials such as polyester and polyamide have been widely studied, but the proportion of commonly used monomers used in graft polymerization is low, and it is difficult to achieve cost-effective results. The current situation is that it is expensive and has not been industrialized. For example, Special Publick No. 53-1859
0 shows that when graft polymerizing methacrylic acid-acrylic acid using the immersion method, the grafting rate can be improved by using naphthalene in combination, but the effective utilization rate of the monomer is less than 30%, making it difficult to find an effective method. It's hard to say. Further, Example 4 of Japanese Patent Publication No. 50-13400 discloses a method of graft polymerizing polyethylene glycol acrylate by a bonding method, but in this case as well, the monomer utilization rate is only about 25%. The present inventors investigated ways to improve monomer utilization in immersion graft polymerization using such catalysts, and found that by using a quaternary ammonium salt in combination, grafting was much more efficient than with conventional methods. It was discovered that it can be polymerized.

That is, the modification processing method of the present invention consists of: [1] A monomer having two or more polymerizable double bonds and a polyalkylene oxide segment; of polyalkylene oxide segments, m
A quaternary ammonium compound, a water-resistant polymerization initiator having a peroxide group, and a monomer mixture containing only tl- or This is a method in which a monomer is polymerized on a synthetic fiber material by simultaneously reacting with a hydrophobic organic solvent.

Many substances have been known to have a decomposition-promoting effect on peroxides, which are catalysts for radical polymerization.
Although it is described on page 101, promoting the decomposition of the catalyst is not necessarily an effective means in graft polymerization of fiber materials.

This is because it is necessary for polymerization to occur selectively on the fibers, and if polymerization is promoted in solution, the utilization rate will decrease, leading to losses. We found that when used in combination with a quaternary ammonium compound, the utilization efficiency of the monomer increases. However, if we estimate the mechanism, the quaternary ammonium salt has a negative zeta potential in the liquid. It is thought that the polymerization of the monomer is accelerated only on the fiber, which reduces the production of homopolymers and improves the monomer utilization efficiency.

The purpose of modifying synthetic fiber materials is mostly to make them hydrophilic, and the monomers used in the present invention are also hydrophilic.

For example, the monomers for '1} include the following, and the monomers for {2) include methacrylic acid, acrylic acid, hydroxyethyl methacrylate, acrylonitrile, sodium styrene sulfonate, and 2-acrylamide 2- Methyrp.

Pansulfonic acid, glycidyl methacrylate, acrylamide, vinylpyridine, pinylpyrrolidone, etc.
{1} and ■ may be used alone, m and '2} may be used in combination, and two or more of {1} and ■ may be used in combination.

As the quaternary ammonium salt of '3}, there are those represented by the following general formula, and specific examples thereof include the following.

It should be noted that quaternary ammonium compounds with methacrylic groups are also effective; in this case, they not only work to improve monomer utilization efficiency, but also polymerize themselves and contribute to their function as modifiers. . [41] Examples of polymerization initiators include penzoyl peroxide, lauroyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, Dicumil et al.

The organic solvent of '5-' is generally used as a solvent for a polymerization initiator, but it is desirable that it has a carrier effect on the synthetic fiber material.

Specific examples include monochlorobenzene, dichlorobenzene, trichlorobenzene, halogenated aromatic hydrocarbons such as monochlorotoluene, trichloroethylene, trichloroethane, and tetrac. halogenated aliphatic hydrocarbons such as ruethane, butrachlorethylene, biphenyls,
These include aromatic hydrocarbons such as methylnaphthalene, aromatic esters such as benzoic acid methyl ester, and aromatic ethers such as ethylene oxide adducts of phenol. The actual modification process involves adding a polymerization initiator dissolved in an organic solvent and an appropriate surfactant to the monomer dissolved in water to emulsify it, and then adding an appropriate amount of A method can be applied in which a quaternary ammonium compound is added, a woven or knitted fabric is immersed in this, the mixture is purged with nitrogen, and then polymerized on the fibers by heating using a dyeing machine or the like.

The concentration of monomer used is 0.1-1.0% o. w. S is preferable, and the quaternary ammonium salt is 0.01 to 0.5%.
o. w. s is better, but usually 0.05 to 0.3
%o. w. s is sufficient, and if it is too small, the efficiency improvement effect will be reduced by 4. If it is used in excess, there is a risk of coloring.

The concentration of the organic solvent used is 0.1 to 2.0% o. w. s, more preferably 0.5 to 1.5% o.s. W.
S range. The concentration of the polymerization catalyst used is 0.01-0.
2%o. w. It is better to be s, but 0.05 to 0.15
%o. w. A range of s is more preferable; if it is too small or too large, the grafting rate tends to decrease, and there is an optimum concentration. The fiber materials targeted by the present invention include woven and knitted materials such as polyester, polyamide, and polyacrylic materials, but may also be blended or knitted materials with natural fibers.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 200 cc of a treatment liquid having the following composition was injected into two Hi-dj color washing machine pots (Todoroki Sangyo Co., Ltd.).

Methacrylic acid 0.2% Penzoyl peroxide 0.08% C-924
0 (Nicca Chemical, chlorobenzene carrier)
Next, prepare two sheets of 0.9% polyester processed yarn fabric and put them into the above dyeing pot, and one pot is filled with a quaternary ammonium compound having the following structure.
．． 16 minutes (0.08%) was added.

Then, nitrogen substitution was performed for 2 minutes and the container was sealed.

This product was placed in a dyeing machine, heated to 70 qo at a rate of 100/min, and rotated for 3 cycles. 9 at a further rate of 1°C/min.
The temperature was raised to 0:00 and maintained for one female to complete polymerization. After cooling, the sample was taken out and washed with hot water at 90°C containing 1% sodium carbonate for 1 minute, and after washing and drying,
It was set at 0qo for 1 minute. Weight gain and monomer utilization were calculated for each sample. Further, as a performance evaluation, the frictional charging voltage at a relative humidity of 30% was measured.
The results are shown in Table 1. From Table 1, it was found that the method of the present invention almost doubled the monomer utilization rate.

It still has excellent antistatic properties. Example 2 A modification treatment liquid having the following composition was prepared.

Methacrylic acid 0.7% Hydroxyethyl methacrylate 0.7% Dichlorobenzene 0.8% Plysurf A217E (Daiichi Kogyo Seiyaku Co., Ltd. Weak anionic surfactant) 0.2% Penzoyl peroxide
0.08% In this system, a comparative test was conducted in the same manner as in Example 1, with and without the addition of the following quaternary ammonium salt.

Out C. 2 days 25N(cH3)3c,e The weight increase rate and monomer utilization rate are shown in Table 2.

Table 2 From this, it is clear that the method of the present invention improves the utilization rate of a single farm.

Example 3 Processing liquid 420 having the following composition in a jet dyeing machine
I made it.

Methacrylic acid 0.08% C day spot-(CH3)3C・eo-1% teryl carrier S-61 (Meisei Chemical, chlorobenzene carrier) 1.0% penzoyl peroxide
0.08%, then put in a 6.3k9 knitted fabric made of 100% polyester, press nitrogen gas for 1 minute to replace the air, and then reduce the fabric speed to 2.
700 at a rate of 1℃/min while rotating at 0 h/min.
The temperature was raised to 0 and held for 30 minutes.

The temperature was further raised to 80 CO and maintained for 30 minutes to complete polymerization. After the reaction solution was cooled, it was drained, and 500 kg of water and 1 kg of sodium carbonate were added thereto, followed by refinement at 80 °C for 20 minutes.
Repeat washing with water twice and take out the processed fabric.
After drying at 00, it was set at 18,000 between three top sands.
The weight increase rate of this product was 7.3%, and the monomer utilization rate was 53%. For comparison, the same machine was treated without adding quaternary ammonium salt, and the weight increase rate was 1.
5%, and the monomer utilization rate was only 11%. Example 4 200 cc of each treatment liquid having the following composition was injected into four pots for a dyeing machine.

Methacrylic acid 0.2% Monochlorobenzene 0.8% Plysurf A217E O. 2% penzoyl peroxide 0.1% To this, the amount of quaternary ammonium compound with the following structure was 0.
, 0.05, 0.1, and 0.15%, and was treated in exactly the same manner as in Example 1.

The results are shown in Table 3. Table 3 Since the quaternary ammonium salt itself is polymerizable, the monomer utilization rate was calculated by taking its amount into consideration, but the effect of its addition is obvious, and a significant increase in the utilization rate can be seen.

Claims (1)

[Claims] 1. For a synthetic fiber material, (1) a monomer containing two or more polymerizable double bonds and a polyalkylene oxide segment; (2) a monomer containing one polymerizable double bond; (3) a quaternary ammonium compound; (4) a water-insoluble polymerization initiator containing a peroxide group;
) Among water-insoluble organic solvents, (3), (4) and (5) for monomer mixtures containing both (1) and (2) or monomers consisting only of (1) or (2). ) at the same time to efficiently polymerize monomers on fibers.