JPS61282476A - Modification 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] (Industrial application field) The present invention uses 9 synthetic fibers with high reaction efficiency.

This invention relates to a method for homogeneous and economical modification.

(Prior art) Conventionally, as a method for efficiently graft-polymerizing a hydrophilic vinyl monomer onto a hydrophobic synthetic fiber, Japanese Patent Publication No. 59+51 has been developed.
No. 26 and Japanese Unexamined Patent Publication No. 51-87592.

The former method relates to a monomer composition for a two-step in-bath method in which graft polymerization is performed after activation pretreatment, but it is uneconomical because it requires two steps: an activation pretreatment step and a graft polymerization step. Furthermore, the latter relates to a one-stage method in a bath that does not require pre-activation treatment, but the immersion heating method in a bath leaves a large amount of unreacted monomer and the grafting reaction efficiency is not high, and a large amount of homogeneous material is generated in the bath. Problems arise in that the polymer contaminates processing machines and even wastewater.

Therefore, it is difficult to say that it is economical overall.

(Means to solve the problem) (1) In a method of modifying synthetic fibers by graft polymerizing a hydrophilic vinyl monomer, a quaternary ammonium salt type surfactant, a graft polymerization initiator, and a hydrophilic vinyl monomer are used. After applying the aqueous mixture of Tsumar to the synthetic fiber,
A method for modifying synthetic fibers, characterized by heating.

(2) The method for modifying synthetic fibers according to claim 1, wherein the heating means uses microwaves or a combination of steam and microwaves.

(Description of Means) The synthetic fibers referred to in the present invention are fibers made of two ordinary fiber-forming synthetic resins, and include, for example, polyalkylene terephthalate fibers, polyamide fibers, polyolefin fibers, polyacrylonitrile fibers, etc. Furthermore, these modified polymer fibers, a mixture thereof, or a combination of these and natural fibers were used. It includes mixed fibers in various forms. The form of these synthetic fibers may be any type, such as tow, two-knit fabric, or non-woven fabric.

The quaternary ammonium salt type surfactant as used in the present invention is:
It is generally commercially available as a cationic surfactant. Examples include halogenated tetraalkylammonium salts, halogenated trialkylbenzyl ammonium salts, halogenated tetraalkylpicolinium salts, halogenated trialkylbenzylpicolinium salts, halogenated tetraalkylpyridinium salts, and the like. , these alkyl Jl
Examples include methyl groups, stearyl groups, etc., and chlorine, bromine, etc., but are not limited to these. These quaternary ammonium salt type surfactants are added for the purpose of stabilizing the solution, and may be used alone or in combination of two or more types.

With other anionic, nonionic, and amphoteric ionic surfactants, it is difficult to obtain a stable aqueous mixture, and phase separation occurs within a short period of time, making it impossible to perform a uniform reaction. However, some surfactants form stable emulsified dispersions by adding a considerable amount (40% or more); however, adding such a large amount of surfactants is not only uneconomical, but also leads to graft polymerization. This results in various problems such as reduced efficiency and foaming during cleaning.

The hydrophilic vinyl monomer referred to in the present invention is generally applied to graft polymerization. A compound containing at least one polymerizable unsaturated group can be used regardless of its molecular weight.

Such monomers include, for example, acrylic acid.

Unsaturated carboxylic acids such as methacrylic acid, maleic acid, fumaric acid, itaconic acid, unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide, vinylpyrrolidone, unsaturated phosphorus compounds such as vinylphosphonic acid, and vinyl Examples include various unsaturated compounds such as unsaturated aromatic compounds such as sulfonic acid and styrene sulfonic acid. In the present invention, derivative compounds of these hexamers can also be applied. As such a derivative compound, for example, ethylene oxide is added to the above monomer. For example, various monomers such as polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, and acrylamide ethylene oxide adducts can be mentioned, but there is no need to limit them to these monomers.In short, it is a compound containing a polymerizable unsaturated group. If any, it can be applied as a monomer in the present invention. Such monomers can be used alone or in combination of two or more.

Examples of the graft polymerization initiator in the present invention include:
Examples include, but are not limited to, radical polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile.

Although the present invention does not particularly require the addition of a fiber swelling agent, it is possible to add a fiber swelling agent in order to obtain higher graft polymerization efficiency.

As the fiber swelling agent, compounds such as chlorobenzene, phenol, and benzoic acid can be used.

The present invention maintains an aqueous mixture containing a hydrophilic vinyl monomer, a graft polymerization initiator, and if necessary a fiber swelling agent in an extremely uniform and stable state, and then transfers the aqueous mixture to a synthetic fiber by dipping the aqueous mixture into a synthetic fiber. Graft polymerization is carried out in a single processing step by adding the aqueous mixture to a quaternary ammonium salt type interface and heating it. It is characterized by the addition of an activator. The monomer concentration of the aqueous mixture is preferably adjusted to a range of 5% to 70%. Below this range, the stability of the solution is extremely reduced and the grafting efficiency is also reduced. Moreover, if it exceeds this range, the grafting efficiency will decrease, probably due to a decrease in the carrier effect of water. And because the concentration of quaternary ammonium salt type surfactant changes depending on the monomer concentration! It is preferable to add it in the minimum necessary amount from the viewpoint of both grafting efficiency and economy. The concentration range of the surfactant is
It is 1% to 20%. Graft polymerization initiator concentration is 0.1
It is in the range of 3.0 to 3.0. If it deviates from this range, homopolymer generation will increase and the grafting efficiency will decrease.

Further, as mentioned above, the fiber swelling agent is not particularly required, but when added, the concentration as a pure product is preferably 5% or less. Beyond this, the grafting efficiency decreases.

The order in which these hydrophilic vinyl monomers and graft polymerization initiators are added is not particularly limited, but in other words, the graft polymerization initiator is first dissolved in the hydrophilic vinyl monomer, and then the other water and the quaternary ammonium salt type interface are added. It is better to add an activator.

It was obtained by adjusting in this way. The required amount of the aqueous mixture is applied to the synthetic fibers by a padding method or the like. Another application method is spraying.

Possible methods include applying and squeezing with a centrifugal dehydrator after immersion, but the method can be selected as appropriate depending on the form of the object to be treated, the required amount, etc.

The object to be treated to which the aqueous mixture containing the 7-mer is applied is then transferred to a heating system. When heat-treating the object transferred to the heating system by leaving it still.

Normally, the processing liquid moves downward due to its own weight, and it is preferable to maintain a state in which liquid movement is small by rotating the object to be processed to an extent that liquid movement does not occur due to centrifugal force.

As the heating means, a normal heating mechanism can be applied.

Preferably, heating using microwaves or a combination of steam and microwaves may be selected from the viewpoint of temperature increase rate and ease of control.

When using this heating method, the temperature increase rate depends on the frequency, the type and amount of dielectric material, the movement speed of the object to be treated, etc.
The maximum temperature is different, but by adjusting each,
The heating rate and maximum temperature can be regulated.

Although the graft polymerization initiation temperature varies somewhat depending on the type of polymerization initiator and the type of monomer, a temperature condition of usually 80° C. or higher, preferably 100° C. or higher, but up to 180° C. is applied.

(Example) Example 1 0.5 g of organic peroxide (NIPER MT-80 manufactured by NOF) as a graft polymerization initiator, 1 g of monochlorobenzene as a swelling agent for polyethylene terephthalate fibers,
30g of methacrylic acid as a hydrophilic monomer and 3g of a quaternary ammonium salt type surfactant (Cationogen AN Super manufactured by Dai-Kogyo Seiyaku) were diluted with water to prepare 100g of an aqueous mixture. A polyethylene terephthalate processed yarn fabric (made by Toshi Co., Ltd.≠2525) from the scouring intermediate set was squeezed with a soaking mangle, wound into a roll, and then sealed with a vinylidene chloride film.

The pick-up rate at this time was 70% of the weight of the processed yarn fabric. Next, this processed yarn fabric was placed in a microwave treatment device (Apolopet manufactured by Ichikin), heated and irradiated with 100°C steam and microwave for 5 minutes, washed with hot water, washed with water, dried, and then weighed against the initial weight of the processed yarn fabric. The increase rate was calculated.

The reaction efficiency of the monomer corresponding to the weight increase rate was calculated as follows, taking the pickup rate into consideration.

The results are shown in Table 1.

Monomer reaction efficiency = Grafting efficiency Grafting efficiency (1) = [Weight increase rate / 0.7 x monomer concentration) xloo [In the formula, 1 weight increase 7 Jll rate double weight ratio, monomer concentration double weight ratio] Comparative Examples 1 and 2 Examples Nonionic surfactant (Neugen ET manufactured by Dai-Kogyo Seiyaku Co., Ltd.
160) 5g was added (Comparative Example 1).

Next, in place of the quaternary ammonium salt type surfactant of Example 1, 5 g of an anionic surfactant (Plysurf A2171 manufactured by Dai-Kogyo Seiyaku Co., Ltd.) was added (Comparative Example 2).

In Example 1, a uniform and stable aqueous mixture was obtained, but
In Comparative Examples 1 and 2, the mixed liquid separated into two layers and was unsuitable as a pad liquid.

Comparative Example 3 Graft polymerization initiator (NOF Niper MT-80)
2g, swelling agent for polyethylene terephthalate fiber;
10 g of monochlorobenzene, 5 g of (Noigen EA160 manufactured by NOF Corporation) as an emulsifier, and 20 g of a 1=1 (by weight) mixture of acrylic acid and methacrylic acid as a hydrophilic vinyl monomer were diluted with water to give a total weight of 1000 mt. Next, 10 g of a polyethylene terephthalate processed yarn fabric (+2525 manufactured by Toshi Co., Ltd.), which had been set as a scouring intermediate, was immersed in this solution at 300 mA and heat-treated at 100'0 for 60 minutes. Next, after washing with hot water, washing with water, and drying, the weight increase rate with respect to the initial fabric was determined 2
Grafting efficiency was calculated using the following formula. The results are shown in Table 1.

Table 1 As is clear from Table 1, the fabric treated with graft polymerization in one step using the aqueous mixture obtained in Example 1 showed high grafting efficiency. The grafting efficiency of Comparative Example B was low. In addition, in Comparative Example 1 using a nonionic surfactant instead of a quaternary ammonium salt type surfactant and Comparative Example 2 using an anionic surfactant, a stable aqueous mixture was not formed and one-step graft polymerization was performed. I was unable to proceed with the process.

(Effects of the Invention) The present invention can uniformly and extremely economically modify synthetic fibers with excellent reaction efficiency.

Claims (2)

[Claims] (1) In a method of modifying a synthetic fiber by graft polymerizing a hydrophilic vinyl monomer, an aqueous mixture of a quaternary ammonium salt type surfactant, a graft polymerization initiator, and a hydrophilic vinyl monomer is applied to the synthetic fiber. A method for modifying synthetic fibers, which comprises heating the fibers after heating the fibers. (2) The method for modifying synthetic fibers according to claim 1, wherein the heating means uses microwaves or a combination of steam and microwaves.