JPS62110979A - 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 relates to a method for improving the color development, optical fastness and wet fastness of a fabric containing synthetic fibers modified by graft polymerization.

(Prior Art) Conventional examples of modifying synthetic fibers by graft polymerizing hydrophilic vinyl monomers are disclosed in Japanese Patent Publication No. 48-27744 and Japanese Patent Application Laid-Open No. 59-5126.

These disclose means for efficiently achieving graft polymerization in a bath, and do not mention color development, light fastness, and wet fastness. In bath graft polymerization, monomer utilization efficiency (grafting efficiency)
Not only is it low (&l), but because a fiber swelling agent is used, a decrease in color fastness, including color fastness, is unavoidable.

Fibers modified by graft polymerization have unique properties and performance in addition to the original properties of the fiber, but on the other hand, due to changes in the internal structure of the fiber, there are changes in the physical properties of the fiber, a decrease in color development, and a change in brightness. Deterioration in performance such as a decrease in color fastness also occurs.

Furthermore, these performance deteriorations may also be caused by chemicals used in the graft polymerization reaction, particularly polymerization initiators, fiber swelling agents, and reaction by-products after the graft polymerization reaction. In the method of applying a hydrophilic vinyl monomer, a graft polymerization initiator, and, if necessary, a fiber swelling agent to the treated material by padding, spraying, etc., and then heating and modifying the material by graft polymerization, after the grafting process, the rough fiber surface,
Alternatively, due to the graft polymerization initiator, fiber swelling agent, reaction by-products, etc. remaining inside the fibers, if the fibers are dyed directly from the normal washing process, a significant decrease in color development, light color fastness, and color fastness cannot be avoided. Therefore, compared to the bath immersion method, pad heating requires less liquid at the end (lower bath ratio).
Alternatively, with spray heating methods, etc., the development of products is limited unless reaction residues are removed before the dyeing process to prevent deterioration in color development, double light and color fastness.

The object of the present invention is to overcome the drawbacks of the prior art and to provide a method that can fully exhibit the effects of graft polymerization while improving color development, brightness, and color fastness.

(Means for solving the problem) The present invention uses microwaves or high frequency waves as heating means,
A method for modifying synthetic fibers, which comprises polymerizing a hydrophilic vinyl monomer onto synthetic fibers and performing a residue removal step after the graft polymerization step and before the dyeing step.

The residue removal step in the present invention refers to the filtration agent used in the graft polymerization step, especially the graft polymerization initiator, the fiber swelling agent, and the peroxides and homopolymers produced as by-products in the reaction. This is a process to remove residues that remain on the surface or inside of the treated object. As mentioned above, dyeing without removing these residues results in poor color development due to decomposition of the dye, as well as a decrease in both light and color fastness.

One effective method for removing these residues is dry heat treatment at 130° C. or higher, preferably 160° C. to 200° C. or lower, for at least 20 seconds or more. It goes without saying that it is desirable to use this dry heat treatment in combination with the intermediate setting because it also prevents edges during dyeing.

Furthermore, after the graft polymerization process, a hot water process is usually carried out, and during this hot water process, 0.5g of surfactant is added.
/j to 10 g/j, preferably 2 g/1 or more and 5 g/l or less, and it is desirable to wash with hot water of 70° C. or higher for 20 minutes or more. This step may be a washing step at the end of graft polymerization, or may be performed in a dyeing machine before dyeing.

Effective surfactants include, for example, soda soaps, p-++, which are used as soaping agents and detergents.
Examples include alkylbenzene sulfonate sodium i such as sodium luenesulfonate, high alpha alcohol sulfate ester salts, fatty acid polyglycol ethers, and particularly preferred are nonionic and anionic surfactants.

Although the hot water washing treatment using a surfactant and the dry heat treatment described above are effective alone, it is more preferable to use both in combination because they exhibit a synergistic effect. Since this synergistic effect is not affected by the processing order, an advantageous processing order can be arbitrarily set.

In this way, by performing a dry heat heat treatment with an intermediate set after the graft polymerization process, there is no need for a set before the graft polymerization process, and it is possible to proceed to the graft polymerization process after the relaxing scouring and drying process. can. In the present invention, it is preferable that the agent used in the grafting step be applied by a pad method or a spray method. This is because the workpiece is rolled up in a roll or the like, so no processing wrinkles occur during graft processing compared to the bath immersion method. Gelaft polymerization without imparting a thermal history of 150° C. or higher during the graft polymerization step can significantly improve graft efficiency (monomer reaction efficiency) and is also more economical.

Heating by high frequency and microwave as used in the present invention refers to processing technology Vol. ]6. As introduced in No. IO (1981), this method is called high frequency dielectric heating. , one frequency ranges from several hundred KHz to several tens! A[Izc/
) Refers to electromagnetic waves, and several MHz is used industrially. Microwave refers to electromagnetic waves ranging from aG[lz] to 2450M[lz and 915M[lz], which are industrially approved.

The synthetic fibers used in the present invention are fibers made of ordinary fiber-forming synthetic resins, such as polyalkylene terephthalate fibers and polyamide tan fibers.

It includes polyolefin fibers, polyacrylonitrile fibers, etc., and further includes m-fibers made of modified polymers of these, mixtures thereof, or mixed m-fibers in various forms in which these are combined with natural fibers. The forms of these synthetic fibers are tow, thread, 11-strand fabric,
It doesn't matter what kind of material it is, such as cloth.

The hydrophilic vinyl monomer referred to in the present invention means at least one
A compound containing a polymerizable unsaturated group can be used regardless of the size of the molecular cap, as long as the polymer is more hydrophilic than the polymer constituting the fiber to be treated. Generally, vinyl monomers with hydrophilic groups are used. Examples of such monomers include various unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid, unsaturated amides such as acrylamide and N-vinylpyrrolidone, and unsaturated sulfonic acid compounds such as vinylsulfonic acid and styrenesulfonic acid. Name a saturated compound. Further, derivative compounds of these monomers can also be used. For example, various products such as polyethylene glycol monoacrylate and acrylamide ethylene oxide adducts, which are obtained by adding ethylene oxide to the above monomers, can be mentioned. Particularly preferred are acrylic acid, methacrylic acid and their derivatives. These may be used alone or in combination of two or more.

The graft polymerization process referred to in the present invention includes padding or t
Aqueous arms containing polymerization initiators, hydrophilic vinyl monomers, etc. using methods such as IT spraying? Applying the r liquid to the object to be treated:
Thereafter, the object to be treated to which the chemical solution has been applied is heated using the aforementioned microwave or high frequency as a heating means to complete the graft polymerization. Examples of the polymerization initiator used here include, but are not limited to, radical polymerization initiators such as ben'jyl peroxide and azobisisobutyl L1 nitrile, and derivatives thereof.

Next, an example of the method for modifying synthetic fibers of the present invention will be explained in detail.

A synthetic fiber structure to be treated after relaxing scouring and drying is immersed in an aqueous mixture containing a hydrophilic vinyl monomer, a graft polymerization initiator, and a surfactant, and then a desired effect is applied to the object by a nip or centrifugal dehydration method. Adjust.

As a method for applying the liquid, in addition to the nip method, a pad vacuum method, a spray method, a coating method, etc. can be used, and any method can be appropriately selected depending on the form of the object to be treated, the amount of liquid applied, etc.

The object to be treated, to which the aqueous mixture containing the monomer has been applied in this manner, is then transferred to a heating system. When a workpiece transferred to a heating system is left standing and heat-treated, the processing liquid normally moves downward due to its own weight, and the workpiece is maintained in a state where liquid movement does not occur due to centrifugal force. It is preferable to do so.

Although a conventional heating mechanism can be used as the heating means, heating using microwaves, high frequency waves, steam and microwaves, or a combination of steam and high frequency waves is particularly preferable in terms of temperature increase rate and ease of control. When using this heating method, the heating rate and maximum temperature vary depending on requirements such as frequency, type and amount of dielectric material, and moving speed of the object to be processed. Temperature can be easily regulated.

Although the graft polymerization initiation temperature varies somewhat depending on the type of polymerization initiator and the MM of the monomer, a single condition of usually 80°C or higher, preferably 100°C or higher, and at most 180°C is used.

As mentioned above, it is economical and desirable to simultaneously add a monomer and a polymerization initiator to carry out graft polymerization in one step, but it is preferable to apply the polymerization initiator to the object in advance, and then bring it into contact with the monomer to perform the graft polymerization. A two-stage method of carrying out the polymerization may also be used.

After graft polymerization, the object to be treated is lightly washed with hot water using an oven soaper or the like, dried, and subjected to dry heat treatment to remove residues and form an intermediate pit. In this case, the usual 7-year-old conditions can be applied as is, but 160°C or more
It is preferable to adopt a one-time condition of 0° C. or lower, and it is preferable that the processing time is at least 20 seconds or more.

The dry heat treated object is transferred to a dyeing machine, and then transferred to a step of removing residues. It goes without saying that the dyeing machine can be selected as appropriate depending on the form of the object to be processed. As mentioned earlier, the anionic and nonionic 5Ii! A surfactant is preferred, and the soaping conditions are preferably carried out in the w1 recess described above.

Next, after washing with water, the process moves on to the dyeing process, but depending on the dye UN used, it is possible that a complex may be formed with the remaining soaping agent due to insufficient washing. In that case, it is desirable to add an appropriate amount of an anti-settling agent to the dye liquor. As the dyeing conditions, normal dyeing conditions can be applied. Furthermore, even after removing the residue according to the present invention, synthetic fibers modified by graft polymerization cannot completely maintain the light fastness originally possessed by the synthetic fibers. If necessary, it is desirable to add a light fastness improver, which has been used for a long time in automotive interior materials, which generally require real light fastness, into the dye liquor.

(Effects of the Invention) The present invention includes a step between the graft polymerization step and the dyeing step to remove chemicals and reaction by-products used in the graft polymerization reaction, thereby improving color development, dual light and color fastness. Moreover, since no dry heat setting is required before the graft polymerization process, the monomer utilization efficiency is also improved.

With the present invention, in addition to the original performance obtained by graft processing such as hygroscopicity, electrophoresis, and melt resistance, the conventional drawbacks of low color development and low fastness have been solved, resulting in more vivid color and high fastness. It became possible to provide abundant materials more economically.

(Example) Next, the present invention will be explained based on examples.

Example 1 Gelaph 1-7ff Organic peroxide (Nipper MT-80 manufactured by Nippon Oil & Fats Co., Ltd.) Ig as an initiator, 30 g meccrylic acid as a hydrophilic vinyl monomer 1 quaternary ammonium salt type surfactant (Cation Gen manufactured by Daiichi Kogyo ■) AN Super) 5
g was diluted with water, and 100 g of an aqueous mixed solution was prepared by WJ.

Next, after relaxing scouring and drying, the polyethylene terephthalate processed yarn knitted fabric (Toshi % 91630) was immersed in the above-mentioned aqueous mixture, squeezed with a mangle, wound into a roll, and sealed with vinylidene chloride film. The pi-sofa-tsubu ratio at this time was 8396 based on the weight of the dried processed yarn knitted material. Next, this sealed processed yarn knitted fabric is placed in a microwave treatment device (Apolopetto manufactured by Ichikin), heated and irradiated with 100℃ steam and microwave for 5 minutes, washed with hot water, and dried, and then the initial processed yarn knitted fabric is prepared. The rate of increase in starvation relative to weight was determined. The reaction efficiency of the monomer corresponding to the weight increase rate (taking into account the pickup rate) was calculated as follows.

Monomer reaction efficiency = Grafting efficiency Gra-7j・Efficiency sink) - [Weight increase rate/(Pickup rate/100)
Pickup rate: ffl amount %] Next, the processed yarn knitted fabric was subjected to a dry heat treatment at 180° C. for 30 seconds using a dry heat treatment machine (manufactured by Federal Sensei Kogyo, hot air test pin tenter).

Next, the processed yarn knitted fabric was dyed using a dyeing machine (manufactured by Todoroki Sangyo ■, Hl-DI).
Dyeing 8! The fabric was soaped with an aqueous solution containing 3 g/l of soda soap (Marcel Semme rJ manufactured by Daiichi Kogyo ■) for 30 minutes at 100° C., washed with water, and then dyed using the same dyeing machine. The dye solution used included Sumikalon as a dye, Turquoise Blue 5-GL (Jinmin Kagaku! 1% OWF), Sunsolt #1200 (manufactured by Nikka Kagaku) as a dispersant, 0.5 g/e,
p) Acetic acid and sodium acetate were added as regulators to adjust the pH of the dye liquor to 45, and Chipatex LF (manufactured by Ciba Geigy) 3% OWF was added as a lightfastness improver. Then, it was dyed at 130° C. for 60 minutes, washed with water, and then dried.

Next, it was treated with an aqueous solution of 10 g/l of soda ash at 60°C for 30 minutes, washed with water, dried, and finished at 180°C for 30 seconds.

Next, color development, double light, washing, and abrasion fastness were evaluated. The results are shown in Table-1.

The color development was determined using a non-grafted polyethylene terephthalate-processed yarn knitted fabric (Toshi #1) that had finished intermediate setting.
630) was dyed under the same dyeing conditions as in the above example, and the L value, a value, and b value of the dyed product were measured using a digital color difference meter (Suga Test Instruments fM). It is expressed as the hue difference (ΔE) from the dyed cloth.

The light fastness was determined by 4th grade irradiation according to JISLO842, and the evaluation was expressed in terms of gray scale for discoloration and fading.

Washing fastness was determined in accordance with JISLO844, A-2 method, and expressed as a gray scale grade for discoloration and staining.

The abrasion fastness was evaluated according to JISLO849 and expressed as a contamination gray scale grade.

Example 2 Same as Example 1 except that the nonionic surfactant Sukiset 20-X (manufactured by Dai-Kogyo Seiyaku Co., Ltd.) was changed to 2 g/l as the soaping agent before the dyeing process in the processing method of Example 1. The results are shown in Table 1.

Example 3 The processing method of Example 1 was performed in the same manner as in Example 1 except for the soaping step before the dyeing step, and the results are shown in Table 1.

Example 4 The processing method of Example 1 was performed in the same manner as in Example 1 except for the dry heat treatment following the graft processing step, and the results are shown in Table 1.

Comparative Example 1 A polyethylene terephthalate processed yarn knitted fabric (#1630 made by Toshi) that had been subjected to dry heat treatment before the graft processing step was used, and the same processing as in Example 1 was performed, and the results are shown in Table 1.
Shown below.

Comparative Example 2 Using the same sample as in Comparative Example 1, the same processing as in Example 1 was performed except for the dry heat treatment and soaping step after the graft processing step, and the results are shown in Table 1.

Comparative Example 3 Using the same sample as in Example 1, the same processing as in Comparative Example 2 was performed, and the results are shown in Table-1.

Table 1 As is clear from Table 1, in Examples 1 and 2 and Comparative Example 1, the residue was removed by dry heat treatment and soaping with a surfactant and a sex agent after the grafting process, so a residue removal process was incorporated. Compared to Comparative Examples 2 and 3, which did not have the same color, significant improvements were achieved in color development (hue difference ΔE from the unprocessed product) and fastness, particularly in both light and wet fastness. In addition, although Examples 3 and 4 each performed one of the two residue removal steps, the effects were slightly inferior compared to Examples 1 and 2.
Recognize the synergistic effect of dry heat treatment and surfactant soaping in the residue removal process.

In Comparative Examples 1 and 2, dry heat treatment (intermediate setting) was performed before grafting, so the grafting efficiency was lower than in other examples in which dry heat setting was not performed before grafting, resulting in a lack of economic efficiency.

Claims (1)

[Claims] A method for modifying synthetic fibers, which comprises graft-polymerizing a hydrophilic vinyl monomer onto synthetic fibers using microwaves or high-frequency waves as a heating means, and carrying out a residue removal step after the graft polymerization step and before a dyeing step.