JPS59187033A - Method for modifying molded polyester based article - Google Patents

Abstract

PURPOSE:To impart the cottonlike characteristics to a molded polyester based article without deteriorating color fastness nor physical properties in dyeing the molded polyester based article modified by the graft polymerization method and substituting the dyed article with an alkali metal, by removing a swelling agent before the substitution treatment with the alkali metal. CONSTITUTION:A molded polyester based article is modified with a swelling agent, e.g. monochlorobenzene, a polymerization initiator, e.g. benzoyl peroxide, and a vinylcarboxylic acid monomer, acrylic acid, by the graft polymerization method, and the swelling agent is removed (preferably by dry heat treatment at 160 deg.C or above). The treated article is then dyed and subjected to the substitution treatment with an alkali metal.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the modification of polyester molded articles by graft polymerization. More specifically, the present invention relates to a modification method for imparting cotton-like properties to polyester molded articles while preventing deterioration in color fastness and physical properties.

Conventionally, modification of polyester molded products by graft polymerization was disclosed in Japanese Patent Publication No. 45-502. As is known from Japanese Patent Publication No. 48-27743, Japanese Patent Application Publication No. 48-68694, etc., after graft polymerization using a swelling agent such as monochlorobenzene, a polymerization initiator such as benzoyl peroxide, and a vinyl monomer having an acidic group, Heat over 80℃,
Either use a process of substitution treatment and dyeing with various metal salts, or carry out the above-mentioned graft polymerization and then carry out normal dyeing.
Next, a process of substitution treatment with various metal salts is adopted. However, in any case, when such a process is adopted, the fastness of the dyed product, especially the light fastness, is significantly reduced.

This was one of the major reasons why graft modification of polyester molded products could not be commercialized.

The present inventors have focused on this point, and have conducted extensive research to develop a graft-modified polyester molded product with a small decrease in dye fastness, and have arrived at the present invention.

The present invention has a secondary structure to achieve the above object.

(1) Swelling agent 1 When dyeing a polyester molded product modified by a graft polymerization method using a polymerization initiator and a vinyl carboxylic acid monomer and subjecting it to substitution treatment with an alkali metal, before the substitution treatment with an alkali metal. A method for modifying a polyester molded product, which comprises treating it with a deswelling agent.

(2) The modification method according to claim (1), wherein the deswelling agent step is a dry heat treatment at 160° C. or higher.

With such a configuration, it is possible to prevent a decrease in color fastness such as light fastness in dyed products of graft-modified polyester molded products, which has been a big problem in the past.
It becomes possible to provide highly practical dyed products.

The method of the present invention will now be explained in more detail.

The swelling agent referred to in the present invention is used to introduce a polymerization initiator, which will be described later, into the inside of a polyester molded product.
Monochlorobenzene, dichlorobenzene, trichlorobenzene, benzoic acid, phenol, methyl chloride, diphenyl, diphenylmethane, triphenylmethane, O-phenylphenol, P-phenylphenol,
0-cresol etc.

Next, the term "polymerization initiator" as used in the present invention means benzoyl peroxide, methoxybenzoyl peroxide metals, and the like.

Since most of these polymerization initiators are water-insoluble, surfactants such as ethylene oxide adducts of alkylphenols and ethylene oxide adducts of alkyl phosphate esters are used.

Process by emulsifying and dispersing.

(2) Vinyl carboxylic acid monomers referred to in the present invention include acrylic acid, methacrylic acid, and maleic acid.

Refers to hydrophilic vinylcarboxylic acid monomers such as itaconic acid and butenetricarboxylic acid. In addition, hydroxyethyl acrylate 1 is added to these vinyl carboxylic acid monomers.
Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylamide.

Hydrophilic monomers such as methacrylamide and N-methylolacrylamide; hydrophobic monomers such as methyl acrylate and methyl methacrylate;

Although a mixture of various vinyl monomers may be used, in the present invention, a monomer rich in hydrophilic vinyl carboxylic acid monomers is preferable in order to modify the polyester molded product to be cotton-like.

As a method for graft polymerizing vinyl monomers having acidic groups onto polyester molded articles, an organic peroxide such as benzoyl peroxide is added in advance to a polyester molded article using a swelling agent such as monochlorobenzene. A method in which a vinyl monomer having an acidic group such as acrylic acid or methacrylic acid as described above is introduced alone or is heated in a mixed aqueous solution for graft polymerization, or an organic peroxide catalyst such as benzoyl peroxide is used. There are various methods, including graft polymerization by heat treatment in a liquid containing a swelling agent such as monochlorobenzene and the aforementioned vinyl monomer having an acidic group.

The method is not limited to these methods.

Note that the term "alkali metal" as used in the present invention means a general alkali metal shown in the periodic table. Specifically, the carboxyl group introduced into the polyester molded product is reacted with lithium hydroxide, potassium hydroxide, sodium hydroxide, lithium carbonate, potassium carbonate, sodium carbonate, etc. to form an alkali metal salt. That is, 1. Generally, a graft-polymerized polyester molded article is immersed in an aqueous solution of an alkali metal compound and subjected to a substitution treatment at a temperature of 80°C or lower, preferably 60°C or lower.
A cold system, a batch system, a nokurado steam system, etc. may also be used.

Next, two polyester molded products referred to in the present invention are terephthalic acid, isophthalic acid and ethylene glycol, 1,4
-It means a normal polyester-based molded product known as an ester reaction product with butanediol, 1,6-hexanediol, etc. In addition, 5-sodume sulfoisophthalate and polyamite-based compounds can be copolymerized or They may be mixed in by a blending method, or may be a composite molded product formed by trench, side-by-side, or core-set formation. The forms of such molded products include staples, tows, filaments, webs, slivers, spun yarns, and textured yarns.

It may be in any form, such as knitted fabric, woven fabric, non-woven fabric, or film, and may be a blended, blended, or interwoven fabric with natural fibers or other synthetic fibers.

Conventionally, a polyester molded product graft-polymerized by the method described above is processed as is using a general disperse dye.
After high-temperature and high-pressure dyeing at 120 to 135°C, an alkali treatment is performed which combines reduction washing and a process of replacing carboxyl groups with an alkali metal, or after graft polymerization, a process of replacing carboxyl groups with an alkali metal is performed. After fermentation, high-temperature and high-pressure dyeing is performed at 120 to 165° C. using a general disperse dye, and then, if necessary, reduction washing is performed. However, as mentioned above, no matter which of these methods is adopted, there is a problem in that the fastness of the dyed product, particularly the light fastness, is significantly reduced.

Therefore, in the present invention, the above-mentioned graft polymerization was performed. Afterward, and before the substitution treatment with alkali metal, a deswelling agent treatment is always performed. In other words, if a swelling agent remains in a dyed product, it may promote the fading of the dye during home washing or the decomposition of the dye due to sunlight irradiation.The present invention improves these problems. be.

This deswelling agent treatment method includes dry heat treatment at 160°C or higher or washing treatment using an anionic or nonionic surfactant. , simple and highly effective. If such a deswelling agent treatment is performed before the substitution treatment with an alkali metal,
It may be incorporated at any stage after graft polymerization. That is, after performing a substitution treatment with an alkali metal, 16
This is because if high temperature heat treatment such as dry heat treatment at 0° C. or higher is performed, a serious problem arises in that the strength of the polyester molded product is significantly reduced. Therefore, in the present invention, a step of applying a deswelling agent is necessarily included before the substitution treatment with an alkali metal, and this point is one of the greatest features of the present invention.

Furthermore, even if a deswelling agent treatment step is introduced before the alkali metal replacement treatment, if the dyeing step and the alkali metal replacement treatment step are reversed in the subsequent steps, the strength will decrease significantly. Because of this problem, the most preferable embodiment is graft polymerization, swelling agent treatment, dyeing, and alkali metal substitution treatment, or graft polymerization, dyeing, swelling agent treatment, and alkali metal substitution treatment, which requires 9 steps for process passability. From a gender perspective, the former mode is the best.

In addition, if the polyester molded product is in the form of a fabric, after dyeing and alkali metal substitution treatment.

Fabric softener and antistatic agent for finishing set and as required.

Finishing with resin processing agent etc. Knee dry heat setting is applied,
In the case of modified polyester molded products that have been given cotton-like properties by graft polymerization, the dry heat setting after the alkali metal substitution treatment is 160°C or lower, preferably 140°C.
It is preferable to set it at a temperature below ℃ to prevent loss of strength.

According to the method of the present invention, cotton-like moisture absorption and permeability with little change in physical properties and little decrease in dye fastness can be obtained.

It is possible to obtain modified polyester molded articles with excellent properties such as water absorption, antifouling properties, antistatic properties, and antimelt properties in an extremely safe manner.

The two methods of the present invention will be further explained below with specific examples.

Example 1 Comparative Examples 1 to 6 150 denier 4 made of ordinary polyester fiber
8 filament false twisted yarn with a basis weight of 180 g/m
2 twill fabric. After relaxing, scouring, drying, and intermediate setting the fabric under normal conditions.

(A) Graft polymerization step: emulsifier and nonylphenol ethylene oxide 1
In a mixture consisting of 2 g7'l of 4 mol adduct, 5112 temonochlorobenzene as a swelling agent, 2171 benzoyl peroxide as a polymerization initiator, the bath ratio was 1:6.
The polymerization initiator pretreatment was carried out under conditions of 0. Next, a bath containing acrylic acid and methacrylic acid from 8 to 8 each at a ratio of 1:0
The woven fabric pretreated with a polymerization initiator was immersed in the solution, the temperature was raised, and graft polymerization was performed at 110° C. for 60 minutes (Step A).

next.

(B) Deswelling agent process The Niger raft-polymerized fabric was subjected to dry heat treatment at 180° C. for 60 seconds to be treated with a deswelling agent (Step B).

Next, this one.

(C) Dyeing process Rainbow Eye Disperse Blue 224 3%ow
f, immersed in a dye solution consisting of 0.5 g of tamol-based dispersant and 0.2 g of acetic acid at a bath ratio of 1:30, and dyed with a Colorbet dyeing tester (manufactured by Nippon Senzo Kikai ■ Co., Ltd.) at 130 g.
High temperature and high pressure staining was carried out at ℃ for 60 minutes (Step C).

Next, this dyed product.

(D) Alkali metal replacement step: The sample was immersed in a solution containing 7 g of sodium carbonate/p at a bath ratio of 1:0 and subjected to alkali metal replacement treatment at 75 V for 0 minutes (D step).

After thoroughly washing this material with hot water, dehydrating it and heating it at 140℃ for 6 minutes.
It has a dry heat finish set for 0 seconds, has a moisture absorption rate of 83 cm, which is the same as cotton, and has no problems with physical properties such as 2 dimensional stability 2 loss of strength, and has poor dye fastness such as washing fastness and light fastness. A good modified polyester fabric was obtained (this example)
. For reference, the carboxyl group substituted with an alkali metal in this product was determined by acid-alkali neutralization titration to be 6.9 x 10''-'gram equivalent/gram fiber.

Next, as a comparison, there are two cases in which step B is omitted in the processing steps of this example (A-c-D...Comparative Example 1), one in which step B is the last step in the processing steps of this example (eighth). -〇-D-B...
...Comparative example 2) One example in which step D was placed before step B (A-D-B-1:!...Comparative example 3) Two examples in this example , B step and D step were replaced (A-D-c-B... Comparative Example 4).

In this example, C process and D process were replaced (A-B
-D-C...Comparative example 5) was processed.

Both have physical properties such as 1-dimensional stability, 9 strength, or
Problems have arisen in terms of dye fastness, such as light resistance and washing. These results are summarized in the table below.

The moisture absorption rate was measured at 110°C for 2 hours, completely dry, and then in an atmosphere consisting of a saturated aqueous solution of thorium nitrite (20°C x 65%
RH) for one day and night, and the moisture absorption rate was measured from the change in weight.

Dimensional strength measurements were made based on JIS-L1079. Dye fastness was based on:

Washing fastness: JIS LO844 Light fastness: JIS LO842 Dimensional stability (
Washing shrinkage rate) was measured based on JIST-1018.

Example 2 A fabric similar to that of Example 1 was processed in the following processing step using the same processing conditions as Example 1. 1. Good dimensional stability 2.
It is possible to obtain dyed products with little loss of strength and good fastness to washing and light resistance.

Processing process: A-+C-B-LD

Claims (2)

[Claims] (1) Swelling agent 9 When dyeing a polyester molded product modified by graft polymerization using a polymerization initiator and a vinyl carboxylic acid monomer and subjecting it to substitution treatment with an alkali metal, before the substitution treatment with an alkali metal. A method for modifying a polyester molded product, which comprises treating it with a deswelling agent. (2) The modification method according to claim (1), wherein the deswelling agent step is a dry heat treatment at 160° C. or higher.