JPS58132171A - Treatment of polyester molded product - 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 The present invention relates to a method for treating polyester moldings. More specifically, the present invention relates to a treatment method for imparting durable and excellent stain removability to polyester molded articles.

It is well known that products obtained by molding thermoplastic polyester, such as fibers, films, and resin molded products, are currently widely used for various purposes. 4I: Fibers are used for clothing, industrial use, and 1. It is used in extremely large quantities.

However, these polyester molded products have the disadvantage that it is difficult to remove stains. In other words, when [7'''C is used with clothing, for example, it gradually darkens.In order to improve this drawback, various studies have been made and many proposals have been made.For example, polyethylene glycol or A method of attaching this derivative to the surface of a molded article, a method of graft polymerizing an acrylic acid monomer to the surface of a molded article, a method of treating with an alkaline aqueous solution such as sodium hydroxide, a method of attaching a fluorine-based compound to the surface of a molded article. Typical examples include methods.However, 1.
Therefore, these methods are not effective enough, their effectiveness decreases with repeated washing [7], the process is complicated, and dirt is difficult to adhere to, but once it does, it cannot be removed by normal washing. Each of the different types of sake had its own drawbacks, and none of them were completely satisfactory.

The inventors of the present invention have conducted repeated studies to find a simple method for treating polyester molded articles that can easily remove dirt.
It was discovered that by JILM with a metal salt of 71-nocarboxylic acid, it was possible to easily impart durable dirt removal properties with a simple treatment.11 The present invention was achieved.1. It is something that

That is, the present invention is a method for treating a polyester molded article, which is characterized by treating a molded article made of thermoplastic polyester with an aminocarboxylic acid metal salt.

In the present invention, the polyester molded product refers to a thermoplastic polyester molded into a fiber, film, or other shape, and is particularly preferably used for molded into a fiber. Also, when it is made into fibers, even if it is made into cloth, it is mourning. In addition, the term "thermoplastic polyester" here refers to a thermoplastic polyester obtained from dicarboxylic acid and diol or oxycarboxylic acid, and in particular, polyester containing terephthalene as the main dicarboxylic acid component and ethylene glycol or tetramethylene glycol as the main diol component. 1 ru is preferable 1. stomach.

Any method may be used to produce such a molded product made of polyester, including a melt spinning method in which molten polyester is discharged from a spinneret to obtain S, an extrusion molding method in which the polyester is extruded through a slit, etc. A common molding method is an injection molding method in which the material is injected.

The present invention provides 7! such polyester molded products. The removal of stains is improved by treatment with a metal nocarboxylate, but the 74-nocarboxylic acid that constitutes the metal 747-carboxylate used for removal usually has 2 to 12 carbon atoms.
)71/carboxylic acid is used, specifically represented by the general formula 1N-lt-C0OH, where 8 is an aliphatic, alicyclic or aromatic divalent radical. In particular, when it has an aromatic ring, it is preferable that the amino group is directly bonded to the aromatic ring, or that the amino group is bonded to the aromatic ring via an alkylene group. or,
R may have a side chain, X, S, or one group that does not form a salt with an amine other than a hydrocarbon, for example, an S-gen group, a nitro group, a cyano group. , hydroxyl group,
ether group.

Carboxyl group salts, amide groups, ester groups.

It may also contain salts of sulfonic acid groups, etc.

The metals forming the aminocarboxylic acid salts are preferably alkali metals or alkaline earth metals, with alkali metals such as Na, K and Li being particularly preferred.

In addition, these 7-minocarboxylic acid metal salts are often used as aqueous solutions, so their solubility in water is 19G.
As mentioned above, preferably 5 or more compounds are preferably used.

Any method may be used for the treatment with the above metal salt of aminocarboxylic acid, but for example, the metal salt of 7-minocarboxylic acid may be treated with 0.
001 weight or more, preferably I<4io, at-io weight, as an aqueous solution or suspension, and a method of applying it to the polyester molding is used. This aqueous solution or suspension contains water, polyalkylene glycol*, which is generally used as a spinning or drawing oil component for polyester fibers, fatty acid esters, etc. (rough-ins,
Contains various surfactants, etc. (1) In the case of containing these oil components, it is preferable that the aminocarboxylic acid metal salt can be attached together with the oil component during the fiber spinning and drawing process. 1° The adhesion treatment of the aminocarboxylic acid metal salt to the polyester molded article can be carried out at any stage after the polyester is molded.For example, in the case of fibers, it can be carried out during the stretching heat treatment during spinning. The treatment can be carried out at the time of spinning, twisting, spinning, weaving, dyeing after the fabric is dyed, or after it is made into a product such as clothing.

In addition, methods for adhering aminocarboxylic acid metal salts include immersing the molded product in a treatment bath, spraying a treatment liquid onto the molded product, and using a coating roller (oil ruler).
Any method can be employed, such as a method of applying a treatment liquid to the molded product through a method.

In this way, the aminocarboxylic acid metal salt is attached to the polyester molded article.1. After this, the aminocarboxylic acid metal salt is chemically bonded to the surface of the polyester molded product, and the polyester molded product is left for a certain period of time in order to increase its durability and prevent it from being easily detached from the molded product. This standing time varies depending on the temperature at that time, the concentration of the aminocarboxylic acid metal salt, etc., and it is difficult to define it unambiguously. - In this case, it will be at room temperature for 1 hour or more, and at 100°C for about 10 seconds to 30 minutes. 41, it becomes possible to increase the reaction rate and shorten the standing time by heating. In this case, the neglect processing time t (seconds) may be selected so as to satisfy the following formula.

t≧6×10-'@! p (7,li X 108
/T ) (Here, T is the temperature at the time of standing treatment and is an absolute temperature.) However, in reality, it varies depending on the type and concentration of the 7-minocarboxylic acid metal salt, so it is necessary to check by Test 1 each time. is preferred.

On the other hand, instead of attaching the aminocarboxylic acid metal salt to the polyester molded article and leaving it for treatment as described above, the aminocarboxylic acid metal salt is treated at the stage of adhering the aminocarboxylic acid metal salt to the polyester molded article. Heating the liquid or polyester molded article for 1"C also has the effect of promoting chemical bonding reactions and cures the problem. For example, heating the aminocarboxylic acid metal salt treatment liquid and placing the polyester molded article in the treatment liquid for a certain amount of time will cure the problem. If the material is immersed for a certain period of time, sufficient washing durability can be obtained without having to leave it for a long time after the treatment.

5. In the present invention, it is preferable to treat the polyester molded article with an aminocarboxylic acid and then heat it.
Aminocarboxylic acid metal salts precipitate as solids, do not adhere uniformly to the surface of polyester molded products, and often fall off from polyester molded products. It is preferable to heat the metal salt to a temperature higher than its melting point.

Furthermore, in order to prevent problems caused by water evaporation due to such heating, the aminocarboxylic acid metal salt (3)K is an odorless liquid at the processing temperature, is water soluble, and has substantially the same composition as the aminocarboxylic acid metal salt. It is an extremely effective method to mix and process non-contrary compounds. This compound CB) has a boiling point of 100°C or more, preferably 150°C or more, and is soluble in water [10% or more, preferably 20% or more].
Of course, it is necessary that it not decompose at the processing temperature. Specific examples of this compound include ethylene glycol, polyethylene glycol with an average molecular weight of 500 or less, glycerin, )rimethylolpropane, dimethylformamide, etc., and in particular, with an average molecular weight of 1 g [SO
Polyethylene glycol having a molecular weight of 0 to 3000 is preferred.

The aminocarboxylic acid metal salt (4) and compound +B) may be mixed in advance and attached to the polyester molded product, or either one of them may be applied to the polyester molded product first.
5K
Although t- may be used, the former method is preferable in that it can be processed uniformly. For example, this mixture may be simply mixed together, but it is more preferable to use it in the form of a solution using water. At this time, the concentration of the prisoner component is 0.01 to 1 G 0 f/l, and the concentration of the (■) component is 0.01
~1 o o f/l, and (A): of) is l:50
It is preferable to use the ratio of 10:1 to 10:1. Further, this aqueous solution may contain other substances, such as oil components for spinning and drawing.

In this manner, a compound that is liquid at the processing temperature, water soluble, and substantially non-reactive with the aminocarboxylic acid metal salt is mixed into the 7-minocarboxylic acid metal salt.1. Even if the water in the treatment solution evaporates due to heating [2], since the aminocarboxylic acid metal salt is dissolved or dispersed in the liquid compound, it will not become a solid and precipitate. Such troubles will not occur. Therefore, it is possible to perform heat treatment at a high temperature, and the treatment time can be shortened, which is extremely desirable.

The polyester molded article to which the aminocarboxylic acid salt is attached in this manner is easily cleaned of dirt, and its effectiveness does not decrease even after repeated washing at ℃, and re-contamination during washing can be prevented. In addition, the treatment method of the present invention can improve m-
One of the characteristics is that the above effects can be obtained without changing the sex. Other effects of the present invention include improved hydrophilicity, improved adhesion, and improved printability.

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

The stain removability was evaluated based on the following criteria.

Class 1: No stains removed at all.

Grade 2: Slight stains coming off.

Grade 3: Most of the dirt is removed.

Grade 4: Slight stains remain.

Grade 5: No stains left.

Example! Polyethylene terephthalate (intrinsic viscosity OOS)
150 f/L I
F) a-7 sodium minocabronate aqueous solution 100
After immersing at ℃ for 1 minute at a bath ratio of 1/4゜, immediately rinse with water [-
Dry. The weight limit at this time was approximately 2-. A stain of activated carbon/olive oil == 1/4 (weight ratio) was applied to this sample and heat treated at 100°C for 1 hour.
After washing and rinsing for 10 minutes using f/1 detergent (ZAB ■ manufactured by Kao Soap Co., Ltd.) K at a bath ratio of 1/100, no stains remained at all (stain removal grade 5).

Also, after washing 10 times under the above washing conditions, the same stain as above was applied again, heat treated and washed, and no stain remained at all (stain removability for 1 day).

Comparative Example 1 The stockinette knit sample of Example 1 was not treated with the ζ-7i sodium caproate aqueous solution.

When the same stain removal test as in Example 1 was carried out, almost no stain was removed, and stains were still attached to the areas where stains had not been applied (stain removal grade 1). ).

Comparative Example 2 In Example 1K, except that an aqueous solution of 92 f/l sodium hydroxide (sodium concentration is the same as the 1-7ξ sodium aqueous solution of Example 1) was substituted for the sodium 8-aminocaproate solution. As a result of the primary stain removal test performed in the same manner as in Example 1, it was confirmed that the area where the stain was applied was clearly darkened (stain removal grade 3).

Example 2 Polyethylene terephthalate (intrinsic viscosity OOSS)
Melt-spun 11, before the number of turns, add 3F of sodium 1-aminocaproate and 10F of lithium laurylphosphone.
The liquid dissolved in water of j was applied and wound up. This yarn was stretched 4.5 times using heating a-5,- at 85 DEG C., and then heat-set at 1 DEG C. in 1-1 turns.

The obtained drawn yarn was knitted into a knitted fabric, heat-treated at 140°C for 10 minutes, and the stain removability was examined using K in the same manner as in Example 1. No stains remained at all (stain removability 5).
・Class).

Example 3 A stain removal test was conducted in the same manner as in Example 1 except that polybutylene terephthalate fiber (intrinsic viscosity 1.0) was used instead of the polyethylene terephthalate fiber in Example 1. As a result, no stain remained. (stain removability 1
1゜Examples 4 to 10 In Example 1, the same treatment as in Example 1 was performed except that the compounds shown in the table were used instead of sodium 1-7 minocaproate, and the stain removability was evaluated. As a result, we obtained the results shown in the following table.

Example 13 Sodium 1-aminocaproate IIF and polyethylene glycol (average molecular weight 5oo) were added to polyethylene terephthalate (intrinsic viscosity 00@S) before winding up the melt-spun L1.
tof and a solution consisting of 1 t of water was applied and wound up (1.0% by weight based on the two adhering lid fibers), and the resulting undrawn yarn was heated at 80°C for 4. After stretching for s times Km, heat treatment under tension at 220°C for 3 seconds 1. I wound it up.

The obtained yarn was made into a stockinette knit, washed with water, dried, and coated with a stain consisting of a mixture of activated carbon and olive oil (mixed weight ratio of 1:4), and then treated with 3 f/l detergent (Zab ■ manufactured by Kao Soap Co., Ltd.). As a result of washing and rinsing for 10 minutes with a washing solution containing the product at a bath ratio of 1/100 K, no stains remained (stain removability 11°) Furthermore, after repeated washing 100 times under the above washing conditions. As a result of applying the stain in the same manner as above and washing, no stain remained at all (stain removability 10゜Example 14 In Example IK, instead of polyethylene terephthalate 11, polyethylene terephthalate fiber #11 (intrinsic viscosity 1
．． 0) ~・, heat treatment after stretching at 1110℃, 1
The same operation as in Example 1 was performed except that the time was 5 seconds. As a result, the stain removability was grade 14. Even after repeated washing 100 times, the stain removability was still grade 4.

Claims (1)

[Claims] L. A method for treating a polyester molded article, which comprises treating a molded article made of thermoplastic polyester with an aminocarboxylic acid metal salt. 2. The method for treating a polyester molded article according to claim 1, wherein the aminocarboxylic acid metal salt is an alkali replacement metal salt. A method for treating a polyester molded article according to claim 1, wherein the molded article is treated with an aqueous solution or suspension of a 7ξnocarboxylic acid metal salt. The method for treating a polyester molded article according to any one of claims 1 to 3, wherein the thermoplastic polyester is polyethylene terephthalate F and/or polybutylene prephthalate. 4. The method for treating a polyester molded article according to any one of claims 1 to 4, wherein the polyester molded article is a fiber.