JPS6034580B2 - Method for modifying synthetic polymer molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for modifying a graft polymer obtained by graft polymerizing an ethylenically unsaturated organic acid to a synthetic polymer molded article.

Synthetic polymer molded products, especially hydrophobic synthetic polymer molded products such as polyester and polyamide, have excellent mechanical properties, but on the other hand, they have poor hygroscopicity compared to natural polymers, so they are easily charged and oil-based stains. It has drawbacks such as being difficult to remove, and it also has drawbacks such as poor heat resistance, so it is easily melted by a cigarette or the like and creates holes.

Furthermore, when used as clothing, it has drawbacks such as pilling and being sticky and stuffy when worn because it has almost no water absorption or hygroscopicity. Conventionally, as a method to improve these drawbacks, a method has been used in which an ethylenically unsaturated organic acid such as acrylic acid or methacrylic acid is graft-polymerized onto a synthetic polymer molded article, and then the acid group introduced by the graft polymerization is treated with an alkali metal salt. is proposed.

However, not only harsh conditions are required for alkali metal chlorination, but also the performance of the obtained metal chloride graft polymer is insufficient in anti-pilling properties, anti-melting properties, etc., and these properties fluctuate. , a major problem in practical application is that it is difficult to obtain excellent performance with high reproducibility.

The inventors of the present invention have conducted extensive research in order to solve the above-mentioned drawbacks, convert acid-grafted polymers into alkali metal salts easily and in a short time, and obtain excellent modification effects with high reproducibility, anti-pilling properties, and anti-melting properties. As a result, the method of the present invention was achieved.

That is, the present invention is characterized in that after graft polymerizing an ethylenically unsaturated organic acid to a synthetic polymer molded article, the article is treated with an aqueous liquid containing a basic alkali metal compound and a sequestering agent. When the method of the present invention is used, the acid groups introduced by graft polymerization are easily converted into alkali metal salts, giving excellent hydrophilicity and melt porosity prevention properties (melting resistance), and also provides excellent resistance to polyester molded products. It also has the characteristic of providing pilling properties.

In addition, not only are the obtained effects on the drum tissue excellent, but the reproducibility of the effects is always excellent, which provides a great advantage in industrialization. The synthetic polymers used in the present invention are polyester-based, polyamide-based, polyolefin-based, polyacrylic-based polymers, etc., and the molded products include cotton,
Examples include, but are not limited to, yarn, tow, woven or knitted fabrics, synthetic paper, nonwoven fabrics, films, rugs, etc.

Of course, in the case of fibers, hollow fibers may be used. However, since it also provides excellent pill resistance, it is particularly effective when applied to polyester. Any known method may be used to graft polymerize the ethylenically unsaturated organic acid onto the synthetic polymer molded article, including radiation irradiation, ion discharge, light irradiation, thermal oxidation, and ozone oxidation. A method using a catalyst can be adopted, and there are no particular limitations.

The grafting rate of the ethylenically unsaturated organic acid, expressed as the weight increase rate after removing the homopolymer (non-grafted polymer), is generally 0.5 to 30% to achieve the desired degree of modification. can get. The ethylenically unsaturated organic acids referred to in the present invention include, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, styrenesulfonic acid,
Q-acrylic hydroxyacetic acid, butenetricarboxylic acid, etc., with particular preference given to acrylic acid and/or methacrylic acid. Examples of basic alkali metal compounds used for alkali metal chlorination of graft molded products include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, potassium carbonate, and 2-phosphoric acid.
Alkali metal salts of inorganic weak acids such as sodium and 3-sodium phosphate; alkali metal salts of organic weak acids such as sodium acetate and sodium propionate; sodium sulfite;
It is a compound that dissolves in water and exhibits alkalinity, such as sodium silicate, and these are used alone or as a mixture of two or more types.

Note that the amount of the alkali metal compound used is usually 0.1 night/night.
That's enough for 10 evenings. In the present invention, known substances are used as the metal ion sequestering agent used together with the above-mentioned alkali metal compound. Commonly used sequestrants include sodium pyrophosphate and sodium triphosphate. Condensed phosphates such as sodium trimetaphosphate, sodium tetrametaphosphate, and sodium polyphosphate;
Ethylenediaminetetraacetic acid salts, such as disodium salt of ethylenediaminetetraacetic acid, tetrasodium salt of ethylenediaminetetraacetic acid, diammonium salt of ethylenediaminetetraacetic acid, tetraammonium salt of ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine Examples include N-N,NN-triacetic acids, jethylene triamine pentaacetic acid, glycol ether diamine tetraacetic acid, cyclohexane diamine tetraacetic acid, and nitrilotriacetic acid. The amount of these metal ion sequestering agents used depends on the amount of polyvalent metal ions dissolved in the water, but 0.01/5/day is sufficient. The alkali metal chlorination treatment of the grafted molded product using an aqueous solution containing the above-mentioned alkali metal compound and sequestering agent is generally carried out at a temperature in the range of room temperature to 100°C, but pad steaming is performed by increasing the concentration of the alkali metal compound. It can also be done with etc.

The present invention is particularly effective when using water in which polyvalent metal ions are dissolved in water with a total hardness calculated as calcium carbonate of 5 ppm or more, particularly 1 ppm or more. For the first time, effective modification of graft molded products has been achieved.

A rare product made of an ethylenically unsaturated organic acid-grafted synthetic polymer that has been chlorinated with an alkali metal according to the method of the present invention has excellent water absorption, hygroscopicity, antifouling properties, and antistatic properties.
Furthermore, corrosion resistance and, in the case of polyester graft polymer molded articles, anti-pilling properties are also imparted in a complex manner, and the effects are remarkable.

In addition, various properties such as dyeability, adhesion, metal dust landing, gas permeability, and reactivity with other compounds can be improved through treatment, and these properties can be applied to applications that utilize these properties. be able to. In particular, when high-speed spun polyester hollow fibers or films are graft-polymerized and then subjected to alkali metal salting, unique voids can be generated, and they can also be used for reverse osmosis, pressure dialysis, ion exchange, etc.
Hereinafter, the present invention will be specifically explained with reference to Examples.

Note that all parts and % in the examples are parts by weight and % by weight, and oM. means the weight relative to the fiber material. Example 1 1 part of penzoyl peroxide, 8 parts of monochlorobenzene
In an aqueous emulsified dispersion consisting of 1 part of /igen ET-160 (nonionic surfactant, Daiichi Kogyo Seiyaku Co., Ltd.), 1 part of Neogen T (anionic surfactant, Daiichi Kogyo Seiyaku Co., Ltd.), and 100 parts of water, Two pieces of polyester staple knitted fabric (40 count, fabric weight 110) were soaked in a graft bath prepared by adding 15 parts of a mixture of equal parts of acrylic acid and methacrylic acid, and soaked in a nitrogen atmosphere at 100 q○ for 1 hour. Graft polymerization was performed.

Next, the non-grafted polymer was removed by extraction with boiling water for 5 hours to obtain a grafted polymer with a graft ratio of 11.0%. On the other hand, groundwater (total hardness calculated as calcium carbonate: 41
．． pm) for 1.5 pm/an aqueous solution containing sodium hydroxide, or 1 pm/an aqueous solution containing sodium hydroxide and 0.0 pm).
2 nights/Aqueous solutions containing the diethylenediaminetetraacetic acid-4-sodium salt (EDTA4Na) were prepared, and these solutions were used to incubate the above graft polymers at 70°C and 0.
．． It was treated immediately, washed with the same well water, and then dried.
The anti-pilling properties of the sodified graft polymer thus obtained were measured by the ICI method according to JIS standard L-107 mouse NI, and the results shown in Table 1 were obtained. In addition, 2000, 65%
The absorption rate at RH is also shown. Table 1 Excellent pill resistance and hygroscopicity were obtained by the method of the present invention.

Furthermore, the excellent anti-pilling properties did not change at all even after washing with hard well water. In addition, in the case of treatment using only sodium hydroxide, even if the treatment time was extended to 5 hours, the result was 0. There was almost no difference in pill resistance and moisture absorption compared to the fabric treated with bending time.
Example 2 A graft polymerization solution having the same composition and concentration as in Example 1 was prepared, and 20 parts of a processed yarn knitted fabric of polyethylene terephthalate (7 m/24 f, fabric weight 160 m/pillow) was immersed in the solution, and the mixture was soaked in the solution under a nitrogen atmosphere. , 1 graft polymerization was carried out at 100°C.

Then extraction was carried out with boiling water for 5 hours. Graft rate 1
0.2% of graft polymer was obtained. Next, the obtained graft polymer was dyed with Sumikalon Flu E-FBL (disperse dye,
Sumitomo Chemical Co., Ltd.) 1%oM. Disper TL (dispersant, Meisei Chemical Co., Ltd.) 0.1% staining solution at 130 x 0 for 1 hour.
It was stained with a Yu ratio of 1:100. Then, it was converted into sodium salt in the same manner as in Example 1. Table 2 shows the moisture absorption rate and enemy resistance of the obtained graft polymer sodium salt. Furthermore, the defense against enemies is as follows: When a hollow glass sphere with a diameter of 1.5 mm and a weight of 1.5 mm heated to a predetermined temperature in an electric furnace is placed on a piece of cloth held horizontally, the glass sphere melts the cloth and falls. It was measured as the lowest possible glass bulb heating temperature. Table 2 Excellent anti-melting properties and moisture absorption properties were obtained by the method of the present invention.

In addition, in the comparative example treatment using only sodium hydroxide, even if the treatment time was extended to 5 hours, the melting resistance and hygroscopicity were 0.
There was almost no difference from the cloth treated in the morning. The excellent melt-proofing properties obtained by the present invention are not lost at all even when washed with hard water, and in fact are even slightly improved.

Example 3 The graft polymer before dyeing obtained in Example 2 was injected into ground water (total hardness calculated as calcium carbonate: 41.5 ppm), tap water (total hardness calculated as calcium carbonate: 22.4 ppm), and municipal water A (total hardness converted to calcium carbonate: 14.5 ppm). 8p
Sodium carbonate 2 hours/so or Sodium carbonate 2 hours/sototrilin prepared using various types of water such as irrigation water B (total hardness 9.pm) and irrigation water C (total hardness 5.pm) The graft polymer was treated with an aqueous solution containing 0.5 μl of sodium chloride at 70° C. for a predetermined time to convert the graft polymer into a sodium salt, and thoroughly washed with the respective water for 4 μl.

The wicking properties, hygroscopic properties, and anti-melt properties of the graft polymer sodium salt thus obtained were evaluated, and the results shown in Table 3 were obtained. The wicking property was determined by dropping a drop of water using a burette from a piece of cloth held horizontally and measuring the time from that point until the specular reflection on the cloth disappeared.

Table 3 It is clear that excellent quality properties can be obtained only when sodium chloride treatment is performed by the method of the present invention, even when using water in which polyvalent metal ions are dissolved.

When using water containing dissolved polyvalent metal ions, it was completely impossible to obtain the desired excellent reforming properties even if the treatment time was extended when treating with only sodium carbonate. . Example 4 Nylon 6 textured yarn knitted fabric (7M/24f fabric weight 95 Y/L) was prepared using the same amount of graft polymerization solution as in Example 1 except that 15 parts of acrylic acid was used as the unsaturated organic acid.
2 was graft-polymerized under the same conditions as in Example 1 and subjected to extraction treatment to obtain a graft polymer with a graft ratio of 9.7%.

Using the same groundwater as in Example 1 and under the same conditions as in Example 1, the graft polymer was converted to sodium salt using sodium carbonate or sodium carbonate and sodium triphosphate. Table 4 shows the moisture absorption rate and melt resistance of the obtained graft polymer sodium salt. Table 4 Excellent anti-melting properties and moisture absorption properties were obtained by the method of the present invention.

Example 5 Thickness 2 was used instead of the polyester staple knitted fabric of Example 1.
Example 1 except that a polyester film with 0 Buddha skin was used.
A graft film with a graft ratio of 9.1% was obtained by carrying out the same graft polymerization and extraction treatment.

This was converted into sodium chloride by the same treatment as in Example 1, and the melt resistance of the obtained film was measured by the method of Example 2.

The results are shown in Table 5. Table 5: Excellent melt resistance was obtained by the method of the present invention.

Claims (1)

[Scope of Claims] 1. A synthetic polymer characterized in that an ethylenically unsaturated organic acid is graft-polymerized onto a synthetic polymer molded article and then treated with an aqueous liquid containing a basic alkali metal compound and a sequestering agent. Method for modifying molded products. 2. The method according to claim 1, wherein the synthetic polymer molded article is a polyester molded article. 3. The method according to claim 1, wherein the synthetic polymer molded product is a polyester fiber product. 4. The method according to claim 1, wherein the ethylenically unsaturated organic acid is acrylic acid and/or methacrylic acid.