JPH11116711A - Modified pva-containing polymer molded product and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified PVA-containing polymer molded product having any one or more functions of a deodorizing effect, an antibacterial effect, hygroscopicity and water absorption, and a process of producing the same. SOLUTION: A modified PVA-containing polymer molded product is obtained by a graft copolymerization reaction of a polyvinyl alcohol(PVA)-containing polymer molded product with methacrylic acid and/or a hydroxyl group- containing methacrylate, wherein a graft ratio of the methacrylic acid and/or the hydroxyl group-containing methacrylate to the PVA-containing polymer molded product is 3-30 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer molded article containing a modified PVA (polyvinyl alcohol) and a method for producing the same.

[0002]

2. Description of the Related Art As a technique for modifying a PVA by graft copolymerization with a vinyl monomer, a method has been proposed in which PVA is dissolved and graft-copolymerized in a homogeneous system, followed by spinning or film formation. 252610). In this method, the graft polymerization is carried out under an inert gas atmosphere, and the reaction in air is impaired by the presence of oxygen. Furthermore, it cannot be processed into a molded article by this method. In addition, the deodorizing process generally performed on polyvinyl alcohol fiber only provides a deodorizing agent by post-processing, and the bonding force between the fiber and the agent is weak. There was only one that lacked durability.

[0003]

An object of the present invention is to provide a modified PVA-containing polymer molded article and a method for producing the same. Another object of the present invention is to provide a modified PVA-containing polymer molded article having at least one of a deodorizing effect, an antibacterial effect, a moisture absorbing property and a water absorbing function, and a method for producing the same. Still another object of the present invention is to provide a PV
An object of the present invention is to provide a method for graft copolymerizing methacrylic acid and / or a hydroxyl group-containing methacrylate onto an A-containing polymer molded product.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a PVA-containing polymer molded product is subjected to a graft copolymerization reaction of methacrylic acid and / or a hydroxy group-containing methacrylate, and the methacrylic acid and / or hydroxyl is added to the PVA-containing polymer molded product. A modified PVA-containing polymer molded article is provided, wherein the grafting ratio of the group-containing methacrylate is 3 to 30% by weight. Further, according to the present invention, in an aqueous solution containing hydrogen peroxide and a ferrous salt, a methacrylic acid and / or a hydroxy group-containing methacrylate are grafted onto a polyvinyl alcohol-containing insoluble polymer molded product at a grafting rate of 3 to 30% by weight. The present invention provides a method for producing a modified PVA-containing polymer molded article, which is characterized by graft copolymerization at a ratio.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The PVA-containing polymer molded article used in the present invention is a polyvinyl alcohol or a polymer article containing polyvinyl alcohol, which is insolubilized by a method such as heat treatment or acetalization. The alcohol content is 10 to 100% by weight, more preferably 30 to 100% by weight, and may be previously colored with a dye or pigment. In addition, the shape includes a fiber shape, a film shape, a plate shape, a rod shape, a container, and other article shapes. Further, the fiber may be in the form of a thread, cotton, cloth, tow, or non-woven fabric, and other fibers may be mixed.

In the present invention, a methacrylic acid and / or a hydroxyl group-containing methacrylate (hereinafter, referred to as a methacrylate) is added to a PVA-containing insoluble polymer molded product (hereinafter, also simply referred to as a molded product).
In order to introduce methacrylic monomer), PVA is graft-copolymerized with PVA in an aqueous solution containing hydrogen peroxide and a ferrous salt.
As the methacrylic monomer having a hydroxyl group, for example, a monomer represented by the following general formula (1) is preferably used. CH ₂ ＣC (CH ₃ ) CO (OCnH ₂ n) mOH (1) (wherein, n represents a number of 2 to 4, and m represents a number of 1 to 10). 2-hydroxyethyl acid, 3-hydroxypropyl methacrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, dipropylene glycol methacrylate, tripropylene glycol methacrylate,
4-hydroxybutyl methacrylate and the like.

[0007] As the ferrous salt, any one can be used as long as it can release ferrous ions in water. Such as ferrous sulfate, ferrous chloride,
There are ferrous ammonium sulfate and ferrous nitrate. The combination of this ferrous salt and hydrogen peroxide constitutes a redox catalyst and promotes a graft copolymerization reaction of a methacrylic monomer. Hydrogen peroxide concentration in aqueous solution is 0.01 ~
0.2 mol / l, preferably 0.03 to 0.15 mo
1 / l. The iron salt concentration is 0.2 to 2 mmol /
l, preferably 0.4 to 1.5 mmol / l.

[0008] If necessary, an acid can be added to the aqueous solution. By adding this acid, the reaction rate (grafting rate) of the methacrylic monomer can be improved. Examples of the acid include sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, formic acid and the like. The acid concentration in the aqueous solution is
2 to 10 mmol / l, preferably 2.5 to 8 mmol
/ L. Further, in this aqueous solution, conventionally known sequestering agents, for example, phosphoric acid type, phosphonic acid type, EDTA, NTA and the like can be added. PV
The weight ratio (bath ratio) of the aqueous solution to A (dry weight) is 5 to 5.
30, preferably 5 to 15. The reaction temperature is 70-
The temperature is 100 ° C, preferably 80 to 95 ° C. The reaction time is 20 to 180 minutes, preferably 30 to 120 minutes. The use ratio of the methacrylic monomer used in the present invention is 5 to 100 parts by weight based on 100 parts by weight of the molded product (dry weight).
Parts by weight, preferably 10 to 60 parts by weight. When the use ratio of the methacrylic monomer is smaller than this, the modifying effect is not sufficient because the introduction ratio of the methacrylic monomer is too small, while the introduction ratio of the methacrylic monomer increases as the amount increases, but the effect is increased. No particular improvement is obtained, which is economically disadvantageous.

The modified molded article of the present invention has a grafting ratio of the methacrylic monomer (reaction weight ratio of the methacrylic monomer to the molded article) of 3 to 30% by weight, preferably 5 to 2%.
5% by weight. If the grafting ratio exceeds the above range, the graft copolymerization reaction requires a long time, which is economically disadvantageous. On the other hand, if it is less than the above range, a sufficient reforming effect cannot be obtained. The grafting ratio can be adjusted by the ratio of the methacrylic monomer to the fiber and the reaction conditions. The molded product obtained by graft copolymerization of the methacrylic monomer obtained as described above may be reacted with a salt-forming cation, if necessary, to convert the carboxyl group COOH into COOM (where M is a salt-forming monomer). (Indicating a cation). Cations in this case include sodium ions, calcium ions,
In addition to metal ions such as iron ions, copper ions, zinc ions, manganese ions, and silver ions, quaternary ammonium ions, quaternary organic ammonium ions, and the like can be given. In addition, by reacting at least one of antibacterial copper ion, silver ion, quaternary ammonium ion, quaternary organic ammonium ion and the like from these salt-forming cations with a carboxyl group, , Easily obtain antibacterial effect.

[0010]

Next, the present invention will be described in more detail by way of examples. The percentages shown below are percentages by weight unless otherwise specified.

Example 1 Hydrogen peroxide solution (H ₂ O ₂ concentration: 35%): 0.4%, ferrous sulfate (FeSO ₄ .7H ₂ O): 0.02%, methacrylic acid: 1.6 %, Killest NTB (Kiresto Chemical Co., Ltd.)
, Metal sequestering agent): 0.03%, sulfuric acid (50 ° Be):
10 g of well-washed Kuraray vinylon (2d × 51 mm, T-13, vinylon fiber manufactured by Kuraray Co., Ltd.) was immersed in 150 ml of an aqueous solution containing 0.03%, and the temperature was gradually raised from room temperature, and the temperature was increased to 90 ° C. for 80 minutes. Treat, wash well and dry. No adhesion of the homopolymer was found in the processor and on the fiber surface. The graft ratio calculated by chemical analysis was 12.4%.

Example 2 The same processing as in Example 1 was performed except that Kuraray vinylon was changed to flame retardant Kuraray vinylon (2d × 51 mm, T-18). The graft ratio calculated by chemical analysis was 11.3%.

Example 3 In Example 2, the flame-retardant Kuraray vinylon was added to Mike thren Navy B at 4.0% by weight of the fiber.
Using dye NCH s / f (manufactured by Mitsui Toatsu Dyeing Co., Ltd., vat dye) according to a standard method, the same treatment was performed. The graft ratio by chemical analysis was 11.0%.

Example 4 600 g of Krake vinylon yarn 34 /-was wound around a dyeing tube, hydrogen peroxide: 0.5%, ferrous sulfate: 0.02%,
Methacrylic acid: 2.2%, Chirest NTB: 0.05
%, Sulfuric acid 0.05%, treated with a cheese dyeing machine at 90 ° C. for 80 minutes, washed well with water and dried. The graft ratio by chemical analysis was 9.1%.

Example 5 Aqueous hydrogen peroxide: 0.4%, ferrous sulfate: 0.02%, methacrylic acid: 1.6%, CHEST NTB: 0.03%,
10 g of a well-washed corderan (3d × 51 mm FBCH, polychlor fiber manufactured by Kojin Co., Ltd.) is immersed in 150 ml of an aqueous solution containing 0.03% of sulfuric acid, treated at 85 ° C. for 100 minutes, thoroughly washed with water, and dried. The graft ratio by chemical analysis was 8.1%.

Example 6 The same treatment as in Example 5 was carried out except that 2-hydroxyethyl methacrylate was used instead of methacrylic acid. The rate of increase in fiber weight after the treatment was 8.6%.

Example 7 Hydrogen peroxide solution: 0.4%, ferrous sulfate: 0.02%, methacrylic acid: 0.8%, 2-hydroxyethyl methacrylate: 0.8%, Chilestin NTB: 10 g of the well-washed corderan is immersed in 150 ml of an aqueous solution containing 0.03% and 0.03% of sulfuric acid, treated at 85 ° C. for 100 minutes, washed well with water, and dried. The rate of increase in fiber weight after treatment is 9.
At 2%, the graft ratio by chemical analysis was 4.9%.

Example 8 Aqueous hydrogen peroxide: 0.4%, ferrous sulfate: 0.02%, diethylene glycol methacrylate (Blemmer PME)
1.6, Nippon Yushi Co., Ltd.) 1.6%, Kyrest NT
B: 150 m aqueous solution containing 0.03% and sulfuric acid 0.03%
Then, 10 g of flame-retardant Kuraray vinylon, which has been well washed, is immersed in the mixture, treated at 87 ° C. for 120 minutes, washed well with water and dried. The rate of increase in fiber weight after the treatment was 11.6%.

[0019]

As described above, in the modified PVA-containing polymer molded article and the method for producing the same according to the present invention, since the amount of the iron salt used as the catalyst is extremely small, the modified molded article has no coloring. The iron removal treatment such as washing and removing the iron salt from the modified molded product is not particularly required. Further, since the reaction temperature can be easily controlled, the graft copolymerization of the methacrylic monomer to the molded product can be performed uniformly. The modified PVA-containing polymer molded article of the present invention is excellent in adsorptivity to basic malodorous substances such as ammonia, amines, and urine odor, because a carboxyl group is introduced into the molecule. It shows the action as.
Further, an antibacterial effect can be imparted by reacting a salt-forming cation having antibacterial properties with a carboxyl group.

Claims (2)

[Claims] 1. A graft copolymerization reaction of a methacrylic acid and / or a hydroxy group-containing methacrylate on a polyvinyl alcohol-containing insoluble polymer molded article,
A modified PVA-containing polymer molded article characterized in that the graft ratio of methacrylic acid and / or hydroxyl group-containing methacrylate to the polyvinyl alcohol-containing polymer molded article is 3 to 30% by weight. 2. Grafting methacrylic acid and / or hydroxy group-containing methacrylate onto a polyvinyl alcohol-containing insoluble polymer molded article in an aqueous solution containing hydrogen peroxide and a ferrous salt at a grafting ratio of 3 to 30% by weight. A method for producing a modified PVA-containing polymer molded product, comprising copolymerizing.