KR910003714B1 - Polymeric materials having nondripped ness and process for preparation thereof - Google Patents

Abstract

The polymeric meterial is prepared. by surface treating the polymer film, coating the liq. mixt. comprising the water soluble monomer or polymer and the cross linking agent dissolved in the solvent theron, and radiating the coated film by UV. The polymer film is selected from one of PE, PVC, PP, polystyrene, polyamide-6, polycarbonate, polyethyleneterephthalate, poly-4-methyl- 1-pentene, PMMA or polypentadiene. The obtd. polymeric material is useful as the film or sheet having nondripping properties.

Description

Invincible polymer materials and preparation method thereof

The present application relates to an invincible polymer material and a method for preparing the same.

More specifically, the present invention relates to an invincible polymer material obtained by applying a surface of a polymer film to a solution of a water-soluble monomer or a water-soluble polymer and a crosslinking agent in a solvent, and irradiating it with ultraviolet light, and a method for producing the same.

Polymer films are widely used due to their useful properties such as excellent mechanical properties, flexibility and non-toxic optical properties, but they have defects in poor surface properties.

For example, in the case of agricultural vinyl houses, the transparency of the house is reduced when water vapor in the air in the house forms on the surface of film and polymer sheet, thus preventing the growth of crops, and the water droplets are germinating and sprouting. If they fall on petals, they will die. In addition, there is a drawback in the food packaging list that the degeneration of the contents, such as corruption, is promoted.

As a solution to this problem, there are conventionally applied a special surfactant, a method of kneading an uninhibiting agent with a polymer film material, a graft polymerization method of a water-soluble polymer using radiation and low temperature plasma treatment, a graft polymerization method by ultraviolet light treatment, and the like.

The application method of the special surfactant is that the thickness of the layer containing the invincible agent is thin, so that the absorption capacity is low and the durability is short.

Hydrophilic surfactants are used for this special surfactant, but in actual use, it is accompanied by a drop of water on the surface of the film attachment part, so that the uninhibiting agent is easily lost. Therefore, all of them have a good initial effect but extremely poor sustainability.

In addition, the method of kneading an invincible agent with a polymer film has a poor compatibility between the resin and the invincible agent, which causes bulging phenomenon due to the release of the invincible agent on the surface of the film. This happens. This phenomenon can be avoided by selecting an invincible agent having good compatibility, but since the invincible agent should have hydrophilicity, it is eluted by water droplets when present on the surface of the film. That is, in the case of this mixed film, the blooming phenomenon is inevitably accompanied depending on the degree.

Graft polymerization of water-soluble polymers into films using radiation and low-temperature plasma treatment has the advantages of greater treatment effect and wider variety of treatment effects, but the disadvantages of high initial equipment cost and reduced productivity of workability. It is difficult. On the other hand, the method of graft polymerization on the polymer film by ultraviolet light is simpler than the above radiation and low temperature plasma polymerization, which is relatively useful for the purpose of improving the properties such as printability and adhesion. These graft weights are the only weaknesses in water droplets and other environmental conditions that cannot be applied to agricultural films.

Therefore, the present invention provides a polyolefin film having extremely excellent invincibility as a method of graft polymerization and crosslinking a water-soluble monomer with a photoinitiator using light, and the method has the characteristics of continuous, low-cost investment cost, and easy manufacturing method. In addition, the thickness of the coating film thereof is 1 μm or less, and there is almost no increase in the overall weight.

The polymer film that can be used in the present invention can generate radicals, ions, etc., which can cause graft polymerization when light is received, and the first side of the polymer as a polymer capable of generating an active point capable of initiating polymerization in the polymer main chain or side chain. The polymer capable of generating an active point in the polymer is polystyrene, polypropylene, polyethylene, poly-4-methyl-1-pentene, methyl methacrylate, polyamide-6, and a polymer capable of generating an active point in the main chain. Furnace is polypentadiene. In addition, the water-soluble monomers that can be used in the present invention are acrylic acid, methacrylic acid, acrylamide, methacrylamide, 2-hydroxyethyl methacrylate, en-vinylpyrrolidone, and the like. In addition, as the water-soluble polymer, a mono-alcohol consisting of the above water-soluble monomer and two or more kinds of copolymers may be used.

The light source is 200 ~ 700nm and can generate active points such as radicals and ions by decomposing the photoinitiator as a light source of low pressure mercury lamp, high pressure mercury lamp, fluorescent lamp, xenon lamp, metal halide lamp, con-arc lamp, tungsten lamp, solar light. As a light source which exists, the irradiation time is good for 0.1 second-24 hours.

Examples of the photoinitiator include benzophenone, acetophenone, isopropylbenzoin ether, benzoyl peroxide, N, and N'-azobisisobutyronitrile. As a solvent for dissolving the water-soluble monomer, the water-soluble polymer, the photoinitiator, the crosslinking agent, and the like, methyl alcohol, ethyl alcohol, acetone, water, methyl ethyl ketone, and a mixture of two or more kinds thereof can be used.

Crosslinking agents that crosslink to increase the durability of graft polymers imparted by invincibility are ene, n'-methylenebisacrylamide, arylmethacrylates, ethylene glycol dimethacrylates and derivatives thereof.

Corona moth pretreatment, gas phase treatment, Liquid treatment, etc.

The corona discharge is treated with a spark-cap method or a vacuum tube method, and the liquid chemical treatment is pretreated with one of sulfuric acid solution, dichromic acid solution, calcium permanganate solution and surface hydrolysis. In addition, the gas phase treatment can be carried out in one of flame treatment ozone treatment, oxygen treatment, chlorine treatment, sulfurous acid gas treatment and nitric acid treatment, and pretreatment with ultraviolet light.

In order to test the invincibility of the surface-treated polymer film in the present invention, a beaker with a diameter of 8 cm and a height of 10 cm was filled with 4.5 cm of water, and the water temperature was always maintained at 40 to 45 ° C.

Surface treated films were placed on top of this beaker to test their durability against invincibility, and contact angles were measured for each film.

The method for producing an invincible polymer film according to the present invention is excellent in obtaining an invincible polymer film in which water droplets are not electrolyzed on the surface of the film without improving the defects of the inherent properties of the polymer film while reducing the inherent mechanical properties. It works.

An example and a comparative example are given as follows.

Example 1

As a light source, five high-pressure mercury lamps of 100 W were installed at a distance of 30 cm in succession from the top of the film at 100 cm. 100 g of acrylic acid, 42 g of N-vinylpyrrolidone, 18 g of benzophenone, and 10 g of ethylene glycol dimethacrylate were uniformly dissolved in 410 g of acetone as a crosslinking agent, and used as a photopolymerization solution. A polypropylene film with a thickness of 30μ and a width of 15cm was output to the corona processor at 200W and 5m / min, and then subjected to full surface treatment. After the above photopolymerization solution was applied with a thickness of 5μ by immersion, at 50˚ ± 5 ℃ The surface was modified by irradiating an ultraviolet light source at a speed of 5 m / min.

The experimental results are shown in Table 1.

Example 2

100 g of acrylic acid, 54 g of acrylamide, 20 g of benzophenone, and 14 g of aryl methacrylate were uniformly mixed with 490 g of methyl ethyl ketone and used as a photopolymerization solution.

Polyvinyl chloride film 50μ thick and 20cm wide was treated with concentrated nitric acid gas or chlorine gas for 15 minutes, and then the surface was washed with water, dried and evenly applied by immersion method. UV light at 50˚ ± 5 ℃, 5m / min The surface was modified by irradiating the light source continuously.

The experimental results are shown in Table 1.

Example 3

180 g of acrylic acid, 5 g of polyacrylic acid, 20 g of acetophenone, 10 g of ethylene glycol dimethacrylate, 2 g of N, and N'-azobisisobutyronitrile were uniformly mixed with 500 g of ethanol, and used as a photopolymerization solution.

A polyethylene film having a thickness of 15 mu and a width of 20 cm was pretreated with a corona discharge processor as in Example 1, and the photopolymerization solution was uniformly applied using a metering bar. The surface was modified by continuously irradiating ultraviolet rays at a rate of 1.5 m / min in the presence of a 50 ° ± 5 ° C. nitrogen stream. The experimental results are shown in Table 1.

Example 4

42 g of methacrylic acid, 25 g of en-vinylpyrrolidone, 27 g of polyvinylpyrrolidone, 18 g of isopropylbenzoin ether and 10 g of en, m'-methylenebisacrylamide were dissolved in 600 g of methanol and used as a photopolymerization solution. The polyamide-6 film having a thickness of 50 mu and a width of 20 cm was pretreated as in Example 1), and the photopolymerization solution was applied to a thickness of 5 mu using a metering bar. This was continuously irradiated with ultraviolet light at a rate of 4m / min at 50 ° ± 5 ℃. The results of the experiment are shown in Table 1.

Example 5

130 g of acrylic acid, 18 g of benzophenone and 10 g of ethylene glycol dimethacrylate were evenly dissolved in 410 g of acetone and used as a photopolymerization solution. A polyethylene film having a thickness of 25 mu and a width of 20 cm was pretreated as in Example 1), and the above photopolymerization solution was uniformly applied by an immersion method. This was continuously irradiated with ultraviolet light at a speed of 50 ° ± 5 ℃ 1.5m / min. The experimental results are shown in Table 1.

Example 6

After the surface hydrolysis treatment of a polyethylene terephthalate film having a thickness of 12 mu and a width of 20 cm with an aqueous 15% NaOH solution, the photopolymerization solution of Example 1) was uniformly coated with a thickness of 5 mu and then UV light at a rate of 5 m / min at 50 ° ± 5 ° C. The surface was modified by irradiation. The experimental results are shown in Table 1.

Example 7

In the polymer sheet, a polystyrene sheet having a thickness of 3 mm and a width of 10 cm was pretreated with sulfuric acid solution for 5 minutes and applied with the photopolymerization solution of Example 5) to modify the polystyrene surface with ultraviolet light. The experimental results are shown in Table 1.

Example 8

54 g of methacrylamide, 130 g of 2-hydroxyethyl methacrylate, 20 g of benzophenone, and 14 g of aryl methacrylate were uniformly mixed with 580 g of ethanol and used as a photopolymerization solution.

Poly-4-methyl-1-pentene having a thickness of 1 mm and a width of 20 cm was pretreated with a corona discharge processor as in Example 1), and the photopolymerization solution was uniformly applied thereto. The surface was modified by continuously irradiating ultraviolet rays at a rate of 4 m / min at 50˚ ± 5 ° C. The experimental results are shown in Table 1.

Example 9

Polymethyl methacrylate sheets having a thickness of 2 mm, a width of 10 cm, and a length of 10 cm were uniformly coated with the photopolymerization solution of Example 8) using a corona discharge treatment, and then irradiated with ultraviolet rays for 5 minutes to modify the surface. . The experimental results are shown in Table 1.

Example 10

The surface of the polycarbonate sheet having a thickness of 2 mm, a width of 10 cm, and a length of 10 cm was modified in the same manner as in Example 9). The experimental results are shown in Table 1.

Example 11

A polypentadiene film having a thickness of 50 mu and a width of 20 cm was surface modified in the same manner as in Example 5. The experimental results are shown in Table 1.

The invincible high molecular material produced in Examples 1 to 11 was chemically bonded to a hydrophobic high molecular compound, a hydrophilic monomer, or a high molecular compound to have both hydrophilicity and hydrophobicity, and also to be crosslinked, so that it was insoluble in water.

Comparative Example 1

In the same manner as in Example 3), only pretreatment of corona discharge was not performed. The experimental results are shown in Table 1.

Comparative Example 2

Example 5) was carried out in the same manner, and the photopolymerization solution was prepared without the addition of the crosslinking agent ethylene glycol dimethacrylate, followed by photopolymerization using ultraviolet light. The experimental results are shown in Table 1.

TABLE 1

Durability Table for Changes and Drops in Contact Angle of Each Surface Treated Film for Examples and Comparative Examples

In Examples 1 to 11 of Table 1, the contact angle after the treatment was 20 ° to 0 °, so that no water droplets occurred on the surface of the film, and the durability was excellent. In Comparative Examples 1 to 2, the contact angle after the treatment was treated. It is almost the same as the previous contact angle, so that water droplets are generated, and it can be seen that the durability is very low.

In order to confirm that the polymer material given invincibility is a new substance, the invincible film of Example 5 was extracted with boiling water for 1 hour.

A dry film taken with ATR-IR is shown in Figure 1.

As shown in the spectrum was identified as a strong -COOH stretching peak at 1718cm ^-1, 1370 ~ 1030cm ^-1 as a peak of the amplified acrylic acid shown in the open grafted polyethylene film (ICT).

Confirmation device: BID-RAD DIGLAB DIVISION FT 80 ATR-IR

Claims (12)

An invincible high molecular material obtained by surface treatment of a polymer film, which is coated with a water-soluble monomer or a water-soluble polymer and a crosslinking agent dissolved in a solvent and then irradiated with ultraviolet light. The polymer film is one selected from polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyamide-6, polycarbonate, polyethylene terephthalate, poly-4-methyl-1-pentene, polymethylmethacrylate, and polypentadiene. Claims 1. Polymeric material according to claim 1. Surface treatment is an invincible polymer material according to claim 1, which is one of corona discharge, acid, and vapor phase treatment. As a water-soluble monomer, the polymeric material of Claim 1 which is 1 type chosen from acrylic acid, methacrylic acid, en-vinylpyrrolidone, acrylamide, methacrylamide, and 2-hydroxyethyl methacrylate. The water-soluble polymer is a polymer material according to claim 1 which is one kind selected from polyacrylic acid, polyene-vinylpyrrolidone and polyacrylamide. As a crosslinking agent, the polymeric material of Claim 1 which is 1 type chosen from aryl methacrylate, ethylene glycol dimethacrylate, N, and ene-methylene bis acrylamide. A method for producing an invincible polymer film obtained by surface treatment of a polymer film, which is coated with a water-soluble monomer or a water-soluble polymer and a crosslinking agent dissolved in a solvent and then irradiated with ultraviolet light. The polymer film is one selected from polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyamide-6, polycarbonate, polyethylene terephthalate, poly-4-methyl-1-pentene, polymethylmethacrylate, and polypentadiene. The method as described in claim 7. The surface treatment is the method of Claim 7 which is 1 type | mold in a corona discharge and an acidic gas phase treatment. As a water-soluble monomer, the method of Claim 7 of 1 type of claims chosen from acrylic acid, methacrylic acid, en-vinylpyrrolidone, acrylamide, methacrylamide, and 2-hydroxyethyl methacrylate. The method according to claim 7, wherein the water-soluble polymer is one selected from polyacrylic acid, polyene-vinylpyrrolidone, and polyacrylamide. As a crosslinking agent, the method of Claim 7 which is 1 type chosen from aryl methacrylate, ethylene glycol dimethacrylate, N, and ene-methylene bis acrylamide.