KR100328684B1 - Fluorescence film for an agriculture having fog-preventing property - Google Patents

Abstract

The present invention relates to a fog-resistant agricultural fluorescent film, more specifically, a fluorescent agent that absorbs ultraviolet light of 400nm or less to fluoresce red light, weathering agent that absorbs 250-400nm ultraviolet light and a single absorption band is dispersed, Solbi The oil-fatting agent which mixed the carbonic acid ester and the glycerol fatty acid ester, the waterproofing agent which consists of a fluorine-type surfactant, and the remainder are related to the fog prevention agricultural fluorescent film which consists of a thermoplastic resin. The anti-fog agricultural fluorescent film according to the present invention has excellent general oil repellency, warmth and weather resistance, and at the same time, can prevent or remove fog generated inside the house, and a fluorescent that can fluoresce light necessary for photosynthesis of crops. This is excellent and can increase crop growth more effectively.

Description

Fluorescence film for an agriculture having fog-preventing property

The present invention relates to a fog-resistant agricultural fluorescent film, more specifically, a fluorescent agent for absorbing ultraviolet light of less than 400nm to fluoresce the light required for photosynthesis of crops, and absorbs ultraviolet light of 250-400nm As a weatherproof agent with a single dispersion band, sorbitan fatty acid esters and glycerol fatty acid esters, oil repellents, and fluorine-based surfactants for suppressing or removing mist generated inside the house. The configured antifouling agent and the remainder are related to an anti-fog agricultural fluorescent film made of a thermoplastic resin used as an agricultural film.

Generally, resins used for agricultural films include mainly polyethylene, ethylene vinyl acetate copolymer, polyvinyl chloride, and the like. When using this thermoplastic resin as an agricultural film, it is necessary to make the film more transparently in order to increase sunlight transmission, or to prescribe a warming agent to keep the temperature inside the house high, or the water droplets falling on the surface of the house fall on the crop or the sunlight. Techniques such as adding a oil repellent to prevent scattering and lowering the amount of light transmitted or a weathering agent to prevent the film from being oxidized by ultraviolet rays of sunlight even if the film is covered in the open field for about a year are common. Technology.

Most of these agricultural films were single-layer films, but recently, methods of manufacturing two-layer or three-layer films to improve agricultural film characteristics have been developed. For example, Japanese Patent Laid-Open No. 62-179939 describes a method of impregnating a middle and inner layer of a multi-layer film in order to further improve the film's oil repellency, and Japanese Patent Laid-Open No. 63-115743 In order to further improve the heat retention, a method of manufacturing a three-layer film is described. In addition, Japanese Patent Laid-Open No. 4-47936 discloses a method in which the oil repellent is evenly impregnated on each layer of the three-layer film to further improve the oil repellency. However, these conventional films have been able to improve the specific characteristics of one of the characteristics of agricultural films, but they do not transmit much of the rays necessary for crop growth, that is, photosynthesis. Could not contribute

In addition, the inside of the house is inevitable to generate fog due to the temperature difference between the outside of the house, and if a lot of mist generated in this way, the humidity inside the house becomes high and the crops are easily damaged by the increased humidity. The prior arts have difficulty in suppressing the generation of fog or removing the generated fog because there is no characteristic (non-banging) that can suppress or remove fog generation in addition to the fluorescent property.

Japanese Patent Application Laid-Open No. 50-88147 and Japanese Patent Laid-Open No. 2-147651 disclose agricultural films in which fluorescent agents exhibiting blue light in the range of 420 to 470 nm are mixed, but they do not exhibit red light effective for photosynthesis of plants. It was not seen as invalid. In addition, Japanese Patent Laid-Open No. 56-80459 solves the problem of shortening the period of fluorescence characteristics by using an organic fluorescent agent in Japanese Patent Laid-Open No. 49-16301 by mixing an inorganic fluorescent agent. It was not possible to suppress development. WO 85-01945 and Japanese Patent Laid-Open No. 2-40266 describe a film which fluoresces red light, which is advantageous for photosynthesis, but since it is not prescribed a weathering agent, it can not actually be used for a long period of more than 1 year, There is also a disadvantage. Korean Patent Laid-Open Nos. 96-17748 and 96-17749 describe films effective for photosynthesis of crops by fluorescing red light, but have disadvantages that cannot suppress fog generation.

Anti-fog agricultural film that suppresses the generation of fog refers to a film that quickly disappears the fog generated inside the house. In order to eliminate the fog, the fog generated inside the house quickly drops on the surface of the house film so that the fog appears to disappear. At this time, the water droplets formed on the surface of the film as a function of the antifouling agent flow down along the surface of the film due to the effect of the additive added for the film's repellency. Therefore, the water layer due to water droplets becomes very thick on the film surface that is prescribed with the anti-fog agent and the oil-repellent agent at the same time than the film surface when only the oil-repellent agent is used. Therefore, in the case of the film using both the anti-rust agent and the oil-repellent agent at the same time, the relict period is significantly reduced compared to the film using only the oil-repellent agent. The methods of Japanese Patent Laid-Open Nos. 55-91663 and 57-12070 prescribe silicone-based surfactants to suppress the generation of fog, but do not overcome the disadvantage of deterioration of oil repellency. The method of Japanese Patent Laid-Open No. 57-14648 Although a fluorine-based surfactant was added as a spinning agent, there was a problem in that the amount thereof was not added properly and a small amount of the spinning effect was inadequate. In addition, Japanese Patent Application Laid-Open No. 59-93739 and Japanese Patent Laid-Open No. 1-216947 describe a method of improving the anti-fogging property by prescribing a fluorine-based surfactant, but this also does not suppress a decrease in the retentive period. . In addition, the technology of the anti-fog agricultural film to suppress the generation of fog is not only effective for the resin is mainly limited to vinyl chloride, it was not effective in crop growth because a fluorescent agent that can promote photosynthesis is not prescribed.

As can be seen in the above-mentioned prior arts, the above-mentioned techniques emphasizing each specific technique have many problems for use together. For example, in the case of a fluorescent film, the fluorescent agent absorbs ultraviolet rays of sunlight and fluoresces with red or blue light. When the weathering agent that increases the weather resistance of the film is absorbed, the weathering agent and the fluorescent agent are also absorbed. Competitively absorb ultraviolet light and the absorption of ultraviolet light that the fluorescent agent can fluoresce is insufficient, resulting in a significant decrease in the fluorescence function. In addition, since oil repellents that prevent water droplets from forming on the film surface interfere with each other with fluorescent agents or weathering agents, it is very difficult to select and mix appropriate fluorescent agents, weathering agents, and oil repellents, and anti-fogging agents interfere with oil repellents. And it is very difficult to show the long-term suppression of mist generation and oil remnant function at the same time because the disturbing effect is very large, and also it is practically impossible to prescribe a fluorescent agent and a weathering agent at the same time so that each characteristic appears.

As a result of continuous studies to solve the above problems and to produce agricultural films having excellent fluorescence, weather resistance, oil repellency, and anti-fogging property, the present inventors absorbed ultraviolet rays of 400 nm or less, and fluorescing red light, 250-. We find a weatherproof agent that absorbs 400nm UV light and has a single dispersion band, a sorbent mixed with sorbitan fatty acid esters and glycerol fatty acid esters, a spinning agent composed of fluorine-based surfactants, and a mist-resistant agricultural fluorescent film made of thermoplastic resin. The present invention has been completed based on this.

It is an object of the present invention to solve the problems of the prior art, while excellent in oil repellency and weather resistance and at the same time excellent in anti-fogging properties that can suppress the generation of fog, and also effective in photosynthesis of crops to prevent the fog to increase crop growth more effectively To provide a sex agricultural fluorescent film.

Agricultural fluorescent film of the present invention for achieving the above object

0.005 to 1.0 wt% of a fluorescent agent absorbing ultraviolet rays below 400 nm, having a general formula (1), 0.4 to 1.2 wt% weathering agent absorbing 250 to 400 nm ultraviolet rays and having a single absorption band, sorbitan fatty acid ester and glycerol fatty acid ester Is 0.7 to 3.0% by weight of a low oil agent mixed at a mixing ratio of 0.5 to 0.95: 0.05 to 0.5, 0.005 to 0.5% by weight of the antifoaming agent having the following formula (2), and the remainder of the thermoplastic resin.

MeY _n L _k

Where Me is Eu, Y is NO ₃ or TTA, n is 2 or 3, k is an integer from 1 to 2, L is 1,10-Phenanthroline and the structural formula is

to be.

RfCH ₂ CH ₂ O (CH ₂ CH ₂ O) _y H

Here, Rf = F (CF ₂ CF ₂ ) _x , and x = 1-7, y = 0-25.

Hereinafter, the present invention will be described in more detail.

In obtaining the fog preventing agricultural fluorescent film of the present invention, the most important is the selection of a fluorescent agent having excellent fluorescence characteristics, the selection of weathering agent and oil-repellent agent with little interference effect with the fluorescent agent while increasing the weatherability and oil-resistance, the additives and In particular, it is the selection of the anticorrosive agent having low interference effect with the oil-repellent agent, and the appropriate content ratio of each additive.

As described above, the fluorescent agent absorbs ultraviolet rays of sunlight to fluoresce red or blue light, and since the weathering agents used to suppress oxidation of the film due to ultraviolet rays also absorb ultraviolet rays, The property is deteriorated. Therefore, finding a different ultraviolet absorption wavelength range of the fluorescent agent and the weathering agent is a method of simultaneously improving the fluorescence and weathering properties.

As a fluorescent agent used in the present invention, a compound which absorbs ultraviolet rays of 400 nm wavelength or less and fluoresces red light is used, and has the following Chemical Formula 1.

Formula 1

MeY _n L _k

Where Me is Eu, Y is NO ₃ or TTA (Tenoyl trifluoroacetone), n is 2 or 3, k is an integer from 1 to 2, L is

to be.

The fluorescent agent is used at 0.005 to 1.0% by weight based on the total resin composition, and preferably has excellent fluorescence at 0.005 to 0.6% by weight. The fluorescent agent according to the present invention concentrates fluorescence around 600 to 650 nm, which absorbs 400 nm wavelength ultraviolet light in the sunlight and fluoresces red light. When the amount of the fluorescent agent used is less than 0.005% by weight based on the total resin composition, it does not exhibit fluorescence characteristics. If it exceeds 1.0% by weight, there is an economic disadvantage.

Weathering agents which have a direct relationship with the fluorescent agent should consider the ultraviolet absorption wavelength band as described above. Typically, the weathering agent absorbs ultraviolet rays having a wavelength of 230 to 360 nm and has a different wavelength range depending on the type of weathering agent. . Ultraviolet absorption wavelength range of the weathering agent is 270 ~ 360nm, the fluorescence properties are greatly reduced by mutual interference with the fluorescent agent used in the present invention, the weatherability is increased but the fluorescence properties are decreased as the amount of the weathering agent is increased. Accordingly, weathering agents consistent with the object of the present invention select weathering agents that absorb 250-400 nm ultraviolet light but have a monodisperse absorption band. Such weathering agents are manufactured by Ciba-Geigy, and are made of Tinuvin 622LD (Dimethyl succinate polymer with 4-hydroxyl-2,2,6,6-tetramethyl-1-piperidine) or Chimassorb. ) 944LD (Poly [[6-[(1,1,3,3-tetramethyl butyl) amino] -1,3,5-triazine-2,4-diyl] [2,2,6,6-tetramethyl-4 -piperidinyl] imino] -1,6-hexanediyl [2,2,6,6-tetramethyl-4-piperidinyl) imino]], and the structural formulas of the tinubin 622LD and the catmetsolve 944LD are, respectively.

And

to be.

In addition, when the film to which the weathering agent is added is coated on the paper, a preferable addition amount which can maintain film properties even after one year or more elapses is preferably 0.4 to 1.2% by weight relative to the final resin composition. If the content is less than 0.4% by weight can not exhibit weather resistance, if the content exceeds 1.2% by weight does not improve the weather resistance anymore, rather there is a problem that the transparency of the film is lowered.

In addition, the oil repellent is a surfactant that connects the water droplets formed on the surface of the film to flow downward along the surface of the film, that is, toward the ground. As the house covering period lasts, the surfactant forms water droplets formed on the surface of the film. It is washed away by the soil, and the characteristics of the ruins begin to gradually decrease. However, since the antifog agent is a surfactant that suppresses the generation of mist by forming mist generated inside the house into droplets faster on the film surface, it can be said to have the opposite function in terms of oil repellent and effect. In the case of using a waterproofing agent, a lot of water droplets are formed on the surface of the film, it is easily washed off, and the oil repellency and the anti-fogging performance tend to decrease together. In particular, it is highly likely that the remains will be poor, and in this case, the cold damage of crops is a concern. In addition, since both the antifoaming agent and the antifoaming agent, the fluorescent agent and the weathering agent must be prescribed at the same time.

In general, the oil repellent exhibits the opposite function as the anti-fog agent, and the type and content of the oil repellent greatly affects the water repellent function and the water repellent function. It is preferable to use sorbitan fatty acid ester and glycerol fatty acid ester at the same time as the oil-soluble agent suitable for the present invention. At this time, the oil-in-water period varies greatly according to the mixing ratio of sorbitan fatty acid ester and glycerol fatty acid ester. The mixing ratio of sorbitan fatty acid ester: glycerin fatty acid ester according to the present invention is 0.5 to 0.95: 0.05 to 0.5. If the amount of glycerin fatty acid ester is less than 5%, there is a problem that the oil repellency performance is lowered in winter, if it exceeds 50%, the transparency of the film is sharply worsened and the working period is significantly reduced. The sorbitan fatty acid ester and the glycerol fatty acid ester are mixed at a mixing ratio of 0.5 to 0.95: 0.05 to 0.5, and in the present invention, the oil-and-oil agent is used in an amount of 0.7 to 3.0% by weight based on the final resin composition. If there is a problem of poor oil repellent performance exceeds 3.0% by weight there is a problem that the transparency of the film is lowered.

In addition, the anti-corrosive agent according to the present invention has the formula (2) as a fluorine-based surfactant.

Formula 2

RfCH ₂ CH ₂ O (CH ₂ CH ₂ O) _y H

Here, Rf = F (CF ₂ CF ₂ ) _x , and x = 1-7, y = 0-25.

The content of the anti-corrosive agent is preferably 0.005 to 0.5% by weight, and if the content is less than 0.005% by weight, there is a problem in that the anti-corrosion effect does not appear. When the content exceeds 0.5% by weight, the transparency of the film is lowered and the oil repellency is also lowered. There is.

The thermoplastic resin used in the present invention is low density polyethylene or linear low density polyethylene having a density of 0.916 to 0.930 g / cc and a melt index of 0.1 to 5.0 g / 10 min, and a vinyl acetate content of 1 to 21 wt% and a melt index of 0.2 One or a mixture selected from ethylene vinyl acetate copolymers having a g / 10 min to 5.0 g / 10 min is used as the base resin.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples.

Example 1

The base resin of the film was a low density polyethylene having a melt index of 0.8 g / 10 min and a density of 0.920 g / cc. The fluorescent agent was mixed 1: 1 of Eu (NO ₃ ) ₃ Phen and Eu (TTA) ₃ Phen by 0.1 wt% in the base resin. Where Phen is 1,10-phenanthrone and TTA is thinoyltrifluoroacetone. As a weathering agent, 0.9% by weight of Tinuvin 622LD of Ciba-Geigi Co., Ltd. was added, and 1.5% by weight of sorbitan fatty acid ester and glycerol fatty acid ester were mixed at a compounding ratio of 0.6: 0.4 respectively. As the antifoaming agent, 0.2 wt% of DuPont ZONYL fluorine-based surfactant was mixed. The additive-added film was prepared to a thickness of 60μ to evaluate the fluorescence characteristics, weathering properties, oil repellent properties, anti-fog properties and the results are shown in Table 1 below.

Comparative Example 1

The commercially available LDPE monolayer film (ruin, weather resistance) of Ilshin Chemical Industries Co., Ltd. was commercially available for purchase and evaluated in comparison with the film produced in the above examples.

Comparative Example 2

A film was prepared under the same conditions as in Example 1 except that 1.5 wt% of sorbitan fatty acid ester and glycerol fatty acid ester were mixed at a compounding ratio of 0.3: 0.7, respectively, and the fluorescence, weather resistance, and It is shown in Table 1 to evaluate the ruins characteristics, the waterproofing characteristics.

The method and kind used to measure the film properties in the Examples and Comparative Examples are as follows.

The fluorescence characteristics of the film were excimation / emisson monochrometers of Simazhu Co., Ltd., and the scanning range was 450-650 nm with an excitation wavelength of 350 nm. Weather resistance evaluation is an Atlas UV condensation instrument with temperature and time of 60 ° C, 8 hours, and cooling and temperature of 40 ° C, 4 hours when irradiated with UV light using an FS40UV lamp. The residual elongation of the film was measured for each of the elapsed days after the cycle. The oil repellent was filled with water in a beaker having a diameter of 15 cm using a self-made refrigeration and a water bath, tilted at an inclination of about 20 °, and the beaker inlet was sealed with a film to be measured. Then, the external temperature and internal temperature of the beaker were fixed at -4 ° C and 30 ° C, respectively, and the water droplets formed on the film surface were observed for each day. The oiliness status was measured by dividing the grades, where A is the period until no water droplets exist on the surface of the film, and B is the period of days in which water droplets are less than 10% of the total film area. The film haze was measured using Hazegard XL-211 manufactured by Pacific Scientific Co., Ltd., according to ASTM D1003.

The anti-corrosion property was coated with the film to measure the hotbed of 20m in length and 2m in height in November, and then observed whether fog occurred inside the house for 90 days until February of the following year. The fog was observed inside the house for 8-10 am and 4-6 pm.

Meanwhile, in various embodiments of the present invention including the above examples and comparative examples, in the case of low density polyethylene, linear low density polyethylene and ethylene vinyl acetate, a wide film extruder having a screw diameter of 150 mm and a die diameter of 1200 mm The expansion ratio was adjusted to 2.5, the processing temperature was 170 ~ 220 ℃, the film thickness was adjusted to 60μ. The mechanical properties of the film were measured in accordance with ASTMD882 using the Universal tester 1122 of Instron, tensile strength, elongation, and tensile tear strength.

Characteristics of Anti-Fog Fluorescent Films Comparative Example 1 Comparative Example 2 Example 1 Fluorescence Major Fluorescent Wavelength - 600-650 nm 600-650 nm Total strength none 0.79 0.82 Weather days * 56 53 55 Cloudy road Right after manufacturing 8.0 7.5 7.6 10 days later 15.7 31.6 16.9 30 days later 24.5 51.5 25.8 Ruins A 31 18 37 B 23 17 24 Sum 54 35 61 Waterproof property Mist occurs one day after coating Mist occurs 30 days after coating No fog for 90 days

* Weathering days: The number of days that the residual elongation of the film is 50% of the initial elongation after UV irradiation in UV condensation.

As can be seen from Table 1 comparing the Examples and Comparative Examples, the film of the present invention has a conventional weather resistance, oil repellency, or the like as the conventional level or further improved, and also obtained excellent fluorescence and anti-fog properties, The problem of fog generation that general agricultural film or fluorescent film had was excellently complemented.

Claims (3)

0.005 to 1.0% by weight of a fluorescent agent represented by the following Chemical Formula 1 and absorbing ultraviolet rays of 400 nm or less, Weathering agent 0.4-1.2% by weight, which absorbs 250-400nm UV and has a single dispersion band, 0.7-3.0% by weight of oil-repellent agent, in which sorbitan fatty acid ester and glycerol fatty acid ester were mixed at a mixing ratio of 0.5-0.95: 0.05-0.5, 0.005 to 0.5% by weight of a defoaming agent represented by the following formula (2), and The remainder is a fog preventing agricultural fluorescent film, characterized in that made of a thermoplastic resin. Formula 1 MeY _n L _k Where Me is Eu, Y is NO ₃ or TTA, n is 2 or 3, k is an integer from 1 to 2, and L is to be. Formula 2 RfCH ₂ CH ₂ O (CH ₂ CH ₂ O) _y H Here, Rf = F (CF ₂ CF ₂ ) _x , and x = 1-7, y = 0-25. According to claim 1, wherein the weathering agent is a fog prevention agricultural fluorescent film, characterized in that the one selected from the group consisting of Tinuvin 622LD and Kimmatsolve 944LD. The low density polyethylene or linear low density polyethylene having a density of 0.916 to 0.930 g / cc and a melt index of 0.1 to 5.0 g / 10 min, and a vinyl acetate content of 1 to 21 wt% and a melt index. The fog preventing agricultural fluorescent film, characterized in that one or a mixture selected from ethylene vinyl acetate copolymer of 0.2g / 10min to 5.0g / 10min.