KR100983602B1 - Polymer Composition for Production of Light Transforming Agriculture Greenhouse Films and Manufacturing Method of Greenhouse Film Using Same and Greenhouse Film thereof - Google Patents

Abstract

The present invention relates to a polymer composition for manufacturing a light conversion agricultural green house film, a method for manufacturing a green house film using the same, and a green house film, the object of which is to convert UV light or short wavelength light into red visible light. The present invention provides a polymer composition comprising an ethylene copolymer and a light emitting active additive, and a light conversion film and a method of manufacturing the light conversion film using the same.

The composition of the present invention is a polymer composition for use in a film for converting UV light or short wavelength light into red spectral light, comprising: a mixture of A-Eu oxide and La oxide in an ethylene copolymer polymer composition; B-one or more compounds selected from the group consisting of organic acids; One or more compounds selected from the group consisting of C-nitrogen heterocycle; A polymer composition comprising a three-component active additive mixture is added, a method for producing a green house film using the same, and the green house film It features.

Agricultural Greenhouse Film, Polymer Composition, Ethylene Copolymer, Red Spectrum, UV Light

Description

Polymer composition for production of light transforming agriculture greenhouse films and manufacturing method of greenhouse film using same and greenhouse film

The present invention relates to a polymer composition for producing a light conversion agricultural green house film, a method for producing a green house film using the same, and a green house film. The present invention specifically includes additives capable of converting UV light into red spectral light. The present invention relates to a polymer composition suitable for an agricultural green house, a method of manufacturing a green house film using the same, and a film thereof.

Until now, various light conversion polymers have been used in agricultural green house films.

For example, Russian patent RU 2036217 (May 27, 1995) describes a molar ratio of 1: 0.1 to 1: 100 between a thermoplastic polymer and Eu and another metal of the group consisting of Y, La, Bi, Tb, Lu and Gd. It relates to a light conversion polymer composition composed of a complex having.

However, the above composition has a drawback that the active additive can be used only after the synthesis and purification process.

In addition, there is a disadvantage that the particle size of the additive obtained by this method is relatively large, 0.2-0.3 μm and more. This is a very important factor because the optical properties of solid particles in the polymer film depend on the shape and size of the particles, more precisely the particle size distribution. The problem is that large particles increase the light scattering of the film, resulting in loss of light intensity. .

Further examples are given in Russian patent RU 2202567 (April 20, 2003). In this patent, a luminescent material that selectively absorbs light consists of a solution of a polymer and an active additive having the general formula [A (COO) _x ] ₃ EuB. In this general formula A is an alkyl radical having 1-4 carbon atoms and B is composed of 1,10-phenanthroline, α, α-dipyridine, picoline, tetrahydrofuran, dimethylsulfoxide, quinoline and its derivatives Is selected from the group.

However, the above compositions also have the disadvantage that the synthesis, purification and drying of the active additives must be carried out in advance and their application is limited by the casting procedure.

In addition, patents most similar to the present invention can be found in US Pat. No. 5,958294 (September 28, 1999). This patent relates to polymer compositions for the production of polyethylene based films. The polymer composition is selected from the group consisting of Eu oxides, organic salts or inorganic salts, component B selected from the group β-diketone, component C selected from the group consisting of bidentate ligand nitrogen heterocycles or trialkyl substituted phosphine oxides. It contains a three component mixture consisting of.

The advantage of the composition is that it is the simplest light conversion film production procedure, but has the disadvantage that the stability is somewhat poor when exposed to UV light for a long time.

An object of the present invention for solving the above problems is to provide a polymer composition comprising an ethylene copolymer and a luminescent active additive for the production of a light conversion film for converting UV light or short wavelength light into red visible light.

It is another object of the present invention to provide a light conversion film for converting UV light or short wavelength light into red visible light, which can be used in agriculture or other applications requiring conversion of UV light into red spectral light.

It is another object of the present invention to provide a method for producing a light conversion film that converts UV light or short wavelength light into red visible light, which can be used in agriculture or other applications requiring conversion of UV light into red spectral light.

Another object of the present invention is to provide a polymer film and a method of manufacturing the same, which have increased stability against prolonged exposure to UV light.

The present invention to achieve the object as described above and to perform the problem for removing the conventional defects in the polymer composition used in the film for converting UV light or short wavelength light into the light of the red spectral region,

Ethylene Copolymer Polymer Composition

A mixture of A-Eu oxide and La oxide;

B-one or more compounds selected from the group consisting of organic acids;

One or more compounds selected from the group consisting of C-nitrogen heterocycle; is achieved by providing a polymer composition for producing a light conversion agricultural green house film, characterized in that the composition is added with a three-component active additive mixture consisting of .

The ratio between the active additive mixtures of the three component composition is that component A is composed of one molecule, component B is six molecules, and component C is composed of two molecules, where the number of molecules of each component is determined by Water and the number of molecules of H ⁺ of the organic acid required to deposit A on the ligand by removing oxygen of the A oxide.

The content of the active additive mixture of the three-component composition is characterized in that the composition of 0.05-15.0 wt.% Of the total polymer composition.

The component A is characterized in that the Eu oxide and La oxide are mixed in a molar ratio of 1: 99-99: 1.

Component B is selected from an organic acid group consisting of acetic acid, acetic acid derivatives, acetic acid homologs, benzoic acid, benzoic acid derivatives, phenylacetic acid, phenylacetic acid derivatives, pyridinecarboxylic acids, pyridinecarboxylic acid homologs, quinaldic acid, quinaldic acid derivatives, and quinaldic acid isomers It is done.

In the group consisting of nitrogen heterocyclo free base or inorganic acid salts such as component C is 2,2'-dipyridine, 1,10-phenanthroline, 2,2'-dipyridine or 1,10-phenanthroline derivative It is characterized in that at least one selected.

The ethylene copolymer polymer composition may be polyethylene or vinyl acetate or propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-dekene, 1-hendeken, 1- It is characterized in that it is a copolymer with any one of the terminal alkenes of dodecene.

The ethylene copolymer polymer composition is characterized in that a single ethylene copolymer or a mixture with two or more different ethylene copolymers.

In another aspect, the present invention is a method for manufacturing a polymer film after mixing or after mixing the polymer composition is prepared and injected to absorb a light 90% or more of the solar UV region to convert to a light of the red spectral region of the optical film characterized in that It is achieved by providing a method for producing a polymer film using the polymer composition for producing a transformed agricultural green house film.

In another aspect, the present invention is achieved by providing a light conversion agricultural greenhouse film, characterized in that the absorption of more than 90% of the light of the solar UV region prepared according to the manufacturing method is converted to light of the red spectral region.

According to the present invention, a polymer film having improved performance capable of converting light in the UV region into red visible spectrum light can be obtained.

In addition, it is possible to obtain a polymer film with increased stability against long-term exposure to UV light.

In addition, according to the present invention is a useful invention having the advantage that the performance is improved and the polymer film containing the low-cost composition of the ethylene copolymer and the light-emitting active additive is possible and can be applied to all fields that require light conversion as well as for agriculture As such, the invention is expected to be greatly utilized in the industry.

Hereinafter, the configuration and the operation of the embodiment of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

The polymer composition of the present invention comprises the following three component active additives.

A) A mixture of Eu oxide and La oxide in a molar ratio of 1:99 to 99: 1

B) one or more compounds selected from the group consisting of organic acids

C) One or more compounds selected from the group consisting of nitrogen heterocycles in the form of free base or inorganic acid salts such as 2,2'-dipyridine or 1,10-phenanthroline.

The electrons of the component A are activated at the wavelength introduced into the nitrogen heterocycle to cause a wavelength change depending on the deviation between the d-f electron angles and the energy level of the feedback. Eu is a lanthanide-based element suitable for deviating and returning electrons by ultraviolet rays, but the conversion efficiency of wavelength does not drop significantly even if it is replaced with La, an expensive, rarely similar, and inexpensive electron with a rare earth metal. However, if more than 99% is replaced, the conversion efficiency drops drastically.

The acid (H ⁺ ) of component B serves to deposit A on the ligand by removing the oxygen of A when introducing A into the nitrogen heterocycle.

Component C serves to absorb ultraviolet wavelengths.

The ratio between the active additive mixtures of the three component composition is composed of one molecule of component A, six molecules of component B, and two molecules of component C. Here, the number of molecules of each component represents the number of molecules required to form the structure of the ligand and the number of molecules of H ⁺ of the organic acid required to deposit A on the ligand by removing oxygen of the A oxide.

The amount of active additive may be added to the polymer composition in various ways, but the addition of 0.005-15.0 wt.% Of the total composition is preferred, and the addition of 0.05-1.0 wt.% Of the total composition is more preferred. Here, the composition of the active additive for the polymer is less than 0.005% by experiment, the light conversion effect is insignificant, and it is not worth it as a light conversion film, and if the ratio is gradually increased, it reaches the highest point (90% conversion) but decreases more than 15%. As well as waste of active additives.

The organic acid group of component B means the following compound.

1) Acetic acid or perfluorinated derivative or perchlorinated derivative or C ₃ -C ₁₈ homologue

2) Substituted derivatives containing benzoic acid or C ₁ -C ₄ alkyl substituents, chlorine atoms or C ₁ -C ₄ alkoxy groups or benzoyl substituents

3) phenylacetic acid or a C ₁ -C ₄ alkyl substituents, a chlorine atom or a C ₁ -C ₄ alkoxy-substituted derivatives thereof containing an aryl nucleus

4) Pyridinecarboxylic acid or its homologue containing picolinic acid, nicotinic acid, isnicotinic acid, dipicolinic acid or similar one or two carboxyl groups or optionally one or two hydroxyl groups

5) Quinolinecarboxylic acids, such as quinaldic acid or positional isomers thereof.

The nitrogen heterocycle of component C is a free base or hydrochloric acid, nitric acid or sulfuric acid as an unsubstituted compound of a compound such as 2,2'-dipyridine or 1,10-phenanthroline and an optional substituent of one or more chlorine atoms or methyl groups. It includes inorganic acid salts such as.

Ethylene copolymers constituting the main component of the polymer composition of the present invention is polyethylene or vinyl acetate or propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-deken, It means any one selected from copolymers with any one terminal alkene selected from 1-hendeken, 1-dodeken.

When mixing the polymer of the component A, component B, component C with the polymer, the amount of the three-component active additive is preferably 0.005-15.0 wt.% Of the total composition, more preferably 0.05-1.0 wt.% Of the total composition. The final film can be prepared by mixing the polymer composition.

In addition, when the mixture of the component A, component B, component C and the polymer is mixed, the amount of the three-component active additive is mixed to be 10 wt.% Of the total composition to prepare a masterbatch first, and then using the three-component active The final film may be prepared such that the amount of the additive is preferably 0.005-15.0 wt.% Of the total composition, more preferably 0.05-1.0 wt.% Of the total composition.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the technical scope of the present invention is not limited to the following examples.

Example 1

Active additive mixture containing Eu oxide and La oxide mixed with component A in a molar ratio of 0.5: 0.5, nicotinic acid with component B, and 1,10-phenanthroline as component C, having a weight ratio of 1: 2.1: 0.5 The additive mixture was mechanically mixed with low density polyethylene pellets to a concentration of 1 wt.% And then injection molded into a film.

Example 1a

An active additive mixture containing Eu oxide as component A, nicotinic acid as component B, and 1,10-phenanthroline as component C, having a weight ratio of 1: 2.1: 0.5 and having an active additive mixture at a concentration of 1 wt.%. Mechanical mixing with low density polyethylene pellets was followed by injection molding into films.

Example 2

An active additive mixture containing Eu oxide and La oxide mixed with component A in a molar ratio of 0.3: 0.7, dipicolinic acid as component B, and 1,10-phenanthroline as component C, has a weight ratio of 1: 1.43: 1.0 Mechanically mixed with ethylene-ethylvinylacetate copolymer pellets so that the active additive mixture has a concentration of 10 wt.%, Injection molded into a masterbatch in particulate form, and then mixed with low density polyethylene pellets in a weight ratio of 1: 9. Injection molding into a film.

Example 2a

An active additive mixture containing Eu oxide as component A, dipicolinic acid as component B, 1,10-phenanthroline as component C, having a weight ratio of 1: 1.43: 1.0 and a concentration of 10 wt.% Active additive mixture It was mechanically mixed with ethylene-ethyl vinyl acetate pellets so as to be injection molded into a masterbatch in the form of particles, which was then mixed with low density polyethylene in a weight ratio of 1: 9 and injection molded into a film.

Example 3

A weight ratio of 1: 3.8: 0.87 with an active additive mixture containing Eu oxide and La oxide mixed with component A in a molar ratio of 0.1: 0.9, 2-benzoylbenzoic acid as component B, and 2,2'-dipyridine as component C And mechanically mixed with low density polyethylene pellets such that the active additive mixture is at a concentration of 1 wt.%, Followed by injection molding into a film.

Example 3a

An active additive mixture containing Eu oxide as component A, 2-benzoylbenzoic acid as component B, and 2,2'-dipyridine as component C, having a weight ratio of 1: 3.83: 0.87 and having an active additive mixture of 1 wt.% Mechanically mixed with low density polyethylene pellets to concentration, then injection molded into films.

Each component A, B, C in each of the above examples is one molecule, six molecules, two molecules. If this is changed to the weight ratio of the material used as each component, it becomes the weight ratio of each Example. Of course, a single component may be possible, but it may be cheaper to substitute Eu with La.

Comparative Example 1

Active additive mixtures containing the composition described in US patent USP 5958294 (September 28, 1999), namely Eu oxide, tenoyltrifluoroacetone, 2,2'-dipyridine, for use as a standard for light stability testing. Mechanically mixed with low density polyethylene pellets having a weight ratio of 1: 3.778: 0.88 and having an active additive mixture at a concentration of 1 wt.%, Followed by injection molding into a film.

In the light stability test, artificial sunlight was irradiated for 30-371 hours using a Suntest device (Atlas Corporation). This time is equivalent to 0.48-6 months, assuming no consideration of the effect of actual temperature. Light stability is defined as the time taken for the initial emission intensity to be halved. Luminescence intensity was measured using a spectrofluorometer Jobin Ivon JY3. The light stability test results are shown in Table 1. _ㅍ t (h) denotes the time at which the initial luminescence intensity it takes half.

Table 1 below is a characteristic result table of the polymer film of the Examples and Comparative Examples.

TABLE 1

sample _ㅍ t (h) Transparence in visible spectra region (%) Comparative Example 1 30 82 Example 1 320 87 Example 1a 335 91 Example 2 371 86 Example 2a 350 79 Example 3 310 93 Example 3a 295 90

For reference, in the table,% represents transparency in the visible light region. It only absorbs 90% or more of the UV light and the above percentage is not related to 90% of the UV light.

The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

Claims (12)

In the polymer composition used for the film which converts UV light or short wavelength light into light of a red spectral region, Ethylene Copolymer Polymer Composition A mixture of A-Eu oxide and La oxide; B-a compound selected from the group consisting of organic acids; C-a compound selected from the group consisting of nitrogen heterocycles; A polymer composition for producing a light conversion agricultural green house film, characterized in that the composition is added by the active additive mixture of the three-component composition. The method according to claim 1, The ratio between the active additive mixtures of the three component compositions is that component A is composed of one molecule, component B is six molecules, and component C is composed of two molecules, where the number of molecules of each component is determined by A number and the number of molecules of the organic acid H ⁺ required to deposit A on the ligand by removing the oxygen of the A oxide, the polymer composition for manufacturing a light conversion agricultural green house film. The method according to claim 1, The polymer composition for manufacturing a light conversion agricultural green house film, characterized in that the content of the active additive mixture of the three-component composition is 0.005-15.0 wt.% Of the total polymer composition. The method according to claim 1, The polymer composition for manufacturing a light conversion agricultural green house film, characterized in that the component A is a mixture of Eu oxide and La oxide in a molar ratio of 1: 99-99: 1. The method according to claim 1, Component B is at least one organic acid group selected from acetic acid, acetic acid derivatives, acetic acid homologs, benzoic acid, benzoic acid derivatives, phenylacetic acid, phenylacetic acid derivatives, pyridinecarboxylic acids, pyridinecarboxylic acid homologs, quinalic acid, quinalic acid derivatives, and quinalic acid isomers Polymer composition for producing a light conversion agricultural green house film, characterized in that. The method according to claim 5, The polymer composition for producing a light conversion agricultural green house film, characterized in that the component B consists of one or more compounds. The method according to claim 1, In the group consisting of nitrogen heterocyclo free base or inorganic acid salts such as component C is 2,2'-dipyridine, 1,10-phenanthroline, 2,2'-dipyridine or 1,10-phenanthroline derivative Polymer composition for manufacturing a light conversion agricultural green house film, characterized in that at least one selected. The method according to claim 7, The polymer composition for producing a light conversion agricultural green house film, characterized in that the component C consists of one or more compounds. The method according to claim 1, The ethylene copolymer polymer composition may be polyethylene or vinyl acetate or propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-dekene, 1-hendeken, 1- A polymer composition for producing a photoconversion agricultural green house film, characterized in that the copolymer with any one of the terminal alkenes of dodeken. The method according to claim 9, The ethylene copolymer polymer composition is a polymer composition for manufacturing a light conversion agricultural green house film, characterized in that a single ethylene copolymer or a mixture with two or more different ethylene copolymers. A method of manufacturing a polymer film which absorbs 90% or more of the solar UV region and converts it into light of a red spectral region after injecting the polymer composition according to any one of claims 1 to 10 after mixing or after mixing. Method for producing a polymer film using a polymer composition for producing a light conversion agricultural green house film characterized in that the method. Light conversion agricultural greenhouse film, characterized in that to absorb more than 90% of the light of the solar UV region prepared according to the method of claim 11 to the light of the red spectral region.