KR100761942B1 - Optically active inorganic additive for light transforming greenhouse film and the greenhouse film comprising the additive - Google Patents

Abstract

The present invention provides an optically active inorganic additive for a polymer composite film and a light conversion green house film containing the same, including one or two or more mixtures selected from the following compositions 1) and 2).

1) Y _2-pqz (TR _Ⅲ ) _p (TR _Ⅳ ) _q (TR _Ⅴ ) _z O ₂ S

p = 0.01 to 0.1, q = 0 to 0.001, z = 0 to 0.0002, TR _III = Eu, TR _IV = Pr or Sm, TR _V = Pr or Tb

2) Y _2-xy (TR _I ) _x (TR _II ) _y SiO ₅

x = 0.01 to 0.1, y = 0 to 0.005, TR _I = Ce, TR _II = Nd or Tm

According to the present invention having the above configuration, it is possible to convert the UV region of the light spectrum into a spectral region useful for plant growth.

Light conversion, green house film, inorganic additive

Description

Optically active inorganic additive for light converting green house film and the green house film containing the same {Optically active inorganic additive for light transforming greenhouse film and the greenhouse film comprising the additive}

The present invention relates to an inorganic additive having a light activity for a light conversion green house film and a green house film containing the same. More specifically, for a green house film for light conversion of the UV region of the light spectrum into a spectral region useful for plant growth It relates to an inorganic additive and a green house film containing the same.

Green houses are widely distributed in the northern and southern hemispheres of the earth, which have a large cross-over climate during crop growth. In order to reduce this undesirable day and night temperature differential, a temporary or permanent green house with facilities for maintaining the temperature and light desirable for plant growth has been required. Inorganic (glass) and organic (transparent organic glass, polymers) materials with high light transmittance in the visible region of the light spectrum are made into sheets or rolls to form a green house for thermal insulation as a package.

In 1869, Russian scientist K. A. Timiryazev and others demonstrated for the first time that the light spectrum reaching the crops greatly influences the growth rate and yield of the plants in the green house. They found that orange-red (590-700 nm) or blue (420-470 nm) light greatly increased the yield of the plant. Photosynthetic properties of these plants are related to the optical factors of chlorophyll, the green pigment of plants. This theory, proposed by K. A. Timiryazev, has long been of great interest in the research and foundation of agriculture.

Based on this theory, the field of “plant lighting” has been created for the light intensity, light irradiation time and spectral properties of the green house. It was used to promote plant growth. Results from this field have been used to achieve high yields of large-scale horticultural crops, vegetables, strawberries, flowers, cabbage over the fall-winter-spring. However, the cost of growing horticulture also skyrocketed due to the sharp increase in the electricity costs for lighting green houses. Therefore, in order to promote the demand of the green house polymer film in the autumn-winter-spring, a polymer film having the following characteristics is required.

-Strong wind pressure strong mechanical strength without sticking well

-High transmission of light spectrum in the entire visible range

High absorption and re-emission of infrared radiation with a wavelength of 10-25 microns emitted by the soil in the green house

-UV spectrum absorption in short and medium wavelengths of sunlight, which prevents sunburn of plants by recently increased UV due to ozone layer breakage (appearance of ozone layer holes) in the atmosphere

Russian patent 2131661 uses organic glass as the light conversion cover of the green house in the polymer film for the green house film of the Russian patent 2094978. However, neither film affected the photosynthetic photofactor of the plant in the green house.

Patent SU1780309 discloses 1,10-phenantroline (1,10-phenantrolyne), 2,2'-dipyridine, 4,4'-dimethyl-2,2'-dipyridine (4,4 A polymer film containing a complex of '-dimethyl-2,2'-dipyridine) or paraffin europium nitrate was used as the green house film. The Russian patent 2053247 also relates to a polymer film for horticultural crops consisting of a phosphor, which emits light in a pigmented region, such as thermoplastic polymer, kaolin, aluminum or copper metal, blue or red pigment.

The polymer film for green house of Russian patent 2127511 is composed of a thermoplastic polymer, an optical stabilizer, and an europium compound-based inorganic phosphor. Phenozan-23 (phenozan-23) was used as the light stabilizer. Inorganic phosphorus: strontium sulfide activated with europium ② europium or dysprosium or / and calcium sulfide activated with turbium ③ europium Strontium calcium sulfide activated with, disprosium or / and terbium was used. The film absorbs the UV spectrum in the 290-330 nm or 400-440 nm region of the light spectrum and emits a red spectrum in the 580-760 nm region with maximum intensity at 618-680 nm. The film also has fluorescence properties for up to 2 hours.

The light conversion film of the Russian patent 2059999 consists of a thermoplastic polymer which is a light transmitting component and a light active additive. The general formula of this photoactive additive is [(La _1-x Eu _x ) O] _m (Lig) _n . If the equation m = n = 1 Lig = F -, Cl -, Br - to, in the case of m = 2, n = 1 Lig = S 2-, represents a SiO ₄ ^2-, PO ₄ ^3- of the final film The composition is as follows.

Optically active additives: 0.02-5.0 wt%

-Light transmitting polymer: rest

The patent film is easy to mass production, but has the following disadvantages in use.

The component emits secondary light only in the orange-red region of the spectrum and does not emit secondary light in the blue region. This adversely affects legumes and crops.

The emission intensity is high only when the content of the additive in the inorganic oxy sulfide-based polymer composition is 0.2-0.5% by weight.

Nevertheless, the patented film "Redlight", produced by varying the above-mentioned polymer composition, was produced in 1996, but the film had a weak emission intensity in the red region, which had little effect on plant growth. This may be due to the low light factor efficiency for photosynthesis due to the difficulty of film production technology, the control of the concentration of Europium yttrium oxy-sulfide additive, and the optimization of the emission spectrum content in the orange-red region. do. This is because the emission spectrum of Europium yttrium oxy sulfide is composed of light peaks of different light wavelengths of 585 nm, 616 nm and 626 nm. That is, there is a problem that the 40 nm intervals of the peak wavelengths do not match photosynthesis or are uneven.

The present invention has been proposed to overcome the limitations of the prior art as described above, and the inorganic additive for the green house film and the green house film containing the same to convert the UV region of the light spectrum into a spectral region useful for plant growth In providing.

In order to achieve the above object, the present invention provides a composition of the optically active inorganic additive for light conversion green house film comprising one or two or more mixtures selected from the following compositions 1) and 2).

1) Y _2-pqz (TR _Ⅲ ) _p (TR _Ⅳ ) _q (TR _Ⅴ ) _z O ₂ S

p = 0.01 to 0.1, q = 0 to 0.001, z = 0 to 0.0002, TR _III = Eu, TR _IV = Pr or Sm, TR _V = Pr or Tb

2) Y _2-xy (TR _I ) _x (TR _II ) _y SiO ₅

x = 0.01 to 0.1, y = 0 to 0.005, TR _I = Ce, TR _II = Nd or Tm

The present invention also provides a light conversion green house film comprising one or two or more mixtures selected from the above-described photoactive inorganic additives 1) and 2).

The light conversion green house film according to the present invention preferably comprises a light stabilizer.

Hereinafter, the content of the present invention in more detail as follows.

The present invention provides an inorganic additive applicable to the optically active inorganic additive and a light conversion green house film containing the same to improve the light conversion characteristics of the green house film.

The photoactive inorganic additive according to the present invention comprises one or a mixture of two or more selected from the following compositions 1) and 2).

1) Y _2-pqz (TR _Ⅲ ) _p (TR _Ⅳ ) _q (TR _Ⅴ ) _z O ₂ S

p = 0.01 to 0.1, q = 0 to 0.001, z = 0 to 0.0002, TR _III = Eu, TR _IV = Pr or Sm, TR _V = Pr or Tb

2) Y _2-xy (TR _I ) _x (TR _II ) _y SiO ₅

x = 0.01 to 0.1, y = 0 to 0.005, TR _I = Ce, TR _II = Nd or Tm

The inorganic additive represented by the above compound 1) is excellent in absorbing light in the UV region and converting it into light in the red region useful for general plant growth. The compound 1) may be added so as to contain 0.0001 to 0.02% by weight relative to the film weight as an additive of the light conversion green house film.

In addition, the inorganic additive represented by the compound 2) is excellent in absorbing light in the UV region and converting it into light in the blue region, which is particularly useful for legumes and crops. The compound 2) is preferably added as an additive of the light conversion green house film so as to contain 0.0001 to 0.005% by weight based on the weight of the film.

Compounds 1) and 2) may be added to the light conversion green house film polymer material alone or a mixture of the two materials may be added. Preferably, both compounds may be added. In this case, the addition ratio of the compound 1) and the compound 2) is preferably added so as to be adjusted in the range of 1: 1 to 3: 1.

In addition, a predetermined light stabilizer may be added for the purpose of increasing the light safety of the light conversion green house film according to the present invention. Representative examples of such light stabilizers include ternary amino succinate. In the case where the light stabilizer is to be added, the content thereof is preferably added in a ratio of 1: 1 to 1: 3, more preferably 1: 1.2 to 1: 1.5 with an inorganic additive.

The thermoplastic polymer usable in the light conversion green house film according to the present invention is not particularly limited, and examples thereof include polyethylene, polyvinyl chloride, EVA, polycarbonate glass, and the like.

The UV light transmission experiment was performed on the light conversion green house film according to the present invention. Furthermore, it was confirmed that when the inorganic additives represented by the compounds 1) and 2) were added together, blue-orange-red light was emitted regardless of artificial UV light or natural UV light. The amount of photon energy in the blue, orange, and red regions of the spectrum depends on the ratio of the two additives and the weight ratio of the additives in the film, but the light-integrated radiation intensity does not change linearly with the amount of additives, and blue-orange The radiation intensity in each red region also varies nonlinearly. That is, no light conversion occurs in proportion to the amount of additive (nonlinear increase). That is, even if the additive composition of the green house film increases the ratio of the inorganic additive of compound 2) by 50% than the above, the intensity of the 425 nm blue light increases by only 20%.

In the examples described below, the additive content dependence on the emission intensity of light in the blue or red region of the light spectrum was measured, and various crop experiments were performed.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the following examples are presented for the purpose of more easily understanding the contents of the present invention and are not intended to limit the scope of the present invention.

<Example 1>

Y _1.95 Ce _0.05 SiO ₅ was used as a blue phosphor and Y _1.95 Eu _0.05 O ₂ S was used as a red phosphor.

0.5 kg blue phosphor and 2.0 kg red phosphor were used to produce 1000 kg of film. First, the two phosphors were already heated to 100 ° C, containing 20 kg of low-density polyethylene with 0.5 kg of heat stabilizer and antioxidant, 0.5 kg IRGANOX 1010 (Ciba, Switzerland) and 3 kg TINUVIN 622 (Ciba, Switzerland), light stabilizers from Oligomeric Hindered Amine Light Stable. The mixture was heated to a rotary mix until 1 hour to mix. This material was transferred to a horizontal extruder and the temperature of the output plate was maintained at 150 ° C.

When the molten state was completely melted, injection was started with a thin rod type, cooled with cooling water, and cut into 4-8 mm granules.

This is called masterbatch and the brightness for UV light was higher than that of standard samples. When the luminance L value of the standard sample was 100%, the brightness of this masterbatch was 120%. Therefore, it can be seen that the UV light is removed and the radiation intensity in the blue-orange-red region is increased.

Moreover, the two-layer film was manufactured using the twin head extruder. Of the total masterbatch inputs, 35% masterbatch was used for the inner layer of the film and 65% masterbatch for the outer layer, and low density polyethylene was used as the main material of the film. The film thickness was 120 µm, and the film width was 10 m. The light transmittance of the film was about 91%, and the tensile strength was about 130 kgf / cm ² .

<Example 2>

0.25 g of blue phosphor Y _1.95 Ce _0.05 SiO _{5 and} 0.25 g of standard blue phosphor, Ba _0.9 MgEu _0.1 Al ₁₀ O ₁₇ (BMA), were mixed and used. As red phosphor, 1.5 kg of Y _1.95 Eu _0.05 O ₂ S, which is the same as in Example 1, was used. 1 kg and 3 kg of light stabilizer, IRGANOX 1010 (Swiss Ciba) and Oligomeric Hindered Amine Light Stable, TINUVIN 622 (Swiss Ciba), respectively, were used as a heat stabilizer and antioxidant. 20 kg was used by mixing in a ratio of 4: 1. The mixing to prepare the masterbatch was the same as in Example 1 except that the injection was started in a thin rod type, maintaining the temperature of the output plate of the horizontal extruder at 160 ° C. Cut to

Next, a three-layer film having a thickness of 160-180 μm was prepared. Of the total master batch input, 15% masterbatch was used for the inner layer of the film, 35% masterbatch for the middle layer, and 50% masterbatch for the outer layer, and low density polyethylene, the main material of the film, was used.

In addition, in order to avoid the accumulation of fog in the inner layer, that is, to prevent dewdrop formation, an inner layer of a fluoride low density polyethylene was added.

The tensile strength of this three-layer film is about 200 kgf / cm ^{2, which} is very high and can withstand snow slip or strong winter winds.

Experimental Example Crop Experiment

The test method is the same as the method used in the existing green house test to measure the reduction rate of carbon dioxide gas by the carbon assimilation of plants in a closed plastic house. Compared to the green house made of pure polyethylene film in the experimental results, the green house made of the film according to the present invention increases the growth rate of the plant (depending on the crop, but one week for tomatoes and peppers) The period was confirmed to be accelerated (one week for tomato).

According to the present invention, it is possible to efficiently convert the UV region of the light spectrum into a spectral region useful for plant growth. The polymer composite film containing the photoactive inorganic additive according to the present invention has a short wavelength absorption rate comparable to that of thick organic glass even with a thin thickness. The photon yield at the time of re-emission of the film according to the invention is high, 0.75 to 0.9, and the brightness of the emission spectrum exceeds the brightness of the light spectrum with the same wavelength and at the same time exhibits the thymirazep spectral effect. In addition, the polymer film increases the soil temperature of the green house by scattering or reflecting the infrared rays of the long wavelength in the green house.

Claims (6)

Optical active inorganic additive for a polymer composite film comprising one or a mixture of two or more selected from the following compositions 1) and 2). 1) Y _2-pqz (TR _Ⅲ ) _p (TR _Ⅳ ) _q (TR _Ⅴ ) _z O ₂ S p = 0.01 to 0.1, q = 0 to 0.001, z = 0 to 0.0002, TR _III = Eu, TR _IV = Pr or Sm, TR _V = Pr or Tb 2) Y _2-xy (TR _I ) _x (TR _II ) _y SiO ₅ x = 0.01 to 0.1, y = 0 to 0.005, TR _I = Ce, TR _II = Nd or Tm Polymer composite film comprising one or two or more mixtures selected from the following compositions 1) and 2) as an optically active inorganic additive. 1) Y _2-pqz (TR _Ⅲ ) _p (TR _Ⅳ ) _q (TR _Ⅴ ) _z O ₂ S p = 0.01 to 0.1, q = 0 to 0.001, z = 0 to 0.0002, TR _III = Eu, TR _IV = Pr or Sm, TR _V = Pr or Tb 2) Y _2-xy (TR _I ) _x (TR _II ) _y SiO ₅ x = 0.01 to 0.1, y = 0 to 0.005, TR _I = Ce, TR _II = Nd or Tm The polymer composite film of claim 2, further comprising an oligomeric hindered amine light stabilizer. The polymer composite film of claim 2, wherein the compound 1) contains 0.0001 to 0.02 wt% based on the weight of the film. The polymer composite film of claim 2, wherein the compound 2) contains 0.0001 to 0.005 wt% based on the weight of the film. The polymer composite film according to claim 2, wherein the composition ratio of the compounds 1) and 2) is 1: 1 to 3: 1.