A light-converting agent masterbatch, a light-converting film and a preparation method thereof

Abstract

This application discloses a light-converting agent masterbatch, a light-converting film, and a preparation method thereof. The light-converting agent masterbatch comprises the following components by weight: 0.01-5 parts of a light-converting agent, 40-90 parts of a light-converting agent carrier, and 10-35 parts of other additives, with the light-converting agent and other additives encapsulated in the light-converting agent carrier. The light-converting film comprises the light-converting agent masterbatch and a light-converting film substrate. The light-converting film exhibits high weather resistance and long service life.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a light-converting agent masterbatch, a light-converting film, and a preparation method thereof. Background Art

[0002] Light-conversion film is a film that converts light by adding a light-conversion agent. While retaining the light transmittance of standard film, it also converts harmful, plant-unabsorbable ultraviolet light into blue-violet and red-orange light, which is beneficial for photosynthesis, thereby increasing plant photosynthetic efficiency. Numerous experiments have shown that light-conversion film not only promotes crop growth and yield, but also promotes early maturity and improves crop quality. Consequently, the development and research of light-conversion film and light-conversion agents has become a hot topic in the agricultural film industry worldwide.

[0003] CN106945365B discloses a long-life agricultural light-conversion film and its preparation method. The light-conversion agents used are primarily rare earth inorganic sulfide light-conversion agents and aluminate light-conversion agents. The light-conversion layer is composed of a base resin, the light-conversion agent, a lubricant, a light stabilizer, and an antioxidant. The film comprises a first protective layer, a light-conversion layer disposed on the first protective layer, and a second protective layer disposed on the light-conversion layer. However, the inorganic light-conversion agents have poor compatibility with polymer materials and are prone to agglomeration, which affects the performance of the agricultural light-conversion film.

[0004] CN106967101B discloses a rare earth organic light conversion agent and an anti-aging light conversion film, which mainly comprises a rare earth organic light conversion agent Eu (BMPD) n L and antioxidants are added to the film matrix, thereby improving the aging resistance of the prepared light-converting film. Although the above-mentioned organic light-converting agents have good compatibility with polymer materials, high initial brightness, and significant effects on improving crop yield and quality, they have poor weather resistance, i.e., they easily decompose in sunlight, and the luminous intensity decreases rapidly.

[0005] Therefore, how to improve the weather resistance and service life of the light-converting film has become a technical problem that needs to be solved by those skilled in the art. Summary of the Invention

[0006] The present application provides a light-converting agent masterbatch, a light-converting film and a preparation method thereof. The light-converting film has high weather resistance and service life.

[0007] The present application provides the following solution: a light conversion agent masterbatch, comprising the following components in parts by weight:

[0008] 0.01-5 parts of light conversion agent, 40-90 parts of light conversion agent carrier, and 10-35 parts of other auxiliary agents. The light conversion agent and the other auxiliary agents are coated in the light conversion agent carrier.

[0009] Furthermore, the light conversion agent includes a rare earth organic light conversion agent, and the rare earth organic light conversion agent includes (1,10-phenanthroline) tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione] europium (III) (Eu(TTA)3phen), and the particle size of the Eu(TTA)3phen is below 500nm.

[0010] Furthermore, the light conversion agent carrier includes at least one of styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene block copolymer (SEBS), and styrene block copolymer (SBC);

[0011] or,

[0012] At least one of a blend of styrene-butadiene-styrene block copolymer (SBS) and polyethylene (PE), a blend of hydrogenated styrene-butadiene block copolymer (SEBS) and polyethylene (PE), and a blend of styrenic block copolymer (SBC) and polyethylene (PE).

[0013] Furthermore, the other auxiliary agents include at least one of an antioxidant, an ultraviolet absorber, and a dripping agent.

[0014] Furthermore, the other additives include at least one of antioxidant S2225P, antioxidant 168, antioxidant 1010, and antioxidant 1098;

[0015] If / or,

[0016] The other adjuvants include 2-(2′-hydroxy-3′, 5′-dicumylphenyl)-benzotriazole (UV-234);

[0017] and or,

[0018] The other auxiliary agents include at least one of glyceryl monostearate, sorbitan monopalmitate, and coconut oil diethanolamide.

[0019] The present application also provides a light-converting film, which includes the above-mentioned light-converting agent masterbatch and a light-converting film substrate.

[0020] Furthermore, the light conversion agent masterbatch is distributed in the light conversion film in an island structure.

[0021] Furthermore, the mass of the light conversion agent masterbatch is 0.1-5% of the mass of the light conversion film, and the mass of the light conversion film substrate is 95-99.9% of the mass of the light conversion film.

[0022] Furthermore, the light-converting film substrate includes at least one of linear low-density polyethylene, high-density polyethylene, polyvinyl chloride, polypropylene, polyamide, polystyrene, polyethylene terephthalate, and polyethylene acetate.

[0023] In addition, the present application also provides a method for preparing the aforementioned light-converting film, comprising the following steps:

[0024] By weight, 0.01-5 parts of a light conversion agent, 40-90 parts of a light conversion agent carrier, and 10-35 parts of other additives are mixed uniformly in a mixer to obtain a mixture;

[0025] adding the mixture into a twin-screw extruder for melt blending to obtain a light conversion agent masterbatch;

[0026] The light-converting film substrate and the light-converting agent masterbatch are evenly mixed and processed into a film to obtain the light-converting film.

[0027] Furthermore, the film forming is performed by a blowing method, a calendering method or an extrusion method.

[0028] Preferably, the film forming is performed by a blow molding method.

[0029] Furthermore, the extrusion temperature of the aforementioned light conversion agent masterbatch is 140-180°C.

[0030] Preferably, the extrusion temperature of the aforementioned light conversion agent masterbatch is 180°C.

[0031] Furthermore, the screw speed of the aforementioned twin-screw extruder is 300-500 rpm.

[0032] Preferably, the screw speed of the aforementioned twin-screw extruder is 350 rpm.

[0033] According to the specific embodiments provided in this application, this application discloses the following technical effects:

[0034] The present application provides a light-converting agent masterbatch, a light-converting film, and a method for preparing the same. First, a light-converting agent is encapsulated in a light-converting agent carrier to form the masterbatch, which is then dispersed in a film matrix to form the film. The light-converting agent is first prepared as a masterbatch, and then the masterbatch is used to prepare the film. Encapsulating the light-converting agent in the light-converting agent carrier effectively prevents oxidation and deliquescence, improving its weather resistance and service life. Furthermore, the light-converting agent can be pre-dispersed, enhancing its dispersibility in the film matrix and resulting in a highly stable light-converting film.

[0035] In addition, the rare earth organic light conversion agent in the present application has good compatibility with the light conversion agent carrier, the prepared light conversion agent masterbatch has strong stability, and the light conversion film prepared by mixing the light conversion agent masterbatch with the film matrix has a long service life.

[0036] Of course, any product implementing the present application does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0038] Figure 1 A schematic diagram of the structure of the light-converting film provided in this application;

[0039] Figure 2 This is a flow chart of the method for preparing the light-converting film provided in this application. DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the embodiments described are only part of the embodiments of the present application, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present application are within the scope of protection of this application.

[0041] As described in the background art, the light-converting agent is the core material of the light-converting film and is the key to achieving the light energy conversion of the light-converting film. Inorganic light-converting agents have poor compatibility with polymer materials and are easily agglomerated, which affects the performance of the light-converting film. Although organic light-converting agents have good compatibility with polymer materials, they have poor weather resistance and a short service life. In the present application, the light-converting agent is first coated in a light-converting agent carrier to prepare a light-converting agent masterbatch, and then the light-converting agent masterbatch is dispersed in a film matrix to prepare a light-converting film. Coating the light-converting agent in a light-converting agent carrier can effectively prevent its oxidation and deliquescence, thereby improving the weather resistance and service life of the light-converting film. Based on this, the present application proposes a light-converting agent masterbatch, a light-converting film, and a method for preparing the same.

[0042] As a preferred embodiment, in the embodiment of the present application, the components of the light conversion agent masterbatch include, by weight: 0.01-5 parts of light conversion agent, 40-90 parts of light conversion agent carrier, and 10-35 parts of other additives. The light conversion agent and the other additives are encapsulated in the light conversion agent carrier.

[0043] The light-conversion agent is the core material of the light-conversion film and is the key to achieving the light energy conversion of the light-conversion film. It can convert ultraviolet rays in sunlight that are harmful to crops and cannot be absorbed into blue-violet light and red-orange light that are beneficial to crop photosynthesis. Since rare earth organic light-conversion agents have the characteristics of high absorbance, strong luminous brightness, and good compatibility with polymer materials, the light-conversion agent in this application is preferably a rare earth organic light-conversion agent. More specifically, the rare earth organic light-conversion agent includes (1,10-phenanthroline) tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione] europium (III) (Eu(TTA)3phen). Furthermore, the particle size of the Eu(TTA)3phen is less than 500nm. More specifically, the particle size of the Eu(TTA)3phen is 100nm, 200nm, 300nm, 400nm, or 500nm. Due to space limitations, this will not be exhaustively listed here.

[0044] Although rare earth organic light converters (LECs) exhibit good compatibility with polymer materials, they exhibit poor weather resistance, i.e., they readily decompose in sunlight and experience a rapid decrease in luminous intensity. To address this issue, the present invention first encapsulates the LCs in a LC carrier to form a masterbatch, which is then dispersed in a film matrix to form a light-conversion film. Encapsulating the LCs in the LC carrier effectively prevents oxidation and deliquescence, improving its weather resistance and service life. Furthermore, encapsulating the LCs in the LC carrier allows for pre-dispersion of the LCs, enhancing their dispersibility within the film matrix and resulting in a highly stable LC film. In an embodiment of the present application, the light-converting agent carrier includes at least one of styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene block copolymer (SEBS), and styrene-block copolymer (SBC), or at least one of a styrene-butadiene-styrene block copolymer (SBS) and polyethylene (PE) blend, a hydrogenated styrene-butadiene block copolymer (SEBS) and polyethylene (PE) blend, and a styrene-block copolymer (SBC) and polyethylene (PE) blend. The rare earth organic light-converting agent provided in the present application contains benzene rings, which are not compatible with conventional polyethylene materials. The rare earth organic light-converting agent particles in the polyethylene film may have gaps on their surface, allowing water vapor to penetrate and render the light-converting agent ineffective. The present application uses a light-converting agent carrier containing a styrene structure to coat the light-converting agent, which improves compatibility (reducing the effects of moisture and heat) and enhances light resistance. In addition, the benzene rings in the light-converting agent carrier can also absorb ultraviolet rays.

[0045] Wherein, the other auxiliary agents include at least one of an antioxidant, an ultraviolet absorber, and a dripping agent.

[0046] Antioxidants can effectively reduce the thermal oxidation reaction rate of polymer materials, delaying the thermal and oxidative degradation of polymer materials, significantly improving the heat resistance of polymer materials, and extending the service life of the products. In the embodiments of the present invention, the antioxidant includes at least one of antioxidant S2225P, antioxidant 168, antioxidant 1010, and antioxidant 1098. Users can select the antioxidant according to actual needs and there is no specific limitation here.

[0047] Because sunlight contains a large amount of ultraviolet light that is harmful to objects, this harmful ultraviolet light causes the color molecules to decompose and fade through chemical redox reactions. To address this problem, the present application adds a UV absorber to the material. The UV absorber can absorb the ultraviolet portion of sunlight without changing itself. In the embodiment of the present application, the UV absorber includes 2-(2′-hydroxy-3′,5′-dicumylphenyl)-benzotriazole (UV-234).

[0048] A de-drip agent is a surfactant that breaks the interfacial tension between the water droplets and the light-converting film, distributing the condensed water droplets into a continuous, transparent layer. This reduces the contact angle between the water and the light-converting film, preventing the formation of water droplets on the film's surface. In the present embodiment, the de-drip agent comprises at least one of glyceryl monostearate, sorbitan monopalmitate, and coconut oil diethanolamide. Users can select the agent based on their needs and are not specifically limited here.

[0049] The present application also provides a light-converting film, which includes the above-mentioned light-converting agent masterbatch and a light-converting film matrix, wherein the light-converting agent masterbatch is distributed in the light-converting film in an island-like structure. The mass of the light-converting agent masterbatch is 0.1-5% of the mass of the light-converting film, and the mass of the light-converting film matrix is ​​95-99.9% of the mass of the light-converting film. More specifically, the mass of the light-converting agent masterbatch is 0.1%, 0.5%, 1%, 2%, 3%, 4%, or 5% of the mass of the light-converting film, and the examples are not listed here due to space limitations; the mass of the light-converting film matrix is ​​95%, 96%, 97%, 98%, 99%, or 99.9% of the mass of the light-converting film, and the examples are not listed here due to space limitations.

[0050] Furthermore, the light-converting film substrate includes at least one of linear low-density polyethylene, high-density polyethylene, polyvinyl chloride, polypropylene, polyamide, polystyrene, polyethylene terephthalate, and polyethylene acetate.

[0051] In a specific embodiment, the structure of the light-converting film is as follows: Figure 1As shown, the light-converting film comprises a light-converting agent masterbatch 100 and a light-converting film substrate 200. The light-converting agent masterbatch 100 includes a light-converting agent 110, a light-converting agent carrier 120, and other additives 130. The light-converting agent 110 and other additives 130 are encapsulated in the light-converting agent carrier 120 to form the light-converting agent masterbatch 100. The light-converting agent masterbatch 100 is dispersed in the light-converting film substrate 200 in an island-like structure to form the light-converting film. Encapsulating the light-converting agent 110 in the light-converting agent carrier 120 effectively prevents oxidation and deliquescence, thereby improving its weather resistance and service life.

[0052] Corresponding to the above-mentioned light-converting film, the present application also provides a method for preparing the light-converting film. Figure 2 As shown, the method for preparing the light-converting film includes the following steps:

[0053] S1: By weight, 0.01-5 parts of a light conversion agent, 40-90 parts of a light conversion agent carrier, and 10-35 parts of other additives are mixed uniformly in a mixer to obtain a mixture;

[0054] S2: adding the mixture into a twin-screw extruder for melt blending to obtain a light conversion agent masterbatch;

[0055] S3: uniformly mixing the light-converting film substrate and the light-converting agent masterbatch, and processing the mixture into a film to obtain the light-converting film.

[0056] Furthermore, the film-forming process adopts a blow molding method, a calendering method or an extrusion method to form the film. In the embodiment of the present application, the film-forming process adopts a blow molding method to form the film.

[0057] Preferably, the extrusion temperature of the aforementioned light conversion agent masterbatch is 180°C.

[0058] Preferably, the screw speed of the aforementioned twin-screw extruder is 350 rpm.

[0059] All of the above optional technical solutions can be combined in any way to form optional embodiments of the present application, and will not be described in detail here.

[0060] The beneficial effects of the present application will be further illustrated below with reference to examples and comparative examples.

[0061] The raw materials used in the embodiments and comparative examples are described below:

[0062] Linear low-density polyethylene (LLDPE): produced by ExxonMobil, 6101XR;

[0063] (1,10-phenanthroline)tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione]europium(III) (Eu(TTA)3phen)

[0064] 2-(2′-hydroxy-3′,5′-dicumylphenyl)-benzotriazole (UV-234): produced by BASF, Tinuvin 234;

[0065] Styrene-butadiene-styrene block copolymer (SBS): produced by Zhonghe, Maoming Zhonghe K glue 838;

[0066] Hydrogenated styrene-butadiene block copolymer (SEBS): produced by Kraton, USA, G1657VS;

[0067] Antioxidant S2225P: Produced by Albemarle, USA, S2225P;

[0068] Glyceryl monostearate: produced by Aladdin, CAS number: 123-94-4.

[0069] Material performance test methods:

[0070] 1. Fluorescent UV aging test: Tested according to ISO4892 standard.

[0071] Comparative Example 1

[0072] 3 parts of Eu(TTA)3phen, 10 parts of antioxidant S2225P, and 87 parts of LLDPE were mixed uniformly by a mixer, and added to a twin-screw extruder for melt blending to obtain a light conversion agent masterbatch;

[0073] 98.8 parts of LLDPE, 0.2 parts of glyceryl monostearate, and 1 part of light-converting agent masterbatch were uniformly mixed and blown into a film using a single-screw extruder to obtain a light-converting film with a thickness of 100 μm, wherein the mass of the light-converting agent masterbatch was 1 wt% of the light-converting film.

[0074] Comparative Example 2

[0075] By weight, 3 parts of Eu(TTA)3phen, 10 parts of antioxidant S2225P, 20 parts of UV-234, and 67 parts of LLDPE were mixed uniformly in a mixer, added to a twin-screw extruder for melt blending, and a light conversion agent masterbatch was obtained;

[0076] 98.8 parts of LLDPE, 0.2 parts of glyceryl monostearate, and 1 part of light-converting agent masterbatch were uniformly mixed and blown into a film using a single-screw extruder to obtain a light-converting film with a thickness of 100 μm, wherein the mass of the light-converting agent masterbatch was 1 wt% of the light-converting film.

[0077] Example 1

[0078] By weight, 3 parts of Eu(TTA)3phen, 10 parts of antioxidant S2225P, 20 parts of UV-234, and 67 parts of SBS were mixed uniformly in a mixer, added to a twin-screw extruder for melt blending, and a light conversion agent masterbatch was obtained;

[0079] 98.8 parts of LLDPE, 0.2 parts of glyceryl monostearate, and 1 part of light-converting agent masterbatch were uniformly mixed and blown into a film using a single-screw extruder to obtain a light-converting film with a thickness of 100 μm, wherein the mass of the light-converting agent masterbatch was 1 wt% of the light-converting film.

[0080] Example 2

[0081] Compared with Example 1, the difference is that SBS is replaced by SEBS.

[0082] The test results of the light-converting films prepared in Examples 1-2 and Comparative Examples 1-2 are shown in Table 1.

[0083]

[0084] From the test results in Table 1 above, we can see that:

[0085] 1. The test results of Comparative Examples 1-2 and Examples 1-2 show that compared to the light-conversion agent masterbatch prepared from the rare earth organic light-conversion agent Eu(TTA)3phen and LLDPE, the light-conversion film formed by first preparing the rare earth organic light-conversion agent Eu(TTA)3phen and the light-conversion agent carrier SBS (or SEBS) to form a light-conversion agent masterbatch and then adding the light-conversion agent masterbatch to the light-conversion film substrate LLDPE showed significantly improved fluorescence intensity retention after UV-accelerated aging or wet-heat-accelerated aging. This demonstrates that the SBS or SEBS provided in the examples of the present application, used as a light-conversion agent carrier to coat the rare earth organic light-conversion agent Eu(TTA)3phen, improves its compatibility, thereby increasing the weather resistance and service life of the light-conversion film.

[0086] The above detailed description of the light-converting agent masterbatch, light-converting film, and preparation method thereof provided by this application is provided. Specific examples are used herein to illustrate the principles and implementation methods of this application. The above examples are intended only to facilitate understanding of the method and core concept of this application. Furthermore, those skilled in the art will appreciate that variations in the specific implementation methods and scope of application may occur based on the concepts of this application. In summary, the contents of this specification should not be construed as limiting this application.

Claims

1. A light conversion agent masterbatch, characterized in that: The composition comprises the following components in parts by weight: 0.01-5 parts of a light conversion agent, 40-90 parts of a light conversion agent carrier, and 10-35 parts of other auxiliary agents, wherein the light conversion agent and the other auxiliary agents are coated in the light conversion agent carrier; The light conversion agent comprises a rare earth organic light conversion agent containing a benzene ring, and the light conversion agent carrier contains a styrene structure.

2. The light conversion agent masterbatch according to claim 1, characterized in that: The rare earth organic light conversion agent includes (1,10-phenanthroline) tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione] europium (III) (Eu(TTA)3phen), and the particle size of the Eu(TTA)3phen is less than 500 nm.

3. The light conversion agent masterbatch according to claim 1, characterized in that: The light conversion agent carrier includes at least one of styrene-butadiene-styrene block copolymer (SBS) and hydrogenated styrene-butadiene block copolymer (SEBS); or, At least one of a blend of styrene-butadiene-styrene block copolymer (SBS) and polyethylene (PE), and a blend of hydrogenated styrene-butadiene block copolymer (SEBS) and polyethylene (PE).

4. The light conversion agent masterbatch according to claim 1, characterized in that: The other auxiliary agents include at least one of an antioxidant, an ultraviolet absorber, and a dripping agent.

5. The light conversion agent masterbatch according to claim 1, characterized in that: The other additives include at least one of antioxidant S2225P, antioxidant 168, antioxidant 1010, and antioxidant 1098; and / or, The other adjuvants include 2-(2'-hydroxy-3',5'-dicumylphenyl)-benzotriazole (UV-234); and / or, The other auxiliary agents include at least one of glyceryl monostearate, sorbitan monopalmitate, and coconut oil diethanolamide.

6. A light-converting film, characterized in that: The light-converting film comprises the light-converting agent masterbatch according to any one of claims 1 to 5 and a light-converting film matrix.

7. The light-converting film according to claim 6, wherein: The light conversion agent masterbatch is distributed in the light conversion film in an island structure.

8. The light-converting film according to claim 6, wherein: The mass of the light-converting agent masterbatch is 0.1-5% of the mass of the light-converting film, and the mass of the light-converting film matrix is ​​95-99.9% of the mass of the light-converting film.

9. The light-converting film according to claim 6, wherein: The light-converting film substrate includes at least one of linear low-density polyethylene, high-density polyethylene, polyvinyl chloride, polypropylene, polyamide, polystyrene, polyethylene terephthalate, and polyethylene acetate.

10. A method for preparing a light-converting film according to claim 6, characterized in that: The preparation method comprises: By weight, 0.01-5 parts of a light conversion agent, 40-90 parts of a light conversion agent carrier, and 10-35 parts of other additives are mixed uniformly in a mixer to obtain a mixture; adding the mixture into a twin-screw extruder for melt blending to obtain a light conversion agent masterbatch; The light-converting film substrate and the light-converting agent masterbatch are evenly mixed and processed into a film to obtain the light-converting film.

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