CN110684330B - PC material with high light transmittance and high haze and application thereof - Google Patents
PC material with high light transmittance and high haze and application thereof Download PDFInfo
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- CN110684330B CN110684330B CN201910926493.4A CN201910926493A CN110684330B CN 110684330 B CN110684330 B CN 110684330B CN 201910926493 A CN201910926493 A CN 201910926493A CN 110684330 B CN110684330 B CN 110684330B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention relates to the technical field of PC materials, in particular to a PC material with high light transmittance and high haze and application thereof. The composite material comprises the following raw materials in parts by weight: 100 portions of PC, 2 to 6 portions of special light diffusant, 0.5 to 1 portion of antioxidant, 0.4 to 0.6 portion of light stabilizer and 0.4 to 0.6 portion of ultraviolet absorbent. The refractive index of polyacrylonitrile copolymerized by acrylonitrile and methyl acrylate is about 1.4, so that polymethyl methacrylate also has a certain light diffusion effect through secondary refraction, and the nano silicon dioxide serving as a core is used as an inorganic light diffusing agent to play a strong refraction effect, so that the PC haze is remarkably improved; in addition, the three-layer structure of the nano-silica-polymethyl methacrylate-polyacrylonitrile also reduces the dosage of the nano-silica, so that the influence on the light transmittance of PC is small.
Description
Technical Field
The invention relates to the technical field of PC materials, in particular to a PC material with high light transmittance and high haze and application thereof.
Background
At present, energy-saving and environment-friendly lamps are becoming more popular, development of lamp shade materials of LED lamp tubes is receiving more and more attention, and common lamp shade materials of the lamp tubes are PC (polycarbonate), PMMA (acrylic) and the like. PC is thermoplastic engineering plastic with excellent comprehensive performance, has excellent weather resistance, high impact resistance, excellent electric insulation, high light transmittance and less light energy loss, and is widely used in the fields of electric lighting and the like. Therefore, the LED lamp tube lampshade material is biased to select the light diffusion PC resin, which is the development trend in the future.
In the LED lamp, it is required to add a light diffusing agent to the PC resin, because the light transmittance is maintained as much as possible and the light utilization rate is improved without causing glare. The light diffusant has a spherical structure, is uniformly dispersed in the PC resin to form a sea-island structure, and because the refractive indexes of the PC resin and the light diffusant are different, light rays can be reflected on the surface of the light diffusant like a mirror surface, and the light diffusant achieves a light diffusion effect after multiple reflections. The addition amount, the particle size and the distribution of the light diffusant and the refractive index determine the optical performance of the material.
The invention patent of CN108276750 discloses a light diffusion composition with a core-shell structure, the light diffusion effect of which is good, but the applicant finds that the light transmittance of microcrystalline cellulose is low, the influence on the light transmittance of the material is large, and the requirement of high light transmittance cannot be met when the microcrystalline cellulose is used in a PC material.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a PC material with high light transmittance and high haze and application thereof.
The purpose of the invention is realized by the following technical scheme:
a PC material with high light transmittance and high haze comprises the following raw materials in parts by weight:
the special light diffusant is prepared by the following steps:
(1) adding 80-100 parts by weight of methyl methacrylate, 10-20 parts by weight of methyl acrylate, 40-50 parts by weight of nano silicon dioxide and 0.2-0.4 part by weight of n-dodecyl mercaptan into 100 parts by weight of organic solvent, adding 0.1-0.3 part by weight of first initiator in the stirring process, and then reacting for 1-3 hours at 40-50 ℃ to obtain a pre-polymerization solution;
(2) adding 40-60 parts by weight of acrylonitrile and 5-10 parts by weight of methyl acrylate into the prepolymerization liquid, adding 0.1-0.3 part by weight of a second initiator in the stirring process, and then reacting for 2-4h at 40-50 ℃ to obtain polymer liquid;
(3) and (3) carrying out electrostatic spraying on the polymer liquid to obtain the special light diffusant.
The light diffusion agent is a three-layer structure microsphere of nano silicon dioxide-polymethyl methacrylate-polyacrylonitrile, and the particle size is 30-50 mu m.
Polymethyl methacrylate (PMMA) is a plastic with high light transmittance, and is usually blended and modified with PC to manufacture optical products, but the refractive indexes of the PMMA and the PC are both about 1.5, so that polymethyl methacrylate is basically not used as a light diffusion modification material. However, the refractive index of polyacrylonitrile copolymerized by acrylonitrile and methyl acrylate is about 1.4, so that polymethyl methacrylate also has a certain light diffusion effect through secondary refraction, and the nano silicon dioxide serving as a core is used as an inorganic light diffusing agent to play a strong refraction effect, so that the PC haze is obviously improved; the three-layer structure of the nano-silica-polymethyl methacrylate-polyacrylonitrile also reduces the dosage of the nano-silica, so that the influence on the light transmittance of PC is small; in addition, the polyacrylonitrile with a higher melting point is used as the shell, so that the structural stability of the microsphere can be maintained in the melt extrusion process, and the batch quality of the product is more stable.
Wherein the organic solvent is one of toluene, xylene and ethyl acetate.
Wherein the first initiator and the second initiator are both azobisisobutyronitrile.
Wherein the particle size of the nano silicon dioxide is 10-20 nm.
Wherein the spraying voltage of the electrostatic spraying is 20-30kV, and the spraying temperature is 20-30 ℃.
Wherein the antioxidant is antioxidant 168 and/or antioxidant 1076.
Wherein the light stabilizer is bis (1, 2,2,6, 6-pentamethyl-4-piperidyl) sebacate and/or poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate.
Wherein the ultraviolet absorbent is 2-cyano-3, 3' -diphenylacrylic acid-2-ethylhexyl ester and/or 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole.
The PC material with high light transmittance and high haze is prepared by the following method: all the raw materials are put into a double-screw extruder for extrusion granulation, and the melting temperature is 200-250 ℃.
The application of the PC material with high light transmittance and high haze is applied to the manufacturing of LED lamps.
The invention has the beneficial effects that: the refractive index of polyacrylonitrile copolymerized by acrylonitrile and methyl acrylate is about 1.4, so that polymethyl methacrylate also has a certain light diffusion effect through secondary refraction, and the nano silicon dioxide serving as a core is used as an inorganic light diffusing agent to play a strong refraction effect, so that the PC haze is remarkably improved; the three-layer structure of the nano-silica-polymethyl methacrylate-polyacrylonitrile also reduces the dosage of the nano-silica, so that the influence on the light transmittance of PC is small; in addition, the polyacrylonitrile with a higher melting point is used as the shell, so that the structural stability of the microsphere can be maintained in the melt extrusion process, and the batch quality of the product is more stable.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A PC material with high light transmittance and high haze comprises the following raw materials in parts by weight:
the special light diffusant is prepared by the following steps:
(1) adding 80 parts by weight of methyl methacrylate, 10 parts by weight of methyl acrylate, 40 parts by weight of nano-silica and 0.2 part by weight of n-dodecyl mercaptan into 100 parts by weight of organic solvent, adding 0.1 part by weight of first initiator in the stirring process, and then reacting for 1 hour at 40 ℃ to obtain a pre-polymerization solution;
(2) adding 40 parts by weight of acrylonitrile and 5 parts by weight of methyl acrylate into the prepolymerization liquid, adding 0.1 part by weight of a second initiator in the stirring process, and then reacting for 2 hours at 40 ℃ to obtain polymer liquid;
(3) and (3) carrying out electrostatic spraying on the polymer liquid to obtain the special light diffusant.
Wherein the organic solvent is toluene.
Wherein the first initiator and the second initiator are both azobisisobutyronitrile.
Wherein the particle size of the nano silicon dioxide is 10 nm.
Wherein the spraying voltage of the electrostatic spraying is 20kV, and the spraying temperature is 20 ℃.
Wherein the antioxidant is antioxidant 168.
Wherein the light stabilizer is bis (1, 2,2,6, 6-pentamethyl-4-piperidyl) sebacate.
Wherein the ultraviolet absorbent is 2-cyano-3, 3' -diphenylacrylic acid-2-ethylhexyl ester.
Example 2
A PC material with high light transmittance and high haze comprises the following raw materials in parts by weight:
the special light diffusant is prepared by the following steps:
(1) adding 100 parts by weight of methyl methacrylate, 20 parts by weight of methyl acrylate, 50 parts by weight of nano-silica and 0.4 part by weight of n-dodecyl mercaptan into 100 parts by weight of organic solvent, adding 0.3 part by weight of first initiator in the stirring process, and then reacting for 3 hours at 50 ℃ to obtain a pre-polymerization solution;
(2) adding 60 parts by weight of acrylonitrile and 10 parts by weight of methyl acrylate into the prepolymerization liquid, adding 0.3 part by weight of a second initiator in the stirring process, and then reacting for 4 hours at 50 ℃ to obtain polymer liquid;
(3) and (3) carrying out electrostatic spraying on the polymer liquid to obtain the special light diffusant.
Wherein the organic solvent is ethyl acetate.
Wherein the first initiator and the second initiator are both azobisisobutyronitrile.
Wherein the particle size of the nano silicon dioxide is 20 nm.
Wherein the spraying voltage of the electrostatic spraying is 30kV, and the spraying temperature is 30 ℃.
Wherein the antioxidant is an antioxidant 1076.
Wherein the light stabilizer is poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate.
Wherein the ultraviolet absorbent is 2- (2-hydroxy-3 tert-butyl-5-methylphenyl) -5-chlorobenzotriazole.
Example 3
A PC material with high light transmittance and high haze comprises the following raw materials in parts by weight:
the special light diffusant is prepared by the following steps:
(1) adding 90 parts by weight of methyl methacrylate, 15 parts by weight of methyl acrylate, 45 parts by weight of nano-silica and 0.3 part by weight of n-dodecyl mercaptan into 100 parts by weight of organic solvent, adding 0.2 part by weight of first initiator in the stirring process, and then reacting for 2 hours at 45 ℃ to obtain a pre-polymerization solution;
(2) adding 50 parts by weight of acrylonitrile and 7.5 parts by weight of methyl acrylate into the prepolymerization liquid, adding 0.2 part by weight of a second initiator during stirring, and then reacting for 3 hours at 45 ℃ to obtain polymer liquid;
(3) and (3) carrying out electrostatic spraying on the polymer liquid to obtain the special light diffusant.
Wherein the organic solvent is xylene.
Wherein the first initiator and the second initiator are both azobisisobutyronitrile.
Wherein the particle size of the nano silicon dioxide is 15 nm.
Wherein the spraying voltage of the electrostatic spraying is 25kV, and the spraying temperature is 25 ℃.
Wherein the antioxidant is prepared from antioxidant 168 and antioxidant 1076 according to a weight ratio of 1: 1 in a certain proportion.
Wherein the light stabilizer is prepared from bis (1, 2,2,6, 6-pentamethyl-4-piperidyl) sebacate and poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate according to the weight ratio of 1: 1 in a certain proportion.
Wherein the ultraviolet absorbent is prepared from 2-cyano-3, 3' -diphenylacrylic acid-2-ethylhexyl ester and 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole according to the weight ratio of 1: 1 in a certain proportion.
Comparative example 1
This comparative example differs from example 3 in that:
the special light diffusant is replaced by nano silicon dioxide with equal mass.
Comparative example 2
This comparative example differs from example 3 in that:
the special light diffusant is prepared by the following steps:
(1) adding 90 parts by weight of methyl methacrylate, 15 parts by weight of methyl acrylate, 45 parts by weight of nano silicon dioxide and 0.3 part by weight of n-dodecyl mercaptan into 100 parts by weight of organic solvent, adding 0.2 part by weight of azobisisobutyronitrile during stirring, and then reacting for 3 hours at 45 ℃ to obtain a pre-polymerization solution;
(2) and (3) carrying out electrostatic spraying on the polymer liquid to obtain the special light diffusant.
Comparative example 3
This comparative example differs from example 3 in that:
the special light diffusant is prepared by the following steps:
(1) adding 90 parts by weight of methyl methacrylate, 15 parts by weight of methyl acrylate and 0.3 part by weight of n-dodecyl mercaptan into 100 parts by weight of organic solvent, adding 0.2 part by weight of first initiator in the stirring process, and then reacting for 2 hours at 45 ℃ to obtain a pre-polymerization solution;
(2) adding 50 parts by weight of acrylonitrile and 7.5 parts by weight of methyl acrylate into the prepolymerization liquid, adding 0.2 part by weight of a second initiator during stirring, and then reacting for 3 hours at 45 ℃ to obtain polymer liquid;
(3) and (3) carrying out electrostatic spraying on the polymer liquid to obtain the special light diffusant.
The PC materials of example 3 and comparative examples 1-3 were tested for light transmittance and haze using ASTM D638, ASTM D790, ASTM D256, ASTM D1003, respectively, and the results are given in the following Table:
as can be seen from comparative example 1, the influence of nano-silica as an opaque substance on light transmittance is the largest, and haze is not more than that of example 3 due to the decrease of light transmittance; from comparative example 2, it can be seen that only polymethyl methacrylate is used to coat nano-silica, and the relative dosage of nano-silica is increased, so that the light transmittance is slightly reduced, and meanwhile, polymethyl methacrylate alone has no light diffusion effect, so the haze is also low; it can be seen from comparative example 3 that the microsphere without the nano-silica core has very good light transmittance, and the light transmittance of PC reaches the highest, but the light diffusion effect of the nano-silica is lost, and the improvement effect on the haze is very limited.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (9)
1. A PC material with high light transmittance and high haze is characterized in that: the composite material comprises the following raw materials in parts by weight:
the special light diffusant is prepared by the following steps:
(1) adding 80-100 parts by weight of methyl methacrylate, 10-20 parts by weight of methyl acrylate, 40-50 parts by weight of nano silicon dioxide and 0.2-0.4 part by weight of n-dodecyl mercaptan into 100 parts by weight of organic solvent, adding 0.1-0.3 part by weight of first initiator in the stirring process, and then reacting for 1-3 hours at 40-50 ℃ to obtain a pre-polymerization solution;
(2) adding 40-60 parts by weight of acrylonitrile and 5-10 parts by weight of methyl acrylate into the prepolymerization liquid, adding 0.1-0.3 part by weight of a second initiator in the stirring process, and then reacting for 2-4h at 40-50 ℃ to obtain polymer liquid;
(3) and (3) carrying out electrostatic spraying on the polymer liquid to obtain the special light diffusant.
2. The PC material with high light transmittance and high haze as claimed in claim 1, wherein: the organic solvent is one of toluene, xylene and ethyl acetate.
3. The PC material with high light transmittance and high haze as claimed in claim 1, wherein: the first initiator and the second initiator are both azobisisobutyronitrile.
4. The PC material with high light transmittance and high haze as claimed in claim 1, wherein: the particle size of the nano silicon dioxide is 10-20 nm.
5. The PC material with high light transmittance and high haze as claimed in claim 1, wherein: the spraying voltage of the electrostatic spraying is 20-30kV, and the spraying temperature is 20-30 ℃.
6. The PC material with high light transmittance and high haze as claimed in claim 1, wherein: the antioxidant is antioxidant 168 and/or antioxidant 1076.
7. The PC material with high light transmittance and high haze as claimed in claim 1, wherein: the light stabilizer is bis (1, 2,2,6, 6-pentamethyl-4-piperidyl) sebacate and/or poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate.
8. The PC material with high light transmittance and high haze as claimed in claim 1, wherein: the ultraviolet absorbent is 2-cyano-3, 3' -diphenylacrylic acid-2-ethylhexyl ester and/or 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole.
9. The application of the PC material with high light transmittance and high haze is characterized in that: the method is applied to the manufacturing of the LED lamp.
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| CN114058169B (en) * | 2020-08-06 | 2023-03-28 | 中石化南京化工研究院有限公司 | Light diffusing agent and preparation method and application thereof |
| CN113628528B (en) * | 2021-08-16 | 2024-02-09 | 赛维精密科技(广东)有限公司 | Label code spraying and overprinting process |
| CN116240730A (en) * | 2023-02-06 | 2023-06-09 | 吉林大学 | Anti-dazzle electrostatic spinning composite nanofiber membrane and preparation method thereof |
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| US20160297965A1 (en) * | 2015-04-10 | 2016-10-13 | China Petroleum & Chemical Corporation | Resin Composition Having Improved Haze and Light Transmittance and Process for Preparing the Same |
| CN108219394A (en) * | 2017-12-22 | 2018-06-29 | 东莞市基烁实业有限公司 | One kind disappear it is yellow, brighten, blast master batch and polyester regenerated material and preparation method |
| CN108276750A (en) * | 2017-12-22 | 2018-07-13 | 东莞市基烁实业有限公司 | A kind of smooth diffusion master batch and PET film and preparation method |
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