CN111978699A - High-shading thin-wall flame-retardant PC material and preparation method and application thereof - Google Patents

High-shading thin-wall flame-retardant PC material and preparation method and application thereof Download PDF

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CN111978699A
CN111978699A CN202010807144.3A CN202010807144A CN111978699A CN 111978699 A CN111978699 A CN 111978699A CN 202010807144 A CN202010807144 A CN 202010807144A CN 111978699 A CN111978699 A CN 111978699A
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retardant
flame
shading
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wall
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CN111978699B (en
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李中诚
周国剑
王浩
叶文琼
姜小龙
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Cgn Juner New Materials Co ltd
Zhongguang Nuclear Juner Zhejiang New Materials Co ltd
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Zhongguang Nuclear Juner Zhejiang New Materials Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21VFUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V11/00Screens not covered by groups F21V1/00, F21V3/00, F21V7/00 or F21V9/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21YINDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2115/00Light-generating elements of semiconductor light sources
    • F21Y2115/10Light-emitting diodes [LED]

Abstract

The invention discloses a high-shading thin-wall flame-retardant PC material, a preparation method thereof and application thereof in the field of LED illumination shading. The high-shading thin-wall flame-retardant PC material comprises the following raw materials in percentage by mass of 100 percent: 70-90% of PC resin, 5-20% of shading filler, 2-4% of toughening agent, 0.2-0.5% of antioxidant, 0.2-0.5% of lubricant, 0.1-0.3% of ultraviolet absorbent, 0.1-1% of flame retardant A, 1-10% of flame retardant B, 0.1-0.5% of anti-dripping agent and 0.2-0.5% of silicone master batch. The preparation method of the high-shading thin-wall flame-retardant PC material comprises the following steps: and fully drying all the raw materials, uniformly mixing, adding into a double-screw extruder, extruding, cooling an extruded product by a water tank, granulating and packaging to obtain the composite material. The high-shading thin-wall flame-retardant PC material has a good shading effect, a high flame-retardant effect, excellent mechanical properties and easiness in forming and processing, and the prepared PC composite material can be used for shell products such as automobile instrument panels, liquid crystal display backlight plates and LED lamps.

Description

High-shading thin-wall flame-retardant PC material and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-shading thin-wall flame-retardant PC material and a preparation method and application thereof.
Background
With the development of high and new technologies, the photoelectric technology has been applied to various industries, and various conveniences are brought to people. However, due to the poor light-shielding performance of conventional Polycarbonate (abbreviated as PC), the special requirements in the field of electronic lighting, such as high light-shielding performance required by some parts of LED displays and LCD displays and high light-shielding performance required by some parts of doorbells, cannot be met. Therefore, PC is required to be modified to improve its light-shielding properties.
When applying the photoelectric technology, it is often necessary to reduce or prevent the transmission of light, and therefore, the light-shielding functional plastics are produced. Shading plastics have the performance of preventing light from transmitting, and have been applied to a plurality of fields, such as shell products requiring shading, such as automobile instrument panels, liquid crystal display backlight plates, LED lamps and the like.
Some popular LED lamps (such as a spot light) in the market at present use shading materials to shade the unnecessary light-emitting parts, and the development process of the shading materials is metal plates, metal foil composite plastic sheets, metal evaporation products of the plastic sheets and foamed and stretched polyethylene terephthalate (PET) films.
Polycarbonate is a generic term for a polymer compound containing a carbonate in the molecular main chain. The polycarbonate has outstanding impact toughness and dimensional stability, excellent mechanical property and electrical insulation property, wide application temperature range, good creep resistance and weather resistance, low water absorption, no toxicity and self-extinguishing property, and is engineering plastic with excellent comprehensive performance. But because the polycarbonate is an amorphous polymer, the pure polycarbonate is colorless and transparent, has good visible light transmission capability, and can be well applied to the field of LED illumination.
The conventional PC material is a transparent material, common fillers such as calcium carbonate cannot achieve the shading effect, light leakage and other phenomena can occur in the using process, the high shading filler is added to achieve the good shading effect, however, if the shading fillers are added too much, the mechanical property of the material is seriously reduced, and the subsequent use of the material is badly influenced.
Many materials in the LED illumination field need flame retardant requirements while shading, when the mechanical properties of the materials are greatly influenced by excessive addition of some flame retardants, the balance of flame retardance and shading on the mechanical properties of the materials needs to be researched, so that the materials have good shading performance and thin-wall flame retardant effect.
The patent specification with publication number CN 110734635A discloses a light-shielding high-temperature-resistant flame-retardant PC material, which is composed of the following components in parts by weight: 60-80 parts of polycarbonate resin, 5-10 parts of impact modifier, 10-20 parts of light-screening agent, 5-10 parts of flame retardant, 0.4-0.6 part of flame-retardant synergist, 0.1-0.3 part of antioxidant, 0.1-0.3 part of heat stabilizer, 0.2-0.6 part of processing aid and 0.1-0.6 part of silicone oil. The main flame retardant of the patent technology is an inorganic flame retardant, the addition amount is large, and the impact property of the material can be obviously reduced, so that a higher-content impact modifier needs to be added, the cost of the material is increased, and meanwhile, the thin-wall flame retardant effect of 1.0mm cannot be realized along with the increase of the content of the opacifier.
Disclosure of Invention
Aiming at the defects in the field, the invention provides the high-shading thin-wall flame-retardant PC material which has high shading performance, can keep good mechanical property, and has good flame-retardant effect under the condition of a very thin workpiece by selecting a proper flame retardant.
A high-shading thin-wall flame-retardant PC material comprises the following raw materials by weight percent of 100 percent:
Figure BDA0002629560410000021
Figure BDA0002629560410000031
the flame retardant A is at least one of sulfonate flame retardants and silicon flame retardants;
the flame retardant B is an organic flame retardant, specifically at least one of a phosphorus flame retardant and a bromine flame retardant;
the dispersing agent is silicone master batch.
Tests show that although the shading effect is improved by increasing the shading filler, the mechanical property and the thin-wall flame retardant effect of the material are reduced, and the two properties are important for the application of the PC material in the field of LED illumination shading. Therefore, the components and the proportion of the raw materials are optimized, so that the obtained PC material still keeps good mechanical property and thin-wall flame retardant property under the condition of adding high light-shielding powder.
Preferably, the flame retardant A is a silicon flame retardant, and the flame retardant B is a bromine flame retardant. In the PC material system, the two preferable flame retardants are compounded to have the best flame retardant effect.
Preferably, the PC resin has a melt index of 15-25 g/10min at 300 ℃ and 1.2 kg.
Preferably, the light-shielding filler is at least one of rutile titanium dioxide, zinc sulfide and silica.
Preferably, the toughening agent is at least one of ABS high rubber powder, MBS (methyl methacrylate-butadiene-styrene copolymer), ACR (acrylate copolymer) and EVA (ethylene-vinyl acetate copolymer).
Preferably, the antioxidant is compounded by a main antioxidant (preferably the antioxidant 1076) and an auxiliary antioxidant (preferably the antioxidant 168) according to the mass ratio of 1: 1.
Preferably, the lubricant is at least one of fatty acid amide, fatty acid ester, paraffin wax and polyethylene wax. The fatty acid ester is preferably a stearate.
Preferably, the ultraviolet absorber is a benzotriazole-based ultraviolet absorber.
Preferably, the anti-dripping agent is an anti-dripping agent in which PTFE (polytetrafluoroethylene) is coated with a SM (styrene)/MMA (methyl methacrylate) composition, and is high-fluidity white particles with a melt index of more than 20g/10min, the particle diameter is 0.1-0.5 μm, and the PTFE content is 40-60 wt%.
Preferably, the particle size of the aggregate of the silicone master batch is 400-800nm, and the content of silicone in the silicone master batch is more than or equal to 80 wt%.
The PC material obtained by the preferable combination has excellent shading performance, mechanical property and thin-wall flame retardant effect, and is particularly suitable for application in the field of LED lighting shading.
The invention also provides a preferable preparation method of the high shading thin-wall flame-retardant PC material, which comprises the following steps: and fully drying all the raw materials, uniformly mixing, adding into a double-screw extruder, extruding at the screw rotating speed of 300-400 rpm and the extrusion temperature of 240-265 ℃, cooling the extrudate by a water tank, and then cutting into particles and packaging to obtain the high-shading thin-wall flame-retardant PC material.
The PC material raw material formula is combined with the preparation process of the optimized rotating speed and temperature, and the obtained PC material has the best comprehensive properties such as light shielding property, mechanical property, thin-wall flame retardant effect and the like.
The high-shading thin-wall flame-retardant PC material has excellent shading effect, high flame-retardant effect, excellent mechanical property and easy forming and processing, and the prepared PC composite material can be used for shell products such as automobile instrument panels, liquid crystal display backlight plates, LED lamps and the like.
The invention also provides application of the high-shading thin-wall flame-retardant PC material in the field of LED illumination shading, such as preparation of indicator light signboards, shading plates and the like.
Compared with the prior art, the invention has the main advantages that:
1. the high-shading thin-wall flame-retardant PC material disclosed by the invention can still keep good mechanical properties under the condition of adding high shading powder content, and through the addition of special types and proper amounts of toughening agent and dispersing agent which are synergistic, the shading powder can be well dispersed in a matrix in the material processing process, so that the mechanical properties are maintained at a high level. Tests show that the toughening agent and the dispersing agent are not indispensable, otherwise, the mechanical properties such as notch impact strength and the like of the obtained PC material are reduced obviously.
2. The high-shading thin-wall flame-retardant PC material disclosed by the invention has high shading and thin-wall flame-retardant effects through the optimized design of the type and the proportion of a flame-retardant system. According to the invention, different flame retardants are compounded, so that the addition amount is small, the flame retardant efficiency is high, the influence on the reduction of mechanical properties is small, meanwhile, the silicone dispersant is added, so that the light-shading agent can be better dispersed, and even if 20% of the light-shading agent is added, the notch impact strength can be kept at 50KJ/m2The above.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
The information of the types, manufacturers, brands and the like of the raw materials adopted by the embodiments and the comparative examples of the invention are as follows:
PC resin, kesichu polymer (china) ltd, PC 2400;
a light-shielding filler, rutile titanium dioxide;
tougheners, MBS;
the antioxidant is compounded by an antioxidant 1076 and an antioxidant 168 according to the mass ratio of 1: 1;
lubricants, pentaerythritol stearate (PETS);
ultraviolet absorbers, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole;
flame retardant A, organic silsesquioxane flame retardant Si 9800;
flame retardant B, brominated triazine flame retardant FR 245;
the anti-dripping agent is an anti-dripping agent which is formed by coating PTFE with an SM/MMA composition, is high-fluidity white particles with the melt index of more than 20g/10min, has the particle size of 0.2 mu m and the PTFE content of 50wt percent, and specifically adopts TS-30A, Shenzhen Shenzechen chemical engineering Co., Ltd;
the dispersing agent is silicone master batch, the particle size of the aggregate of the silicone master batch is 400-800nm, and the silicone content in the silicone master batch is 85 wt%.
The PC material raw material formulation of each example and comparative example of the present invention is shown in Table 1, and the preparation method comprises:
1. the required raw materials are thoroughly dried.
2. The PC raw materials with different proportions, the required shading auxiliary agent, other auxiliary agents and other raw materials are put into a stirring pot to be stirred for 5 minutes, and then are fully and uniformly mixed.
3. And adding the fully and uniformly mixed mixture into a double-screw extruder, extruding at the rotating speed of 300-400 r/min and the temperature of 240-265 ℃, cooling by a water tank, and then granulating and packaging to obtain the PC material.
TABLE 1
Figure BDA0002629560410000051
The results of the PC material property test of each example of the present invention and comparative example are shown in Table 2.
TABLE 2
Figure BDA0002629560410000061
As can be seen from tables 1 and 2, example 3 exhibited an excellent light-screening effect at a light-screening agent content of 20 wt%. It can be seen from examples 1 and 2 in the table that the flame retarding effect is deteriorated as the content of the opacifier is increased, and it can be seen from comparative examples 1 and 2 that the flame retarding grade of V0 cannot be achieved by adding only one flame retardant. In comparative example 3, no toughening agent and no dispersant were added, and it was found that the notched impact strength of the material decreased significantly.
By combining the data, the notch impact strength of the shading thin-wall flame-retardant PC material can be kept at 50KJ/m2Thus, the light-shielding effect is excellent. The high shading PC has good mechanical property and impact strength, and can be widely used for liquid crystal display reflecting plates, LED lamp bases and the like. The invention has simple process, realizes good treatment effect on the titanium dioxide opacifier by adding a small amount of dispersant, thereby ensuring that the PC material still has excellent mechanical properties such as notch impact strength and the like under high opacifier content, and simultaneously achieves thin-wall flame retardant effect by compounding two flame retardants. The shading thin-wall flame-retardant PC material disclosed by the invention is excellent in comprehensive performance and has a wide application prospect.
In conclusion, the silicon-containing flame retardant is introduced while the light shielding performance is high, a good flame retardant effect is achieved under the condition of a very small addition amount, and meanwhile, the bromotriazine flame retardant is introduced to achieve the thin-wall flame retardant effect, so that the material can reach the V0 grade even when the thickness is 1.0mm by compounding with the silicon system. In order to ensure that the light-shading agent can be well dispersed in the formula, a silicone dispersant is added, and the combination and optimization of the formula ensure that the notch impact strength of the material can be kept at 50KJ/m even if 20 wt% of the light-shading agent is added2The above.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (10)

1. The high-shading thin-wall flame-retardant PC material is characterized by comprising the following raw materials by taking the total mass as 100 percent:
Figure FDA0002629560400000011
the flame retardant A is at least one of sulfonate flame retardants and silicon flame retardants;
the flame retardant B is an organic flame retardant, specifically at least one of a phosphorus flame retardant and a bromine flame retardant;
the dispersing agent is silicone master batch.
2. The high-shading thin-wall flame-retardant PC material according to claim 1, wherein the PC resin has a melt index of 15-25 g/10min at 300 ℃ and 1.2 kg.
3. The high shading thin wall flame retardant PC material of claim 1, wherein the shading filler is at least one of rutile type titanium dioxide, zinc sulfide, silica.
4. The high shading thin wall flame retardant PC material of claim 1, wherein the toughening agent is at least one of ABS high rubber powder, MBS, ACR, EVA.
5. The high shading thin-wall flame-retardant PC material according to claim 1, wherein the antioxidant is compounded by a main antioxidant and an auxiliary antioxidant according to a mass ratio of 1: 1.
6. The highly light-shielding thin-walled flame-retardant PC material according to claim 1, wherein the lubricant is at least one of fatty acid amide, fatty acid ester, paraffin wax, polyethylene wax;
the ultraviolet absorbent is benzotriazole ultraviolet absorbent.
7. The highly light-shielding thin-walled flame-retardant PC material according to claim 1, wherein the anti-dripping agent is an anti-dripping agent obtained by coating PTFE with a SM/MMA composition, and is high-fluidity white particles having a melt index of more than 20g/10min, the particle size of the high-fluidity white particles is 0.1-0.5 μm, and the content of PTFE is 40-60 wt%.
8. The high-shading thin-wall flame-retardant PC material as claimed in claim 1, wherein the particle size of the aggregate of the silicone master batch is 400-800nm, and the silicone content in the silicone master batch is not less than 80 wt%.
9. The preparation method of the high shading thin-wall flame retardant PC material according to any one of claims 1 to 8, characterized by comprising the following steps: and fully drying all the raw materials, uniformly mixing, adding into a double-screw extruder, extruding at the screw rotating speed of 300-400 rpm and the extrusion temperature of 240-265 ℃, cooling the extrudate by a water tank, and then cutting into particles and packaging to obtain the high-shading thin-wall flame-retardant PC material.
10. The application of the high-shading thin-wall flame-retardant PC material in the LED illumination shading field according to any one of claims 1 to 8.
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CN112898761A (en) * 2021-01-27 2021-06-04 东莞市聚龙高科电子技术有限公司 Shading material and preparation thereof, intelligent terminal shell and manufacturing method thereof, and intelligent terminal
CN113637191A (en) * 2021-09-13 2021-11-12 惠州莹光塑胶颜料有限公司 PMMA-based flame-retardant shading anti-aging master batch, preparation method and PC sheet
CN114316556A (en) * 2021-12-06 2022-04-12 中广核俊尔(浙江)新材料有限公司 High-impact permanent antistatic flame-retardant PC material and preparation method thereof
CN114316553A (en) * 2021-11-29 2022-04-12 中广核俊尔(浙江)新材料有限公司 Halogen-free flame-retardant antistatic PC material and preparation method thereof
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