CN114656781B - Gray semi-aromatic polyamide molding material and preparation method and application thereof - Google Patents
Gray semi-aromatic polyamide molding material and preparation method and application thereof Download PDFInfo
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Abstract
The gray semi-aromatic polyamide molding material comprises the following components in parts by weight: 40-75 parts of PA10T/X resin; 30-60 parts of wollastonite; 0.5-2.5 parts of toner; 5-35 parts of white pigment; wollastonite has an average diameter of 4-20 microns, an average length of 40-250 microns, and a white pigment has an average particle size ranging from 0.10-0.50 microns; the gray semi-aromatic polyamide molding material is heated to 345 ℃ by differential scanning calorimetry and then measured by the peak half-width delta T of crystallization at the cooling rate of 20 ℃/min 1/2 3.5-11 ℃; the whiteness range of the gray semi-aromatic polyamide molding material is 50-80, the reflectivity range of a purple light (400 nm wavelength) light source is 16-36%, the reflectivity range of a blue light (460 nm wavelength) light source is 22-49%, and the reflectivity of a red light (650 nm wavelength) light source is lower than the reflectivity of the blue light by more than 1%. The molding materials of the invention have properties of low violet reflectance in gray, high brightness (high blue reflectance) and high contrast (red reflectance lower than blue reflectance).
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a gray semi-aromatic polyamide molding material and a preparation method and application thereof.
Background
The LED light source mainly comprises a semiconductor chip, an LED light source reflecting support, gold wires and packaging adhesive. The LED light source reflection support is a 'skeleton' of an LED light source and is also a functional piece. The LED packaging process needs to be solidified through die bonding, bonding wires and packaging glue, and other materials and components are integrated. The LED reflection bracket needs to reflect the light emitted by the LED chip through a certain angle, reduces light loss, and then forms a light source for LED illumination or display through packaging materials such as epoxy resin or silica gel. The LED reflective support material is a core material of LED illumination, and is directly related to the performance and service life of an LED light source.
At present, the material selection of the LED reflecting support needs to consider the reflectivity of the LED reflecting support besides the characteristics of encapsulation, fluidity, weather resistance and the like:
in the field of LED display applications, brightness and contrast of a display screen are very important indicators for displaying sharp and clear image quality. At present, more schemes are mainly used in the market, namely, an LED bracket produced by a pure white LED reflecting material, black printing ink is needed on the surface of the LED bracket, the procedures are complicated, the efficiency is influenced, the cost is high, but the side surface and the surface of a reflecting cup are still white, and the contrast and the gray level displayed by an LED display screen are reduced. However, in the field of outdoor display, higher brightness is often required, so that the reflectivity is mainly improved by plating silver on the bottom of the bowl of the LED bracket or the light quantity of the light source is improved in the prior art. But this increases the cost. If a white LED is reflective, the contrast is low.
Regarding the light source: the LED full-color display screen light source is formed by packaging three chips of red (R), green (G) and blue (B), wherein the brightness of the blue light chip is the lowest, namely the contrast ratio is the highest, so that the blue light reflectivity of the LED light source bracket for the chip can directly influence the overall contrast ratio of the LED display screen. In order to improve the brightness and contrast of the outdoor LED display screen, a better method is to increase the reflectivity of blue light so that the brightness of the blue light is as much as possible larger than that of red light.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a gray semi-aromatic polyamide molding material which has high contrast ratio and high reflectivity under gray tone so as to achieve the effect of simultaneously achieving the contrast ratio, gray level and brightness of an LED display screen.
The invention is realized by the following technical scheme:
the gray semi-aromatic polyamide molding material comprises the following components in parts by weight:
40-75 parts of PA10T/X resin;
30-60 parts of wollastonite;
0.5-2.5 parts of toner;
5-35 parts of white pigment;
based on the PA10T/X mole percent, the 10T unit content is 60-100 mole percent, and the X unit content is 0-40 mole percent; wherein the X unit is composed of a diacid unit and a diamine unit, the diacid unit is at least one selected from terephthalic acid unit, isophthalic acid unit, 1, 6-adipic acid and 1, 10-sebacic acid unit, and the diamine unit is at least one selected from 1, 6-hexamethylenediamine unit, 1, 9-nonanediamine unit, 2-methyl-1, 5-pentanediamine unit, 2-methyl-1, 8-octanediamine unit, 1, 10-decanediamine unit and 1, 12-dodecanediamine unit;
wollastonite has an average diameter of 4-20 microns, an average length of 40-250 microns, and a white pigment has an average particle size ranging from 0.10-0.50 microns;
the gray semi-aromatic polyamide molding material is prepared by differential scanningCalorimeter method, after heating to 345 deg.C, measuring the half-height width delta T of crystallization peak at 20 deg.C/min 1/2 3.5-11 ℃;
the whiteness range of the gray semi-aromatic polyamide molding material is 50-80, the reflectivity range of a 400nm wavelength ultraviolet light source is 16-36%, the reflectivity range of a 460nm wavelength blue light source is 22-49%, and the reflectivity of a 650nm wavelength red light source is less than 1% of the reflectivity of a 460nm wavelength blue light source.
The semi-aromatic polyamide molding materials exhibit a gray color in the whiteness range of 50 to 80.
The PA10T/X resin is at least one selected from PA10T, PA T/10I, PA T/6T, PA10T/66, PA10T/1010, PA10T/610, PA10T/612 and PA 10T/12T.
Preferably, the semi-aromatic polyamide molding composite material is heated to 345 ℃ by differential scanning calorimetry, and then the crystallization peak half-width delta T is measured at the cooling rate of 20 ℃/min 1/2 4.5-8deg.C. The preferred semi-aromatic polyamide molding composite material with a half-width of the crystallization peak has a larger difference between the reflectance of a 650nm wavelength red light source and the reflectance of a blue light source.
The PA10T/X resin of the present invention may be a commercially available product or may be synthesized according to the following method. For more accurate experiments, the PA10T/X adopted in the examples and the comparative examples is a self-made sample, and raw materials such as reaction monomers, end capping agents and the like are derived from commercial products.
(1) Prepolymerization: polymerization monomers (diacid, diamine), end-capping agent benzoic acid and deionized water are charged into a stainless steel autoclave equipped with mechanical agitation. Vacuum is applied and N is used 2 After three times of replacement, heating and stirring are started, the temperature is raised to 170-190 ℃ at the heating rate of 4-6 ℃/min, the temperature is kept for 1-2 hours, the temperature is slowly stirred and kept at the constant temperature of 3-5 h at the heating rate of 260-280 ℃ at the heating rate of 1-3 ℃/min, and the prepolymerization reaction is fully carried out. After the constant temperature is finished, the temperature is slowly increased to 270-290 ℃ and water drainage is started to normal pressure. And after the pressure is reduced to normal pressure, closing the drain valve, ending the reaction, and discharging after the temperature is reduced to room temperature.
(2) Solid phase tackifying: the materials prepared in the prepolymerization process are put into a vacuum rotary drum, the rotary drum rotating speed is set to be 10-15 r/min, and the vacuum degree is set to be 25-35Pa. Heating at 15-25deg.C/min, sampling to test viscosity when temperature reaches 260-270 deg.C, and determining discharge end point according to viscosity (or number average molecular weight) result.
The number average molecular weight of the PA10T/X resin is 1500-28000.
The number average molecular weight test method is a conventional method, and specifically comprises the following steps: the number average molecular weight (Mn) of the PA10T/X resin samples was determined by gel permeation chromatography (gel permeation chromatography, GPC). Agilent HPLC-1260 high performance liquid chromatograph, preparing: eppendorf column incubator, shodex KF-801, 802, 802.5 and 803 gel permeation chromatography columns, differential detector, G7129A autosampler. The molecular weight of the resin was measured at a column temperature of 40℃using hexafluoroisopropanol as the mobile phase. The data were processed using chromatographic workstation cirrus software to obtain the number average molecular weight Mn.
The white pigment is at least one selected from titanium white powder and zinc sulfide.
From the standpoint of increasing the difference in reflectance between blue light and red light, wollastonite preferably has an average diameter of 6 to 13 μm, an average length of 80 to 120 μm, and a white pigment having an average particle diameter in the range of 0.15 to 0.35. Mu.m. Wollastonite is powder with certain length-diameter ratio, and its microstructure is fibrous, and its length and diameter are almost unchanged in the course of melt shearing in screw. Experiments show that the PA10T and wollastonite (with the average diameter of 17 mu m and the average length of 180 mu m) are subjected to melt shearing blending through a production process, and then the solvent is adopted to dissolve out the resin, so that the average diameter and the average length of the wollastonite are tested, and the diameter of the wollastonite is hardly changed in the shearing of a screw rod, and the average length is changed by about 0.5%.
The toner is at least one or a plurality of color mixed toners selected from carbon black, black seeds and amorphous carbon toner.
Preferably, the reflectance of the 650nm wavelength red light source is less than 2% or more of the reflectance of the 460nm wavelength blue light source.
The gray semi-aromatic polyamide molding material of the invention can also contain additives such as lubricants, antioxidants and the like.
The preparation method of the gray semi-aromatic polyamide molding material comprises the following steps of adding all the components into a mixer, uniformly mixing, and extruding and granulating by a double-screw extruder to obtain the gray semi-aromatic polyamide molding material; wherein the temperature range of the screw is 280-330 ℃ and the rotating speed is 400-500r/min.
The grey semi-aromatic polyamide molding material is applied to preparing LED display screen light source reflecting supports, in particular to outdoor LED display screen light source reflecting supports.
The invention has the following beneficial effects:
the reflectivity of the light source of the LED display screen is mainly related to the whiteness (L value) of the material (the lower the whiteness is, the lower the reflectivity of the ultraviolet light with the wavelength of 400nm is), but is also affected by the surface roughness of the material (the larger the roughness of the surface of the object is within a certain range, the diffuse reflection of the light emitted by the light source occurs on the surface of the object, and finally, the less the energy of the light is received at the light receiving end). The influence of the light source reflection bracket of the LED display screen on the brightness, the gray level and the contrast of the LED display screen is mainly due to the whiteness and the reflectivity of the light source reflection bracket. In order to realize good balance of brightness, gray scale and contrast of the outdoor display screen, the invention is mainly realized by the following scheme:
firstly, a tone product with the whiteness of 50-80 can be obtained through the blending of white pigment and toner, and compared with a product with the whiteness of less than 30, the tone product has higher light source reflectivity; and the negative effect of grey hues on grey scale and contrast can be controlled within acceptable limits compared to white products.
Secondly, the reflectivity of the 460nm light source can be improved to a certain extent by exploring the length/diameter of wollastonite, the particle size range of the white pigment and the half-width of the crystallization peak of the gray semi-aromatic polyamide molding material, so that the blue light reflectivity is higher than the red light reflectivity, and the brightness and the contrast of the display screen are improved.
Specifically, in the technical scheme of the invention, the half-width of the crystallization peak of the gray semi-aromatic polyamide molding material is mainly adjusted by adjusting the addition amount and specification of the toner, wollastonite and white pigment, and can be obtained by selecting PA10T/X with different specifications.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The raw materials used in the examples and comparative examples are as follows:
the monomers used in the following polyamide polymerizations are commercially available products, pure in polymerization.
PA10T: number average molecular weight 7300, peak width at half maximum ΔT 1/2 Self-made by referring to the method of the invention content part at 5 ℃;
PA10T/1010-1:10T unit content 80mol%, number average molecular weight 7500, peak width at half maximum DeltaT 1/2 Is made by referring to the method of the invention content part at 15.1 ℃;
PA10T/1010-2:10T unit content 85mol%, number average molecular weight 9000, peak half height width DeltaT 1/2 Self-made at 16 ℃ by referring to the method of the invention content part;
PA10T/1010-3:10T unit content 90mol%, number average molecular weight 8500, peak width at half maximum DeltaT 1/2 Is made by referring to the method of the invention content part at 12.8 ℃;
PA10T/1010-4:10T unit content 95mol%, number average molecular weight 13000, peak half-width at half-height DeltaT 1/2 At 8.4 ℃, self-made by referring to the method of the invention content part;
PA10T/1010-5:10T unit content 90mol%, number average molecular weight 4300, peak half-width at half-height DeltaT 1/2 Is made by referring to the method of the invention content part at 14.2 ℃;
PA10T/1010-6:10T unit content 90mol%, number average molecular weight 21000, peak half-width DeltaT 1/2 Is made by referring to the method of the invention content part at 18.3 ℃;
PA10T/1010-7:10T unit content 75mol%, number average molecular weight 8800, peak half-width at half-height DeltaT 1/2 At 18.0℃with reference to hairThe method for preparing the clear content part is self-made;
PA10T/1010-8:10T unit content 97mol%, number average molecular weight 8000, peak half-width DeltaT 1/2 Self-made at 7.5 ℃ with reference to the summary of the invention part method;
PA10T/10I-1:10T unit content 80mol%, number average molecular weight 10500, peak width at half maximum DeltaT 1/2 Is made by referring to the method of the invention content part at 17.1 ℃;
PA10T/10I-2:10T unit content 85mol%, number average molecular weight 9800, peak half-width at half-height DeltaT 1/2 At 12 ℃, self-making according to the method of the invention content part;
PA10T/10I-3:10T unit content 90mol%, number average molecular weight 8500, peak width at half maximum DeltaT 1/2 At 8.3 ℃, self-made by referring to the method of the invention content part;
PA10T/10I-4:10T unit content 95mol%, number average molecular weight 8000, peak half-width DeltaT 1/2 Self-made at 7.1 ℃ with reference to the summary part method;
PA10T/10I-5:10T unit content 60mol%, number average molecular weight 8000, peak half-width DeltaT 1/2 Is made by referring to the method of the invention content part at 15 ℃;
PA10T/66:10T unit content 90mol%, number average molecular weight 8000, peak half-width DeltaT 1/2 Is made by referring to the method of the invention content part at 13.4 ℃;
wollastonite a: average diameter 4 microns and average length 60 microns;
wollastonite B: average diameter of 6 microns and average length of 120 microns;
wollastonite C: an average diameter of 13 microns and an average length of 80 microns;
wollastonite D: the average diameter was 19 microns and the average length was 230 microns.
Wollastonite used in the invention is screened after being purchased in the market to obtain the required average diameter and average length range.
Talc powder: AH-1250, guangxi Longshenghuamei Talc development Co., ltd.
Titanium white powder A: average particle size 0.11 microns;
titanium white powder B: average particle size 0.15 microns;
titanium white powder C: average particle size 0.35 microns;
titanium white powder D: average particle size 0.50 microns;
the titanium dioxide is purchased from the boa Baili, and a sample with corresponding particle size is obtained through screening.
Zinc sulfide: sachtolith HD-S, average particle size 0.14 microns, purchased from Sha Ha Liben, germany.
Toner a: amorphous carbon toner N774, tianjin day Yang Qiu, chemical technology limited;
toner B: carbon black M570, cabo chemical company, inc;
toner C: black UN2014, cabo chemical company, inc;
toner D: mazcol Blue 153K, shenzhen chemical Co., ltd.
An antioxidant: the same antioxidant is used in parallel experiments.
Examples and comparative examples preparation of gray semiaromatic polyamide molding materials: adding PA10T/X resin, wollastonite, toner and white pigment into a mixer, uniformly mixing, and extruding and granulating by a double-screw extruder to obtain a gray semi-aromatic polyamide molding material; wherein the temperature range of the screw is 280-330 ℃ and the rotating speed is 450r/min.
The testing method comprises the following steps:
(1) Whiteness: the contrast of the material is evaluated as characterized by the whiteness index of the material: test pieces of 60mm in length, 60mm in width and 1mm in thickness prepared by injection molding of gray semiaromatic polyamide molding materials were measured for L, a, b values using Color Eye 7000A-type Color difference meter to calculate whiteness:
W H =100-[(100-L) 2 +a 2 +b 2 ] 1/2 。
(2) Reflectivity: a test piece having a length of 60mm, a width of 60mm and a thickness of 1mm was prepared by injection molding a gray semi-aromatic polyamide molding material. Reflectance of the test piece was measured for light of wavelengths of 400nm, 460nm, 650nm using Color Eye 7000A Color difference meter.
(3) Gray colorSemi-aromatic polyamide molding material with peak width at half maximum delta T 1/2 : using a differential scanning calorimeter analyzer manufactured by NETZSCH corporation, the temperature was raised from 30 ℃ to 345 ℃ at a rate of 20 ℃/min under a nitrogen atmosphere, the temperature was kept constant for 2 minutes, the temperature was lowered at a temperature lowering rate of 20 ℃/min, the peak temperature at which the crystallization occurred was set to a crystallization temperature Tc (c), and the half temperature of the measured peak width was set to a peak width at half height Δt of the crystallization 1/2 。
Table 1: examples 1 to 7 Gray semiaromatic Polyamide Molding Material Components (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| PA10T | 75 | 70 | 65 | 60 | 55 | 50 | 40 |
| Wollastonite A | 30 | 35 | 40 | 45 | 50 | 55 | 60 |
| Titanium white powder A | 35 | 25 | 20 | 20 | 20 | 15 | 5 |
| Toner A | 2.5 | 2 | 1.5 | 1 | 1 | 1 | 0.5 |
| Peak width at half maximum deltat 1/2 ，℃ | 3.5 | 3.8 | 4 | 4.3 | 4.5 | 4.6 | 4.8 |
| Whiteness degree | 50.4 | 51.5 | 53.5 | 57.3 | 64.1 | 69.1 | 74.0 |
| 400nm wavelength reflectance% | 16.48 | 18.37 | 20.26 | 22.57 | 26.66 | 30.7 | 35.74 |
| 460nm wavelength reflectance% | 22.12 | 23.93 | 24.73 | 27.5 | 34.26 | 41.17 | 48.09 |
| Difference between 460nm wavelength reflectance and 650nm wavelength reflectance% | 1.80 | 1.95 | 1.08 | 1.80 | 2.25 | 2.26 | 2.29 |
From examples 1 to 7, it is understood that the contents of the components of the formulation significantly affect the half-width at half-height and whiteness of the crystalline peak of the molding material, and that the reflectance of the 400nm wavelength violet light source is 16 to 36%, the reflectance of the 460nm wavelength blue light source is 22 to 49%, and the reflectance of the 650nm wavelength red light source is less than 1% of the reflectance of the blue light source within the scope of the present invention.
Table 2: examples 8 to 14 Gray semiaromatic Polyamide Molding Material Components (parts by weight) and test results
| Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | |
| PA10T/1010-1 | 60 | ||||||
| PA10T/1010-2 | 60 | ||||||
| PA10T/1010-3 | 60 | ||||||
| PA10T/1010-4 | 60 | ||||||
| PA10T/1010-5 | 60 | ||||||
| PA10T/1010-6 | 60 | ||||||
| PA10T/1010-7 | 60 | ||||||
| Wollastonite A | 45 | 45 | 45 | 45 | 45 | 45 | 45 |
| Titanium white powder A | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Toner A | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Peak width at half maximum deltat 1/2 ，℃ | 8.3 | 9.0 | 6.9 | 5.1 | 8.5 | 10.3 | 9.7 |
| Whiteness degree | 57.2 | 58.0 | 57.6 | 57.0 | 57.5 | 56.9 | 57.4 |
| 400nm wavelength reflectance% | 22.75 | 23.01 | 22.84 | 22.90 | 23.11 | 22.50 | 22.81 |
| 460nm wavelength reflectance% | 27.53 | 27.72 | 27.49 | 27.70 | 28.04 | 27.88 | 27.46 |
| Difference between 460nm wavelength reflectance and 650nm wavelength reflectance% | 1.75 | 1.66 | 2.04 | 2.19 | 1.89 | 1.54 | 1.92 |
As is clear from examples 4/8-21, the object of the present invention can be attained by obtaining a gray semiaromatic polyamide molding material having a peak width at half maximum in the range of 3.5 to 11℃by compounding wollastonite, a white pigment and a toner, and further, when the peak width at half maximum is in the range of 4.5 to 8℃the difference between the reflectance at 460nm wavelength and the reflectance at 650nm wavelength is more than 2%.
Table 3: examples 15 to 21 Gray semiaromatic Polyamide Molding Material Components (parts by weight) and test results
| Example 15 | Example 16 | Example 17 | Example 18 | Example 19 | Example 20 | Example 21 | |
| PA10T/1010-8 | 60 | ||||||
| PA10T/10I-1 | 60 | ||||||
| PA10T/10I-2 | 60 | ||||||
| PA10T/10I-3 | 60 | ||||||
| PA10T/10I-4 | 60 | ||||||
| PA10T/10I-5 | 60 | ||||||
| PA10T/66 | 60 | ||||||
| Wollastonite A | 45 | 45 | 45 | 45 | 45 | 45 | 45 |
| Titanium white powder A | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Toner A | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Peak width at half maximum deltat 1/2 ，℃ | 4.9 | 9.6 | 6.4 | 4.9 | 4.2 | 8.2 | 6.3 |
| Whiteness degree | 56.9 | 58.1 | 57.5 | 57.7 | 57.2 | 56.7 | 57.1 |
| 400nm wavelength reflectance% | 22.25 | 23.20 | 23.16 | 22.84 | 23.05 | 23.32 | 22.50 |
| 460nm wavelength reflectance% | 27.38 | 28.06 | 28.34 | 28.55 | 28.61 | 28.03 | 27.81 |
| Difference between 460nm wavelength reflectance and 650nm wavelength reflectance% | 2.30 | 1.84 | 2.51 | 2.15 | 1.99 | 1.54 | 2.36 |
Table 4: examples 22 to 27 Gray semiaromatic Polyamide Molding Material Components (parts by weight) and test results
| Example 22 | Example 23 | Example 24 | Example 25 | Example 26 | Example 27 | |
| PA10T | 60 | 60 | 60 | 60 | 60 | 60 |
| Wollastonite A | 45 | 45 | ||||
| Wollastonite B | 45 | |||||
| Wollastonite C | 45 | |||||
| Wollastonite D | 45 | 45 | ||||
| Titanium white powder A | 20 | |||||
| Titanium white powder B | 20 | 20 | ||||
| Titanium white powder C | 20 | 20 | ||||
| Titanium white D | 20 | |||||
| Toner A | 1 | 1 | 1 | 1 | 1 | 1 |
| Peak width at half maximum deltat 1/2 ，℃ | 4.2 | 4.5 | 4.6 | 4.4 | 4.2 | 4.3 |
| Whiteness degree | 57.9 | 57.5 | 56.9 | 57.2 | 57.4 | 56.9 |
| 400nm wavelength reflectance% | 22.72 | 22.83 | 23.00 | 23.16 | 23.42 | 22.84 |
| 460nm wavelength reflectance% | 27.90 | 28.10 | 28.41 | 28.06 | 28.80 | 27.87 |
| Difference between 460nm wavelength reflectance and 650nm wavelength reflectance% | 2.35 | 2.84 | 2.08 | 1.85 | 1.86 | 1.66 |
As is clear from examples 4/22-27, the particle size of wollastonite and titanium white powder also affects the half-width of the crystallization peak of the gray semi-aromatic polyamide molding material, and the preferred particle size range of wollastonite and titanium white powder can further increase the difference between the reflectance at 460nm and the reflectance at 650nm, and when the half-width of the crystallization peak of the gray semi-aromatic polyamide molding material is at 4.5 ℃, the difference between the reflectance at 460nm and the reflectance at 650nm is further increased.
Table 5: examples 28 to 31 Gray semiaromatic Polyamide Molding Material Components (parts by weight) and test results
| Example 28 | Example 29 | Example 30 | Example 31 | |
| PA10T | 60 | 60 | 60 | 60 |
| Wollastonite A | 45 | 45 | 45 | 45 |
| Titanium white powder A | 20 | 20 | 20 | |
| Zinc sulfide | 20 | |||
| Toner A | 0.5 | 1 | ||
| Toner B | 1 | |||
| Toner C | 1 | |||
| Toner D | 0.5 | |||
| Peak width at half maximum deltat 1/2 ，℃ | 4.1 | 4.3 | 4.4 | 4.1 |
| Whiteness degree | 58.15 | 57.34 | 59.90 | 55.66 |
| 400nm wavelength reflectance% | 23.04 | 22.72 | 23.63 | 22.53 |
| 460nm wavelength reflectance% | 28.27 | 28.05 | 28.61 | 27.77 |
| Difference between 460nm wavelength reflectance and 650nm wavelength reflectance% | 1.54 | 1.83 | 1.77 | 1.51 |
As can be seen from examples 4/28-31, the reflectivity of zinc sulfide is lower than that of titanium dioxide.
Table 6: comparative example Gray semiaromatic Polyamide Molding Material Components (parts by weight) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| PA10T | 60 | 60 | 60 | 40 | |
| PA10T/1010-6 | 60 | ||||
| Wollastonite A | 45 | 45 | 45 | 45 | |
| Talc powder | 45 | ||||
| Titanium white powder A | 20 | 5 | 20 | 10 | 35 |
| Toner A | 0.2 | 2.5 | 1 | 0.5 | 3.0 |
| Peak width at half maximum deltat 1/2 ，℃ | 4.7 | 3.6 | 4.1 | 11.1 | 3.2 |
| Whiteness degree | 97.14 | 43 | 58.15 | 69.12 | 46.75 |
| 400nm wavelength reflectance% | 46.62 | 12.28 | 23.04 | 29.7 | 16.07 |
| 460nm wavelength reflectance% | 93.6 | 13.12 | 28.27 | 41.17 | 16.16 |
| Difference between 460nm wavelength reflectance and 650nm wavelength reflectance% | -0.88 | 0.16 | 0.24 | 0.47 | 0.84 |
As is clear from comparative example 1, when the whiteness is too high, the reflectance of red light is higher than that of blue light.
As is clear from comparative example 2, when the whiteness is too low, the reflectance of each spectrum is low, and the reflectance difference between blue light and red light is also small.
As is clear from comparative example 3, when talc was used as a filler instead of wollastonite, the reflectance difference between blue light and red light was small.
As is clear from comparative examples 4 and 5, when the half width of the crystallization peak of the gray semi-aromatic polyamide molding material is not in the range of 3.5 to 11℃the reflectance difference of blue light and red light is also small.
Claims (8)
1. The gray semi-aromatic polyamide molding material is characterized by comprising the following components in parts by weight:
40-75 parts of PA10T/X resin;
30-60 parts of wollastonite;
0.5-2.5 parts of toner;
5-35 parts of white pigment;
based on the PA10T/X mole percent, the 10T unit content is 60-100 mole percent, and the X unit content is 0-40 mole percent; wherein the X unit is composed of a diacid unit and a diamine unit, the diacid unit is at least one selected from terephthalic acid unit, isophthalic acid unit, 1, 6-adipic acid and 1, 10-sebacic acid unit, and the diamine unit is at least one selected from 1, 6-hexamethylenediamine unit, 1, 9-nonanediamine unit, 2-methyl-1, 5-pentanediamine unit, 2-methyl-1, 8-octanediamine unit, 1, 10-decanediamine unit and 1, 12-dodecanediamine unit;
wollastonite has an average diameter of 4-20 microns, an average length of 40-250 microns, and a white pigment has an average particle size ranging from 0.10-0.50 microns;
the gray semi-aromatic polyamide molding material is heated to 345 ℃ by differential scanning calorimetry and then measured by the peak half-width delta T of crystallization at the cooling rate of 20 ℃/min 1/2 3.5-11 ℃;
the white pigment is at least one of titanium white powder and zinc sulfide;
the toner is at least one or a plurality of color mixed toners selected from carbon black, black seeds and amorphous carbon toner;
the whiteness range of the gray semi-aromatic polyamide molding material is 50-80, the reflectivity range of a 400nm wavelength ultraviolet light source is 16-36%, the reflectivity range of a 460nm wavelength blue light source is 22-49%, and the reflectivity of a 650nm wavelength red light source is less than 1% of the reflectivity of a 460nm wavelength blue light source.
2. The gray semiaromatic polyamide molding material of claim 1, wherein the PA10T/X resin is selected from at least one of PA10T, PA T/10I, PA T/6T, PA10T/66, PA10T/1010, PA10T/610, PA10T/612, PA 10T/12T.
3. The gray semiaromatic polyamide molding material as claimed in claim 1, wherein the semiaromatic polyamide molding composite material has a peak width at half maximum Δt measured by differential scanning calorimetry at a cooling rate of 20 ℃/min after heating to 345 ℃ 1/2 4.5-8deg.C.
4. The gray semiaromatic polyamide molding material as claimed in claim 1, wherein the number average molecular weight of the PA10T/X resin is 1500 to 28000.
5. The gray semiaromatic polyamide molding material as claimed in claim 1, wherein the wollastonite has an average diameter of 6 to 13 μm, an average length of 80 to 120 μm and an average particle diameter of the white pigment in the range of 0.15 to 0.35. Mu.m.
6. The gray semiaromatic polyamide molding material as claimed in claim 1, wherein the reflectance of a 650nm wavelength red light source is lower than the reflectance of a 460nm wavelength blue light source by more than 2%.
7. The method for preparing gray semi-aromatic polyamide molding material according to any one of claims 1 to 6, comprising the steps of adding the components into a mixer, mixing uniformly, and extruding and granulating by a twin-screw extruder to obtain gray semi-aromatic polyamide molding material; wherein the temperature range of the screw is 280-330 ℃ and the rotating speed is 400-500r/min.
8. Use of a grey semi-aromatic polyamide molding material according to any of claims 1 to 6 for the preparation of a reflective support for a light source of an LED display screen.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006257314A (en) * | 2005-03-18 | 2006-09-28 | Kuraray Co Ltd | Polyamide resin composition for molding led reflector and led reflector |
| CN103890040A (en) * | 2011-08-19 | 2014-06-25 | 索尔维特殊聚合物美国有限责任公司 | Improved polyamide compositions for LED applications |
| CN112745672A (en) * | 2020-12-16 | 2021-05-04 | 金发科技股份有限公司 | Polyamide molding composition and preparation method and application thereof |
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| US8865807B2 (en) * | 2011-12-29 | 2014-10-21 | Cheil Industries Inc. | Polyamide resin composition having improved physical properties including thin-wall moldability |
| KR101831097B1 (en) * | 2014-06-30 | 2018-02-21 | 미쯔이가가꾸가부시끼가이샤 | Resin composition for reflective material, and reflective panel including same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257314A (en) * | 2005-03-18 | 2006-09-28 | Kuraray Co Ltd | Polyamide resin composition for molding led reflector and led reflector |
| CN103890040A (en) * | 2011-08-19 | 2014-06-25 | 索尔维特殊聚合物美国有限责任公司 | Improved polyamide compositions for LED applications |
| CN112745672A (en) * | 2020-12-16 | 2021-05-04 | 金发科技股份有限公司 | Polyamide molding composition and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Mechanical properties of wollastonite reinforced thermoplastic composites: A review;Jia X. Chan, Joon F. Wong, Azman Hassan, Zurina Mohamad, Norhayani Othman;polymer composites;第41卷(第2期);395-429 * |
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