CN116333489A - Semi-aromatic polyamide molding composite material and preparation method and application thereof - Google Patents
Semi-aromatic polyamide molding composite material and preparation method and application thereof Download PDFInfo
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- CN116333489A CN116333489A CN202211602258.XA CN202211602258A CN116333489A CN 116333489 A CN116333489 A CN 116333489A CN 202211602258 A CN202211602258 A CN 202211602258A CN 116333489 A CN116333489 A CN 116333489A
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- polyamide molding
- white pigment
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000000465 moulding Methods 0.000 title claims abstract description 30
- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229920006119 nylon 10T Polymers 0.000 claims abstract description 73
- 239000012463 white pigment Substances 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000292 calcium oxide Substances 0.000 claims abstract description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 7
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 7
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 7
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 229920002943 EPDM rubber Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000004427 diamine group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical group NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical group NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical group NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical group NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical group NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 3
- 239000011324 bead Substances 0.000 abstract description 25
- 230000035945 sensitivity Effects 0.000 abstract description 19
- 239000000843 powder Substances 0.000 abstract description 17
- 238000004383 yellowing Methods 0.000 abstract description 12
- 238000002310 reflectometry Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229920003317 Fusabond® Polymers 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000001579 optical reflectometry Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- CLOMYZFHNHFSIQ-UHFFFAOYSA-N clonixin Chemical compound CC1=C(Cl)C=CC=C1NC1=NC=CC=C1C(O)=O CLOMYZFHNHFSIQ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 241000482268 Zea mays subsp. mays Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004295 calcium sulphite Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a semi-aromatic polyamide molding composite material, which comprises the following components in parts by weight: 40-75 parts of PA10T/X, 30-60 parts of white pigment, 2-5 parts of maleic anhydride graft polymer and 1.8-4.2% of dispersing agent by weight of white pigment; the reflectivity of the semi-aromatic polyamide molding composite material is more than 93% when the blue light source with the wavelength of 460nm is used. The invention can obviously promote white pigment (titanium white) by selecting PA10T/X resin with specific chain segment structure and maleic anhydride grafted copolymer and simultaneously selecting dispersing agent (calcium oxide and zinc oxide) with specific contentPowder, zinc sulfide) and to make the peak half-width at of the crystal of the composite material delta T 1/2 The temperature is 4-15 ℃, the defect that the powder with high viscosity of the PA10T/X resin is difficult to disperse is overcome, the reflectivity of blue light with the wavelength of 460nm can be obviously improved (which indicates that the LED reflecting bracket can realize higher light source reflectivity), the yellowing resistance can be improved, and the humidity sensitivity level of a finished product lamp bead device can be improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a semi-aromatic molding polyamide composite 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.
In the application fields of illumination light sources and backlight sources, in order to reduce the use quantity of lamp beads and achieve the effect of energy conservation and environmental protection, the brightness of a single lamp bead light source is a very important index. The light source brightness of the single lamp bead is related to the reflectivity of the LED light source bracket besides the chip power: the larger the chip power is, the higher the brightness of an LED single lamp bead is; meanwhile, the higher the reflectivity of the LED light source bracket is, the higher the brightness of a single lamp bead light source is. However, in the prior art, the whiteness of the surface can be improved by adding the titanium dioxide with the ultra-high content (the content is more than 65wt percent) so as to improve the light reflectivity, but the light reflectivity is reduced due to the fact that the surface of the LED light source bracket is uneven due to the fact that the processability is reduced, and the processing difficulty is improved.
Another performance related to LED light source lifetime is LED bead moisture sensitivity level, moisture absorption sensitivity, moisture sensitivity Test (MSL Test), i.e., when confirming whether the LED bead sample contains too much moisture, during SMT Reflow (Reflow) assembly, causing chip, gold wire Delamination (degradation), popcorn effect, leading to shorter LED bead lifetime or lamp death. The traditional LED light source support material mainly comprises a semi-aromatic high-temperature-resistant polyamide material, a reinforcing filler and white pigment, wherein the semi-aromatic polyamide material is not good in combination with hardware, moisture easily enters the inside of a lamp bead after long-term placement or adjustment under a high humidity condition, and the problems of lamp death such as glue surface breakage, chip stripping, gold wire breakage and the like easily occur after SMT. Meanwhile, the material is affected by shearing and heat in the processing process, and is easy to yellow under the condition of a high-power LED light source, so that the brightness of the material is affected. In addition, in highly white pigment filled material systems, the dispersibility of the white pigment can affect the brightness of the material.
If the material is required to be applied to a Jiang Guangyuan LED reflecting plate, the yellowing resistance is required to be higher, and the material is required to be applied to a high-humidity environment and high reliability, so that the yellowing resistance of the material and the humidity sensitivity level of a device are required to be improved.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a semi-aromatic polyamide molding composite material with high light reflectivity, high humidity-sensitive grade and good yellowing resistance, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
the semi-aromatic polyamide molding composite material comprises the following components in parts by weight:
PA 10T/X40-75 parts;
30-60 parts of white pigment;
2-5 parts of maleic anhydride graft polymer;
1.8 to 4.2 percent of dispersant white pigment by weight;
based on the PA10T/X mole percent, the 10T unit content is 80-95 mole percent, the X unit is 5-20 mole percent, and the X unit is not 10T; 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;
the dispersing agent is at least one of calcium oxide and zinc oxide;
the average particle size of the white pigment ranges from 0.10 to 0.50 microns, and the average particle size of the dispersing agent ranges from 1 to 6 microns;
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 4-15 ℃;
the reflection rate of the 460nm wavelength blue light source of the semi-aromatic polyamide molding composite material is more than 93%.
Preferably, the 10T unit content is from 85 to 90mol% and the X unit content is from 10 to 15mol% based on the PA10T/X mole percent.
The PA10T/X resin is at least one selected from PA10T/10I, PA T/6T, PA10T/66, PA10T/1010, PA10T/610, PA10T/612 and PA 10T/12T.
The number average molecular weight of the PA10T/X resin is 1500-28000.
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 distribution Mn.
The maleic anhydride grafted polymer is at least one of POE-g-MAH, PP-g-MAH, PE-g-MAH, EPDM-g-MAH and HDPE-g-MAH; preferably at least one of MAH-g-POE and MAH-g-EPDM. The grafting ratio of maleic anhydride is not particularly required, and the aim of the invention can be achieved with the conventional grafting ratio of 0.5-3wt% on the market.
Preferably, the content of the dispersant is 2.5 to 3.5% by weight of the white pigment.
Preferably, the white pigment has an average particle size in the range of 0.15 to 0.35 microns and the dispersant has an average particle size in the range of 3 to 4 microns.
Preferably, when the white pigment is selected from titanium dioxide, the dispersant is selected from calcium oxide; when the white pigment is selected from zinc sulfide, the dispersant is selected from zinc oxide.
The preparation method of the semi-aromatic polyamide molding composite material comprises the following steps: adding the components into a mixer for mixing, and extruding and granulating by a double-screw extruder to obtain the semi-aromatic polyamide molding composite material, wherein the temperature of the screw ranges from 280 ℃ to 330 ℃ and the rotating speed is 400 r/min to 500r/min.
The semi-aromatic polyamide molding composite material is applied to the preparation of LED lighting and backlight source reflection brackets.
The invention has the following beneficial effects
The invention can obviously promote the dispersion of white pigment (titanium white powder and zinc sulfide) by selecting PA10T/X resin with specific chain segment structure and maleic anhydride grafted copolymer and selecting dispersing agent with specific content, and simultaneously the semi-aromatic polyamide molding composite material has a crystallization peak half-height width delta T 1/2 When the temperature is 4-15 ℃, the reflectivity of blue light with the wavelength of 460nm can be obviously improved, the defect that powder with high viscosity of PA10T/X resin is difficult to disperse is overcome, meanwhile, the yellowing resistance can be improved, and the moisture sensitivity grade of a finished product lamp bead device can be improved when the light-emitting diode (LED) lighting device is applied to the LED lighting device.
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:
semi-aromatic polyamide crystal peak half-width delta T 1/2 : from 30 under nitrogen atmosphere using a differential scanning calorimeter analyzer manufactured by NETZSCH corporationHeating to 345 deg.C at 20deg.C/min, maintaining the temperature for 2min, cooling at 20deg.C/min, setting the crystallization peak temperature at this time as crystallization temperature Tc (deg.C), and setting half of the measured peak width as crystallization peak half-width DeltaT 1/2 。
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 a number average molecular weight distribution Mn.
| The following PA10T/X resin is self-made | 10T unit content, mol% | Number average molecular weight | ΔT 1/2， ℃ |
| PA10T/1010-1 | 80 | 7500 | 15.1 |
| PA10T/1010-2 | 85 | 9000 | 16 |
| PA10T/1010-3 | 90 | 8500 | 12.8 |
| PA10T/1010-4 | 95 | 13000 | 8.4 |
| PA10T/1010-5 | 90 | 2300 | 14.2 |
| PA10T/1010-6 | 90 | 26000 | 18.3 |
| PA10T/1010-7 | 75 | 8800 | 18.0 |
| PA10T/1010-8 | 97 | 8000 | 7.5 |
| PA10T | 100 | 7500 | 5.8 |
| PA10T/10I-1 | 80 | 10500 | 17.1 |
| PA10T/10I-2 | 85 | 9800 | 12 |
| PA10T/10I-3 | 90 | 8500 | 8.3 |
| PA10T/10I-4 | 95 | 8100 | 7.1 |
| PA10T/10I-5 | 60 | 8300 | 15 |
| PA10T/66 | 90 | 8200 | 13.4 |
| PA10T/12T | 80 | 8100 | 10.6 |
Titanium dioxide is purchased from the boa Baili, and then the required average particle size is obtained through screening:
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;
titanium white powder E: average particle size 0.06 microns;
titanium white powder F: average particle size 0.65 microns;
zinc sulfide: sachtolith HD-S, average particle size 0.14 microns, available from sa Ha Liben, germany;
calcium oxide was purchased from 280954, available from new materials technology, inc., and then screened to obtain the desired average particle size:
calcium oxide a: average particle size 1.2 microns;
calcium oxide B: an average particle size of 3.1 microns;
calcium oxide C: average particle size 4.0 microns;
calcium oxide D: average particle size 5.9 microns;
calcium oxide E: average particle size 0.4 microns;
calcium oxide F: average particle size 8.4 microns;
zinc oxide: the average particle size was 3.1 microns.
PP-g-MAH: OREVAC CA100, available from Acomax;
EPDM-g-MAH: FUSABOND N416, available from DOW Dow;
POE-g-MAH: FUSABOND N493 from DOW Dow;
PE-g-MAH: FUSABOND E226, available from DOW Dow.
Examples and comparative examples semi-aromatic polyamide molding composite materials were prepared by: adding polyamide resin, white pigment and dispersing agent into a mixer, uniformly mixing, and extruding and granulating by a double-screw extruder to obtain a semi-aromatic polyamide molding composite 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) Moisture sensitivity rating of the bead device: PA10T/X molding composite material is formed into an LED reflecting support through injection molding, the LED reflecting support is subjected to die bonding, welding wires and silica gel glue packaging to obtain lamp beads, the lamp beads are placed for 8 hours at the temperature of 85 ℃ in an environment with 85% humidity, 100 LED lamp bead samples are taken to be subjected to SMT test, and the humidity sensitivity level of the lamp beads is judged by observing the performance of the LED lamp beads:
if the humidity is regulated, after SMT, the appearance of the lamp beads is changed, the lamp beads are lightened without abnormal conditions, and the humidity-sensitive grade is judged to be grade A;
if the surface of the glue is cracked after the SMT is performed, but the glue and the metal strip part (the lamp bead functional area) inside the LED reflecting bracket are not delaminated, the lamp bead is lightened and is not abnormal, and the humidity-sensitive grade is judged as B grade: wherein the ratio of cracks (number of lamp beads with cracks/100 x 100%) is less than 5% and defined as B-1 level, the ratio of cracks is 5% -10% and defined as B-2 level, the ratio of cracks is 10% -20% and defined as B-3 level, and the ratio of cracks is 20% -50% and defined as B-4 level.
If the SMT is performed after humidity adjustment, the glue and the hardware in the functional area are delaminated, the lamp bead is not abnormal when being lightened, or the glue surface is provided with cracks, but the glue and the hardware in the functional area are not delaminated, the crack proportion is more than 50%, and the humidity-sensitive grade is judged to be grade C;
if the humidity is regulated, the lamp beads cannot be lightened after SMT, the humidity-sensitive grade is judged to be grade D, and the grade D lamp beads of the humidity-sensitive grade are invalid.
(2) Reflectivity: a test piece having a length of 60mm, a width of 60mm and a thickness of 1mm was prepared by injection molding the PA10T/X molded composite material. The reflectance of the test piece to 460nm wavelength light was measured using a Color Eye 7000A Color difference meter and recorded as an initial reflectance R1.
(3) Testing yellowing resistance: test pieces of 60mm in length, 60mm in width and 1mm in thickness, prepared by injection molding of the PA10T/X molded composite, were subjected to SMT three times, and the reflectance of the test pieces to light of 460nm wavelength was measured using Color Eye 7000A type Color difference meter and recorded as reflectance R2 after aging. The yellowing resistance is characterized by the difference between the initial reflectance R1 and the aged reflectance R2.
ΔR460=R1-R2
(4) Semi-aromatic polyamide molding composite material crystallization peak half-width delta T 1/2 : using a differential scanning calorimeter analyzer manufactured by NETZSCH, heating from 30deg.C to 20deg.C/min under nitrogen atmosphere to 345 deg.C, maintaining the temperature for 2min, cooling at 20deg.C/min, and setting the crystallization peak temperature at this time as crystallization temperature Tc (. Degree.C.), to obtainThe half temperature of the peak width of (2) is defined as the half height width DeltaT of the crystallization peak 1/2 。
Table 1: examples 1 to 8 the proportions (parts by weight) of the components and the results of the tests
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| PA10T/1010-1 | 40 | 50 | 60 | 75 | 60 | 60 | 60 | 60 |
| MAH-g-PP | 2 | 3 | 4 | 5 | 4 | 4 | 4 | 4 |
| Titanium white powder A | 30 | 40 | 50 | 60 | 50 | 50 | 50 | 50 |
| Calcium oxide A | 0.9 | 1.2 | 1.5 | 1.8 | 0.9 | 1.25 | 1.75 | 2.1 |
| Peak width at half maximum deltat 1/2 ，℃ | 11.2 | 10.8 | 10.5 | 11.1 | 12.1 | 11.6 | 9.8 | 9.4 |
| Reflectance at 460 nm% | 94.9 | 95.5 | 96.0 | 95.4 | 94.7 | 95.5 | 96.2 | 95.3 |
| Moisture sensitivity rating | B-2 | B-1 | B-1 | B-1 | B-2 | B-1 | B-1 | B-1 |
| ΔR460 | 4 | 4.5 | 3 | 3.7 | 4.5 | 3.5 | 2.8 | 2.7 |
As is clear from examples 3/5-8, the preferable dispersant content range is that the 460nm reflectance is higher, the humidity sensitivity level is higher, and the yellowing resistance DeltaR 460 can be controlled to be lower than 4.
Table 2: examples 9 to 16 the proportions (parts by weight) of the components and the test results
| Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 | |
| PA10T/1010-1 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| MAH-g-PP | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Titanium white powder A | 50 | 50 | ||||||
| Titanium white powder B | 50 | |||||||
| Titanium white powder C | 50 | 50 | ||||||
| Titanium white D | 50 | |||||||
| Zinc sulfide | 50 | 50 | ||||||
| Calcium oxide A | 1.5 | 1.5 | ||||||
| Calcium oxide B | 1.5 | 1.5 | ||||||
| Calcium oxide C | 1.5 | |||||||
| Calcium oxide D | 1.5 | |||||||
| Zinc oxide | 1.5 | 1.5 | ||||||
| CrystallizationPeak half width deltat 1/2 ，℃ | 9.7 | 9.9 | 10.1 | 9.6 | 9.6 | 9.8 | 9.8 | 9.5 |
| Reflectance at 460 nm% | 96.7 | 96.4 | 95.1 | 96.1 | 95.8 | 95.4 | 94.9 | 95.2 |
| Moisture sensitivity rating | B-1 | B-1 | B-2 | B-1 | B-1 | B-1 | B-1 | B-1 |
| ΔR460 | 3.3 | 3.7 | 4.1 | 3.1 | 3.5 | 3.9 | 4.5 | 3.9 |
As is clear from examples 3/9-13, the preferable white pigment, dispersant particle size, 460nm light reflectance, humidity sensitivity rating are higher, and yellowing resistance DeltaR 460 can be controlled to be lower than 4.
As can be seen from examples 3/14 and examples 15/16, when the white pigment is selected from titanium pigment, the dispersant is preferably calcium oxide; when the white pigment is selected from zinc sulfide, the dispersant is preferably zinc oxide.
Table 3: examples 17 to 24 the proportions (parts by weight) of the components and the test results
| Example 17 | Example 18 | Example 19 | Example 20 | Example 21 | Example 22 | Example 23 | Example 24 | |
| PA10T/1010-1 | 60 | 60 | 60 | |||||
| PA10T/1010-2 | 60 | |||||||
| PA10T/1010-3 | 60 | |||||||
| PA10T/1010-4 | 60 | |||||||
| PA10T/1010-5 | 60 | |||||||
| PA10T/1010-6 | 60 | |||||||
| MAH-g-PP | 4 | 4 | 4 | 4 | 4 | |||
| MAH-g-EPDM | 4 | |||||||
| MAH-g-POE | 4 | |||||||
| MAH-g-HDPE | 4 | |||||||
| Titanium white powder A | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Calcium oxide A | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Peak width at half maximum deltat 1/2 ，℃ | 9.3 | 9.0 | 9.5 | 10.0 | 6.7 | 4.5 | 9.9 | 13.4 |
| Reflectance at 460 nm% | 96.2 | 96.3 | 96.0 | 95.9 | 96 | 96.2 | 95.9 | 95.9 |
| Moisture sensitivity rating | A | A | B-1 | A | A | B-1 | A | A |
| ΔR460 | 3 | 2.8 | 3 | 3.2 | 2.8 | 2 | 2.7 | 3.5 |
As is evident from examples 3/17-19, the maleic anhydride graft polymer is preferably MAH-g-POE, MAH-g-EPDM.
Table 4: examples 25 to 30 the proportions (parts by weight) of the components and the test results
| Example 25 | Example 26 | Example 27 | Example 28 | Example 29 | Example 30 | |
| PA10T/10I-1 | 60 | |||||
| PA10T/10I-2 | 60 | |||||
| PA10T/10I-3 | 60 | |||||
| PA10T/10I-4 | 60 | |||||
| PA10T/66 | 60 | |||||
| PA10T/12T | 60 | |||||
| MAH-g-PP | 4 | 4 | 4 | 4 | 4 | 4 |
| Titanium white powder A | 50 | 50 | 50 | 50 | 50 | 50 |
| Calcium oxide A | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Peak width at half maximum deltat 1/2 ，℃ | 12.3 | 8.1 | 4.9 | 4.1 | 7.9 | 6.1 |
| Reflectance at 460 nm% | 95.9 | 96.2 | 96.3 | 96.4 | 96.2 | 96 |
| Moisture sensitivity rating | B-1 | A | A | B-1 | A | B-1 |
| ΔR460 | 2.9 | 2.6 | 2.3 | 1.9 | 2.1 | 2.3 |
As is evident from examples 20 to 30, it is preferable that the 10T unit content is 85 to 90mol%, the X unit content is 10 to 15mol% and the moisture sensitive rating is higher based on the PA10T/X mole percent.
Table 5: comparative examples 1 to 8 Each component was compounded in parts by weight and the results of the test
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| PA10T/1010-1 | 60 | 60 | 60 | 60 | ||||
| PA10T/1010-7 | 60 | |||||||
| PA10T/1010-8 | 60 | |||||||
| PA10T | 60 | |||||||
| PA10T/10I-5 | 60 | |||||||
| MAH-g-PP | 4 | 4 | 4 | 4 | 4 | 4 | 1 | 6 |
| Titanium white powder A | 50 | 50 | 50 | 65 | 50 | 50 | 50 | 50 |
| Calcium oxide A | 1.5 | 1.5 | 1.5 | 2 | 0.75 | 2.5 | 1.5 | 1.5 |
| Peak width at half maximum deltat 1/2 ，℃ | 15.2 | 3.9 | 3.5 | 3.8 | 12.5 | 9.1 | 9.5 | 13.5 |
| Reflectance at 460 nm% | 95.1 | 94.9 | 96.2 | 94.7 | 95.5 | 94.5 | 95.9 | 94.5 |
| Moisture sensitivity rating | B-4 | C | C | B-4 | B-3 | B-3 | C | C |
| ΔR460 | 4.5 | 2 | 1.8 | 2.7 | 5 | 6 | 2 | 3.5 |
As is clear from comparative examples 1 to 3, the moisture sensitivity level was low when the segment structure of the polyamide resin was out of the range of the present invention.
As is evident from comparative example 4, the use of excessive white pigment reduces the half-width at half-height below 4℃and reduces the moisture sensitivity level and yellowing resistance.
As is clear from comparative examples 5/6, too low or too high a dispersant content lowers the humidity sensitivity level and severely lowers the yellowing resistance for insufficient dispersion of the white pigment.
As is evident from comparative examples 7/8, the addition amount of the maleic anhydride-grafted polymer was too high or too low, and the humidity-sensitive grade was low.
Table 6: comparative examples 9 to 14 Each component was compounded in parts by weight and the results of the test
| Comparative example 9 | Comparative example 10 | Comparative example 11 | Comparative example 12 | Comparative example 13 | Comparative example 14 | |
| PA10T/1010-1 | 60 | 60 | 60 | 60 | 60 | 60 |
| MAH-g-PP | 4 | 4 | 4 | 4 | 4 | 4 |
| Titanium white powder A | 50 | 50 | ||||
| Titanium white E | 50 | 50 | ||||
| Titanium dioxide F | 50 | 50 | ||||
| Calcium oxide A | 1.5 | 1.5 | ||||
| Calcium oxide E | 1.5 | 1.5 | ||||
| Calcium oxide F | 1.5 | 1.5 | ||||
| Peak width at half maximum deltat 1/2 ，℃ | 9.5 | 9.5 | 9.7 | 10.1 | 9.5 | 10 |
| Reflectance at 460 nm% | 95.4 | 95 | 94.3 | 94.1 | 94 | 93.8 |
| Moisture sensitivity rating | B-3 | B-4 | B-3 | B-4 | B-4 | B-4 |
| ΔR460 | 4.5 | 5 | 4.1 | 4.5 | 4.8 | 5.5 |
From comparative examples 9 to 14, it is understood that when the particle size of the white pigment and/or the dispersant is out of the range of the present invention, not only the 460nm light reflectance but also the humidity sensitive grade and yellowing resistance are significantly affected.
Claims (10)
1. The semi-aromatic polyamide molding composite material is characterized by comprising the following components in parts by weight:
PA 10T/X40-75 parts;
30-60 parts of white pigment;
2-5 parts of maleic anhydride graft polymer;
1.8 to 4.2 percent of dispersant white pigment by weight;
based on the PA10T/X mole percent, the 10T unit content is 80-95 mole percent, the X unit is 5-20 mole percent, and the X unit is not 10T; 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;
the dispersing agent is at least one of calcium oxide and zinc oxide;
the average particle size of the white pigment ranges from 0.10 to 0.50 microns, and the average particle size of the dispersing agent ranges from 1 to 6 microns;
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 4-15 ℃;
the reflection rate of the 460nm wavelength blue light source of the semi-aromatic polyamide molding composite material is more than 93%.
2. The semiaromatic polyamide molding composite as claimed in claim 1, characterized in that the 10T unit content is from 85 to 90mol% and the X unit content is from 10 to 15mol%, based on the PA10T/X mole percent.
3. The semiaromatic polyamide molding compound as claimed in claim 1, wherein said PA10T/X resin is selected from at least one of PA10T/10I, PA T/6T, PA10T/66, PA10T/1010, PA10T/610, PA10T/612, PA 10T/12T.
4. The semiaromatic polyamide molding compound as claimed in claim 1, wherein said PA10T/X resin has a number average molecular weight of 1500-28000.
5. The semiaromatic polyamide molding composite as claimed in claim 1, wherein the maleic anhydride graft polymer is at least one of POE-g-MAH, PP-g-MAH, PE-g-MAH, EPDM-g-MAH, HDPE-g-MAH; preferably at least one of MAH-g-POE and MAH-g-EPDM.
6. The semiaromatic polyamide molding composite as claimed in claim 1, wherein the dispersant is contained in an amount of 2.5 to 3.5% by weight based on the weight of the white pigment.
7. The semiaromatic polyamide molding composite as claimed in claim 1, wherein said white pigment has an average particle size in the range of 0.15 to 0.35 μm; the dispersant has an average particle size in the range of 3-4 microns.
8. The semiaromatic polyamide molding composite as claimed in claim 1, wherein, when the white pigment is selected from titanium white, the dispersant is selected from calcium oxide; when the white pigment is selected from zinc sulfide, the dispersant is selected from zinc oxide.
9. A process for the preparation of a semiaromatic polyamide molding composite as claimed in any of claims 1 to 8, characterized in that it comprises the following steps: adding the components into a mixer for mixing, and extruding and granulating by a double-screw extruder to obtain the semi-aromatic polyamide molding composite material, wherein the temperature of the screw ranges from 280 ℃ to 330 ℃ and the rotating speed is 400 r/min to 500r/min.
10. Use of a semiaromatic polyamide molding compound as claimed in any of claims 1 to 8 for the preparation of LED lighting, backlight source reflection supports.
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| KR20100039652A (en) * | 2008-10-08 | 2010-04-16 | 에스에스씨피 주식회사 | Non-solvent type, uv-curable white ink composition |
| WO2014193046A1 (en) * | 2013-05-31 | 2014-12-04 | 제일모직주식회사 | Polyamide-based resin composition having excellent reflectivity and discoloration resistance |
| CN109553949A (en) * | 2018-11-21 | 2019-04-02 | 金发科技股份有限公司 | A kind of antibacterial makrolon composite material and preparation method |
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| CN114656781A (en) * | 2022-03-17 | 2022-06-24 | 珠海万通特种工程塑料有限公司 | Gray semi-aromatic polyamide molding material and preparation method and application thereof |
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| KR20100039652A (en) * | 2008-10-08 | 2010-04-16 | 에스에스씨피 주식회사 | Non-solvent type, uv-curable white ink composition |
| WO2014193046A1 (en) * | 2013-05-31 | 2014-12-04 | 제일모직주식회사 | Polyamide-based resin composition having excellent reflectivity and discoloration resistance |
| CN109553949A (en) * | 2018-11-21 | 2019-04-02 | 金发科技股份有限公司 | A kind of antibacterial makrolon composite material and preparation method |
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| CN114656781A (en) * | 2022-03-17 | 2022-06-24 | 珠海万通特种工程塑料有限公司 | Gray semi-aromatic polyamide molding material and preparation method and application thereof |
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