CN104610739A - Polyamide composition for reflective plate - Google Patents
Polyamide composition for reflective plate Download PDFInfo
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- CN104610739A CN104610739A CN201510029804.9A CN201510029804A CN104610739A CN 104610739 A CN104610739 A CN 104610739A CN 201510029804 A CN201510029804 A CN 201510029804A CN 104610739 A CN104610739 A CN 104610739A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
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Abstract
The invention discloses polyamide composition for a reflective plate. The polyamide composition comprises (A) 100 parts of semi-aromatic polyamide PA/Z and (B) 9-300 parts of white pigment (B1) and/or reinforcing filler (B2), wherein on the basis of all monomeric units, PA/Z comprises at least 20 mol% of terephthalic-acid-based repetitive units, and on the basis of mole content of diamine, PA/Z further comprises 0.01mol%-5mol% of compounds Z containing secondary amine groups; on the basis of the weight of all components, the phosphorus content of the polyamide composition is 30-3,000 ppm. According to the polyamide composition, specific content of compounds containing secondary amine groups and specific content of phosphorus are adopted, the easily-occurring technical problems that silica gel is undercured and even silica gel cannot be completely cured in the packaging process of an LED device can be solved, and later complete silica gel curing is realized.
Description
Technical field
The present invention relates to modifying polyamide polymers compositions field, particularly a kind of reflector daiamid composition.
Background technology
LED is used as light source more and more because it exceedes many advantages of conventional light source.LED compares with other light sources with incandescent source generally, consumes less power, requires lower operating voltage and have good resistibility to mechanical shock.Therefore, LED light source is just substituting incandescent source with other light sources and in not identical field in many purposes, as traffic signals, inside and outside illumination, mobile phone display screen, automobile display screen and photoflash lamp etc.
LED component, as shell and reflection support require that material has excellent colour stability and high temperature resistance discolouration., pottery can meet above requirement, but the pottery processing treatment technology that not only price is high but also needs are higher, working (machining) efficiency is low.Thermoplastic polymer is because it can be used as injection moulding, succinct, flexible, efficient, therefore conducts extensive research polymer composition and develops so that the material as lower cost substitutes pottery.LED reflection stent applications requires to have good opaqueness and outstanding reflection characteristic.But thermoplastic polymer is easy to jaundice when being exposed in light and high temperature usually.Such as in LED process, so that cured epoxy resin or silicon encapsulants at LED parts are heated to about 180 DEG C.When carrying out reflow soldering operation, under LED parts are also exposed to the temperature higher than 260 DEG C.In addition, in use, LED light source parts are as headlight for vehicles, and use temperature is higher than the temperature of 80 DEG C.This exposure in high temperature causes the jaundice of the polymer composition for the formation of LED parts.
Therefore be applied to the thermoplastic polymer composition of LED reflection support, should meet and multiplely require to include high luminous reflectance factor (visible light reflectance), high whiteness, good workability (such as good moldability), high dimensional stability (low coefficient of linear expansion), high physical strength and high thermotolerance (low when being exposed to high temperature fade and low reflection loss).
As previously mentioned, in LED process, LED component is heated to certain temperature and solidifies to make silica gel.This is the requisite link of LED, and is vital link.Research finds, is easy in this process produce the incomplete problem of even not solidifying completely of silica gel solidification, and cause the production process in later stage to carry out, product cannot use.For how solving the LED reflection support problem that whiteness and reflectivity decline when being exposed in light and heat, more patent and document is had to be described; But rarely have the problem mentioning silica gel solidification in LED process, more do not mention the impact that LED reflection support solidifies silica gel.
Summary of the invention
The technical problem that the silica gel solidification being easy to occur in encapsulation process to solve LED component not exclusively cannot be solidified even completely, the object of the present invention is to provide one can realize later stage silica gel and solidifies reflector daiamid composition completely.
A kind of reflector daiamid composition, by weight, comprises following component:
(A) the semiaromatic polyamide composition PA/Z of 100 parts; Wherein, based on whole monomeric unit, PA/Z comprises the repeating unit based on terephthalic acid of at least 20mol%; Based on the molar content of diamines, in PA/Z, also comprise the compound Z containing secondary amine group of 0.01 ~ 5mol%;
(B) white pigment (B1) of 9-300 part and/or reinforcing filler (B2);
Based on whole component weight, the phosphorus content of this daiamid composition is 30-3000ppm.
Preferably, based on whole component weight, the phosphorus content of this daiamid composition is 50 ~ 1000ppm.
Wherein, the content of described partially aromatic polyamide PA/Z is 20 ~ 95wt% based on this daiamid composition gross weight, is preferably 30 ~ 70wt%.
The described compound Z containing secondary amine group is selected from NH (C
2h
4nH
2)
2, H
2n [C
2h
4nH]
2c
2h
4nH
2, H
2n [C
2h
4nH]
3c
2h
4nH
2, NH [(CH
2)
4nH
2)
2, NH [(CH
2)
5nH
2)
2, NH [(CH
2)
6nH
2)
2, NH [(CH
2)
7nH
2)
2, NH [(CH
2)
8nH
2)
2, NH [(CH
2)
9nH
2)
2, NH [(CH
2)
10nH
2)
2, NH [(CH
2)
11nH
2)
2, NH [(CH
2)
12nH
2)
2, NH [(CH
2)
13nH
2)
2, NH [(CH
2)
14nH
2)
2, NH [(CH
2)
15nH
2)
2, NH [(CH
2)
16nH
2)
2, NH [(CH
2)
17nH
2)
2, NH [(CH
2)
18nH
2)
2, H
2n (H
2c)
10nH (CH
2)
5nH
2, H
2n (H
2c)
10nH (CH
2)
6nH
2, H
2n (H
2c)
10nH (CH
2)
7nH
2, H
2n (H
2c)
10nH (CH
2)
8nH
2, H
2n (H
2c)
10nH (CH
2)
9nH
2, H
2n (H
2c)
10nH (CH
2)
11nH
2, H
2n (H
2c)
10nH (CH
2)
12nH
2, H
2n (H
2c)
9nH (CH
2)
6cH (CH
3) CH
2nH
2, H
2n (H
2c)
9nHCH
2cH (CH
3) (CH
2)
6nH
2, NH [(CH
2)
6cH (CH
3) CH
2nH
2]
2, NH [CH
2cH (CH
3) (CH
2)
6nH
2]
2in one or more.
Preferably, the molar content of the described compounds X containing secondary amine group is 0.05 ~ 2mol%.
Described white pigment (B1) minimizes as fundamental to make the change of xanthochromia and gives good reflection, is selected from and comprises but be not limited only to titanium dioxide, zinc oxide, zinc sulphide, white lead, zinc sulfate, barium sulfate, calcium carbonate, aluminum oxide.The shape of these particles is not particularly limited; They can be notably round, laminar, flat etc.
This white pigment is preferably titanium dioxide (TiO
2); The form of titanium dioxide is not particularly limited and can uses diversified crystallized form, as anatase form, rutile form and oblique crystal type.But rutile form is preferred, because its specific refractory power is higher and its light stability is superior.The preparation method of titanium dioxide also can be diversified, as sulfuric acid process, and chlorination process.But chlorination process is preferred.
In the surface treatment of titanium dioxide, independent inorganic surface treatment can be used, also can use independent organic surface treatment, inorganic and organic combination treatment can also be used.Even more preferably separately inorganic surface treatment with inorganic organic combination treatment.
Inorganic surface treatment agent includes but not limited to Al
2o
3, SiO
2, ZrO
2, water glass, sodium aluminate, sodium aluminium silicate (sodium silicate aluminium), zinc oxide, mica etc.Surface treatment agent can be used alone or combinationally uses with it.
Organic surface treatment includes but not limited to polydimethylsiloxane, trimethyl propane (TMP), tetramethylolmethane etc.Surface treatment agent can be used alone or combinationally uses with it.
Based on the titanium dioxide of 100 weight parts, about 0.3 weight part or less titanium dioxide can be coated with inorganic or organic surface treatment.Based on the titanium dioxide of 100 weight parts, preferably by the Al being less than 5 weight parts
2o
3as the titanium dioxide of inorganic surface treatment agent coating.
The median size of titanium dioxide excessive or too small all exist luminous reflectance factor reduce situation, therefore preferred at 0.1 ~ 0.5 μm, more preferably at 0.15 ~ 0.4 μm, particularly preferably in the scope of 0.2 ~ 0.3 μm.Herein, also block or that median size is large titanium dioxide suitably can be pulverized, carry out classification with sieve etc. as required, thus use after reaching above-mentioned median size.
If existed, then the amount that exists of this white pigment is preferably at least 1wt%, preferably at least 6wt%, more preferably at least 10wt% and most preferably at least 15wt% based on the gross weight of said composition.In addition, when it is present, the amount that exists of this white pigment is also preferably maximum 50wt%, more preferably maximum 40wt% based on the gross weight of composition according to the present invention.
If the consumption of white pigment is too low, reflectivity and yellowing resistance can be deteriorated.If when the consumption of white pigment is too much, the toughness of material and formability can be deteriorated.
Described reinforcing filler (B2) is selected from threadiness, tabular, needle-like, cross-like strengthening material, described fibee reinforced material is selected from glass fibre, carbon fiber, Kevlar, liquid crystalline polymers (LCP) fiber, the one of steel fiber or its combination, described tabular strengthening material is selected from mica, the one of talcum or its combination, described needle-like strengthening material is selected from potassium titanate crystal whisker, aluminium borate whisker, calcium carbonate crystal whisker, magnesium sulfate crystal whisker, wollastonite, sepiolite, xonotlite, the one of ZnOw or its combination, described cross-like strengthening material silicon-dioxide, aluminum oxide, barium carbonate, magnesiumcarbonate, aluminium nitride, boron nitride, potassium titanate, pure aluminium silicate (kaolin, clay, agalmatolite, wilkinite), Calucium Silicate powder, Magnesium Silicate q-agent (attapulgite), aluminum borate, calcium sulfate, barium sulfate, magnesium sulfate, asbestos, granulated glass sphere, graphite, carbon nanotube, silicon carbide, sericite, hydrotalcite, molybdenumdisulphide, resol, cross-linked styrene system resin, the one of cross-linked acrylic acid system resin or its combination.
In order to improve dispersiveness in polymeric amide or improve and the binding property of polymeric amide, surface treatment can be carried out by the polymers such as silane coupling agent, titanate coupling agent, acrylic resin, urethane resin, epoxy resin or other low molecular compound in the surface of these strengthening materials.
In above-mentioned reinforcing filler, from low cost, the high products formed of mechanical strength can be obtained consider, the reinforcing filler of optimum fiber shape and/or needle-like reinforcing filler.From the viewpoint of high strength, low cost, this reinforcing filler preferably uses glass fibre, from the viewpoint of obtaining the high products formed of surface smoothness, preferably uses needle-like strengthening material.Particularly from the viewpoint of maintenance whiteness, at least one be selected from glass fibre, wollastonite, potassium titanate crystal whisker, calcium carbonate crystal whisker and aluminium borate whisker be can preferably use, more preferably glass fibre and/or wollastonite used.
The amount that described reinforcing filler exists is the 0wt% to 40wt% based on this daiamid composition gross weight.Preferred 10wt%-30wt%.
Daiamid composition of the present invention, optionally can comprise P contained compound further, as being selected from one in potassiumphosphate, sodium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, phosphoric acid ester, phosphorous acid ester, Sodium Acid Pyrophosphate etc. or its combination.
Daiamid composition of the present invention, optionally can comprise magnesium oxide and/or magnesium hydroxide further, and its content is 0.5 ~ 10wt% based on this daiamid composition gross weight, is preferably 1 ~ 5wt%.Thus, though carry out especially for a long time heat treated time, also can suppress the reduction of xanthochromia and whiteness.When this content is lower than 0.5wt%, suppress the color changeable effect after heat treated little, and during more than 10wt%, the formability of material reduce.
The median size of magnesium oxide and/or magnesium hydroxide is not particularly limited, from the view point of the various physical property of raising, is preferably 0.05 ~ 10 μm, is more preferably 0.1 ~ 5 μm.In addition, in order to improve adaptation and the dispersiveness of itself and polymeric amide, also surface treated magnesium oxide and/or magnesium hydroxide can be used.As surface treatment agent, comprise the silane coupling agent such as aminosilane, epoxy silane; The silicoorganic compound such as organosilicon; The organic titanic compounds such as titanium coupling agent; The organism such as organic acid, polyvalent alcohol etc.
This daiamid composition can also comprise calcium carbonate, and/or tetrafluoroethylene, and/or has the styrene analog thermoplastic resin of syndiotactic structure.
Suitable calcium carbonate mineral is the Natural Types of grinding and the type (PCC) of precipitation, and it preferably has the calcium carbonate content of at least 97 % by weight and maximum Fe of 0.2 % by weight
2o
3content.Chalk, grinding calcite, ground marble and grinding stone lime stone is divided into according to naturally occurring form.Preferred crystalline structure is aragonite and calcite, preferred needle-like, cigar shape and cubes crystalline form.Especially preferred be cigar shape crystalline form, as by product Socal P2 or P3 from Solvay Chemicals have.The example of natural whiting of grinding is: Hydrocarb, Setacarb-OG(from Pl ü ss-Staufer AG are ultra-fine), Calcigloss-GU(extra-fine grinding marble).
Natural whiting filler can obtain with multiple classified grinding fineness.This be classified as from d50m value be about 1 micron and maximum particle diameter is that the superfine product of 6 to 10 microns is to the form of chips within the scope of millimeter with narrow size distribution.Specific surface area is 1 to 10 m
2/ g, but only just can reach 10 m when being ground to the thinnest
2/ g.When PCC type, this fine type has 6 to 10 m
2the specific surface area of/g, ultra-fine type specific surface area is 20-35 m
2/ g.
In order to improve the dispersion of calcium carbonate in thermoplastics, can by suitable surface treatment (coating) to give calcium carbonate lipotropy.Suitable surface treatment agent is such as calcium stearate and stearic acid, and for the carboxylic acid that the organic surface treatment of titanium dioxide has been mentioned.
If existed, the content of this calcium carbonate mostly is 50% most, mostly preferably most is 30%.
This daiamid composition can comprise the styrene analog thermoplastic resin with syndiotactic structure further.Wherein said styrene analog thermoplastic resin has 10,000 to 5,000, the weight-average molecular weight within the scope of 000 gram/mol.Wherein said styrene analog thermoplastic resin has the fusing point within the scope of 200 to 320 DEG C.
Optionally can comprise a kind of anti-impact modifier further.Preferred anti-impact modifier comprises typically for those of polymeric amide, and comprise the polyolefins of carboxyl substituted, these polyolefinss have to be attached on it, or is attached at the polyolefins of the carboxylic acid group on self polyolefin backbone or side chain.These carboxylic acid groups mean hydroxy-acid group, as one or more omega-dicarboxylic acids, and diester class, diacyloxy monoesters class, anhydrides, and monocarboxylic acid class and ester class.
This anti-impact modifier can preferably based on ethylene/alpha-olefin polyolefine.Two vinyl monomer is as Isosorbide-5-Nitrae-divinyl; Isosorbide-5-Nitrae-hexadiene; Or dicyclopentadiene can optionally for this polyolefinic preparation.Preferably polyolefins comprises ethylene-propylendiene (EPDM) polymkeric substance and styrene-ethylene=butadiene-styrene (SEBS) polymkeric substance prepared by Isosorbide-5-Nitrae-hexadiene and/or dicyclopentadiene.This impact modifier can have or can not have a multiple carboxy moiety be attached on it of work.
This carboxy moiety can by introducing with many undersaturated carboxyl group-containing monomer copolymerization during this polyolefinic preparation.The preferably multipolymer of ethene and maleic anhydride monoethylester.This carboxy moiety can also by with a kind of unsaturated compound containing carboxy moiety as acid, ester, diacid, diester, acid esters or this polyolefine acid anhydride-grafted and introduce.A kind of preferred grafting agent is maleic anhydride.A kind of preferred anti-impact modifier is a kind of EPDM polymkeric substance or the POE polymkeric substance that are grafted with maleic anhydride.
The another kind of additive that may reside in polymer composition is polytetrafluoroethylene polymer.Comprise reflectivity and whiteness index that polytetrafluoroethylene polymer can improve the goods manufactured by polymer composition.Can be less than about 50 microns to have, polytetrafluoroethylene polymer is added to composition by the form being such as less than the fine powder of the mean particle size of about 10 microns.Such as, in one embodiment, polytetrafluorethylepowder powder can have the mean particle size of about 1 micron of-Yue 8 microns.Polytetrafluoroethylene polymer can be about 10wt% with about 0.05wt%-, and the amount that such as about 0.1wt%-is about 6wt% is present in composition.
Daiamid composition of the present invention, optionally can comprise inorganic nucleator further, described inorganic nucleator is selected from silica, talcum, clay, aluminum oxide, mica, zirconium white, titanium dioxide, stannic oxide, tin indium oxide, titanium tetrachloride, calcium carbonate, the one of zeolite or its combination, obtains excellent result when using talcum; The content of described inorganic nucleator is 0.5 ~ 5wt% based on this daiamid composition gross weight, is preferably 2 ~ 4wt%.
Term " inorganic nucleator " is intended to represent the mineral grain of the weight average size (equivalent diameter) with at least 1 μm.Preferably, the weight average size of these particles is at least 2 μm.In addition, it is preferably maximum 10 μm.
In the present invention, also can in the scope not damaging invention effect, following additive is added, i.e. the one of antioxidant, heat-resisting stabilizing agent, photostabilizer, other polymkeric substance, impact modifier, fire retardant, white dyes, lubricant, softening agent, thickening material, static inhibitor, releasing agent, pigment or its combination according to purposes; Described antioxidant is selected from phenols, amine, the one of sulphur class or its combination; Described heat-resisting stabilizing agent is selected from lactone compound, vitamin-E class, hydroquinones, copper halide, the one of iodine compound or its combination; Described photostabilizer is selected from benzotriazole category, triazines, benzophenone, benzoates, hindered amines, the one of oxanilide (Oxanilide) class or its combination; Other polymkeric substance described are selected from polyolefins, ethene-propylene copolymer, ethene-1-butylene copolymer olefin copolymer, the olefin copolymers such as propylene-1-butylene copolymer, the one of polystyrene, polymeric amide, polycarbonate, polyacetal, polysulfones, polyphenylene oxide, fluoro-resin, silicone resin, LCP or its combination; Described fire retardant is selected from bromine system, chlorine system, phosphorus system, antimony system, the one of inorganic system or its combination.When adding these compositions in daiamid composition of the present invention, its content is preferably below 5wt%.
The present invention adopts the daiamid composition containing the compound of secondary amine group and the phosphorus content of certain content of certain content, the incomplete technical problem cannot solidified even completely of silica gel solidification that LED component is easy to occur in encapsulation process can be solved, realize later stage silica gel completion of cure.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that reflector daiamid composition particle of the present invention is injection molded into sample;
Fig. 2 is another schematic diagram that reflector daiamid composition particle of the present invention is injection molded into sample.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Glass fibre: as OCV995 from OWENS CORNING matrix material company (OCVTM Reinforcements) commercially available E-glass fibre.
Titanium dioxide: be purchased from Ishihara Sangyo Kaisha, Ltd. (Ishihara Sangyo Kaisha).
The rutile TiO that PC-3-is manufactured by chloride process
2, by silica and alumina treatment mistake.
Phosphorus containg substances 1: tripoly phosphate sodium STPP, from Yixing, Tian Peng Fine Chemical Co., Ltd is purchased.
Phosphorus containg substances 2:Hostanox
p-EPQ, is purchased from Clariant Corporation (Clariant).
Phosphorus containg substances 3: potassium metaphosphate, from Jiangsu, Rui Feng Chemical Co., Ltd. is purchased.
Inorganic nucleator: as HTP4 from Yi meter Fa ratio (IMl FabiTM) commercially available talcum.
Lubricant: from the commercially available PED191 of AmeriLubes, L.L.C, a kind of polyethylene wax of oxidation of high molecular.
LED silica gel: from the commercially available LED silica gel of Beijing Kang Meite Science and Technology Ltd., MO-006 AB glue.
the measuring method of each performance index
The testing method of the relative viscosity of polymeric amide: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: 25 ± 0.01
oc 98% the vitriol oil in measure the relative viscosity that concentration is the polymeric amide of 0.25g/dl
η r;
The testing method of the fusing point of polymeric amide: with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; Concrete testing method is: the fusing point adopting Perkin Elmer Diamond dsc analysis instrument test sample; Nitrogen atmosphere, flow velocity is 40mL/min; First with 10 during test
oc/min is warming up to 340
oc, 340
oc keeps 2min, then with 10
oc/min is cooled to 50
oc, then with 10
oc/min is warming up to 340
oc, is set to fusing point by endotherm peak temperature now
t m;
The phosphorus detection of daiamid composition: measure according to USEPA method 3052:1996, adopts ICP-OES to analyze.
Silica gel curing performance is tested: the daiamid composition particle injection moulding of gained is become test sample as illustrated in fig. 1 and 2;
MO-006 A glue is got 0.02g and is dropped in the pit of exemplar upper surface after mixing with mass ratio 1:4 with MO-006 B glue, layer of silica gel is made to be laid in the end, hole, then exemplar is put into baking oven, Procuring 1h under 80 DEG C of conditions, terminate after being then warming up to 150 DEG C of continuation solidification 4h.Take out dull and stereotyped, with the naked eye directly observe the silica gel solidification situation in pit.Solidification is expressed as " ⊙ " completely, does not solidify and is expressed as " ↓ ".
the polyamide resin of embodiment A ~ E and comparative example F ~ G synthesizes by the following method:
Reaction raw materials is added in the ratio in form in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth; Add sodium hypophosphite, phenylformic acid and deionized water again.Sodium hypophosphite weight is 0.1% of deionizing water other charged material weight outer, and the amount of benzoic acid species is 4% of the total amount of substance of diacid, and deionized water weight is 30% of total charged material weight.Vacuumize and be filled with high pure nitrogen as protection gas, start reaction.Reaction mixture is warming up to 220 DEG C to stir 1 hour, then under agitation makes the temperature of reactant be elevated to 230 DEG C; React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure by removing formed water, opening valve discharging after having reacted, obtaining prepolymer.Prepolymer vacuum-drying at 80 DEG C, after 24 hours, is carried out solid-phase tack producing 10 hours, is obtained polyamide resin.The performance index such as the fusing point of polyamide resin are listed in table 1.
Table 1
the preparation of daiamid composition:
Listing each component concentration in table 2 ~ 4 is its parts by weight, is fed in first machine barrel of the ZSK-26 twin screw extruder comprising 12 districts by polyamide resin via a weight-loss type feed appliance.The set point temperatures of this machine barrel is in the scope of 150 DEG C-330 DEG C and by resin melting before the 5th district.In the 5th district, other solids components are passed through a weight-loss type feed appliance via the charging of a side direction sizer.This screw speed is in the scope of 150rpm to 220rpm.Extrudate is cooled and uses conventional equipment granulation.
Table 2
Table 3
Table 4
As can be seen from the embodiment 1 ~ 16 in table 2 ~ 4 and comparative example 1 ~ 9, there is not silica gel and solidify the problem not exclusively or completely cannot solidified in the daiamid composition that embodiment prepares in the silica gel solidification process in later stage.
Comparative example 1 and 2 meets the phosphorus content requirement of daiamid composition, but does not meet the requirement containing the compounds content of secondary amine group in polyamide resin, and gained daiamid composition exists the defect that silica gel does not solidify.Although comparative example 3 ~ 9 meets the requirement of terephthalic acid and the compounds content containing secondary amine group in polyamide resin, but the phosphorus content of daiamid composition is not in specified range of the present invention, and gained daiamid composition exists the defect that silica gel does not solidify equally.
Claims (10)
1. a reflector daiamid composition, by weight, comprises following component:
(A) the semiaromatic polyamide composition PA/Z of 100 parts; Wherein, based on whole monomeric unit, PA/Z comprises the repeating unit based on terephthalic acid of at least 20mol%; Based on the molar content of diamines, in PA/Z, also comprise the compound Z containing secondary amine group of 0.01 ~ 5mol%;
(B) white pigment (B1) of 9-300 part and/or reinforcing filler (B2);
It is characterized in that, based on whole component weight, the phosphorus content of this daiamid composition is 30-3000ppm.
2. reflector daiamid composition according to claim 1, is characterized in that, based on whole component weight, the phosphorus content of this daiamid composition is 50 ~ 1000ppm.
3. reflector daiamid composition according to claim 1 and 2, is characterized in that, the described compound Z containing secondary amine group is selected from NH (C
2h
4nH
2)
2, H
2n [C
2h
4nH]
2c
2h
4nH
2, H
2n [C
2h
4nH]
3c
2h
4nH
2, NH [(CH
2)
4nH
2)
2, NH [(CH
2)
5nH
2)
2, NH [(CH
2)
6nH
2)
2, NH [(CH
2)
7nH
2)
2, NH [(CH
2)
8nH
2)
2, NH [(CH
2)
9nH
2)
2, NH [(CH
2)
10nH
2)
2, NH [(CH
2)
11nH
2)
2, NH [(CH
2)
12nH
2)
2, NH [(CH
2)
13nH
2)
2, NH [(CH
2)
14nH
2)
2, NH [(CH
2)
15nH
2)
2, NH [(CH
2)
16nH
2)
2, NH [(CH
2)
17nH
2)
2, NH [(CH
2)
18nH
2)
2, H
2n (H
2c)
10nH (CH
2)
5nH
2, H
2n (H
2c)
10nH (CH
2)
6nH
2, H
2n (H
2c)
10nH (CH
2)
7nH
2, H
2n (H
2c)
10nH (CH
2)
8nH
2, H
2n (H
2c)
10nH (CH
2)
9nH
2, H
2n (H
2c)
10nH (CH
2)
11nH
2, H
2n (H
2c)
10nH (CH
2)
12nH
2, H
2n (H
2c)
9nH (CH
2)
6cH (CH
3) CH
2nH
2, H
2n (H
2c)
9nHCH
2cH (CH
3) (CH
2)
6nH
2, NH [(CH
2)
6cH (CH
3) CH
2nH
2]
2, NH [CH
2cH (CH
3) (CH
2)
6nH
2]
2in one or more.
4. the reflector daiamid composition according to any one of claim 1 ~ 3, is characterized in that, the molar content of the described compounds X containing secondary amine group is 0.05 ~ 2mol%.
5. reflector daiamid composition according to claim 1, is characterized in that, described white pigment (B1) is selected from and comprises but be not limited only to titanium dioxide, zinc oxide, zinc sulphide, white lead, zinc sulfate, barium sulfate, calcium carbonate, aluminum oxide.
6. reflector daiamid composition according to claim 5, is characterized in that, described reinforcing filler (B2) is selected from threadiness, tabular, needle-like, cross-like strengthening material, described fibee reinforced material is selected from glass fibre, carbon fiber, Kevlar, liquid crystalline polymers (LCP) fiber, the one of steel fiber or its combination, described tabular strengthening material is selected from mica, the one of talcum or its combination, described needle-like strengthening material is selected from potassium titanate crystal whisker, aluminium borate whisker, calcium carbonate crystal whisker, magnesium sulfate crystal whisker, wollastonite, sepiolite, xonotlite, the one of ZnOw or its combination, described cross-like strengthening material silicon-dioxide, aluminum oxide, barium carbonate, magnesiumcarbonate, aluminium nitride, boron nitride, potassium titanate, pure aluminium silicate (kaolin, clay, agalmatolite, wilkinite), Calucium Silicate powder, Magnesium Silicate q-agent (attapulgite), aluminum borate, calcium sulfate, barium sulfate, magnesium sulfate, asbestos, granulated glass sphere, graphite, carbon nanotube, silicon carbide, sericite, hydrotalcite, molybdenumdisulphide, resol, cross-linked styrene system resin, the one of cross-linked acrylic acid system resin or its combination.
7. reflector daiamid composition according to claim 1, is characterized in that, also comprises magnesium oxide and/or magnesium hydroxide, and its content is 0.5 ~ 10wt% based on this daiamid composition gross weight, is preferably 1 ~ 5wt%.
8. reflector daiamid composition according to claim 1, is characterized in that, also comprise calcium carbonate, and/or tetrafluoroethylene, and/or has the styrene analog thermoplastic resin of syndiotactic structure.
9. reflector daiamid composition according to claim 1, it is characterized in that, also comprise inorganic nucleator, described inorganic nucleator is selected from silica, talcum, clay, aluminum oxide, mica, zirconium white, titanium dioxide, stannic oxide, tin indium oxide, titanium tetrachloride, calcium carbonate, the one of zeolite or its combination, its content is 0.5 ~ 5wt% based on this daiamid composition gross weight, is preferably 2 ~ 4wt%.
10. reflector daiamid composition according to claim 1, it is characterized in that, also comprise antioxidant, heat-resisting stabilizing agent, photostabilizer, other polymkeric substance, impact modifier, fire retardant, white dyes, lubricant, softening agent, thickening material, static inhibitor, releasing agent, the one of pigment or its combination; Described antioxidant is selected from phenols, amine, the one of sulphur class or its combination; Described heat-resisting stabilizing agent is selected from lactone compound, vitamin-E class, hydroquinones, copper halide, the one of iodine compound or its combination; Described photostabilizer is selected from benzotriazole category, triazines, benzophenone, benzoates, hindered amines, the one of oxanilide (Oxanilide) class or its combination; Other polymkeric substance described are selected from polyolefins, ethene-propylene copolymer, ethene-1-butylene copolymer olefin copolymer, the olefin copolymers such as propylene-1-butylene copolymer, the one of polystyrene, polymeric amide, polycarbonate, polyacetal, polysulfones, polyphenylene oxide, fluoro-resin, silicone resin, LCP or its combination; Described fire retardant is selected from bromine system, chlorine system, phosphorus system, antimony system, the one of inorganic system or its combination.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602243A (en) * | 2015-11-24 | 2016-05-25 | 金发科技股份有限公司 | Polyamide composition and application thereof |
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| CN110922749A (en) * | 2019-10-26 | 2020-03-27 | 张家港大塚化学有限公司 | Preparation method of high-weather-resistance and high-reflectivity polyamide composite material for LED |
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1890323A (en) * | 2003-12-09 | 2007-01-03 | 三井化学株式会社 | Resin composition for reflector, and reflector |
| CN101155878A (en) * | 2005-04-15 | 2008-04-02 | 三井化学株式会社 | Resin composition for reflector and reflector |
| JP2008182172A (en) * | 2006-12-27 | 2008-08-07 | Toyoda Gosei Co Ltd | Resin composition for led reflector |
| CN102782048A (en) * | 2010-08-27 | 2012-11-14 | 东洋纺织株式会社 | Polyamide resin composition used for reflective plate for surface mount LED |
| CN103270114A (en) * | 2010-12-15 | 2013-08-28 | 第一毛织株式会社 | Polyamide resin composition having excellent reflectivity, heat resistance, and water resistance |
| CN103328573A (en) * | 2011-01-28 | 2013-09-25 | 可乐丽股份有限公司 | Polyamide composition for reflective plate, reflective plate, light-emitting device comprising said reflective plate, and illumination device and image display device comprising said light-emitting device |
| CN103443160A (en) * | 2011-03-15 | 2013-12-11 | 气体产品与化学公司 | Polyamides and amidoamines from selectively modified amine |
| JP2014005406A (en) * | 2012-06-26 | 2014-01-16 | Asahi Kasei Chemicals Corp | Copolymerized polyamide and copolymerized polyamide composition |
| CN103619934A (en) * | 2011-06-24 | 2014-03-05 | 阿克马法国公司 | Composition including a semi-aromatic polyamide and uses thereof, in particular for a reflector having a light-emitting diode |
| CN103642036A (en) * | 2013-11-12 | 2014-03-19 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed of same |
| CN103827209A (en) * | 2011-10-26 | 2014-05-28 | 大塚化学株式会社 | Resin composition for reflective plate and reflective plate |
| CN103911000A (en) * | 2012-12-31 | 2014-07-09 | 第一毛织株式会社 | Thermoplastic resin composition having excellent surface gloss, reflectance, anti-yellowing property and moldability |
| TW201434968A (en) * | 2013-01-11 | 2014-09-16 | Asahi Kasei Chemicals Corp | Polyamide composition and molded article |
-
2015
- 2015-01-21 CN CN201510029804.9A patent/CN104610739B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1890323A (en) * | 2003-12-09 | 2007-01-03 | 三井化学株式会社 | Resin composition for reflector, and reflector |
| CN101155878A (en) * | 2005-04-15 | 2008-04-02 | 三井化学株式会社 | Resin composition for reflector and reflector |
| JP2008182172A (en) * | 2006-12-27 | 2008-08-07 | Toyoda Gosei Co Ltd | Resin composition for led reflector |
| CN102782048A (en) * | 2010-08-27 | 2012-11-14 | 东洋纺织株式会社 | Polyamide resin composition used for reflective plate for surface mount LED |
| CN103270114A (en) * | 2010-12-15 | 2013-08-28 | 第一毛织株式会社 | Polyamide resin composition having excellent reflectivity, heat resistance, and water resistance |
| CN103328573A (en) * | 2011-01-28 | 2013-09-25 | 可乐丽股份有限公司 | Polyamide composition for reflective plate, reflective plate, light-emitting device comprising said reflective plate, and illumination device and image display device comprising said light-emitting device |
| CN103443160A (en) * | 2011-03-15 | 2013-12-11 | 气体产品与化学公司 | Polyamides and amidoamines from selectively modified amine |
| CN103619934A (en) * | 2011-06-24 | 2014-03-05 | 阿克马法国公司 | Composition including a semi-aromatic polyamide and uses thereof, in particular for a reflector having a light-emitting diode |
| CN103827209A (en) * | 2011-10-26 | 2014-05-28 | 大塚化学株式会社 | Resin composition for reflective plate and reflective plate |
| JP2014005406A (en) * | 2012-06-26 | 2014-01-16 | Asahi Kasei Chemicals Corp | Copolymerized polyamide and copolymerized polyamide composition |
| CN103911000A (en) * | 2012-12-31 | 2014-07-09 | 第一毛织株式会社 | Thermoplastic resin composition having excellent surface gloss, reflectance, anti-yellowing property and moldability |
| TW201434968A (en) * | 2013-01-11 | 2014-09-16 | Asahi Kasei Chemicals Corp | Polyamide composition and molded article |
| CN103642036A (en) * | 2013-11-12 | 2014-03-19 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed of same |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602243A (en) * | 2015-11-24 | 2016-05-25 | 金发科技股份有限公司 | Polyamide composition and application thereof |
| CN105602243B (en) * | 2015-11-24 | 2018-08-31 | 金发科技股份有限公司 | A kind of daiamid composition and its application |
| WO2017197657A1 (en) * | 2016-05-16 | 2017-11-23 | 苏州新区华士达工程塑胶有限公司 | Modified polyamide filled plastic |
| CN105907083A (en) * | 2016-05-30 | 2016-08-31 | 张日龙 | Multi-interface mobile phone charger |
| CN106084753A (en) * | 2016-06-17 | 2016-11-09 | 皖西学院 | Ultraviolet resistance stretch-proof organic composite material that a kind of LED lens are special and preparation method thereof |
| CN106084753B (en) * | 2016-06-17 | 2018-06-29 | 皖西学院 | A kind of dedicated ultraviolet resistance stretch-proof organic composite material of LED lens and preparation method thereof |
| CN110922749A (en) * | 2019-10-26 | 2020-03-27 | 张家港大塚化学有限公司 | Preparation method of high-weather-resistance and high-reflectivity polyamide composite material for LED |
| CN111500062A (en) * | 2020-05-27 | 2020-08-07 | 杭州本松新材料技术股份有限公司 | Antistatic heat-aging-resistant polyamide composite material and preparation method and application thereof |
| CN111500062B (en) * | 2020-05-27 | 2023-02-28 | 杭州本松新材料技术股份有限公司 | Antistatic heat-aging-resistant polyamide composite material and preparation method and application thereof |
| CN112940492A (en) * | 2021-03-30 | 2021-06-11 | 江苏江山红化纤有限责任公司 | Flame-retardant polyamide composite material and preparation method thereof |
| WO2024078571A1 (en) * | 2022-10-13 | 2024-04-18 | 金发科技股份有限公司 | Polyamide resin composite material, and preparation method therefor and use thereof |
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