CN102675865A - Polyamide resin composition and preparation method and application thereof - Google Patents
Polyamide resin composition and preparation method and application thereof Download PDFInfo
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- CN102675865A CN102675865A CN201210135255XA CN201210135255A CN102675865A CN 102675865 A CN102675865 A CN 102675865A CN 201210135255X A CN201210135255X A CN 201210135255XA CN 201210135255 A CN201210135255 A CN 201210135255A CN 102675865 A CN102675865 A CN 102675865A
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Abstract
The invention discloses a polyamide resin composition which comprises, by weight percentage, a. 20-82 wt% of high temperature resisting polyamide, b. 5-15 wt% of halogen-free flame retardant, c. 0.1-15 wt% of laser sensitive additive and d. 0-60 wt% of other additives, wherein a chemical general formula of the laser sensitive additive is XY2O4, the laser sensitive additive belongs to an isometric system, axial length a=b=c, and axial angle alpha=beta=gamma=90 degrees. X is a metal element and is a metal atom from the IIIA group, the IB group, the IIB group, the VIB group and the VIII group in the periodic table of elements. Y is a metal element and is a metal atom from the IIIA group, the IB group, the IIB group, the VIB group and the VIII group in the periodic table of elements. The other additives are one of or composition of intensifier, a powder filling agent, antioxidant and a processing agent. The sum of the total content of the weight of the components from the component a to component d is 100 wt%, and the polyamide resin composition can meet a UL94V-0 flame level under the condition of the thickness of 0.5 mm and above. The polyamide resin composition has the advantages of being capable of depositing metal selectively, having good electrical performance, and being capable of meeting the UL94V-0 flame level.
Description
Technical field
The present invention relates to a kind of Amilan polyamide resin composition, particularly a kind of can be selectively under lasing in the zone of laser scanning the Amilan polyamide resin composition of metal refining; The invention still further relates to a kind of preparation method of Amilan polyamide resin composition.
Background technology
Polyamide resin (claiming nylon again) have superior, moulding fast, advantage such as good fluidity, chemical resistance be good, often be used in fields such as mobile phone, automobile, electric component, notebook computer, household electrical appliances.In above-mentioned field, some concrete application also requires daiamid composition to have flame retardant resistance.Yet, use halogen flame that a series of shortcomings are arranged, can cause the apparent mass variation usually; Particularly under the processing temperature of heat resistant polyamide (such as 320 ℃); Halogen flame decomposes or degraded easily, and uses the product of halogen flame under the situation of being heated, also to be prone to cause environmental pollution, and it also is health risk that toxicology shows; Because people's environmental consciousness improves constantly and to the consideration of safety in utilization, halogen-free flameproof is only the inexorable trend of flame-retarded technology development.
In addition,, satisfy the various demands of electron device, particularly satisfy the three-dimensional design requirement of schematic circuit because some products of electric association area need be integrated in conducting channel on the electron device towards miniaturized, functionalization, the development of integrated aspect.In the making processes of ultra-fine schematic circuit, laser processing is a kind of important techniques means.
U.S. Pat 5773556 disclosed relevant fire retardants and compsn thereof have comprised phosphonate and/or phosphinates and/or diphosphinic acid salt and compsn thereof; Relatively stable under the processing temperature of heat-resisting semiaromatic polyamide composition compsn, but do not have to disclose it has metal refining under the effect of laser characteristic.
Chinese patent CN200480009662. X, Chinese patent CN 1860168A, Chinese patent CN 1771292A, Chinese patent CN20048028446 all disclose phosphinates and and/or diphosphinic acid salt and/or their polymkeric substance, but all do not have to disclose it has metal refining under the effect of laser characteristic.
Chinese patent CN102066122A has announced a kind of fire retardant material that can under the effect of laser, have the metal refining characteristic, can in 0.4-1.2mm, satisfy UL 94 V-0 burning grade, and mechanical property is excellent.But what require emphasis a bit is, the resin matrix in this patent is the compsn of polycarbonate or PC resin, and the typical process temperature is lower, is about 260 ℃.And in surface mounting technology (SMT), the general peak value temperature is all more than 270 ℃, and for the harsh product of ask for something, peak temperature can rise to 290 ℃, and this moment, polycarbonate and compsn thereof then can not meet the demands.
In laser processing procedure, the laser-sensitive additive in the resin matrix plays a part crucial.Patent according to having announced can know that these laser-sensitive additives can be divided into organic and inorganic two big types.Wherein the heat resisting temperature of organic laser sensitive additives probably about 200 ℃, if processing temperature is higher than 250 ℃, serious thermal weight loss phenomenon then can occur; And mostly inorganic laser-sensitive additive is under high-temperature calcination, to make; Can anti-ly surpass 600 ℃ high temperature, involved patent has Chinese patent ZL 03814691.6, Chinese patent CN 200910106506.X, U.S. Pat 006207344B1, U.S. Pat 20040241422A1, U.S. Pat 20090292051A1, PCT patent WO 2009141799A1, U.S. Pat 20090292048A1.
Along with the miniaturized of electric product, laser processing and surface mounting technology have compound Development Trend.Both required the product can be, and required the product can be high temperature resistant in SMT technology again, resin fusion and defective such as softening had not taken place at the effect deposit metal of laser; Thus; The resin that needs a kind of high temperature resistant suitable SMT technology is as carrier, such as the heat resistant polyamide compsn, so that overcome above defective.
Summary of the invention
The purpose of this invention is to provide a kind of modified resin composition, provide a kind of laser capable of using to process the high temperature resistant halogen-free flame-retardant daiamid composition that ultra-fine stereo circuit figure is fit to the SMT processing procedure simultaneously again especially.
A kind of Amilan polyamide resin composition, said compositions in weight percentage comprises:
A) the heat resistant polyamide compsn of 20-82wt%;
B) halogen-free flame retardants of 5-15wt%;
C) the laser-sensitive additive of 0.1-15wt%, its chemical general formula is XY
2O
4, tesseral system, axial length a=b=c, shaft angle α=β=γ=90 °;
Wherein, X is a metallic element, from the atoms metal of group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements, comprises a kind of in chromium metal, manganese, iron, cobalt, nickel, copper, zinc, palladium, the aluminium;
Y is a metallic element, from the atoms metal of group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements, comprises a kind of of chromium metal, manganese, iron, cobalt, nickel, copper, zinc, palladium, aluminium;
D) other additives of 0-60wt%;
Said other additives are a kind of or its compsn in the toughener, powder filled dose, oxidation inhibitor, processing aid.
Said components a)-d) the weight total content add and for 100wt%, resultant composition can satisfy UL 94 V-0 burning grade at 0.5mm and above thickness.
The heat resistant polyamide compsn of being selected for use comprises the blend composition of heat resistant polyamide, heat resistant polyamide and fatty polyamide.
Said heat resistant polyamide is made up of di-carboxylic acid unit and two amine units; Wherein the di-carboxylic acid unit comprises the aromatic dicarboxylic acid unit of 45-100 molar percentage and the aliphatic dicarboxylic acid unit with 4-12 carbon atom of 0-55 molar percentage, and two amine units are 4-14 carbon atom straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
The aromatic dicarboxylic acid unit comprises terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-dichloroterephthalicacid acid, 1,4-naphthalic acid, 4,4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid.
The aliphatic dicarboxylic acid unit comprises 1,4-Succinic Acid, 1,6-hexanodioic acid, 1,8-suberic acid, 1,9-nonane diacid, 1,10-sebacic acid, 1,11-undecane diacid, 1,12-dodecanedioic acid.
The straight chain aliphatic diamine comprises 1,4-tetramethylenediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 carbon diamines, 1,12-12 carbon diamines.
The side chain aliphatic diamine comprises the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl--1,6-hexanediamine, 2; 2,4-trimethylammonium-1,6-hexanediamine, 2,4; 4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine.
Cycloalphatic diamine comprises cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
The fatty polyamide carbochain of selecting for use is made up of 4-36 carbon atom, and typical fatty polyamide comprises PA6, PA66, PA610, PA612, the compsn of one or more among PA1010, PA11, PA12, the PA1012, but be not limited to these combinations.
The typical process temperature of the heat resistant polyamide compsn that the present invention selected for use is higher than 270 ℃.
The general formula of the halogen-free flame retardants of being selected for use is:
Wherein, R1, R2 are identical or different, comprise the alkyl and/or the aryl of 1-6 carbon atom of line style or branching.
R3 comprises the alkylidene group of 1-10 carbon atom of line style or branching, arylidene, alkyl arylene or the aryl alkylene of a 6-10 carbon atom.
M comprises the metals ion in the second and the 3rd main group in the periodic table of elements or the subgroup.
M is 2 or 3.
N is 1 or 3.
X is 1 or 2.
Employed halogen-free flame retardants comprises dimethyl-phospho acid, ethyl-methyl phospho acid, diethylammonium phospho acid, methyl-n-propylphosphinic acid, two (methyl phospho acid) methane, 1; 2-two (methyl phospho acid) ethane, 1; 6-two (methyl phospho acid) hexane, 1,4-two (methyl phospho acid) benzene, aminomethyl phenyl phospho acid, diphenyl phosphonic acid.
Employed halogen-free flame retardants can be according to the method production of having announced, such as EP 0699708.
Preferred calcium ion of M metals ion or aluminum ion.
In laser processing procedure, the laser-sensitive additive plays an important role; Laser beam is inswept at product surface, and resin matrix is ablated, and forms rough zone, can increase the cohesive strength of chemical plating metal layer and resin matrix; On the other hand; The laser-sensitive additive is under the effect of laser; Restore metallic particles attached on the rough resin matrix, in follow-up no electrochemistry plating, these metallic particles play the effect of active center; Impel the metals ion in the chemical plating fluid to deposit selectively, form mf.
The laser-sensitive additive that the present invention selected for use is a kind of high temperature resistant inorganic additive, the temperature that can bear surpass 600 ℃, the minimal structure unit that is wherein comprised is tetrahedral structure and octahedral structure.Wherein oxonium ion occupies all center of area positions, forms close-packed, and two kinds of different metallic ions are distributed to tetrahedron central position and octahedra central position respectively.The tetrahedron central position is exactly the tetrahedron intermediary space that four oxonium ions surround, and octahedra central position then is the octahedra intermediary space that six oxonium ions surround.Usually contain eight tetrahedron atoms, 16 octahedra atoms and 32 Sauerstoffatoms in a kind of complete cell configuration, so in its structural unit, the ratio of the simplest atom number that it is corresponding is 1:2:4.
The present invention selects for use in the laser-sensitive additive tetrahedron central atom from the atoms metal of group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements, comprises a kind of in chromium metal, manganese, iron, cobalt, nickel, copper, zinc, palladium, the aluminium.
Tetrahedron central atom wherein preferably comes from transition metal atoms, most preferably comes from I B family.
The present invention selects for use octahedra central atom in the laser-sensitive additive to come from the atoms metal of group IIIA in the periodic table of elements, I B family, II B family, VI B family, VII B family, VIII family, comprises a kind of in chromium metal, manganese, iron, cobalt, nickel, copper, zinc, palladium, the aluminium.
Octahedra central atom wherein preferably comes from transition metal atoms, most preferably comes from group VIB, VII B family.
The laser-sensitive additive that the present invention selected for use comprises the type of doped metallic oxide modification; MOX mainly plays the effect that improves the product form and aspect in the laser-sensitive additive; In the process of high temperature sintering; MOX can be reset its structure, and its atoms metal can enter into tetrahedron or octahedron, becomes tetrahedron central atom or octahedra central atom; Substitute the atoms metal in the original lattice, these MOXs comprise or their compsn in cupric oxide, red stone, zinc oxide, manganese oxide, aluminum oxide, titanium oxide, powder blue, Natural manganese dioxide, nickel oxide, the weisspiessglanz.
The amount of the laser-sensitive additive that the present invention selected for use is 0.1-15wt%, and preferred addition is 3-7wt%.When the addition of laser-sensitive additive during greater than 15wt%, product causes degradation phenomenas such as different plating easily in the process of no electrochemistry plating, influence the electric function of product.
Other additives that the present invention selected for use comprise a kind of or their compsn in the toughener, powder filled dose, oxidation inhibitor, processing aid.
The adding of toughener helps improving the intensity and the rigidity of resin matrix, and toughener comprises thomel, short glass fiber, special crosssection spun glass, milled glass fiber, solid or hollow glass micropearl, glass flake etc.Wherein, the length of milled glass fiber is 0.1mm-0.3mm, preferred 0.1mm-0.2mm; Chopped strand length is 1mm-5mm.
Powder filled dose adding helps improving products appearance, improves the specific inductivity/tangent of the dielectric loss angle of material, improves the functions such as flame retardant properties of material; Powder filled dose comprises talcum powder, wollastonite, kaolin, barium titanate, white titanium pigment, cupric silicate calcium, boehmite etc.
Used processing aid comprises free-flow ejector half fluoropolymer, and it forms the lubricant film of running balance between metallic walls and polymer melt in the forcing machine plastication and extrusion process, can reduce the friction of melt and metallic walls, thereby reduces the broken and die head buildup of melt.Used free-flow ejector half fluoropolymer can be selected Dynamar for use
TMFluoropolymer process aid (PPA).
What need particularly point out is that the laser-sensitive additive that the present invention selected for use also has the effect of fire-retardant synergistic except in no electrochemistry plating process, providing the metallic core in system.Reach the UL 94 V-0 burning grade of 0.5mm and above thickness; Need to add a certain amount of halogen-free flame retardants; The quality proportioning of used resin matrix and halogen-free flame retardants is 3.8:1-1.0:1, and more preferably the quality proportioning is 3.5:1-2.5:1, and the adding of laser-sensitive additive can obviously reduce the addition of halogen-free flame retardants; Make the quality proportioning of resin matrix and halogen-free flame retardants greater than 4:1, promptly the usage quantity of halogen-free flame retardants obviously reduces.
A kind of preparation method of Amilan polyamide resin composition; Comprise the steps: weight proportion weighing by feed composition; Heat resistant polyamide, laser-sensitive additive and other additives are mixed in high-speed mixer, pour Preblend in twin screw extruder master feeding hopper charging then; Fill toughener and adopt the first side feeding or the second side feeding hopper charging; Halogen-free flame retardants adopts the second side feeding or the first side feeding charging; Then through twin screw extruder extrude, pelletizing obtains title product.
Compsn according to the invention; Can be selectively under lasing in the zone of laser scanning heat resistant polyamide compsns metal, that have the halogen-free flameproof characteristic such as deposited copper, nickel, gold, tin, palladium, be mainly used in making mobile phone, computer, automobile, household electrical appliances, field such as electric.
Modified resin composition according to the invention, its advantage is:
1. said resin combination be specifically related to a kind of can be in chemical medicinal liquid after the laser ablation effect modified resin composition of mfs such as deposited copper, nickel, gold selectively; Mainly be used for making film; Prepared product has the advantage that wiring is even, minimum spacing is little, is particularly suitable for SMT and uses film article;
This film can with the base material pressing after be applied in the technology of intellective IC card and laser formation stereo circuit; Wherein the laser-sensitive additive is an inorganic additives; Its heat resisting temperature surpasses 600 ℃, is fit to the courses of processing such as the extruding of fire resistant resin matrix, injection moulding, mold pressing, extruding, coextrusion or lamination fully;
3. described laser-sensitive additive has also played the effect of fire-retardant synergistic in flame-retardant formulations, can obviously reduce the addition of halogen-free flame retardants;
4. resultant composition can satisfy UL94V-0 burning grade at 0.5mm and above thickness.
Description of drawings
Fig. 1 is the cell configuration of laser-sensitive additive;
Fig. 2 is octahedra synoptic diagram;
Fig. 3 is the tetrahedron synoptic diagram.
Embodiment
Below in conjunction with embodiment and Comparative Examples the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Because said inventive principle is to the universal validity of other polyamide resin matrixes of not mentioning, thereby be not suitable for claim of the present invention is contracted in the scope of embodiments that provides.
The laser-sensitive additive of selecting for use among the embodiment has copper chromium type laser-sensitive additive, copper manganese type laser-sensitive additive, and its structure is shown in Fig. 1-3, and wherein, stain is that tetrahedron atom, cross point are that octahedra atom, hollow dots are Sauerstoffatom.Chromium ion and mn ion all can be oxidized to high valence state metals ion under the effect of laser, and chromium will become the poisonous hexavalent chromium metals ion.However; Copper manganese type additive cited in claims is one of optimal selection; No toxic metal ion produces in laser processing procedure, no electrochemistry plating process; But can not deny in view of the above that other laser-sensitive additives can play same effect in laser processing procedure and follow-up no electrochemistry plating process, can not deny the cupric chromium laser-sensitive additive of doping vario-property and the keying action that copper manganese laser-sensitive additive is played in laser processing procedure, no electrochemistry plating process.
Embodiment 1
The resin matrix of selecting for use is PA10T, and addition is 40wt%, from golden hair science and technology; Halogen-free flame retardants is diethylammonium phospho acid aluminium, and 10wt% is from Clariant company (following examples are identical with Comparative Examples); The laser-sensitive additive is a copper manganese type laser-sensitive additive, and metallic zinc is oxide doped and modified, 5wt%, and pigment (following examples are identical with Comparative Examples) is reined in by the section of coming from.Above-mentioned each component is proportionally mixed the back from the blanking of twin screw extruder master feeding hopper.Other adds the 45wt% glass, from the charging of side feeding.Extrude, cooling, pelletizing promptly obtains title product.Test no electrochemistry plating gained thickness of metal film 8-12 um, hundred lattice test mf come off area 5%, the UL94 grade/thickness 0.5mm that burns, V-0 grade.
Embodiment 2
The resin matrix of selecting for use is PA9T/66, and addition is 20wt%; Halogen-free flame retardants is diethylammonium phospho acid aluminium, 5wt%; The laser-sensitive additive is a copper chromium type laser-sensitive additive, 15wt%.Above-mentioned each component is proportionally mixed the back from the blanking of twin screw extruder master feeding hopper.Other adds the 60wt% glass, from the charging of side feeding; Extrude, cooling, pelletizing promptly obtains title product.Test no electrochemistry plating gained thickness of metal film 8-12 um, hundred lattice test mf come off area 5%, the UL94 grade/thickness 0.5mm that burns, V-0 grade.
Embodiment 3
The resin matrix of selecting for use is PA6T/66+PA610, and addition is 68wt%; Halogen-free flame retardants is diethylammonium phospho acid aluminium, 15wt%; The laser-sensitive additive is a copper chromium type laser-sensitive additive, manganese metal oxide doped and modified, 7wt%.Above-mentioned each component is proportionally mixed the back from the blanking of twin screw extruder master feeding hopper.Other adds the 10wt% wollastonite, from the charging of side feeding.Extrude, cooling, pelletizing promptly obtains title product.Test no electrochemistry plating gained thickness of metal film 8-12 um, hundred lattice test mf come off area 5%, the UL94 grade/thickness 0.5mm that burns, V-0 grade.
Embodiment 4
The resin matrix of selecting for use is PA4T/66+PA66, and addition is 56wt%; Halogen-free flame retardants is diethylammonium phospho acid aluminium, 13wt%; The laser-sensitive additive is a copper chromium type laser-sensitive additive, manganese metal oxide doped and modified, 1wt%.Above-mentioned each component is proportionally mixed the back from the blanking of twin screw extruder master feeding hopper.Other adds the 30wt% talcum powder, from the charging of side feeding.Extrude, cooling, pelletizing promptly obtains title product.Test no electrochemistry plating gained thickness of metal film < 8 um, hundred lattice test mf come off area>5%, the UL94 grade/thickness 0.5mm that burns, V-1 grade.
Comparative Examples 1
The resin matrix of selecting for use is PA10T/66+PA1012, and addition is 69wt%; Halogen-free flame retardants is diethylammonium phospho acid aluminium, 18wt%.Above-mentioned each component is proportionally mixed the back from the blanking of twin screw extruder master feeding hopper.Other adds 13wt% profiled-cross-section glass (long-width ratio is greater than 2), from the charging of side feeding.Extrude, cooling, pelletizing promptly obtains title product.Test UL94 burning grade/thickness 0.5mm, the V-0 grade.Owing to do not add the laser-sensitive additive, so resin matrix can not metal plated in follow-up no electrochemistry plating process.
Comparative Examples 2
The resin matrix of selecting for use is PA46, and addition is 37wt%; Halogen-free flame retardants is diethylammonium phospho acid aluminium, 13wt%.Above-mentioned each component is proportionally mixed the back from the blanking of twin screw extruder master feeding hopper.Other adds 50wt% profiled-cross-section glass (long-width ratio >=2), from the charging of side feeding.Extrude, cooling, pelletizing promptly obtains title product.Test UL94 burning grade/thickness 0.5mm, the V-2 grade.Owing to do not add the laser-sensitive additive, so resin matrix can not metal plated in follow-up no electrochemistry plating process.
The judgement criteria that adopts has: metal film thickness test, the test of hundred lattice.Wherein, The test of hundred lattice is lattice that the mf that deposits is divided into 1mm*1mm with hundred lattice cuttves or cutter; Stick the rapidly vertical pull-up in back with adhesive tape, calculate the mf zone and the regional percentage of virgin metal film that come off, qualified less than 5%.Embodiment and Comparative Examples result show as shown in table 1.
The result shows that the laser-sensitive additive can produce metallic core under the effect of laser, and in follow-up no electrochemistry plating process, can make the smooth metal plated film of product; In addition, the adding of laser-sensitive additive can also be played the fire-retardant effect of synergistic, can obviously reduce the usage quantity of halogen-free flame retardants.
Table 1 embodiment and Comparative Examples test result
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 |
| Resin matrix/wt% | 40 | 20 | 68 | 56 | 69 | 37 |
| Halogen-free flame retardants/wt% | 10 | 5 | 15 | 13 | 18 | 13 |
| Laser-sensitive additive/wt% | 5 | 15 | 7 | 1 | 0 | 0 |
| Thickness of metal film test/um | 8-12 | 8-12 | 8-12 | <8 | 0 | 0 |
| Hundred lattice test/% | <5 | <5 | <5 | <5 | - | - |
| UL94 grade/thickness the 0.5mm that burns | V-0 | V-0 | V-0 | V-1 | V-0 | V-2 |
Claims (21)
1. an Amilan polyamide resin composition is characterized in that, said compositions in weight percentage comprises:
The heat resistant polyamide compsn of 20-82wt%;
The halogen-free flame retardants of 5-15wt%;
The laser-sensitive additive of 0.1-15wt%, its chemical general formula are XY
2O
4, tesseral system, axial length a=b=c, shaft angle α=β=γ=90 °;
Wherein, X is a metallic element, from the atoms metal of group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements, comprises a kind of in chromium metal, manganese, iron, cobalt, nickel, copper, zinc, palladium, the aluminium;
Y is a metallic element, from the atoms metal of group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements, comprises a kind of of chromium metal, manganese, iron, cobalt, nickel, copper, zinc, palladium, aluminium;
Other additives of 0-60wt%;
Said other additives are a kind of or its compsn in the toughener, powder filled dose, oxidation inhibitor, processing aid;
Said components a)-d) the weight total content add and for 100wt%, resultant composition can satisfy UL 94 V-0 burning grade at 0.5mm and above thickness.
2. Amilan polyamide resin composition according to claim 1 is characterized in that said heat resistant polyamide compsn comprises the blend composition of heat resistant polyamide or heat resistant polyamide and fatty polyamide.
3. Amilan polyamide resin composition according to claim 1 is characterized in that said heat resistant polyamide compsn comprises the blend composition of heat resistant polyamide or heat resistant polyamide and fatty polyamide.
4. Amilan polyamide resin composition according to claim 2; It is characterized in that; Said heat resistant polyamide is made up of di-carboxylic acid unit and two amine units; Wherein the di-carboxylic acid unit comprises the aromatic dicarboxylic acid unit of 45-100 molar percentage and the aliphatic dicarboxylic acid unit with 4-12 carbon atom of 0-55 molar percentage, and two amine units are 4-14 carbon atom straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
5. Amilan polyamide resin composition according to claim 3; It is characterized in that said aromatic dicarboxylic acid unit comprises terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2; 6-dichloroterephthalicacid acid, 1; 4-naphthalic acid, 4,4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid.
6. Amilan polyamide resin composition according to claim 3 is characterized in that, said aliphatic dicarboxylic acid unit comprises 1,4-Succinic Acid, 1; 6-hexanodioic acid, 1,8-suberic acid, 1,9-nonane diacid, 1; 10-sebacic acid, 1,11-undecane diacid or 1,12-dodecanedioic acid.
7. Amilan polyamide resin composition according to claim 3 is characterized in that, said straight chain aliphatic diamine comprises 1,4-tetramethylenediamine, 1; 6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1; 10-decamethylene diamine, 1,11-11 carbon diamines or 1,12-12 carbon diamines.
8. Amilan polyamide resin composition according to claim 3 is characterized in that, said side chain aliphatic diamine comprises the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid; 5-pentamethylene diamine, 2,4-dimethyl--1,6-hexanediamine, 2,2; 4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1; 6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine.
9. Amilan polyamide resin composition according to claim 3 is characterized in that, said cycloalphatic diamine comprises cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
10. Amilan polyamide resin composition according to claim 2; It is characterized in that; Said fatty polyamide carbochain is made up of 4-36 carbon atom, specifically comprises PA6, PA66, PA610, PA612, the compsn of one or more among PA1010, PA11, PA12, the PA1012.
11. Amilan polyamide resin composition according to claim 1 is characterized in that, the general formula of the halogen-free flame retardants of being selected for use is:
Wherein, R1, R2 are identical or different, comprise the alkyl and/or the aryl of 1-6 carbon atom of line style or branching;
R3 comprises the alkylidene group of 1-10 carbon atom of line style or branching, arylidene, alkyl arylene or the aryl alkylene of a 6-10 carbon atom;
M comprises the metals ion in the second and the 3rd main group in the periodic table of elements or the subgroup;
M is 2 or 3;
N is 1 or 3;
X is 1 or 2.
12. Amilan polyamide resin composition according to claim 1; It is characterized in that; Employed halogen-free flame retardants comprises dimethyl-phospho acid, ethyl-methyl phospho acid, diethylammonium phospho acid, methyl-n-propylphosphinic acid, two (methyl phospho acid) methane, 1; 2-two (methyl phospho acid) ethane, 1,6-two (methyl phospho acid) hexane, 1, the compsn of one or more in 4-two (methyl phospho acid) benzene, aminomethyl phenyl phospho acid or the diphenyl phosphonic acid.
13. Amilan polyamide resin composition according to claim 1 is characterized in that, the tetrahedron atom of the laser-sensitive additive of being selected for use is selected from I B family.
14. Amilan polyamide resin composition according to claim 1 is characterized in that, the octahedra atom override of the laser-sensitive additive of being selected for use is selected from group VIB, VII B family.
15., it is characterized in that the tetrahedron atom override of described laser-sensitive additive is selected from the period 4 element according to claim 1 or 13 described Amilan polyamide resin compositions.
16., it is characterized in that the octahedra atom override of described laser-sensitive additive is selected from the period 4 element according to claim 1 or 14 described Amilan polyamide resin compositions.
17., it is characterized in that described laser-sensitive additive comprises the type of doped metallic oxide modification according to the described Amilan polyamide resin composition of arbitrary claim among claim 1, the 11-14.
18. Amilan polyamide resin composition according to claim 1; It is characterized in that said filling toughener comprises a kind of or its compsn in thomel, short glass fiber, special crosssection spun glass, milled glass fiber, solid or hollow glass micropearl, the glass flake.
19. Amilan polyamide resin composition according to claim 1 is characterized in that, the length of said milled glass fiber is 0.1-0.3mm.
20. the preparation method of the said Amilan polyamide resin composition of claim 1-16; Comprise the steps; Press the weight proportion weighing of feed composition; Heat resistant polyamide, laser-sensitive additive and other additives are mixed in high-speed mixer, pour Preblend in twin screw extruder master feeding hopper charging then; Fill toughener and adopt the first side feeding or the second side feeding hopper charging; Halogen-free flame retardants adopts the second side feeding or the first side feeding charging; Then through twin screw extruder extrude, pelletizing obtains title product.
21. the application of the described Amilan polyamide resin composition of claim 1-19 in making mobile phone, computer, automobile, household electrical appliances, electric part field.
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| CN103450654A (en) * | 2013-09-04 | 2013-12-18 | 上海锦湖日丽塑料有限公司 | Resin capable of directly formed by laser and preparation method thereof |
| WO2014008669A1 (en) * | 2012-07-13 | 2014-01-16 | 金发科技股份有限公司 | Modified resin composition used for depositing a metal film, preparation method and use thereof |
| CN103694698A (en) * | 2012-09-27 | 2014-04-02 | 金发科技股份有限公司 | Polyamide composition for selectively depositing metals, and preparation method and application thereof |
| CN106675012A (en) * | 2016-12-05 | 2017-05-17 | 广东中塑新材料有限公司 | LDS polyamide composite material and preparation method thereof |
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| CN106675012A (en) * | 2016-12-05 | 2017-05-17 | 广东中塑新材料有限公司 | LDS polyamide composite material and preparation method thereof |
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Application publication date: 20120919 |