Summary of the invention
Based on this, the object of the present invention is to provide a kind of high-temp resistant fire-retarding polybutylene terephthalate composition that can laser direct forming.
Concrete technical scheme is as follows:
Polybutylene terephthalate composition that can laser direct forming, its raw material by following weight percentage prepares:
Polybutylene terephthalate, 20-75%;
Mineral dye, 0.5-10%;
Organic hypophosphite, 5-15%;
Nitrogenated flame retardant, 5-15%
Toughner, 1-5%
Glass fibre, 10-40%;
Hinered phenols antioxidant, 0.01-1%;
Phosphite ester kind antioxidant, 0.01-1%; The summation of above-mentioned raw materials is 100%.
In some embodiment, its raw material by following weight percentage prepares therein:
Polybutylene terephthalate, 40-50%;
Mineral dye, 5-10%;
Organic hypophosphite, 5-10%;
Nitrogenated flame retardant, 5-8%
Toughner, 2%
Glass fibre, 30%;
Hinered phenols antioxidant, 0.2%;
Phosphite ester kind antioxidant, 0.2%; The summation of above-mentioned raw materials is 100%.
In some embodiment, described mineral dye is LDS additive therein.Make polybutylene terephthalate composition can be used in laser direct forming.In laser direct forming technique, described mineral dye, with after laser radiation, can discharge metal simple-substance, the reductive agent during as electroless copper, the deposition of catalytic copper metal.
Above-mentioned mineral dye is metal oxide hybrid pigment, has spinel structure or structure relevant to spinel as cupric and chromic oxide spinel; Generated through high temperature solid state reaction by Multimetal oxide, the metallic element in metal oxide is one or more in the periodic table of elements the 9th, 10 and 11 row metallic elements and Ti, Cr, Co, Mn, Ce, Nb, Fe.Powder density is at 4.5-5.8g/cm
3between, preferably at 4.8-5.6g/cm
3between, further preferably at 4.9-5.4 g/cm
3between.Particle diameter is 0.1-30 μ m, is preferably 1-8 μ m.Oil number is 5-40 g/100g, is preferably 10-30g/100g.
In some embodiment, described organic hypophosphite structural formula is therein
, wherein R
1, R
2be selected from hydrogen, C
1-C
6alkyl or aryl; M is selected from calcium, aluminium, magnesium, strontium, barium or zinc; M is 2 or 3.Hypophosporous Acid, 50 in described organic hypophosphite is selected from dimethyl Hypophosporous Acid, 50, ethylmethylphosphiniacid acid acid, methyl n-propyl Hypophosporous Acid, 50, methane two (methyl Hypophosporous Acid, 50), benzene-Isosorbide-5-Nitrae (dimethyl Hypophosporous Acid, 50), aminomethyl phenyl Hypophosporous Acid, 50 or phenylbenzene Hypophosporous Acid, 50.
Therein in some embodiment, described nitrogenated flame retardant melamine polyphosphate.
In some embodiment, described toughner is ethene-methyl acrylate-glycidyl methacrylate random terpolymer therein, and wherein active group glycidyl methacrylate accounts for the 5-11% of terpolymer gross weight; Methyl acrylate accounts for the 20-30% of terpolymer gross weight.
In some embodiment, described glass fibre is that surface is through coupling agent modified short glass fiber therein.
In some embodiment, described Hinered phenols antioxidant is β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid octadecyl ester therein; Described phosphite ester kind antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.
Another object of the present invention is to provide the preparation method of above-mentioned polybutylene terephthalate composition.
The preparation method of above-mentioned polybutylene terephthalate composition, comprises the steps:
(1) by polybutylene terephthalate in 110-130 DEG C of drying treatment 3-5h, then by dried polybutylene terephthalate and mineral dye, organic hypophosphite, nitrogenated flame retardant, toughner, Hinered phenols antioxidant, phosphite ester kind antioxidant are placed in mixing machine to be mixed 20 minutes, obtains premix;
(2) premix step (1) being obtained adds in parallel double-screw extruder through feeder, melt extrude, glass fibre adds in parallel double-screw extruder 6th district, complete processing is as follows: parallel double-screw extruder one district temperature 180-200 DEG C, two district temperature 210-220 DEG C, three district temperature 220-230 DEG C, four district temperature 220-230 DEG C, five district temperature 230-235 DEG C, six district temperature 230-235 DEG C, seven district temperature 230-235 DEG C, eight district temperature 230-235 DEG C, nine district temperature 230-235 DEG C, die head temperature 230-235 DEG C, material residence time in parallel double-screw extruder barrel is controlled at 1-3 minute,
(3) material step (2) being obtained, through tie rod, cooling, pelletizing, obtains described polybutylene terephthalate composition.
Compared with prior art, tool of the present invention has the following advantages:
1. the advantages such as polybutylene terephthalate composition of the present invention has environment-protecting asepsis, low price, and complete processing is simple.
2. polybutylene terephthalate composition of the present invention, when the thickness of 1.5mm obtains UL94 V0, also has good thermotolerance and good mechanical property.
3. polybutylene terephthalate composition of the present invention can be used for laser direct structuring technique, the bonding force good with having of metal plating.
Embodiment
The raw material that the embodiment of the present invention is used is as follows:
Polybutylene terephthalate is purchased from Changchun artificial resin company; The trade mark is 1100;
Organic hypophosphite is purchased from Clariant Exolit OP 1240;
Melamine polyphosphate clings to Melapur200-70 purchased from vapour
Glass fibre is CPP187 purchased from the Changchun artificial resin company trade mark;
Toughner ethene-methyl acrylate-glycidyl methacrylate random terpolymer is purchased from French A Kema LOTADER AX8900; ;
Mineral dye is metal oxide hybrid pigment, and purchased from Hunan Ke Le pigment company limited, its density is 4.9-5.4 g/cm
3, particle diameter is 1-8 μ m, oil number is 10-30g/100g;
The present invention is further elaborated by the following examples.
Embodiment 1
A kind of polybutylene terephthalate composition, its raw material composition and weight percentage are as follows: polybutylene terephthalate, 48.6%; Mineral dye, 5%; Organic hypophosphite (Clariant Exolit OP 1240), 8%; Melamine polyphosphate, 6%; Toughner ethene-methyl acrylate-glycidyl methacrylate random terpolymer, 2%; Hinered phenols antioxidant β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid octadecyl ester, 0.2%; Phosphite ester kind antioxidant three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 0.2%; Glass fibre, 30%.
The preparation method of above-mentioned polybutylene terephthalate composition, comprises the steps:
(1) by polybutylene terephthalate in 110-130 DEG C of drying treatment 3-5h, then by dried polybutylene terephthalate and mineral dye, organic hypophosphite, nitrogenated flame retardant, toughner, Hinered phenols antioxidant, phosphite ester kind antioxidant are placed in mixing machine to be mixed 20 minutes, obtains premix;
(2) premix step (1) being obtained adds in parallel double-screw extruder through feeder, melt extrude, glass fibre adds in parallel double-screw extruder 6th district, complete processing is as follows: parallel double-screw extruder one district temperature 180-200 DEG C, two district temperature 210-220 DEG C, three district temperature 220-230 DEG C, four district temperature 220-230 DEG C, five district temperature 230-235 DEG C, six district temperature 230-235 DEG C, seven district temperature 230-235 DEG C, eight district temperature 230-235 DEG C, nine district temperature 230-235 DEG C, die head temperature 230-235 DEG C, material residence time in parallel double-screw extruder barrel is controlled at 1-3 minute,
(3) material step (2) being obtained, through tie rod, cooling, pelletizing, obtains described polybutylene terephthalate composition.
Embodiment 2
A kind of polybutylene terephthalate composition, its raw material composition and weight percentage are as follows: polybutylene terephthalate, 45.6%; Mineral dye, 8%; Organic hypophosphite (Clariant Exolit OP 1240), 8%; Melamine polyphosphate, 6%; Toughner ethene-methyl acrylate-glycidyl methacrylate random terpolymer, 2%; Hinered phenols antioxidant β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid octadecyl ester, 0.2%; Phosphite ester kind antioxidant three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 0.2%; Glass fibre 30%.
The preparation method of above-mentioned polybutylene terephthalate composition, comprises the steps:
(1) by polybutylene terephthalate in 110-130 DEG C of drying treatment 3-5h, then by dried polybutylene terephthalate and mineral dye, organic hypophosphite, nitrogenated flame retardant, toughner, Hinered phenols antioxidant, phosphite ester kind antioxidant are placed in mixing machine to be mixed 20 minutes, obtains premix;
(2) premix step (1) being obtained adds in parallel double-screw extruder through feeder, melt extrude, glass fibre adds in parallel double-screw extruder 6th district, complete processing is as follows: parallel double-screw extruder one district temperature 180-200 DEG C, two district temperature 210-220 DEG C, three district temperature 220-230 DEG C, four district temperature 220-230 DEG C, five district temperature 230-235 DEG C, six district temperature 230-235 DEG C, seven district temperature 230-235 DEG C, eight district temperature 230-235 DEG C, nine district temperature 230-235 DEG C, die head temperature 230-235 DEG C, material residence time in parallel double-screw extruder barrel is controlled at 1-3 minute,
(3) material step (2) being obtained, through tie rod, cooling, pelletizing, obtains described polybutylene terephthalate composition.
Embodiment 3
A kind of polybutylene terephthalate composition, its raw material composition and weight percentage are as follows: polybutylene terephthalate, 43.6%; Mineral dye, 10%; Organic hypophosphite (Clariant Exolit OP 1240), 8%; Melamine polyphosphate, 6%; Toughner ethene-methyl acrylate-glycidyl methacrylate random terpolymer, 2%; Hinered phenols antioxidant β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid octadecyl ester, 0.2%; Phosphite ester kind antioxidant three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 0.2%; Glass fibre 30%.
The preparation method of above-mentioned polybutylene terephthalate composition, comprises the steps:
(1) by polybutylene terephthalate in 110-130 DEG C of drying treatment 3-5h, then by dried polybutylene terephthalate and mineral dye, organic hypophosphite, nitrogenated flame retardant, toughner, Hinered phenols antioxidant, phosphite ester kind antioxidant are placed in mixing machine to be mixed 20 minutes, obtains premix;
(2) premix step (1) being obtained adds in parallel double-screw extruder through feeder, melt extrude, glass fibre adds in parallel double-screw extruder 6th district, complete processing is as follows: parallel double-screw extruder one district temperature 180-200 DEG C, two district temperature 210-220 DEG C, three district temperature 220-230 DEG C, four district temperature 220-230 DEG C, five district temperature 230-235 DEG C, six district temperature 230-235 DEG C, seven district temperature 230-235 DEG C, eight district temperature 230-235 DEG C, nine district temperature 230-235 DEG C, die head temperature 230-235 DEG C, material residence time in parallel double-screw extruder barrel is controlled at 1-3 minute,
(3) material step (2) being obtained, through tie rod, cooling, pelletizing, obtains described polybutylene terephthalate composition.
Embodiment 4
A kind of polybutylene terephthalate composition, its raw material composition and weight percentage are as follows: polybutylene terephthalate, 47.6%; Mineral dye, 8%; Organic hypophosphite (Clariant Exolit OP 1240), 7%; Melamine polyphosphate, 5%; Toughner ethene-methyl acrylate-glycidyl methacrylate random terpolymer, 2%; Hinered phenols antioxidant β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid octadecyl ester, 0.2%; Phosphite ester kind antioxidant three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 0.2%; Glass fibre 30%.
The preparation method of above-mentioned polybutylene terephthalate composition, comprises the steps:
(1) by polybutylene terephthalate in 110-130 DEG C of drying treatment 3-5h, then by dried polybutylene terephthalate and mineral dye, organic hypophosphite, nitrogenated flame retardant, toughner, Hinered phenols antioxidant, phosphite ester kind antioxidant are placed in mixing machine to be mixed 20 minutes, obtains premix;
(2) premix step (1) being obtained adds in parallel double-screw extruder through feeder, melt extrude, glass fibre adds in parallel double-screw extruder 6th district, complete processing is as follows: parallel double-screw extruder one district temperature 180-200 DEG C, two district temperature 210-220 DEG C, three district temperature 220-230 DEG C, four district temperature 220-230 DEG C, five district temperature 230-235 DEG C, six district temperature 230-235 DEG C, seven district temperature 230-235 DEG C, eight district temperature 230-235 DEG C, nine district temperature 230-235 DEG C, die head temperature 230-235 DEG C, material residence time in parallel double-screw extruder barrel is controlled at 1-3 minute,
(3) material step (2) being obtained, through tie rod, cooling, pelletizing, obtains described polybutylene terephthalate composition.
Embodiment 5
A kind of polybutylene terephthalate composition, its raw material composition and weight percentage are as follows: polybutylene terephthalate, 41.6%; Mineral dye, 8%; Organic hypophosphite (Clariant Exolit OP 1240), 10%; Melamine polyphosphate, 8%; Toughner ethene-methyl acrylate-glycidyl methacrylate random terpolymer, 2%; Hinered phenols antioxidant β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid octadecyl ester, 0.2%; Phosphite ester kind antioxidant three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 0.2%; Glass fibre 30%.
The preparation method of above-mentioned polybutylene terephthalate composition, comprises the steps:
(1) by polybutylene terephthalate in 110-130 DEG C of drying treatment 3-5h, then by dried polybutylene terephthalate and mineral dye, organic hypophosphite, nitrogenated flame retardant, toughner, Hinered phenols antioxidant, phosphite ester kind antioxidant are placed in mixing machine to be mixed 20 minutes, obtains premix;
(2) premix step (1) being obtained adds in parallel double-screw extruder through feeder, melt extrude, glass fibre adds in parallel double-screw extruder 6th district, complete processing is as follows: parallel double-screw extruder one district temperature 180-200 DEG C, two district temperature 210-220 DEG C, three district temperature 220-230 DEG C, four district temperature 220-230 DEG C, five district temperature 230-235 DEG C, six district temperature 230-235 DEG C, seven district temperature 230-235 DEG C, eight district temperature 230-235 DEG C, nine district temperature 230-235 DEG C, die head temperature 230-235 DEG C, material residence time in parallel double-screw extruder barrel is controlled at 1-3 minute,
(3) material step (2) being obtained, through tie rod, cooling, pelletizing, obtains described polybutylene terephthalate composition.
Comparative example
A kind of polybutylene terephthalate composition, its raw material composition and weight percentage are as follows: polybutylene terephthalate, 53.6%; Organic hypophosphite (Clariant Exolit OP 1240), 8%; Melamine polyphosphate, 6%; Toughner ethene-methyl acrylate-glycidyl methacrylate random terpolymer, 2%; Hinered phenols antioxidant β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid octadecyl ester, 0.2%; Phosphite ester kind antioxidant three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 0.2%; Glass fibre 30%.
The preparation method of above-mentioned polybutylene terephthalate composition, comprises the steps:
(1) by polybutylene terephthalate in 110-130 DEG C of drying treatment 3-5h, then by dried polybutylene terephthalate and organic hypophosphite, nitrogenated flame retardant, toughner, Hinered phenols antioxidant, phosphite ester kind antioxidant are placed in mixing machine to be mixed 20 minutes, obtains premix;
(2) premix step (1) being obtained adds in parallel double-screw extruder through feeder, melt extrude, glass fibre adds in parallel double-screw extruder 6th district, complete processing is as follows: parallel double-screw extruder one district temperature 180-200 DEG C, two district temperature 210-220 DEG C, three district temperature 220-230 DEG C, four district temperature 220-230 DEG C, five district temperature 230-235 DEG C, six district temperature 230-235 DEG C, seven district temperature 230-235 DEG C, eight district temperature 230-235 DEG C, nine district temperature 230-235 DEG C, die head temperature 230-235 DEG C, material residence time in parallel double-screw extruder barrel is controlled at 1-3 minute,
(3) material step (2) being obtained, through tie rod, cooling, pelletizing, obtains described polybutylene terephthalate composition.
Embodiment 6 application experiments
The plastic component that the polybutylene terephthalate composition injection molding that the various embodiments described above and comparative example are obtained is definite shape.Use according to conventional methods wavelength 900-1080nm, energy 150-300mJ/cm
2laser carries out laser ablation to the prospective region of above-mentioned plastic component according to setting shape under the scanning speed of 0.1-1mm/s, carries out electroless plating through the plastic component of laser ablation, forms metal plating in the laser ablation district of described plastic component.
Made above-mentioned each example plastic component sample is carried out to following performance test (result is as shown in table 1):
Tensile property: press ASTM-D638 standard testing, rate of extension 50mm/min;
Impact property: press ASTM-D256 standard testing, batten thickness is 3.2mm;
Bending property: press ASTM-D790 standard testing, bending speed 10mm/min;
Flame retardant properties: press UL94 standard testing;
Plastic component surface metal plating layer sticking power test (hundred lattice tests): press ASTM D3359 standard testing
23 ± 2 DEG C of room temperatures, under the condition of relative humidity 50 ± 5%, draw 10 × 10 little grids of 1mm × 1mm with sharp cutter (knife edge angle is 15 °-30 °) in test sample surface, each is rule deeply and coating bottom; Hairbrush cleans down test zone; Firmly cling tested little grid with 3M600 adhesive tape, and with the eraser wiping adhesive tape of exerting oneself, to strengthen contact area and the dynamics in adhesive tape and tested region; Catch adhesive tape one end with hand, shut down rapidly gummed paper in the vertical direction with 60 ° of angles, same position carries out same test 2 times.
Result is judged: while requiring sticking power >=4B as qualified.
5B-scribing edge is smooth, line edge and point of crossing place all without peeling paint;
4B-has the peeling paint of small pieces at the point of crossing place of line, and the total area that comes off is less than 5%;
3B-has the peeling paint of small pieces at edge and the point of crossing place of line, and comes off the total area between 5%~15%;
2B-has peeling paint in blocks at edge and the point of crossing place of line, and comes off the total area between 15%~35%;
1B-has peeling paint in blocks at edge and the point of crossing place of line, and comes off the total area between 35%~65%;
0B-has peeling paint in blocks at edge and the point of crossing place of line, and the total area that comes off is greater than 65%.
Table 1 embodiment 1-5 and comparative example the performance test results
As seen from the above table, polybutylene terephthalate composition (embodiment 1,2,3 and comparative example) that can laser direct forming of the present invention is adding after mineral dye, there is fine sticking power with metal plating, in embodiment 2, sticking power can reach 5B, simultaneously of the present invention can laser direct forming composition also there is good thermotolerance and good mechanical property.Above-described embodiment 3, embodiment 4, embodiment 5 compare known, and embodiment 3, when the thickness that reaches 1.5mm obtains UL94 V0, also has good thermotolerance and good mechanical property.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.