CN111087797A - Laser direct forming resin composition with improved impact resistance, preparation method and application thereof - Google Patents
Laser direct forming resin composition with improved impact resistance, preparation method and application thereof Download PDFInfo
- Publication number
- CN111087797A CN111087797A CN201811235064.4A CN201811235064A CN111087797A CN 111087797 A CN111087797 A CN 111087797A CN 201811235064 A CN201811235064 A CN 201811235064A CN 111087797 A CN111087797 A CN 111087797A
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- CN
- China
- Prior art keywords
- resin composition
- maleic anhydride
- laser
- ethylene
- laser direct
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 41
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 16
- 239000012190 activator Substances 0.000 claims abstract description 12
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- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 19
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- 238000004898 kneading Methods 0.000 claims description 9
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 9
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 9
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- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
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- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- YJLVKRVGSARISS-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphite Chemical compound CC1=CC=CC(C)=C1OP(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C YJLVKRVGSARISS-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention relates to a laser direct structuring resin composition with improved shock resistance, a preparation method and application thereof, and mainly solves the problems of low impact strength and toughness of a high molecular composite material which can be used for laser direct structuring in the prior art. The resin composition directly molded by adopting laser comprises the following components: 50-90 parts of thermoplastic resin; 1-15 parts of a laser activator; 3-15 parts of a toughening compatilizer; 0.1-5 parts of a surface modifier; 1-20 parts of an auxiliary agent; the toughening compatilizer is selected from at least one of maleic anhydride graft copolymer, ethylene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene-octene-maleic anhydride copolymer, ethylene-vinyl acetate-maleic anhydride copolymer and ethylene-acrylate-maleic anhydride copolymer, so that the problems are well solved, and the toughening compatilizer can be used for parts such as communication, electronics, automobiles, medical treatment, aerospace and the like.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and relates to a laser direct forming resin composition with improved impact resistance and a preparation method thereof. The laser direct structuring resin composition with improved impact resistance is suitable for parts such as communication, electronics, automobiles, medical treatment, aerospace and the like.
Background
Laser direct structuring is a 3D molded interconnect device production technique that combines processing modification, injection molding, laser lasing, and electroless plating processes. The principle is that the universal plastic elements, circuit boards and the like are endowed with electrical interconnection functions, so that the plastic shell and the structural device have the functions of supporting, protecting and the like, and also have the functions of shielding, antenna and the like generated by combining with a conductive circuit.
The laser direct forming material is mainly characterized in that a laser activating agent is introduced into matrix resin to obtain modified plastic particles, the plastic particles are formed into a workpiece through injection molding, and then the workpiece is activated by laser and then chemically plated to form a conductive path. The technology has the advantages that the number of electronic components can be reduced, the space is saved, and the production flexibility is improved; if the conductive circuit needs to be changed, the method can be realized only by adjusting the laser scanning motion track without redesigning a mold, has the advantages of freer circuit design, quicker production speed, simpler flow, more controllable cost and the like, and is widely applied to the aspects of mobile phone antennas, notebook computers, electronic medical treatment, automobile instrument panels, aerospace and the like.
The laser direct structuring technology was first developed by the company LPKF laser and electronics, germany, whose patent CN1518850A describes a conductor track structure on a non-conductive carrier material and a method for its production. Saudi basic Global technology Limited patent CN 105102520A reports a process for the preparation of high flexural and tensile modulus laser direct structuring composites containing glass reinforcement components, which at the same time poses the problem of a great compromise in the toughness of the material. The company patents CN105026494A and CN 104937032A disclose that a polysiloxane-polycarbonate copolymer and a high rubber graft acrylonitrile-butadiene-styrene copolymer are respectively compounded with polycarbonate to prepare a high impact laser direct forming material. However, the above-mentioned polymer materials are used in large amounts and have high production costs themselves, resulting in economical problems in industrial applications and thus limiting the applications thereof.
Therefore, it is important to develop a laser direct structuring material having an optimum balance among workability, platability, usability, and economy.
Disclosure of Invention
The invention aims to solve the technical problem that the high polymer composite material for laser direct forming in the prior art is low in impact strength and toughness after being added with a laser activator, and provides a laser direct forming resin composition with improved impact resistance. The laser direct forming resin composition with improved impact resistance meets the requirements of usability and formability of parts, and meanwhile, the impact toughness is obviously improved, so that the resin composition is suitable for parts such as communication, electronics, automobiles, medical treatment, aerospace and the like.
The second technical problem to be solved by the present invention is to provide a method for preparing a laser direct structuring resin composition having improved impact resistance in accordance with the first technical problem.
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a laser direct structuring resin composition having improved impact resistance.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a laser direct structuring resin composition with improved impact resistance comprises the following components in parts by weight:
(A) 50-90 parts of thermoplastic resin;
(B) 1-15 parts of a laser activator;
(C) 3-15 parts of a toughening compatilizer;
(D) 0.1-5 parts of a surface modifier;
(E) 1-20 parts of an auxiliary agent;
wherein the toughening compatibilizer is at least one selected from the group consisting of a maleic anhydride graft copolymer of polyethylene, a maleic anhydride graft copolymer of polypropylene, a maleic anhydride graft copolymer of ethylene-propylene copolymer, a maleic anhydride graft copolymer of ethylene-octene copolymer, a maleic anhydride graft copolymer of ethylene-vinyl acetate copolymer, a maleic anhydride graft copolymer of ethylene-acrylate copolymer, and an ethylene-maleic anhydride copolymer, an ethylene-propylene-maleic anhydride copolymer, an ethylene-octene-maleic anhydride copolymer, an ethylene-vinyl acetate-maleic anhydride copolymer, and an ethylene-acrylate-maleic anhydride copolymer.
In the above technical solution, the thermoplastic resin is preferably at least one selected from the group consisting of polyester, polyamide, acrylonitrile-butadiene-styrene copolymer, and polyphenylene sulfide.
In the above technical solution, the laser activator is preferably at least one of oxides and salts containing aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, palladium, silver, tin, antimony, platinum, and gold.
In the above technical solution, the surface modifier is preferably at least one selected from polysiloxane, organosiloxane, organic titanate, and organic aluminate.
In the technical scheme, the auxiliary agent is preferably selected from reinforcing agents, flame retardants, plasticizers, heat stabilizers, lubricants, antistatic agents, antioxidants, UV absorbers and mold release agents.
In the above-mentioned aspect, the molded sample of the laser direct structuring resin composition having improved impact resistance preferably has a function of being plated after laser activation to form a conductive path and has a thickness of more than 15kJ/m2The impact strength of the gap of the simply supported beam.
In the above technical solution, the reinforcing agent is preferably at least one selected from talc, mica, glass beads, glass fibers, carbon fibers, asbestos fibers, ceramic fibers, cotton fibers, and aramid fibers.
In the technical scheme, the flame retardant is preferably at least one of triphenyl phosphate, triisopropylphenyl phosphate, tributyl phosphate and trioctyl phosphate.
In the above technical solution, the plasticizer is preferably at least one selected from phthalate, glyceryl tristearate and epoxidized soybean oil.
In the above technical solution, the heat stabilizer is preferably at least one selected from triphenyl phosphite, tris- (2, 6-dimethylphenyl) phosphite, trimethyl phosphate, dimethylphenyl phosphate, and benzotriazole.
In the above technical solution, the lubricant is preferably at least one selected from methyl stearate, polyethylene glycol and polypropylene glycol.
In the above technical solution, the antistatic agent is preferably at least one selected from glyceryl monostearate, sodium stearyl sulfonate, sodium dodecylbenzenesulfonate and carbon materials.
In the above technical solution, the antioxidant is preferably at least one selected from the group consisting of tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2, 6-di-tert-butyl-4-methylphenol.
In the above technical solution, the UV absorber is preferably at least one selected from hydroxybenzodiazole, hydroxybenzotriazine, hydroxybenzophenone, benzoxazinone, nano-sized titanium dioxide, and zinc oxide.
In the above technical solution, the release agent is preferably at least one selected from zinc stearate, calcium stearate, barium stearate, magnesium stearate, stearyl stearate, pentaerythritol tetrastearate, and paraffin.
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a laser direct structuring resin composition with improved impact resistance according to any one of the above-mentioned technical solutions to solve any one of the above-mentioned problems, comprising the steps of:
and blending required amounts of the thermoplastic resin, the laser activator, the toughening compatilizer, the surface modifier and the auxiliary agent, and then carrying out melt kneading extrusion or calendaring molding to obtain the laser direct forming resin composition with improved impact resistance.
In the technical scheme, the laser activator and the auxiliary agent can be subjected to surface treatment in advance.
In order to solve the third technical problem, the invention adopts the technical scheme that: use of the laser direct structuring resin composition with improved impact resistance according to any one of the above-mentioned technical solutions to solve one of the technical problems.
In the above technical solutions, the applications are not particularly limited, and those skilled in the art can use the present invention in addition to the prior art, for example, but not limited to, the present invention is used for manufacturing electronic and electric components.
In the technical scheme, the laser activator plays an important role in the laser processing process of the resin composition. The laser beam quickly sweeps over the surface of a workpiece made of the resin composition to ablate the matrix resin to form an uneven scanning area, so that the bonding strength between the electroless metal plating layer and the matrix resin can be increased. Meanwhile, the laser activator reduces metal particles to be attached to the uneven surface of the matrix resin under the action of laser, and in the subsequent chemical plating process, the metal particles play a role of activating points to promote metal ions in the chemical plating solution to selectively deposit on the surface of the metal particles, so that a metal plating layer film is formed.
The method of the invention introduces the proper toughening compatilizer and laser activator into the thermoplastic resin, the inventor finds that the impact toughness of the prepared laser direct forming resin composition with improved impact resistance is obviously improved while the usability and the processing formability of the material are kept, a molded sample prepared from the resin composition has the function of being plated to form a conductive path after being activated by laser, and the molded sample shows more than 15kJ/m2The impact strength of the simple beam notch is superior to that of a conventional toughening agent modification system, probably because reactive maleic anhydride contained in toughening compatilizer molecules and amide groups in matrix resin generate an anhydride-amide exchange reaction, the compatibility between the matrix resin and the toughening compatilizer is improved through a formed new covalent bond, and the interfacial stress is reduced, so that a smaller and better-dispersed toughening agent system is formed.
By adopting the technical scheme of the invention, the obtained laser direct forming resin composition with improved impact resistance has obviously improved impact toughness while maintaining the usability and the processing formability of materials, and the composition is prepared fromThe molded sample made of the resin composition has a function of being plated to form a conductive path after laser activation, and exhibits more than 15kJ/m2The impact strength of the simple supporting beam gap obtains better technical effect.
The performance of the invention was determined as follows:
and (3) testing the impact strength of the notch of the simply supported beam: measured according to ISO 179 standard with a pendulum impact tester, Ceast, Italy.
And (3) testing the thickness of the chemical plating layer: measured according to ASTM B568(2009) using a Fischer scope x-ray fluorescence coating thickness gauge, Germany.
The invention is further illustrated by the following specific examples.
Detailed Description
[ examples 1 to 5 ]
A laser direct structuring resin composition having improved impact resistance was prepared by feeding 93 parts in total of dried polyamide 6 chips (PA6, 250 ℃ C., 2160g melt index 9.3g/10min) and an ethylene-propylene copolymer-grafted maleic anhydride copolymer (EPGM, ethylene content 82.0%, propylene content 18.0%, graft ratio 1.2%), 2 parts of silicone powder, 5 parts of basic copper phosphate, 0.8 part of tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 1 part of white oil into a high-speed mixer, blending for 1 minute, introducing the blended materials into a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40), melt-kneading, extruding and granulating to obtain laser direct structuring resin compositions I to III, and processing parameters are shown in Table 1.
TABLE 1
| Examples | Composition comprising a metal oxide and a metal oxide | PA 6/portion | EPGM per part | Processing temperature/. degree.C | Screw speed/revolution/minute | torque/N.m | Melt pressure/bar |
| 1 | I | 87 | 6 | 260 | 250 | 11.0～12.0 | 14～19 |
| 2 | II | 84 | 9 | 270 | 250 | 9.3～10.3 | 11～20 |
| 3 | III | 81 | 12 | 270 | 250 | 11.7～12.4 | 29～35 |
Injection molding test: the processing temperature is 265 ℃ and the die temperature is 55 ℃. And (3) adopting a BOY injection molding machine to injection mold the dried laser direct structuring resin composition I-III into a standard sample strip, placing the standard sample strip in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
Laser activation: a semiconductor end face pump solid laser is adopted, the laser wavelength is 1064nm, the laser speed is 2000 mm/s, the laser energy is 15W, and the pulse repetition frequency is 30 kHz.
Chemical plating: the laser-activated samples were electroless plated using electroless plating methods and processes known in the art, with a copper plating time of 2 hours and a nickel plating time of 10 minutes.
The results of the comprehensive property tests of the laser direct structuring resin compositions I to III are shown in Table 2.
TABLE 2
| Composition comprising a metal oxide and a metal oxide | Impact strength/kJ/m of simply supported beam gap2 | Thickness of copper plating layer/. mu.m | Thickness of nickel plating layer/mum |
| I | 17.7 | 15.3 | 2.0 |
| II | 49.4 | 15.6 | 2.3 |
| III | 67.0 | 15.0 | 2.1 |
The maleic anhydride structural units on the EPGM molecular chains of the ethylene-propylene copolymer grafted maleic anhydride copolymers adopted in the embodiments I-III can perform anhydride-amide exchange reaction with amide groups in the matrix resin to form block type, graft type and net-shaped macromolecular structures, so that the molecular weight of the matrix polymer is enlarged, the compatibility between the toughening agent and the matrix resin is improved, and the toughness and the impact resistance of the composition are improved.
[ examples 4 to 6 ]
A laser direct structuring resin composition having improved impact resistance was prepared by subjecting 84 parts of dried polyamide 6 chips (PA6, 250 ℃ C., 2160g melt index 9.3g/10min), an ethylene-vinyl acetate copolymer-grafted maleic anhydride copolymer (EVGM, ethylene content 80.0%, vinyl acetate content 20.0%, graft ratio 1.3%), an ethylene-octene copolymer-grafted maleic anhydride copolymer (OEGM, ethylene content 87.0%, octene content 13.0%, graft ratio 0.8%), or a polyethylene-grafted maleic anhydride copolymer (PEGM, graft ratio 0.8%), 2 parts of silicone powder, 5 parts of basic copper phosphate, 0.8 parts of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1 part of white oil to a high-speed mixer, mixing for 1 minute, introducing the mixed material into a LABTECH co-rotating twin screw extruder (screw diameter 16 mm, kneading 40), melt-extruding and pelletizing the resulting resin composition as indicated in Table IV-3.
TABLE 3
| Examples | Composition comprising a metal oxide and a metal oxide | Toughening agent | Processing temperature/. degree.C | Screw speed/revolution/minute | torque/N.m | Melt pressure/bar |
| 2 | II | EPGM | 270 | 250 | 9.3～10.3 | 11～20 |
| 4 | IV | EVGM | 270 | 250 | 14.8～15.8 | 14～18 |
| 5 | V | OEGM | 270 | 250 | 12.4～12.9 | 8～11 |
| 6 | VI | PEGM | 270 | 250 | 1.6～1.9 | 0～1 |
Injection molding test: the processing temperature is 265 ℃ and the die temperature is 55 ℃. And (3) adopting a BOY injection molding machine to injection mold the dried laser direct structuring resin composition IV-VI into a standard sample strip, placing the standard sample strip in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
Laser activation: a semiconductor end face pump solid laser is adopted, the laser wavelength is 1064nm, the laser speed is 2000 mm/s, the laser energy is 15W, and the pulse repetition frequency is 30 kHz.
Chemical plating: the laser activated coupons were electroless plated for 2 hours using electroless plating methods and processes known in the art.
The results of the comprehensive property tests of the laser direct structuring resin compositions IV to VI are shown in Table 4.
TABLE 4
| Composition comprising a metal oxide and a metal oxide | Impact strength/kJ/m of simply supported beam gap2 | Thickness of copper plating layer/. mu.m |
| II | 49.4 | 15.6 |
| IV | 32.2 | 14.5 |
| V | 42.0 | 15.0 |
| VI | 30.3 | / |
The maleic anhydride structural units on the molecular chains of the different polyolefin polymer grafted maleic anhydride copolymers used in examples 2 and 4 to 6 can undergo an anhydride-amide exchange reaction with amide groups in the matrix resin to form block, graft and network macromolecular structures, the molecular weight of the matrix polymer is expanded, the compatibility between the two is improved by the formed new covalent bonds, and the polyolefin polymer has the extremely high flexibility and is combined with the polyamide polymer to endow the polyamide polymer with high impact strength and improve the toughness of the matrix resin.
[ examples 7 to 8 ]
A laser direct structuring resin composition with improved impact resistance was prepared by subjecting 84 parts of dried polyamide 6 chips (PA6, 250 ℃ C., 2160g melt index 9.3g/10min), 9 parts of ethylene-methyl acrylate-maleic anhydride copolymer (EAM, ethylene content 84.0%, methyl acrylate content 15.0%, maleic anhydride content 1.0%) or ethylene-glycidyl acrylate-maleic anhydride copolymer (EGM, ethylene content 89.0%, glycidyl acrylate content 10.2%, maleic anhydride content 0.8%), 2 parts of silicone powder, 5 parts of basic copper phosphate, 0.8 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1 part of white oil to a blending treatment in a high-speed mixer for 1 minute, introducing the blended material into a double-screw extruder (screw diameter 16 mm, length-diameter ratio 40), granulating and melt kneading to obtain a laser direct structuring resin composition VII-VIII, processing parameters are shown in Table 5.
TABLE 5
| Examples | Composition comprising a metal oxide and a metal oxide | Toughening agent | Processing temperature/. degree.C | Screw speed/revolution/minute | torque/N.m | Melt pressure/bar |
| 7 | VII | EAM | 270 | 250 | 10.8～13.0 | 10～16 |
| 8 | VIII | EGM | 270 | 250 | 9.5～12.8 | 8～15 |
Injection molding test: the processing temperature is 265 ℃ and the die temperature is 55 ℃. And (3) adopting a BOY injection molding machine to injection mold the dried laser direct structuring resin composition VII-VIII into a standard sample strip, placing the standard sample strip in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
Laser activation: a semiconductor end face pump solid laser is adopted, the laser wavelength is 1064nm, the laser speed is 2000 mm/s, the laser energy is 15W, and the pulse repetition frequency is 30 kHz.
Chemical plating: the laser activated coupons were electroless plated for 2 hours using electroless plating methods and processes known in the art.
The results of the comprehensive performance tests on the laser direct structuring resin compositions VII to VIII are shown in Table 6.
TABLE 6
| Composition comprising a metal oxide and a metal oxide | Impact strength/kJ/m of simply supported beam gap2 | Thickness of copper plating layer/. mu.m |
| VII | 40.8 | 14.5 |
| VIII | 45.5 | 14.9 |
The maleic anhydride structural units and the acrylic ester structural units on the molecular chains of the polyethylene-acrylic ester-maleic anhydride copolymers adopted in examples 7 to 8 can respectively perform anhydride-amide exchange reaction or ester-amide exchange reaction with amide groups in the matrix resin to form block type, graft type and net-shaped macromolecular structures, the molecular weight of the matrix polymer is increased, the compatibility between the polyolefin toughening grade and the polyamide matrix resin is improved by newly formed covalent bonds, and the polyethylene-acrylic ester-maleic anhydride copolymers are combined with the polyamide polymer by virtue of the extremely high flexibility property of the polyethylene-acrylic ester-maleic anhydride copolymers, so that the latter is endowed with high impact strength, and the toughness of the matrix resin is improved.
[ examples 9 to 10 ]
A laser direct structuring resin composition having improved impact resistance was prepared by feeding 84 parts of dried polyamide 6 chips (PA6, 250 ℃ C., 2160g melt index 3.8g/10min) or polyamide 6 chips (PA6, 250 ℃ C., 2160g melt index 19.9g/10min), 9 parts of ethylene-propylene copolymer graft maleic anhydride copolymer (EPGM, ethylene content 82.0%, propylene content 18.0%, graft ratio 1.2%), 2 parts of silicone powder, 5 parts of basic copper phosphate, 0.8 parts of pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] and 1 part of white oil into a high-speed mixer for blending for 1 minute, introducing the blended materials into a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40), melt kneading, extruding and granulating to obtain a laser direct structuring resin composition IX-X. processing parameters shown in Table 7.
TABLE 7
| Examples | Composition comprising a metal oxide and a metal oxide | PA6 melt index/g/10 min | Processing temperature/. degree.C | Screw speed/revolution/minute | torque/N.m | Melt pressure/bar |
| 2 | II | 9.3 | 270 | 250 | 9.3～10.3 | 11～20 |
| 9 | IX | 3.8 | 270 | 250 | 14.5～17.5 | 15～25 |
| 10 | X | 19.9 | 270 | 250 | 5.2～8.8 | 5～12 |
Injection molding test: the processing temperature is 265 ℃ and the die temperature is 55 ℃. And (3) adopting a BOY injection molding machine to injection mold the dried laser direct forming resin composition IX-X into a standard sample strip, placing the standard sample strip in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
Laser activation: a semiconductor end face pump solid laser is adopted, the laser wavelength is 1064nm, the laser speed is 2000 mm/s, the laser energy is 15W, and the pulse repetition frequency is 30 kHz.
Chemical plating: the laser activated coupons were electroless plated for 2 hours using electroless plating methods and processes known in the art.
The results of the comprehensive property tests of the laser direct structuring resin composition IX-X are shown in Table 8.
TABLE 8
| Composition comprising a metal oxide and a metal oxide | Impact strength/kJ/m of simply supported beam gap2 | Thickness of copper plating layer/. mu.m |
| II | 49.4 | 15.6 |
| IX | 65.0 | 15.7 |
| X | 45.9 | 15.0 |
The different PA6 matrix resins used in examples 2 and 9-10, whose amide groups can undergo an anhydride-amide exchange reaction with the anhydride groups of the ethylene-propylene copolymer grafted maleic anhydride copolymer to form block, graft and network macromolecular structures, expand the molecular weight of the matrix polymer and improve the compatibility between the two, and the ethylene-propylene copolymer grafted maleic anhydride copolymer has its own extremely high flexibility property combined with the polyamide polymer to give the latter higher impact strength and improve the toughness of the matrix resin. Meanwhile, the melt index or molecular weight level of the matrix resin has a significant influence on the mechanical properties of the laser direct structuring resin composition.
[ example 11 ]
A laser direct structuring resin composition having improved impact resistance was prepared by subjecting 80 parts of dried polyamide 6/66 chips (PA6/66(75/25), 250 ℃ C., 2160g melt index 12.5g/10min), 13 parts of an ethylene-vinyl acetate copolymer graft maleic anhydride copolymer (EVGM, ethylene content 80.0%, vinyl acetate content 20.0%, graft ratio 1.3%) and an ethylene-vinyl acetate copolymer (EVA, ethylene content 86.0%, vinyl acetate content 14.0%, Yangzabasfu brand V4110) in total, 2 parts of silicone powder, 5 parts of basic copper phosphate, 0.8 parts of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1 part of white oil to a blending treatment in a high-speed mixer for 1 minute, introducing the blended materials into a LAECH co-rotating twin-screw extruder (screw diameter 16 mm, screw diameter: 40), kneading, extruding and pelletizing to obtain a laser direct structuring resin composition (XI) having an aspect ratio of 9.
Injection molding test: the processing temperature is 260 ℃ and the die temperature is 55 ℃. And (3) adopting a BOY injection molding machine to injection mold the dried laser direct structuring resin composition XI into a standard sample strip, placing the standard sample strip in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
Laser activation: a semiconductor end face pump solid laser is adopted, the laser wavelength is 1064nm, the laser speed is 2000 mm/s, the laser energy is 15W, and the pulse repetition frequency is 30 kHz.
Chemical plating: the laser activated coupons were electroless plated for 2 hours using electroless plating methods and processes known in the art.
The results of the comprehensive property tests of the laser direct structuring resin composition XI are shown in Table 10.
Comparative example 1
Preparation of resin composition 80 parts of dried polyamide 6/66 chips (PA6/66(75/25), 250 ℃ C., 2160g melt index 12.5g/10min), 13 parts of ethylene-vinyl acetate copolymer (EVA, ethylene content 86.0%, vinyl acetate content 14.0%, Yangzoba brand V4110), 2 parts of silicone powder, 5 parts of basic copper phosphate, 0.8 part of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1 part of white oil were put into a high-speed mixer to be blended for 1 minute, and the blended materials were introduced into a LABTECH co-rotating extruder (screw diameter 16 mm, length-diameter ratio 40) to be melt-kneaded, extruded and pelletized to obtain a laser direct molding resin composition i. the processing parameters are shown in Table 9.
Injection molding test: the processing temperature is 260 ℃ and the die temperature is 55 ℃. And (3) injection molding the dried resin composition i into a standard sample strip by using a BOY injection molding machine, placing the standard sample strip in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
Laser activation: a semiconductor end face pump solid laser is adopted, the laser wavelength is 1064nm, the laser speed is 2000 mm/s, the laser energy is 15W, and the pulse repetition frequency is 30 kHz.
Chemical plating: the laser activated coupons were electroless plated for 2 hours using electroless plating methods and processes known in the art.
The results of the comprehensive property tests of the resin composition i are shown in Table 10.
Comparative example 2
Preparation of resin composition 80 parts of dried polyamide 6/66 chips (PA6/66(75/25) with a melt index of 12.5g/10min at 250 ℃ and 2160 g), 13 parts of styrene-butadiene rubber powder (with a styrene content of 65%, a butadiene content of 35% and a number average molecular weight of 12 ten thousand), 2 parts of silicone powder, 5 parts of basic copper phosphate, 0.8 part of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1 part of white oil were put into a high-speed mixer to be blended for 1 minute, the blended materials were introduced into a LABTECH co-rotating twin-screw extruder (with a screw diameter of 16 mm and a length-diameter ratio of 40) and subjected to melt kneading and extrusion granulation to obtain a laser direct molding resin composition ii. the processing parameters are shown in Table 9.
Injection molding test: the processing temperature is 260 ℃ and the die temperature is 55 ℃. And (3) injection molding the dried resin composition ii into a standard sample bar by using a BOY injection molding machine, placing the standard sample bar in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
Laser activation: a semiconductor end face pump solid laser is adopted, the laser wavelength is 1064nm, the laser speed is 2000 mm/s, the laser energy is 15W, and the pulse repetition frequency is 30 kHz.
Chemical plating: the laser activated coupons were electroless plated for 2 hours using electroless plating methods and processes known in the art.
The results of the comprehensive property test of the resin composition ii are shown in Table 10.
Comparative example 3
Preparation of resin composition A resin composition was obtained by subjecting dried polyamide 6/66 chips (PA6/66(75/25) having a melt index of 12.5g/10min at 250 ℃ and 2160 g) 93 parts, silicone powder 2 parts, copper hydroxide phosphate 5 parts, pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] 0.8 part, and white oil 1 part to blending treatment in a high-speed mixer for 1 minute, introducing the blended material into a LABTECH co-rotating twin-screw extruder (screw diameter: 16 mm, aspect ratio: 40), melt-kneading, extrusion-granulating to obtain a resin composition iii, and the processing parameters are shown in Table 9.
Injection molding test: the processing temperature is 265 ℃ and the die temperature is 55 ℃. And (3) injection molding the dried resin composition iii into a standard sample bar by using a BOY injection molding machine, placing the standard sample bar in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
Laser activation: a semiconductor end face pump solid laser is adopted, the laser wavelength is 1064nm, the laser speed is 2000 mm/s, the laser energy is 15W, and the pulse repetition frequency is 30 kHz.
Chemical plating: the laser activated coupons were electroless plated for 2 hours using electroless plating methods and processes known in the art.
The results of the comprehensive property test of the resin composition iii are shown in Table 10.
TABLE 9
| Origin of origin | Composition comprising a metal oxide and a metal oxide | EVGM | EVA | Styrene butadiene rubber powder | Processing temperature/. degree.C | Screw speed/revolution/minute | torque/N.m | Melt pressure/bar |
| Example 11 | XI | 10 | 3 | 0 | 250 | 250 | 9.0～15.0 | 7～11 |
| Comparative example 1 | i | 0 | 13 | 0 | 250 | 250 | 6.6～12.1 | 6～9 |
| Comparative example 2 | ii | 0 | 0 | 13 | 250 | 250 | 8.9～17.5 | 9～15 |
| Comparative example 3 | iii | 0 | 0 | 0 | 250 | 250 | 7.6～15.3 | 4～10 |
Watch 10
| Composition comprising a metal oxide and a metal oxide | Impact strength/kJ/m of simply supported beam gap2 | Thickness of copper plating layer/. mu.m |
| XI | 55.5 | 13.6 |
| i | 48.9 | 13.5 |
| ii | 42.3 | 13.0 |
| iii | 6.0 | 13.2 |
In the composite system of the EVA and the EVA graft maleic anhydride copolymer toughened and compatibilized polyamide 6/copper hydroxide phosphate adopted in XI in example 11, the maleic anhydride structural unit on the molecular chain of the graft polymer can perform an anhydride-amide exchange reaction with the amide group in the matrix resin to form a block-type, graft-type, and mesh-type macromolecular structure, and the molecular weight of the matrix polymer is enlarged, while the EVA further compatibilizes the composite system composed of the EVA graft copolymer, the polyamide 6, and the ester-amide exchange product of the EVA graft copolymer and the polyamide 6. The polyolefin polymer has the great flexibility and is combined with the polyamide polymer, so that the polyamide polymer has higher impact strength and the toughness of the matrix resin is improved.
In comparison with comparative example 1 and comparative example 2, when conventional toughening agents such as EVA and styrene-butadiene rubber powder are used alone, due to the lack of anhydride-amidation reaction between the graft type maleic anhydride copolymer and the matrix involved in the present invention, the formation of an amorphous macromolecular structure, their toughening efficiency is not high, and the excellent graft compatibilization toughening effect of the graft type maleic anhydride copolymer in the present invention is not exhibited. In contrast, comparative example 3 does not use any toughening compatibilizer, the impact strength of the notch of the simply supported beam is very low, and the composite material composition has an obvious brittle behavior. In contrast, the impact resistance of the laser direct structuring resin composition in the above embodiment is significantly improved, the chemical plating effect is significantly improved, the comprehensive performance is effectively improved, and a better technical effect is obtained.
Claims (10)
1. A laser direct structuring resin composition with improved impact resistance comprises the following components in parts by weight:
(A) 50-90 parts of thermoplastic resin;
(B) 1-15 parts of a laser activator;
(C) 3-15 parts of a toughening compatilizer;
(D) 0.1-5 parts of a surface modifier;
(E) 1-20 parts of an auxiliary agent;
wherein the toughening compatibilizer is at least one selected from the group consisting of a maleic anhydride graft copolymer of polyethylene, a maleic anhydride graft copolymer of polypropylene, a maleic anhydride graft copolymer of ethylene-propylene copolymer, a maleic anhydride graft copolymer of ethylene-octene copolymer, a maleic anhydride graft copolymer of ethylene-vinyl acetate copolymer, a maleic anhydride graft copolymer of ethylene-acrylate copolymer, and an ethylene-maleic anhydride copolymer, an ethylene-propylene-maleic anhydride copolymer, an ethylene-octene-maleic anhydride copolymer, an ethylene-vinyl acetate-maleic anhydride copolymer, and an ethylene-acrylate-maleic anhydride copolymer.
2. The laser direct structuring resin composition with improved impact resistance according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of polyesters, polyamides, acrylonitrile-butadiene-styrene copolymers, and polyphenylene sulfides.
3. The laser direct structuring resin composition with improved impact resistance according to claim 1, wherein the laser activator is selected from at least one of the oxides and salts containing aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, palladium, silver, tin, antimony, platinum, gold.
4. The laser direct structuring resin composition with improved impact resistance according to claim 1, wherein the surface modifier is at least one member selected from the group consisting of polysiloxanes, organosiloxanes, organotitanates, and organoaluminates.
5. The laser direct structuring resin composition with improved impact resistance according to claim 1, wherein said auxiliaries are optionally selected from the group consisting of reinforcing agents, flame retardants, plasticizers, heat stabilizers, lubricants, antistatic agents, antioxidants, UV absorbers, mold release agents.
6. The improved impact resistance laser direct structuring resin composition according to claim 1, wherein a molded sample of the improved impact resistance laser direct structuring resin composition has a function of being plated to form a conductive path after laser activation and has a thickness of more than 15kJ/m2The impact strength of the gap of the simply supported beam.
7. The laser direct structuring resin composition according to claim 5, wherein the reinforcing agent is at least one member selected from the group consisting of talc, mica, glass beads, glass fibers, carbon fibers, asbestos fibers, ceramic fibers, cotton fibers and aramid fibers.
8. The laser direct structuring resin composition with improved impact resistance according to claim 5, wherein the flame retardant is at least one selected from the group consisting of triphenyl phosphate, triisopropylphenyl phosphate, tributyl phosphate, and trioctyl phosphate.
9. A method for preparing the laser direct structuring resin composition with improved impact resistance according to any one of claims 1 to 8, comprising the steps of:
the laser direct forming resin composition with improved impact resistance is prepared by blending the required amount of thermoplastic resin, laser activator, toughening compatilizer, surface modifier and auxiliary agent, and then performing melt kneading extrusion or calendaring forming.
10. Use of the laser direct structuring resin composition with improved impact resistance according to any one of claims 1 to 8.
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