CN112662159B - Polycarbonate laser direct forming material with good plating property and degradation resistance, preparation method and product - Google Patents
Polycarbonate laser direct forming material with good plating property and degradation resistance, preparation method and product Download PDFInfo
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Abstract
A polycarbonate laser direct structuring material with good plating property and degradation resistance is composed of the following raw materials by weight percent: polycarbonate substrate: 40-95%, other resin matrix: 0-30%, LDS additive: 3-15%, filler: 0-30%, acid auxiliary agent: 0.01-2%, toughening agent: 0-5%, and other auxiliary agents: 0.5-2%, wherein the LDS additive is an alkaline copper-containing LDS additive; the main component of the acid auxiliary agent is one or more of phosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid, hypophosphorous acid and acid salts of the acids. The invention can improve the copper plating efficiency of the laser direct forming material. The data in the embodiment of the invention conclude that the phosphate compounds are easier to release copper ions than copper-chromium spinel LDS additives when irradiated by laser energy, and meanwhile, the generated phosphate compounds are usually easy to migrate to the surface of the resin in PC resin, thereby further improving the copper plating efficiency of the material.
Description
Technical Field
The invention belongs to the field of laser direct forming materials, and particularly relates to a polycarbonate laser direct forming material with good plating property and degradation resistance, a preparation method and a product.
Background
Laser Direct Structuring (also called LDS, short for Laser Direct Structuring) is a 3D-MID production technology for specialized Laser processing, injection and electroplating processes, and the principle thereof is to combine the functions of electrical interconnection, supporting components, supporting and protecting plastic housing, etc. of common plastic components/circuit boards, and the functions of shielding, antenna, etc. generated by combining mechanical entities and conductive patterns into a whole, forming a so-called 3D-MID, which is suitable for local fine circuit fabrication.
The laser activator is added, so that on one hand, when the plastic matrix is irradiated by laser, particles which can cause metal deposition are released from the surface of the plastic matrix, and on the other hand, the surface of a workpiece is roughened, and the bonding force between the matrix and a coating is enhanced.
At present, the copper-chromium composite material of the copper-chromium spinel crystal form has the advantages of wide source, low price, easy reduction of metal particles into metal particles after laser irradiation, quick plating starting in the chemical plating process and the like, and is commonly used as an LDS additive, but the composite system has a certain content of free metal ions or atoms which can affect the performance of a resin matrix. Particularly for polycarbonate systems, free metal ions or atoms are the catalyst that catalyzes the degradation of the resin; meanwhile, the inorganic metal compound or the organic metal mixture is alkaline to different degrees, and the degradation reaction degree of the polycarbonate compound is further increased, so that some properties of the material are greatly influenced.
In the prior art, in order to utilize the chemical plating performance (such as short chemical plating time) of the copper-containing LDS additive, most of the materials ignore the mechanical property reduction caused by the degradation of the copper-containing LDS additive to a polycarbonate system, or increase the mechanical property of the materials by adopting an inorganic filler, and the degradation of the copper-containing LDS additive cannot be reduced from the main body of the copper-containing LDS additive.
In order to reduce the degradation effect of the alkaline copper-containing LDS additive on polycarbonate, the prior art adopts the dosage control of the alkaline copper-containing LDS additiveDegradation, for example, the Chinese patent with publication No. CN106928682A discloses a laser direct forming material with good comprehensive performance and a preparation method thereof, the chemical plating is fast by utilizing copper-containing LDS additive, and the material is black or dark, which is easy to cause the degradation of PC; the chemical plating of the tin-containing LDS additive is slow, is light color, is not easy to cause the degradation of PC, and the two are compounded, thereby substantially sacrificing the amount of the copper-containing LDS additive and reducing the chemical plating performance of the material. Publication No. CN102770491A discloses an aromatic polycarbonate composition, which is a method for improving the notch impact strength of a PC material by reducing the degradation of PC by an LDS additive through the synergistic action of sulfonate and oxyphosphoric acid, but the sulfonate contains sulfur, so that the sulfonate may have certain influence on the electroless copper plating efficiency of a laser forming material. In addition, other LDS additives not containing copper are directly adopted for replacement, laser direct forming can be achieved, but the advantage of fast chemical plating of the LDS additives containing copper is completely abandoned, so that the plating time is long, and the production efficiency is low. For example, chinese invention patent CN106751389A discloses a light-colored engineering plastic for LDS technology and a method for preparing the same, by replacing a commonly used copper-containing LDS additive (such as basic copper phosphate, copper chrome black, etc.) with at least 80% of titanium dioxide (TiO) 2 ) And tin dioxide ((Sb, sn) O) doped with antimony 2 ) The light-colored engineering plastic which can be used for the LDS technology is prepared by the formed additive, but the cost of the raw materials such as tin oxide is high, and the plating time is long during the subsequent electroless copper plating. Meanwhile, if an oxide containing antimony, tin and the like is used as an LDS additive to prepare a black product, a black pigment such as carbon black and the like needs to be added, so that the mechanical properties such as processability, impact strength and the like of the material can be reduced, and the mechanical properties of the material can be sacrificed.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention aims to provide a laser direct structuring material which can effectively reduce the influence of the alkaline LDS additive on the polycarbonate system, and has good plating performance and good mechanical properties. The method is realized by the following technical scheme:
a polycarbonate laser direct structuring material with good plating property and degradation resistance is composed of the following raw materials in percentage by weight:
polycarbonate substrate: 40-95%
Other resin matrix: 0 to 30 percent
LDS additive: 3 to 15 percent
Filling: 0 to 30 percent
Acid auxiliary agent: 0.01 to 2 percent
A toughening agent: 0 to 5 percent
Other auxiliary agents: 0.5 to 2 percent
The LDS additive is an alkaline copper-containing LDS additive;
the main component of the acid auxiliary agent is one or more of phosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid, hypophosphorous acid and acid salt of the acid, and the metal ion of the acid salt of the acid is one or more of potassium, sodium, zinc, calcium, magnesium and aluminum. The copper ions contained in the LDS additive can generate stable copper ion phosphate compounds with the phosphate acid salts of the metals; phosphoric acid is preferably selected when the material system has no flame retardant requirement, so that the cost is lower; phosphite is preferred when the material system has flame retardant requirements. In view of thermal stability of processing, safety, environmental protection, etc., acid salts of phosphoric acid are preferred.
Optionally, the polycarbonate comprises homopolycarbonate and copolycarbonate with a repeating structural carbonate unit, and can be one or a mixture of two of aliphatic polycarbonate, alicyclic polycarbonate, aromatic polycarbonate or silicon copolycarbonate with a molecular main chain containing silicon element. In the present invention, a suitable polycarbonate can be prepared by a method such as phosgene method, interfacial polymerization and melt polymerization to obtain a copolymerized or homopolycarbonate. In a specific embodiment, the polycarbonate is a linear homopolymer derived from bisphenol A, i.e., a homopolycarbonate comprising bisphenol A structures.
Optionally, the other resin matrix is one or more of polyolefin, polyester, polyamide, polyarylether, polyesterimide, acrylonitrile-butadiene-styrene (ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyimide (PI), polysulfone (PSU), polyether ether ketone (PEEK) or Polybenzimidazole (PBI); the other resin matrix can also be one or more of phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin, epoxy resin, alkyd resin and polyurethane. Specifically, the polyolefin may be at least one selected from the group consisting of Polystyrene (PS), polypropylene (PP), polymethyl methacrylate, and poly (acrylonitrile-butadiene-styrene); the polyester may be at least one selected from the group consisting of polycyclohexanedimethylene terephthalate (PCT), polydiallyl isophthalate (PDAIP), polydiallyl terephthalate (PDAP), polybutylen naphthalate (PBN), polyethylene terephthalate (PET), and polybutylene terephthalate (PBT); the polyamide may be at least one selected from the group consisting of polyhexamethylene adipamide (PA-66), polyhexamethylene azelamide (PA-69), polyhexamethylene succinamide (PA-64), polyhexamethylene dodecanoamide (PA-612), polyhexamethylene sebacamide (PA-610), decamethylenesebacamide (PA-1010), polyundecanoamide (PA-11), polydodecanoamide (PA-12), polycaprylamide (PA-8), poly 9-aminononanoic acid (PA-9), polycaprolactam (PA-6), polyparaphenylene terephthalamide (PPTA), polyhexamethylene isophthalamide (MXD 6), polyhexamethylene terephthalamide (PA 6T) and polyparaphenylene terephthalamide (PA 9T). The thermosetting plastic may be at least one of a phenol-formaldehyde resin, a urea-formaldehyde resin, a melamine-formaldehyde resin, an epoxy resin, an alkyd resin, and a polyurethane.
In the present invention, the laser direct structuring additive (LDS additive) can expose the metal nuclei in the LDS additive after being irradiated with laser light, and the exposed metal nuclei serve as nuclei for crystal growth during a subsequent metallization or plating process such as copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, and the like.
Optionally, the basic copper-containing LDS additive of the invention comprises a chemical formula AB having a spinel structure 2 O 4 Or ABO 3 A metal oxide or metal complex of (a); wherein, A in the chemical formula is divalent metal cation, and B is trivalent metal cation.
Optionally, the chemical formula is AB 2 O 4 Or ABO 3 Of the spinel typeThe divalent metal cation in the metal oxide or the metal complex with the structure is copper, or the mixture of copper and a small amount of one of cobalt, iron, magnesium, titanium, aluminum, nickel, manganese, zinc, calcium and tin; the trivalent metal cation is one or two of chromium, cobalt, iron, magnesium, titanium, aluminum, nickel, manganese, zinc, calcium and tin. In the embodiment of the invention, one or more of copper chromium oxide, copper chromium manganese mixed oxide, copper chromium iron mixed oxide and copper iron spinel are mainly selected.
Optionally, in the present invention, the filler includes one or more of glass reinforcing filler, carbon fiber, mineral, silicic acid, silicate, metal oxide, and non-metal oxide. At least one of glass fiber, carbon fiber, talcum powder, calcium carbonate, glass bead, calcium sulfate, barium sulfate, titanium dioxide, pearl powder, wollastonite, diatomite, kaolin, coal powder, argil, mica, oil shale ash, aluminum silicate, alumina, silicon dioxide, zinc oxide and the like is mainly selected.
Optionally, in the present invention, the toughening agent includes one or more of POE, SEBS, EPDM, SBS, ABS, MBS, PPO, silicone core-shell polymer, silicone, and polymer-grafted maleic anhydride, wherein preferably one or a mixture of two of ABS (acrylonitrile-butadiene-styrene polymer), MBS (methacrylic acid-butadiene-styrene copolymer), SBS (styrene-butadiene-styrene block copolymer), and SEBS (styrene-ethylene/butylene-styrene block copolymer).
Optionally, the other auxiliary agents in the present invention include one or more of a lubricant, an antioxidant, a plasticizer, a mold release agent, and a toner.
Optionally, in the invention, the lubricant is one or more of metal stearate, polyethylene wax, aliphatic series and lipid thereof, and organic silicon, wherein at least one of pentaerythritol stearate, metal stearate, and organic silicon is preferred; the antioxidant comprises one or more of hindered phenols, organic phosphites and phosphates, and is preferably at least one of a compound mixture of pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite, triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acrylonitrile and tris (2, 4-di-tert-butylphenol) phosphite. According to other embodiments, plastic additives such as a release agent, a plasticizer, and a toner may be added.
In another aspect, the present application provides a method of making the above-described material useful for laser direct structuring. The preparation method comprises the following steps: according to the mass ratio, firstly premixing the LDS additive and the acidic auxiliary agent, then mixing the premixed LDS additive and the acidic auxiliary agent with the polycarbonate matrix, other resin matrix, the inorganic filler and other auxiliary agent, and performing melt blending extrusion granulation through a double-screw extruder to obtain the laser direct forming material.
The application also provides the application of the acid auxiliary agent in a polycarbonate laser direct structuring material system, wherein the acid auxiliary agent can reduce the degradation of PC and improve the chemical copper plating performance of a laser direct structuring material.
The present application also provides an article made of the laser direct structuring material. Such as three-dimensional circuit boards for car lamps, mobile phone antennas and other parts or circuit-related parts in products such as intelligent watches, cash dispenser shells, hearing aids and the like.
Compared with the prior art, the method has the following beneficial effects:
the LDS additive used in the invention is a metal oxide or metal complex with a copper-containing spinel structure and has mature preparation process and relatively low price, and the additive is dark, so that the LDS material with dark color is made without color matching treatment.
In the prior art, when a basic copper spinel structure metal oxide or metal complex is used as an LDS additive in a polycarbonate resin, in order to solve the problem that the polycarbonate resin is not alkali-resistant, an acidic copper-containing LDS additive is generally selected or the influence of alkalinity on the degradation performance of the polycarbonate resin is ignored.
The invention improves the safety of production. Generally, phosphoric acid additives can generate toxic phosphorus oxide and phosphorus cyanide under the condition of high temperature (about 200 ℃) when being heated, but researches find that phosphoric acid substances can generate phosphate compounds with stable physicochemical properties with heavy metals such as copper, lead and the like, so that the phosphoric acid additives can generate stable phosphate compounds with copper ions, the possibility of discharging toxic phosphorus oxide and phosphorus cyanide under heating can be effectively reduced in the production process, and the production safety is improved.
The invention can improve the copper plating efficiency of the laser direct forming material. The data in the embodiment of the invention conclude that the phosphate compounds are easier to release copper ions than copper-chromium spinel LDS additives when irradiated by laser energy, and meanwhile, the generated phosphate compounds are usually easy to migrate to the surface of the resin in PC resin, thereby further improving the copper plating efficiency of the material. Therefore, under the same conditions, the addition of the phosphoric acid auxiliary agent can further improve the copper plating efficiency of the laser direct structuring material.
Drawings
FIG. 1 is a sample diagram of an embodiment of D2, S2, and D6 (in left-to-right order) after electroless copper plating in the same environment;
FIG. 2 is a diagram showing gold phases of the D2, S2 and D6 embodiments after electroless copper plating in the same environment.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific embodiments, and it should be noted that the specific embodiments described in the embodiments of the present invention are not intended to limit the claims of the present invention.
In the embodiment, the components are as follows according to the weight percentage: 40-95% of PC; blending resin: 0 to 30 percent; 3-15% of LDS additive; 0-30% of filler; 0-5% of a toughening agent; acid auxiliary agent: 0.01-2%; 0.5 to 2 percent of other auxiliary agents;
the performance test method in the examples is as follows:
the MFR (melt index) was tested according to ISO 1133 1997, with test conditions chosen at 260 ℃,5kg; the impact strength was tested according to ISO 527-1. The copper deposition rate of electroless copper plating is tested according to a weighing method on page 24 in the research on electroless copper plating with sodium hypophosphite, and the influence factors of the copper deposition rate include the properties of electroless plating solution, base material, reaction time, reaction temperature, pH of the electroless plating solution and the like. Testing of LDS platability (plating adhesion): injection molded samples having dimensions of 5cm × 3cm × 2mm were aged at 25 ℃ for 6 hours, and then the surface of the sample was activated in a block shape (1 cm × 1 cm) by laser direct structuring. Then, a copper layer of 10 to 15 μm thickness was formed on the activated square surface of the sample by electroplating (copper electroless plating), thereby preparing an electroplated sample. The samples were then tested and evaluated for plating adhesion using the standard method of ASTM D3359, and the color distribution of the copper layer was tested according to CIE Lab color model.
In the embodiment of the application, the polycarbonate with a bisphenol A structure prepared by a phosgene method is used as the PC, the relative molecular mass is 20000-30000, and the MFR is 10-25g/min under the conditions of 260 ℃ and 5kg; in a specific example, PC with MFR around 15g/min is selected.
Other resin matrices used in embodiments of the present application include at least one of polyolefins, polyesters, polyamides, polyarylethers, polyesterimides, acrylonitrile-butadiene-styrene (ABS), polycarbonate/(acrylonitrile-butadiene-styrene) alloys (PC/ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyimide (PI), polysulfone (PSU), polyether ether ketone (PEEK), and Polybenzimidazole (PBI). In a particular embodiment, the selected polymer blend is acrylonitrile-butadiene-styrene polymer (ABS).
The LDS additive used in the embodiments of the present application includes copper-containing LDS additives, mainly metal oxides or metal complexes of spinel structure, such as one or two of copper chromium oxide, copper chromium manganese mixed oxide, copper chromium iron mixed oxide, and copper iron spinel. In a specific embodiment, the selected copper-containing LDS additive is copper chromium oxide and copper chromium manganese mixed oxide, wherein LDS-1 is copper chromium manganese mixed oxide (brand: COLORDUR BLACK 9028A, hangzhou Sitan pigment chemical Co., ltd.), and LDS-2 is copper chromium oxygen mixed oxide (brand: PS 24-3095 PK BLACK pigment, ferro Corp.).
The filler used in the embodiments of the present application includes one or more of glass reinforcing fillers, carbon fibers, minerals, silicic acids, silicates, metal oxides, and non-metal oxides. Mainly comprises at least one of glass fiber, carbon fiber, talcum powder, calcium carbonate, glass beads, calcium sulfate, barium sulfate, titanium dioxide, pearl powder, wollastonite, diatomite, kaolin, coal powder, argil, mica, oil shale ash, aluminum silicate, alumina, silicon dioxide, zinc oxide and the like. In a particular embodiment, the filler selected is calcium carbonate.
The lubricant used in the examples herein was pentaerythritol stearate and the antioxidant was 1076.
The toughening agent used in the examples of the present application is one or a mixture of two of ABS (acrylonitrile-butadiene-styrene polymer), MBS (methacrylic acid-butadiene-styrene copolymer), SBS (styrene-butadiene-styrene block copolymer), SEBS (styrene-ethylene/butylene-styrene block copolymer). Selected in the specific examples is MBS (methacrylic acid-butadiene-styrene copolymer) with the specific designation S-2001, available from Mitsubishi Yang.
The acid auxiliary used in the embodiment of the present application is a phosphoric acid auxiliary, and mainly includes one or two of phosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid and hypophosphorous acid, and may also include acid salts containing these phosphoric acids. Sodium dihydrogen phosphate and phosphoric acid are selected in specific examples.
The sulfonate used in the examples of this application was RM65 (MITENI corporation).
In the embodiment of the application, the specific preparation method comprises the following steps: the LDS additive and the acidic auxiliary agent are premixed according to the mass ratio, then the premixed material is uniformly mixed with the PC inorganic filler, the toughening agent and other auxiliary agents, and then the mixture is subjected to melt blending extrusion granulation by a double-screw extruder to obtain the plastic molding compound material capable of being directly formed by laser. The specific process is as follows: weighing the desired raw materials while premixing in a high speed mixer at a speed of about 500 to 2000 rpm; the premix is then fed into a twin screw extruder, after extrusion, cooled by a cooling water bath and cut into pellets by a cutter to obtain sample particles, the sample is prepared by melt blending extrusion, using a set temperature of the screw in the range of about 240 ℃ to about 270 ℃, a screw speed of about 300 revolutions per minute and a torque value of about 55% to about 70%, and operating under technically mature standard processing conditions. Before the pellets are used for making a sample strip, the pellets are dried at a temperature of about 110 ℃ for 4-6h, and then a mold sample strip is made under the conditions that the temperature range is 240-260 ℃ and the mold temperature is maintained at 80 ℃.
The raw material components and performance data used in the examples are shown in tables 1 and 2:
TABLE 1 formulation Components (wt.%) and Performance data for examples 1-5 (S1-S5) and comparative examples 1-4 (D1-D4)
As can be seen from the data in Table 1, D1 and D2 as control samples show the comparative test of the significant reduction of the notched impact strength of PC material by adding the copper-chromium black filler, which can be explained by the fact that the copper-chromium black is an inorganic filler and the degradation of PC is caused by the existence of the copper-chromium black, and the important effect of the LDS additive on the laser direct structuring material can also be obtained. D2 and S1-S4 are used as comparison samples, and the fact that the notch impact strength can be improved to a certain extent by adding a small amount of acid additives (phosphoric acid and sodium dihydrogen phosphate) is shown, and the molten finger of the sample is reduced at the same time, which can be explained by the fact that the acid additives can neutralize the alkalinity of the copper-chromium black and reduce the degradation of the copper-chromium black on PC, but as the PC can also undergo reversible degradation reaction under the acidic condition, the excessive addition of the acid additives can also have certain influence on the molten finger and the notch impact strength; S1-S4 also show that the acidic auxiliary agent has an influence on the copper deposition rate during electroless copper plating, and the addition of a small amount of the acidic auxiliary agent sample significantly increases the copper deposition rate, which can be explained by the fact that phosphate ions in the acidic auxiliary agent react with copper ions in copper chromium black to generate stable copper phosphate salt substances (copper ions are more easily released when the copper ions are irradiated by laser), so that more active centers on the substrate are formed. D2, D3 and S5 are used as control samples, and it can be found that the addition of the toughening agent (S2001) can effectively improve the notch impact strength of the material and simultaneously reduce the molten index of the material, and the toughening agent can not influence the copper deposition efficiency and electroplating adhesiveness of the sample during electroless copper plating, and the conclusion that the acidic auxiliary agent is helpful for improving the copper deposition rate can be further shown from the copper deposition rate data.
TABLE 2 formulation Components (wt.%) and Performance data for examples 6-10 (S6-S10) and comparative examples 4-6 (D4-D6)
As can be seen from the data in tables 1 and 2, D1, D2, D4 and S6 are comparative data, and the talcum powder filler can obviously reduce the notch impact strength of the material and can improve the copper deposition rate of the material during electroless copper plating to a certain extent. The comparison data of D1 and D5 show that the change of the resin base material does not influence the copper deposition rate and the electroplating adhesiveness of the material, and the comparison data of D5 and S7 show that the copper deposition rate of the material can be effectively improved by adding a small amount of acidic auxiliary agent.
TABLE 3 data of Lab color model of D2, S2, D6 examples after electroless copper plating in the same environment (wherein the position names of three color patches from left to right on each example are 1,2,3, as shown in FIG. 1)
TABLE 3 data of Lab color model for examples
As can be seen from FIG. 1, the three coatings in S2 have the best color uniformity; as can be seen from the data in Table 3, the difference in color difference (. DELTA.E) among the three plated layers after electroless copper plating was the smallest among the S2 samples, indicating that the uniformity of the three laser-irradiated copper plated layers was the best among the S2 samples.
It can be seen from fig. 2 that after electroless copper plating under the same conditions, ablation traces after laser etching can be clearly seen in the D2 and D6 gold phase diagrams, which shows that the thickness of the copper plating layer is not very thick, while the ablation traces after laser etching are not so obvious in the gold phase diagram of the S2 embodiment, so that the copper plating layer is very thick, which also shows that the addition of the phosphoric acid assistant can improve the copper deposition rate in the electroless copper plating step under the same conditions.
It should be noted that the above contents described in the present specification are only illustrations of the technical solutions of the present invention. All simple and equivalent changes, which are made according to the characteristics and principles described in the present patent concepts, are included in the scope of protection of the present patent. Various modifications, additions and substitutions for the specific embodiments described may be made by those skilled in the art without departing from the technical spirit of the invention or exceeding the scope of the claims.
Claims (11)
1. A polycarbonate laser direct structuring material with good plating property and degradation resistance is characterized in that: comprises the following components in percentage by weight:
polycarbonate substrate: 40-95%
Other resin matrix: 0 to 30 percent
LDS additive: 3 to 15 percent
Filling: 0 to 30 percent
Acid auxiliary agent: 0.01 to 2 percent
Toughening agent: 0 to 5 percent
Other auxiliary agents: 0.5 to 2 percent
The LDS additive is an alkaline copper-containing LDS additive; the alkaline copper-containing LDS additive comprises a chemical general formula AB with a spinel structure 2 O 4 Or ABO 3 Wherein, in the chemical formula, A is a divalent metal cation, and B is a trivalent metal cation; the main component of the acid auxiliary agent is one or more of phosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid, hypophosphorous acid and acid salt of the acid, and the metal ion of the acid salt of the acid is one or more of potassium, sodium, zinc, calcium, magnesium and aluminum.
2. The laser direct structuring material of claim 1, wherein: the polycarbonate substrate is one or more of homopolycarbonate and copolycarbonate with a repeating structural carbonate unit.
3. The laser direct structuring material of claim 1, wherein: the other resin matrix is one or more of polyolefin, polyester, polyamide, polyarylether, polyesterimide, acrylonitrile-butadiene-styrene (ABS), polyphenyl ether (PPO), polyimide (PI), polysulfone (PSU), polyether ether ketone (PEEK) or Polybenzimidazole (PBI); the other resin matrix can also be one or more of phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin, epoxy resin, alkyd resin and polyurethane.
4. The laser direct structuring material of claim 1, wherein: the chemical formula is AB 2 O 4 Or ABO 3 The divalent metal cation in the spinel-type metal oxide or metal complex is copper, or a mixture of copper and a small amount of one of cobalt, iron, magnesium, titanium, aluminum, nickel, manganese, zinc, calcium and tin; the trivalent metal cation is one or two of chromium, cobalt, iron, titanium, aluminum, nickel and manganese.
5. The laser direct structuring material of claim 4, wherein: the alkaline copper-containing LDS additive comprises one or more of copper chromium oxide, copper chromium manganese mixed oxide, copper chromium iron mixed oxide and copper iron spinel.
6. The laser direct structuring material of claim 1, wherein: the toughening agent comprises one or more of POE, SEBS, EPDM, SBS, MBS, PPO, organosilicon and polymer grafted maleic anhydride.
7. The laser direct structuring material of claim 1, wherein: the other auxiliary agents comprise one or more of a lubricant, an antioxidant, a plasticizer, a release agent and toner.
8. The laser direct structuring material of claim 1, wherein: the filler comprises one or more of glass fiber, carbon fiber, mineral, silicic acid, silicate, metal oxide and non-metal oxide.
9. The use of an acidic adjuvant according to claim 1 in a polycarbonate laser direct structuring material system to reduce degradation of PC while improving electroless copper plating performance of laser direct structuring materials.
10. A method of making a laser direct structuring material of any of claims 1-8, comprising the steps of: premixing the LDS additive and the acidic auxiliary agent, mixing the premixed LDS additive and the acidic auxiliary agent with a polycarbonate matrix, other resin matrixes, a toughening agent, a filler and other auxiliary agents, and performing melt blending extrusion granulation by a double-screw extruder to obtain the laser direct forming material.
11. An article made from the laser direct structuring material of any of claims 1-8.
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| CN114479410B (en) * | 2022-02-16 | 2023-08-04 | 无锡赢同新材料科技有限公司 | Low dielectric loss LDS engineering plastic and preparation method thereof |
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| CN109575554A (en) * | 2018-10-30 | 2019-04-05 | 中广核高新核材科技（苏州）有限公司 | High finished product rate laser direct forming LDS composite material and preparation method |
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| CN103756278A (en) * | 2013-12-30 | 2014-04-30 | 安徽科聚新材料有限公司 | Engineering plastic applicable to LDS (Laser Direct Structuring) forming process as well as preparation method and application thereof |
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| CN106928682A (en) * | 2017-03-01 | 2017-07-07 | 无锡赢同新材料科技有限公司 | A kind of laser direct forming material with good combination property and preparation method thereof |
| CN109575554A (en) * | 2018-10-30 | 2019-04-05 | 中广核高新核材科技（苏州）有限公司 | High finished product rate laser direct forming LDS composite material and preparation method |
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