WO2014047845A1

WO2014047845A1 - Resin composition for selectively depositing metal, preparation method and application thereof

Info

Publication number: WO2014047845A1
Application number: PCT/CN2012/082193
Authority: WO
Inventors: 严峡; 姜苏俊; 蔡彤旻; 曾祥斌; 宁凯军
Original assignee: 金发科技股份有限公司; 珠海万通化工有限公司; 上海金发科技发展有限公司
Priority date: 2012-09-27
Filing date: 2012-09-27
Publication date: 2014-04-03

Abstract

The present invention provides a modified resin composition used for depositing metal thin film, a method for preparing said modified resin composition, and an application for said modified resin composition. Said modified resin composition comprises a resin base and a metal oxide solid solution; the metal elements in the solvent of the metal oxide solid solution are elements which come from periods 3, 4, 5, and 6 of the periodic table; the metal elements in the solute are elements which come from periods 3, 4, 5, and 6 of the periodic table; the weight content ratio of solute to solvent in the metal oxide solid solution is between 1:9 and 1:1. In the modified resin composition of the present invention, when under the influence of laser light, metal particles are released from the metal oxide solid solution; during subsequent electroless chemical plating, these metal particles function as an active center, causing metal ions from a chemical plating solution to selectively deposit, forming a metal thin film; the above can be used in the Surface Mount Technology (SMT) process.

Description

Resin composition capable of selectively depositing metal and preparation method and application thereof

The present invention relates to a resin composition, and more particularly to a modified resin composition for selectively depositing a metal thin film, a preparation method thereof, and use thereof. Background technique

Laser direct molding (Laser Direct Structurin says g, LDS) refers to the use of a computer to control the laser beam to illuminate the laser beam onto the workpiece. The area irradiated by the laser beam has an activation capability, and the activation region of the workpiece can be A metal such as copper, nickel or gold is deposited in the electroless plating solution, and a metal such as copper, nickel, or gold cannot be deposited in a region not irradiated with the laser beam, so that the resin composition is selective in depositing metal.

With the rapid development of LDS technology, Moulded Interconnect Device is faster, more streamlined, more cost-effective, and has a wider application area. Its biggest advantage is that it can reduce the number of electronic products. The number of devices and space saving. For example, antennas made with LDS technology are widely used in mobile terminals such as smartphones, notebook computers, GPS, etc. Sensors manufactured by LDS technology have a minimum wire width of 150 μm and a minimum line width of 150 μm. This not only reduces the number of components, but also saves space and reduces weight.

The advantages of LDS technology are also reflected in its flexibility. If you need to change the conductive path on the component, you only need to change the circuit graphic design in the CAD, no need to redesign the mold. Because LDS technology does not require a mask, the process is simpler and the processing cost is lower.

In addition, the advantages of LDS technology are also reflected in the freedom of design. LDS technology uses laser beams to process parts and has great advantages in making 3D circuits. The copper foil patch process is used to make the three-dimensional circuit. Then, in the place where the metal pattern has curvature, especially in the corner with sharp corners, defects such as copper foil lifting are likely to occur, which affects the electrical and electronic functions of the workpiece, and the LDS technology can This difficulty is well overcome because the metal film deposited during the electroless plating process eliminates the internal stress of the metal layer.

At the same time, the material science applied to LDS technology has also developed rapidly. The base covers general-purpose plastics, engineering plastics, and specialty engineering plastics, as well as ceramic materials. Typical applications are high molecular materials such as polycarbonate, polycarbonate and acrylonitrile/butadiene/styrene alloys due to their excellent dimensional stability, good processability and mechanical properties. Appearance aesthetics, so LDS antennas made with them have been widely used in smartphones, tablets and laptops.

There are also some high-heat-resistant polymer materials used in surface mount technology (SMT). Generally, the processing temperature of the SMT process is as high as 270 ° C. Even in more severe cases, the temperature will rise to 290 ° C. At this temperature, general plastics and engineering plastics will have problems such as softening, deformation, and foaming of the substrate. However, special engineering plastics have excellent performance. For example, high temperature semi-aromatic nylon, liquid crystal polymer, polyaryl ether ketone and other polymers have processing temperatures above 30CTC.

Among the LDS technologies, laser sensitive additives play a key role. Under the action of the laser beam, he releases metal particles and acts as an activation center in the subsequent electroless plating to accelerate the redox reaction in the plating solution to deposit metallic copper. The laser-sensitive additive commonly used is a metal-copper-containing spinel and also contains heavy metal chromium, which poses a potential environmental risk during use. Summary of the invention

In view of the above, it is necessary for the present invention to provide a modified resin composition which can selectively deposit a metal which does not contain heavy metal chromium, and also provides a process for producing such a resin composition.

A modified resin composition for selectively depositing a metal film, comprising the following components:

a resin matrix, and a metal oxide solid solution;

Wherein, the metal element in the solvent in the metal oxide solid solution is derived from the elements in the third, fourth, fifth, and sixth cycles of the periodic table, and the metal element in the solute is from the third, fourth, and fifth in the periodic table. The element in the 6-cycle period, the weight ratio of the solute to the solvent in the metal oxide solid solution is 1:9-1:1.

The metal element in the metal oxide solid solution solvent is preferably derived from Ti, Sn, Pb, Nb, W, Mn, Ge, Ta.

The metal element in the solvent of the metal oxide solid solution is further preferably selected from Sn.

The metal element in the solute of the metal oxide solid solution is preferably derived from Mg, Al, Ca, Mn, Fe, Ti, Ni, Cu, Zn, Ge, Nb, Pd, Ag, Sn, Sb.

Chromium is not included in the metal oxide.

The weight percentage of the resin matrix is preferably from 35 to 99% by weight; from 40 to 90% by weight _{; from} 45 to 80% by weight.

The weight percentage of the metal oxide solid solution is preferably l_10 rt%; 2-9 wt% ₀

The resin matrix selected for use in the present invention is selected from the group consisting of thermoplastics, thermosets, rubbers or elastomers.

Wherein, the thermoplastic resin is selected from the group consisting of: polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate and acrylonitrile-butadiene-styrene alloy (PC/ABS), liquid crystal Polymer (LCP), polyamide (PA), polyphenylene sulfide (PPS), polyphenylene ether (PPE), polysulfone, polyarylate, polyetheretherketone (PEEK), polyetherketoneketone (PEKK), Polyetheretherketoneketone (PEEKK), thermoplastic polyimide (TPI), polyacetal, polyethylene (ΡΕ), polypropylene (ΡΡ), polystyrene (PS), polytetrafluoroethylene (PTFE), poly Acrylates, styrene-acrylonitrile copolymers (SA), polybutylene terephthalate (PBT), and polyethylene terephthalate (PET), polybutylene terephthalate An ester, or a composition comprising at least one of the above polymers.

The polyamide resin selected is selected from the group consisting of an aliphatic polyamide, a semi-aromatic polyamide, or a blended composition of a semi-aromatic polyamide and an aliphatic polyamide.

The aliphatic polyamide carbon chain selected consists of 4 to 36 carbon atoms, and a typical aliphatic polyamide includes a combination of one or more of PA6, PA66, PA610, PA612, PA1010, PA11, PA12, PA1012, But not limited to these combinations.

The semi-aromatic polyamide consists of a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit comprises 45-100 mole percent of aromatic dicarboxylic acid units and 0-55 mole percent of 4-12 The aliphatic dicarboxylic acid unit of a carbon atom, the diamine unit being a linear aliphatic diamine of 4 to 14 carbon atoms, a branched aliphatic diamine or an alicyclic diamine.

The aromatic dicarboxylic acid unit includes terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 2,5-dichloroterephthalic acid, 2,6-dichloroterephthalic acid, 1, 4-naphthalene dicarboxylic acid, 4, 4'-diphenyl phthalate or 2, 2 '-diphenyl phthalic acid.

The aliphatic dicarboxylic acid unit includes 1,4-succinic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,9-sebacic acid, 1, 10-sebacic acid, 1, 11 - undecanedioic acid, or 1,12-dodecanedioic acid.

The linear aliphatic diamine includes 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1, 10-decanediamine, 1, 11- Undecyldiamine, or 1,12-dodecanediamine.

Branched aliphatic diamines include 2-methyl-1, 5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2,4-dimethyl-1,6-hexanediamine, 2, 2, 4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, or 2-methyl-1, 8-octanediamine or 5-methyl-1,9-nonanediamine.

The alicyclic diamine includes cyclohexanediamine, methylcyclohexanediamine or 4,4'-diaminodicyclohexylmethane.

The thermosetting plastic is selected from the group consisting of epoxy resins, phenolic resins, unsaturated polyesters, polyimide resins, or a combination of at least one of the foregoing polymers.

The rubber is selected from the group consisting of natural rubber and synthetic rubber, or a combination of at least one of the foregoing polymers.

The elastomer is selected from the group consisting of styrene elastomers, polyolefin elastomers, polyester elastomers, polyamide elastomers, and polyurethane elastomers, or a combination of at least one of the foregoing polymers.

The resin composition of the present invention may contain one or more additives. These additives act to improve a specific property in the resin matrix, such as reinforcement, toughening, flame retardancy, processing stability, and product appearance. The additives are selected from the group consisting of fibers, toughening agents, flame retardants, nucleating agents, lubricants, mold release agents, antioxidants, mineral fillers, curing agents, weathering agents, and the like.

The fiber is a combination of one or more of carbon fiber, glass fiber, boron fiber or mineral fiber.

The mineral filler may be round, needle or flake.

The mineral filler is selected from the group consisting of talc, wollastonite, titanium dioxide, kaolin, mica, barium sulfate, solid hollow glass microbeads, calcium carbonate, barium titanate, kaolin or copper calcium titanate.

The toughening agent is preferably a core-shell structured silicon-based toughening agent.

The preparation method of the modified resin composition of the invention is as follows: the material is weighed, the material is uniformly mixed, fed from the main feeding hopper of the twin-screw extruder, uniformly mixed by screw shearing, and then extruded, cooled and cut. The granules give the target product.

The modified resin composition of the present invention can also be obtained by the following preparation method: uniformly mixing the materials, charging the obtained resin composition into a suitable mold, heat-treating, and molding the resin composition by press molding. The object is the target part.

The region of the modified resin composition of the present invention which has been scanned by the laser beam has the ability to deposit metals such as copper, nickel, gold, etc. in the electroless plating process, and the region not scanned by the laser does not have the ability to deposit metal. The modified resin composition also includes an extreme case in which all metallization is performed on the surface of the article in order to satisfy the electromagnetic shielding effect in the electronic technology. The preferred laser wavelength of the modified resin composition in the laser laser engraving process includes 248 nm, 308 nm, 335 nm, 532 nm, 1064 nm, and 10600 nm. The laser is preferably Nd : YAG (yttrium-doped yttrium aluminum garnet laser).

The modified resin composition of the present invention is insulative and stable in an acidic or alkaline electroless plating solution, and the laser beam scanned region can generate a metal core and promote oxidation of the electroless plating solution in contact therewith. The reduction reaction, thereby depositing metal, achieves metallization. The metal oxide solid solution can withstand temperatures exceeding 40 CTC, and can form a stable system with the resin matrix without causing degradation of the resin; and the metal oxide solid solution is free of heavy metal chromium and has no potential risk of environmental pollution.

The resin composition of the present invention can be used for making films, and can also be applied to injection molded products, which can be applied to smart phone antennas, notebook computers, automobiles, home appliances, mobile terminals and the like. detailed description

The modified resin composition, the preparation method, the effect and the use of the present invention for depositing a metal thin film are described in further detail below with reference to the examples and comparative examples, but the embodiment of the invention is not limited thereto. And the film thickness test is performed on the modified resin composition, and the test used The method is a Cross-Cut Test.

The film thickness test is to test the thickness of the metal film deposited on the LDS material in the absence of electrochemical plating. The industry requires that the film thickness distribution within 7-12 rn is acceptable. If the metal oxide solid solution releases too little metal particles under the action of the laser, it will affect the efficiency of copper plating in the subsequent electroless electroless plating process. In the limit without adding a metal oxide solid solution, the part will completely lose the function of electroless copper plating. At this time, the film thickness is 0 mm, and nickel plating and gold plating are also lost.

100-gauge test, that is, using a utility knife to cut 100 lmm*lmm squares on the metal film, stick it with 3M 610 tape and place it for about 2 minutes, then pull it up vertically, and the falling area of the metal film is less than 5%.

The sources of materials used in the embodiments of the present invention are as follows:

Polycarbonate, from Taiwan, brand: PC FN1900

Core-shell structured silicon-based toughening agent, produced by Japan's Zhongyuan Chemical Industry Co., Ltd., grade UF-100;

The metal oxide solid solution can be purchased or homemade. The metal oxide solid solution of the present invention is prepared by the following method: weighing the material according to the raw material ratio of each component, wet grinding, drying the ground material to remove moisture 5-3hrs, The target solid solution product is obtained. The pulverized powder is placed in a high-temperature furnace and heated to 1000-150 CTC for 0. 5-3 hrs to obtain a target solid solution product.

Polyphenylene sulfide, purchased from Sichuan Deyang Chemical Co., Ltd., grade: PPS-HB1;

Nylon 66, from Shenma Group Plastics Technology Co., Ltd., grade: PA66 EPR27;

Polyetheretherketone, from Victrex, UK, grade: VICTREX PEEK 150P;

Liquid crystal polymer LCP, from Solvay, grade XYDAR;

Glass fiber, from Jushi Group Co., Ltd., grade ECS 560A.

The rest of the material is from commercially available products.

Example 1, the resin matrix was selected from 85 rt% polycarbonate, the processing temperature was controlled at 240-270 ° C, and the melt flow rate tested under the condition of 26 CTC/5KG was 21.68 g/10 min _; and 6 rt% of the core-shell structure. Silicon-based toughening agent; and 9%% metal oxide solid solution, metal oxide solid solution tin oxide and cerium oxide blend, solvent is tin oxide, solute is cerium oxide, solvent and solute weight content The ratio is 3:2, and after mixing, it is extruded from a twin-screw extruder, cooled, and pelletized. The obtained pellets were injection molded to obtain a part. The parts were scanned by laser under the laser Nd: YAG (yttrium-doped yttrium aluminum garnet laser, 1064 nm), cleaned with ultrapure water, and immersed in an electroless copper plating bath to selectively deposit copper metal.

In the film thickness test, the thickness of the metal copper layer was 10.25 mm, and the metal-free copper layer was peeled off in the hundred-square test, and the film thickness test and the pass test were qualified. Example 2, the resin matrix is selected from 90 rt% polyphenylene sulfide; and 10% by mass of a metal oxide solid solution, a mixture of a metal oxide solid solution manganese oxide and a cuprous oxide, the solvent is manganese oxide, and the solute is Cuprous oxide, solvent to solute weight ratio of 9: 1, mixed uniformly, extruded from a twin-screw extruder, cooled, pelletized. The obtained pellets were injection molded to obtain a part. After scanning the laser under the laser Nd : YAG (yttrium-doped yttrium aluminum garnet laser), the parts were cleaned with ultrapure water and immersed in a non-electrochemical copper plating tank to selectively deposit copper metal.

The test method is referred to in Example 1. In the film thickness test, the thickness of the metal copper layer was 11.75 mm, and the metal-free copper layer was peeled off in the 100-gauge test, and the film thickness test and the Baige test were qualified.

Example 3, the resin substrate is selected from 64 rt% nylon 66; glass fiber 35 rt%; and 1% by mass metal oxide solid solution, metal oxide solid solution lanthanum oxide and zinc oxide blend, solvent is lanthanum oxide , the solute is zinc oxide, the weight ratio of solvent to solute 4: 3, after mixing uniformly, extruding from a twin-screw extruder, cooling, and pelletizing. The obtained pellets were injection molded to obtain a part. After the laser is scanned by the laser of Nd: YAG (yttrium-doped yttrium aluminum garnet laser), it is cleaned with ultrapure water and immersed in a non-electrochemical copper plating tank to selectively deposit copper metal.

The test method is referred to in Example 1. In the film thickness test, the thickness of the metal copper layer was 7.31 mm, and the metal-free copper layer was peeled off in the test of 100 grids, and the film thickness test and the pass test were qualified.

Example 4, the resin matrix is selected from 40 rt% polyetheretherketone; carbon fiber 50 rt%; and 10% by mass metal oxide solid solution, metal oxide solid solution tungsten oxide and cerium oxide blend, solvent is tungsten oxide The solute is cerium oxide, and the weight ratio of solvent to solute is 5:4. After mixing, it is extruded from a twin-screw extruder, cooled, and pelletized. The obtained pellets were injection molded to obtain a part. After scanning the laser under the laser Nd : YAG (yttrium-doped yttrium aluminum garnet laser), the parts were cleaned with ultrapure water and immersed in an electroless copper plating bath to selectively deposit copper metal.

The test method is referred to in Example 1. In the film thickness test, the thickness of the metal copper layer was 8.78 mm, and the peeling area of the metal copper layer of the test was <5%, and the film thickness test and the pass test were qualified.

Example 5, the resin matrix was selected from 62 wt% polyphenylene sulfide; glass fiber 36 rt%; and 2% metal oxide solid solution, metal oxide solid solution cerium oxide and cuprous oxide blend, solvent 铌The oxide, the solute is cuprous oxide, and the weight ratio of the solute to the solvent is 1: 1, and the mixture is uniformly extruded, extruded from a twin-screw extruder, cooled, and pelletized. The obtained pellets were injection molded to obtain a part. After the laser is scanned by the laser of Nd: YAG (yttrium-doped yttrium aluminum garnet laser), it is cleaned with ultrapure water and immersed in a non-electrochemical copper plating tank to selectively deposit copper metal.

The test method is referred to in Example 1. In the film thickness test, the thickness of the metal copper layer was 8.43 mm, and the metal-free copper layer was peeled off in the test of 100 grids, and the film thickness test and the pass test were qualified.

Example 6, the resin substrate was selected from 60 rt% liquid crystal polymer LCP; glass fiber 21 wt%; talc powder 10 rt%, and 9 rt% metal oxide solid solution, metal oxide solid solution tin oxide and aluminum oxide blend, The solvent is tin oxide, the solute is aluminum oxide, and the weight ratio of solvent to solute is 6:5. After mixing, it is extruded from a twin-screw extruder, cooled, and pelletized. The obtained pellets were molded by injection molding to obtain a part. After the laser is scanned by the laser of Nd: YAG (yttrium-doped yttrium aluminum garnet laser), it is cleaned with ultrapure water and immersed in a non-electrochemical copper plating tank to selectively deposit copper metal.

The test method is referred to in Example 1. In the film thickness test, the thickness of the metal copper layer was 9.86 mm, and the copper-free copper layer was peeled off, and the film thickness test and the pass test were qualified.

Comparative Example 7: The resin matrix was selected from 41 rt% polycarbonate; carbon fiber 50 rt%; and 9 rt% titanium dioxide, which was uniformly mixed, extruded from a twin-screw extruder, cooled, and pelletized. The obtained pellets were injection molded to obtain a part. After the laser is scanned by the laser of the Nd:YAG (yttrium-doped yttrium aluminum garnet laser), it is cleaned with ultrapure water and immersed in a non-electrochemical copper plating tank. It has been found that titanium dioxide does not have the property of selectively depositing metals, and the film thickness test and the hundred-square test are unqualified.

Comparative Example 8 : The resin matrix was selected from 80% polyamide 6; glass fiber 15 rt%; and 5 rt% copper-nickel binary alloy solid solution, which was uniformly mixed, extruded from a twin-screw extruder, cooled, and pelletized. The obtained pellets were injection molded to obtain a part. After the laser is scanned by the laser of Nd: YAG (yttrium-doped yttrium aluminum garnet laser), it is cleaned with ultrapure water and immersed in a non-electrochemical copper plating tank. It was found that the resin composition did not have the property of selectively depositing metal, and the film thickness test and the Baige test failed.

Example 9 The resin matrix is made of 35rt% polyethylene; glass fiber 45rt%; talc powder 10rt%, and 10% metal oxide solid solution, metal oxide solid solution tin oxide and cuprous oxide blend, solvent is tin oxide The solute is cuprous oxide, and the weight ratio of solvent to solute is 6:5. After mixing, it is extruded from a twin-screw extruder, cooled, and pelletized. The obtained pellets were injection molded to obtain a part. After the laser is scanned by the laser of Nd: YAG (yttrium-doped yttrium aluminum garnet laser), it is cleaned with ultrapure water and immersed in a non-electrochemical copper plating tank to selectively deposit copper metal.

The test method is referred to in Example 1. In the film thickness test, the thickness of the metal copper layer was 9. l lmm, and the copper layer without the metal layer was peeled off, and the film thickness test and the pass test were qualified.

Example 10, the resin matrix was selected from 99 rt% polycarbonate, the processing temperature was controlled at 240-270 ° C, and the melt flow rate tested under the condition of 26 CTC/5KG was 21.68 g/10 min; ^1% of metal oxide Solid solution, a mixture of metal oxide solid solution tin oxide and cerium oxide, the solvent is tin oxide, the solute is cerium oxide, the weight ratio of solvent to solute is 3:2, and the mixture is uniformly extruded from twin screw Extrusion in the machine, cooling, pelletizing. The obtained pellets were injection molded to obtain a part. The parts were scanned with a laser under the laser Nd : YAG (ytterbium-doped yttrium aluminum garnet laser, 1064 nm), cleaned with ultrapure water, and immersed in an electroless copper plating tank to selectively deposit copper metal.

In the film thickness test, the thickness of the metal copper layer was 10.25 mm, and the metal-free copper layer was peeled off in the hundred-square test, and the film thickness test and the pass test were qualified. Comparative example 11

The resin matrix is made of 99rt% polycarbonate, the processing temperature is controlled at 240-270°C, and the melt flow rate tested under the condition of 26CTC/5KG is 21.68g/10min; ^1% metal oxide solid solution, metal metal a mixture of oxide solid solution tungsten oxide and cerium oxide, the solvent is tungsten oxide, the solute is cerium oxide, the weight ratio of solvent to solute is 3:2, and the mixture is uniformly squeezed from the twin-screw extruder Out, cool, pelletize. The obtained pellets were injection molded to obtain a part. The parts were scanned by a laser under the laser Nd : YAG (ytterbium-doped yttrium aluminum garnet laser, 1064 nm), cleaned with ultrapure water, and immersed in an electroless copper plating tank.

In the film thickness test, the thickness of the metal copper layer was 10.25 mm, and the metal-free copper layer was peeled off in the hundred-square test, and the film thickness test and the pass test were qualified. In summary, the region of the modified resin composition of the present invention that has been scanned by the laser beam has the ability to deposit metals such as copper, nickel, gold, etc. in the electroless plating process, and the region not scanned by the laser does not have the deposited metal. The modified resin composition is insulating, stable in an acidic or alkaline electroless plating solution, and the scanned area of the laser beam is capable of generating a metal core and promoting the electroless plating solution in contact therewith. The redox reaction, thereby depositing metal, to achieve metallization; the selected metal oxide solid solution does not contain heavy metal chromium, has the characteristics of non-toxic and environmental protection, is also stable in the resin matrix, does not chemically react with the resin matrix and other additives The reaction is also stable in acidic or alkaline electroless plating water. The metal oxide solid solution can withstand a high temperature exceeding 40 CTC, and can form a stable system with the resin matrix without causing degradation of the resin.

The resin composition of the present invention can be used for making films, and can also be applied to injection molded products, which can be applied to smart phone antennas, notebook computers, automobiles, home appliances, mobile terminals and the like.

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and modifications may be made without departing from the spirit and scope of the invention. Simplifications, which are equivalent replacement means, are included in the scope of the present invention.

Claims

Claim

A modified resin composition for depositing a metal film, comprising the following components:

Resin matrix;

Metal oxide solid solution;

Wherein, the metal element in the solvent in the metal oxide solid solution is derived from the elements in the third, fourth, fifth and/or sixth cycles of the periodic table, and the metal element in the solute is from the third, fourth in the periodic table. For the elements in the 5th, 5th and/or 6th cycle, the weight ratio of the solute to the solvent in the metal oxide solid solution is 1:9-1:1.

The modified resin composition according to claim 1, which comprises the following weight components:

Resin matrix: 35-99wt%;

And metal oxide solid solution: l_10rt%.

The modified resin composition according to claim 1 or 2, wherein the metal element in the metal oxide solid solution solvent is selected from the group consisting of Ti, Sn, Pb, Nb, W, Mn, Ge and/or Ta.

The modified resin composition according to claim 3, wherein the metal element in the solvent of the metal oxide solid solution is selected from the group consisting of Sn.

The modified resin composition according to claim 1 or 2, wherein the metal element in the solute of the metal oxide solid solution is selected from the group consisting of Mg, Al, Ca, Mn, Fe, Ti, Ni, Cu , Zn, Ge, Nb, Pd, Ag, Sn and/or Sb.

The modified resin composition according to claim 1 or 2, wherein the metal element in the solute of the metal oxide solid solution does not contain heavy metal element chromium.

The modified resin composition according to claim 1 or 2, wherein the weight percentage of the metal oxide solid solution is selected from 2 to 9 wt%.

The modified resin composition according to any one of claims 1 to 2, wherein the modified resin composition further comprises a fiber, a toughening agent, a flame retardant, a nucleating agent, a lubricant, and a release agent. Molding agents, antioxidants, mineral fillers, curing agents or weathering agents.

9. A method of preparing a modified resin composition according to any one of claims 1-8, comprising the steps of:

Weighing materials;

Mixture: Add the material to a high speed mixer and mix well;

Extrusion: The uniformly mixed material is fed from the main feed hopper, extruded by a twin-screw extruder, cooled, and pelletized;

Or,

Hot press molding: The obtained resin composition was placed in a mold, heat treated, and a resin composition was molded by press molding.

The use of the modified resin composition according to any one of claims 1 to 8 for producing a film, an injection molded or a molded product, comprising applying the product of the modified resin composition to a laser direct forming process, The use of three-dimensional circuits, smart phone antennas, GPS mobile terminal antennas, IC circuits, MEMS, sensors.