CN112225944B - LDS (laser direct structuring) additive with good dispersibility, LDS material containing additive and application - Google Patents

LDS (laser direct structuring) additive with good dispersibility, LDS material containing additive and application Download PDF

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CN112225944B
CN112225944B CN201910633116.1A CN201910633116A CN112225944B CN 112225944 B CN112225944 B CN 112225944B CN 201910633116 A CN201910633116 A CN 201910633116A CN 112225944 B CN112225944 B CN 112225944B
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lds additive
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CN112225944A (en
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于志省
李应成
白瑜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract

The invention relates to an LDS additive with good dispersibility, an LDS material containing the additive and application thereof, and mainly solves the problem of poor dispersibility of the LDS additive in the prior art. The LDS additive comprises, by weight, 80-95 parts of a laser sensitizer and 5-20 parts of a surface treating agent; wherein the surface treatment agent coats the surface of the laser sensitizer; the surface treating agent has a structure shown as a formula (I), wherein R is C1～C18Aliphatic hydrocarbon groups or aromatic hydrocarbon groups of (1); x is-O-, -NH-, -COO-or-C6H4O-; p is selected from any number of 0-20; q is any number selected from 1 to 20; m is hydrogen, alkali metal, alkaline earth metal or ammonium; the technical scheme that n is 1 or 2 can better solve the problems and can be used for parts such as communication, electronics, automobiles, medical treatment, aerospace and the like.

Description

LDS (laser direct structuring) additive with good dispersibility, LDS material containing additive and application
Technical Field
The invention belongs to the field of polymer composite materials, and relates to an LDS additive with good dispersibility, an LDS material containing the additive and application of the LDS material. The composition containing the LDS additive is suitable for the fields of communication, electronics, medical treatment, automobiles, aerospace and the like.
Background
The three-dimensional molded interconnection device production technology (3D-MID) is an electronic device production technology that rapidly develops in the future by endowing a general plastic component, a circuit board, and the like with an electrical interconnection function, so that the plastic shell and the structural device have functions of supporting, protecting, and the like, and also have functions of shielding, antenna, and the like, which are generated by combining with a conductive circuit. The laser direct forming is a 3D-MID technology combining processing modification, injection molding, laser and chemical plating processes.
The Laser Direct Structuring (LDS) material is mainly characterized in that LDS additive is introduced into matrix resin to obtain modified plastic particles, the plastic particles are molded into a product through injection molding, and then the product is activated by laser and 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 LDS technology was first developed by LPKF laser and electronics, germany, whose patent CN 1518850a describes a conductor track structure on a non-conductive carrier material and a method for its manufacture. 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 compromising the toughness and interfacial properties of the material. Patent CN 104945669A, CN 105037809a discloses a method for modifying laser sensitizer by coating the surface of pyrithione-containing derivative, and the modified additive is used for preparing LDS materials such as PPS, PA66, etc., and improves the peel strength between laser sensitizer and substrate. However, the pyridine derivatives have high toxicity and high cost, and thus have economic problems in industrial application, thereby limiting the application thereof. Therefore, it is significant to develop an LDS material with optimized and balanced processability, platability, usability and economy.
Disclosure of Invention
The invention aims to solve the technical problem that the LDS additive has poor dispersibility in the prior art, and provides the LDS (laser direct structuring) additive with good dispersibility. The LDS additive has the characteristics of good dispersibility and improved compatibility with thermoplastic matrix resin after surface modification treatment.
The second technical problem to be solved by the present invention is to provide a preparation method of LDS additive with good dispersibility, which is suitable for solving the first technical problem. The method is simple and easy to implement, and easy to realize production amplification.
The invention provides a use of LDS additive with good dispersibility, which is suitable for solving one of the technical problems, for example but not limited to the use in LDS materials.
The fourth technical problem to be solved by the present invention is to provide a LDS material containing the LDS additive, which is suitable for solving one of the technical problems, and the LDS material composition containing the LDS additive has significantly improved interface compatibility while satisfying requirements of usability and formability of a part.
The fifth technical problem to be solved by the present invention is to provide a method for preparing an LDS material suitable for solving the fourth technical problem.
The invention aims to solve the technical problems, and the invention provides the application of the LDS material which is suitable for solving the technical problems, and the LDS material composition containing the LDS additive is suitable for parts such as communication, electronics, automobiles, medical treatment, aerospace and the like.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: an LDS additive comprises, by weight, 80-95 parts of a laser sensitizer and 5-20 parts of a surface treating agent; wherein the surface treating agent is coated on the surface of the laser sensitizer; the surface treating agent has a structure shown in a formula (I):
Figure BDA0002129360650000021
in the formula, R is C1～C18Aliphatic hydrocarbon groups or aromatic hydrocarbon groups of (1); x is-O-, -NH-, -COO-or-C6H4O-; p is selected from any number of 0-20; q is any number selected from 1 to 20; m is hydrogen, alkali metal, alkaline earth metal or ammonium; n is 1 or 2.
In the above technical solution, the laser sensitizer is preferably an LDS additive having an absorption coefficient not zero for ultraviolet, infrared or visible radiation. The LDS additive forms a metal seed under the action of electromagnetic radiation, laser radiation, the metal seed effects metal plating deposition in an electroless plating process to produce a printed wire or circuit on the surface of the molded article at the irradiated location. Wherein the LDS additive preferably has an absorption capacity in the visible and infrared radiation range, said absorption capacity having an absorption coefficient of at least 0.02, preferably at least 0.06, more preferably at least 0.15, and/or additionally a radiant energy absorber, said absorber being capable of transferring radiant energy to the LDS additive.
In the above technical scheme, the laser sensitizer preferably has a chemical general formula MxYyOzHpThe metal oxygen-containing compound of (a); wherein M is at least one of beryllium, magnesium, aluminum, zinc, titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, tin and antimony; y is at least one of beryllium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, tin, antimony, nitrogen, boron, carbon, silicon, phosphorus and sulfur; o is an oxygen atom; h is a hydrogen atom; x is selected from any integer from 1 to 6, y is selected from any integer from 0 to 6, z is selected from any integer from 1 to 12, and p is selected from any integer from 0 to 6.
In the above technical scheme, the laser sensitizer can also be selected from doped substrate with chemical general formula MxYyOzHpAt least one of metal oxide-containing compounds of (a); the substrate is selected from talc, feldspar, wollastonite, quartz, mica, chalk, kaolin, diatomite, glass sheet, glass fiber, glass bead, nitrogenSilicon carbide, silicon dioxide, titanium dioxide, iron oxide, aluminum oxide, antimony oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium sulfate, aluminum sulfate, carbon black, carbon nanotubes, graphite, graphene nanoplatelets, and graphene.
In the above technical solution, the particle size of the laser sensitizer is preferably 200 nm to 10 μm.
To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the LDS additive in any one of the technical solutions for solving one of the above technical problems comprises the following steps:
(A) halogenated acetic acid or alkali metal salt thereof and a compound shown as a formula (II) structure are mixed according to a molar ratio of (1-15): 1. reacting for 2-15 hours at the reaction temperature of 10-160 ℃, and treating with acid liquor, alkali liquor and saturated salt water after the reaction is finished to obtain the surface treating agent with the structure shown in the formula (I).
Figure BDA0002129360650000031
Wherein R is aliphatic hydrocarbon or aromatic hydrocarbon of C1-C18; x is-O-, -NH-, -COO-or-C6H4O-; p is selected from any number of 0-20; q is any number selected from 1 to 20.
(B) Mixing the required amount of the surface treating agent shown in the formula (I) structure with the laser sensitizer, carrying out ultrasonic treatment for 1-20 minutes, continuously stirring for 1-6 hours at 40-90 ℃, and carrying out centrifugal separation and drying treatment to obtain the LDS additive with good dispersibility.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the use of an LDS additive, wherein the LDS additive is any one of the aforementioned technical solutions for solving the technical problems.
In the above technical solution, the application is, for example, but not limited to, application in LDS materials.
In order to solve the fourth technical problem, the technical scheme adopted by the invention is as follows: the LDS material comprises the following components in parts by weight:
(A) 55-95 parts of thermoplastic resin;
(B) 1-15 parts of an LDS additive;
(C) 0.1-30 parts of an auxiliary agent.
Wherein, the LDS additive is any one of the technical schemes for solving the technical problems.
In the above technical solution, the thermoplastic resin is at least one selected from the group consisting of polyamide, polycarbonate, polyester, polyphenylene oxide, polyphenylene sulfide, polysulfone, and polyimide.
In the above technical solution, the polyamide is preferably selected from the group consisting of a lactam homopolymer, an aminocarboxylic acid homopolymer, a copolymer of an aliphatic dicarboxylic acid or alicyclic dicarboxylic acid or aromatic dicarboxylic acid monomer and an aliphatic diamine or alicyclic diamine or aromatic diamine monomer, a crystalline or semi-crystalline aliphatic polyamide formed by copolymerizing a lactam or aminocarboxylic acid and/or an aliphatic dicarboxylic acid or alicyclic dicarboxylic acid or aromatic dicarboxylic acid monomer and an aliphatic diamine or alicyclic diamine or aromatic diamine monomer, a semi-crystalline or amorphous polyamide based on an alicyclic diamine, a semi-crystalline or amorphous semi-aromatic polyamide, and a semi-crystalline or amorphous wholly aromatic polyamide. The lactam is selected from butyrolactam, valerolactam, caprolactam, enantholactam, nonanolactam, undecanolactam and dodecanolactam. The amino carboxylic acid is selected from m-aminobenzoic acid, p-aminobenzoic acid, omega-aminocaproic acid, omega-aminoheptanoic acid, omega-aminocaprylic acid, omega-aminononanoic acid, omega-aminodecanoic acid, omega-aminoundecanoic acid and omega-aminododecanoic acid. The aliphatic dicarboxylic acid is selected from malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, and 1, 36-trioxadecanedioic acid. The alicyclic dicarboxylic acid is selected from 1, 4-cyclohexyl dicarboxylic acid and 1, 3-cyclohexyl dicarboxylic acid. The aromatic dicarboxylic acid is selected from isophthalic acid, terephthalic acid and naphthalene dicarboxylic acid. The aliphatic diamine is selected from 1, 4-butanediamine, 1, 5-pentanediamine, 2-methyl-1, 5-pentanediamine, 2-ethyl-2-butyl-1, 5-pentanediamine, 1, 6-hexanediamine, 2, 4-trimethylhexanediamine, 2, 4, 4-trimethylhexanediamine, 1, 8-octanediamine, 2-methyl-1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, 1, 14-tetradecanediamine, 1, 15-pentadecanediamine, 1, 16-hexadecanediamine, 1, 17-heptadecanediamine, 1, 18-octadecanediamine, 1, 36-trioxadecanediamine. The alicyclic diamine is selected from 1, 4-cyclohexyldiamine, 1, 3-cyclohexyldiamine, bis- (4-aminocyclohexyl) methane, 1, 3-diaminomethylcyclohexane, 1, 4-diaminomethylcyclohexane, bis- (4-amino-3-methylcyclohexyl) methane, bis- (4-amino-3-ethylcyclohexyl) methane, bis- (4-amino-3, 5-dimethylcyclohexyl) methane, 2- (4, 4' -diaminodicyclohexyl) propane, 2, 6-norbornane diamine, 2, 6-bis (aminomethyl) norbornane, norbornane dimethylamine and isophorone diamine. The aromatic diamine is selected from m-xylylenediamine, p-xylylenediamine and naphthalene diamine.
In the above-mentioned embodiment, the aliphatic polyamide is preferably selected from polycaprolactam, polyundecanolactam, polydodecanolactam, polytetramethyleneadipamide, polyhexamethyleneadipamide, polyhexamethyleneazelamide, polyhexamethylenesebacamide, polyhexamethyleneundecanedioamide, polyhexamethylenedodecanodiamide, polydecamethylenesebacamide, polydecamethylenedodecanodiamide, polyundecanedioldiamide, polydodecanedioleundecanediamine, and polydodecanedioledodecanediamine. More preferably, said polyamide based on cycloaliphatic diamines is selected from the group consisting of poly (bis- (4-amino-3-methylcyclohexyl) methane-nonanedioyl), poly (bis- (4-amino-3-methylcyclohexyl) methane-decanedioyl, poly (bis- (4-amino-3-methylcyclohexyl) methane-undecanedioyl), poly (bis- (4-amino-3-methylcyclohexyl) methane-dodecanedioyl), poly (bis- (4-amino-3-methylcyclohexyl) methane-hexadecanedioyl, poly (bis- (4-aminocyclohexyl) methane-nonanedioyl, poly (bis- (4-aminocyclohexyl) methane-decanedioyl), poly (bis- (4-aminocyclohexyl) methane-undecanedioyl, poly (bis- (4-aminocyclohexyl) methane-dodecanedioyl), poly (bis- (4-aminocyclohexyl) methane-dodecanedioyl, poly (bis- (4-aminocyclohexyl) methane-dodecanoic acid, poly (bis- (4-amino-3-cyclohexyl) methane-dodecanoic acid), poly (dodecanoic acid) methane-dodecanoic acid, poly (bis- (4-dodecanoic acid, poly (4-dodecanoic acid) methane-dodecanoic acid, poly(s), poly (4-dodecanoic acid, poly(s), poly (bis- (4-amino-2-amino-bis- (4-cyclohexyl) methane, poly(s) methane, poly(s), poly(s), poly(s), and(s) s, and(s) s, and(s) s, Polyhexadecanedioylbis- (4-aminocyclohexyl) methane, polydodecanedioylbis- (4-amino-3-methylcyclohexyl) methane, polydodecanedioisophthaloylbis- (4-amino-3-methylcyclohexyl) methane, polydodecanedioylbis- (4-aminocyclohexyl) methane, poly-dodecanediaminebis- (4-amino-3-methylcyclohexyl) methane, poly-isophthaloyldodecadiaminebis- (4-amino-3-methylcyclohexyl) methane, poly-dodecanediaminebis- (4-aminocyclohexyl) methane, poly-dodecane-co-n-l, poly-l-bis- (4-aminocyclohexyl) methane, poly-dodecane-l-m-4-dodecane-l-m-l-bis- (4-aminocyclohexyl) methane, poly-dodecane-l-m-ol-l-m-l-e-n-e-l-e-n-e-n-e-n-l-n-l-e-n-e-l-n-e-n-e-l-n, Poly (m-xylylene dodecanodiamide) bis- (4-aminocyclohexyl) methane. More preferably, the semi-aromatic polyamide is selected from the group consisting of polybutylene terephthalamide, polyparaphenylene terephthalamide, polyhexamethylene terephthalamide, polyparaphenylene terephthalamide, polydecamethylene terephthalamide, polyparaphenylene isophthalamide, polyhexamethylene isophthalamide, polyparaphenylene isophthalamide, polydecamethylene isophthalamide, polynaphthalenediformamide, polyparaphenylene dicarboxamide, polynaphthalene dodecanediamine, polyparaphenylene succinamide, polyparaphenylene terephthalamide, polyparaphenylene adipamide, polyparaphenylene terephthalamide, and the like, Poly (m-xylylene succinamide), poly (m-xylylene glutarate), poly (m-xylylene adipamide), poly (m-xylylene azepamide), poly (m-xylylene sebacate), poly (m-xylylene dodecanamide), poly (naphthalene dimethylamine succinamide), poly (naphthalene dimethylamine glutarate), poly (naphthalene dimethylamine adipamide), poly (naphthalene dimethylamine azepamide), poly (naphthalene dimethylamine sebacate), poly (naphthalene dimethylamine dodecanoate), poly (hexamethylene adipamide-p-xylylene), poly (hexamethylene adipamide-p-xylylene), poly (hexamethylene adipamide-m-xylylene), poly (hexamethylene adipamide-p-xylylene adipamide), poly (hexamethylene adipamide), Polyhexamethylene sebacamide, polyhexamethylene sebacamide p-xylylenediamine sebacamide, polyhexamethylene sebacamide m-xylylenediamine sebacamide, polyhexamethylene sebacamide p-xylylenediamine sebacamide, polyhexamethylene isophthalamide m-xylylenediamine sebacamide, polyhexamethylene adipamide p-xylylenediamine, polyhexamethylene adipamide m-xylylenediamine, polyhexamethylene dodecanodiamide m-xylylenediamine dodecanodiamide, polyhexamethylene dodecanodiamide p-xylylenediamine dodecanediole, polyhexamethylene isophthalamide m-xylylenediamine dodecanediole, polyhexamethylene isophthalamide p-xylylenediamine dodecanedioleyde, polyhexamethylene isophthalamide m-xylylenediamine dodecanediole.
In the above technical solution, the relative viscosity of the polyamide is preferably 1.2 to 5.0, preferably 1.8 to 4.5, and more preferably 2.5 to 4.2.
In the technical scheme, the relative viscosity of the polyamide is controlled by using a molecular chain regulator. Furthermore, the relative viscosity of the polyamide is adjusted by using an excess of diamine or an excess of dicarboxylic acid.
In the above-mentioned embodiment, the polycarbonate is preferably a linear aromatic polycarbonate obtained by polymerizing a diphenol and a carbonate precursor. The diphenols are selected from aromatic diols. The aromatic diol is selected from 4, 4' -dihydroxybiphenyl, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2, 4-bis (3, 5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (3, 5-dimethyl-4-hydroxyphenyl) cyclohexane, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3-methyl-4-hydroxyphenyl) propane and 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 4-bis (4-hydroxyphenyl) heptane, bis (3, 5-dimethyl-4-hydroxyphenyl) methane, 2- (3, 3 ', 5, 5' -tetrachloro-4, 4 '-dihydroxydiphenyl) propane, 2- (3, 3', 5, 5 '-tetrabromo-4, 4' -dihydroxydiphenyl) propane, (3, 3 '-dichloro-4, 4' -dihydroxyphenyl) methane, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone, bis-4-hydroxyphenyl sulfide. The carbonate precursor is selected from haloformate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, phenyl cresyl carbonate, dinaphthyl carbonate, carbonyl chloride, carbonyl bromide, trichloromethyl chloroformate, bis (trichloromethyl) carbonate, and bis-haloformate. The polycarbonate may also be a branched aromatic polycarbonate formed by polymerizing a diphenol and a trivalent or higher phenolic group-containing compound with a carbonate precursor.
In the above technical scheme, the weight average molecular weight of the polycarbonate is 10000g/mol to 300000g/mol, preferably 25000g/mol to 250000g/mol, and more preferably 50000g/mol to 200000 g/mol. The number-average molecular weight of the polycarbonate is 5000g/mol to 280000g/mol, preferably 15000g/mol to 220000g/mol, more preferably 30000g/mol to 180000 g/mol.
In the above technical solution, the polycarbonate may also be aliphatic/aromatic copolycarbonate formed by polymerization of aliphatic diol and/or diphenol and aromatic diacid or aliphatic diacid. The aliphatic diol is selected from 1, 4-cyclohexyl dimethanol, 1, 3-cyclohexyl dimethanol, 1, 2-ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol. The diphenols are selected from aromatic diols. The aromatic diol is selected from 4, 4' -biphenol, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane. The aromatic diacid is selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid. The aliphatic diacid is selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
In the above embodiment, the aliphatic/aromatic copolycarbonate has an intrinsic viscosity of 0.4dL/g to 1.2dL/g, preferably 0.6dL/g to 1.0dL/g, and preferably 0.7dL/g to 0.9 dL/g.
In the technical scheme, the polycarbonate adopts a catalyst, an acid acceptor and a molecular weight regulator to control the molecular weight. The catalyst is selected from triethylamine, tripropylamine, N-dimethylaniline, N-diethylaniline, tetraethylammonium bromide and methyl triphenyl phosphonium bromide. The acid acceptor is selected from pyridine, triethylamine, N-dimethylaniline, alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate and phosphate. The molecular weight regulator is selected from phenol and C1-C6Para-phenol, para-halophenol, dimethylamine, methylethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine.
In the above technical scheme, the polyester is selected from polyesters or copolyesters formed by polymerization reaction of aromatic dicarboxylic acid or aliphatic dicarboxylic acid and aliphatic diol or alicyclic diol. The aromatic dicarboxylic acid is selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid. The aliphatic dicarboxylic acid is selected from malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid. The aliphatic diol is selected from 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 8-octanediol. The alicyclic diol is selected from 1, 4-cyclohexyl dimethanol and 1, 3-cyclohexyl dimethanol.
In the technical scheme, the intrinsic viscosity of the polyester is preferably 0.4dL/g to 1.6dL/g, more preferably 0.5dL/g to 1.5dL/g, and even more preferably 0.6dL/g to 1.2 dL/g.
In the above technical solution, the polyphenylene ether is selected from a polyphenylene ether homopolymer, a copolymer, a graft copolymer, a block copolymer or an ionomer formed by oxidative coupling polymerization of an alkyl-substituted phenol compound and a catalyst. The alkyl substituted phenol compound is selected from monoalkyl substituted, dialkyl substituted, trialkyl substituted and tetraalkyl substituted phenol compounds. The alkyl is selected from C1-C6An alkyl hydrocarbon group of (1). Wherein, the alkyl groups in the dialkyl, trialkyl and tetraalkyl substitution are selected from the same or different alkyl groups. The catalyst is selected from compounds or complexes of copper, manganese, cobalt, secondary amine, tertiary amine and halogen. The secondary amine is selected from C1-C6The dialkylamine of (a). Wherein said dialkyl is selected from two alkyl groups which may be the same or different. The tertiary amine is selected from C1-C6The trialkylamine of (a). Wherein, the trialkyl is selected from three same or different alkyl groups.
In the above embodiment, the polyphenylene ether is selected from the group consisting of poly (2, 6-dimethyl-1, 4-phenylene) ether, poly (2, 3, 6-trimethyl-1, 4-phenylene) ether, poly (2, 6-diethyl-1, 4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1, 4-phenylene) ether, poly (2, 6-dipropyl-1, 4-phenylene) ether, and poly (2-ethyl-6-propyl-1, 4-phenylene) ether.
In the technical scheme, the intrinsic viscosity of the polyphenylene ether is 0.1dL/g to 0.85dL/g, preferably 0.2dL/g to 0.75dL/g, and more preferably 0.3dL/g to 0.65 dL/g.
In the technical scheme, the polyphenylene sulfide is selected from diiodobenzene and diiodobenzene derivatives, elemental sulfur and a diiodo aromatic compound formed by polymerization reaction of a polymerization inhibitor. The diiodobenzene and the derivative thereof are selected from diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether, diiododiphenyl sulfone or halogenated compounds, hydroxyl, nitro, amino, carboxyl, ester group, aryl, C1-C6 alkoxy, aryl sulfone group and aryl ketone group substituted compounds on aromatic rings of the diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene and diiododiphenyl sulfone. Wherein, the substitution position of 2 iodine atoms of the diiodobenzene and the derivative thereof can be selected from ortho position, meta position, para position, 2 '-position, 2, 3' -position, 2, 4 '-position, 3' -position, 3, 4 '-position and 4, 4' -position, preferably para position, 4 '-position, and more preferably 4, 4' -position.
In the above technical scheme, the elemental sulfur is selected from S2、S4、S6、S8。
In the above technical scheme, the polymerization inhibitor is selected from diphenyl disulfide, monoiodobenzene, thiophenol, 2 '-dibenzothiazole disulfide, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazole sulfenamide, 2- (thiomorpholinyl) benzothiazole, N' -dicyclohexyl-1, 3-benzothiazole-2-sulfenamide or carboxylic acid group (-COOH) substituent or carboxylic acid salt group (-COOM) substituent on the aromatic ring thereof. The carboxylate is selected from lithium carboxylate, sodium carboxylate, potassium carboxylate and ammonium carboxylate.
In the technical scheme, the intrinsic viscosity of the polyphenylene sulfide is 0.1dL/g to 0.85dL/g, preferably 0.2dL/g to 0.75dL/g, and more preferably 0.3dL/g to 0.65 dL/g.
In the above technical solution, the polysulfone is selected from aromatic polysulfones having the general formula-O-Ar-X-Ar-. Wherein Ar represents phenylene, biphenylene, naphthyl or C thereof1-C6Alkyl or phenyl or halo substituted units. The halogen is selected from fluorine, chlorine or bromine. Said C1-C6The alkyl or phenyl or halo substitution of (a) may be mono-, di-, tri-, or tetra-substituted. When the substitution is disubstituted, trisubstituted or tetrasubstituted, the C1-C6The alkyl groups of (A) may be the same or different C1-C6Alkyl group of (1). The di-, tri-and tetra-substitution may be C1-C6Di-, tri-, tetra-substituted with alkyl and/or phenyl and/or halo. X is selected from sulfonyl, sulfinyl or part of the sulfonyl, the sulfinyl or the sulfinyl is replaced by isopropyl.
In the technical scheme, the weight average molecular weight of the polysulfone is 10000g/mol to 150000g/mol, preferably 20000g/mol to 100000g/mol, and more preferably 30000g/mol to 80000 g/mol. The number average molecular weight of the polysulfone is 5000g/mol to 80000g/mol, preferably 10000g/mol to 50000g/mol, more preferably 15000g/mol to 30000 g/mol.
In the technical scheme, the polyimide is aliphatic, semi-aromatic or aromatic polyimide formed by condensation polymerization of a precursor dianhydride and diamine to generate polyamic acid, and dehydration cyclization. Wherein the dianhydride is preferably at least one selected from pyromellitic dianhydride, 3 ', 4, 4 ' -biphenyl tetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic anhydride, isomeric diphenyl sulfide dianhydride, triphendiether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, hexafluoroisopropylidene dititanoic dianhydride, and 3, 3 ', 4, 4 ' -diphenyl sulfone tetracarboxylic anhydride. The diamine is preferably selected from the group consisting of 3, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl ether, dimethyldiphenylmethanediamine, 1, 3-bis (3-aminophenoxy) benzene, 4 ' -bisphenol A diphenyl ether diamine, perfluoroisopropylidenediamine, 4 ' -bis (4-aminophenoxy) diphenylsulfone, 4 ' -bis (4-aminophenoxy) diphenyl ether, diaminodiphenyl (meth) one, 4 ' -diaminotriphenylamine, 4 ' -diaminodiphenylmethane, 3 ' -dimethyl-4, 4 ' -diaminodiphenylmethane, 1, 4- (4 ', 4 ' -diaminodiphenoxy) benzene, 1, 3- (4 ', 4 ' -diaminodiphenoxy) benzene, p, p '- (4, 4' -diaminodiphenoxy) diphenylmethane and/or diaminodiphenyl sulfone.
In the above embodiment, the solution viscosity of the polyamic acid is 1Pa · s to 1000Pa · s, preferably 10Pa · s to 800Pa · s, and more preferably 50Pa · s to 500Pa · s.
In the technical scheme, the auxiliary agent is selected from a compatilizer, a flexibilizer, a reinforcing agent, a flame retardant, a plasticizer, a surface modifier, a heat stabilizer, a lubricant, an antistatic agent, an antioxidant, a UV absorbent and a mold release agent.
In the above technical scheme, the compatilizer is selected from maleic anhydride grafted polyolefin homopolymer or ethylene and unsaturated acid, unsaturated acid salt, unsaturated ester or unsaturated anhydride or C3-C12Or copolymers of other polymers. The unsaturated acid is at least one of acrylic acid, methacrylic acid, maleic acid, fumaric acid and maladic acid. The unsaturated acid salt is selected from at least one of lithium salt, potassium salt, sodium salt and ammonium salt. The unsaturated ester is selected from vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethyl methacrylateAt least one of hexyl ester and monobutyl maleate. The unsaturated anhydride is selected from at least one of itaconic anhydride and maleic anhydride. Said C3-C12The alpha-olefin(s) is (are) at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene. The other polymer is selected from at least one of polystyrene, high impact polystyrene, styrene/acrylonitrile copolymer, styrene/acrylonitrile/butadiene copolymer, styrene/acrylonitrile/isoprene copolymer, styrene/acrylonitrile/acrylate copolymer, styrene/acrylonitrile/ethylene propylene diene rubber copolymer, styrene/butadiene/styrene copolymer, styrene/isoprene/styrene copolymer, styrene/butadiene/isoprene copolymer, styrene/ethylene/butadiene/styrene copolymer.
In the above technical solution, the toughening agent is selected from at least one of natural rubber, polybutadiene, polyisoprene, polyisobutylene, a copolymer of butadiene and/or isoprene and styrene or styrene derivatives and other comonomers, a hydrogenated copolymer and/or a copolymer formed by grafting or copolymerization of acid anhydride, acrylic acid, methacrylic acid and esters thereof. The toughening agent is also selected from grafted rubbers having a crosslinked elastomeric core (consisting of butadiene, isoprene or alkyl acrylates), a grafted shell (homopolymers or copolymers of acrylates, methacrylates, styrene, acrylonitrile), or may be a non-polar or polar olefin homopolymer or copolymer, such as ethylene/propylene, ethylene/propylene/diene and ethylene/octene or ethylene/vinyl acetate rubbers, or may be a non-polar or polar olefin homopolymer or copolymer formed by grafting or copolymerizing anhydrides, acrylic acid, methacrylic acid and esters thereof. The toughening agent is also selected from carboxylic acid functionalized copolymers such as ethylene/acrylic acid copolymers, ethylene/methacrylic acid copolymers, ethylene/1-olefin/acrylic acid copolymers, ethylene/1-olefin/methacrylic acid copolymers, where the 1-olefin can be an olefin or an unsaturated acrylate or methacrylate containing more than 4 atoms, including copolymers in which a portion of the acid groups are neutralized by metal ions.
In the above solution, the toughening agent is also selected from block copolymers of conjugated dienes with alkenyl aromatic compounds such as styrene and its derivatives and/or other vinyl aromatic monomers, hydrogenated block copolymers of alkenyl aromatic compounds with conjugated dienes, or combinations thereof. The block copolymer comprises at least one block derived from a conjugated diene and at least one block derived from an alkenyl aromatic compound. The block copolymer may be selected from at least one of diblock, triblock, tetrablock, pentablock and higher block copolymers of linear structure. In addition, the block copolymer is selected from at least one of diblock, triblock, tetrablock, pentablock and multiblock copolymers with a branched structure or a star structure. The diene monomer is selected from butadiene, 2-methyl-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, isoprene, piperylene, 1, 3-pentadiene, 1, 3-hexadiene and chloroprene. At least one of butadiene and isoprene is preferable. The alkenyl aromatic monomer may be selected from styrene, alpha-methylstyrene, p-methylstyrene, ethylstyrene, propylstyrene, n-butylstyrene, t-butylstyrene, 1, 2-stilbene, 1-stilbene, vinyltoluene, vinylxylene, vinylnaphthalene, divinylnaphthalene, bromostyrene, chlorostyrene, or combinations thereof. Styrene, alpha-methylstyrene, p-methylstyrene, vinylnaphthalene are preferred.
In the above embodiments, other comonomers may be selected in addition to the diene monomer and the alkenyl aromatic monomer. The further comonomers are preferably from 0 to 50% by weight, more preferably from 0 to 30% by weight, particularly preferably from 0 to 15% by weight, based on the total amount of monomers used. Said other comonomer may be selected from C1-C12Of acrylic acid alkyl ester or C1-C12Alkyl methacrylates, such as n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid esters. The comonomer can also be selected from acrylonitrile, methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, diallyl ether of bifunctional alcohol, divinylAt least one of ether, vinyl methyl ether, divinylbenzene and vinyl acetate.
In the above technical scheme, the toughening agent is also selected from polyolefin homopolymer or ethylene/C3-C12Alpha-olefin copolymer or ethylene/C3-C12An elastomer of the alpha-olefin/non-conjugated diene copolymer of (1). Said C3-C12The alpha-olefin(s) is (are) at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and 4-methyl-1-pentene. The non-conjugated diene is selected from bicyclo [2.2.1]At least one of heptadiene, 1, 4-hexadiene, 2-methyl-1, 4-hexadiene, dicyclopentadiene and 5-ethylidene norbornene.
In the above technical scheme, the toughening agent is also selected from ethylene and unsaturated acid, unsaturated acid salt, unsaturated ester or unsaturated anhydride or ethylene and unsaturated acid, unsaturated acid salt, unsaturated ester or unsaturated anhydride and C3-C12At least one of copolymers of alpha-olefins of (a). The unsaturated acid is at least one of acrylic acid, methacrylic acid, maleic acid, fumaric acid and maladic acid. The unsaturated acid salt is selected from at least one of lithium salt, potassium salt, sodium salt and ammonium salt. The unsaturated ester is at least one selected from vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and monobutyl maleate. The unsaturated anhydride is selected from at least one of itaconic anhydride and maleic anhydride. Said C3-C12The alpha-olefin(s) is (are) at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene.
In the above technical solution, the reinforcing agent is preferably at least one selected from talc, mica, glass micro-flakes, 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 surface modifier is preferably at least one selected from polysiloxane, organosiloxane, organosilane, organic titanate, organic aluminate and organic chromium. Wherein, the organosilane is preferably selected from at least one of gamma-chloropropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltrichlorosilane and propenyl trichlorosilane. The organic titanate is preferably selected from at least one of tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, isopropyl triisostearoyl titanate, isopropyl tristearate titanate and ethyl diisostearoyl titanate. The organic aluminate is preferably selected from isopropyl distearylaluminate or a mixture thereof with zirconium aluminate. The organic chromium is preferably selected from a methacryl chromium complex.
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 technical scheme, the antistatic agent is preferably at least one of glyceryl monostearate, sodium stearoyl sulfonate, sodium dodecyl benzene sulfonate, polyethylene glycol, iron powder, aluminum powder, copper powder, lead powder, silver powder, carbon black, carbon fiber, graphite, graphene, carbon nano tube and metal oxide; the metal oxide is preferably alumina whisker.
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, paraffin, silicone oil, and white oil.
In order to solve the fifth technical problem, the technical scheme adopted by the invention is as follows: the preparation method of the LDS material in any one of the four technical schemes for solving the technical problems comprises the following steps:
mixing the required amount of the thermoplastic resin, the LDS additive and the auxiliary agent, and then carrying out melt kneading extrusion molding or calendaring molding or injection molding to obtain the LDS material containing the LDS additive.
In order to solve the sixth technical problem, the invention adopts the technical scheme that: the use of an LDS material, wherein the LDS material is the LDS material according to any one of the four technical solutions for solving the technical problems or the LDS material manufactured by the manufacturing method according to the five technical solutions for solving 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 electrical parts, molded parts, and the like. The molded parts comprise portable electronic devices, such as mobile phones, palm computers, laptop computers, wearable devices, or medical devices, such as hearing aids, sensors, or radio frequency identification transponders, automotive parts, such as airbag modules, steering wheels.
In the technical scheme, the LDS additive with good dispersibility plays an important role in the laser sensitization process and the chemical plating process of the composition containing the LDS additive. The laser beam is quickly scanned on the surface of a workpiece made of the composition to ablate the matrix resin to form an uneven scanning area, so that the bonding strength between the chemical plating layer and the matrix resin can be increased. Meanwhile, the LDS additive reduces metal atoms to be attached to the surface of the uneven matrix resin under the action of laser, and in the subsequent chemical plating process, the metal particles play a role in sensitizing active 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 LDS additive is also called as a laser sensitizer, a laser activator, a laser direct structuring additive, a laser sensitizing catalyst, a laser sensitizing activator or a laser sensitizing catalytic chemical plating agent.
The method of the invention prepares the composition capable of being sensitized by laser by modifying and processing the LDS additive through surface modification and introducing the LDS additive into a thermoplastic resin and auxiliary agent composite system. The invention adopts the technical scheme of the invention to find that the dispersibility of the surface-modified LDS additive is improved, the surface modification layer of the prepared composition containing the LDS additive can be ablated and dispersed particles can be exposed to induce chemical metal plating when the composition is subjected to laser activation, and meanwhile, the impact strength of the composition is obviously improved while the usability, the processing formability and the mechanical strength of the material are maintained, the interaction force among the components of the composition is enhanced, the interface compatibility is obviously improved, and a better technical effect is obtained.
The performance of the invention was determined as follows:
notched impact strength test: measured using a Ceast pendulum impactor according to ASTM D256-2010.
Flexural modulus test: the bending rate was 2mm/min and the span 64mm, determined according to ISO 178 using an Instron model 3344 materials tester.
And (3) testing the grids: measured according to GB/T9286-1998 standard.
The invention is further illustrated by the following specific examples.
Detailed Description
[ example 1 ]
1. Synthesis of surface treating agent:
adding 81 parts of p-methyl benzoyl oxygroup polyoxyethylene ether (20) into a glass reaction kettle provided with a reflux pipe, a thermometer and a stirrer, slowly dropwise adding 33 parts of 70% sodium chloroacetate aqueous solution by using a dropping funnel at 75 ℃, reacting for 7 hours after dropwise adding, and adjusting the pH to 7 by using 10% hydrochloric acid solution to obtain p-methyl benzoyl oxygroup polyoxyethylene ether (20) carboxylic acid; then regulating the pH value to 9 by using a barium hydroxide saturated aqueous solution, washing the solution for three times by using saturated saline solution, and drying the solution to obtain the barium p-methyl benzoyl oxylethylene ether (20) carboxylic acid.
2. Preparation of LDS additive:
30 parts of barium p-methyl benzoyl oxy polyoxyethylene carboxylate, 150 parts of magnesium silicate, 40 parts of barium sulfate and 10 parts of aluminum hydroxide are mixed, ultrasonic treatment is carried out for 15 minutes, stirring is continuously carried out for 2 hours at the temperature of 60 ℃, and centrifugal separation and drying treatment are carried out to obtain the LDS additive A.
3. Preparing an LDS material containing an LDS additive:
45 parts of polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min) after drying treatment, 45 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 5 parts of additive A, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material A1 containing the modified LDS additive A.
Injection molding test: the processing temperature is 250 ℃, and the die temperature is 60 ℃. And (4) injection molding the dried A1 into a standard sample strip by using a BOY injection molding machine, placing the 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 2000mm/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 test of A1 are shown in Table 1.
[ example 2 ]
Preparing an LDS material containing an LDS additive:
46 parts of polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min) after drying treatment, 46 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 3 parts of additive A, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material A2 containing the modified LDS additive A.
Injection molding test, laser activation, electroless plating of a2 were the same as in example 1.
The results of the comprehensive performance test of A2 are shown in Table 1.
[ example 3 ]
Preparing an LDS material containing an LDS additive:
47 parts of polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min) after drying treatment, 47 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 0.8 part of additive A1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material A3 containing the modified LDS additive A.
Injection molding test, laser activation, electroless plating of a3 were the same as in example 1.
The results of the comprehensive performance test of A3 are shown in Table 1.
[ example 4 ]
Preparing an LDS material containing an LDS additive:
43 parts of polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min) after drying treatment, 43 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 9 parts of additive A, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material A4 containing the modified LDS additive A.
Injection molding test, laser activation, electroless plating of a4 were the same as in example 1.
The results of the comprehensive performance test of A4 are shown in Table 1.
[ example 5 ]
Preparing an LDS material containing an LDS additive:
40 parts of polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min) after drying treatment, 40 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 0.8 part of additive A15 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material A5 containing the modified LDS additive A.
Injection molding test, laser activation, electroless plating of a5 were the same as in example 1.
The results of the comprehensive performance test of A5 are shown in Table 1.
Comparative example 1
Preparing an LDS material:
45 parts of dried polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min), 45 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 3.75 parts of magnesium silicate, 1 part of barium sulfate, 0.25 part of aluminum hydroxide, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer to be mixed for 1 min. The mixed material is led into a LABTECH co-rotating twin-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and the LDS material A01 is obtained through melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 r/min, and the feeding speed is 3 kg/h), extrusion and granulation.
Injection molding test, laser activation, electroless plating of a01 were the same as in example 1.
The results of the comprehensive performance test of A02 are shown in Table 1.
Comparative example 2
Preparing an LDS material:
45 parts of polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min) after drying treatment, 45 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 0.8 part of additive A, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material A02 containing the modified LDS additive A.
Injection molding testing, laser activation, electroless plating of a02 were the same as example 1.
The results of the comprehensive performance test of A02 are shown in Table 1.
Comparative example 3
Preparing an LDS material:
45 parts of dried polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min), 45 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 18 parts of additive A, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material A03 containing the modified LDS additive A.
Injection molding test, laser activation, electroless plating of a03 were the same as in example 1.
The results of the comprehensive performance test of A03 are shown in Table 1.
The LDS materials prepared by adopting different parts of the modified LDS additive in the embodiments 1-5 have the advantages that the impact strength and the flexural modulus are regularly changed along with the parts of the additive, the bonding force between the additive and the base material interface is better, the Baige test result is better, and the effect advantage of the method is embodied. The binding force between the unmodified LDS additive and the base material interface is inferior to that of the samples in the same part. In addition, when the part of the modified LDS additive is higher than that of the embodiment, the plating layer is brittle, and the interface bonding force is reduced; when the plating speed is lower than that of the embodiment, the plating speed is slow, and the plating layer is not full.
TABLE 1
Figure BDA0002129360650000171
[ example 6 ]
1. Modification of the LDS additive:
mixing 17 parts of barium p-methyl benzoyl oxy polyoxyethylene carboxylic acid, 150 parts of magnesium silicate, 40 parts of barium sulfate and 10 parts of aluminum hydroxide, carrying out ultrasonic treatment for 15 minutes, continuously stirring for 2 hours at 60 ℃, carrying out centrifugal separation and drying treatment to obtain the LDS additive B.
2. Preparing an LDS material containing an LDS additive:
46 parts of dried polycarbonate (PC, 300 ℃, 1200 g melt index 19.8 g/10 min), 46 parts of polysiloxane carbonate (PCS, 300 ℃, 1200 g melt index 18.5 g/10 min), 5 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA, ethylene content 88%, vinyl acetate content 12%, grafting rate 1.3%), 3 parts of additive B, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 280 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material B1 containing the modified LDS additive B.
Injection molding testing, laser activation, electroless plating of B1 was the same as in example 1.
The results of the comprehensive performance tests of B1 are shown in Table 2.
[ example 7 ]
Mixing 44 parts of barium p-methyl benzoyl oxy polyoxyethylene carboxylic acid, 150 parts of magnesium silicate, 40 parts of barium sulfate and 10 parts of aluminum hydroxide, carrying out ultrasonic treatment for 15 minutes, continuously stirring for 2 hours at 60 ℃, carrying out centrifugal separation and drying treatment to obtain the LDS additive C.
Preparation, injection molding test, laser activation and electroless plating of LDS material C1 containing LDS additive C were the same as in example 1.
The results of the comprehensive performance test of C1 are shown in Table 2.
Comparative example 3
Mixing 10 parts of barium p-methyl benzoyl oxy polyoxyethylene carboxylic acid, 150 parts of magnesium silicate, 40 parts of barium sulfate and 10 parts of aluminum hydroxide, carrying out ultrasonic treatment for 15 minutes, continuously stirring for 2 hours at 60 ℃, carrying out centrifugal separation and drying treatment to obtain the LDS additive D.
Preparation, injection molding test, laser activation and electroless plating of LDS material D01 containing LDS additive D were the same as in example 1.
The results of the comprehensive performance test of D01 are shown in Table 2.
Comparative example 4
56 parts of barium p-methyl benzoyl oxy polyoxyethylene carboxylate, 150 parts of magnesium silicate, 40 parts of barium sulfate and 10 parts of aluminum hydroxide are mixed, ultrasonic treatment is carried out for 15 minutes, stirring is carried out for 2 hours at 60 ℃, and centrifugal separation and drying treatment are carried out to obtain the LDS additive E.
Preparation, injection molding test, laser activation and electroless plating of LDS material E01 containing LDS additive E were the same as in example 1.
The results of the overall performance testing of E01 are shown in Table 2.
The LDS materials prepared by using different parts of the surface treatment agent modified LDS additives in examples 6-7 have high impact strength and no obvious change in flexural modulus, which shows that the bonding force between the additive and the substrate interface is good, and the effect advantage of the method provided by the invention is reflected. The parts of the surface treating agent which are higher or lower than those of the examples have negative effects on the interface bonding force of the modified LDS additive and the base material and the mechanical property of the composition.
TABLE 2
Figure BDA0002129360650000191
[ example 8 ]
1. Synthesis of surface treating agent:
adding 80 parts of n-dodecyl amino polyoxyethylene ether (9) into a glass reaction kettle provided with a reflux pipe, a thermometer and a stirrer, slowly dripping 30 parts of 70% sodium chloroacetate aqueous solution by using a dropping funnel at the temperature of 75 ℃, reacting for 7 hours after dripping is finished, and adjusting the pH to 7 by using 10% hydrochloric acid solution to obtain n-dodecyl amino polyoxyethylene ether (9) carboxylic acid; then regulating the pH value to 9 by using a potassium hydroxide saturated aqueous solution, washing the solution for three times by using saturated salt solution, and drying the solution to obtain the potassium n-dodecyl amino polyoxyethylene ether (9) carboxylate.
2. Preparation of LDS additive:
mixing 14 parts of n-dodecylamine polyoxyethylene ether (9) potassium carboxylate with 100 parts of magnesium silicate, 80 parts of barium sulfate and 20 parts of aluminum silicate, carrying out ultrasonic treatment for 15 minutes, continuously stirring for 2 hours at the temperature of 60 ℃, and carrying out centrifugal separation and drying treatment to obtain the LDS additive F.
3. Preparing an LDS material containing an LDS additive:
60 parts of dried polyamide 6(PA6, 250 ℃, 2160 g melt index of 9.3 g/10 min), 35 parts of semi-aromatic polyamide (PARA, 300 ℃, 1200 g melt index of 14.4 g/10 min), 2 parts of silicone powder, 5 parts of additive F, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of white oil are put into a high-speed mixer for blending treatment for 1 min. And (3) introducing the mixed material into a LABTECH co-rotating double-screw extruder (the screw diameter is 16 mm, the length-diameter ratio is 40), and performing melt kneading (the processing temperature is 270 ℃, the screw rotating speed is 250 rpm, and the feeding speed is 3 kg/h), extrusion and granulation to obtain the LDS material F1 containing the modified LDS additive F.
Injection molding test: the processing temperature is 270 ℃ and the die temperature is 60 ℃. And (3) injection molding the dried F1 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 2000mm/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 notched impact strength of F1 was 180J/m, the flexural modulus was 2.10GPa, and the hundred grid rating was 5B.

Claims (15)

1. An LDS additive comprises, by weight, 80-95 parts of a laser sensitizer and 5-20 parts of a surface treating agent; wherein the surface treatment agent coats the surface of the laser sensitizer; the surface treating agent has a structure shown in formula (I):
Figure FDA0003616157220000011
in the formula, R is C1～C18Aliphatic hydrocarbon groups or aromatic hydrocarbon groups of (1); x is-O-, -NH-, -COO-or-C6H4O-; p is selected from any number of 0-20; q is any number selected from 1 to 20; m is hydrogen, alkali metal, alkaline earth metal or ammonium; n is 1 or 2.
2. The LDS additive of claim 1 wherein the laser sensitiser is of the general chemical formula MxYyOzHmThe metal oxygen-containing compound of (a); wherein M is at least one of beryllium, magnesium, aluminum, zinc, titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, tin and antimony; y is at least one of beryllium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, tin, antimony, nitrogen, boron, carbon, silicon, phosphorus and sulfur; o is an oxygen atom; h is a hydrogen atom; x is selected from any integer from 1 to 6, y is selected from any integer from 0 to 6, z is selected from any integer from 1 to 12, and m is selected from any integer from 0 to 6.
3. The LDS additive of claim 2 wherein the particle size of the laser sensitiser is from 200 nm to 10 microns.
4. The LDS additive of claim 2 wherein the laser sensitizer dopes the substrate.
5. The LDS additive of claim 4 wherein the substrate is selected from at least one of talc, feldspar, wollastonite, quartz, mica, chalk, kaolin, diatomaceous earth, glass flakes, glass fibers, glass beads, silicon nitride, silicon carbide, silica, titanium dioxide, iron oxide, alumina, antimony oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium sulfate, aluminum sulfate, carbon black, carbon nanotubes, graphite, graphene nanoplatelets, graphene.
6. A preparation method of the LDS additive as recited in any one of claims 1 to 5, comprising the following steps:
(A) halogenated acetic acid or alkali metal salt thereof and a compound shown as a formula (II) structure are mixed according to a molar ratio of (1-15): 1. reacting for 2-15 hours at the reaction temperature of 10-160 ℃, and treating with acid liquor, alkali liquor and saturated salt water after the reaction is finished to obtain the surface treating agent with the structure shown in the formula (I);
Figure FDA0003616157220000012
wherein R is C1～C18Aliphatic or aromatic hydrocarbons of (a); x is-O-, -NH-, -COO-or-C6H4O-; p is selected from any number of 0-20; q is any number selected from 1 to 20;
(B) mixing a required amount of the surface treating agent shown in the structure of the formula (I) with a laser sensitizer, carrying out ultrasonic treatment for 1-20 minutes, continuously stirring for 1-6 hours at 40-90 ℃, and carrying out centrifugal separation and drying to obtain the LDS additive.
7. The use of an LDS additive in the preparation of an LDS material, wherein the LDS additive is as defined in any one of claims 1 to 5.
8. The LDS material comprises the following components in parts by weight:
(A) 55-95 parts of thermoplastic resin;
(B) 1-15 parts of LDS additive;
(C) 0.1-30 parts of an auxiliary agent;
wherein the LDS additive is the LDS additive as described in any one of claims 1 to 5.
9. The LDS material of claim 8, wherein the thermoplastic resin is selected from at least one of polyamide, polycarbonate, polyester, polyphenylene oxide, polyphenylene sulfide, polysulfone, and polyimide.
10. The LDS material of claim 8, wherein the additives are selected from the group consisting of compatibilizers, toughening agents, reinforcing agents, flame retardants, plasticizers, surface modifiers, heat stabilizers, lubricants, antistatic agents, antioxidants, UV absorbers, and mold release agents.
11. The LDS material of claim 10, wherein the reinforcing agent is selected from at least one of talc, mica, glass beads, glass fibers, carbon fibers, asbestos fibers, ceramic fibers, cotton fibers, polyaramid fibers.
12. The LDS material of claim 10, wherein the antistatic agent is selected from at least one of glyceryl monostearate, sodium stearoyl sulfonate, sodium dodecylbenzenesulfonate, polyethylene glycol, iron powder, aluminum powder, copper powder, lead powder, silver powder, carbon black, carbon fiber, graphite, graphene, carbon nanotubes, and metal oxides.
13. The LDS material of claim 12 wherein the metal oxide is aluminum oxide whiskers.
14. A method for preparing the LDS material of any one of claims 8-13, comprising the steps of:
mixing the required amount of thermoplastic resin, LDS additive and auxiliary agent, and then carrying out melt kneading extrusion molding or calendaring molding or injection molding to obtain the LDS material.
15. Use of an LDS material in the fields of communication, electronics, medical treatment, automobiles or aerospace, wherein the LDS material is the LDS material according to any one of claims 8 to 13 or the LDS material prepared by the preparation method according to claim 14.
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