CN105492214A

CN105492214A - Flame retardant laser direct structuring materials

Info

Publication number: CN105492214A
Application number: CN201480035523.8A
Authority: CN
Inventors: 李延军; 孟季茹; 邹湘坪
Original assignee: SABIC Innovative Plastics IP BV
Current assignee: SABIC Global Technologies BV
Priority date: 2013-06-21
Filing date: 2014-06-23
Publication date: 2016-04-13
Also published as: KR20160021865A; KR102058072B1; WO2014203227A3; WO2014203227A2; EP3010724A2

Abstract

Flame retardant thermoplastic compositions that are capable of being used in a laser direct structuring process. The compositions include a thermoplastic resin, a laser direct structuring additive, and a flame retardant. The compositions offer flame retardant characteristics while also substantially maintaining the mechanical properties of the base thermoplastic resin, such as the impact strength and/or HDT of the composition. The compositions can be used in a variety of applications such as personal computers, notebook and portable computers, cell phone and other such communications equipment.

Description

Flame retardant laser straight forming material

Technical field

The present invention relates to thermoplastic compounds, and particularly, relate to the flame-retardant thermoplastic compositions that can be used in laser direct forming (laserdirectstructuring) method.The invention still further relates to the method for these compositions of preparation and comprise the goods of these compositions.

Background technology

Electric component can be provided as the printed conductor (printed conductor with expectation, printedconductor) molding injection device (" MID "), namely, when manufacturing in MID technology, use diverse ways, such as, bi-component is injection-molded and electroplate the covering method (mask means of (or electroless plating (electrolessplating)) subsequently, maskingmethod), because for certain situation, it is injection-molded that chemical plating is used for bi-component.Compared to the custom circuit plate be made up of fiberglass reinforced plastics etc., the MID assembly manufactured in this way be have integrated printed circuit cable layout three dimensional molded part and may be other electronics or electromechanical assemblies.Even if assembly only has printed circuit cable and conventional line for replacing electrically or in electronic installation, the use of such MID assembly also saves space, relevant apparatus is made less, and by reduce assembling and contact procedure number reduce manufacturing cost.These MID devices have very large practicality in mobile phone, personal digital assistant (" PDA ") and laptop computer applications.

The installation of stamped metal (stampmetal), flexible printed circuit board (" FPCB ") and molded (two-shotmolding) method of dijection are three kinds of prior aries for the manufacture of MID.But punching press and FPCB installation method have limitation in pattern geometries, and processing is expensive, changes radio frequency (" RF ") pattern in addition and can cause high price to processing and time-consuming change.Molded (bi-component the is injection-molded) method of dijection has been used to produce the 3D-MID with true three-dimensional structure.Antenna can be formed by chemical attack subsequently, chemical surface activation and selective metal coating.This method relates to higher initial cost, and only produces feasible economically for large quantity.Dijection is molded neither environment amenable method.These three kinds of methods all are the technology based on instrument, and it has limited flexibility, longer construction cycle, the prototype of difficulty, expensive design variation and limited miniaturization.

Thus, use laser direct forming (" LDS ") method to form MID to catch on just gradually.In LDS method, computer-controlled laser beam is advanced with the surface of activated plastics on the position arranging conductive path on MID.Use laser direct forming method, the conductive path width of 150 microns or less can be obtained.In addition, the interval between conductive path also can be 150 microns or less.Therefore, the MID that method is formed thus saves space and weight in final use application.Another advantage of laser direct forming is its flexibility.If change the design of circuit, this is only the problem reprograming the computer controlling laser.

Polycarbonate resin (" PC "), or by the one in these and the styrene resin polymer alloy that such as acrylonitrile/butadiene/styrene copolymer (" ABS ") resin alloy is produced are widely used in Electrical and Electronic parts, personal computer, notebook and portable computer, mobile phone and other this communication equipments.Market trends for these application comprise the short construction cycle, design change, reduce costs, miniaturized, variation and functional.Domestic aerial is the key component in the application process of these products.Thus, PC resin is used to form MID will be favourable in the application that can be used for these types.

In addition, in some application, in the design of such as notebook antenna, the anti-flammability of V0 is usually required.Some flame-retardant additives of current use can to the mechanical performance of makrolon material, and such as heat distortion temperature (" HDT ") and/or impact strength are unfavorable.Therefore, verified providing has enough mechanical performances, and the fire retardant combination that simultaneously also can be used in laser direct forming method is difficult.

Thus, the flame-retardant thermoplastic compositions that can be used in laser direct forming method is provided to be favourable.There is provided and can be used in laser direct forming method, the polycarbonate-based fire-retardant combination simultaneously providing the one or more benefits using polycarbonate resin will be also favourable.There is provided the preparation method of the flame-retardant thermoplastic compositions that can be used in laser direct forming method, and the manufacture goods providing the such as antenna comprising the flame-retardant thermoplastic compositions that can be used in laser direct forming method will be also favourable.

Summary of the invention

Described herein is the flame-retardant thermoplastic compositions that can be used in laser direct forming method.Composition comprises thermoplastic resin, laser direct forming additive and fire retardant.Composition can be used in laser direct forming method, also provides good flame-retarding characteristic simultaneously, also maintains favourable mechanical performance simultaneously.Such as, these compositions may be used for various product, such as Electrical and Electronic parts, personal computer, notebook and portable computer, mobile phone and other this communication equipments.

Thus, in one embodiment, thermoplastic compounds comprises the thermoplastic resin of 15 to 85 percentages (%) by weight, wherein thermoplastic resin comprises poly-(arylene ether), poly-(arylene ether)/polystyrene blend, or comprises the combination of at least one in aforementioned resin; The laser direct forming additive of 0.1 to 30% by weight; And by weight 20% or less fire retardant; Wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6 millimeters of (mm) (± 10%).

In one embodiment, thermoplastic compounds comprises the thermoplastic resin of by weight 15 to 85%, and wherein thermoplastic resin comprises polyamide; The laser direct forming additive of 0.1 to 30% by weight; And by weight 20% or less fire retardant; Wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6mm (± 10%).

In another embodiment, the method forming thermoplastic compounds comprises blended following step in an extruder: the thermoplastic resin of 15 to 85% by weight, wherein thermoplastic resin comprises poly-(arylene ether), poly-(arylene ether)/polystyrene blend, or comprises the combination of at least one in aforementioned resin; The laser direct forming additive of 0.1 to 15% by weight; And by weight 20% or less fire retardant; Wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6mm (± 10%).

In another embodiment, the method forming thermoplastic compounds comprises blended following step in an extruder: the thermoplastic resin of 15 to 85% by weight, and wherein thermoplastic resin comprises polyamide; The laser direct forming additive of 0.1 to 15% by weight; And by weight 20% or less fire retardant; Wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6mm (± 10%).

These and other characteristic sum characteristics are below more specifically described.

Detailed description of the invention

In following explanation and embodiment, more specifically describe the present invention, because numerous modifications and variations wherein will be apparent to those skilled in the art, therefore embodiment will be intended to be only exemplary.As used in the specification and in the claims, term " comprise " can comprise embodiment " by ... composition " and " substantially by ... form ".All scopes disclosed herein comprise end points and can independently combine.End points and any numerical value of scope disclosed herein are not limited to accurate scope or numerical value, and they are not exclusively accurate with the numerical value comprising these scopes approximate and/or numerical value.

As used in this article, approximating language can be applied to modify and can change and not cause any quantificational expression that the basic function relevant with it changes.Thus, the value of being modified by a term or multiple term of such as " about " and " substantially " can be not limited to specified exact value in some cases.In at least some example, approximating language corresponds to the precision of the instrument for measuring this value.

The invention provides the flame-retardant thermoplastic compositions that can be used in laser direct forming method.Composition comprises thermoplastic resin, laser direct forming additive and fire retardant.Composition provides flame-retarding characteristic, also substantially maintains the mechanical performance of base thermoplastic's resin (base thermoplastic resin, basethermoplasticresin) simultaneously.Composition may be used for various Electrical and Electronic parts, personal computer, notebook and portable computer, mobile phone and other this communication equipments.

Flame-retardant thermoplastic compositions of the present invention, and the goods using these compositions to make, have excellent physical property compared with the material of prior art.As already discussed, used high-caliber fire retardant to reach excellent flame-retarding characteristic in the composition of prior art.The fire retardant of higher level has adverse effect to HDT and/or impact property.By using laser direct forming (LDS) additive, composition of the present invention overcomes these problems, and described additive not only makes composition can be used in LDS method, also works the synergist of the anti-flammability increasing composition.Although flame retardant levels is lower, LDS additive allows to maintain flame-retarding characteristic, and lower level fire retardant allows the moulded specimens of composition and these compositions to have higher HDT and/or impact strength simultaneously.Therefore, although employ lower level fire retardant, the moulded specimens of thermoplastic compounds can be issued to UL94V0 or V1 grade at 1.5mm (± 10%) or thinner thickness.

In an aspect, thermoplastic compounds of the present invention uses thermoplastic resin as the matrix of composition.The example that may be used for thermoplastic resin of the present invention includes but not limited to: polycarbonate resin, such as Merlon or polycarbonate/acrylonitrile-butadiene-styrene resin mixing thing; Poly-(arylene ether) resin, such as polyphenylene oxide resin, poly-(arylene ether) resin/polystyrene resin blend, polyamide, or comprise the combination of at least one in aforementioned resin.

Thus, in one embodiment, flame-retardant thermoplastic compositions comprises polycarbonate resin.Polycarbonate resin can be selected from Merlon or comprise the resin blend of Merlon.Thus, in one embodiment, Merlon can be used as the matrix resin in composition.The Merlon comprising aromatic carbonate chain units comprises the composition of the construction unit with formula (I):

Wherein R ¹group is aromatic series, aliphatic or alicyclic group.Advantageously, R ¹aromatic organic radicals, and, in interchangeable embodiment, the group of formula (II):

-A ¹-Y ¹-A ²-(II)

Wherein, each A ¹and A ²monocyclic divalent aromatic yl group, and Y ¹be have zero, one or two atom by A ¹with A ²bridging group separately.In an illustrative embodiments, an atom is by A ¹with A ²separately.The illustrative examples of this kind of group be-O-,-S-,-S (O)-,-S (O ₂-C)-, (O)-, methylene, cyclohexyl-methylene, 2-[2,2,1]-dicyclo pitch base, ethidine, isopropylidene, new pentylidene base, cyclohexylidene base, cyclopentadecane fork base, cyclododecane fork base, Buddha's warrior attendant alkylidene radical etc. heptan.In another embodiment, zero atoms is by A ¹with A ²separately, illustrative examples is bis-phenol.Bridging group Y ¹can be alkyl or saturated hydrocarbyl, such as methylene, cyclohexylidene base or isopropylidene.

Merlon can be produced by the Schotten-Bauman interfacial reaction of carbonate precursor and dihydroxy compounds.Usually, aquo-base (aqueous base, aqueousbase) such as NaOH, potassium hydroxide, calcium hydroxide etc. are mixed with the water-fast organic solvent containing dihydroxy compounds such as benzene, toluene, carbon disulfide or carrene.Usual use consisting of phase-transferring agent promotes reaction.Molecular weight regulator can be added individually or with compound in reactant mixture.Also individually or the branching agent described immediately can be added with compound.

Can by wherein only having an atom by A ¹with A ²interfacial reaction polymer precursor separately, such as dihydroxy compounds produces Merlon.As used in this article, term " dihydroxy compounds " comprises, and such as, has the bisphenol compound of following general formula (III):

Wherein R ^aand R ^brepresent hydrogen, halogen atom or univalence hydrocarbyl independently of one another; P and q is the integer of 0 to 4 independently of one another; And X ^aone in the group of expression (IV):

Wherein R ^cand R ^drepresent hydrogen atom or monovalent linear or cyclic hydrocarbon radical independently of one another, and R ^eit is bivalent hydrocarbon radical.

The example of the type of the bisphenol compound that can be represented by formula (IV) comprises two (hydroxyaryl) methane series row, such as 1, two (4-hydroxy phenyl) methane of 1-, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (or bisphenol-A) of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-hydroxy phenyl) octane of 2-, 1, two (4-hydroxy phenyl) propane of 1-, 1, two (4-hydroxy phenyl) normal butane of 1-, two (4-hydroxy phenyl) phenylmethane, 2, two (4-hydroxyl-1-aminomethyl phenyl) propane of 2-, 1, two (the 4-hydroxy-tert-butyl phenyl) propane of 1-, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-etc., two (hydroxyaryl) cycloalkanes series, such as, two (4-hydroxy phenyl) pentamethylene, 1, the 1-bis(4-hydroxyphenyl)cyclohexane etc. of 1,1-, or comprise the combination of at least one in aforementioned bisphenol compound.

It is-O-,-S-,-SO-or-SO that other bisphenol compounds that can be represented by formula (III) comprise wherein X ₂-those.Some examples of this bisphenol compound are two (hydroxyaryl) ether, such as 4,4'-dihydroxydiphenyl ethers, 4,4'-dihydroxy-3,3'-3,5-dimethylphenyl ethers etc.; Two (hydroxy diaryl) thioether, such as 4,4'-dihydroxydiphenyl thioethers, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfides etc.; Two (hydroxy diaryl) sulfoxide, such as 4,4'-dihydroxydiphenyl sulfoxides, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxides etc.; Two (hydroxy diaryl) sulfone, such as 4,4'-dihydroxy-diphenyl sulfones, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfones etc.; Or comprise the combination of at least one in aforementioned bisphenol compound.

Other bisphenol compounds that may be used in the polycondensation of Merlon are represented by formula (V):

Wherein, R ^fit is the alkyl of halogen atom or the alkyl with 1 to 10 carbon atom or halogen substiuted; N is the value of 0 to 4.When n is at least 2, R ^fcan be identical or different.The example of the bisphenol compound that can be represented by formula (IV) is the resorcinol compound of resorcinol, replacement, such as 3-methylresorcinol, 3-ethyl resorcinol, 3-propyl diphenol, 3-butyl resorcinol, 3-tert-butyl resorcin, 3-phenyl resorcinol, 3-cumyl resorcinol, 2,3,4,6-tetrafluoro resorcinol, 2,3,4,6-tetrabromo resorcinol etc.; The quinhydrones of catechol, quinhydrones, replacement, such as 3-methylnaphthohydroquinone, 3-ethyl hydroquinone, 3-propyl group quinhydrones, 3-butylhydroquinone, 3-tertiary butylated hydroquinone, 3-pheny lhydro quinone, 3-cumyl quinhydrones, 2,3,5,6-duroquinol, 2,3,5,6-tetra-tert quinhydrones, 2,3,5,6-tetrafluoro quinhydrones, 2,3,5,6-tetra-bromohydroquinone etc.; Or comprise the combination of at least one in aforementioned bisphenol compound.

Also the bisphenol compound represented by following formula (VI) can be used, such as 2,2,2', 2'-tetrahydrochysene-3,3,3', 3'-tetramethyl-1,1'-spiral shell two-[IH-indenes]-6,6'-glycol.

In one embodiment, bisphenol compound is bisphenol-A.

Typical carbonate precursor comprises carbonyl halide, such as phosgene (phosgene) and carbonyl bromide; Two-haloformate, such as dihydric phenol such as bisphenol-A, quinhydrones etc. two-haloformate, and glycol such as ethylene glycol and neopentyl glycol two-haloformate; And diaryl carbonate, such as dipheryl carbonate base ester, carbonic acid two (tolyl) ester and carbonic acid two (naphthyl) ester.In one embodiment, the carbonate precursor for interfacial reaction is phosgene.

Also can adopt and be polymerized the Merlon of generation when choice for use carbonate copolymer instead of homopolymers by two or more different dihydric phenols or dihydric phenol and glycol or with the polyester of hydroxyl or acid blocked or with binary acid or with carboxylic acid or with the copolymer of aliphatic diacid.Usually, useful aliphatic diacid has about 2 to about 40 carbon.Favourable aliphatic diacid is dodecanedioic acid.

Also branched polycarbonate can be used in the composition, and the blend of Linear polycarbonate and branched polycarbonate.Branched polycarbonate can by adding branching agent preparation in the course of the polymerization process.These branching agents can comprise the multifunctional organic compound of at least three functional groups containing being hydroxyl, carboxyl, carboxylic acid anhydrides, haloformyl, and comprise the combination of at least one in foregoing branching agents.Instantiation comprises trimellitic acid, trimellitic anhydride, partially benzene three acyl chlorides, three-p-hydroxybenzene ethane, isatin-bis-phenol, triphenol TC (1; 3; 5-tri-((p-hydroxybenzene) isopropyl) benzene), triphenol PA (4 (4 (1; two (the p-hydroxybenzene)-ethyl of 1-) α; α-dimethylbenzyl) phenol), 4-chloroformyl phthalic anhydride, trimesic acid, benzophenone tetrabasic carboxylic acid etc., or comprise the combination of at least one in foregoing branching agents.Based in the gross weight of giving Merlon in given layer, branching agent can be added with the level of about 0.05 to about 2.0 percetage by weight (wt%).

In one embodiment, Merlon can be produced by the melt polycondensation reaction between dihydroxy compounds and carbonic diester.Can be dipheryl carbonate base ester, carbonic acid two (2 in order to produce the example of the carbonic diester of Merlon, 4-dichlorophenyl) ester, carbonic acid two (2,4,6-trichlorophenyl) ester, two (2-cyano-phenyl) ester of carbonic acid, two (O-Nitrophenylfluorone) ester of carbonic acid, carboxylol base ester, carbonic acid metacresol base ester, carbonic acid dinaphthyl ester, two (diphenyl) ester of carbonic acid, carbonic acid two (methyl salicyl) ester, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate etc., or comprise the combination of at least one in foregoing carbonic acid diesters.In one embodiment, carbonic diester is two (methyl salicyl) ester of diphenyl carbonate or carbonic acid.

Advantageously, the number-average molecular weight of Merlon is 3,000 to 1,000,000 gram/mol (g/mol).Within the scope of this, advantageously, in one embodiment, have and be more than or equal to 10, the number-average molecular weight of 000, in another embodiment, have and be more than or equal to 20, the number-average molecular weight of 000, and in yet, there is the number-average molecular weight being more than or equal to 25,000g/mol.Also advantageously, in one embodiment, 100 are less than or equal to, the number-average molecular weight of 000, in interchangeable embodiment, be less than or equal to 75, the number-average molecular weight of 000, in another interchangeable embodiment, be less than or equal to 50, the number-average molecular weight of 000, and in another interchangeable embodiment, be less than or equal to the number-average molecular weight of 35,000g/mol.

" Merlon " comprises homo-polycarbonate (each R wherein in polymer ¹identical), in carbonic ester, comprise different R ¹the copolymer (" Copolycarbonate ") of part, comprises the copolymer of the polymer unit such as ester units of carbonate unit and other type, and comprises the combination of at least one in homo-polycarbonate and/or Copolycarbonate.

In another embodiment, the polycarbonate resin used in thermoplastic compounds comprises polycarbonate resin blends, makes Merlon and another resin alloy.In one embodiment, polycarbonate resin comprises the blend of Merlon and poly styrene polymer.Example comprises polycarbonate/acrylonitrile-butadiene-styrene resin mixing thing.

As used in this article, term " polystyrene " comprises the polymer prepared by body, suspension and emulsion polymerisation, and it comprises the polymer precursor with the construction unit of the monomer derived from formula (VII) of at least 25% by weight:

Wherein R ⁵hydrogen, low alkyl group or halogen; Z ¹vinyl, halogen or low alkyl group; And p is 0 to about 5.These organic polymers comprise the homopolymers of styrene, chlorostyrene and vinyltoluene, one or more monomers below enumerated and cinnamic random copolymer: acrylonitrile, butadiene, AMS, vinyl xylene, ethyl vinyl benzene, divinylbenzene and maleic anhydride, and comprise blended and rubber modified polystyrene that is grafting, wherein rubber be polybutadiene or about 98 to about 70wt% styrene and about 2 to the rubbery copolymer of the diene monomers of about 30wt%.

Polystyrene can mix by all proportions with polyphenylene ether, and based on the gross weight of polymer, and any such blend can containing the 5wt% to about 95wt% that has an appointment, and the polystyrene of the amount of about 25wt% to about 75wt% the most usually.

In another embodiment, thermoplastic resin comprises poly-(arylene ether) resin.Suitable poly-(arylene ether) resin comprises containing having with those of the constitutional repeating unit of following formula

Wherein Z ¹each appearance be halogen independently, the C that do not replace or replace ₁-C ₁₂alkyl, condition is alkyl is not tertiary hydrocarbon base, C ₁-C ₁₂sulfenyl, C ₁-C ₁₂oxyl or C ₂-C ₁₂halo oxyl, wherein halogen and oxygen atom separate by least two carbon atoms; And Z ²each appearance be hydrogen independently, halogen, the C that do not replace or replace ₁-C ₁₂alkyl, condition is alkyl is not tertiary hydrocarbon base, C ₁-C ₁₂sulfenyl, C ₁-C ₁₂oxyl or C ₂-C ₁₂halo oxyl, wherein halogen and oxygen atom separate by least two carbon atoms.

As used in this article, no matter independent whether term " alkyl ", use, or as the prefix of another term, suffix or fragment, refer to the residue only comprising carbon and hydrogen.Residue can be aliphatic or aromatic series, straight chain, ring-type, dicyclo, side chain, saturated or undersaturated.It can also contain the combination of aliphatic, aromatic series, straight chain, ring-type, dicyclo, side chain, saturated and undersaturated hydrocarbon part.But when hydrocarbyl residue is described to replace, it can alternatively containing the hetero atom replaced outside the carbon of residue and hydrogen member.Therefore, when specifically describing as replacing, hydrocarbyl residue can also contain one or more carbonyl, amino, hydroxyl etc., or it can contain hetero atom in the main chain of hydrocarbyl residue.As an example, Z ¹it can be the di-n-butyl aminomethyl formed by the di-n-butylamine component reaction of 3,5-dimethyl-Isosorbide-5-Nitrae-phenyl and oxidative polymerization catalyst.

Poly-(arylene ether) can comprise the molecule of the end group containing aminoalkyl with the ortho position being usually located at hydroxyl.What also usually exist is tetramethyl biphenyl quinone (TMDQ) end group, usually obtains from the reactant mixture that wherein there is tetramethyl biphenyl quinone accessory substance.Poly-(phenylene ether) can be the form of homopolymers, copolymer, graft copolymer, ionomer or block copolymer and their combination.

In some embodiments, poly-(arylene ether) comprises 2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether repeat units, 2,3,6-trimethyls-Isosorbide-5-Nitrae-phenylene ether units or their combination.In some embodiments, poly-(arylene ether) is poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether), is also referred to as polyphenylene oxide (PPO).

As passed through gel permeation chromatography, use monodisperse polystyrene standard, styrene divinyl benzene gel at 40 DEG C and there is the chloroform sample of 1 mg/ml (mg/ml) concentration determined, poly-(arylene ether) can have 3,000 to 40, the number-average molecular weight of 000g/mol and 5, the weight average molecular weight of 000 to 80,000g/mol.The combination of poly-(arylene ether) or one or more poly-(arylene ethers) has the inherent viscosity of 0.2 to 1 deciliter/gram (dl/g) measured in chloroform at 25 degrees Celsius (DEG C).Within the scope of this, the inherent viscosity of poly-(arylene ether) can be 0.25 to 0.8 deciliter/gram, more specifically 0.25 to 0.7 deciliter/gram, more specifically 0.3 to 0.65 deciliter/gram, more specifically 0.35 to 0.6 deciliter/gram.

Poly-(arylene ether) resin can with another resin alloy.In one embodiment, thermoplastic resin is the blend of poly-(arylene ether) resin and poly styrene polymer, such as, and poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether)/polystyrene resin blend.Polystyrene can mix by all proportions with polyphenylene ether, and based on the gross weight of polymer, and any such blend can containing the 5wt% to about 95wt% that has an appointment, and the polystyrene of the amount of about 25wt% to about 75wt% the most usually.

The block copolymer of the hydrogenation of the unhydrided block copolymer of homopolystyrene, the polystyrene of modified rubber, alkenyl aroma race monomer and conjugated diene, alkenyl aroma race monomer and conjugated diene can be comprised with the example of the polystyrene of poly-(arylene ether) resin alloy, and comprise the combination of at least one in aforementioned polystyrene resin.

In other embodiments, thermoplastic resin comprises polyamide.Polyamide, is also referred to as nylon, it is characterized in that there is amide groups (-C (O) NH-).The example of polyamide comprises polyamide-6, polyamide-6, 6, polyamide-4, 6, polyamide-11, polyamide-12, polyamide-6, 10, polyamide-6, 12, polyamide 6/6, 6, polyamide-6/6, 12, polyamide MXD, 6 (wherein " MXD " is m-xylylene amine), polyamide-6, T, polyamide-6, I, polyamide-6/6, T, polyamide-6/6, I, polyamide-6, 6/6, T, polyamide-6, 6/6, I, polyamide-6/6, T/6, I, polyamide-6, 6/6, T/6, I, polyamide-6/12/6, T, polyamide-6, 6/12/6, T, polyamide-6/12/6, I, polyamide-6, 6/12/6, I, with their combination.In some embodiments, polyamide comprises polyamide-6, polyamide-6,6 or their combination.

Polyamide can be prepared by many known methods, and polyamide is commercially available from various source.

Amount for the thermoplastic resin in thermoplastic compounds of the present invention can based on the performance of selected thermoplastic compounds and the mechanograph be made up of these compositions.Other factors comprise the impact strength of selected thermoplastic compounds, the HDT of selected thermoplastic compounds, the amount of the fire retardant of use and/or type, the amount of LDS additive of use and/or type, or comprise the combination of at least one in preceding factors.In one embodiment, thermoplastic resin exists with the amount of 15 to 85wt.%.In another embodiment, thermoplastic resin exists with the amount of 20 to 80wt.%.In yet, thermoplastic resin exists with the amount of 25 to 70wt.%.

Except thermoplastic resin, composition of the present invention also comprises laser direct forming (LDS) additive.LDS additive is selected to can be used in laser direct forming method to make composition.In LDS method, laser beam makes LDS additive expose (expose) to be placed on the surface of thermoplastic compounds, and activation is from the metallic atom of LDS additive.Thus, select LDS additive to make when being exposed to laser beam, activation is exposing metal atom also, and in the region do not exposed by laser beam, does not have metallic atom to be exposed.In addition, select LDS additive to make after being exposed to laser beam, (plate) etching area can be plated to form conductive structure.As used in this article, " can plate " refers to a kind of material, wherein, the basic uniform coat of metal can be plated on the region of laser-induced thermal etching, and show wide window (widewindow) for laser parameter.

Except making composition can be used in laser direct forming method, also select to be used for LDS additive of the present invention to strengthen the flame-retarding characteristic of composition.Many known fire retardants adversely affect other mechanical performances (such as impact strength) of heat distortion temperature (HDT) and/or composition.Thus, many fire proofings practicality in the application of structural type is lower.But, by using the LDS additive also enhancing the flame-retarding characteristic of composition, the fire retardant that the anti-flammability obtaining selecting needs is less, thus enables composition of the present invention have the HDT similar to the polycarbonate resin without fire retardant and/or other mechanical performances.

Example for LDS additive of the present invention includes but not limited to: heavy metal mixed oxide spinelle, such as cupric and chromic oxide spinelle; Mantoquita is alkali formula cupric phosphate such as; Cupric phosphate, copper sulphate, cuprous sulfocyanide, or the combination comprising at least one in aforementioned LDS additive.

In one embodiment, LDS additive is heavy metal mixed oxide spinelle, as copper chromium.The use of heavy metal mixed oxide spinelle makes composition can be used in laser direct forming method, also enhances the flame-retarding characteristic of composition simultaneously, makes the amount reducing fire retardant use, thus improves HDT and/or the mechanical performance of composition.In one embodiment, LDS additive exists with the amount of 0.1 to 30wt.%.In another embodiment, LDS additive exists with the amount of 0.2 to 15wt.%.In yet, LDS additive exists with the amount of 0.5 to 8wt.%.

As discussed, select LDS additive to make after use laser active, conductive path can be formed by standard electroless process subsequently.When LDS additive is exposed to laser, metal element discharges.Circuit pattern is plotted on parts and the roughening surface stayed containing the metallic particles embedded by laser.In plated journey (as copper facing process) period subsequently, these particles are as the core for crystal growth.Other electroless process operable, includes but not limited to: gold-plated, nickel plating, silver-plated, zinc-plated, zinc-plated etc.

Except aforementioned component, thermoplastic compounds of the present invention comprises fire retardant further.In one embodiment, fire retardant is phosphonium flame retardant, such as organophosphorus ester and/or the organic compound containing phosphorus-to-nitrogen bonds.

One type of organophosphorus ester is formula (GO) ₃the aromatic phosphoric ester of P=O, wherein, each G is alkyl, cycloalkyl, aryl, alkaryl or aralkyl independently, and condition is at least one G is aromatic group.Two G groups can link together to provide cyclic group, such as, diphenyl pentaerythritol bisphosphate, it is described in U.S. Patent number 4 by Axelrod, and 154, in 775.Other suitable aromatic phosphoric esters can be, two (dodecyl) ester of such as phosphoric acid phenyl, two (neopentyl) ester of phosphoric acid phenyl, phosphoric acid phenyl two (3, 5, 5'-trimethyl) ester, ethyl diphenyl, phosphoric acid 2-ethylhexyl two (p-methylphenyl) ester, two (2-ethylhexyl) the p-methylphenyl ester of phosphoric acid, lindol, two (2-ethylhexyl) phenylester of phosphoric acid, tricresyl phosphate (nonyl phenyl) ester, two (dodecyl) p-methylphenyl ester of phosphoric acid, di(2-ethylhexyl)phosphate butyl phenyl ester, phosphoric acid 2-chloroethyl diphenyl, phosphoric acid p-methylphenyl two (2, 5, 5'-trimethyl) ester, phosphoric acid 2-ethylhexyl diphenyl phosphate etc.Concrete aromatic phosphoric ester is that wherein each G is aromatic series, such as, and the one of Triphenyl phosphate, lindol, isopropylation Triphenyl phosphate etc.

Two-or multifunctional aromatic series phosphorus-containing compound be also useful, such as, the compound of following formula:

Wherein each G ¹the alkyl with 1 to 30 carbon atom independently; Each G ²alkyl or the oxyl with 1 to 30 carbon atom independently; Each X is bromine or chlorine independently; M is 0 to 4, and n is 1 to 30.Suitable two-or the example of multifunctional aromatic series phosphorus-containing compound comprise resorcinol tetraphenyldiphosphate (RDP), two (diphenyl) phosphate of quinhydrones and two (diphenyl) phosphates, their the oligomeric and polymerization homologue etc. of bisphenol-A respectively.In British Patent No. 2,043, describe the method for the preparation of aforesaid two-or polyfunctional aromatic compound in 083.

The amount that the amount adding the fire retardant of thermoplastic compounds of the present invention can exist based on other components in the amount of the LDS additive of the amount of thermoplastic resin used and type, use and/or type and/or thermoplastic compounds.But as discussed, the use of some fire retardant adversely can affect some performance of thermoplastic compounds, such as impact strength and/or HDT.Therefore, in the present invention, in thermoplastic compounds, the amount of fire retardant is enough to give flame-retarding characteristic, still maintains impact strength and/or the HDT of selection simultaneously.In one embodiment, fire retardant is added with the amount up to 20wt.%.In another embodiment, fire retardant is added with the amount up to 15wt.%.In yet, fire retardant is added with the amount up to 10wt.%.

Thermoplastic compounds of the present invention is substantially free of chlorine and bromine, particularly chlorine and bromine flame retardant." be substantially free of chlorine and bromine " as used in this article and refer to the material of not having a mind to add chlorine, bromine and/or the manufacture of materials containing chlorine or bromine.It is to be appreciated, however, that, in the facility of processing multiple product, a certain amount of cross pollution may be there is, cause bromine and/or chlorine ratio by weight usually in the level of 1,000,000/(partspermillion).Understand according to this, can understand easily, be substantially free of bromine and chlorine and can be defined as and be less than or equal to 100/1000000ths (ppm) by weight, be less than or equal to 75ppm, or be less than or equal to bromine and/or the chlorinity of 50ppm.When this definition is applied to fireproof agent, it is the gross weight based on fireproof agent.When this definition is applied to thermoplastic compounds, it is based on the gross weight of Merlon, LDS additive and fire retardant.

Alternatively, also inorganic combustion inhibitor can be used, such as sulfonate, such as potassium perfluorobutane sulfonate (Rimar salt) and potassium diphenylsulfone sulfonate; The salt formed is reacted by such as alkali metal or alkaline-earth metal (preferred lithium salts, sodium salt, sylvite, magnesium salts, calcium salt and barium salt) and inorganic acid double salt, such as, oxygen-anion, the carbonate of such as alkali and alkaline earth metal ions, such as Na ₂cO ₃, K ₂cO ₃, MgCO ₃, CaCO ₃, BaCO ₃, and BaCO ₃or fluoro-anion compound, such as Li ₃alF ₆, BaSiF ₆, KBF ₄, K ₃alF ₆, KAlF ₄, K ₂siF ₆, and/or Na ₃alF ₆deng.When it is present, based on the polycarbonate resin of 100 weight portions, LDS additive and fire retardant, inorganic combustion inhibitor salt is usually with 0.01 to 1.0 weight portion (pbw), and more specifically the amount of 0.05 to 0.5 weight portion exists.

Anti-dripping agent can also be comprised in the composition, and comprise, such as fluoropolymer, such as forms the fluoropolymer of fibrillation or formation non-protofibre, such as forms the polytetrafluoroethylene (PTFE) etc. of fibriilar polytetrafluoroethylene (PTFE) (" PTFE ") or formation non-protofibre; The fluoropolymer of encapsulation, namely encapsulates in the polymer as the fluoropolymer of anti-dripping agent, the PTFE (" TSAN ") etc. of such as SAN encapsulation, or comprises the combination of at least one in foregoing anti-dripping agents.The fluoropolymer of encapsulation can be made by being polymerized under fluoropolymer exists by polymer.TSAN can by making the copolymerization under the aqueous dispersion of PTFE exists of styrene and acrylonitrile.TSAN can provide the remarkable advantage relative to PTFE, this is because TSAN can more easily disperse in the composition.Based on the gross weight of the fluoropolymer of encapsulation, TSAN such as can comprise the SAN of PTFE and 50wt.% of 50wt.%.Based on the gross weight of copolymer, SAN can be, such as, and the styrene of 75wt.% and the acrylonitrile of 25wt.%.Alternatively, fluoropolymer can in some way with the second polymer, such as, aromatic polycarbonate resin or SAN (such as, as U.S. Patent number 5,521,230 and 4,579, in 906) pre-blend, to form the agglomerated materials (agglomeratedmaterial) as anti-dripping agent.Any one method can be used to the fluoropolymer producing encapsulation.Get rid of any filler, based on the total composition based on 100 weight portions of 100 weight portions, usually use anti-dripping agent with the amount of 0.1 to 1.4 weight portion.

Except thermoplastic resin, LDS additive and fire retardant, thermoplastic compounds of the present invention can comprise the various additives be usually combined in such resin combination.The mixture of additive can be used.This additive can be mixed right times in the component mixed process forming composition.Thermoplastic compounds comprises one or more additives, with one or more characteristics selected of any mechanograph giving thermoplastic compounds and manufactured by it.The example that can comprise additive in the present invention comprises, but be not limited to, one or more the combination in heat stabilizer, processing stabilizers, antioxidant, light stabilizer, plasticizer, antistatic additive, releasing agent, UV absorbent, lubricant, pigment, dyestuff, colouring agent, flow improver additive, impact modifier or aforementioned additive.

Suitable heat stabilizer comprises, such as organic phosphite, such as triphenyl phosphite, tricresyl phosphite-(2,6-3,5-dimethylphenyl) ester, tricresyl phosphite-(list-of mixing and two-nonyl phenyl) ester etc., phosphonate ester, such as phosphonic acids dimethyl phenyl ester etc., phosphate, such as trimethyl phosphate etc., or the combination comprising at least one in aforementioned hot stabilizing agent.Get rid of any filler, based on the total composition of 100 weight portions, usually use heat stabilizer with the amount of 0.01 to 0.5 weight portion.

Suitable antioxidant comprises, such as organic phosphite, such as tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, diphosphorous acid two (2,4-di-tert-butyl-phenyl) pentaerythritol ester, Distearyl pentaerythritols (distearylpentaerythritoldiphosphite) etc.; Alkylation list phenol or polyphenol; The alkylation reaction product of polyphenol and diene, such as four [methylene (3,5-di-t-butyl-4-hydroxy hydrocinnamate)] methane etc.; The butylation product of paracresol or bicyclopentadiene; Alkvlated hvdroquinones; Hvdroxvlated thiodiphenvl ether; Alkylidene radical-bis-phenol; Benzyl compounds; The ester of β-(3,5-di-tert-butyl-hydroxy phenyl)-propionic acid and unitary or polyalcohol; The ester of β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl)-propionic acid and unitary or polyalcohol; The ester of sulfanyl or sulphur aryl compound, such as distearyl thiopropionate, two laurylthiopropionate, double tridecyl thiodipropionate, octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, Ji Wusi base-four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester etc.; The acid amides etc. of β-(3,5-di-tert-butyl-hydroxy phenyl)-propionic acid, or comprise the combination of the aforementioned antioxidant of at least one.Get rid of any filler, based on the total composition of 100 weight portions, usually use antioxidant with the amount of 0.01 to 0.5 weight portion.

Suitable light stabilizer comprises, such as BTA, such as 2-(2-hydroxy-5-methyl base phenyl) BTA, 2-(the tertiary pungent phenyl of 2-hydroxyl-5-)-BTA and UV-531 etc. or comprise the combination of at least one in aforementioned light stabilizer.Get rid of any filler, based on the total composition of 100 weight portions, usually use light stabilizer with the amount of 0.1 to 1.0 weight portion.

Suitable plasticizer comprises, such as phthalic acid ester.Such as dioctyl-4,5-epoxies-hexahydrophthalic acid ester, isocyanuric acid three-(octoxycarbonylethyl) ester, glyceryl tristearate, epoxidised soybean oil etc., or comprise the combination of at least one in aforementioned plasticizer.Get rid of any filler, based on the total composition of 100 weight portions, usually use plasticizer with the amount of 0.5 to 3.0 weight portion.

Suitable antistatic additive comprises, such as glycerin monostearate, stearyl sodium sulfonate, neopelex etc., or the combination of foregoing antistatic agents.In one embodiment, to give composition electrostatically dissipative during carbon fiber, carbon nano-fiber, CNT, carbon black or aforesaid any combination may be used for containing chemical antistatic additive polymer resin.

Suitable releasing agent comprises, such as metallic stearate, stearic acid stearyl ester, pentaerythritol tetrastearate, beeswax, montan wax, paraffin etc. or comprise the combination of at least one in aforementioned releasing agent.Get rid of any filler, based on the total composition of 100 weight portions, usually use releasing agent with the amount of 0.1 to 1.0 weight portion.

Suitable UV absorbent comprises, such as dihydroxy benaophenonel; Hydroxybenzotriazole; Hydroxy benzo triazine; Cyanoacrylate; Oxanilide; Benzoxazinone; 2-(2H-BTA-2-base)-4-(1,1,3,3-tetramethyl butyl)-phenol (CYASORB ^tM5411); UV-531 (CYASORB ^tM531); 2-[two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-base of 4,6-]-5-(octyloxy)-phenol (CYASORB ^tM1164); 2,2'-(Isosorbide-5-Nitrae-phenylene) two (4H-3,1-benzoxazine-4-ketone) (CYASORB ^tMuV-3638); Two [[(2-cyano group-3, the 3-diphenylacryloyl) oxygen base] methyl] propane (UVINUL of 1,3-two [(2-cyano group-3,3-diphenylacryloyl) oxygen base]-2,2- ^tM3030); 2,2'-(Isosorbide-5-Nitrae-phenylene) two (4H-3,1-benzoxazine-4-ketone); Two [[(2-cyano group-3, the 3-diphenylacryloyl) oxygen base] methyl] propane of 1,3-two [(2-cyano group-3,3-diphenylacryloyl) oxygen base]-2,2-; Nano-sized inorganic material, such as titanium oxide, cerium oxide and zinc oxide etc., all have the particle diameter being less than 100 nanometers; Deng, or comprise the combination of the aforementioned UV absorbent of at least one.Get rid of any filler, based on the total composition of 100 weight portions, UV absorbent uses with the amount of 0.01 to 3.0 weight portion usually.

Proper lubrication agent comprises, such as fatty acid ester, such as alkyl stearyl, such as, and methyl stearate etc.; Methyl stearate and comprise the hydrophilic and hydrophobic surfactant of polyethylene glycol polymer, polypropylene glycol polymers and their copolymer, such as methyl stearate in a suitable solvent and polyethylene glycol-propylene glycol copolymers; Or comprise the combination of at least one in aforementioned lubricants.Get rid of any filler, based on the total composition of 100 weight portions, usually use lubricant with the amount of 0.1 to 5 weight portion.

Suitable pigment comprises, such as inorganic pigment, the metal oxide of such as metal oxide and mixing, such as zinc oxide, titanium dioxide, iron oxide etc.; Sulfide such as zinc sulphide etc.; Aluminate; Sulfo group sodium metasilicate; Sulfate and chromate; Carbon black; Zinc ferrite; Ultramarine; Pigment brown 24; Paratonere 101; Pigment yellow 119; Organic pigment, such as azo, diazonium, quinacridone, perylene, naphthalene tetracarboxylic acid, flavanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthanthrone, dioxazine, phthalocyanine, and azo lake; Pigment blue 60, pigment red 122, pigment red 149, paratonere 177, pigment red179, paratonere 202, pigment violet 29, pigment blue 15, pigment Green 7, pigment yellow 147 and pigment yellow 150, or comprise the combination of at least one in aforesaid pigments.Get rid of any filler, based on the total composition based on 100 weight portions of 100 weight portions, usually use pigment with the amount of 1 to 10 weight portion.

Suitable dyestuff comprises, such as organic dyestuff, such as cumarin 460 (blueness), coumarin 6 (green), Nile red etc.; Lanthanide complexes; The hydrocarbon dyestuff of hydrocarbon and replacement; Polycyclic aromatic hydrocarbon; Scintillation dyes (You Xuan oxazole is with oxadiazole); Poly-(the 2-8 alkene) of aryl-or heteroaryl-replacement; Carbonyl cyanine dye; Phthalocyanine dyes and pigments; Oxazine dye; Quinolone dyestuff (carbostyryldye); Porphyrin dye; Acridine dye; Anthraquinone dye; Arylmethane dyes; Azo dyes; Diazo colours (diazoniumdye); Nitro dye; Quinoneimine dye; Tetrazolium dye (tetrazoliumdye); Thiazole dye; Perylene dyes; Purple cyclic ketones dyestuff; Dual-benzoxazolyl thiophene (" BBOT "); And xanthene dye; Fluorogen such as to absorb and at the anti-Stokes displacement dyestuff etc. of visible wavelength emission at near-infrared wavelength; Luminescent dye, such as 5-amino-9-diethyl imino group benzo (a) phenoxazine perchlorate (5-amino-9-diethyliminobenzo (a) phenoxazoniumperchlorate); 7-amino-4-methyl quinolone (7-amino-4-methylcarbostyryl); 7-amino-4-methylcoumarin; 3-(2'-benzimidazolyl)-7-N, N-diethyl amino coumarin; 3-(2'-benzothiazolyl)-7-diethyl amino coumarin; 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles; 2-(4-xenyl)-6-Ben base benzoxazolyl-1,3; 2,5-pair-(4-xenyl)-1,3,4-oxadiazoles; 2,5-pair-(4-xenyl)-oxazoles; 4,4'-pair-(2-butyl octyloxy)-p-quaterphenyl; P-two (o-methyl styrene base)-benzene; 5,9-diaminourea benzo (a) phenoxazine perchlorate; 4-dicyano methylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyrans; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4', 5,5'-dibenzo thiophene three carbocyanine iodide (3,3'-diethyl-4,4', 5,5'-dibenzothiatricarbocyanineiodide); 7-diethylamino-4-methylcoumarin; 7-diethylamino-4-trifluoromethyl cumarin; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 7-ethylamino-6-methyl-4-trifluoromethyl cumarin; 7-ethylamino-4-trifluoromethyl cumarin; Nile red; Rhodamine 700; Oxazine 750; Rhodamine 800; IR125; IR144; IR140; IR132; IR26; IR5; Diphenyl hexatriene; Diphenyl diethylene; Tetraphenylbutadiene; Naphthalene; Anthracene; 9,10-diphenylanthrancene; Pyrene; Bend; Rubrene; Coronene; Luxuriant and rich with fragrance etc., or comprise the combination of at least one in abovementioned dyes.Get rid of any filler, based on the total composition of 100 weight portions, generally use dyestuff with the amount of 0.1 to 5 weight portion.

Suitable colouring agent comprises, such as titanium dioxide, anthraquinone, perylene, purple cyclic ketones, indanthrone, quinacridone, xanthene, oxazine, oxazoline, thioxanthene, indigo, thioindigo, naphthalimide, cyanine, xanthene, methine, lactone, cumarin, two-benzoxazolyl thiophene (BBOT), naphthalene tetracarboxylic acid derivative, monoazo and disazo pigment, triarylmethane, amino ketones, two (styryl) biphenyl derivatives etc., and comprise the combination of at least one in foregoing colorants.Get rid of any filler, based on the total composition of 100 weight portions, generally use colouring agent with the amount of 0.1 to 5 weight portion.

Suitable blowing agent comprises such as, low boiling halogenated hydrocarbons and produce those of carbon dioxide; At room temperature be solid and the blowing agent of generation gas (such as nitrogen, carbon dioxide, ammonia) when being heated above their decomposition temperature; the slaine, 4 of such as Celogen Az, Celogen Az; two (benzenesulfonyl hydrazides) (4,4'oxybis (benzenesulfonylhydrazide)) of 4' oxygen, sodium acid carbonate, ammonium carbonate etc. or comprise the combination of at least one in aforementioned foaming agent.Get rid of any filler, based on the total composition of 100 weight portions, usually use blowing agent with the amount of 1 to 20 weight portion.

In addition, can by improving liquidity and the material of other performance, as low molecular weight hydrocarbon resin adds composition.The useful especially classification of low molecular weight hydrocarbon resin is derived from oil C ₅to C ₉those of raw material, its unsaturated C obtained derived from petroleum cracking ₅to C ₉monomer.Nonrestrictive example comprises alkene, such as amylene, hexene, heptene etc.; Alkadienes, such as pentadiene, hexadiene etc.; Cyclic olefin and alkadienes, such as cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, methyl cyclopentadiene etc.; Cyclodiene diene (cyclicdiolefindiene), such as bicyclopentadiene, methylcyclopentadiene dimer etc.; And aromatic hydrocarbon, such as vinyltoluene, indenes, methyl indenes etc.In addition, resin can be partially or even wholly hydrogenation.

Finally, in interchangeable embodiment, composition of the present invention can comprise one or more fillers.These fillers can be selected to give other impact strength and/or to provide the other characteristic of the characteristic based on final selected thermoplastic compounds.Suitable filler or reinforcing agent comprise, such as TiO ₂; Fiber, such as asbestos, carbon fiber etc.; Silicate and SiO 2 powder, such as alumina silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica 3 SiC 2/graphite, natural silica Sand etc.; Boron powder, such as boron nitride powder, boron-silicate powders etc.; Aluminium oxide; Magnesia (magnesia); Calcium sulfate (with its anhydride, dihydrate or trihydrate); Calcium carbonate, the winnofil etc. of such as chalk, lime stone, marble, synthesis; Talcum, comprises threadiness, modularization (modular), needle-like, lamella talc etc.; Wollastonite; Surface-treated wollastonite; Glass marble, such as hollow and solid glass ball, silicate ball (silicatesphere), cenosphere (cenosphere), aluminosilicate (grey microballon (armosphere)) etc.; Kaolin, comprises hard kaolin, soft kaolin, calcined kaolin, comprises various coating known in the art so that the kaolin etc. compatible with polymeric matrix; Mono-crystlling fibre or " whisker ", such as carborundum, aluminium oxide, boron carbide, iron, nickel, copper etc.; Glass fibre (comprising continuously and chopped strand), such as E, A, C, ECR, R, S, D and NE glass and quartz etc.; Sulfide, such as molybdenum sulfide, zinc sulphide etc.; Barium compound, such as barium titanate, barium ferrite, barium sulfate, barite etc.; Metal and metal oxide, such as particle or fibrous aluminium, bronze, zinc, copper and mickel etc.; Flake stuffing, such as sheet glass, thin slice carborundum, aluminium diboride, aluminum slice, steel thin slice etc.; Fiberfill, such as short inorfil, such as derived from those of blend comprising at least one in alumina silicate, aluminium oxide, magnesia and calcium sulfate hemihydrate etc.; Natural stuffing and reinforcing material, such as by grinding the wood powder that timber obtains, fiber product, such as cellulose, cotton, sisal hemp, jute, starch, cork powder, lignin, peanut shell, corn, rice hulls etc.; The organic fibrous fillers of the enhancing formed by the following organic polymer that can form fiber: such as poly-(ether ketone), polyimides, polybenzoxazole, poly-(diphenyl sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, PEI, polytetrafluoroethylene (PTFE), acrylic resin, poly-(vinyl alcohol) etc.; And other filler and reinforcing agent, as mica, clay, feldspar, cigarette ash, fillite, quartz, quartzite, perlite, tripoli, diatomite, carbon black etc., or comprise the combination of at least one in aforementioned filler or reinforcing agent.

Silane surface treatment filler and reinforcing agent can be used, to improve and the adhesiveness of polymeric matrix and dispersiveness.In addition, reinforcer can be provided with the form of monofilament or multifilament, and can combinationally use separately or with other types of fibers, such as, by common braiding or core/sheath, side by side (side-by-side), orange lobe type or matrix and fibrillar structure, or by other method well known by persons skilled in the art in fabric manufacturing area.Suitable common braiding structure comprises, such as aromatic polyimide fibre glass fibre etc.Bat wool can provide with following form, such as, and rove, establishment fibre reinforced materials, such as 0-90 degree fabric etc.; Non-woven fabrics fiber reinforcing material, such as continuous strand felt (continuousstrandmat), short-cut original silk silk felt (choppedstrandmat), thin,tough silk yarn (tissue), paper and woollen blanket etc.; Or three-dimensional reinforcements is as braid (braid).Based on the total composition of 100 weight portions, usually use filler with the amount of 1 to 50 weight portion.

In another embodiment, thermoplastic compounds has specific effectiveness in manufacture is by the fire-retardant product of UL94 vertical combustion test (particularly, UL94V0 standard, it is stricter than UL94V1 standard).In UL94 test, there is special challenge in thin goods, because the composition being applicable to manufacture thin goods tends to have comparatively high fluidity.

The anti-flammability of the sample be made up of thermoplastic compounds of the present invention is excellent.Use this standard, thermoplastic compounds is formed as the mechanograph with given thickness.In one embodiment, the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6mm (± 10%).In another embodiment, the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.2mm (± 10%).In yet another embodiment, the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.0mm (± 10%).In another embodiment, the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 0.8mm (± 10%).

Can use and form thermoplastic compounds of the present invention in conjunction with various ingredients with any known method forming thermoplastic resin.In one embodiment, first blend components in high-speed mixer.Other low sheraing methods, include but not limited to hand mix, also can realize that this is blended.Then, by blend by hopper feed to the charging aperture (throat) of double screw extruder.Alternately, can by one or more components by charging aperture and/or fill mouth (sidestuffer) in downstream by side and be fed directly to extruder and be bonded to composition.Extruder operates usually at higher than the temperature caused needed for composition flowing.Extrudate is quenched immediately in a water bath and granulates.The particle prepared like this when cutting extrudate can have 1/4th inches or less length as required.These particles may be used for follow-up molded, shaping (shaping) or shaping (forming).

Additionally provide the shaping comprising thermoplastic compounds, shaping and molded goods.Can by various method (such as injection-molded, extrude, roational molding, blowing, thermoforming) thermoplastic compounds is molded as useful molded article, to form goods, such as personal computer, notebook and portable computer, antenna for mobile phone and other this communication equipment, medical applications, RFID application, automobile application etc.

The present invention is further illustrated by following limiting examples.

Embodiment

In the first two embodiment, the fire retardant of identical amount (BDADP – can obtain from NagaseCo.Ltd.) is used to test PC/ABS compound (can obtain from SABICInnovativePlastics (SABIC innovates plastics)).LDS additive is cupric and chromic oxide spinelle (can obtain from FerroFarEastLimited).Preparation also comprises other Tian Jia Ji – TSAN (innovating plastics from SABIC), releasing agent (PETS, from FaciAsiaPacificPTELTD), antioxidant (Irganox1076, from vapour bar (Ciba)), stabilizing agent (IRGAFOS168, from vapour bar) and impact modifier (silicone-acrylic class impact modifier METABLENS-2001, from Mitsubishi).For sample A, composition comprise 0.64% TSAN, 0.53% releasing agent, the antioxidant of 0.085%, the stabilizing agent of 0.085% and 4.25% impact modifier.For sample B, composition comprise 0.35% TSAN, 0.5% releasing agent, the antioxidant of 0.08%, the stabilizing agent of 0.08% and 4% impact modifier.

To their flame out time of sample test (FOT), it is measured according to UL94 testing standard.In addition, further define first time by probability (" p (ftp) ", according to U.S. Patent number 6,308, in 142 set forth method measure), the flame-retarding characteristic that wherein higher probability has represented.

In first sample, have the BPADP of 13.5wt%, the flame out time (FOT) of 5 rods (thickness: 0.8mm) under aging condition is 111.8 seconds, and in 10 rods at least 4 excellent burning times more than 10 seconds.But when adding the cupric and chromic oxide spinelle of 5wt%, do not have rod to have burning time more than 10 seconds, wherein the longest FOT is 4.2s.In addition, 5 excellent FOT are only 17.3 seconds.In other words, cupric and chromic oxide spinelle is added as LDS additive and significantly reduces burning time, and because this increasing the anti-flammability of compound.According to UL94V0 regulation, sample A (not containing cupric and chromic oxide spinelle) does not pass through V0 under 0.8mm, but sample B (having 5wt% cupric and chromic oxide spinelle) have passed V0 under 0.8mm.Result can be found out in Table 1.

Table 1

Illustrate in ensuing two embodiments, having required V0 to meet UL94 under 0.8mm, if do not add cupric and chromic oxide spinelle to compound, at least needing the BPADP of 16.5wt%.If but only add the cupric and chromic oxide spinelle of 5wt%, the BPADP of 12.5wt% can pass through, as shown in table 2.Therefore, although employ the FR of relatively low amount, LDS additive unexpectedly contributes to the FR performance improving composition, and it makes it possible to reach higher HDT.For these samples, the type of other additive and amount following-for sample C, composition comprise 0.622% TSAN, 0.518% releasing agent, the antioxidant of 0.0829%, the stabilizing agent of 0.0829% and 3.145% impact modifier; For sample D, composition comprise 0.606% TSAN, 0.505% releasing agent, the antioxidant of 0.0808%, the stabilizing agent of 0.0808% and 4.23% impact modifier.

Table 2

Illustrated in ensuing one group of embodiment, require V0 to meet UL94 under 0.8mm, if add the cupric and chromic oxide spinelle of 8.0wt% or 20.0wt%, the BPADP of 11.0wt% or 10.0wt% can pass through, as shown in table 3.Therefore, although employ the FR of relatively low amount, LDS additive unexpectedly contributes to the FR performance improving composition, and it makes it possible to reach higher HDT.Result can be found out in table 3.For these samples, the type of other additive and amount following-for sample E, composition comprise 0.56% TSAN, 0.46% releasing agent, the antioxidant of 0.07%, the stabilizing agent of 0.08% and 3.05% impact modifier; For sample F, composition comprise 0.62% TSAN, 0.52% releasing agent, the antioxidant of 0.07%, the stabilizing agent of 0.08% and 4.15% impact modifier

Table 3

In ensuing one group of embodiment, use independent LDS additive.In these embodiments, LDS additive is the alkali formula cupric phosphate from SigmaAlrich.In order to be issued to the UL performance level of V0 at 0.8mm, when only having the alkali formula cupric phosphate of 5.0wt% in compound, the BPADP of 15.0wt% is enough.As found out in table 4, although the amount of FR agent (BDADP) is lower, reach better FR performance by the p (ftp) of lower flame out time and Geng Gao.For this sample, the type of other additive and amount following-for sample G, composition comprise 0.622% TSAN, 0.518% releasing agent, the antioxidant of 0.0829%, the stabilizing agent of 0.0829% and 3.345% impact modifier.

Table 4

In ensuing one group of embodiment, use different fire retardants.In these embodiments, the RDP from Supresta is used.Only utilize the cupric and chromic oxide spinelle of 5.0wt%, utilize the RDP of RDP instead of 16.5wt% of 13.5wt% in compound, can V0 be reached under 0.8mm.Again, can find out, when RDP and the LDS additive of relatively low amount uses jointly, unexpectedly cause suitable FR performance and the HDT of Geng Gao.These results can be found out in table 5.For these samples, the type of other additive and amount following-for sample H, composition comprise 0.622% TSAN, 0.521% releasing agent, the antioxidant of 0.083%, the stabilizing agent of 0.083% and 3.6% impact modifier; For sample I, composition comprise 0.622% TSAN, 0.521% releasing agent, the antioxidant of 0.083%, the stabilizing agent of 0.083% and 3.5% impact modifier.

Table 5

In ensuing one group of embodiment, the cupric and chromic oxide spinelle of 10.0wt% is added PPO/RDP compound and be not limited to PC/ABS blend with the effect illustrated before showing.PPO innovates plastics from SABIC.Again find out in these embodiments, when with LDS additive in conjunction with time, the RDP of relatively low amount causes better FR performance.Result can be found out in table 6.For these samples, the type of other additive and amount as follows: for sample J, composition comprise the TSAN of 0.242%, the releasing agent of 0.705% and 0.403% antioxidant; For sample K, composition comprise the TSAN of 0.228%, the releasing agent of 0.665% and 0.38% antioxidant.

Table 6

In various embodiments, the disclosure relates to and comprises at least following embodiment.

Embodiment 1: a kind of thermoplastic compounds, comprise: a) by weight 15 to 85% thermoplastic resin, wherein thermoplastic resin comprises poly-(arylene ether), poly-(arylene ether)/polystyrene blend or comprises the combination of at least one in aforementioned resin; B) by weight 0.1 to 30% laser direct forming additive; And c) by weight 20% or less fire retardant; Wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6mm (± 10%).

Embodiment 2: according to the composition of embodiment 1, wherein thermoplastic resin comprises poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether), poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether)/polystyrene blend or comprise the combination of at least one in aforementioned resin.

Embodiment 3: a kind of thermoplastic compounds, comprises: a) by weight 15 to 85% thermoplastic resin, wherein thermoplastic resin comprises polyamide; B) by weight 0.1 to 30% laser direct forming additive; And c) by weight 20% or less fire retardant; Wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6mm (± 10%).

Embodiment 4: according to the composition of embodiment 3, wherein polyamide comprises polyamide-6, polyamide-6, 6, polyamide-4, 6, polyamide-11, polyamide-12, polyamide-6, 10, polyamide-6, 12, polyamide 6/6, 6, polyamide-6/6, 12, polyamide MXD, 6, polyamide-6, T, polyamide-6, I, polyamide-6/6, T, polyamide-6/6, I, polyamide-6, 6/6, T, polyamide-6, 6/6, I, polyamide-6/6, T/6, I, polyamide-6, 6/6, T/6, I, polyamide-6/12/6, T, polyamide-6, 6/12/6, T, polyamide-6/12/6, I, polyamide-6, 6/12/6, I, or comprise the combination of at least one in foregoing polyamides resin.

Embodiment 5: according to the composition any one of embodiment 1-4, wherein laser direct forming additive is selected from heavy metal mixed oxide spinelle, mantoquita or comprises the combination of at least one in aforementioned laser straight forming additive.

Embodiment 6: according to the composition any one of embodiment 1-5, wherein laser direct forming additive package is containing cupric and chromic oxide spinelle or alkali formula cupric phosphate.

Embodiment 7: according to the composition any one of embodiment 1-6, wherein fire retardant is selected from phosphonium flame retardant, organic compound containing phosphorus-to-nitrogen bonds or comprises the combination of at least one in foregoing flame retardants.

Embodiment 8: according to the composition any one of embodiment 1-7, wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.2mm (± 10%).

Embodiment 9: according to the composition any one of embodiment 1-8, wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.0mm (± 10%).

Embodiment 10: according to the composition any one of embodiment 1-9, wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 0.8mm (± 10%).

Embodiment 11: according to the composition any one of embodiment 1-10, wherein thermoplastic compounds comprises the fire retardant of 0.1 to 15wt.%.

Embodiment 12: a kind of manufacture goods comprising composition any one of embodiment 1-11.

Embodiment 13: according to the goods of embodiment 12, wherein goods are selected from personal computer, notebook computer, portable computer, mobile phone or personal digital assistant.

Embodiment 14: a kind of method forming thermoplastic compounds, comprise blended following step in an extruder: a) by weight 15 to 85% thermoplastic resin, wherein thermoplastic resin comprises poly-(arylene ether), poly-(arylene ether)/polystyrene blend or comprises the combination of at least one in aforementioned resin; B) by weight 0.1 to 15% laser direct forming additive; And c) by weight 20% or less fire retardant; Wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6mm (± 10%).

Embodiment 15: according to the method for embodiment 14, wherein thermoplastic resin comprises poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether), poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether)/polystyrene blend or comprise the combination of at least one in aforementioned resin.

Embodiment 16: a kind of method forming thermoplastic compounds, comprises blended following step in an extruder: a) by weight 15 to 85% thermoplastic resin, wherein thermoplastic resin comprises polyamide; B) by weight 0.1 to 15% laser direct forming additive; And c) by weight 20% or less fire retardant; Wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.6mm (± 10%).

Embodiment 17: according to the method for embodiment 16, wherein polyamide comprises polyamide-6, polyamide-6, 6, polyamide-4, 6, polyamide-11, polyamide-12, polyamide-6, 10, polyamide-6, 12, polyamide 6/6, 6, polyamide-6/6, 12, polyamide MXD, 6, polyamide-6, T, polyamide-6, I, polyamide-6/6, T, polyamide-6/6, I, polyamide-6, 6/6, T, polyamide-6, 6/6, I, polyamide-6/6, T/6, I, polyamide-6, 6/6, T/6, I, polyamide-6/12/6, T, polyamide-6, 6/12/6, T, polyamide-6/12/6, I, polyamide-6, 6/12/6, I, or comprise the combination of at least one in foregoing polyamides resin.

Embodiment 18: according to the method any one of embodiment 14-17, wherein laser direct forming additive is selected from heavy metal mixed oxide spinelle, mantoquita or comprises the combination of at least one in aforementioned laser straight forming additive.

Embodiment 19: according to the method any one of embodiment 14-18, wherein laser direct forming additive package is containing cupric and chromic oxide spinelle or alkali formula cupric phosphate.

Embodiment 20: according to the method any one of embodiment 14-19, wherein fire retardant is selected from phosphonium flame retardant, organic compound containing phosphorus-to-nitrogen bonds or comprises the combination of at least one in foregoing flame retardants.

Embodiment 21: according to the method any one of embodiment 14-20, wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.2mm (± 10%).

Embodiment 22: according to the method any one of embodiment 14-21, wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 1.0mm (± 10%).

Embodiment 23: according to the method any one of embodiment 14-22, wherein the moulded specimens of thermoplastic compounds can reach UL94V0 grade under the thickness of 0.8mm (± 10%).

Embodiment 24: according to the method any one of embodiment 14-23, wherein thermoplastic compounds comprises the fire retardant of 0.1 to 15wt.%.

Although given typical embodiment for illustrative purposes, aforementioned explanation not should be understood to limitation of the scope of the invention.Therefore, those skilled in the art can carry out various improvement, amendment and replacement and not deviate from the spirit and scope of the present invention.

Claims

1. a thermoplastic compounds, comprises:

A) by weight 15 to 85% thermoplastic resin, wherein, described thermoplastic resin comprises poly-(arylene ether), poly-(arylene ether)/polystyrene blend or comprises the combination of at least one in above-mentioned resin;

B) by weight 0.1 to 30% laser direct forming additive; And

C) by weight 20% or less fire retardant;

Wherein, the moulded specimens of described thermoplastic compounds can reach UL94V0 grade at the thickness of 1.6mm (± 10%).

2. composition according to claim 1, wherein, described thermoplastic resin comprises poly-(2,6-dimethyl-1,4-phenylene ether), poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether)/polystyrene blend or comprise the combination of at least one in above-mentioned resin.

3. a thermoplastic compounds, comprises:

A) by weight 15 to 85% thermoplastic resin, wherein, described thermoplastic resin comprises polyamide;

B) by weight 0.1 to 30% laser direct forming additive; And

C) by weight 20% or less fire retardant;

4. composition according to claim 3, wherein, described polyamide comprises polyamide-6, polyamide-6, 6, polyamide-4, 6, polyamide-11, polyamide-12, polyamide-6, 10, polyamide-6, 12, polyamide 6/6, 6, polyamide-6/6, 12, polyamide MXD, 6, polyamide-6, T, polyamide-6, I, polyamide-6/6, T, polyamide-6/6, I, polyamide-6, 6/6, T, polyamide-6, 6/6, I, polyamide-6/6, T/6, I, polyamide-6, 6/6, T/6, I, polyamide-6/12/6, T, polyamide-6, 6/12/6, T, polyamide-6/12/6, I, polyamide-6, 6/12/6, I, or comprise the combination of at least one in above-mentioned polyamide.

5. the composition according to any one of claim 1-4, wherein, described laser direct forming additive is selected from heavy metal mixed oxide spinelle, mantoquita or comprises the combination of at least one in above-mentioned laser direct forming additive.

6. the composition according to any one of claim 1-5, wherein, described laser direct forming additive package is containing cupric and chromic oxide spinelle or alkali formula cupric phosphate.

7. the composition according to any one of claim 1-6, wherein, described fire retardant is selected from phosphonium flame retardant, organic compound containing phosphorus-to-nitrogen bonds or comprises the combination of at least one in above-mentioned fire retardant.

8. the composition according to any one of claim 1-7, wherein, the moulded specimens of described thermoplastic compounds can reach UL94V0 grade at the thickness of 1.2mm (± 10%).

9. the composition according to any one of claim 1-8, wherein, the moulded specimens of described thermoplastic compounds can reach UL94V0 grade at the thickness of 1.0mm (± 10%).

10. the composition according to any one of claim 1-9, wherein, the moulded specimens of described thermoplastic compounds can reach UL94V0 grade at the thickness of 0.8mm (± 10%).

11. compositions according to any one of claim 1-10, wherein, described thermoplastic compounds comprises the described fire retardant of 0.1 to 15wt.%.

12. 1 kinds of manufacture goods comprising the composition according to any one of claim 1-11.

13. goods according to claim 12, wherein, described goods are selected from personal computer, notebook computer, portable computer, mobile phone or personal digital assistant.

14. 1 kinds of methods forming thermoplastic compounds, comprise blended following step in an extruder:

B) by weight 0.1 to 15% laser direct forming additive; And

C) by weight 20% or less fire retardant;

15. methods according to claim 14, wherein, described thermoplastic resin comprises poly-(2,6-dimethyl-1,4-phenylene ether), poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether)/polystyrene blend or comprise the combination of at least one in above-mentioned resin.

16. 1 kinds of methods forming thermoplastic compounds, comprise blended following step in an extruder:

B) by weight 0.1 to 15% laser direct forming additive; And

C) by weight 20% or less fire retardant;

17. methods according to claim 16, wherein, described polyamide comprises polyamide-6, polyamide-6, 6, polyamide-4, 6, polyamide-11, polyamide-12, polyamide-6, 10, polyamide-6, 12, polyamide 6/6, 6, polyamide-6/6, 12, polyamide MXD, 6, polyamide-6, T, polyamide-6, I, polyamide-6/6, T, polyamide-6/6, I, polyamide-6, 6/6, T, polyamide-6, 6/6, I, polyamide-6/6, T/6, I, polyamide-6, 6/6, T/6, I, polyamide-6/12/6, T, polyamide-6, 6/12/6, T, polyamide-6/12/6, I, polyamide-6, 6/12/6, I, or comprise the combination of at least one in above-mentioned polyamide.

18. methods according to any one of claim 14-17, wherein, described laser direct forming additive is selected from heavy metal mixed oxide spinelle, mantoquita or comprises the combination of at least one in above-mentioned laser direct forming additive.

19. methods according to any one of claim 14-18, wherein, described laser direct forming additive package is containing cupric and chromic oxide spinelle or alkali formula cupric phosphate.

20. methods according to any one of claim 14-19, wherein, described fire retardant is selected from phosphonium flame retardant, organic compound containing phosphorus-to-nitrogen bonds or comprises the combination of at least one in above-mentioned fire retardant.

21. methods according to any one of claim 14-20, wherein, the moulded specimens of described thermoplastic compounds can reach UL94V0 grade at the thickness of 1.2mm (± 10%).

22. methods according to any one of claim 14-21, wherein, the moulded specimens of described thermoplastic compounds can reach UL94V0 grade at the thickness of 1.0mm (± 10%).

23. methods according to any one of claim 14-22, wherein, the moulded specimens of described thermoplastic compounds can reach UL94V0 grade at the thickness of 0.8mm (± 10%).

24. methods according to any one of claim 14-23, wherein, described thermoplastic compounds comprises the described fire retardant of 0.1 to 15wt.%.