CN104955896B - Resin composition for laser direct structuring, molded resin article, and method of manufacturing molded resin article having plating film - Google Patents
Resin composition for laser direct structuring, molded resin article, and method of manufacturing molded resin article having plating film Download PDFInfo
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- CN104955896B CN104955896B CN201380071268.8A CN201380071268A CN104955896B CN 104955896 B CN104955896 B CN 104955896B CN 201380071268 A CN201380071268 A CN 201380071268A CN 104955896 B CN104955896 B CN 104955896B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2251—Oxides; Hydroxides of metals of chromium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0236—Plating catalyst as filler in insulating material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09009—Substrate related
- H05K2201/09118—Moulded substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09818—Shape or layout details not covered by a single group of H05K2201/09009 - H05K2201/09809
- H05K2201/0999—Circuit printed on or in housing, e.g. housing as PCB; Circuit printed on the case of a component; PCB affixed to housing
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging
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Abstract
Provided is a resin composition having consistent plating properties as well as exceptional flame retardancy and various mechanical properties such as bending modulus, bending strength, Charpy impact strength, and deflection temperature under load. A resin composition for laser direct structuring containing, with respect to 100 parts by mass of a component containing 40 to 95% by mass of a polycarbonate resin and 5 to 60% by mass of glass fiber, 0.5 to 10 parts by mass of an elastomer, 5 to 20 parts by mass of a laser direct structuring additive containing copper and chromium, 5 to 30 parts by mass of a phosphorus-based flame retardant, and 0.1 to 1 parts by mass of polytetrafluoroethylene. The elastomer contains less than 10% by mass of acrylonitrile/butadiene/styrene copolymer, and the amount of acrylonitrile/butadiene/styrene copolymer is less than 10% by mass of the total polycarbonate resin and acrylonitrile/butadiene/styrene copolymer content.
Description
Technical field
The present invention relates to laser direct forming is with resin combination (below, sometimes referred to simply as " resin combination ").In addition,
It is related to the synthetic resin that is molded with the resin combination and coated tool is formed on the surface of the synthetic resin
The manufacture method of coated synthetic resin.
Background technology
Recently, as including the exploitation of the mobile phone including smart mobile phone, the method to manufacturing built-in antenna of mobile phone is carried out
A variety of researchs.Especially, the method that demand is capable of the antenna of three dimensional design to manufacture in mobile phone.It is such three-dimensional as being formed
One of technology of antenna, laser direct forming (hereinafter sometimes referred to " LDS ") technology receives publicity.LDS technologies are for example to pass through
In the table surface irradiation laser of the synthetic resin comprising LDS additives, the partial activation for having irradiated laser is only made, in the activation
Part forms the technology of coating using metal.The technology is characterised by, can directly manufacture antenna on resin base material surface
Bonding agent etc. is not used Deng metal structure.The LDS technologies are disclosed such as patent document 1~3 etc..
Prior art literature
Patent document
Patent document 1:International Publication WO2011/095632 pamphlet
Patent document 2:International Publication WO2011/076729 pamphlet
Patent document 3:International Publication WO2011/076730 pamphlet
The content of the invention
Problems to be solved by the invention
When herein, in order that mechanical property is improved and is intended to mixture glass fibre, there is the severe tendency of anti-flammability.In addition,
The present inventor's research understands that the species of LDS additives also produces impact to anti-flammability.The present invention is solving the prior art
Problem is used as purpose, it is therefore an objective to provide holding plating and the modulus of elasticity in static bending, bending strength, Charpy impact intensity, load are scratched
The resin combination of the various mechanical properties such as Qu Wendu and excellent in flame retardance.
For solution to problem
In view of the situation, the present inventor is furtherd investigate, and is as a result found by following means<1>, preferably pass through<
2>~<15>, solve above-mentioned problem.
<1>A kind of laser direct forming resin combination, wherein, include 40~95 mass % relative to 100 mass parts
Polycarbonate resin and 5~60 mass % glass fibre composition, the elastomer comprising 0.5~10 mass parts, 5~20 matter
Measure the laser direct forming additive comprising copper and chromium, the phosphorus flame retardant of 5~30 mass parts and 0.1~1 mass parts of part
Polytetrafluoroethylene (PTFE),
10 overall mass % that the content of the acrylonitrile/butadiene/styrene copolymer in foregoing elastomers is not enough,
The content deficiency polycarbonate resin of acrylonitrile/butadiene/styrene copolymer and acrylonitrile/butadiene/benzene second
10 mass % of the total amount of alkene copolymer.
<2>According to<1>Described laser direct forming resin combination, wherein, aforementioned phosphorus flame retardant is condensation phosphorus
Acid esters.
<3>According to<1>Described laser direct forming resin combination, wherein, aforementioned phosphorus flame retardant is phosphonitrile
Compound.
<4>According to<1>~<3>Any one of laser direct forming resin combination, wherein, aforementioned laser is straight
Type additive is connected into for spinel structure body.
<5>According to<1>~<4>Any one of laser direct forming resin combination, wherein, foregoing elastomers
For copolymeric siloxane elastomer.
<6>According to<1>~<5>Any one of laser direct forming resin combination, wherein, will be with aforementioned glass
The major diameter in the rectangular section of the length direction of glass fiber is denoted as major diameter/minor axis ratio (D2/D1) when D2, minor axis are denoted as D1 and represents
Flat ratio be less than 1.5.
<7>According to<1>~<6>Any one of laser direct forming resin combination, wherein, will be with aforementioned glass
The major diameter in the rectangular section of the length direction of glass fiber is denoted as major diameter/minor axis ratio (D2/D1) when D2, minor axis are denoted as D1 and represents
Flat ratio more than 1.5 and for less than 8.0.
<8>According to<1>~<7>Any one of laser direct forming resin combination, wherein, foregoing
Acrylonitrile/butadiene/styrene copolymer is not substantially included.
<9>A kind of synthetic resin, its be by<1>~<8>Any one of laser direct forming resin combination
What thing was molded with.
<10>According to<9>Described synthetic resin, it also has on the surface coating.
<11>According to<9>Or<10>Described synthetic resin, it is mancarried electronic aid part.
<12>According to<10>Or<11>Described synthetic resin, wherein, aforementioned coating possesses the performance as antenna.
<13>A kind of manufacture method of the coated synthetic resin of tool, its be included in by<1>~<8>Any one of
The surface of synthetic resin that is molded with of laser direct forming resin combination on irradiate after laser, formed using metal
Coating.
<14>According to<13>The manufacture method of the described coated synthetic resin of tool, wherein, aforementioned plating is copper plating
Cover.
<15>A kind of manufacture method of the mancarried electronic aid part with antenna, it includes<13>Or<14>Described tool
The manufacture method of coated synthetic resin.
The effect of invention
In accordance with the invention it is possible to provide holding plating and the modulus of elasticity in static bending, bending strength, Charpy impact intensity, load
The resin combination of the various mechanical properties such as lotus deflection temperature and excellent in flame retardance.
Description of the drawings
Fig. 1 is the schematic diagram for illustrating the operation that coating is arranged on the surface of synthetic resin.In Fig. 1,1 represent resin into
Type product, 2 represent that laser, 3 represent that the part of laser irradiation, 4 represent that coating solution, 5 represent coating.
Specific embodiment
Hereinafter, it is described in detail for present disclosure.It should be noted that in present specification, "~"
The numerical value comprising record before and after it is referred to as lower limit and higher limit to use.In addition, in this specification, " (methyl) propylene
Acid esters " represents acrylate and methacrylate, and " (methyl) acryloyl group " represents acryloyl group and methylacryloyl.
The resin combination of the present invention is characterised by, relative to poly- carbonic acid of 100 mass parts comprising 40~95 mass %
The composition of the glass fibre of ester resin and 5~60 mass %, the elastomer comprising 0.5~10 mass parts, 5~20 mass parts are included
The polytetrafluoroethyl-ne of the laser direct forming additive, the phosphorus flame retardant of 5~30 mass parts and 0.1~1 mass parts of copper and chromium
Alkene, not enough 10 overall mass % of content of the acrylonitrile/butadiene/styrene copolymer in foregoing elastomers, acrylonitrile/fourth
The 10 of the content deficiency polycarbonate resin of diene/styrol copolymer and the total amount of acrylonitrile/butadiene/styrene copolymer
Quality %.
Hereinafter, illustrate for the details of the resin combination of the present invention.
<Polycarbonate resin>
As the polycarbonate resin used in the present invention, it is not particularly limited, it is possible to use aromatic copolycarbonate,
Any one of fatty poly-ester carbonate, aromatic-aliphatic Merlon.Wherein optimization aromatic Merlon, so it is more excellent
Choosing makes thermoplastic aromatic's carbonate polymer that aromatic dihydroxy compound is obtained with the diester reaction of phosgene or carbonic acid
Or copolymer.
As the aromatic dihydroxy compound, 2,2- double (4- hydroxy phenyls) propane (=bisphenol-A), tetramethyls can be included
Base bisphenol-A, double (4- hydroxy phenyls)-P- diisopropyl benzenes, quinhydrones, resorcinol, 4,4 '-dihydroxybiphenyl etc. preferably can be arranged
Enumerate bisphenol-A.Further, preparing the purpose of the high composition of anti-flammability, it is possible to use above-mentioned aromatic dihydroxy compound
It is bonded with the compound of more than 1 sulfonic acid tetraalkyl phosphorus or the polymer of two end OH containing the phenol bases with siloxane structure
Or oligomer etc..
The preference of the polycarbonate resin used in the present invention is included by derived from double (4- hydroxy phenyls) propane of 2,2-
Polycarbonate resin;The Merlon by derived from double (4- hydroxy phenyls) propane of 2,2- are with other aromatic dihydroxy compounds is total to
Polymers.
The molecular weight of polycarbonate resin using using dichloromethane as solvent, the solution viscosity determined at 25 DEG C of temperature
The viscosity-average molecular weight meter of conversion, preferably 14,000~30,000, more preferably 15,000~28,000, further preferably
For 16,000~26,000.When viscosity-average molecular weight is aforementioned range, mechanical strength is better, and mouldability also becomes more
It is good, therefore preferably.
For the manufacture method of polycarbonate resin, it is not particularly limited, in the present invention, it is also possible to use phosgenation
The polycarbonate resin of any one method manufacture such as (interfacial polymerization) and fusion method (ester-interchange method).In addition, in the present invention
Can use after the manufacturing process of general fusion method, live through the poly- carbon of the operation manufacture of the OH base unit weights of adjustment terminal groups
Acid ester resin.
Further, the polycarbonate resin used in the present invention, is not only the polycarbonate resin as original raw material, may be used yet
To be the polycarbonate resin regenerated by used product, i.e., the polycarbonate resin of so-called material recycling.
In addition, the polycarbonate resin used for the present invention, such as may be referred to Japanese Unexamined Patent Publication 2012-072338 public affairs
The record of 0018~0066 section of report, by its content combination present specification is introduced to.
The resin combination of the present invention can only include a kind of polycarbonate resin, it is also possible to comprising two or more.
In the resin combination of the present invention, in all resin composition, the ratio of polycarbonate resin is preferably 80 matter
More than amount more than %, more preferably 90 mass %, more than more preferably 95 mass %.
In the resin combination of the present invention, in addition to polycarbonate resin, it is also possible to comprising such as polyamide, gather
Ester resin, phenylethylene resin series etc..But, 10 mass % of the blend amount preferably less than resinous principle of these resins, more preferably
For below 5 mass %, below more preferably 3 mass %.
In the resin combination of the present invention, especially, the mixture of acrylonitrile/butadiene/styrene copolymer (ABS resin)
Measure 10 mass % of the total amount of preferably less than polycarbonate resin and acrylonitrile/butadiene/styrene copolymer, be more preferably 5
Below quality %, below more preferably 3 mass %, below particularly preferably 1 mass %, most preferably it is substantially free of
Have.Contain substantially no and refer to and for example do not carry out on one's own initiative mixture.Therefore, however not excluded that for impurity.ABS resin described herein is
Refer to including the ABS resin that can be included in elastomer for example described later etc..
<Glass fibre>
The resin combination of the present invention includes glass fibre.
Glass fibre includes the glass components such as A glass, C glass, E glass, particularly preferred E glass (alkali-free glass).
Glass fibre refers to that being cut to the cross sectional shape at right angle in length direction is round type, polygon and presents outside threadiness
Embedding material.
The form of glass fibre can be:Obtain by single fiber or by continuous winding of material of many single fiber twisteds
To " glass rove ", be switched to " chopped strand " of 1~10mm of length, crush and " grind fibre for 10~500 μm or so of length
Any one of dimension " etc..As the glass fibre, with ASAHI FIBER GLASS the CO., " Glasron of LTD.
Chopped Strand ", " Glasron Milled Fiber " trade name it is commercially available, can be readily available.Glass fibre
The different fiber of form can be used together.
In addition, as the present invention in glass fibre, the fiber of circular section shape and the fiber of shaped cross-section it is equal
It is preferred that.Herein, cross sectional shape is made a distinction with flat ratio, and the flat ratio is used in the length direction of fiber by the section at right angle
Major diameter/minor axis ratio (D2/D1) when major diameter is denoted as D2, minor axis is denoted as D1 is represented.Flat ratio in the present invention is mean tabular
Rate.
In the present invention, from from the viewpoint of low warpage properties, glass fibre of the preferred flat rate more than 1.5 and for less than 8, more
The glass fibre of the glass fibre of preferred flat rate 2~6, further preferred flat ratio 2~4.For the flat glass, can be with
With reference to 0065~0072 section of the record of Japanese Unexamined Patent Publication 2011-195820 publications, its content is incorporated in present specification.
On the other hand, it is glass fibre of the preferred flat rate below 1.5, more excellent from from the viewpoint of the raising of fusion intensity
Select glass fibre of glass fibre, further preferred flat ratio of the flat ratio below 1.3 below 1.1, particularly preferred flat ratio 1
Glass fibre.
Glass fibre can for example use γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyl group
Silane couplers such as trimethoxy silane, γ aminopropyltriethoxy silane etc. are surface-treated, and its adsorbance is usually
0.01~1 mass % of the quality of glass fibre.And then as needed can be using the lubrication such as fatty acid amide compound, silicone oil
The resin with overlay film Forming ability such as the antistatic additive such as agent, quaternary ammonium salt, epoxy resin, polyurethane resin, formed with overlay film
The resin of ability is surface-treated with the mixture of heat stabilizer, fire retardant etc..
With regard to the blend amount of the glass fibre in the resin combination of the present invention, by polycarbonate resin and glass fibre
When total amount is set to 100 mass %, it is more than 5 mass %, is preferably more than 8 mass %, is more preferably more than 10 mass %, and
And, it is below 60 mass %, below more preferably 55 mass %, below more preferably 40 mass %, is particularly preferably 30
Below quality %.
The present invention resin combination can only include a kind of glass fibre, can also include it is two or more.Comprising two kinds
In the case of above, total amount is above range.
Generally preferably resinous principle and glass fibre are accounted for more than 70 mass % of total composition in the resin combination of the present invention.
<Elastomer>
The resin combination of the present invention includes elastomer.By containing elastomer, the resistance to punching of resin combination can be improved
Hitting property.As the elastomer used in the present invention, MBS (MBS can be included
Resin), it is referred to as the styrene-butadiene system triblock copolymer and its hydride of SBS, SEBS, it is referred to as SPS, SEPS
Styrene-isoprene system triblock copolymer and its hydride, are referred to as the alkene based thermoplastic elastomer of TPO, Polyester bullet
Gonosome, siloxane-based rubber, acrylic ester rubber, silicone copolymers elastomer etc..As elastomer, it is possible to use Japan
Elastomer described in 0075~0088 section of JP 2012-251061 publication, the 0101 of Japanese Unexamined Patent Publication 2012-177047 publications
Elastomer described in~0107 section etc., by its content present specification is introduced to.MBS resins are particularly preferably used in the present invention
Or copolymeric siloxane elastomer, more preferably silicone copolymers elastomer.
10 overall matter that the content of the acrylonitrile/butadiene/styrene copolymer in the elastomer that the present invention is used is not enough
Amount %, below preferably 5 mass %, below more preferably 3 mass %.
(copolymeric siloxane elastomer)
As the copolymeric siloxane elastomer that the present invention is used, polysiloxane is preferably comprised with poly- (methyl) acrylic acid
The organosilicon of Arrcostab-acrylic acid compounded rubber, can also be as needed to make by more than a kind of vinyl compound monomer
The vinyl polymers of composition carry out being grafted the graft copolymer for obtaining.
It is the multilayer structure polymer with inner nuclear layer and outer shell as its basic polymer architecture, the kernel
Polysiloxane of the layer comprising the low i.e. crosslinking component of glass transition temperature mutually winds with poly- (methyl) alkyl acrylate
Structure, the outer shell includes the vinyl polymers that are made up of more than a kind of vinyl compound monomer.Structure
Vinyl polymers into outer shell have the effect of the cementability for improving resin combination and matrix composition.Such grafting
Copolymer for example can be manufactured in method disclosed in Japanese Unexamined Patent Publication 2004-359889 publications.
Polysiloxane used in the manufacture of organosilicon-acrylic acid compounded rubber, is not particularly limited, for example,
Dimethyl siloxane units are preferably comprised as the polymer of construction unit.As the dimethyl silica for constituting polysiloxane
Alkane, can include dimethyl silica methane series ring bodies more than 3 yuan of rings, preferably 3~7 yuan of rings.Specifically, six can be included
Methyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, the siloxanes of ten diformazan basic ring six etc..They can
Individually or to mix two or more and use.Wherein, from the control difficulty of particle diameter distribution, principal component is preferably prestox
Cyclotetrasiloxane.
As polysiloxane, the siloxanes containing vinyl polymerized functional group can be contained as constituent, separately
Outward, it is also possible to be crosslinked using siloxane-based crosslinking agent.In addition, the manufacture method, graft copolymerization for polysiloxane
The manufacture method of thing is not particularly limited.These be referred to [0055] of Japanese Unexamined Patent Publication 2012-131934 publications~
[0080] record of section, by its content present specification is introduced to.
The number average bead diameter of polysiloxane is preferably more than 10nm, is more preferably 50nm~5 μm, is more preferably
100nm~3 μm.By the way that the number average bead diameter of polysiloxane is set to into more than 10nm, in organosilicon-acrylic acid compounded rubber
Poly- (methyl) alkyl acrylate amount does not become excessive, can suppress the reduction of resistance to impact.
Poly- (methyl) alkyl acrylate used in the manufacture of organosilicon-acrylic acid compounded rubber is containing (methyl) third
The polymer of olefin(e) acid alkyl methacrylate unit.
As (methyl) alkyl acrylate, for example, can include methyl acrylate, ethyl acrylate, acrylic acid positive third
The alkyl acrylates such as ester, n-butyl acrylate, acrylic acid -2- b hexyls and methyl methacrylate, methacrylic acid oneself
The alkyl methacrylates such as ester, methacrylic acid -2- b hexyls, the positive lauryl of methacrylic acid.They can be used alone 1
Plant or and use two or more.
In addition, poly- (methyl) alkyl acrylate can also be containing multi-functional monomeric unit being total to as constituent
Polymers.As multi-functional monomer, for example can include allyl methacrylate, ethylene glycol dimethacrylate, the third two
Alcohol dimethylacrylate, 1,3 butylene glycol dimethylacrylate, 1,4- butanediol dimethylacrylates, cyanuric acid three
Allyl ester, cyamelide triallyl etc..They can be used alone or and use two or more.
Content in the case of using multi-functional monomer is not particularly limited, preferably poly- (methyl) acrylic acid alkyl
0.1~2 mass %, more preferably 0.3~1 mass % in mass % of ester 100.By the way that the content of multi-functional monomer is set to
More than 0.1 mass %, existing can suppress because the metamorphosis of compounded rubber causes the tendency of impact strength reduction, in addition,
By the way that the content of multi-functional monomer is set to below 2 mass %, there is the tendency that impact strength is more improved.
In the present invention, as copolymeric siloxane elastomer, preferably make methacrylate polymer glycerol polymerization in
The graft polymers of polysiloxane-poly- (methyl) alkyl acrylate compounded rubber, connect acrylonitritrile-styrene resin
Branch is polymerized in the graft copolymer of polysiloxane-poly- (methyl) alkyl acrylate compounded rubber, as by the beautiful sun of Mitsubishi
" METABLEN S are serial " that Co., Ltd. sells, for example they are preferably used " S-2030 " etc..
The blend amount of elastomer relative to the mass parts of composition 100 comprising polycarbonate resin and glass fibre, be 0.5~
10 mass parts, preferably 1~8 mass parts, more preferably 2~6 mass parts.
The resin combination of the present invention can only include a kind of elastomer, can also include two or more.Comprising of more than two kinds
In the case of, total amount is above range.
<Laser direct forming additive (LDS additives)>
The resin combination of the present invention is included:The LDS additives of cupric and chromium.Added by using the LDS of cupric and chromium
Agent, improves can anti-flammability and plating.
In the present invention, LDS additives are referred to:Relative to polycarbonate resin (Mitsubishi Engineering-
Plastics Corporation systems, lupilon (registration mark), S-3000F) 100 mass parts, adding 4 mass parts can recognize
To be the additive of LDS additives, using the YAG laser of 1064nm, with arbitrary value, speed 1 in the scope of 2.6~13W of power
The condition of arbitrary value is printed by laser irradiation in arbitrary value, the scope of the μ s of frequency 10~50 in~2m/s, then, will be tried
Piece is tested in sulfuric acid after degreasing, with the THP ア Le カ リ ア Network チ and THP ア Le カ リ ア Network of KIZAI CORPORATION manufactures
After セ is processed, when the SEL カ ッ パ ー manufactured with KIZAI CORPORATION carry out plating, coating can be formed
Compound.The LDS additives that the present invention is used can be composite, it is also possible to use commercially available product.In addition, commercially available product is except conduct
Outside the material that LDS additives are sold, as long as meeting the key element of LDS additives in the present invention, or as other use
The material that way is peddled.
As long as the LDS additives in the present invention are just not particularly limited comprising copper and chromium.Add as the LDS in the present invention
Plus agent, preferably comprise mass % of copper 10~30.Additionally, it is preferred that mass % of chromium 15~50 is included,
Oxide of the LDS additives in the present invention preferably comprising copper and chromium.
Contain form, preferred spinel structure as copper and chromium.Spinel structure is referred to and is considered with composite oxides
AB2O4One of representative crystal structure type of compound (A and B is metallic element) of type.
LDS additives can also include micro other metals except copper and chromium.As other metals, illustrate antimony, tin,
Lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, calcium etc., preferred manganese.These metals can also be in the form of the oxide
Exist.
It is 10 that one example of the preferred embodiment of the present invention is the content of the metal oxide beyond cupric and chromic oxide
LDS additives below quality %.
The particle diameter of LDS additives is preferably 0.01~50 μm, more preferably 0.05~30 μm.By being set to such structure
Into the uniformity that there is coating surface state when being applied to plating becomes good tendency.
The blend amount of LDS additives, relative to the mass parts of composition 100 comprising polycarbonate resin and glass fibre, is 5
~20 mass parts, preferably 6~15 mass parts, more preferably 8~13 mass parts.Blend amount is set to more than 20 mass parts be mixed
Timing, impact reduces lower or polycarbonate resin and decomposes or anti-flammability variation.
The resin combination of the present invention can only include a kind of LDS additives, it is also possible to comprising two or more.Comprising two kinds
In the case of above, total amount is above range.
<Phosphorus flame retardant>
The composition of the present invention includes phosphorus flame retardant.The preferred condensed phosphoric acid ester compounds of phosphorus flame retardant and/or phosphonitrile
Compound.
The blend amount of phosphorus flame retardant, relative to the mass parts of composition 100 comprising polycarbonate resin and glass fibre, is 5
~30 mass parts, preferably 8~25 mass parts, particularly preferred 10~20 mass parts.
The resin combination of the present invention can only include a kind of phosphorus flame retardant, it is also possible to comprising two or more.Comprising two
In the case of more than kind, total amount is above range.
《Condensed phosphoric acid esters》
The resin combination of the present invention passes through mixture condensed phosphoric acid esters, it is possible to increase anti-flammability.
As condensed phosphoric acid esters, the material for preferably being represented with following formulas (1).
Formula (1):
(in formula, R1、R2、R3And R4Hydrogen atom or organic group are represented independently of one another.But, R1、R2、R3And R4Entirely
Except portion is for the situation of hydrogen atom.X represents the organic group of divalent, p be 0 or 1, q represent more than 1 integer, r represent 0 or 1 with
On integer.)
In above-mentioned formula (1), organic group refers to alkyl, the cycloalkanes that for example can be included with or without substituent
Base, aryl, the substituent can include alkyl, alkoxyl, alkylthio group, aryl, aryloxy group, arylthio, halogen atom, halogen aryl
Deng.Can also be in addition the group for combining these substituents, or these substituents are passed through into oxygen atom, sulphur atom, nitrogen-atoms
Group being combined Deng bonding etc..In addition the organic group of divalent refers to, one can be removed from above-mentioned organic group
The group more than divalent of carbon atom.For example can include alkylidene, phenylene, substituted phenylene, by derived from bisphenols etc
Multinuclear phenylene etc..
As the concrete example of the condensed phosphoric acid esters represented with above-mentioned formula (1), for example, illustrate trimethyl phosphate, phosphoric acid
Triethyl, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tripotassium phosphate phenyl phenylester, phosphoric acid
Octyl diphenyl, phosphoric acid diisopropyl phenyl ester, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (chlorine
Propyl group) ester, double (2,3- dibromopropyls) ester of phosphoric acid, double (2,3- the dibromopropyls) -2,3- dichloro esters of phosphoric acid, phosphoric acid is double (chloropropyl)
Mono octyl ester, phosphoric acid bisphenol-A tetraphenyl ester, diphosphonic acid bisphenol-A durene base ester, diphosphonic acid bisphenol-A four (xylyl) ester, two phosphorus
A variety of materials such as sour quinhydrones tetraphenyl ester, phosphoric acid quinhydrones durene base ester, diphosphonic acid quinhydrones four (xylyl) ester.
In addition, as commercially available condensed phosphoric acid esters, such as with " CR733S " (isophthalic two of Daihachi Chemical Industry Co., Ltd.
Phenol double (diphenyl phosphoester)), " CR741 " (bisphenol-A is double (diphenyl phosphoester)), " PX-200 " (double (double diformazans of resorcinol
Phenyl phosphate ester)), " ADEKA STAB FP-700 " (2,2- double (p-hydroxybenzene) propane of Asahi Denka Kogyo K. K
The phenol condensate of triclosan oxidation phosphine condensation polymer (degree of polymerization 1~3)) etc the material peddled of trade name be easily obtained.
《Phosphazene compound》
The resin combination of the present invention passes through mixture phosphazene compound, it is possible to increase anti-flammability.
Phosphazene compound is the organic compound in molecule with-P=N- keys, is preferably selected from by with following formulas (1)
The cyclic phosphazene compound of expression, the chain phosphazene compound represented with following formulas (2) and selected from following formulas
(1) crosslinking that at least one phosphazene compound and in the group of following formulas (2) composition carries out being crosslinked by crosslinked group
At least one compound in the group of phosphazene compound composition.
In formula (1), a is 3~25 integer, R1And R2It is optionally identical or different, represent alkyl, cycloalkyl, thiazolinyl, alkynyl,
Allyloxy, amino, hydroxyl, aryl or alkaryl.
In formula (2), b is 3~10000 integer, R3And R4It is optionally identical or different, represent alkyl, cycloalkyl, thiazolinyl, alkynes
Base, allyloxy, amino, hydroxyl, aryl or alkaryl.
R5Represent and be selected from-N=P (OR3)3Base ,-N=P (OR4)3Base ,-N=P (O) OR3Base ,-N=P (O) OR4In base extremely
Few one kind, R6Represent and be selected from-P (OR3)4Base ,-P (OR4)4Base ,-P (O) (OR3)2Base ,-P (O) (OR4)2At least one in base.
In above-mentioned formula (1) and formula (2), as alkyl methyl, ethyl, propyl group, isopropyl, butyl, uncle can be for example included
Butyl, amyl group, hexyl, octyl group, decyl, dodecyl etc., it is usually preferable to methyl, ethyl, propyl group, isopropyl, butyl, uncle
The alkyl of the carbon numbers 1~4 such as the alkyl of the carbon numbers such as butyl, amyl group, hexyl 1~6, particularly preferred methyl, ethyl, propyl group.
The cycloalkyl of the carbon numbers such as cyclopenta, cyclohexyl 5~14 can be for example included as cycloalkyl, wherein it is preferred that carbon number 5
~8 cycloalkyl.
The thiazolinyl of the carbon numbers such as vinyl, pi-allyl 2~8 can be for example included as thiazolinyl, for example can be arranged as cycloalkenyl group
Enumerate the cycloalkenyl group of the carbon numbers such as cyclopenta, cyclohexyl 5~12.
The aryl such as alkynyl, the ethynyl phenyl of the carbon numbers such as acetenyl, propinyl 2~8 for example can be also included as alkynyl
Deng.
Phenyl, aminomethyl phenyl (that is, tolyl), 3,5-dimethylphenyl (that is, dimethylbenzene can be for example included as above-mentioned aryl
Base), trimethylphenyl, the aryl of the carbon number 6~20 such as naphthyl, wherein it is preferred that the aryl of carbon number 6~10, particularly preferred phenyl.
The aralkyl of the carbon numbers such as benzyl, phenethyl, phenyl propyl 6~20 can be for example included as alkylaryl, wherein
It is preferred that the aralkyl of carbon number 7~10, particularly preferred benzyl.
Wherein, the R in above-mentioned formula (1)1And R2, R in above-mentioned formula (2)3And R4Preferably aryl, aralkyl.Pass through
Using such aromatic series phosphonitrile, the heat endurance of resin combination can be effectively improved.It is above-mentioned according to such viewpoint
R1、R2、R3And R4Preferably aryl, particularly preferably phenyl.
The ring-type represented as formula (1) and (2) and/or chain phosphazene compound, for example can example go out phenoxy phosphazene,
(poly-) tolyl oxa- phosphonitriles such as o-tolyl oxa- phosphonitrile, a tolyl oxa- phosphonitrile, p-methylphenyl oxa- phosphonitrile, adjacent/
Xylyl oxa- phosphonitrile, neighbour/paraxylene base oxa- phosphonitrile ,/(poly-) the xylyl oxygen such as paraxylene base oxa- phosphonitrile
Miscellaneous phosphonitrile, adjacent// tolyl oxa- phosphorus between trimethylphenyl oxa- phosphonitrile, phenoxy group o-tolyl oxa- phosphonitrile, phenoxy group
(poly-) phenoxytoluene base oxa- phosphonitriles such as nitrile, phenoxy group p-methylphenyl oxa- phosphonitrile, phenoxy group neighbour/meta-xylene base oxa- phosphorus
Between nitrile, phenoxy group neighbour/paraxylene base oxa- phosphonitrile, phenoxy group/(poly-) the phenoxytoluene base such as paraxylene base oxa- phosphonitrile
Oxa- xylyl oxa- phosphonitrile, phenoxy group neighbour// to trimethylphenyl oxa- phosphonitrile etc., preferably ring-type and/or chain benzene
Epoxide phosphonitrile etc..
As the cyclic phosphazene compound represented with formula (1), particularly preferred R1And R2For the ring-type phenoxy group phosphorus of phenyl
Nitrile.As such ring-type phenoxy phosphazene compound, for example, can include:By making ammonium chloride and phosphorus pentachloride 120~130
React at a temperature of DEG C and take out in the phosphonitrilic chloride mixture of the ring-type and straight-chain for obtaining the phosphonitrile of chlordene ring three, eight chlorination rings
The phenoxy cyclotriphosphazene, eight benzene that obtain are replaced with phenoxy group after four phosphonitriles, the isothrausmatic phosphonitrilic chloride of the phosphonitrile of ten chlorination ring five
The compounds such as the phosphonitrile of epoxide ring four, the phosphonitrile of ten phenoxy group ring five.In addition, ring-type phenoxy phosphazene compound preferred formula (1)
In a be 3~8 integer compound, or the mixture of the different compounds of a.
The mean value of above-mentioned a is preferably 3~5, more preferably 3~4.In addition, the material of wherein preferred a=3 is 50 matter
Amount more than %, the material of a=4 are that 10~40 mass %, the material of more than a=5 add up to compound below 30 mass %
Mixture.
As the chain phosphazene compound represented with formula (2), particularly preferred R3And R4For the chain phenoxy group phosphorus of phenyl
Nitrile.Such chain phenoxy phosphazene compound, for example, can include and the hexachlorocyclotriph,sphazene obtained in above-mentioned method exists
Ring-opening polymerisation is carried out at a temperature of 220~250 DEG C, by the chlorophosphonitrile of straight-chain two of the degree of polymerization 3~10000 that will obtain with benzene
Epoxide carries out replacing the compound for obtaining.B in the formula (2) of the straight-chain phenoxy phosphazene compound is preferably 3~1000,
More preferably 3~100, more preferably 3~25.
As crosslinking phosphazene compound, for example, can include with 4,4 '-sulfonyl diphenylene (that is, bisphenol S residue)
The compound of cross-linked structure, the compound of the cross-linked structure with 2,2- (4,4 '-diphenylene) isopropylidene, with 4,
The compound of the cross-linked structure of 4 '-oxa- diphenylene, compound of the cross-linked structure with 4,4 '-thia diphenylene etc. have
There is compound of the cross-linked structure of 4,4 '-diphenylene etc..
In addition, as crosslinking phosphazene compound, the R in formula (1)1、R2Ring-type phenoxy phosphazene compound for phenyl leads to
Crossing above-mentioned crosslinking group carries out the crosslinked phenoxyphosphazene compounds that are crosslinked or the R in above-mentioned formula (2)3、R4For phenyl
Chain phenoxy phosphazene compound the crosslinked phenoxyphosphazene compounds that are crosslinked are carried out from fire-retardant by above-mentioned crosslinking group
It is preferred from the viewpoint of property;The friendship that more preferably ring-type phenoxy phosphazene compound carries out being crosslinked by above-mentioned crosslinking group
Biphenylyloxy phosphazene compound.
In addition, the cyclic phosphazene that the content of the phenylene in crosslinked phenoxyphosphazene compounds will be represented with formula (1)
Whole phenyl and phenylene number in compound and/or the chain phenoxy phosphazene compound that represented using formula (2) lead to as benchmark
Often it is 50~99.9%, is preferably 70~90%.In addition, the crosslinked phenoxyphosphazene compounds are particularly preferably its intramolecular not
Compound with free hydroxyl group.
Phosphazene compound in the present invention be selected from above-mentioned formula (1) represent ring-type phenoxy phosphazene compound and with
The crosslinked phenoxyphosphazene that the ring-type phenoxy phosphazene compound that above-mentioned formula (1) represents carries out being crosslinked by crosslinking group
It is preferred from the viewpoint of at least one anti-flammability and mechanical property from resin combination in the group of compound composition.
<Polytetrafluoroethylene (PTFE)>
The resin combination of the present invention contains polytetrafluoroethylene (PTFE) (PTFE).As polytetrafluoroethylene (PTFE), preferably with fibrillation
Form the polytetrafluoroethylene (PTFE) of energy.The polytetrafluoroethylene (PTFE) for forming energy with fibrillation is categorized as three types according to ASTM specifications.Make
It is the polytetrafluoroethylene (PTFE) that energy is formed with fibrillation, for example, can includes Du Pont-Mitsui Fluorochemicals
Co., Teflon (registration mark) 6-J of Ltd., the Polyflon F201L of big aurification Industrial Co., Ltd,
FA500B、FA500C.In addition, as the aqueous liquid dispersion of polytetrafluoroethylene (PTFE), big aurification Industrial Co., Ltd system can be included
Fluon D-1, the ptfe compounds with the sandwich construction that vinyl monomer is polymerized.Any class
Type may be incorporated for the resin combination of the present invention.
In order that the outward appearance that the resin combination containing polytetrafluoroethylene (PTFE) carries out injection molding products formed is more improved,
The specific capped polytetrafluoroethylene (PTFE) covered with organic based polymer can be used (below, to be abbreviated as sometimes capped poly-
Tetrafluoroethene).Specific capped polytetrafluoroethylene (PTFE) refers to the containing ratio of the polytetrafluoroethylene (PTFE) in capped polytetrafluoroethylene (PTFE)
For the material in the range of 40~95 mass %, wherein, preferably 43~80 mass %, more preferably 45~70 matter
The material of amount %, particularly preferably 47~60 mass %.As specific capped polytetrafluoroethylene (PTFE), for example, can use Mitsubishi
Poly TS AD001 of METABLEN A-3800, A-3700, KA-5503, PIC company systems of beautiful positive Co. Ltd. system etc..
The blend amount of polytetrafluoroethylene (PTFE) is relative to the mass parts of composition 100 comprising polycarbonate resin and glass fibre
0.1~1 mass parts, more preferably 0.2~0.8 mass parts, particularly preferably 0.3~0.6 mass parts.It should be noted that quilt
In the case of covering polytetrafluoroethylene (PTFE), amount of the addition equivalent to polytetrafluoroethylene (PTFE) purity.The blend amount of polytetrafluoroethylene (PTFE) is not enough
On the other hand it is insufficient as flame retardant effect, more than causing products formed during 1 mass parts sometimes in the case of 0.1 mass parts
The reduction of outward appearance.
The resin combination of the present invention can only include a kind of polytetrafluoroethylene (PTFE), it is also possible to comprising two or more.Comprising two
In the case of more than kind, total amount is above range.
<Organophosphor system stabilizer>
The resin combination of the present invention preferably comprises organophosphor system stabilizer.By mixture organophosphor system stabilizer, LDS adds
Plus agent is not easily decomposed polycarbonate resin, the effect of the present invention is more effectively played.As organophosphor system stabilizer, can refer to
The record of 0073~0095 section of Japanese Unexamined Patent Publication 2009-35691 publications, its content is introduced in present specification.Make
It is the compound represented with following formulas (3) for preferred organophosphor system stabilizer.
Formula (3)
O=P (OH)m(OR)3-m···(3)
(in formula (3), R is alkyl or aryl, each other can be with identical or different.M is 0~2 integer.)
R is preferably the aryl of the alkyl of carbon number 1~30 or carbon number 6~30, the more preferably alkyl of carbon number 2~25, phenyl, nonyl
Base phenyl, stearyl phenyl, 2,4- di-tert-butyl-phenyls, 2,4- di-t-butyl aminomethyl phenyls, tolyl.
Wherein, the phosphate for preferably being represented with following formulas (3 ').
O=P (OH)m’(OR’)3-m’···(3’)
In formula (3 '), R ' is the alkyl of carbon number 2~25, each other can be with identical or different.M ' is 1 or 2.Herein, as
Alkyl, can include octyl group, 2- ethylhexyls, iso-octyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecane
Base, isotridecyl, myristyl, cetyl, octadecyl etc., preferred myristyl, cetyl and octadecyl,
Particularly preferred octadecyl.
As phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate can be included
Phenyl ester, tricresyl phosphate, tricresyl phosphate (nonyl phenyl) ester, phosphoric acid 2- ethylphenyl diphenyls, four (2,4- di-tert-butyls
Base) -4,4- diphenylene phosphite esters, mono phosphoric acid ester stearyl ester, di(2-ethylhexyl)phosphate stearyl ester etc..
As phosphite ester, it is also preferred that the compound represented with following formulas (4).
Formula (4)
(in formula (4), R ' is alkyl or aryl, optionally identical or different each other.)
R ' is preferably the aryl of the alkyl of carbon number 1~25 or carbon number 6~12.In the case that R ' is alkyl, preferred carbon number 1~
30 alkyl.In the case that R ' is aryl, the aryl of preferred carbon number 6~30.
As phosphite ester, for example, can include triphenyl phosphite, trisnonyl phenyl phosphite, three (2,4- bis- tertiary fourths
Base phenyl) phosphite ester, tris(nonyl phenyl) phosphate, tridecyl phosphite, the monooctyl ester of phosphorous acid three, three (octadecyl) phosphite esters,
Distearyl acyl group pentaerythritol diphosphites, the cyclohexyl of phosphorous acid three, phosphorous acid monobutyl diphenyl ester, phosphorous acid list octyl group two
Phenyl ester, double (2,4- di-tert-butyl-phenyls) pentaerythritol phosphites, double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythrites
Three esters, diester, the monoesters of the phosphorous acid such as phosphite ester, 2,2- di-2-ethylhexylphosphine oxides (4,6- di-tert-butyl-phenyls) octyl group phosphite ester
Deng.
, comprising in the case of phosphorus system stabilizer, the blend amount of the phosphorus system stabilizer is relative to bag for the resin combination of the present invention
The mass parts of composition 100 containing polycarbonate resin and glass fibre, more preferably preferably 0.01~5 mass, 0.05~0.3 matter
Amount part, more preferably 0.08~0.25 mass parts.By being set to more than 0.01 mass parts, can effectively suppress due to
The decomposition of polycarbonate resin caused by LDS additives, by being set to below 5 mass parts, it is possible to increase glass fibre and poly- carbon
The dhering strength of acid esters, intensity can be made more to improve.
The resin combination of the present invention can only include a kind of phosphorus system stabilizer, it is also possible to comprising two or more.Comprising two
In the case of more than kind, total amount is preferably above range.
In the present invention, especially, as organophosphor system stabilizer, relative to polycarbonate resin and the matter of glass fibre 100
Amount part, the mass parts monostearate phosphate of preferred mixture 0.01~0.5 and/or distearyl acid phosphoric acid ester, more preferably includes 0.05
~0.3 mass parts, particularly preferably include 0.08~0.25 mass parts.By being set to more than 0.01 mass parts, can significantly press down
The decomposition of polycarbonate resin processed, by being set to below 0.5 mass parts, can make to be improved with the adaptation of glass fibre, can
Significantly increase mechanical strength.
<Antioxidant>
The resin combination of the present invention can also include antioxidant.As antioxidant, preferred phenol antioxidant, more
2,6 di tert butyl 4 methyl phenol, n-octadecane base -3- (3,5- -4 '-hydroxy benzenes of di-t-butyl can specifically be included
Base) propionic ester, four [methylene -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester] methane, three (3,5- di-t-butyl -4-
Hydroxyphenylmethyl) isocyanuric acid ester, 4,4 '-butane double (3 methy 6 tert butyl phenol), triethylene glycol-bis- [3- (uncles 3-
Butyl-hydroxy -5- aminomethyl phenyls)] double { 2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyl of propionic ester and 3,9-
Epoxide] -1,1- dimethyl ethyls } oxaspiro [5,5] hendecanes of -2,4,8,10- four etc..Wherein, preferably four [methylene -3- (3,
5- di-tert-butyl-hydroxy phenyls) propionic ester] methane.
, comprising in the case of antioxidant, the blend amount of the antioxidant is relative to comprising poly- for the resin combination of the present invention
The mass parts of composition 100 of carbonate resin and glass fibre, more preferably preferably 0.01~5 mass parts, 0.05~3 mass
Part.
The resin combination of the present invention can only include a kind of antioxidant, it is also possible to comprising two or more.Comprising two kinds
In the case of above, total amount is preferably above range.
<Releasing agent>
The resin combination of the present invention can also include releasing agent.Releasing agent is preferably selected from aliphatic carboxylic acid, aliphatic carboxylic
At least one compound in the aliphatic hydrocarbon compound of acid esters and number-average molecular weight 200~15000.Wherein, more preferably make
With at least one compound in aliphatic carboxylic acid and aliphatic carboxylic acid esters.
As aliphatic carboxylic acid, saturation or undersaturated aliphatic monocarboxylic acid, dicarboxylic acids or tricarboxylic acids can be included.This theory
In bright book, the term of aliphatic carboxylic acid is used with the also implication comprising ester ring type carboxylic acid.Among aliphatic carboxylic acid, preferably
The aliphatic saturation monocarboxylic acid of the monocarboxylic acid or dicarboxylic acids of carbon number 6~36, more preferably carbon number 6~36.As such aliphatic
The specific example of carboxylic acid, can include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, dodecylic acid, arachidic acid, behenyl
Acid, lignoceric acid, cerinic acid, melissic acid, gheddic acid, montanic acid, glutaric acid, adipic acid, azelaic acid etc..
As the aliphatic carboxylic acid composition for constituting aliphatic carboxylic acid esters, it is possible to use with aforementioned aliphatic carboxylic acid identical thing
Matter.On the other hand, as the alcohol composition for constituting aliphatic carboxylic acid esters, can include saturation or undersaturated monohydric alcohol, saturation or
Undersaturated polyalcohol etc..These alcohol can also have the substituents such as fluorine atom, aryl.Among these alcohol, preferred carbon number 30 with
Under unitary or polynary saturated alcohols, aliphatic saturated monohydroxy alcohol or polyalcohol of the further preferred carbon number below 30.Fat herein
Fat race alcohol also includes alicyclic alcohol.As the concrete example of these alcohol, octanol, Decanol, dodecanol, octadecane can be included
Alcohol, tadenan, ethylene glycol, diethylene glycol (DEG), glycerine, pentaerythrite, 2,2- dihydroxy perfluor propyl alcohol, neopentyl glycol, double three
Hydroxymethyl-propane, two season pentanediol etc..These aliphatic carboxylic acid esterss can be contained in the form of impurity aliphatic carboxylic acid and/or
Alcohol, or the mixture of multiple compounds.As the concrete example of aliphatic carboxylic acid esters, beeswax (main component can be included
For the mixture of myricyl palmitate), stearyl stearate, behenic acid behenyl ester, the diester of behenic acid octyl group ten, single palm
Acid glyceride, glycerin monostearate, distearin, glyceryl tristearate, single pentaerythritol tetrapalmitate, list are hard
Resin acid pentaerythritol ester, distearyl acid pentaerythritol ester, three stearic acid pentaerythritol esters, pentaerythritol tetrastearate etc..
, comprising in the case of releasing agent, the blend amount of the releasing agent is relative to comprising poly- carbonic acid for the resin combination of the present invention
The mass parts of composition 100 of ester resin and glass fibre, more preferably preferably 0.01~5 mass parts, 0.05~3 mass parts.
The resin combination of the present invention can only include a kind of releasing agent, it is also possible to comprising two or more.Comprising two kinds with
In the case of upper, total amount is preferably above range.
Without departing from the scope of the subject in the invention, resin combination of the invention can also include other compositions.As
Other compositions can include stabilizer beyond dephosphorization system stabilizer, ultraviolet absorber, inorganic filler, fluorescent whitening agent, anti-quiet
Electric agent, antifoggant, lubricant, anticaking agent, fluidity improver, plasticizer, dispersant, antiseptic etc..They can be used together
It is two or more.
For these compositions, Japanese Unexamined Patent Publication 2007-314766 publications, Japanese Unexamined Patent Publication No. 2008-127485 number is referred to
The record of publication and Japanese Unexamined Patent Publication 2009-51989 publications, Japanese Unexamined Patent Publication 2012-72338 publications etc., its content is drawn
Enter into present specification.
The manufacture method of the poly carbonate resin composition of the present invention is not particularly limited, can be with widely used known
The manufacture method of thermoplastic resin composition.Specifically, by the way that each composition is various using bucket mixed machine, Henschel mixer etc.
After mixer is pre-mixed, with Banbury mixer, roller, brabender plasticorder, single-screw intermixing extruder, twin-screw mixer
Extruder, kneader etc. carry out melting mixing, can manufacture resin combination.
In addition, for example, it is not pre-mixed each composition or is only pre-mixed a part of composition, is supplied to extrusion using batcher
Machine carries out melting mixing, it is also possible to the resin combination of the manufacture present invention.
Further, for example, by by being pre-mixed the composition of a part and supplying to extruder and carry out what melting mixing was obtained
Resin combination carries out melting mixing and also can manufacture as masterbatch by the way that the masterbatch is mixed once again with remaining composition
The resin combination of the present invention.、
Present invention it is preferred that, using phosphazene compound as masterbatch, in addition, in the way of specific graininess phosphonitrile
Carry out mixture.Specifically, example is following mode.
(first method)
As first method, a kind of flame retardant masterbatch is illustrated, it is characterised in that it is that the weight of 40~65 mass % is equal
The aromatic polycarbonate resin (A) of molecular weight 15000~55000 and the aromatic series phosphazene compound (B) of 35~60 mass %
Carry out melting mixing and obtain flame retardant masterbatch, it is characterised in that (A) composition and (B) composition add up to 95~100 matter
Amount %.By being set to such composition, operational excellent and then mixture when can obtain being carried out with resin melting mixing is to heat
Anti-flammability, mechanical properties excellent flame retardant masterbatch during plastic resin.
(second method)
Used as second method, it is by the aromatic polycarbonate resin (A) of weight average molecular weight 5,000~55,000 and virtue
Fragrant race's phosphazene compound (B) carries out flame retardant masterbatch obtained from melting mixing in pressure kneader.It is such by being set to
Constitute, it is possible to obtain can effectively and stably show the flame retardant masterbatch of anti-flammability and mechanical properties.
(Third Way)
Be a kind of flame retardant masterbatch as Third Way, it is characterised in that its by by 85~20 mass % fragrance adoption
The mass parts of total 100 of the aromatic series phosphazene compound (B) of carbonate resin (A) and 15~80 mass % and 0.005~2 mass
Part fluoropolymer (C) carries out melting mixing and obtains.By being set to such composition, when can obtain being kneaded with resin melting
Operational excellent and then mixture to the excellent flame retardant masterbatch of anti-flammability, mechanical properties during thermoplastic resin.
(fourth way)
It is the ratio to be characterised by being remained on the sieve of 400 μm of mesh as more than 55 mass %, body as fourth way
Product density is the mode of the form of the granular phosphorus nitrile compound of 0.3~1.5g/ml to resin mixture.Phosphazene compound is in normal temperature
It is down micro mist shape, the property for solidifying occurs with relative to compressing, shearing, directly with thermoplastic resin together in an extruder
During melting mixing, a problem that easily producing phosphazene compound and be attached to extruder screw, by using granular phosphorus nitrilation
Compound, can be difficult a problem that causing the attachment to extruder screw.
(the 5th mode)
Which is that, to resin mixture granular phosphorus nitrile compound, the granular phosphorus nitrile compound is characterised by, to
Phosphazene compound (A) will be polycarbonate resin bulk materials (B) more than 30 mass % by the ratio of the sieve of 1000 μm of mesh
Mass ratio with (A)/(B) is 85/15~5/95 to mix, and its bulk density is 0.4~1.5g/ml.By being set to this
The composition of sample, productivity ratio is excellent and operability during thermoplastic resin melting mixing is also excellent.
The method for manufacturing synthetic resin by the resin combination of the present invention, is not particularly limited, and can adopt and be directed to
The method of forming that thermoplastic resin is typically adopted, i.e., conventional injection moulding, ultrahigh speed injection moulding, injection compression molding
The blow molding method such as method, dual-color forming method, gas is auxiliary, the method for forming using heat insulating mold, the method for forming using rapidly heating moulds,
Foaming (including supercritical fluid), insert molding, IMC (mould in the coating) method of forming, extrusion moulding, plate material forming method,
Hot-forming method, rotoforming, method laminated into type and extrusion forming method.In addition, also may be selected using hot runner system into
Type method.
Then, set on the surface that the synthetic resin for being molded the resin combination of the present invention is illustrated with reference to Fig. 1
Put the operation of coating.Fig. 1 is to illustrate the operation for forming coating on the surface of synthetic resin 1 using laser direct structuring technique
Schematic diagram.In FIG, although synthetic resin 1 is flat substrate, synthetic resin is not necessarily flat base
Plate, or the synthetic resin for partly or wholly bending.In addition, synthetic resin not only includes that final products are also included respectively
Plant part.As the synthetic resin of the present invention, the preferably part of electronic apparatus.The part of electronic apparatus is simultaneously
It is with high impact properties and rigid and good heat resistance, and with less anisotropy and low warping characteristics therefore extremely suitable
For the intraware and shell of the PDA of electronic notebook, portable computer etc., pager, mobile phone, PHS etc., tree is especially suitable for
Fat products formed is not below 1.2mm's (specifically not limiting lower limit, for example more than 0.4mm) including the average thickness of arched part
The part of plate shaped electronic apparatus, wherein, it is particularly suitable as shell.
Referring again to Fig. 1, laser 2 is irradiated to synthetic resin 1.Laser is not particularly limited herein, can be suitably
Selected from laser, preferred YAG laser known to YAG laser, excimer laser, electromagnetic radiation etc..In addition, the ripple to laser
Length is also not particularly limited.Preferred wave-length coverage is 200nm to 1200nm.Particularly preferably 800nm to 1200nm.
When being irradiated using laser, synthetic resin 1 is only activated in the part 3 for being excited light irradiation.Under this activation situation,
Coating solution 4 is used in synthetic resin 1.Coating solution 4 is not particularly limited, can widely used known coating solution,
Copper, nickel, gold, silver, palladium, more preferably copper are preferably mixed with as metal component.
For being not particularly limited using the method for coating solution 4 in synthetic resin 1, for example can include by resin into
The input of type product 1 is mixed with the method among the liquid of coating solution 4.Only shone in Stimulated Light using the synthetic resin after coating solution
The part penetrated forms coating 5.
The method of the present invention can form width for below 1mm, further for less than 150 μm (to lower limit without especially limit
Fixed, for example, more than 30 μm) circuit distance between centers of tracks.The circuit is preferably used as the antenna of electronic apparatus part.That is, as
One preferred embodiment of the synthetic resin of the present invention, can include and be arranged on electronic apparatus parts surface
Coating possesses the synthetic resin of the performance as antenna.
Embodiment
Hereinafter, enumerate embodiment further to specifically describe the present invention.In the scope without departing from present subject matter
It is interior, can suitably change material described in following examples, consumption, ratio, the content for processing, the step of process etc..Therefore,
The scope of the present invention is not only restricted to specific embodiment shown below.
<Resinous principle>
S-3000F:Mitsubishi Engineering-Plastics Corporation systems, aromatic copolycarbonate
Resin
AT-08:NIPPON A&L Inc. systems, have carried out the ABS resin of polymerisation in bulk
<Glass fibre>
T-187:Nippon Electric Glass Co., Ltd.s system, a diameter of 13 μm, shearing length 3mm with circle
The glass fibre (flat ratio 1) of tee section
3PA820:Nitto Boseki Co., Ltd.s system, 28 μm of diameter, the glass fibers with flat cross section of 7 μm of minor axis
Dimension (flat ratio 4)
<Elastomer>
S-2030:Mitsubishi Rayon Co., Ltd's system, methyl methacrylate/acrylic acid methyl esters/dimethyl siloxane is total to
Polymers
M711:The core/shell type elasticity of the shell of Kaneka Corporation systems, the core comprising butadiene-based and acrylic acid series
Body.
<LDS additives>
Black1G:Shepherd Color Japan, Inc. systems, the cupric and chromic oxide of spinel structure, cupric and chromic oxide
Composition in addition is below 1 mass %
24-3588PK:Ferro Corporation systems, the cupric and chromic oxide of spinel structure, beyond cupric and chromic oxide
Composition is below 1 mass %
24-3097PK:Ferro Corporation systems, the cupric and chromic oxide of spinel structure, containing 5~7 mass % oxygen
Change manganese
<Phosphorus flame retardant>
《Condensed phosphoric acid esters》
PX-200:Daihachi Chemical Industry Co., Ltd.'s system, resorcinol pair -2,6- dixylenyl phosphates
FP-700:Asahi Denka Kogyo K. K's system, ADEKA STAB FP-700,2,2- double (p-hydroxybenzenes) third
The phenol condensate of alkane triclosan oxidation phosphine condensation polymer (degree of polymerization 1~3)
《Phosphazene compound》
FP-100:Fu Jian Pharmaceutical Co., Ltd system, phenoxy phosphazene compound
<PTFE>
6-J:Du Pont-Mitsui Fluorochemicals Co., Ltd.s system, with fibrillation the fluorine-containing of energy is formed
Polymer
<Phosphorus system stabilizer>
AX-71:Substantially the equimolar mixture (ADEKA of monostearate phosphate and distearyl acid phosphoric acid ester
CORPORATION systems)
<Antioxidant>
Irg1076:BASF AG's system, octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester
<Releasing agent>
VPG861:U グ ニ ス オ レ オ ケ ミ カ Le ズ ジ ャ パ Application company systems, pentaerythritol tetrastearate
<Compound (compound)>
By each composition with each self-weighing of composition shown in table described later, after mixing 20 minutes in the mixed machine of bucket, tool is delivered to
JSW's system (TEX30HSST) of standby 1 ventilating opening, in screw speed 200rpm, discharge rate 20kg/ hour, rotary drum temperature
Kneaded under conditions of 300 DEG C of degree, the molten resin linearly extruded rapidly is cooled down in the sink, carried out using comminutor
Pellet, obtains the pellet of resin combination.
<Anti-flammability (UL94)>
It is just made using Japan's system after the pellet obtained with above-mentioned manufacture method is dried 5 hours at 120 DEG C
J50-EP type injection (mo(u)lding) machines, under conditions of 290 DEG C of barrel temperature, 80 DEG C of mold temperature injection moulding is carried out, and is shaped to length
Degree 125mm, width 13mm, the UL test test films of thickness 0.8mm.
With regard to the evaluation of the anti-flammability of each resin combination, by the UL test test films obtained in above-mentioned method in temperature
Damping 48 hours in 23 DEG C of degree, the thermostatic chamber of humidity 50%, according to U.S. UNDERWRITERS LABORATORIES INC.
(UL) regulation UL94 test (machine part with plastic material combustion test) on the basis of carry out.UL94 is by making holding
Test film for vertical particular size contacts the afterflame time after the flame of 10 seconds burners, dripping evaluating anti-flammability
Method, for the anti-flammability with V-0, V-1 and V-2, it is necessary to meet the benchmark shown in following table.
[table 1]
Table 1 | V-0 | V-1 | V-2 |
The afterflame time of each sample | Less than 10 seconds | Less than 30 seconds | Less than 30 seconds |
Total afterflame time of five samples | Less than 50 seconds | Less than 250 seconds | Less than 250 seconds |
Ignited due to drippage cotton | Nothing | Nothing | Have |
Herein afterflame time is the length for moving the time that the test film after ignition source persistently has scorching burning out.Further, since
Drippage and whether cotton of igniting can be because of the thing of (drippage) of dripping from test film with cotton according to the mark under the lower end about 300mm of test film
Matter and be ignited to judge.Further, among five samples, even if in the case that one does not meet said reference, not meet V-2
Form be evaluated as NR (not rated, not grade).
<The modulus of elasticity in static bending and bending strength>
After the pellet obtained with above-mentioned manufacture method is dried 5 hours at 120 DEG C, using Jing Resin Industries company
The SG75-MII of system, injection moulding is carried out under conditions of 50 seconds in 300 DEG C of barrel temperature, 100 DEG C of mold temperature, molding cycle,
Shaping 4mm thick ISO tension test sheets.
According to ISO178, using above-mentioned ISO tension test sheets (4mm is thick), the elasticity of flexure at a temperature of 23 DEG C is determined
Modulus (unit:) and bending strength (unit MPa:MPa).
<Charpy impact intensity>
Using ISO tension test sheets obtained above (4mm is thick), according to ISO179, determines under conditions of 23 DEG C and cut
The Charpy impact intensity of mouth.
<Temperature of deflection under load (DTUL)>
Using ISO tension test sheets obtained above (4mm is thick), according to ISO75-1 and ISO75-2, in load 1.80MPa
Under conditions of measuring load deflection temperature.
<Plating (LDS is active)-Plating Index>
After the pellet obtained with above-mentioned manufacture method is dried 5 hours at 120 DEG C, using Jing Resin Industries company
The SG75-MII of system, injection moulding is carried out under conditions of 50 seconds in 300 DEG C of barrel temperature, 100 DEG C of mold temperature, molding cycle,
Shaping 3mm thick plate.
The YAG laser of 1064nm is used 3mm obtained above thick plate, it is arbitrary in the scope by 2.6~13W of power
In value, 1~2m/s of speed in any value, the scope of the μ s of frequency 10~50 condition of any value be combined it is various under the conditions of profit
Printed with laser irradiation, then, by test film in sulfuric acid after degreasing, the THP ア manufactured with KIZAI CORPORATION
After Le カ リ ア Network チ and THP ア Le カ リ ア Network セ are processed, the SEL カ ッ パ ー manufactured with KIZAI CORPORATION enter
Row plating.Test film after plating is judged with visual observation, is divided into following 5 grades.
5:In various lasing conditions, the condition for being clearly equipped with coating is 75~100%
4:In various lasing conditions, the condition for being clearly equipped with coating is 50~74%
3:In various lasing conditions, the condition for being clearly equipped with coating is 30~49%
2:In various lasing conditions, the condition for being clearly equipped with coating is 10~29%
1:In various lasing conditions, the condition of coating is clearly equipped with less than 10%.
In showing the result in following tables.
[table 2]
[table 3]
Show really shown by above-mentioned:In the case of having used the composition of the present invention, can be maintained plating and curved
The test of the various mechanical properties such as modulus in elasticity in bending, bending strength, Charpy impact intensity, temperature of deflection under load and excellent in flame retardance
Piece, in the case of having used the composition of comparative example, either of which item is poor.
Claims (15)
1. a kind of laser direct forming resin combination, wherein, it is poly- comprising 40~73.8 mass % relative to 100 mass parts
The composition of the glass fibre of carbonate resin and 5~26.2 mass %, the elastomer comprising 0.5~10 mass parts, 5~20 mass
Part includes the poly- of laser direct forming additive, the phosphorus flame retardant of 8~25 mass parts and 0.1~1 mass parts of copper and chromium
Tetrafluoroethene,
The content of the acrylonitrile/butadiene/styrene copolymer in the elastomer be 3 mass % below,
The content of acrylonitrile/butadiene/styrene copolymer is polycarbonate resin and acrylonitrile/butadiene/styrene copolymerization
Below 3 mass % of the total amount of thing.
2. laser direct forming resin combination according to claim 1, wherein, the phosphorus flame retardant is condensation phosphorus
Acid esters.
3. laser direct forming resin combination according to claim 1, wherein, the phosphorus flame retardant is phosphonitrile
Compound.
4. the laser direct forming resin combination according to any one of claims 1 to 3, wherein, the laser straight
Type additive is connected into for spinel structure body.
5. laser direct forming resin combination according to claim 1 and 2, wherein, the elastomer is siloxanes
Copolymer elastomer.
6. laser direct forming resin combination according to claim 1 and 2, wherein, by with the glass fibre
The major diameter in the rectangular section of length direction is denoted as major diameter/minor axis when D2, minor axis are denoted as D1
1.5 it is following.
7. laser direct forming resin combination according to claim 1 and 2, wherein, by with the glass fibre
The major diameter in the rectangular section of length direction is denoted as major diameter/minor axis when D2, minor axis are denoted as D1 and surpasses than the flat ratio that D2/D1 is represented
Cross 1.5 and for less than 8.0.
8. laser direct forming resin combination according to claim 1 and 2, wherein, the composition is substantially not
Comprising acrylonitrile/butadiene/styrene copolymer.
9. a kind of synthetic resin, it is by the laser direct forming resin combination any one of claim 1~8
It is molded with.
10. synthetic resin according to claim 9, it also has on the surface coating.
11. synthetic resins according to claim 9 or 10, it is mancarried electronic aid part.
12. synthetic resins according to claim 10, wherein, the coating possesses the performance as antenna.
A kind of 13. manufacture methods for having coated synthetic resin, it is included in by any one of claim 1~8
The surface of synthetic resin that is molded with of laser direct forming resin combination on irradiate after laser, formed using metal
Coating.
14. manufacture methods for having coated synthetic resin according to claim 13, wherein, the coating is copper plating
Layer.
A kind of 15. manufacture methods of the mancarried electronic aid part with antenna, it includes the tool described in claim 13 or 14
The manufacture method of coated synthetic resin.
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JP2013100938 | 2013-05-13 | ||
PCT/JP2013/084780 WO2014115475A1 (en) | 2013-01-24 | 2013-12-26 | Resin composition for laser direct structuring, molded resin article, and method of manufacturing molded resin article having plating film |
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KR101783528B1 (en) * | 2014-12-01 | 2017-09-29 | 주식회사 엘지화학 | Polycarbonate resin composition and method for preparing the same |
CN104387742A (en) * | 2014-12-15 | 2015-03-04 | 李哲 | High-temperature-resistant PC composite material |
KR101806597B1 (en) | 2014-12-24 | 2018-01-11 | 롯데첨단소재(주) | Thermoplastic resin composition for laser direct structuring and molded article using thereof |
TWI797069B (en) * | 2015-12-15 | 2023-04-01 | 荷蘭商帝斯曼知識產權資產管理有限公司 | A thermoplastic polymer composition, an article made thereof and a process for preparing the same |
KR101900143B1 (en) * | 2016-02-23 | 2018-11-02 | 롯데첨단소재(주) | Thermoplastic resin composition for laser direct structuring process and article comprising the same |
CN107177180A (en) * | 2016-03-10 | 2017-09-19 | 汉达精密电子(昆山)有限公司 | Glass fiber-reinforced polycarbonate resin combination and products thereof |
CN107177181A (en) * | 2016-03-10 | 2017-09-19 | 汉达精密电子(昆山)有限公司 | High physical property glass fiber-reinforced polycarbonate resin combination and products thereof |
CN107304290A (en) * | 2016-04-22 | 2017-10-31 | 汉达精密电子(昆山)有限公司 | Poly carbonate resin composition and its products formed |
CN106883577A (en) * | 2017-03-23 | 2017-06-23 | 深圳力越新材料有限公司 | A kind of modified LDS laser direct formings PC composites and preparation method thereof |
CN107163534A (en) * | 2017-05-26 | 2017-09-15 | 合肥会通新材料有限公司 | A kind of height for laser direct forming flows fire-retardant PC resin and preparation method thereof |
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CN102066122A (en) * | 2008-05-23 | 2011-05-18 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant laser direct structuring materials |
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CN102066122A (en) * | 2008-05-23 | 2011-05-18 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant laser direct structuring materials |
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