CN104955896B - Resin composition for laser direct structuring, molded resin article, and method of manufacturing molded resin article having plating film - Google Patents

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

Laser direct forming resin combination, synthetic resin and the coated tree of tool The manufacture method of fat products formed

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.