JP2014058603A - Polyamide resin composition, resin molded article, and method for producing resin molded article having plated layer attached thereto - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition which is superior in the appearance of a resin molded article and retention stability at the time of molding, while maintaining plating properties of the resin molded article.SOLUTION: A polyamide resin composition contains, relative to 100 pts.wt. of polyamide resin, a laser direct structuring additive in amounts of 1 to 30 pts.wt., wherein the laser direct structuring additive includes a tin oxide in amounts of 70 wt.% or more and pH of the laser direct structuring additive is 6-8.

Description

  The present invention relates to a polyamide resin composition. Furthermore, it is related with the manufacturing method of the resin molded product formed by shape | molding this polyamide resin composition, and the resin molded product with a plating layer which formed the plating layer on the surface of this resin molded product.

  In recent years, with the development of mobile phones including smartphones, various methods for manufacturing antennas inside mobile phones have been studied. In particular, there is a need for a method of manufacturing an antenna that can be three-dimensionally designed for a mobile phone. As one of the techniques for forming such a three-dimensional antenna, a laser direct structuring (hereinafter, also referred to as “LDS”) technique has attracted attention. LDS technology, for example, irradiates the surface of a resin molded product containing an LDS additive with a laser, activates only the portion irradiated with the laser, and forms a plating layer by applying metal to the activated portion. Technology. A feature of this technique is that a metal structure such as an antenna can be manufactured directly on the surface of the resin base material without using an adhesive or the like. Such LDS technology is disclosed in, for example, Patent Documents 1 to 3 and the like.

Special table 2000-503817 Special table 2004-534408 gazette International Publication WO2009 / 141800 Pamphlet

  The inventors of the present invention have studied a polyamide resin composition in which an LDS additive is blended with a polyamide resin. When various components are blended with the polyamide resin composition so as to improve plating characteristics (plating appearance), a prescription is obtained. Depending on the case, it was found that the appearance of the obtained resin molded product and the retention stability during molding of the resin molded product may be inferior.

  The object of the present invention is to solve the problems of the prior art, and while maintaining the plating characteristics of the resin molded product, the appearance of the resin molded product and the retention during molding of the resin molded product It aims at providing the polyamide resin composition excellent in stability.

  Under such circumstances, as a result of intensive studies by the present inventor, the above problem was solved by blending a polyamide resin with an LDS additive containing tin oxide of 70% by weight or more and having a pH of 6-8. As a result, the present invention has been completed. Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <13>.

<1> 1 to 30 parts by weight of a laser direct structuring additive with respect to 100 parts by weight of a polyamide resin, and the laser direct structuring additive contains 70% by weight or more of tin oxide, A polyamide resin composition having a pH of 6-8.
<2> The polyamide resin composition according to <1>, comprising 10 to 200 parts by weight of inorganic fibers with respect to 100 parts by weight of the polyamide resin.
<3> The polyamide resin composition according to <2>, wherein the inorganic fiber is a glass fiber.
<4> The polyamide resin composition according to any one of <1> to <3>, wherein the laser direct structuring additive has a pH of 6 to 7.
<5> The polyamide resin composition according to any one of <1> to <4>, wherein the laser direct structuring additive further contains phosphorus and / or antimony.
<6> The polyamide resin composition according to any one of <1> to <5>, which contains substantially no alkali.
<7> A resin molded product obtained by molding the polyamide resin composition according to any one of <1> to <6>.
<8> The resin molded product according to <7>, having a plating layer on the surface.
<9> The resin molded product according to <8> or <9>, which is a portable electronic device part.
<10> The resin molded product according to <8> or <9>, wherein the plated layer has performance as an antenna.
<11> Forming a plating layer by applying a metal to the surface of a resin molded product obtained by molding the polyamide resin composition according to any one of <1> to <6> after laser irradiation. A method for producing a resin-molded article with a plating layer.
<12> The method for producing a resin-molded article with a plating layer according to <11>, wherein the plating is copper plating.
<13> A method for manufacturing a portable electronic device part having an antenna, including a method for manufacturing a resin molded product having the plating layer according to <11> or <12>.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide resin composition excellent in the external appearance of the resin molded product and the residence stability at the time of shaping | molding of a resin molded product can be provided, maintaining the plating characteristic of a resin molded product.

It is the schematic which shows the process of providing plating on the surface of a resin molded product.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

<Polyamide resin composition>
The polyamide resin composition of the present invention contains 1-30 parts by weight of an LDS additive with respect to 100 parts by weight of the polyamide resin, the LDS additive contains 70% by weight or more of tin oxide, and the pH of the LDS additive is 6-6. 8 is a feature. Here, when an LDS additive whose pH is not 6 to 8 (neutral), that is, an acidic (less than pH = 6) LSD additive is added to the polyamide resin, the polyamide resin decomposes under acidic conditions and the molecular weight is reduced. It will fall and the fluidity | liquidity of a polyamide resin composition will raise too much. On the other hand, in order to suppress such decomposition of the polyamide resin, for example, when an alkali is used together with an acidic LSD additive, a gas is generated by the alkali during molding of the resin molded product, and this gas causes the resin molded product to be generated. As a result, the appearance of the resin molded product (appearance of the molded product) is not good.

  Thus, since the polyamide resin composition of the present invention has an LDS additive having a pH of 6 to 8, even when it is substantially free of alkali, the plating properties of the resin molded product and the mechanical properties of the resin molded product can be obtained. While maintaining the strength, the appearance of the resin molded product and the retention stability before being molded into the resin molded product can also be improved. Here, “substantially free of alkali” means, for example, 1% by mass or less of the total amount of the polyamide resin composition of the present invention, and further 0.1% by mass or less, and is not particularly actively blended. That means.

<Polyamide resin>
The polyamide resin composition of the present invention contains a polyamide resin. Only one type of polyamide resin may be used, or two or more types may be used in combination.

  The polyamide resin is a polyamide polymer having an acid amide group (—CONH—) in the molecule and capable of being melted by heating. Specifically, various polyamide resins such as a lactam polycondensate, a polycondensate of a diamine compound and a dicarboxylic acid compound, a polycondensate of ω-aminocarboxylic acid, or a copolymerized polyamide resin or blend thereof. It is. Examples of the lactam that is a raw material for polycondensation of polyamide resin include ε-caprolactam and ω-laurolactam.

  Examples of the diamine compound include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2-methylpentamethylene diamine, (2,2,4- or 2,4,4-) trimethylhexamethylene diamine. , 5-methylnonamethylenediamine, metaxylylenediamine (MXDA), paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-amino Methyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) ) Piperazine, aminoethyl Aliphatic, such as piperazine, alicyclic, diamines aromatic or the like.

  Examples of the dicarboxylic acid compound include adipic acid, peric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Aliphatic, alicyclic, and aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. Examples of the ω-aminocarboxylic acid include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid.

  Specific examples of polyamide resins obtained by polycondensation from these raw materials include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyhexamethylene terephthalamide (polyamide 6T). ), Polyhexamethylene isophthalamide (polyamide 6I), polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene decamide, polyamide 9T, polyamide 9MT, and the like. In the present invention, these polyamide homopolymers or copolymers can be used alone or in the form of a mixture.

  Among the polyamide resins as described above, xylylenediamine obtained by polycondensation of polyamide 6, polyamide 66, or α, ω-linear aliphatic dibasic acid and xylylenediamine from the viewpoint of moldability and heat resistance. A polyamide resin (MX nylon) is more preferably used. Among these, MX nylon is more preferable from the viewpoints of heat resistance and flame retardancy. When the polyamide resin is a mixture, the ratio of MX nylon in the polyamide resin is preferably 50% by weight or more, and more preferably 80% by weight or more.

  Since MX nylon has a slightly slower crystallization speed than aliphatic polyamide resins such as polyamide 66, polyamide 6, polyamide 46, and polyamide 9T, MX nylon is used to shorten the molding cycle when using MX nylon. It is preferable to mix and use an aliphatic polyamide resin. Examples of the aliphatic polyamide resin used for blending for the purpose of shortening the molding cycle include polyamide resins having a high crystallization speed such as polyamide 66, polyamide 6, polyamide 46, and polyamide 9T, and polyamides 66 / 6T, 66 / Examples thereof include polyamide resins having a high melting point such as 6T / 6I, and polyamide 66 or polyamide 6 is preferable from the viewpoint of economy. From the balance of moldability and physical properties, the content of the aliphatic polyamide resin is preferably less than 50% by weight in the total polyamide resin. By making the content of the aliphatic polyamide resin less than 50% by weight, the heat resistance can be kept good.

  Among α, ω-linear aliphatic dibasic acids that are raw materials for MX nylon, α, ω-linear aliphatic dibasic acids having 6 to 20 carbon atoms such as adipic acid, sebacic acid, suberic acid, Dodecanedioic acid, eicodioic acid and the like can be preferably used. Among these α, ω-linear aliphatic dibasic acids, sebacic acid is particularly preferable in view of the balance of moldability and molded product performance.

  The xylylenediamine used as another raw material of MX nylon is metaxylylenediamine or a mixed xylylenediamine of paraxylylenediamine and metaxylylenediamine. The molar ratio of metaxylylenediamine to paraxylylenediamine (metaxylylenediamine / paraxylylenediamine) in the mixed xylylenediamine is preferably 55/45 to 100/0, more preferably 70/30 to 100/0. . It is preferable that the molar ratio of paraxylylenediamine is less than 45 mol% because the melting point of the polyamide resin is kept low and the polymerization of MX nylon and the molding process of the composition containing MX nylon are facilitated.

  The blending amount of the polyamide resin in the polyamide resin composition of the present invention is preferably 30% by weight or more, and more preferably 40% by weight.

  The polyamide resin composition may contain a thermoplastic resin other than the polyamide resin. For example, olefin resins such as polypropylene (PP) and polyethylene (PE), styrene polymers, polyester resins such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), polycarbonate resins, polyphenylene ether resins, poly Examples include methyl methacrylate resin, polyphenylene sulfone resin, polytetrafluoroethylene resin, novolak phenol resin, and liquid crystal resin. In particular, from the viewpoint of compatibility, a styrene polymer, a polycarbonate resin, and a polyphenylene ether resin are preferable, and a polyphenylene ether resin or a mixed resin of a polyphenylene ether resin and a styrene polymer is particularly preferable.

  Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2,6 -Dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether -Tell etc. are mentioned, and poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred.

  Examples of the styrene polymer include general-purpose polystyrene (GPPS), rubber-reinforced polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate- In addition to styrene resins such as butadiene-styrene copolymer (MBS resin), styrene elastomers such as styrene-ethylene-butadiene-styrene copolymer (SEBS) and styrene-ethylene-propylene-styrene copolymer (SEPS). And a styrene-based elastomer is preferable.

  In the case where a polyphenylene ether resin and a styrene polymer are used in combination, the content ratio (polyphenylene ether resin / styrene polymer) of both is preferably 99/1 to 20/80, and 97/3 to 40 / 60 is more preferable. By setting it as such a content weight ratio, sufficient flame retardance can be ensured, the fluidity | liquidity at the time of shaping | molding is favorable, and the bleed-out of a flame retardant can fully be suppressed.

  The content of the thermoplastic resin other than these polyamide resins is preferably 0.5 to 5% by weight in the polyamide resin composition of the present invention, more preferably 0.8 to 3% by weight (however, The total of the components is 100% by weight). By setting the content to 0.5% by weight or more, generation of mold deposits and bleedout of the flame retardant can be sufficiently suppressed, and by setting the content to 5% by weight or less, tracking resistance characteristics can be reduced. Reduction can be suppressed and productivity can also be improved.

<LDS additive>
The LDS additive in the present invention is a YAG laser having a wavelength of 1064 nm, which is obtained by adding 4 parts by weight of an additive considered to be an LDS additive to 100 parts by weight of a polyamide resin (for example, PAMP10 synthesized in Examples described later). , Irradiation at an output of 10 W, frequency of 80 kHz, speed of 3 m / s, and the subsequent plating process was performed in an electroless MacDermid M-Copper85 plating tank, and a metal was applied to the laser irradiated surface And a compound capable of forming a plating. The LDS additive used in the present invention may be a synthetic product or a commercial product. In addition to those that are commercially available as LDS additives, commercially available products may be substances that are sold for other uses as long as they satisfy the requirements of the LDS additive in the present invention.

The polyamide resin composition of the present invention contains an LDS additive containing 70% by weight or more of tin oxide and having a pH of 6 to 8 of the LDS additive. As the pH of the LDS additive, a pH value of a dispersion obtained by dispersing the LDS additive in water at 25 ° C. so as to be 5% by weight at room temperature (for example, 25 ° C.) can be adopted.
Only one type of LDS additive may be used, or two or more types may be used in combination.

  The LDS additive used in the present invention can improve the plating characteristics of the resin molded product by containing 70% by weight or more, preferably 75% by weight or more of tin oxide. Can be formed.

  In the first preferred embodiment of the LDS additive used in the present invention, tin oxide accounts for 90% by weight or more (preferably 95% by weight or more), and in the second preferred embodiment, tin oxide is the main component. And further containing phosphorus and / or antimony.

  When using tin oxide as the main component and further containing phosphorus and / or antimony, it is more preferable that the content of tin is larger than the content of phosphorus and / or antimony. The amount of tin relative to the total amount is more preferably 80% by weight or more. Examples of such LDS additives include tin oxide doped with antimony, tin oxide doped with antimony oxide, tin oxide doped with phosphorus, and tin oxide doped with phosphorus oxide. For example, in an LDS additive containing phosphorus and tin oxide, the phosphorus content is preferably 1 to 20% by weight. In the LDS additive containing antimony and tin oxide, the content of antimony is preferably 1 to 20% by weight. In the LDS additive containing phosphorus, antimony and tin oxide, the phosphorus content is preferably 0.5 to 10% by weight, and the antimony content is preferably 0.5 to 10% by weight.

  Further, the LDS additive used in the present invention has an appearance of the resin molded product while maintaining the plating characteristics of the resin molded product and the mechanical strength of the resin molded product, because the pH of the LDS additive is 6 to 8. The residence stability before being molded into a resin molded product can also be improved. In particular, the LDS additive used in the present invention preferably has a pH of 6 to 7 from the viewpoint of making the appearance and the retention stability better.

  The LDS additive used in the present invention preferably has a powder resistivity of 1000 Ω · cm or less, and more preferably 100 Ω · cm or less. When the powder resistivity of the LDS additive is 1000 Ω · cm or less, the effects of the present invention can be exhibited better.

  As the LDS additive of the present invention, a commercially available product may be used, a commercially available product that has been neutralized to adjust the pH to 6-8, or a synthesized product may be used. For example, it can be obtained by neutralizing tin oxide, tin oxide containing antimony, tin oxide containing phosphorus, tin oxide containing antimony and phosphorus, tin oxide containing antimony oxide, tin oxide containing phosphorus oxide, and the like. .

  A commercially available product may be used as the LDS additive containing 70% by weight or more of tin oxide, and the pH of the LDS additive is 6 to 8, or an LDS additive having a pH of the LDS additive outside the range of 6 to 8 It may be used after neutralization. As a neutralization treatment method, tin oxide, tin oxide containing antimony, tin oxide containing phosphorus, tin oxide containing antimony and phosphorus, tin oxide containing antimony oxide, tin oxide containing phosphorous oxide, etc. The method of adding is mentioned. For example, there is a method in which an alkali is added to an aqueous dispersion of an LDS additive to neutralize and then dried. The alkali is not particularly limited, and for example, calcium hydroxide, magnesium hydroxide and the like can be used.

  The average particle size of the LDS additive used in the present invention is preferably 0.01 to 100 μm, and more preferably 0.05 to 10 μm. By setting it as such an average particle diameter, the uniformity of the plating surface state at the time of applying a plating can be made more favorable.

  The compounding amount of the LDS additive in the polyamide resin composition of the present invention is 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 15 to 22 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. By setting the blending amount of the LDS additive in such a range, the plating characteristics and flame retardancy can be improved. Further, as will be described later, by using talc together with the LDS additive, plating can be formed even when the amount of the LDS additive added is reduced.

<Inorganic fiber>
The polyamide resin composition of the present invention may further contain inorganic fibers. By blending inorganic fibers, the mechanical strength can be further improved. Furthermore, the dimensional accuracy can be further improved. In addition, LDS characteristics can be improved. Only one type of inorganic fiber may be used, or two or more types may be used in combination.

  Examples of the inorganic fiber include glass fiber, milled fiber, alumina fiber, potassium titanate whisker, and the like, and examples of the metal fiber include steel fiber and stainless steel fiber, and glass fiber is particularly preferable.

  The glass fiber preferably used in the present invention preferably has an average diameter of 20 μm or less, and further 1 to 15 μm further increases the balance of physical properties (strength, rigidity, heat-resistant rigidity, impact strength) and molding. This is preferable in that the warpage is further reduced. In general, glass fibers having a circular cross-section are generally used in many cases. However, the present invention is not particularly limited, and for example, the cross-sectional shape can be used similarly for eyebrows, ovals, and rectangles.

  The length of the glass fiber is not particularly limited, and can be selected from a long fiber type (roving) or a short fiber type (chopped strand). The number of bundles in this type of glass fiber is preferably about 100 to 5000. If the average length of the glass fibers in the polyamide resin composition after kneading the polyamide resin composition is 0.1 mm or more, a so-called milled fiber or a pulverized product of strands called glass powder may be used. The glass fiber may be a continuous single fiber sliver.

  The composition of the raw glass is preferably alkali-free, and examples thereof include E glass, C glass, and S glass. In the present invention, E glass is preferable. The glass fiber is preferably surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like. The amount is usually from 0.01 to 1% by weight of the glass fiber weight. Furthermore, if necessary, a lubricant such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin or a urethane resin, a resin having a film forming ability and a heat. What was surface-treated with a mixture of a stabilizer, a flame retardant, etc. can also be used.

  In the polyamide resin composition of the present invention, the amount of inorganic fibers is usually 10 to 200 parts by weight, preferably 20 to 180 parts by weight, more preferably 30 to 150 parts by weight, based on 100 parts by weight of the polyamide resin. Part. In the polyamide resin composition of the present invention, the polyamide resin and the inorganic fibers usually occupy 60% by weight or more of the total components, and more preferably 80% by weight or more.

<Titanium oxide>
The polyamide resin composition of the present invention may further contain titanium oxide. By including titanium oxide in the polyamide resin composition, the plating property can be further improved while maintaining a high reflectance.

  The compounding quantity of the titanium oxide in the polyamide resin composition of this invention is 1-100 weight part with respect to 100 weight part of polyamide resins, Preferably it is 5-30 weight part. By making the compounding quantity of titanium oxide into such a range, the fall of the reflectance after heat processing can be prevented.

Of the commercially available titanium oxides, titanium oxide containing 80% by weight or more of titanium oxide is preferably used in terms of whiteness and concealment. Examples of the titanium oxide used in the present invention include titanium monoxide (TiO), titanium trioxide (Ti ₂ O ₃ ), titanium dioxide (TiO ₂ ), and any of these may be used. Titanium dioxide is preferred. Further, as the titanium oxide, those having a rutile type crystal structure are preferably used.

  The average primary particle diameter of titanium oxide is preferably 1 μm or less, more preferably in the range of 0.001 to 0.5 μm, and still more preferably in the range of 0.002 to 0.1 μm. . By setting the average particle diameter of titanium oxide in such a range and the blending amount in the above-described range, a polyamide resin composition that gives a molded product having high whiteness and high surface reflectance can be obtained.

  As the titanium oxide, a surface-treated one may be used. As the surface treatment agent, inorganic materials and / or organic materials are preferable. Specific examples include metal oxides such as silica, alumina, and zinc oxide, silane coupling agents, titanium coupling agents, organic materials such as organic acids, polyols, and silicones. Moreover, you may use what is marketed for titanium oxide. Further, as the titanium oxide, those having a mass or a large average particle size may be appropriately pulverized and classified by sieving or the like as necessary to obtain the above-mentioned average particle size.

<Talc>
The polyamide resin composition of the present invention may further contain talc. In the present invention, by adding talc, dimensional stability and product appearance can be improved, and even if the amount of LDS additive is reduced, the plating characteristics of the resin molded product can be improved. It is possible to form an appropriate plating on the resin molded product.

  Further, talc may be used that has been surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. In this case, the adhesion amount of the siloxane compound in talc is preferably 0.1 to 5% by weight of talc.

  The blending amount of talc in the polyamide resin composition of the present invention is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin composition. More preferably, it is ˜15 parts by weight. Moreover, when the talc is surface-treated with a siloxane compound, the blending amount of the talc surface-treated with the siloxane compound is preferably within the above range.

<Elastomer>
The polyamide resin composition of the present invention may further contain an elastomer. Thus, the impact resistance of a polyamide resin composition can be improved by containing an elastomer.

  The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

  The rubber component usually has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .

  Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable. The core / shell type in the present invention does not necessarily have to be clearly distinguishable between the core layer and the shell layer, and includes a wide range of compounds obtained by graft polymerization of a rubber component around the core portion. It is the purpose.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include a styrene copolymer, a methyl methacrylate- (acryl / silicone IPN rubber) copolymer, and a styrene-ethylene-butadiene-styrene copolymer. Such rubbery polymers may be used alone or in combination of two or more.

  The content of the elastomer in the polyamide resin composition of the present invention is preferably 0.1 to 40% by weight, more preferably 0.5 to 25% by weight, and still more preferably 1 to 10% by weight.

<Release agent>
The polyamide resin composition of the present invention may further contain a release agent. The mold release agent is mainly used for improving the productivity at the time of molding the resin composition. Examples of the release agent include aliphatic carboxylic acid amides, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oils, and the like. Can be mentioned. Among these release agents, carboxylic acid amide compounds are particularly preferable.

  Examples of the aliphatic carboxylic acid amide system include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and / or a polybasic acid and a diamine.

  The higher aliphatic monocarboxylic acid is preferably a saturated aliphatic monocarboxylic acid or hydroxycarboxylic acid having 16 or more carbon atoms, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. .

  Examples of polybasic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid and azelaic acid, aromatic dicarboxylic acids such as phthalic acid and terephthalic acid, cyclohexanedicarboxylic acid, and cyclohexylsuccinic acid. Examples include alicyclic dicarboxylic acids such as acids.

  Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine.

  As the carboxylic acid amide compound, a compound obtained by polycondensation of stearic acid, sebacic acid and ethylenediamine is preferable, and a compound obtained by polycondensation of 2 mol of stearic acid, 1 mol of sebacic acid and 2 mol of ethylenediamine is more preferable. In addition to bisamide compounds obtained by reacting diamines with aliphatic carboxylic acids such as N, N′-methylenebisstearic acid amide and N, N′-ethylene bisstearic acid amide, N, N′— Dicarboxylic acid amide compounds such as dioctadecyl terephthalic acid amide can also be suitably used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 44200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. The number average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less.

  The content of the release agent is usually 0.001 parts by weight or more, preferably 0.01 parts by weight or more, and usually 2 parts by weight or less, based on 100 parts by weight of the total of the polyamide resin and the inorganic fibers. Preferably it is 1.5 weight part or less. By making the content of the release agent 0.001 part by weight or more, the release property can be improved, and by making the content of the release agent 2 parts by weight or less, hydrolysis resistance is improved. Reduction and mold contamination at the time of injection molding can be prevented.

<Other additives>
The polyamide resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include heat stabilizers, light stabilizers, antioxidants, UV absorbers, dyes and pigments, fluorescent whitening agents, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, Examples include fluidity improvers, plasticizers, dispersants, and antibacterial agents. These components may use only 1 type and may use 2 or more types together.

<Manufacturing method of polyamide resin composition>
Any method can be adopted as a method for producing the polyamide resin composition of the present invention. For example, there is a method in which a polyamide resin, an LDS additive, and inorganic fibers are mixed using a mixing means such as a V-type blender, a batch blend product is prepared, and then melt-kneaded with a vented extruder to be pelletized. Can be mentioned. Alternatively, as a two-stage kneading method, components other than inorganic fibers, etc., are mixed in advance and then melt-kneaded with a vented extruder to produce pellets, and then the pellets and inorganic fibers are mixed and then vented The method of melt-kneading with an extruder is mentioned.

Furthermore, what mixed components other than inorganic fiber sufficiently with a V-type blender or the like is prepared in advance, and this mixture is supplied from the first chute of the vented twin-screw extruder, and the inorganic fiber is in the middle of the extruder. A method of supplying from the second chute and melt-kneading and pelletizing can be mentioned.
As for the screw configuration of the kneading zone of the extruder, it is preferable that the element that promotes kneading is arranged on the upstream side, and the element having a boosting ability is arranged on the downstream side.

  Examples of elements that promote kneading include a progressive kneading disk element, an orthogonal kneading disk element, a wide kneading disk element, and a progressive mixing screw element.

  The heating temperature at the time of melt kneading can be appropriately selected from the range of usually 180 to 360 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration that takes into account shearing heat generation and the like. Moreover, it is desirable to use an antioxidant or a heat stabilizer from the viewpoint of suppressing decomposition during kneading or molding in the subsequent process.

  The method for producing the resin molded product is not particularly limited, and a molding method generally adopted for the polyamide resin composition can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method. A molding method using a hot runner method can also be used.

<Method for producing resin molded product with plating layer>
Next, the manufacturing method of the resin molded product with a plated layer of the present invention, specifically, the step of providing plating on the surface of the resin molded product formed of the polyamide resin composition of the present invention will be described with reference to FIG.

  FIG. 1 is a schematic view showing a process of forming plating on the surface of a resin molded product 1 by a laser direct structuring technique. In FIG. 1, the resin molded product 1 is a flat substrate. However, the resin molded product 1 is not necessarily a flat substrate, and may be a resin molded product that is partially or entirely curved. Further, the resin molded product 1 is not limited to the final product, and includes various parts.

  As the resin molded product 1 in the present invention, a portable electronic device component is preferable. Portable electronic device parts have both high impact resistance, rigidity, and excellent heat resistance, as well as low anisotropy and low warpage. PDAs such as electronic notebooks and portable computers, pagers, and mobile phones. It is extremely effective as an internal structure and case such as a telephone and PHS. In particular, the molded product is suitable for flat-plate-shaped portable electronic device parts whose average thickness excluding ribs is 1.2 mm or less (the lower limit is not particularly defined, for example, 0.4 mm or more). Particularly suitable as a housing.

Returning to FIG. 1 again, in the method for producing a resin molded product with a plated layer of the present invention, the resin molded product 1 is irradiated with a laser 2.
The laser 2 is not particularly limited, and can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and electromagnetic radiation, and a YGA laser is particularly preferable. Further, the wavelength of the laser 2 is not particularly limited. The wavelength range of the preferable laser 2 is 200 nm to 1200 nm, and particularly preferably 800 to 1200 nm.

  When the laser molded product 1 is irradiated with the laser 2, the resin molded product 1 is activated only in the portion 3 irradiated with the laser 2. The resin molded product 1 is applied to the plating solution 4 in the activated state. The plating solution 4 is not particularly defined, and a wide variety of known plating solutions can be used. A metal component in which copper, nickel, gold, silver, and palladium are mixed is preferable, and copper is more preferable.

  The method of applying the resin molded product 1 to the plating solution 4 is not particularly limited, and examples thereof include a method of putting the resin molded product 1 in a solution containing the plating solution. In the resin molded product 1 after applying the plating solution, the plating layer 5 is formed only in the portion irradiated with the laser 2.

  In the method of the present invention, it is possible to form a line interval (a lower limit value is not specifically defined, for example, 30 μm or more) having a width of 1 mm or less, and further 150 μm or less. Such a circuit is preferably used as an antenna of a portable electronic device component. That is, as an example of a preferred embodiment of the resin molded product 1 of the present invention, a resin molded product in which a plating layer provided on the surface of a portable electronic device component has performance as an antenna can be mentioned.

  In addition, within the range which does not deviate from the meaning of the present invention, JP2011-219620A, JP2011-195820A, JP2011-178873A, JP2011-168705A, JP2011-148267A. The description of the publication can be taken into consideration.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Polyamide resin>
(Synthesis of polyamide (PAMP10))
After heating and dissolving sebacic acid in a reactor under a nitrogen atmosphere, while stirring the contents, paraxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) The temperature was raised to 235 ° C. while gradually dropping a mixed diamine having a molar ratio of 3: 7 under pressure (0.35 Mpa) so that the molar ratio of diamine to sebacic acid was about 1: 1. I let you. After completion of the dropping, the reaction was continued for 60 minutes to adjust the amount of the component having a molecular weight of 1000 or less. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain polyamide. Hereinafter, it is referred to as “PAMP10”.
<LDS additive>
(1) T-1-20L (manufactured by Mitsubishi Materials Corporation): tin-antimony oxide (SnO ₂ : 80%, Sb ₂ O ₅ : 20%, antimony content: 15.1% by weight), moisture content 1.5%, pH measured for 5% by weight aqueous dispersion of LDS additive = 3.4)
(2) T-1-20L neutralized product (manufactured by Mitsubishi Materials Corporation): tin-antimony oxide (SnO ₂ : 80% by weight, Sb ₂ O ₅ : 20% by weight, antimony content: 15.1% by weight %), PH measured with 5 wt% aqueous dispersion of LDS additive = 6.3)
(3) Neutralized product of S-2000 (Mitsubishi Materials Co., Ltd .: tin oxide, pH measured with 5% by weight aqueous dispersion of LDS additive = 6.5)
<Inorganic fiber>
03T-786H: Glass fiber (Owens Corning)
<Titanium oxide>
Titanium dioxide: CR63 (made by Ishihara Sangyo)
<Talc>
Micron White 5000S (Made by Hayashi Kasei)
<Elastomer>
SEBS: FT1901GT (made by Kraton Polymer)
<Release agent>
CS8CP (Nitto Kasei Kogyo)
<Alkali>
Ca (OH) ₂

<Compound>
Each component was weighed so as to have the composition shown in the table to be described later, components other than inorganic fibers were blended with a tumbler, charged from the root of a twin-screw extruder (Toshiki Machine Co., Ltd., TEM26SS), and melted. Later, inorganic fibers were side-fed to create resin pellets. The temperature setting of the extruder was carried out at 280 ° C.

<Preparation of ISO tensile test piece>
After the pellets obtained by the above production method were dried at 80 ° C. for 5 hours, an ISO tensile test was performed at a cylinder temperature of 280 ° C. and a mold temperature of 130 ° C. using a FANUC injection molding machine (100T). A piece (4 mm thick) was injection molded.

Injection speed: The resin flow rate was calculated from the cross-sectional area at the center of the ISO tensile test piece, and was set to 300 mm / s. The pressure was switched to the holding pressure so that the VP was switched at about 95% filling. The holding pressure was increased to 500 kgf / cm ² for 25 seconds without causing burrs.

<Bending strength and flexural modulus>
Based on ISO178, bending strength (unit: MPa) and bending elastic modulus (unit: GPa) were measured at a temperature of 23 ° C. using the ISO tensile test piece (4 mm thickness).

<Charpy impact strength>
Using the ISO tensile test piece (4 mm thickness) obtained by the above-described method, the notched Charpy impact strength and the notched Charpy impact strength were measured at 23 ° C. in accordance with ISO1799-1 or ISO179-2. The results are shown in Table 1 below.

<Appearance of molded product>
Using the pellets obtained by the above manufacturing method, the state of transfer by gas on the mold surface at the filling end when a box-shaped resin molded product having a depth of 10 mm was molded with five pin gates was visually observed. Specifically, FANUC α-100iA was used as an injection molding machine, under conditions of cylinder temperature 290 ° C., cooling 10 sec, mold temperature 110 ° C., suck back 3 mm, filling time 6 sec, holding pressure 80 MPa, holding pressure 5 sec. A resin molded product having a length of 120 mm, a width of 60 mm, and a thickness of 1 mm was produced using a pin gate mold.
The appearance of the weld part of the molded product was evaluated as follows. The results are shown in Table 1 below.
○: The mold was transferred, and no whitening or the like was confirmed.
X: The mold was not transferred, and whitening was observed.

<Stability of residence>
Using the pellets obtained by the above manufacturing method, molding was performed in a spiral flow 1 mmt mold under predetermined conditions. The flow length at the residence time of 10 minutes and 20 minutes in the cylinder was measured, and the difference (change in flow length) was confirmed. The flow length was measured by using an injection molding machine (SE50 manufactured by Sumitomo Heavy Industries, Ltd.), resin temperature (measured temperature of purge resin): 290 ° C., mold temperature: 100 ° C., mold (flow cross section): 6 mm. The measurement was performed under the conditions of width × 1 mm thickness and pressure: 50 MPa · 5 sec. The results are shown in Table 1 below.

<Platting appearance>
Molding was performed by filling a cavity having a size of 60 mm × 60 mm and a thickness of 2 mm as a mold from a fan gate having a resin temperature of 280 ° C. and a mold temperature of 110 ° C. and a side of 60 mm having a thickness of 1.5 mm. The gate portion was cut to obtain a plate test piece.
A 10 × 10 mm range of the obtained plate test piece was irradiated with an output of 80%, a frequency of 60 kHz, and a speed of 2 m / s using a VMf1 laser irradiation device (maximum output of YAG laser with a wavelength of 1064 nm of 15 W) manufactured by Trumpf. . The subsequent plating process was carried out in an electroless Enthone, ENPLATE LDS CU 400 PC 48 ° C. plating bath. The plating performance was determined by visual observation of the thickness of copper plated for 20 minutes.
Evaluation was performed as follows. The results are shown in Table 1 below.
○: Good appearance (confirmed that the copper color is dark and the plating is thick)
Δ: Plating is on, but slightly thin (practical level)
×: No plating at all

  As is clear from Table 1 above, the polyamide resin compositions obtained in Examples 1 and 2 were excellent in the appearance of the resin molded product and the retention stability during molding while maintaining the plating characteristics of the resin molded product. . The mechanical strength was also high.

  On the other hand, since the polyamide resin composition obtained in Comparative Example 1 used an LDS additive in which the pH of the LDS additive did not satisfy 6 to 8, the residence stability was not good. That is, in Comparative Example 1, since an acidic LSD additive was used, the polyamide resin was decomposed under acidic conditions to decrease the molecular weight, and as a result, the fluidity of the polyamide resin composition was increased.

  Since the polyamide resin composition obtained in Comparative Example 2 uses an LDS additive whose pH of the LDS additive does not satisfy 6 to 8, the residence stability before being molded into a resin molded product is more than that of Comparative Example 1. Although it was good, the appearance of the resin molded product was not good. That is, in Comparative Example 2, although an acidic LSD additive was used as in Comparative Example 1, since the alkali was added to the polyamide resin composition, the decomposition of the polyamide resin as in Comparative Example 1 was suppressed. The generated alkali generated gas during molding, and this gas caused whitening of the resin molded product.

  Thus, according to the present invention, 1 to 30 parts by weight of the LDS additive is contained with respect to 100 parts by weight of the polyamide resin, the LDS additive contains 70% by weight or more of tin oxide, and the pH of the LDS additive is 6 to 6%. It was found that a polyamide resin composition having excellent appearance and retention stability of the resin molded product can be provided while maintaining the plating characteristics of the resin molded product. Further, it has been found that excellent mechanical strength can be provided.

1 resin molded product, 2 laser, 3 laser irradiated part, 4 plating solution, 5 plating layer

Claims (13)

1 to 30 parts by weight of a laser direct structuring additive with respect to 100 parts by weight of the polyamide resin,
The polyamide resin composition in which the laser direct structuring additive contains 70% by weight or more of tin oxide, and the pH of the laser direct structuring additive is 6 to 8. The polyamide resin composition according to claim 1, comprising 10 to 200 parts by weight of inorganic fibers with respect to 100 parts by weight of the polyamide resin. The polyamide resin composition according to claim 2, wherein the inorganic fibers are glass fibers. The polyamide resin composition according to any one of claims 1 to 3, wherein the laser direct structuring additive has a pH of 6 to 7. The polyamide resin composition according to any one of claims 1 to 4, wherein the laser direct structuring additive further contains phosphorus and / or antimony. The polyamide resin composition of any one of Claims 1-5 which does not contain an alkali substantially. The resin molded product formed by shape | molding the polyamide resin composition of any one of Claims 1-6. The resin molded product according to claim 7, which has a plating layer on a surface thereof. The resin molded product according to claim 8 or 9, which is a portable electronic device part. The resin molded product according to claim 8 or 9, wherein the plated layer has performance as an antenna. Plating including forming a plating layer by applying a metal to a surface of a resin molded product obtained by molding the polyamide resin composition according to any one of claims 1 to 6 after laser irradiation Manufacturing method of resin molded product with layer. The manufacturing method of the resin molded product with a plating layer of Claim 11 whose said plating is copper plating. A method for manufacturing a portable electronic device part having an antenna, comprising the method for manufacturing a resin molded product having a plating layer according to claim 11.

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