JP2014058604A - Thermoplastic 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 thermoplastic resin composition which enables proper formation of a plated layer on the surface of a resin molded article under a wide range of laser irradiation conditions, and enables formation of a black resin molded article.SOLUTION: A thermoplastic resin composition contains: a thermoplastic resin; a laser direct structuring additive in amounts of 1 to 30 parts by weight relative to 100 parts by weight of the thermoplastic resin; and a black colorant with an L value of 30 or less other than carbon black.

Description

  The present invention relates to a thermoplastic resin composition. Furthermore, the present invention relates to a resin molded product obtained by molding this thermoplastic resin composition and a method for producing a resin molded product with a plating layer in which a plating layer is formed on the surface of the 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

By the way, also when forming a plating layer on the surface of the resin molded product formed by shape | molding a thermoplastic resin composition, the improvement of productivity is calculated | required. That is, it is required to appropriately form a plating layer even under a wide range of laser irradiation conditions, particularly even when the irradiation dose is small.
Moreover, the improvement of mechanical strength is calculated | required about the resin molded product formed by shape | molding a thermoplastic resin composition.

  The present invention is intended to solve the problems of the prior art, and can appropriately form a plating layer on the surface of a resin molded product under a wide range of laser irradiation conditions. It aims at providing the thermoplastic resin composition which can form.

  Under such circumstances, as a result of intensive studies by the present inventors, an LDS additive and a black colorant other than carbon black having an L value of 30 or less are blended in the thermoplastic resin. As a result, it has been found that the above problems can be solved, and the present invention has been completed. Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <15>.

<1> A thermoplastic resin, 1 to 30 parts by weight of a laser direct structuring additive with respect to 100 parts by weight of the thermoplastic resin, and a black colorant having an L value other than carbon black of 30 or less. , A thermoplastic resin composition.
<2> The thermoplastic resin composition according to <1>, including 10 to 200 parts by weight of inorganic fiber with respect to 100 parts by weight of the thermoplastic resin.
<3> The thermoplastic resin composition according to <2>, wherein the inorganic fiber is a glass fiber.
<4> The black colorant includes an oxide containing copper, chromium and manganese, an oxide containing iron and manganese, an oxide containing iron and chromium, an azine dye containing nigrosine and an anthraquinone. The thermoplastic resin composition according to any one of <1> to <3>, comprising at least one selected from polycyclic condensed dyes.
<5> The thermoplastic resin composition according to any one of <1> to <4>, wherein the laser direct structuring additive is an oxide containing antimony and tin.
<6> The thermoplastic resin composition according to <5>, wherein the laser direct structuring additive has a higher content of tin than antimony.
<7> The thermoplastic resin composition according to any one of <1> to <6>, wherein the thermoplastic resin is a polyamide resin.
<8> The thermoplastic resin composition according to any one of <1> to <7>, wherein the black colorant has an L value of 20 or less.
<9> A resin molded product obtained by molding the thermoplastic resin composition according to any one of <1> to <8>.
<10> The resin molded product according to <9>, having a plating layer on the surface.
<11> The resin molded product according to <9> or <10>, which is a portable electronic device part.
<12> The resin molded product according to <10> or <11>, wherein the plated layer has performance as an antenna.
<13> Forming a plating layer by applying a metal to a surface of a resin molded product obtained by molding the thermoplastic resin composition according to any one of <1> to <8>, after irradiating a laser. The manufacturing method of the resin molded product with a plating layer containing.
<14> The method for producing a resin-molded article with a plating layer according to <13>, wherein the plating is copper plating.
<15> A method for manufacturing a portable electronic device part having an antenna, including a method for manufacturing a resin molded product having a plating layer according to <13> or <14>.

  According to the present invention, it is possible to provide a thermoplastic resin composition capable of appropriately forming a plating layer on the surface of a resin molded product under a wide range of laser irradiation conditions and capable of forming a black resin molded product. Therefore, productivity at the time of forming a plating layer on the surface of a resin molded product formed by molding the thermoplastic resin composition obtained in the present invention can be improved.

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.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains a thermoplastic resin, 1 to 30 parts by weight of an LDS additive, and a black colorant having an L value of 12 or less with respect to 100 parts by weight of the thermoplastic resin. It is characterized by.

  In the thermoplastic resin composition of the present invention, the L value is preferably 20 or less, the L value is preferably 15 or less, and the L value is more preferably 13 or less. Since the blackness becomes better when the L value of the thermoplastic resin composition is 20 or less, the thermoplastic resin composition can be molded to form a black resin molded product. The lower limit value of the L value is not particularly defined, but can be 3 or more, for example. The L value of the thermoplastic resin composition can be measured using, for example, a colorimetric color difference meter.

<Thermoplastic resin>
The thermoplastic resin composition of the present invention contains a thermoplastic resin. The type of thermoplastic resin is not particularly limited. For example, polycarbonate resin, alloy of polyphenylene ether resin and polystyrene resin, alloy of polyphenylene ether resin and polyamide resin, thermoplastic polyester resin, methyl methacrylate / acrylonitrile / butadiene / styrene Examples thereof include a polymerization resin, a methyl methacrylate / styrene copolymer resin, a methyl methacrylate resin, a rubber-reinforced methyl methacrylate resin, a polyamide resin, a polyacetal resin, a polylactic acid resin, and a polyolefin resin.

  In the present invention, a polyamide resin and a thermoplastic polyester resin are preferably used, and a polyamide resin is more preferable. Only one type of thermoplastic 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 a blend thereof. is there.

  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. Further, 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 and 66 / 6T. Examples thereof include polyamide resins having a high melting point such as / 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, more preferably 1 to 20% 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 better.

  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, adipic acid is particularly preferable in view of balance of moldability, molded product performance, and the like.

  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.

  As the thermoplastic polyester resin, the description of paragraph numbers 0013 to 0016 of JP 2010-174223 A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the polyester resin include a mixture in which polybutylene terephthalate resin and polybutylene terephthalate resin occupy 60% by weight or more, preferably 80% by weight or more.

  The total amount of the thermoplastic resin in the thermoplastic resin composition of the present invention is preferably 35% by weight or more, and more preferably 40% by weight or more.

<LDS additive>
The LDS additive in the present invention is obtained by adding 4 parts by weight of an additive considered to be an LDS additive to 100 parts by weight of a thermoplastic resin (for example, a polyamide resin synthesized in Examples described later), and having a wavelength of 1064 nm. Using a YAG laser, irradiate at an output of 10W, a frequency of 80kHz, and a speed of 3m / s. The subsequent plating process was performed in an electroless MacDermid M-Copper85 plating tank, and metal was applied to the laser irradiation surface. Refers to a compound that can form 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. 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 preferably contains tin oxide as a main component and contains tin oxide in an amount of 70% by weight or more, preferably 75% by weight or more. For example, the LDS additive used in the present invention is an oxide containing antimony and / or phosphorus and tin, preferably an oxide containing antimony and tin. By using such an LDS additive, the plating characteristics of the resin molded product can be improved, so that plating can be appropriately formed on the surface of the resin molded product.

  When an oxide containing antimony and / or phosphorus and tin is used as the LDS additive, it is more preferable that the amount of tin is larger than the amount of phosphorus and / or antimony. The amount of tin with respect to the total amount is more preferably 80% by weight or more.

  In particular, the LDS additive is preferably an oxide containing antimony and tin, more preferably the amount of tin is larger than the amount of antimony, and the amount of tin relative to the total amount of tin and antimony is 80 wt. % Or more is more preferable.

  Specifically, as the LDS additive used in the present invention, for example, tin oxide doped with antimony, tin oxide doped with antimony oxide, tin oxide doped with phosphorus, doped with phosphorus oxide Examples thereof include tin oxide, tin oxide doped with antimony and tin oxide doped with antimony oxide are preferable, and tin oxide doped with antimony oxide is more preferable. 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.

In the present invention, 90% by weight or more is tin, 5% by weight or more is antimony, and an LDS additive containing lead and / or copper as a trace component can also be used. More preferably, such LDS additive is 90% by weight or more tin, 5-9% by weight antimony, contains lead in the range of 0.01-0.1% by weight, 0.001 Contains copper in a range of ~ 0.01 wt%.
More specifically, the LDS additive preferably includes 90% by weight or more of tin oxide and 3 to 8% by weight of antimony oxide, and 0.01 to 0.1% by weight of lead oxide and / or copper oxide. It is preferable to contain 0.001 to 0.01 weight%. Preferably, an LDS additive containing 90% by weight or more of tin oxide, 3 to 8% by weight of antimony oxide, 0.01 to 0.1% by weight of lead oxide, and 0.001 to 0.01% by weight of copper oxide. . Particularly preferably, the LDS additive comprises 93% by weight or more of tin oxide, 4 to 7% by weight of antimony oxide, 0.01 to 0.05% by weight of lead oxide, and 0.001 to 0.006% by weight of copper oxide. is there.

The LDS additive used in the present invention may be an oxide containing copper. The oxide containing copper is preferably an oxide containing copper and chromium (copper chromium oxide), and more preferably an oxide containing only copper and chromium as metal components. Examples of such an LDS additive include CuCr ₂ O ₄ and Cu ₃ (PO ₄ ) ₂ Cu (OH) ₂ , and CuCr ₂ O ₄ is particularly preferable. The copper content in such an LDS additive is preferably 20 to 95% by mass.
Moreover, the LDS additive used in the present invention may contain a trace amount of metals other than those mentioned above. Examples of other metals include indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, and calcium. These metals may exist as oxides. The content of these metals is preferably 0.001% by weight or less of the metal component contained in the LDS additive.

  Among the LDS additives described above, tin oxide doped with antimony and tin oxide doped with antimony oxide are particularly preferable.

  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.

  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 blending amount of the LDS additive in the thermoplastic resin composition of the present invention is 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 10 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin. 22 parts by weight. By setting the blending amount of the LDS additive in such a range, the plating characteristics 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.

<Black colorant>
The thermoplastic resin composition of the present invention contains a black colorant having an L value of 30 or less other than carbon black. The thermoplastic resin composition of the present invention is a thermoplastic resin containing a black colorant having an L value of more than 30 by blending a black colorant having an L value of 30 or less other than carbon black together with an LDS additive. Compared with a resin composition and a thermoplastic resin composition that does not contain such a black colorant, the laser is easily absorbed. Therefore, when the thermoplastic resin composition of the present invention is a resin molded product, the resin on the surface portion of the resin molded product irradiated with the laser is removed, and the LDS additive can be exposed. The exposed LDS additive is easily irradiated with a laser, and as a result, the thermoplastic resin composition of the present invention appropriately forms a plating layer on the surface of a resin molded product even under a wider range of laser irradiation conditions than before. Can be formed. In particular, productivity can be improved because plating can be formed even with a small amount of laser irradiation. On the other hand, when carbon black is used, there is a problem that carbon black remains on the surface of the molded product and hinders plating formation.

  Moreover, the thermoplastic resin composition of the present invention contains not only a two-dimensional structure but also a three-dimensional structure by blending a black colorant having an L value other than carbon black of 30 or less together with an LDS additive. A plating layer can also be appropriately formed on the surface of a structure (for example, a corner portion of a portable electronic device component).

  The black colorant used in the present invention usually has an L value of 30 or less, preferably an L value of 25 or less, and more preferably an L value of 20 or less. The lower limit of the L value is not particularly defined, but can be, for example, 3 or more, and can be 5 or more.

  Moreover, L value of the obtained thermoplastic resin composition can be made smaller by mix | blending a black colorant whose L value is 30 or less with a thermoplastic resin. That is, as the L value becomes smaller, the hue of the obtained thermoplastic resin becomes darker, so that a blacker thermoplastic resin composition can be obtained. The L value of the black colorant can be measured using, for example, a colorimetric colorimeter.

As the black colorant having an L value of 30 or less other than carbon black used in the present invention, black pigments and black dyes other than carbon black can be used. Specific examples include those composed only of inorganic materials and organic materials containing components other than carbon (C), such as titanium black, black iron oxide, oxides containing copper, chromium and manganese, iron and the like. An oxide containing manganese, an oxide containing iron and chromium, an azine dye containing nigrosine, and a polycyclic condensed dye containing anthraquinone can be used. As an azine dye containing nigrosine, for example, a mixture of oil-soluble azine dyes containing nigrosine can be used. Moreover, as a polycyclic condensed dye containing anthraquinone, for example, a mixture of polycyclic condensed dyes containing anthraquinone can be used.
Among these black colorants, oxides containing copper, chromium and manganese, oxides containing iron and manganese, oxides containing iron and chromium, azine dyes containing nigrosine and anthraquinones A polycyclic condensed dye is preferable, and an azine dye containing nigrosine and a polycyclic condensed dye containing anthraquinone are particularly preferable. Moreover, the black colorant whose L value other than carbon black is 30 or less may use only 1 type, and may use 2 or more types together.

  In addition to the above, examples of the black colorant having an L value other than carbon black of 30 or less that can be used in the present invention include those described in JP-A-10-324807. It is incorporated herein.

  The average particle size of the black colorant having an L value other than carbon black used in the present invention of 30 or less is preferably 0.01 to 50 μm, and more preferably 0.1 to 10 μm.

  In the thermoplastic resin composition of the present invention, the blending amount of the black colorant having an L value other than carbon black of 30 or less is usually 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermoplastic resin, Preferably it is 0.05-10 weight part, More preferably, it is 0.1-5 weight part. By making the blending amount of the black colorant having an L value other than carbon black 30 or less 15 parts by weight or less, the compound can be made easier and a better surface appearance can be formed. it can.

<Inorganic fiber>
The thermoplastic resin composition of the present invention may further contain inorganic fibers. By blending inorganic fibers, the mechanical strength can be further improved. Moreover, dimensional accuracy can be improved more by mix | blending inorganic fiber. 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 fiber in the thermoplastic resin composition after kneading the thermoplastic 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 thermoplastic resin composition of the present invention, the amount of the inorganic fiber is usually 10 to 200 parts by weight, preferably 20 to 180 parts by weight, more preferably 30 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. 150 parts by weight. Moreover, in the thermoplastic resin composition of this invention, it is preferable that a thermoplastic resin and an inorganic fiber occupy 80 weight% or more of all the components.

<Talc>
The thermoplastic resin composition of the present invention may further contain talc. By blending talc, dimensional stability and product appearance can be improved, and even if the amount of LDS additive is reduced, the plating characteristics of resin molded products can be improved, and resin molding Appropriate plating can be formed on the product. As the talc, one having a surface treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes may be used. 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 thermoplastic resin composition of the present invention is preferably 0.1 to 50 parts by weight and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition. Preferably, it is 5 to 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.

<Alkali>
The thermoplastic resin composition of the present invention may further contain an alkali. When the LDS additive used in the present invention is an acidic substance (for example, pH 6 or lower), the color may become a mottled pattern due to reduction by the combination itself, but the resin molding obtained by adding alkali The color of the product can be made more uniform.

The type of alkali is not particularly limited, and for example, calcium hydroxide (Ca (OH) ₂ ) or magnesium hydroxide (Mg (OH) ₂ ) can be used. Only one type of alkali may be used, or two or more types may be used in combination.

  In the thermoplastic resin composition of the present invention, the blending amount of alkali depends on the type of LDS additive and the type of alkali, but is preferably 0.01 to 15% by weight of the blending amount of LDS additive, and more. Preferably, it is 1 to 10% by weight of the amount of the LDS additive.

<Release agent>
The thermoplastic 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 200 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 thermoplastic resin and the inorganic fibers. The amount is preferably 1.5 parts by weight or less. By setting the content of the release agent to 0.001 part by weight or more with respect to 100 parts by weight of the total of the thermoplastic resin and the inorganic fiber, the release property can be improved. In addition, by reducing the content of the release agent to 2 parts by weight or less with respect to a total of 100 parts by weight of the thermoplastic resin and the inorganic fibers, it is possible to prevent a decrease in hydrolysis resistance, Mold contamination during injection molding can be prevented.

<Other additives>
The thermoplastic resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include titanium oxide, heat stabilizer, flame retardant, light stabilizer, antioxidant, ultraviolet absorber, dye / pigment, fluorescent whitening agent, anti-dripping agent, antistatic agent, antifogging agent, A lubricant, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, an antibacterial agent, and the like can be given. These components may use only 1 type and may use 2 or more types together.

<Method for producing thermoplastic resin composition>
Any method can be adopted as a method for producing the thermoplastic resin composition of the present invention. For example, a method of mixing a thermoplastic resin, an LDS additive, and an inorganic fiber using a mixing means such as a V-type blender, adjusting a batch blend, and then melt-kneading with a vented extruder to pelletize Is 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 thermoplastic 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 obtained by molding the thermoplastic 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>
T-1-20L: Tin-antimony oxide (SnO ₂ : 80%, Sb ₂ O ₅ : 20%, antimony content: 15.1% by weight), water content 1.5%, pH = 3.4) (Mitsubishi Materials Corporation)

<Black colorant>
42-302A: Oxide containing copper, chromium and manganese (manufactured by Toago Material Technology Co., Ltd.)
42-303B: Oxide containing copper, chromium and manganese (manufactured by Toago Material Technology Co., Ltd.)
42-313A: Oxide containing iron and manganese (manufactured by Toago Material Technology Co., Ltd.)
42-707A: Oxide containing iron and chromium (manufactured by Toago Material Technology Co., Ltd.)
NUBIAN BLACK PC-5857: Mixture of polycyclic condensation dyes containing anthraquinone (black colorant), (produced by Orient Chemical Co., Ltd.)
NUBIAN BLACK TH-807: Mixture of oil-soluble azine-based dyes containing nigrosine (black colorant) (manufactured by Orient Chemical Co., Ltd.)
Vulcan XC72 (Vulcan XC72): Masterbatch containing 30% by weight of carbon black (manufactured by Cabot)
# 960B: Carbon black (Mitsubishi Chemical Corporation)
The results of measuring the L value of each black colorant are shown in Table 1. The L value of the black colorant is obtained by placing the black colorant on a glass petri dish, covering with a dark box (dark box), and using a color difference meter (Spectro Color Meter SE2000) apparatus (manufactured by Nippon Denshoku Industries Co., Ltd.). It was measured.

<Inorganic fiber>
JA-FT807A: Glass fiber (Owens Corning)

<Talc>
Talc: Micron White 5000S (Made by Hayashi Kasei)

<Alkali>
Ca (OH) ₂

<Release agent>
CS8CP (Nitto Kasei Kogyo)

<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 specimen (4 mm thickness) obtained by the above-described method, the Charpy impact strength with a notch was measured under the condition of 23 ° C. based on ISO 179-1 or ISO 179-2. The results are shown in Table 1 below.

<Plating characteristics>
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.
In the range of 10 × 10 mm of the obtained plate specimen, a VMf1 laser irradiation device (maximum output of YAG laser with a wavelength of 1064 nm: 15 W) manufactured by Trump is used, the output (Power) is 6 W or 8 W, and the frequency (Frequency) is 60 kHz or Irradiation was performed at 80 kHz and a speed of 4 m / s. 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.
The plating characteristics were evaluated as follows for the laser condition width and the plating appearance. The results are shown in Table 1 below.
<Laser condition width>
○: Plating is good on any condition △: Plating is thin on some conditions (practical level)
×: Plating does not ride under more than half of conditions <Platting appearance>
Of the above four conditions (with respect to the output and frequency of the laser irradiation condition, the output is 6 W and the frequency is 60 kHz, the output is 6 W and the frequency is 80 kHz, the output is 8 W and the frequency is 60 kHz, and the output is 8 W and the frequency is 80 kHz). evaluated.
○: 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

<L value of molded product>
Using a color difference meter (Spectro Color Meter SE2000) apparatus (manufactured by Nippon Denshoku Industries Co., Ltd.), the L value (lightness) of a test piece having a thickness of 60 mm and a thickness of 2 mm was measured. The results are shown in Table 1 below.

  As is apparent from the results in Table 1, in the thermoplastic resin compositions of Examples 1 to 6, the LDS additive is 1 to 30 parts by weight and other than carbon black with respect to 100 parts by weight of the thermoplastic resin and the thermoplastic resin. Therefore, the plating layer can be appropriately formed on the surface of the resin molded product under a wide range of laser irradiation conditions. Therefore, it has been found that the productivity when forming a plating layer on the surface of a resin molded product obtained by molding the thermoplastic resin composition obtained in the present invention can be improved.

  Moreover, in Examples 1-6, it turned out that the L value of a molded article is 20 or less, and can provide the thermoplastic resin composition which can form a black resin molded article.

  On the other hand, since the thermoplastic resin composition obtained in Comparative Example 1 contains carbon black as a black colorant, a plating layer could not be appropriately formed on the surface of the resin molded product. Moreover, compared with Examples 1-6, the restriction | limiting of the irradiation conditions which can form plating appropriately is large, and the plating layer was not able to be appropriately formed on the surface of the resin molded product under a wide irradiation condition.

  Moreover, since the thermoplastic resin composition obtained in Comparative Example 2 does not contain a black colorant, compared with Examples 1 to 6, there is a large limitation on irradiation conditions that allow plating to be appropriately formed, and a wide range. A plating layer could not be properly formed on the surface of the resin molded product under irradiation conditions.

  Moreover, since the thermoplastic resin composition obtained in Comparative Example 3 contains carbon black as a black colorant, a plating layer is appropriately formed on the surface of the resin molded product as compared with Examples 1 to 6. Could not be formed.

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

Claims (15)

Thermoplastic, including 1 to 30 parts by weight of a laser direct structuring additive and a black colorant having an L value other than carbon black of 30 or less with respect to 100 parts by weight of the thermoplastic resin Resin composition. The thermoplastic 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 thermoplastic resin. The thermoplastic resin composition according to claim 2, wherein the inorganic fiber is a glass fiber. The black colorant includes an oxide containing copper, chromium and manganese, an oxide containing iron and manganese, an oxide containing iron and chromium, an azine dye containing nigrosine and a polycyclic condensation containing anthraquinone. The thermoplastic resin composition according to any one of claims 1 to 3, comprising at least one selected from dyes. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the laser direct structuring additive is an oxide containing antimony and tin. The thermoplastic resin composition according to claim 5, wherein the laser direct structuring additive has a higher content of tin than antimony. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the thermoplastic resin is a polyamide resin. The thermoplastic resin composition according to any one of claims 1 to 7, wherein an L value of the black colorant is 20 or less. The resin molded product formed by shape | molding the thermoplastic resin composition of any one of Claims 1-8. Furthermore, the resin molded product of Claim 9 which has a plating layer on the surface. The resin molded product according to claim 9 or 10, which is a portable electronic device component. The resin molded product according to claim 10 or 11, wherein the plated layer retains performance as an antenna. Including applying a metal to the surface of a resin molded article formed by molding the thermoplastic resin composition according to any one of claims 1 to 8, and then forming a plating layer. Manufacturing method of resin molded product with plating layer. The manufacturing method of the resin molded product with a plating layer of Claim 13 whose said plating is copper plating. The manufacturing method of the portable electronic device component which has an antenna including the manufacturing method of the resin molded product with a plating layer of Claim 13 or 14.

Images