JP2017206590A - Thermoplastic resin composition, resin molding, method for producing plated resin molding, and method for producing portable electronic device component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that can provide a resin molding having excellent mechanical strength and also excellent plating properties even after wet heat treatment, and a resin molding using the thermoplastic resin composition, a method for producing a plated resin molding, and a method for producing a portable electronic device component.SOLUTION: A thermoplastic resin composition contains thermoplastic resin 100 pts.mass, and a laser direct structuring additive of 1-30 pts.mass, a glass fiber, and glass beads. The mass ratio of the glass beads to the glass fiber (glass beads/glass fiber) is 0.5-5.0.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition, a resin molded product, a method for producing a plated resin molded product, and a method for producing a portable electronic device component.

  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. The LDS technique is, for example, a technique for forming a plating layer by irradiating a surface of a resin molded article containing an LDS additive by irradiating a laser and applying a metal to the activated part. A feature of this technique is that a metal structure such as an antenna can be manufactured directly on the surface of a resin molded product without using an adhesive or the like. Such LDS technology is disclosed in Patent Documents 1 to 4, for example.

Special table 2000-503817 Special table 2004-534408 gazette International Publication WO2009 / 141800 Pamphlet International Publication WO2012 / 128219 Pamphlet

However, as a result of studies by the inventor, it has been found that the plating property may be inferior when an attempt is made to form a plating after wet-heat treatment of a resin molded product. In particular, in order to improve mechanical strength, it has been found that the tendency is remarkable in a resin molded product containing glass fiber.
The present invention aims to solve such problems, and is a thermoplastic resin composition that is capable of providing a resin molded article having excellent mechanical strength and excellent plating properties even after wet heat treatment, and Another object of the present invention is to provide a resin molded product, a method for producing a resin-molded product with plating, and a method for producing a portable electronic device part using the thermoplastic resin composition.

Under such a problem, the present inventor has examined, in addition to glass fiber, by blending glass beads and maintaining the mechanical strength by making the mass ratio of glass fiber and glass beads a predetermined ratio. On the other hand, it has been found that it is possible to provide a resin molded product having excellent plating properties even after wet heat treatment. Specifically, the above problem has been solved by the following <1>, preferably by <2> to <16>.
<1> thermoplastic resin and 1 to 30 parts by mass of a laser direct structuring additive, glass fiber, and glass beads with respect to 100 parts by mass of the thermoplastic resin,
A thermoplastic resin composition having a glass bead / glass fiber mass ratio of 0.5 to 5.0, which is a mass ratio of glass beads to glass fibers.
<2> The thermoplastic resin composition according to <1>, wherein the total amount of glass fibers and glass beads occupies 10 to 50% by mass of the thermoplastic resin composition.
<3> The thermoplastic resin composition according to <1> or <2>, wherein the glass fiber has a circular cross section and a number average fiber diameter of 4.0 to 15.0 μm.
<4> The thermoplastic resin composition according to <1> or <2>, wherein the glass fiber has a circular cross section and a number average fiber diameter of 4.0 to 9.0 μm.
<5> The thermoplastic resin composition according to any one of <1> to <4>, wherein the thermoplastic resin is a polyamide resin.
<6> The thermoplastic resin is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, and 70 mol% or more of the structural unit derived from the diamine is derived from at least one of metaxylylenediamine and paraxylylenediamine. Any one of <1> to <4>, wherein 70 mol% or more of the structural unit derived from dicarboxylic acid is a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. The thermoplastic resin composition as described in one.
<7> The thermoplastic resin composition according to any one of <1> to <6>, wherein the number average particle diameter of the glass beads is 2 to 100 μm.
<8> The thermoplastic resin composition according to any one of <1> to <7>, further including 0.1 to 200 parts by mass of talc with respect to 100 parts by mass of the laser direct structuring additive.
<9> The thermoplastic resin composition according to any one of <1> to <8>, wherein the laser direct structuring additive is a compound containing copper and chromium.
<10> A resin molded product formed by molding the thermoplastic resin composition according to any one of <1> to <9>.
<11> The resin molded product according to <10>, wherein a surface of the resin molded product is plated.
<12> The resin molded product according to <11>, wherein the plating has performance as an antenna.
<13> The resin molded product according to any one of <10> to <12>, which is a portable electronic device part.
<14> A metal is applied to the surface of a resin molded product obtained by molding the thermoplastic resin composition according to any one of <1> to <9>, and then a metal is applied to form a plating. The manufacturing method of the resin molded product with plating including this.
<15> The method for producing a plated resin molded product according to <14>, wherein the plating is copper plating.
<16> A method for manufacturing a portable electronic device part having an antenna, including the method for manufacturing a plated resin molded product according to <14> or <15>.

  INDUSTRIAL APPLICABILITY According to the present invention, a thermoplastic resin composition that can provide a resin molded article having excellent mechanical strength and excellent plating properties even after wet heat treatment, and a resin molded article using the thermoplastic resin composition, plating It has become possible to provide a method for manufacturing a resin-molded article and a method for manufacturing a portable electronic device part.

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.

The thermoplastic resin composition of the present invention includes a thermoplastic resin, 1 to 30 parts by mass of a laser direct structuring additive, glass fibers, and glass beads with respect to 100 parts by mass of the thermoplastic resin. Glass beads / glass fiber, which is a mass ratio of beads and glass fiber, is 0.5 to 5.0. By adopting such a configuration, it is possible to maintain a high plating property even after the wet heat treatment while maintaining a high mechanical strength.
This mechanism is assumed to be as follows.
That is, in order to improve the plating property, it is desirable that the resin amount of the surface layer for forming the plating layer is large in the resin molded product. However, when glass fiber is blended, the amount of resin on the surface layer of the resin molded product is reduced. Here, in this invention, this point is solved by mix | blending glass beads in addition to glass fiber. That is, by blending glass beads, even if the amount of glass fiber is reduced, the amount of resin on the surface layer of the resin molded product can be relatively increased while maintaining high mechanical strength to some extent. And in this invention, by adjusting the mass ratio (glass bead / glass fiber) of glass fiber and glass bead to 0.5-5.0, plating property by the increase in the quantity of resin of the surface layer of a resin molded product We have succeeded in improving and balancing the high mechanical strength.
Details of the present invention will be described below.

<Thermoplastic resin>
The thermoplastic resin used in the present invention is preferably selected from polyamide resin, polyester resin, polyolefin resin, polypropylene resin, polyethylene resin, polycarbonate resin and acrylic resin. Among these, a polyamide resin, a polyester resin, and a polycarbonate resin are more preferable, and a polyamide resin is more preferable. These may be used alone or in combination of two or more.

  As the polyester resin, description in paragraphs 0013 to 0016 of JP 2010-174223 A can be referred to.

As the polyamide resin, the description in paragraphs 0011 to 0013 of JP2011-132550A can be referred to.
The polyamide resin used in the present invention is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from at least one of metaxylylenediamine and paraxylylenediamine. In addition, a polyamide resin in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (hereinafter referred to as “xylylenediamine-based polyamide resin”) Is preferred).
The structural unit derived from the diamine of the xylylenediamine-based polyamide resin is more preferably 80 mol% or more, further preferably 85 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. Derived from at least one of amines and paraxylylenediamine. The structural unit derived from dicarboxylic acid of the xylylenediamine-based polyamide resin is more preferably 80 mol% or more, further preferably 85 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. It is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 atoms.

  Examples of diamines other than metaxylylenediamine and paraxylylenediamine that can be used as raw material diamine components for xylylenediamine polyamide resins include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, and heptamethylene. Aliphatic diamines such as diamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3- Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) meta 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, alicyclic diamines such as bis (aminomethyl) tricyclodecane, bis (4-aminophenyl) ether, paraphenylenediamine, bis Examples include diamines having an aromatic ring such as (aminomethyl) naphthalene, and one or a mixture of two or more can be used.

  Preferred examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms to be used as the raw material dicarboxylic acid component of the xylylenediamine-based polyamide resin include succinic acid, glutaric acid, pimelic acid, suberic acid, and azelain. Examples thereof include aliphatic dicarboxylic acids such as acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid, and one or a mixture of two or more can be used. Among these, the melting point of the polyamide resin is molded. Therefore, adipic acid or sebacic acid is more preferable, and sebacic acid is more preferable.

  Examples of the dicarboxylic acid component other than the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3- Examples thereof include naphthalenedicarboxylic acids such as isomers such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and one kind or a mixture of two or more kinds can be used.

  In addition, the constitutional unit derived from a diamine and the constitutional unit derived from a dicarboxylic acid are used as main components, but other constitutional units are not completely excluded, and lactams such as ε-caprolactam and laurolactam, aminocaproic acid Needless to say, structural units derived from aliphatic aminocarboxylic acids such as aminoundecanoic acid may be included. Here, the main component means that among the constituent units constituting the xylylenediamine-based polyamide resin, the total number of constituent units derived from diamine and constituent units derived from dicarboxylic acid is the largest among all constituent units. In the present invention, the total of diamine-derived structural units and dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin preferably occupies 90% or more of all the structural units, and more preferably 95% or more. .

Moreover, it is preferable that a polyamide resin contains 0.5-5 mass% of components with a weight average molecular weight of 1,000 or less. By containing 0.5% by mass or more of a component having a weight average molecular weight of 1,000 or less, the strength of the obtained resin molded product can be further increased and warpage can be further decreased. Further, when the component having a weight average molecular weight of 1,000 or less is adjusted to 5% by mass or less, the low molecular weight component is less likely to bleed, and the surface appearance of the resin molded product tends to be improved.
The preferred content of the component having a weight average molecular weight of 1,000 or less is 0.6 to 4.5% by mass, more preferably 0.7 to 4.0% by mass, and still more preferably 0.8 to It is 3.5 mass%, More preferably, it is 0.9-3.0 mass%, More preferably, it is 1.0-2.5 mass%.

  The content of the low molecular weight component having a weight average molecular weight of 1,000 or less can be adjusted by adjusting the melt polymerization conditions such as the temperature and pressure at the time of polyamide resin polymerization and the dropping rate of diamine. In particular, the inside of the reaction apparatus can be depressurized at the latter stage of the melt polymerization to remove low molecular weight components and adjusted to an arbitrary ratio. Further, the polyamide resin produced by melt polymerization may be subjected to hot water extraction to remove low molecular weight components, or after melt polymerization, the low molecular weight components may be removed by solid phase polymerization under reduced pressure. In the solid phase polymerization, the low molecular weight component can be controlled to an arbitrary content by adjusting the temperature and the degree of vacuum. It can also be adjusted by adding a low molecular weight component having a molecular weight of 1,000 or less to the polyamide resin later.

  In addition, the measurement of the amount of components having a weight average molecular weight of 1,000 or less is based on a standard polymethyl methacrylate (PMMA) conversion value according to gel permeation chromatography (GPC) measurement using “HLC-8320GPC” manufactured by Tosoh Corporation. Can be sought. In addition, two “TSKgel SuperHM-H” are used as the measurement column, hexafluoroisopropanol (HFIP) having a sodium trifluoroacetate concentration of 10 mmol / L is used as the solvent, the resin concentration is 0.02% by mass, and the column temperature is It can be measured with a refractive index detector (RI) at 40 ° C., a flow rate of 0.3 mL / min. A calibration curve is prepared by dissolving 6 levels of PMMA in HFIP.

  As the polycarbonate resin, the description in paragraphs 0011 to 0018 of JP-A-2014-074162 can be referred to. Further, when a polycarbonate resin is used as the thermoplastic resin, a styrene resin may be blended, and the description of paragraphs 0019 to 0027 of JP-A No. 2014-074162 can be referred to as the styrene resin. When blending a polycarbonate resin and a styrene resin, among the thermoplastic resins contained in the thermoplastic resin composition of the present invention, the polycarbonate resin is 30 to 80% by mass and the styrene resin is 70 to 20% by mass. It is preferable that the polycarbonate resin is 55 to 70% by mass and the styrene resin is 30 to 45% by mass.

The lower limit of the content of the thermoplastic resin in the thermoplastic resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and 45% by mass or more. Further preferred. The upper limit of the content is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 55% by mass or less. .
The thermoplastic resin may contain only 1 type and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.

<Laser direct structuring additive (LDS additive)>
The thermoplastic resin composition of the present invention includes a laser direct structuring (LDS) additive. The LDS additive in the present invention is 10 parts by mass of an additive considered to be an LDS additive with respect to 100 parts by mass of a thermoplastic resin (for example, a polyamide resin synthesized in Examples described later), and has a wavelength of 1064 nm. Using a YAG laser, irradiation is performed at an output of 13 W, a frequency of 20 kHz, and a scanning speed of 2 m / s, and the subsequent plating process is performed at 60 ° C. in an electroless copper plating tank, and plating can be formed on the laser irradiation surface. Refers to a compound. 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 first embodiment of the LDS additive used in the present invention is a compound containing copper and chromium. The LDS additive of the first embodiment preferably contains 10 to 30% by mass of copper. Moreover, it is preferable that 15-50 mass% of chromium is included. The LDS additive in the first embodiment is preferably an oxide containing copper and chromium.

As the copper and chromium content, a spinel structure is preferable. The spinel structure is one of the typical crystal structure types found in double oxide AB ₂ O ₄ type compounds (A and B are metal elements).

The LDS additive of the first embodiment may contain a trace amount of other metals in addition to copper and chromium. Examples of other metals include antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium and calcium, and manganese is preferable. These metals may exist as oxides.
A preferred example of the LDS additive of the first embodiment is an LDS additive in which the content of metal oxides other than copper chromium oxide is 10% by mass or less.

  The second embodiment of the LDS additive used in the present invention is an oxide containing at least one of antimony and phosphorus and tin, preferably an oxide containing antimony and tin.

  The LDS additive of the second embodiment preferably has a tin content higher than that of phosphorus and antimony, and the amount of tin with respect to the total amount of tin, phosphorus and antimony is 80% by mass or more. More preferably.

  In particular, the LDS additive of the second embodiment is preferably an oxide containing antimony and tin, more preferably an oxide having a tin content higher than the content of antimony, relative to the total amount of tin and antimony. An oxide in which the amount of tin is 80% by mass or more is more preferable.

  More specifically, as the LDS additive of the second embodiment, tin oxide doped with antimony, tin oxide doped with antimony oxide, tin oxide doped with phosphorus, doped with phosphorous oxide Examples include tin oxide, tin oxide doped with antimony and tin oxide doped with antimony oxide are preferred, and tin oxide doped with antimony oxide is more preferred. For example, in the LDS additive containing phosphorus and tin oxide, the phosphorus content is 1 to 20% by mass. Moreover, in the LDS additive containing antimony and tin oxide, the content of antimony is preferably 1 to 20% by mass. Moreover, in the LDS additive containing phosphorus, antimony and tin oxide, the phosphorus content is preferably 0.5 to 10% by mass, and the antimony content is preferably 0.5 to 10% by mass.

The third embodiment of the LDS additive used in the present invention preferably contains a conductive oxide containing at least two kinds of metals and having a resistivity of 5 × 10 ³ Ω · cm or less. The resistivity of the conductive oxide is more preferably 8 × 10 ² Ω · cm or less, further preferably 7 × 10 ² Ω · cm or less, and further preferably 5 × 10 ² Ω · cm or less. Although there is no restriction | limiting in particular about a minimum, For example, 1 * 10 < ¹ > ohm * cm or more may be sufficient, Furthermore, 1 * 10 < ² > ohm * cm or more may be sufficient.
The resistivity of the conductive oxide in the present invention usually refers to the powder resistivity, and 10 g of the fine powder of the conductive oxide is charged into a cylinder having an inner diameter of 25 mm and subjected to Teflon (registered trademark) processing on the inner surface. pressurized to 100 kgf / cm ² Te (filling rate 20%) can be measured by Yokogawa Electric Corp. "3223 Model" tester.

The LDS additive used in the third embodiment is not particularly limited as long as it contains a conductive oxide having a resistivity of 5 × 10 ³ Ω · cm or less, but preferably contains at least two metals. Specifically, it preferably contains a metal of group n (n is an integer of 3 to 16) and a metal of group n + 1 of the periodic table. n is more preferably an integer of 10 to 13, and further preferably 12 or 13.
In the LDS additive, the LDS additive used in the third embodiment is 100 mol of the total content of the metal of group n (n is an integer of 3 to 16) and the metal content of group n + 1 in the periodic table. %, The content of one metal is preferably 15 mol% or less, more preferably 12 mol% or less, and even more preferably 10 mol% or less. Although there is no restriction | limiting in particular about a minimum, 0.0001 mol% or more is preferable. By setting the content of two or more kinds of metals in such a range, the plating property can be improved. In the present invention, an n group metal oxide doped with an n + 1 group metal is particularly preferable.
Further, in the LDS additive used in the third embodiment, 98% by mass or more of the metal component contained in the LDS additive is composed of the content of the group n metal and the group n + 1 of the periodic table. It is preferable.

  Examples of the metal of group n in the periodic table include group 3 (scandium, yttrium), group 4 (titanium, zirconium, etc.), group 5 (vanadium, niobium, etc.), group 6 (chromium, molybdenum, etc.), group 7 ( Manganese, etc.), group 8 (iron, ruthenium, etc.), group 9 (cobalt, rhodium, iridium, etc.), group 10 (nickel, palladium, platinum), group 11 (copper, silver, gold etc.), group 12 (zinc, Cadmium, etc.), group 13 (aluminum, gallium, indium, etc.), group 14 (germanium, tin, etc.), group 15 (arsenic, antimony, etc.), group 16 (selenium, tellurium, etc.). Among them, a Group 12 (n = 12) metal is preferable, and zinc is more preferable.

  Examples of the metal of group n + 1 of the periodic table include group 4 (titanium, zirconium, etc.), group 5 (vanadium, niobium, etc.), group 6 (chromium, molybdenum, etc.), group 7 (manganese, etc.), group 8 (iron). , Ruthenium, etc.), group 9 (cobalt, rhodium, iridium, etc.), group 10 (nickel, palladium, platinum), group 11 (copper, silver, gold, etc.), group 12 (zinc, cadmium, etc.), group 13 (aluminum) , Gallium, indium, etc.), 14 groups (germanium, tin, etc.), 15 groups (arsenic, antimony, etc.), 16 groups (selenium, tellurium, etc.). Among them, a Group 13 (n + 1 = 13) metal is preferable, aluminum or gallium is more preferable, and aluminum is more preferable.

  The LDS additive used in the third embodiment may contain a metal other than the conductive metal oxide. Examples of the metal other than the conductive oxide include antimony, titanium, indium, iron, cobalt, nickel, cadmium, silver, bismuth, arsenic, manganese, chromium, magnesium, calcium, and the like. These metals may exist as oxides. The content of these metals is preferably 0.01% by mass or less with respect to the LDS additive.

  The average particle size of the LDS additive used in the present invention is preferably 0.01 to 100 μm, more preferably 0.05 to 30 μm, and further preferably 0.05 to 15 μm. By setting it as such an average particle diameter, the surface of a plating layer can be made more uniform.

  The particle diameter of the LDS additive is preferably 0.01 to 100 μm, and more preferably 0.05 to 10 μm. By setting it as such a structure, the surface of the plating layer at the time of applying plating can be made more uniform.

  The content of the LDS additive in the thermoplastic resin composition is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 5 to 100 parts by mass of the thermoplastic resin. 20 parts by mass. By setting the content of the LDS additive in such a range, it is possible to improve the plating property of the obtained resin molded product. Further, as described later, by combining with talc, it becomes possible to form a plating layer with a small content. When two or more LDS additives are included, the total amount is preferably within the above range.

<Glass fiber>
The thermoplastic resin composition of the present invention contains glass fibers. The glass fiber in the present invention means a glass fiber, more specifically, a chopped shape in which 1,000 to 10,000 glass fibers are converged and cut to a predetermined length. Is preferred.
The glass fiber in the present invention preferably has a number average fiber length of 0.5 to 10 mm, more preferably 1 to 5 mm. By using glass fibers having such a number average fiber length, the mechanical strength can be further improved. The number average fiber length is obtained by randomly extracting the glass fiber to be measured for the image obtained by observation with an optical microscope, measuring the long side, and calculating the number average fiber length from the obtained measured value. calculate. The observation magnification is 20 times, and the number of measurement is 1,000 or more. Generally corresponds to the cut length.
The cross section of the glass fiber may be any shape such as a circle, an ellipse, an oval, a rectangle, a shape in which a semicircle is combined with both short sides of the rectangle, an eyebrow shape, etc., but a circle is preferable. The circular shape here includes not only a circular shape in a mathematical sense but also what is generally called a circular shape in the technical field of the present invention. By using a glass fiber having a circular cross section, the amount of resin on the surface layer of the resin molded product can be increased.
The lower limit of the number average fiber diameter of the glass fibers is preferably 4.0 μm or more, more preferably 4.5 μm or more, and further preferably 5.0 μm or more. The upper limit of the number average fiber diameter of the glass fibers is preferably 15.0 μm or less, more preferably 9.0 μm or less, and even more preferably 7.5 μm or less. By using glass fibers having a number average fiber diameter in such a range, a resin molded product having better plating properties can be obtained even after wet heat. Furthermore, high plating properties can be maintained even when the resin molded product is stored for a long period of time or is heat-treated for a long period of time. The number average fiber diameter of the glass fibers is obtained by randomly extracting the glass fibers to be measured for the image obtained by observation with an electron microscope and measuring the fiber diameters near the center. Calculated from the measured values. The observation magnification is 1,000 times, and the number of measurement is 1,000 or more. The number average fiber diameter of glass fibers having a cross section other than a circle is the number average fiber diameter when converted to a circle having the same area as the cross section.

  Glass fiber is obtained by melt-spinning glass such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), and alkali-resistant glass that are generally supplied. Although the fiber obtained is used, any composition can be used as long as it can be made into glass fiber, and it is not particularly limited. In this invention, it is preferable that E glass is included.

  The glass fiber used in the present invention is surface-treated with a surface treatment agent such as a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. It is preferable that It is preferable that the adhesion amount of a surface treating agent is 0.01-1 mass% of glass fiber. 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.

  Glass fiber is available as a commercial product. Examples of commercially available products include Nippon Electric Glass, T-286H, T-289H, Owens Corning, DEFT2A, PPG, HP3540, Nittobo, CSG3PA820, and the like.

The content of the glass fiber in the thermoplastic resin composition of the present invention is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and 25 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Or more. The upper limit of the content is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 48 parts by mass or less, and particularly preferably 45 parts by mass or less.
The thermoplastic resin composition of the present invention may contain only one kind of glass fiber, or may contain two or more kinds. When 2 or more types are included, the total amount is preferably within the above range.

<Glass beads>
The thermoplastic resin composition of the present invention contains glass beads. By blending glass beads, the overall anisotropy of the inorganic filler contained in the resin molded product can be reduced, linear expansion can be reduced, and dimensional stability can be achieved. In particular, the effect is remarkable as compared with scale-like inorganic fillers such as talc and flakes.
Glass beads refer to spherical glass. The term “spherical” as used herein refers to a resin that includes what is commonly referred to as a sphere in the technical field of the present invention in addition to a sphere in a mathematical sense. The glass beads used in the present invention are not particularly limited as long as they are spherical glass, but industrial glass beads are preferable among those classified as road glass beads, industrial glass beads, and reflective glass beads.
Industrial glass beads are classified into sandblasting, sandmilling, filtration, and filler, with fillers being preferred.

  On the other hand, the glass components used for the glass beads include commonly supplied E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), and alkali resistance. It is selected from glass such as glass, and E glass is preferred.

Moreover, the lower limit of the number average particle diameter of the glass beads is preferably 2 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, more preferably 20 μm or more, even more preferably 25 μm or more, and even more preferably 30 μm or more. preferable. The upper limit of the number average particle diameter of the glass beads is preferably 100 μm or less, more preferably 50 μm or less, further preferably 40 μm or less, and further preferably 35 μm or less.
The number average particle size of the glass beads is calculated from the measured values obtained by randomly extracting the glass beads to be measured for the image obtained by observation with an electron microscope and measuring the particle size. The observation magnification is 1,000 times, and the number of measurements is 1,000 or more.

  From the viewpoint of enhancing the dispersibility and adhesion of the glass beads in the polyamide resin, the glass beads are preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include silane compounds, chromium compounds, titanium compounds, and the like, and aminosilane compounds are preferable.

The content of the glass beads in the thermoplastic resin composition of the present invention is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and 35 parts by mass with respect to 100 parts by mass of the thermoplastic resin. More preferably, it is at least part. The upper limit of the content is preferably 80 parts by mass or less, more preferably 75 parts by mass or less, further preferably 70 parts by mass or less, and particularly preferably 65 parts by mass or less.
The thermoplastic resin composition of the present invention may contain only one type of glass bead, or may contain two or more types of glass beads. When 2 or more types are included, the total amount is preferably within the above range.

<Mass ratio of glass beads to glass fibers (glass beads / glass fibers)>
The thermoplastic resin composition of the present invention has a glass bead / glass fiber ratio of 0.5 to 5.0, which is a mass ratio of glass beads to glass fibers. By setting it as such mass ratio, the plating strength fall by wet heat conditions can be suppressed, reducing the anisotropy of a molded article dimension. The lower limit of the mass ratio is 0.5 or more, preferably 0.7 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and still more preferably 0.95 or more. The upper limit of the mass ratio is 5.0 or less, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.5 or less, and still more preferably 3.2 or less.

  In the thermoplastic resin composition of the present invention, the total amount of glass fibers and glass beads preferably occupies 10 to 50% by mass of the thermoplastic resin composition. The lower limit of the total amount is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 35% by mass or more. The upper limit of the total amount is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 43% by mass or less.

  Furthermore, the thermoplastic resin composition of the present invention may contain a filler mainly composed of glass other than glass fibers and glass beads, and a filler mainly composed of glass other than glass fibers and glass beads. It can be set as the structure which does not contain substantially. The term “substantially free” means that in the thermoplastic resin composition, the filler mainly composed of glass other than glass fibers and glass beads is 1% by mass or less of the total amount of glass fibers and glass beads. The phrase “mainly composed of glass” means that the component having the largest filler content is glass, and 80% by mass or more is preferably glass.

<Talc>
The thermoplastic resin composition of the present invention may further contain talc. By blending talc, the dimensional stability and product appearance can be improved, and the plating property of the resin molded product can be improved even if the content of the LDS additive is reduced. As the talc, one having a surface treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes may be used. In this case, it is preferable that the adhesion amount of the siloxane compound in talc is 0.1 to 5% by mass of talc.
The number average particle diameter of talc is preferably 1 to 50 μm, and more preferably 2 to 25 μm. Talc is usually scaly, but the length of the longest part is the average diameter. The number average particle size of talc is calculated from the measured values obtained by randomly extracting talc to be measured for particle size from an image obtained by observation with an electron microscope and measuring the particle size. The observation magnification is 1,000 times, and the number of measurements is 1,000 or more.

The content of talc in the thermoplastic resin composition of the present invention is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass with respect to 100 parts by mass of the thermoplastic resin when blended. More preferably, it is 5-20 mass parts.
When blended, the content of talc in the thermoplastic resin composition of the present invention is preferably 0.1 to 200 parts by mass, and 1 to 150 parts by mass with respect to 100 parts by mass of the LDS additive. Is more preferable, and it is further more preferable that it is 20-120 mass parts. When talc is surface-treated with a siloxane compound, the content of talc surface-treated with a siloxane compound is preferably within the above range.

  The thermoplastic resin composition of the present invention can also be configured to be substantially free of inorganic fillers other than the glass fibers, glass beads and talc. “Substantially free” means that the content of the inorganic filler other than glass fiber, glass bead and talc in the thermoplastic resin composition is 10% by mass or less of the total amount of glass fiber, glass bead and talc. Say. In the present invention, in the thermoplastic resin composition, the content of the inorganic filler other than glass fiber, glass bead and talc is preferably 5% by mass or less of the total amount of glass fiber, glass bead and talc, and more Preferably it is 1 mass% or less. Thus, by reducing the amount of scale-like inorganic filler and the like, it is possible to more effectively suppress the decrease in the resin amount of the surface layer of the resin molded product.

<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 thermoplastic 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.

  As the higher aliphatic monocarboxylic acid, a saturated aliphatic monocarboxylic acid having 16 or more carbon atoms and a hydroxycarboxylic acid are preferable, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, 12-hydroxystearic acid and the like. It is done.

  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, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic or alicyclic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are 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.

  When blended, the content of the release agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and the upper limit with respect to the thermoplastic resin composition. Is preferably 2% by mass or less, more preferably 1.5% by mass or less. By setting it as such a range, mold release property can be made favorable and the mold contamination at the time of injection molding can be prevented. A mold release agent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types, it is preferable that a total amount becomes the said range.

<Heat stabilizer>
The thermoplastic resin composition of the present invention may further contain an organic and / or inorganic heat stabilizer.
It is preferable that the heat stabilizer used in the present invention does not substantially contain copper. “Substantially” means below the detection limit. Thus, discoloration can be suppressed by reducing the copper content.
The organic heat stabilizer is preferably at least one selected from the group consisting of phenolic compounds, phosphite compounds, hindered amine compounds, triazine compounds, and sulfur compounds.
As a heat stabilizer, only 1 type may be used and it may be used in combination of 2 or more type.

  When it contains, it is preferable that content of a heat stabilizer is 0.01-5 mass parts with respect to 100 mass parts of the thermoplastic resin composition of this invention, and is 0.03-4 mass parts. More preferably. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

<Light stabilizer>
The thermoplastic resin composition of the present invention may contain an organic and / or inorganic light stabilizer.
Examples of the organic light stabilizer include ultraviolet light absorbing compounds such as benzophenone compounds, salicylate compounds, benzotriazole compounds, and cyanoacrylate compounds, and radicals such as hindered amine compounds and hindered phenol compounds. Examples thereof include compounds having a capturing ability.
As a light stabilizer, a higher stabilizing effect can be exhibited by using a compound having an ultraviolet absorption effect and a compound having a radical scavenging ability in combination.
As a light stabilizer, only 1 type may be used and it may be used in combination of 2 or more type.

  The content of the light stabilizer is preferably 0.01 parts by mass to 5 parts by mass and more preferably 0.01-4 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention. preferable.

<Alkali>
The thermoplastic resin composition of the present invention may contain an alkali. When the LDS additive used in the present invention is an acidic substance (for example, pH 6 or less), there is a case where the color becomes a mottled pattern by reducing itself by the combination, but the resin molding obtained by adding an alkali The color of the product can be made more uniform. The kind of alkali is not particularly defined, and calcium hydroxide, magnesium hydroxide and the like can be used. Only 1 type may be used for an alkali and it may use 2 or more types together.
The content of alkali in the thermoplastic resin composition of the present invention depends on the type of LDS additive and the type of alkali, but is preferably 0.01 to 20% by mass of the content of LDS additive, More preferably, it is 0.05-15 mass%.

<Other additives>
In addition to the above, the thermoplastic resin composition of the present invention may contain other components. Other components include elastomers, titanium oxide, antioxidants, hydrolysis resistance improvers, matting agents, UV absorbers, nucleating agents, plasticizers, dispersants, flame retardants, flame retardant aids, antistatic agents Examples thereof include coloring inhibitors, anti-gelling agents, and coloring agents. Details of these can be referred to the description of paragraphs 0130 to 0155 of Japanese Patent No. 4894982, the contents of which are incorporated herein. These components are preferably a total of 20% by mass or less of the thermoplastic resin composition. These components may use only 1 type and may use 2 or more types together.

<Method for producing resin composition>
Arbitrary methods are employ | adopted as a manufacturing method of the thermoplastic resin composition of this invention.
For example, thermoplastic resins, glass fibers, glass beads, LDS additives, etc. are mixed using a mixing means such as a V-type blender to prepare a batch blend product, and then melt-kneaded with an extruder equipped with a vent to be pelletized. A method is mentioned. Alternatively, as a two-stage kneading method, components such as glass fiber and glass beads are mixed in advance and then melt-kneaded with an extruder with a vent to produce pellets, and then the pellets, glass fibers, and glass beads And then kneading and kneading with a vented extruder.
Further, a material in which components other than glass fiber and glass beads are sufficiently mixed with a V-type blender or the like is prepared in advance, and is supplied from the first chute of a vented twin screw extruder. Can be supplied from a second chute in the middle of the extruder and melt kneaded and pelletized.

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 in consideration of shear heat generation. In order to suppress decomposition at the time of kneading or molding in a subsequent process, it is desirable to use an antioxidant or a heat stabilizer.

<Resin molded product>
The present invention also discloses a resin molded product obtained by molding the thermoplastic resin composition of the present invention.
The manufacturing method of the resin molded product is not particularly limited, and a molding method generally adopted for the 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.

  The resin molded product formed by molding the thermoplastic resin composition of the present invention is preferably used as a plated resin molded product having plating on the surface of the resin molded product. The plating in the resin molded product of the present invention preferably has an antenna performance.

<Manufacturing method of resin molded product with plating>
Next, a method for producing a resin-molded article with plating, which comprises forming a plating by applying a metal to the surface of a resin-molded article formed by molding the thermoplastic resin composition of the present invention after laser irradiation It discloses about.
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 having a partially or entirely curved surface. Moreover, the resin molded product with plating obtained is not limited to the final product, and includes various parts.

Returning again to FIG. 1, the resin molded product 1 is irradiated with a laser 2. The laser here is not particularly defined, and can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and electromagnetic radiation, and a YGA laser is preferable. Further, the wavelength of the laser is not particularly defined. A preferable wavelength range is 200 nm to 1200 nm, and more preferably 800 to 1200 nm.
When the laser is irradiated, the resin molded product 1 is activated only in the portion 3 irradiated with the laser. In this activated state, the resin molded product 1 is applied to the plating solution 4. The plating solution 4 is not particularly defined, and a known plating solution can be widely used. As the metal component, a plating solution comprising at least one of copper, nickel, silver, gold, and palladium (in particular, Electroless plating solution) is preferred, plating solution comprising at least one of copper, nickel, silver, and gold (especially electroless plating solution) is more preferred, and plating solution containing copper (especially electroless plating solution). Plating solution) is more preferable. That is, in the plating according to the present invention, the metal component is preferably made of at least one of the above metals.
The method of applying the resin molded product 1 to the plating solution 4 is not particularly defined, but for example, a method of introducing the resin molded product 1 into a solution containing the plating solution. In the resin molded product after applying the plating solution, the plating 5 is formed only on the portion irradiated with the laser.
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. In order to suppress corrosion and deterioration of the formed circuit, the plating can be further protected with nickel or gold after performing electroless plating, for example. Similarly, the required film thickness can be formed in a short time by using electroplating after electroless plating.
The method for producing a plated resin molded product is preferably used as a method for producing a portable electronic device part having an antenna, including the method for producing the plated resin molded product.

  Molded articles obtained from the thermoplastic resin composition of the present invention include, for example, electronic parts such as connectors, switches, relays and conductive circuits (particularly portable electronic equipment parts), reflectors such as lamp reflectors, gears and cams. Such sliding parts, automobile parts such as air intake manifolds, water-circulating parts such as sinks, various decorative parts, or various applications such as films, sheets, and fibers can be used.

  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.

Raw materials The raw materials shown below were used.
<Synthesis of polyamide resin PXD10>
8950 g of sebacic acid (manufactured by Ito Oil Co., Ltd., Sebacic acid TA) precisely weighed in a reaction vessel with an internal volume of 50 liters equipped with a stirrer, a partial condenser, a cooler, a thermometer, a dropping device and a nitrogen introduction tube, and a strand die (44.25 mol), calcium hypophosphite 12.54 g (0.074 mol), and sodium acetate 6.45 g (0.079 mol) were weighed and charged. After sufficiently purging the inside of the reaction vessel with nitrogen, the pressure was increased to 0.4 MPa with nitrogen, the temperature was raised from 20 ° C. to 190 ° C. with stirring, and sebacic acid was uniformly melted in 55 minutes. Next, 5960 g (43.76 mol) of paraxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) was added dropwise over 110 minutes with stirring. During this time, the internal temperature of the reaction vessel was continuously increased to 293 ° C. In the dropping step, the pressure was controlled to 0.42 MPa, and the generated water was removed from the system through a partial condenser and a cooler. The temperature of the partial condenser was controlled in the range of 145 to 147 ° C. After completion of dropwise addition of paraxylylenediamine, the polycondensation reaction was continued for 20 minutes at a reaction vessel internal pressure of 0.42 MPa. During this time, the temperature inside the reaction vessel was raised to 296 ° C. Thereafter, the internal pressure of the reaction vessel was reduced from 0.42 MPa to 0.12 MPa over 30 minutes. During this time, the internal temperature rose to 298 ° C. Thereafter, the pressure was reduced at a rate of 0.002 MPa / minute, the pressure was reduced to 0.08 MPa over 20 minutes, and the amount of the component having a molecular weight of 1,000 or less was adjusted. The temperature in the reaction vessel at the time of completion of decompression was 301 ° C. Thereafter, the inside of the system was pressurized with nitrogen, the temperature in the reaction vessel was 301 ° C., the resin temperature was 301 ° C., the polymer was taken out from the strand die into a strand shape, cooled with 20 ° C. cooling water, pelletized, and about 13 kg. A polyamide resin was obtained. The cooling time in cooling water was 5 seconds, and the strand take-up speed was 100 m / min. Hereinafter, it is referred to as “PXD10”. The melting point was 290 ° C.

<LDS additive>
Black1G: Copper chromium oxide (CuCr ₂ O ₄ ) (manufactured by Shepherd Japan)
<Glass fiber>
ECS03T-296GH: Glass fiber having a circular cross section, number average fiber diameter 10 μm, number average fiber length 3 mm (manufactured by Nippon Electric Glass Co., Ltd.)
DEFT2A: Glass fiber having a circular cross section, number average fiber diameter 6 μm, number average fiber length 3 mm (manufactured by Owens Corning)
<Glass beads>
EGB731A: Glass beads treated with a surface treatment agent (aminosilane coupling agent), number average particle size 32 μm (manufactured by Potters Barotini)
<Talc>
5000S: Micron White 5000S, average diameter 4.7 μm (manufactured by Hayashi Kasei Co., Ltd.)
<Release agent>
CS8CP: Calcium montanate (Nitto Kasei Kogyo Co., Ltd.)

Example 1
<Compound>
Each component was weighed so as to have the composition shown in Table 1 below, and the components excluding glass fibers and glass beads were blended with a tumbler. From the root of a twin screw extruder (Toshiki Machine Co., Ltd., TEM26SS). After charging and melting, glass fibers and glass beads were side-fed to produce pellets. The temperature setting of the twin screw extruder was 300 ° C.

<Plating property (initial) (LDS activity)-Placing Index>
After drying the pellet obtained by the above-mentioned manufacturing method at 120 ° C. for 5 hours, using Nissei Plastic Industries, SG75-MII, conditions of a cylinder temperature of 300 ° C., a mold temperature of 130 ° C., and a molding cycle of 50 seconds And 3 mm thick plate was formed by injection molding.
A 1064 nm YAG laser was used for the 3 mm-thick plate obtained above, and the output was any of 2.6 to 13 W, the speed was 1 to 2 m / s, and the frequency was in the range of 10 to 50 μs. After printing with laser irradiation under various conditions combined from above, the test piece was degreased with sulfuric acid, treated with Kizai Co., Ltd., THP Alkali Acti and THP Alkali Axe, and then plated with Kizai SEL Copper went. The test pieces after the plating treatment were visually determined and classified into the following three stages.
A: Plating is formed on one side and a good appearance is confirmed B: Plating is partially formed but practical level C: Plating is not formed at all, or plating is partially formed Not level

<Plating property (after wet heat treatment) (LDS activity) -Plating Index>
After drying the pellet obtained by the above-mentioned manufacturing method at 120 ° C. for 5 hours, using Nissei Plastic Industries, SG75-MII, conditions of a cylinder temperature of 300 ° C., a mold temperature of 130 ° C., and a molding cycle of 50 seconds And 3 mm thick plate was formed by injection molding.
The obtained resin molded product was allowed to stand in an environment of 85% relative humidity and 85 ° C. for 1000 hours, and the plating property was evaluated in the same manner as the above plating property (initial).

<Measurement method of bending strength and flexural modulus>
After drying the pellet obtained by the above-mentioned manufacturing method at 120 ° C. for 4 hours, an ISO tensile test piece having a thickness of 4 mm was injection-molded using NEX140III manufactured by Nissei Plastic Industry Co., Ltd. The cylinder temperature was 280 ° C and the mold temperature was 130 ° C.
Based on ISO178, the bending strength (unit: MPa) and the bending elastic modulus (unit: GPa) were measured at a temperature of 23 ° C. using the ISO tensile test piece (4 mm thickness).

<Linear expansion coefficient>
After drying the pellet obtained by the above-mentioned manufacturing method at 120 ° C. for 4 hours, an ISO tensile test piece having a thickness of 4 mm was injection-molded using NEX140III manufactured by Nissei Plastic Industry Co., Ltd. The cylinder temperature was 280 ° C and the mold temperature was 130 ° C.
In accordance with JIS K7197 method, the obtained test piece was measured for the linear expansion coefficient for MD (Machine Direction, injection direction during resin injection molding) and TD (Transverse Direction, width direction during resin injection molding), respectively. It was measured. Furthermore, TD / MD was calculated. It can be said that the smaller the TD / MD, the better the dimensional stability.

Examples 2, 3 and Comparative Examples 1-3
In Example 1, the amount of each component was changed as described in Table 1, and the others were performed in the same manner. The results are shown in Table 1.

In the above table, the unit of each component is part by mass.
As is clear from the above results, when the thermoplastic resin composition of the present invention was used (Examples 1 to 3), excellent plating properties could also be achieved for the resin molded product after the wet heat treatment. Furthermore, high mechanical strength could be maintained and dimensional stability was excellent. In particular, when glass fibers having a number average fiber diameter in the range of 4.0 to 9.0 μm are used (Examples 1 and 2), particularly excellent plating properties can be achieved for the resin molded products after the wet heat treatment. It was.
On the other hand, when glass beads / glass fibers, which are the mass ratio of glass beads to glass fibers, are outside the range of 0.5 to 5.0 (Comparative Examples 1 to 3), plating of the resin molded product after the wet heat treatment The sex was much inferior. In particular, when the compounding ratio of the glass beads was small (Comparative Examples 1 and 2), the results were significantly inferior in dimensional stability. On the other hand, when the compounding ratio of the glass beads was large (Comparative Example 3), the mechanical strength was inferior.

DESCRIPTION OF SYMBOLS 1 Resin molding 2 Laser 3 Laser irradiated part 4 Plating solution 5 Plating layer

Claims (16)

1 to 30 parts by mass of a laser direct structuring additive, glass fiber, and glass beads with respect to 100 parts by mass of the thermoplastic resin and the thermoplastic resin,
A thermoplastic resin composition having a glass bead / glass fiber mass ratio of 0.5 to 5.0, which is a mass ratio of glass beads to glass fibers. The thermoplastic resin composition according to claim 1, wherein the total amount of glass fibers and glass beads occupies 10 to 50% by mass of the thermoplastic resin composition. The thermoplastic resin composition according to claim 1 or 2, wherein the glass fiber has a circular cross section and a number average fiber diameter of 4.0 to 15.0 µm. The thermoplastic resin composition according to claim 1 or 2, wherein the glass fiber has a circular cross section and a number average fiber diameter of 4.0 to 9.0 µm. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin is a polyamide resin. The thermoplastic resin is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from at least one of metaxylylenediamine and paraxylylenediamine, 70 or more mol% of the structural unit derived from the acid is a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Thermoplastic resin composition. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the number average particle diameter of the glass beads is 2 to 100 µm. Furthermore, the thermoplastic resin composition of any one of Claims 1-7 which contains 0.1-200 mass parts with respect to 100 mass parts of laser direct structuring additives for a talc. The thermoplastic resin composition according to any one of claims 1 to 8, wherein the laser direct structuring additive is a compound containing copper and chromium. The resin molded product formed by shape | molding the thermoplastic resin composition of any one of Claims 1-9. The resin molded product according to claim 10, wherein the resin molded product has a plated surface. The resin molded product according to claim 11, wherein the plating retains performance as an antenna. The resin molded product according to any one of claims 10 to 12, which is a portable electronic device component. A plating comprising applying a metal to a surface of a resin molded product obtained by molding the thermoplastic resin composition according to any one of claims 1 to 9, and then applying a metal to form a plating. Manufacturing method of resin-molded products. The manufacturing method of the resin molded product with plating of Claim 14 whose said plating is copper plating. A method for manufacturing a portable electronic device part having an antenna, comprising the method for manufacturing a plated resin molded product according to claim 14.