JP6745226B2 - Method for producing polyamide resin composition for laser direct structuring, resin molded article, plated resin molded article and method for producing portable electronic device parts - Google Patents

Description

The present invention relates to a polyamide resin composition for laser direct structuring, a resin molded product, a method for manufacturing a plated resin molded product, and a method for manufacturing a portable electronic device component.

In recent years, with the development of mobile phones including smartphones, various methods for manufacturing an antenna inside a mobile phone have been studied. In particular, there is a demand for a method of manufacturing an antenna that enables a three-dimensional design for a mobile phone. As one of the techniques for forming such a three-dimensional antenna, a laser direct structuring (hereinafter sometimes referred to as “LDS”) technique has been attracting attention. The LDS technique is, for example, a technique of irradiating a surface of a resin molded product containing an LDS additive with a laser to activate it, and applying a metal to the activated portion to form a plating. The feature of this technique is that a metal structure such as an antenna can be directly manufactured on the surface of a resin molded product without using an adhesive or the like. Such LDS technology is disclosed in Patent Document 1, for example. Specifically, in Patent Document 1, (A) 100 parts by weight of a crystalline thermoplastic resin having a melting point of 250° C. or higher measured by a differential scanning calorimetry (DSC) at a heating rate of 10° C./min, (B) 2 to 30 parts by weight of a laser direct structuring additive having a reflectance of 25% or more at a wavelength of 450 nm, (C) 30 to 150 parts by weight of titanium oxide, and (D) 5.5 parts by weight of a phosphorus-based flame retardant. A thermoplastic resin composition containing one part or more is disclosed.

JP, 2005-25127, A

In recent years, with the progress of LDS technology, it is required for the polyamide resin composition for LDS that the plating is not easily peeled off and the growth rate of the plating is high. The present invention is to solve the above problems, in which plating is difficult to peel off, and a polyamide resin composition for LDS capable of providing a resin molded product having a high plating growth rate, and a resin using the resin composition An object of the present invention is to provide a molded product, a method for manufacturing a plated resin molded product, and a method for manufacturing a portable electronic device component.

Based on the above problems, as a result of the study by the present inventors, it was found that the above problems can be solved by adding zinc borate. Specifically, the above-mentioned problems have been solved by the following means <1>, preferably <2> to <17>.
<1> 100 parts by weight of the polyamide resin, 1 to 30 parts by weight of the laser direct structuring additive, 1 to 30 parts by weight of zinc borate and 10 to 150 parts by weight of inorganic fibers, and the content of the flame retardant is the above. A polyamide resin composition for laser direct structuring, which is 5 parts by weight or less based on 100 parts by weight of the polyamide resin, and 100% by weight or less of the content of the zinc borate.
<2> The polyamide resin composition for laser direct structuring according to <1>, wherein the inorganic fiber is glass fiber.
<3> The polyamide resin composition for laser direct structuring according to <1> or <2>, wherein the laser direct structuring additive contains at least one of copper, antimony and tin.
<4> The polyamide resin composition for laser direct structuring according to any one of <1> to <3>, wherein the polyamide resin is a semi-aromatic polyamide resin.
<5> At least one kind of the polyamide resin is composed of a constitutional unit derived from a diamine and a constitutional unit derived from a dicarboxylic acid, and 70 mol% or more of the constitutional unit derived from the diamine is derived from xylylenediamine and derived from a dicarboxylic acid. 70% by mole or more of the structural unit is derived from an α,ω-straight chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and the laser direct structuring according to any one of <1> to <3>. Polyamide resin composition for use.
<6> The polyamide resin composition for laser direct structuring according to any one of <1> to <5>, containing 10 to 30 parts by weight of the zinc borate with respect to 100 parts by weight of the polyamide resin.
<7> The polyamide for laser direct structuring according to any one of <1> to <6>, further containing 0.1 to 200 parts by weight of talc with respect to 100 parts by weight of the laser direct structuring additive. Resin composition.
<8> The polyamide resin composition for laser direct structuring according to any one of <1> to <7>, wherein the polyamide resin has a melting point of 200 to 330°C.
<9> The polyamide resin composition for laser direct structuring according to any one of <1> to <8>, containing 20 to 80 parts by weight of the inorganic fiber with respect to 100 parts by weight of the polyamide resin.
<10> A resin molded product obtained by molding the polyamide resin composition for laser direct structuring according to any one of <1> to <9>.
<11> The resin molded product according to <10>, wherein a part of the resin molded product has a surface roughness Ra of 4.0 μm or more and another part of the surface roughness Ra is 1.0 μm or less.
<12> The resin molded product according to <10> or <11>, which has plating on the surface of the resin molded product.
<13> The resin molded product according to <12>, wherein the plating has a performance as an antenna.
<14> The resin molded product according to any one of <10> to <13>, which is a mobile electronic device component.
<15><1> to <9> The surface of a resin molded article obtained by molding the polyamide resin composition for laser direct structuring according to any one of <1>, after irradiating a laser, applying a metal, A method for producing a resin-molded product with plating, which comprises forming plating.
<16> The method for producing a plated resin molded article according to <15>, wherein the plating is copper plating.
<17> A method for manufacturing a portable electronic device component having an antenna, including the method for manufacturing a plated resin molded product according to <15> or <16>.

ADVANTAGE OF THE INVENTION According to the present invention, a polyamide resin composition for laser direct structuring capable of providing a resin molded product that is hard to peel off and has a high plating growth rate, and a resin molded product and a plated resin using the resin composition It is possible to provide a method for manufacturing a molded product and a method for manufacturing a mobile electronic device component.

It is a schematic diagram showing a process of providing plating on the surface of a resin molding.

The details of the present invention will be described below. In addition, in this specification, "-" is used in the meaning including the numerical values described before and after it as the lower limit and the upper limit.

The polyamide resin composition for laser direct structuring of the present invention (hereinafter sometimes referred to as “resin composition of the present invention”) comprises 1 to 30 parts by weight of a laser direct structuring additive with respect to 100 parts by weight of a polyamide resin, Including 1 to 30 parts by weight of zinc borate and 10 to 150 parts by weight of inorganic fibers, the content of the flame retardant is 5 parts by weight or less with respect to 100 parts by weight of the polyamide resin, and the content of zinc borate. The amount is 100% by weight or less. With such a configuration, it is possible to provide a resin molded product in which the plating does not easily peel off and the plating growth rate is high.
That is, by blending zinc borate, carbonization of the resin is promoted when the laser is irradiated, and the surface of the resin molded product is likely to be roughened. It is presumed that the roughened resin molded product is likely to have an anchor effect on plating. Furthermore, it is presumed that by blending the glass fiber, the glass fiber exposed when the resin on the surface of the resin molded product is carbonized also enters the plating side, and further enhances the plating adhesion of the resin molded product. ..
Furthermore, by using the resin composition of the present invention, it becomes possible to improve the growth rate of plating. It is considered that this is because the roughened surface increases the surface area of the LDS active region and increases the metal seeds necessary for growing the copper plating.

<Polyamide resin>
The polyamide resin used in the present invention is not particularly limited, and known polyamide resins can be used. For example, as the polyamide resin, the description in paragraphs 0011 to 0013 of JP 2011-132550 A can be referred to.
The polyamide resin may be a crystalline polyamide resin or an amorphous polyamide resin, but a crystalline polyamide resin is preferable. When the crystalline polyamide resin is used, the resin molded product can be cured more quickly when it is molded, and thus the unevenness can be more effectively formed on the surface of the resin molded product. Therefore, the adhesion between the resin molded product and the plating can be further improved.

The polyamide resin used in the present invention is preferably a semi-aromatic polyamide resin. Here, the semi-aromatic polyamide resin is composed of a constitutional unit derived from a diamine and a constitutional unit derived from a dicarboxylic acid, and 30 to 70 mol% of a total constitutional unit of the constitutional unit derived from the diamine and the constitutional unit derived from the dicarboxylic acid is used. It means a constitutional unit containing an aromatic ring, and 40 to 60 mol% of the total constitutional units of the constitutional unit derived from a diamine and the constitutional unit derived from a dicarboxylic acid is preferably a constitutional unit containing an aromatic ring. By using such a semi-aromatic polyamide resin, the mechanical strength of the obtained resin molded product can be increased. Examples of the semi-aromatic polyamide resin include polyamide 6T, polyamide 9T, and xylylenediamine-based polyamide resin described later.

At least one kind of the polyamide resin used in the present invention is composed of a constitutional unit derived from a diamine and a constitutional unit derived from a dicarboxylic acid, and 70 mol% or more of the constitutional unit derived from the diamine is derived from xylylenediamine. A polyamide resin in which 70 mol% or more of the derived constitutional unit is derived from an α,ω-straight chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms (hereinafter, may be referred to as “xylylenediamine-based polyamide resin”) preferable.
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, even more preferably 90 mol% or more, even more preferably 95 mol% or more. Derived from. The constituent unit derived from the dicarboxylic acid of the xylylenediamine-based polyamide resin is more preferably 80 mol% or more, still more preferably 85 mol% or more, still more preferably 90 mol% or more, and even more preferably 95 mol% or more is carbon. It is derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 atoms.
The xylylenediamine is preferably paraxylylenediamine and metaxylylenediamine, and more preferably contains at least paraxylylenediamine.

Examples of diamines other than metaxylylenediamine and paraxylylenediamine that can be used as the raw material diamine component of the xylylenediamine-based polyamide resin 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)methane, 2,2-bis(4-amino) Alicyclic diamines such as cyclohexyl)propane, bis(aminomethyl)decalin and bis(aminomethyl)tricyclodecane, aromatic rings such as bis(4-aminophenyl)ether, paraphenylenediamine and bis(aminomethyl)naphthalene. The diamine etc. which it has can be illustrated, and can be used 1 type or in mixture of 2 or more types.

Preferred α,ω-straight chain aliphatic dicarboxylic acids having 4 to 20 carbon atoms to be used as the starting dicarboxylic acid component of the xylylenediamine-based polyamide resin include, for example, succinic acid, glutaric acid, pimelic acid, suberic acid, and azelaine. Examples thereof include aliphatic dicarboxylic acids such as acids, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. One kind or a mixture of two or more kinds can be used. Among them, the melting point of the polyamide resin is processed. Adipic acid or sebacic acid is more preferred, and sebacic acid is even more preferred, since it is in a range suitable for

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, 1, 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 acid such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. One kind or a mixture of two or more kinds can be used.

It should be noted that although it is composed mainly of a constitutional unit derived from a diamine and a constitutional unit derived from a dicarboxylic acid, it does not completely exclude constitutional units other than these, and lactams such as ε-caprolactam or laurolactam, aminocaproic acid. Needless to say, it may contain a constitutional unit derived from an aliphatic aminocarboxylic acid such as aminoundecanoic acid. Here, the main component means that, out of the constituent units constituting the xylylenediamine-based polyamide resin, the total number of constituent units derived from a diamine and constituent units derived from a dicarboxylic acid is the largest among all constituent units. In the present invention, the total of the constituent units derived from the diamine and the constituent units derived from the dicarboxylic acid in the xylylenediamine-based polyamide resin preferably accounts for 90% or more of all the constituent units, and more preferably 95% or more. ..

The melting point of the polyamide resin is preferably 150 to 350°C, more preferably 180 to 330°C, further preferably 200 to 330°C, and further preferably 200 to 320°C.
The melting point is measured according to the method described in Examples below.

The lower limit of the number average molecular weight (Mn) of the polyamide resin is preferably 6,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and 15,000 or more. Is more preferable, 20,000 or more is more preferable, and 22,000 or more is still more preferable. The upper limit of Mn is preferably 35,000 or less, more preferably 30,000 or less, further preferably 28,000 or less, and further preferably 26,000 or less. Within such a range, heat resistance, elastic modulus, dimensional stability, and moldability become better.

The lower limit of the content of the polyamide resin in the resin composition of the present invention is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 45% by weight or more. The upper limit of the content is preferably 80% by weight or less, more preferably 70% by weight or less, further preferably 60% by weight or less, and further preferably 55% by weight or less. ..
The polyamide resin may contain only one kind, or may contain two kinds or more. When two or more kinds are contained, the total amount is preferably within the above range.

The resin composition of the present invention may or may not contain a thermoplastic resin other than the polyamide resin. The content of the thermoplastic resin other than the polyamide resin in the resin composition of the present invention is preferably 5% by weight or less of the resin composition of the present invention, more preferably 3% by weight or less, and 1% by weight. The following is more preferable.

<Laser direct structuring additive (LDS additive)>
The resin composition of the present invention contains a laser direct structuring (LDS) additive. As the LDS additive in the present invention, 10 parts by weight of an additive considered to be an LDS additive is added to 100 parts by weight of a polyamide resin, a YAG laser having a wavelength of 1064 nm is used, and an output of 10 W, a frequency of 80 kHz and a speed of 3 m/s are obtained. And a subsequent plating step is carried out in an electroless M-Copper85 plating bath manufactured by MacDermid Co., which is a compound capable of forming plating when a metal is applied to the laser irradiation surface. The LDS additive used in the present invention may be a synthetic product or a commercially available product. Further, the commercially available product may be a substance marketed as an LDS additive or a substance sold for other purposes as long as the requirements of the LDS additive in the present invention are satisfied. The LDS additive may be used alone or in combination of two or more.

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 weight of copper. Further, it is preferable to contain chromium in an amount of 15 to 50% by weight. The LDS additive in the first embodiment is preferably an oxide containing copper and chromium.

A spinel structure is preferable as a form of containing copper and chromium. The spinel structure is one of typical crystal structure types found in AB ₂ O ₄ type compounds (A and B are metallic elements) which are complex oxides.

The LDS additive of the first embodiment may contain trace amounts 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 be present as oxides.
A preferred example of the LDS additive of the first embodiment is an LDS additive containing 10% by weight or less of a metal oxide other than copper chromium oxide.

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 more preferably has a tin content higher than the phosphorus and antimony contents, and the amount of tin is 80% by weight or more based on the total amount of tin and phosphorus and antimony. Is more preferable.

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

More specifically, as the LDS additive of the second embodiment, antimony-doped tin oxide, antimony oxide-doped tin oxide, phosphorus-doped tin oxide, and phosphorus oxide-doped are used. Examples thereof include tin oxide, and 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 the LDS additive containing phosphorus and tin oxide, the content of phosphorus is 1 to 20% by weight. Further, in the LDS additive containing antimony and tin oxide, the content of antimony is preferably 1 to 20% by weight. In addition, 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.

The third embodiment of the LDS additive used in the present invention preferably contains at least two kinds of metals and also contains a conductive oxide 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. The lower limit is not particularly limited, but may be, for example, 1×10 ¹ Ω·cm or more, and further may be 1×10 ² Ω·cm or more.
The resistivity of the conductive oxide in the present invention usually means powder resistivity, and 10 g of the conductive oxide fine powder is charged into a cylinder having an inner diameter of 25 mm and having Teflon (registered trademark) processing on the inner surface. It can be measured with a "3223 type" tester manufactured by Yokogawa Electric Co., Ltd. by pressurizing to 100 kgf/cm ² (filling rate 20%).

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 it is preferable that it contains at least two metals. Specifically, it is preferable to include 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 even more preferably 12 or 13.
The LDS additive used in the third embodiment has a total content of the metal of the n group (n is an integer of 3 to 16) and the metal content of the n+1 group of the periodic table in the LDS additive being 100 mol. %, the content of one metal is preferably 15 mol% or less, more preferably 12 mol% or less, still more preferably 10 mol% or less. The lower limit is not particularly limited, but 0.0001 mol% or more is preferable. By setting the content of two or more kinds of metals within such a range, it is possible to improve the plating property. In the present invention, an n-group metal oxide doped with an n+1-group metal is particularly preferable.
Furthermore, in the LDS additive used in the third embodiment, 98% by weight or more of the metal component contained in the LDS additive is composed of the content of the n-group metal and the n+1-group metal of the above periodic table. It is preferable.

Examples of the n-group metal of 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, Group 12 (n=12) metals are preferable, and zinc is more preferable.

Examples of metals of the n+1 group 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.), group 14 (germanium, tin, etc.), group 15 (arsenic, antimony, etc.), group 16 (selenium, tellurium, etc.). Among them, Group 13 (n+1=13) metals are preferable, aluminum or gallium is more preferable, and aluminum is further 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 and calcium. These metals may be present as oxides. The content of each of these metals is preferably 0.01% by weight or less with respect to the LDS additive.

Among the above, in the present invention, the LDS additive preferably contains at least one of copper, antimony and tin, and contains the LDS additive of any one of the first embodiment and the second embodiment. Is more preferable.

The number average particle diameter 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. With such an average particle diameter, the surface of the plating can be made more uniform.

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

<Zinc borate>
The resin composition of the present invention contains zinc borate. By including zinc borate, it becomes difficult for the plating to peel off when plating is formed on the resin molded product, and the plating growth rate can be increased. Zinc borate is a compound known as a flame retardant aid, but nothing is known about increasing the plating growth rate. In particular, it is surprising that the effect of the present invention is exerted only when zinc borate is used, and it does not exhibit with other flame retardant aids (for example, magnesium hydroxide and zinc stannate).
In the present invention, 1 to 30 parts by weight of zinc borate is included with respect to 100 parts by weight of polyamide resin. The lower limit of the compounding amount of zinc borate is more preferably 2 parts by weight or more, further preferably 8 parts by weight or more, further preferably 10 parts by weight or more, and may be 14 parts by weight or more. The upper limit of the compounding amount of zinc borate is preferably 26 parts by weight or less.

In the resin composition of the present invention, the weight ratio of the LDS additive and zinc borate is preferably 0.1 to 3.0, and 1.0 to 3.0 with respect to 1 part of the LDS additive. Is more preferable, and it is still more preferable that it is 1.5 to 2.6. By setting it as such a range, the effect of this invention is exhibited more effectively.

The resin composition of the present invention may or may not contain a flame retardant aid other than zinc borate. As an example of the embodiment of the present invention, the other flame retardant aid may be 5% by weight or less, further 3% by weight or less, and particularly 1% by weight or less of the amount of zinc borate.

<Inorganic fiber>
The resin composition of the present invention contains inorganic fibers. Examples of the inorganic fiber include carbon fiber and glass fiber, and glass fiber is preferable.

The inorganic fiber in the present invention means a fibrous inorganic material, and more specifically, a chopped shape in which 1,000 to 10,000 inorganic fibers are bundled and cut into a predetermined length is preferable. ..
The number average fiber length of the inorganic fibers in the present invention is preferably 0.5 to 10 mm, more preferably 1 to 5 mm. By using the inorganic fiber having such a number average fiber length, the mechanical strength can be further improved. The number average fiber length is, with respect to the image obtained by observation with an optical microscope, the long side is measured by randomly extracting the target inorganic fiber whose fiber length is to be measured, and the number average fiber length is obtained from the obtained measurement value. calculate. The observation magnification is 20 times and the number of measurements is 1,000 or more. It roughly corresponds to the cut length.
The cross section of the inorganic 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 a rectangle, and an eyebrow shape, but a circle is preferable. The term "circle" as used herein is intended to include what is usually called a circle in the technical field of the present invention, in addition to a circle in a mathematical sense.
The lower limit of the number average fiber diameter of the inorganic 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 inorganic fibers is preferably 15.0 μm or less, more preferably 9.0 μm or less, and further preferably 7.5 μm or less. By using the inorganic fibers having the number average fiber diameter in such a range, a resin molded product having excellent plating properties can be obtained even after moist 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. Incidentally, the number average fiber diameter of the inorganic fibers, with respect to the image obtained by observation with an electron microscope, randomly extract the glass fiber of the object whose fiber diameter is to be measured, measure the fiber diameter in the vicinity of the central portion, and obtain Calculate from the measured values. The observation magnification is 1,000 times, and the number of measurements 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 into a circle having the same area as the area of the cross section.

Next, the glass fiber preferably used in the present invention will be described.
The 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. The fiber to be obtained is used, but it is not particularly limited as long as it can be a glass fiber. In the present invention, it is preferable to include E glass.

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. Is preferably provided. The amount of the surface treatment agent attached is preferably 0.01 to 1% by weight of the glass fiber. Further, if necessary, a fatty acid amide compound, a lubricant such as silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin and a urethane resin, a resin having a film forming ability and heat. It is also possible to use those surface-treated with a mixture of a stabilizer, a flame retardant and the like.

Glass fiber is commercially available. Examples of commercially available products include T286H, T56H, T289H, Nippon Electric Glass Co., Ltd., Owens Corning Co., DEFT2A, PPG Co., HP3540, Nitto Boseki, CSG3PA820 and the like.

The lower limit of the content of the inorganic fibers in the resin composition of the present invention is 10 parts by weight or more, preferably 15 parts by weight or more, and more preferably 20 parts by weight or more with respect to 100 parts by weight of the polyamide resin. preferable. The upper limit of the content is 150 parts by weight or less, preferably 100 parts by weight or less, more preferably 80 parts by weight or less, and further preferably 70 parts by weight or less.
The resin composition of the present invention may include only one type of inorganic fiber, or may include two or more types of inorganic fiber. When two or more kinds are contained, the total amount is preferably within the above range.

The total amount of the polyamide resin and the inorganic fiber in the resin composition of the present invention preferably accounts for 60% by weight or more of the resin composition, and more preferably 70% by weight or more.

<talc>
The resin composition of the present invention may further contain talc. By adding talc, dimensional stability and product appearance can be improved, and by adding talc, the plating growth rate can be further increased. Furthermore, by blending talc, it is possible to improve the plating property of the resin molded product even if the content of the LDS additive is reduced. The talc may be surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. In this case, the amount of the siloxane compound attached to talc is preferably 0.1 to 5% by weight of talc.
The number average particle diameter of talc is preferably 1 to 50 μm, more preferably 2 to 25 μm. Talc is usually scale-shaped, but the average length is the length of the longest part. The number average particle size of talc is calculated from the measured value obtained by randomly extracting the talc of which the particle size is to be measured from 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.

When compounded, the content of talc in the resin composition of the present invention is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and further preferably 100 parts by weight of the polyamide resin. 5 to 20 parts by weight.
When compounded, the content of talc in the resin composition of the present invention is preferably 0.1 to 200 parts by weight, more preferably 1 to 150 parts by weight, based on 100 parts by weight of the LDS additive. The amount is preferably 20 to 120 parts by weight, more preferably 80 to 120 parts by weight. 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.

<Release agent>
The resin composition of the present invention may further contain a release agent. The release agent is mainly used to improve productivity during molding of the resin composition. Examples of the release agent include aliphatic carboxylic acid amide-based compounds, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oil. Can be mentioned. Among these release agents, carboxylic acid amide compounds are particularly preferable.

Examples of the aliphatic carboxylic acid amide-based compound include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and/or a polybasic acid and a diamine.
The details of the release agent can be referred to the descriptions in paragraphs 0037 to 0042 of JP-A-2016-196563 and the descriptions in paragraphs 0048 to 0058 of JP-A-2016-078318, the contents of which are incorporated herein. ..

The content of the release agent, when compounded, is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and the upper limit, relative to the resin composition. It is preferably 2% by weight or less, more preferably 1.5% by weight or less. With such a range, mold releasability can be improved, and mold contamination during injection molding can be prevented. The release agents may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

<Heat stabilizer>
The resin composition of the present invention may further contain an organic and/or inorganic heat stabilizer.
The organic heat stabilizer is preferably at least one selected from the group consisting of phenol compounds, phosphite compounds, hindered amine compounds, triazine compounds, and sulfur compounds.
As the heat stabilizer, only one kind may be used, or two or more kinds may be used in combination.

When contained, the heat stabilizer content is preferably 0.01 to 5 parts by weight, and preferably 0.03 to 4 parts by weight, based on 100 parts by weight of the resin composition of the present invention. Is more preferable. If the amount of the heat stabilizer is too small, the heat stabilizing effect may be insufficient, and if the amount of the heat stabilizer is too large, the effect may reach the ceiling and may be uneconomical.

<Light stabilizer>
The resin composition of the present invention may contain an organic and/or inorganic light stabilizer.
Examples of the organic light stabilizers include compounds having an ultraviolet absorption effect 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 the light stabilizer, a compound having an ultraviolet absorbing effect and a compound having a radical scavenging ability can be used in combination to exert a higher stabilizing effect.
As the light stabilizer, only one kind may be used, or two or more kinds may be used in combination.

The content of the light stabilizer is preferably 0.01 to 5 parts by weight, and more preferably 0.01 to 4 parts by weight, based on 100 parts by weight of the resin composition of the present invention.

<Alkali>
The 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 is mottled due to reduction by itself depending on the combination, but resin molding obtained by adding alkali The color tone of the product can be made more uniform. The type of alkali is not particularly limited, and calcium hydroxide, magnesium hydroxide or the like can be used. As the alkali, only one kind may be used, or two or more kinds may be used in combination.
The content of alkali in the 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 weight of the content of LDS additive, and more preferably Is 0.05 to 15% by weight.

<Other additives>
The resin composition of the present invention may contain other components besides the above. Other components include elastomers, fillers other than inorganic fibers, titanium oxide, antioxidants, hydrolysis resistance improvers, matting agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, antistatic agents, colorings. Examples include an inhibitor, an antigelling agent, a coloring agent and the like. For details of these, the description in paragraphs 0130 to 0155 of Japanese Patent No. 4894982 can be referred to, and the contents thereof are incorporated herein. The total amount of these components is preferably 20% by weight or less of the resin composition. Each of these components may be used alone or in combination of two or more.
Further, the resin composition of the present invention has a flame retardant content of 5 parts by weight or less with respect to 100 parts by weight of the polyamide resin, and 100% by weight or less of the content of the zinc borate. Preferably, the content of the flame retardant in the resin composition is 3 parts by weight or less with respect to 100 parts by weight of the polyamide resin, and 50% by weight or less of the content of the zinc borate. More preferably, the content of the flame retardant in the resin composition is 3 parts by weight or less with respect to 100 parts by weight of the polyamide resin, and 10% by weight or less of the content of zinc borate. More preferably, the content of the flame retardant in the resin composition is substantially zero. The flame retardant includes a phosphorus flame retardant, a halogen flame retardant, and the like.

<Method for producing resin composition>
As a method for producing the resin composition of the present invention, any method is adopted.
For example, a method of mixing polyamide resin, inorganic fiber, LDS additive and the like using a mixing means such as a V-type blender to prepare a batch blended product, and then melt-kneading with a vented extruder to form pellets can be mentioned. .. Alternatively, as a two-step kneading method, components other than the inorganic fibers are sufficiently mixed in advance, and then melt-kneaded in an extruder with a vent to produce pellets, and then the pellets and the inorganic fibers are mixed with a vent. A method of melt-kneading with an extruder can be mentioned.
Further, components other than the inorganic fibers are thoroughly mixed in a V-type blender or the like to prepare in advance, and the mixture is supplied from the first chute of the twin-screw extruder with a vent. A method of supplying from two shoots, melt-kneading, and pelletizing can be mentioned.

With respect to the screw configuration of the kneading zone of the extruder, it is preferable that an element that promotes kneading is arranged on the upstream side and an element having a pressurizing ability is arranged on the downstream side.
Examples of the element that promotes kneading include a progressive kneading disc element, an orthogonal kneading disc element, a wide kneading disc element, and a progressive feeding 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 extrusion failure such as strand breakage. Therefore, it is desirable to select a screw configuration that takes shear heat generation and the like into consideration. It is desirable to use an antioxidant or a heat stabilizer in order to suppress decomposition during kneading or during molding in a subsequent step.

<Resin molded product>
The present invention also discloses a resin molded product obtained by molding the resin composition of the present invention. Part of the surface roughness Ra of the resin molded product of the present invention is preferably 4.0 μm or more, more preferably 4.2 μm or more, and further preferably 5.0 μm or more. The upper limit of the surface roughness Ra is, for example, 7.0 μm or less, and may be 6.5 μm or less. Such a portion having a large surface roughness is formed by irradiating a laser. On the other hand, the surface roughness Ra of the other part of the resin molded product is preferably 1.0 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. In this way, by increasing the surface roughness only in a part of the area irradiated with the laser, it is possible to obtain a resin molded product having an excellent appearance and a high adhesion to the plating.

The method for producing a resin molded product in the present invention is not particularly limited, and a molding method generally adopted for resin compositions can be arbitrarily adopted. Examples include 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, and rapid heating mold. 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, laminated molding method, press molding method, A blow molding method and the like can be mentioned. A molding method using a hot runner method can also be used.

The resin molded product obtained by molding the 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 a performance as an antenna.

<Manufacturing method of plated resin moldings>
Next, disclosed is a method for producing a plated resin molded article, which comprises irradiating a laser on the surface of a resin molded article obtained by molding the resin composition of the present invention, and then applying a metal to form plating. To do.
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 part or all of a curved surface. The obtained resin molded product with plating is not limited to the final product, and is intended to include various parts.

Returning to FIG. 1 again, the resin molded product 1 is irradiated with the laser 2. The laser here is not particularly limited, and can be appropriately selected from known lasers such as YAG laser, excimer laser, and electromagnetic radiation, and YAG laser is preferable. Also, the wavelength of the laser is not particularly limited. A preferred wavelength range is 200 nm to 1200 nm, more preferably 800 to 1200 nm.
When the laser irradiation is performed, the resin molded product 1 is activated only in the laser-irradiated portion 3. In this activated state, the resin molded product 1 is applied to the plating liquid 4. The plating solution 4 is not particularly limited, and widely known plating solutions can be widely used. The plating solution containing at least one of copper, nickel, silver, gold, and palladium as a metal component (particularly, An electroless plating solution) is preferable, a plating solution containing at least one of copper, nickel, silver, and gold (in particular, an electroless plating solution) is more preferable, and a plating solution containing copper (in particular, an electroless plating solution) is used. Plating liquid) is more preferable. That is, in the plating according to the present invention, the metal component preferably comprises at least one of the above metals.
The method of applying the resin molded product 1 to the plating solution 4 is also not particularly limited, but for example, a method of adding the plating solution 4 to a plating solution may be used. In the resin molded product after applying the plating liquid, the plating 5 is formed only on the portion irradiated with the laser.
According to the method of the present invention, it is possible to form a plating (circuit) having an interval of a width of 1 mm or less, and further a width of 150 μm or less (the lower limit value is not particularly set, but for example, 30 μm or more). In order to suppress corrosion and deterioration of the formed plating (circuit), the plating may be further protected with nickel or gold after performing electroless plating, for example. Similarly, electroless plating may be used after electroless plating to form a required film thickness in a short time.
The method for producing a plated resin molded article is preferably used as a method for producing a portable electronic device component having an antenna, including the method for producing a plated resin molded article.

The resin molded product obtained from the resin composition of the present invention can be used in various applications such as electronic parts such as connectors, switches, relays and conductive circuits (particularly mobile electronic device parts).

In addition, within the scope of the present invention, JP 2011-219620 A, JP 2011-195820 A, JP 2011-178873 A, JP 2011-168705 A, and JP 2011-148267 A. The description in the publication can be referred to.

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed 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.

The following raw materials were used.
<Synthesis of Polyamide Resin PXD10>
8950 g (44.25 mol) of sebacic acid (TA, sebacic acid) precisely weighed in a reaction vessel equipped with a stirrer, a dephlegmator, a cooler, a thermometer, a dropping device, a nitrogen introducing tube, and a strand die. Then, 12.54 g (0.074 mol) of calcium hypophosphite and 6.45 g (0.079 mol) of sodium acetate were weighed and charged. After sufficiently replacing 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 (manufactured by Mitsubishi Gas Chemical Co., Inc.) was added dropwise under stirring over 110 minutes. During this period, the temperature inside the reaction vessel was continuously raised to 293°C. In the dropping step, the pressure was controlled to 0.42 MPa, and the produced water was removed from the system through the partial condenser and the cooler. The temperature of the partial condenser was controlled in the range of 145 to 147°C. After the completion of dropping the paraxylylenediamine, the polycondensation reaction was continued for 20 minutes at a pressure in the reaction vessel of 0.42 MPa. During this period, the temperature inside the reaction vessel was raised to 296°C. Then, the pressure in the reaction vessel was reduced from 0.42 MPa to 0.12 MPa in 30 minutes. During this time, the internal temperature rose to 298°C. Then, the pressure was reduced at a rate of 0.002 MPa/min, and the pressure was reduced to 0.08 MPa in 20 minutes. The temperature inside the reaction vessel at the time of completion of the reduced pressure was 301°C. Then, the inside of the system was pressurized with nitrogen, the polymer was taken out in a strand form from a strand die at a reactor temperature of 301° C. and a resin temperature of 301° C., and cooled with cooling water at 20° C. to pelletize the polymer. The melting point of the obtained polyamide resin was 290°C.

<<Measurement of melting point>>
The melting point was measured as the temperature of the peak top of the endothermic peak at the time of temperature increase observed by the DSC (differential scanning calorimetry) method.
A DSC measuring instrument was used for the measurement, the sample amount was about 1 mg, nitrogen was flowed at 30 mL/min as an atmosphere gas, and the temperature rising rate was 10° C./min from room temperature to a temperature above the expected melting point. The melting point was determined from the peak top temperature of the endothermic peak observed when heating and melting.
As the DSC measuring device, DSC-60 manufactured by Shimadzu Corporation (SHIMADZU CORPORATION) was used.
The unit of melting point is °C.

<Synthesis of polyamide resin MP10>
In a reaction vessel equipped with a stirrer, a partial condenser, a total condenser, a thermometer, a dropping funnel and a nitrogen introducing tube, and a strand die, precisely weighed sebacic acid 12,135 g (60 mol), sodium hypophosphite monohydrate. (NaH ₂ PO ₂ .H ₂ O) 3.105 g (50 ppm by weight as phosphorus atom concentration in polyamide resin) and 1.61 g sodium acetate were added, and after sufficiently substituting with nitrogen, under a small amount of nitrogen stream. The system was heated to 170° C. with stirring. The molar ratio of sodium acetate/sodium hypophosphite monohydrate was 0.67.
A mixture of metaxylylenediamine and paraxylylenediamine in a ratio of 7:3 (8,172 g, 60 mol) was added dropwise to the mixture with stirring, and the system was continuously heated while removing the condensed water produced. .. After the dropwise addition of the mixed metaxylylenediamine was completed, the internal temperature was set to 260° C. and the melt polymerization reaction was continued for 40 minutes.
Then, the system was pressurized with nitrogen, the polymer was taken out from the strand die, and this was pelletized. The melting point of the obtained polyamide was 215°C.

<Synthesis of polyamide resin MP6>
In a reaction vessel equipped with a stirrer, a partial condenser, a total condenser, a thermometer, a dropping funnel and a nitrogen introduction tube, and a strand die, adipic acid (manufactured by Roadia) 7.22 kg (49.4 mol) and sodium acetate/next After charging 11.66 g of sodium phosphite monohydrate (molar ratio = 1/1.5) and thoroughly substituting with nitrogen, heating up to 170°C while stirring the system under a small amount of nitrogen stream. Melted
6.647 kg of mixed xylylenediamine in which the molar ratio of metaxylylenediamine and paraxylylenediamine is 70/30 (34.16 mol of metaxylylenediamine, 14.64 mol of paraxylylenediamine, manufactured by Mitsubishi Gas Chemical Co., Inc.), The internal temperature was continuously raised to 240° C. over 2.5 hours while the condensation water generated was added dropwise to the melt in the reaction vessel under stirring and discharged to the outside of the system.
After the completion of the dropping, the internal temperature was raised, and when the temperature reached 250° C., the pressure inside the reaction vessel was reduced, the internal temperature was further raised, and the melt polycondensation reaction was continued at 270° C. for 20 minutes. Then, the system was pressurized with nitrogen, the obtained polymer was taken out from the strand die, and was pelletized to obtain a polyamide resin. The melting point was 255°C.

<LDS additive>
Black1G: copper chromium oxide (CuCr ₂ O ₄₎ (manufactured by Shepherd Japan Inc.)
CP5C: Antimony-doped tin oxide (tin oxide 95% by weight, antimony oxide 5% by weight) (Keeling & Walker)

<Zinc borate or substitute>
Zinc borate: FirebrakeZB, manufactured by Borax Magnesium hydroxide: manufactured by Junsei Chemical Co., special grade zinc stannate: Flametard-S, manufactured by Nippon Light Metal Co., Ltd.

<Flame retardant>
Phosphazene FB-110: manufactured by Fushimi Pharmaceutical Co., Ltd.

<Glass fiber>
T756H: manufactured by Nippon Electric Glass Co., Ltd., urethane sizing agent, cut length (number average fiber length) 3 mm, number average fiber diameter 10 μm, and glass fiber has a circular cross section.

<talc>
5000S: Micron White 5000S, average diameter 4.7 μm (Hayashi Kasei Co., Ltd.)

<Release agent>
CS8CP: Calcium montanate (manufactured by Nitto Kasei Co., Ltd.)

Example 1
<Compound>
Each component was weighed so as to have the composition shown in Table 1 below, and the components except the glass fiber were blended with a tumbler, and the mixture was charged from the root of a twin-screw extruder (Toshiba Machinery Co., Ltd., TEM26SS). After melting, the glass fibers were side-fed to make pellets. The temperature of the twin-screw extruder was set to 300°C.

<Surface roughness Ra>
After drying the pellets obtained by the above-mentioned manufacturing method at 120° C. for 5 hours, using SG75-MII manufactured by Nissei Plastic Co., Ltd., a cylinder temperature of 300° C., a mold temperature of 130° C., and a molding cycle of 50 seconds. By injection molding to form a plate having a thickness of 3 mm. The obtained plate was irradiated with a YAG laser having a wavelength of 1064 nm at an output of 10 W, a speed of 80 m/s, and a frequency of 3 μs. After irradiation, Ra of the laser irradiation portion was measured according to JIS B 0601. At the time of measurement, SURFCOM 3000A-3DF-STD manufactured by Tokyo Seimitsu Co., Ltd. was used. The results are shown in Table 1.
Further, Ra of the laser non-irradiated portion was measured in the same manner.

<Peeling strength>
After drying the pellets obtained by the above-mentioned manufacturing method at 120° C. for 5 hours, using SG75-MII manufactured by Nissei Plastic Co., Ltd., a cylinder temperature of 300° C., a mold temperature of 130° C., and a molding cycle of 50 seconds. By injection molding to form a plate having a thickness of 3 mm. The obtained plate was irradiated with a YAG laser having a wavelength of 1064 nm at an output of 10 W, a speed of 80 m/s, and a frequency of 3 μs. After degreasing the test piece with sulfuric acid, it was treated with THP Alkaline Acti and THP Alkali Access made by Kizai Co., Ltd., and copper-plated with a SEL copper made by Kizai Co., Ltd. The obtained copper plating pattern was subjected to a 90-degree peeling test, and an integrated average value was calculated from the detected load when peeling 10 mm at a speed of 20 mm/min. For the measurement, a load cell 2kN manufactured by Instron was used. The results are shown in Table 1.

<Plating growth rate>
After drying the pellets obtained by the above-mentioned manufacturing method at 120° C. for 5 hours, using SG75-MII manufactured by Nissei Plastic Co., Ltd., a cylinder temperature of 300° C., a mold temperature of 130° C., and a molding cycle of 50 seconds. By injection molding to form a plate having a thickness of 3 mm. The obtained plate was irradiated with a YAG laser having a wavelength of 1064 nm at an output of 10 W, a speed of 80 m/s, and a frequency of 3 μs. After degreasing the test piece with sulfuric acid, it was treated with THP Alkaline Acti and THP Alkali Access made by Kizai Co., Ltd., and copper-plated with a SEL copper made by Kizai Co., Ltd. The film thickness of the obtained copper plating pattern was measured using a fluorescent X-ray film thickness meter FT110 manufactured by Yamato Scientific Co., Ltd. The plating thickness was calculated from the average value of three arbitrary measurement points.
The film thickness of each Example and Comparative Example was compared with the film thickness of Comparative Example 1 being 1.0. It can be said that the thicker the film, the faster the growth rate. The results are shown in Table 1.

Examples 2-7, Comparative Examples 1-6
In Example 1, changes were made as shown in Table 1 or Table 2, and the other steps were the same. The results are shown in Table 1 or Table 2.

As is clear from the above results, the resin composition of the present invention was able to increase the surface roughness of the portion irradiated with the laser. Furthermore, the peeling strength of the plating can be increased, and it is possible to make the plating hard to peel off.
Furthermore, it has become possible to increase the plating growth rate.
On the other hand, when zinc borate is not added (Comparative Examples 1 and 2), or when zinc borate is not added and a compound known as a known flame retardant aid is added instead (Comparison) In Examples 4 and 5), the peeling strength of the plating was low and the plating was easy to peel off.
Moreover, when the amount of zinc borate exceeds the range of the present invention (Comparative Example 3), extrusion was difficult.
Furthermore, even when zinc borate was added, when the flame retardant was also compounded (Comparative Example 6), the peeling strength of the plating was reduced and the plating was easily peeled off.

1 Resin molded product 2 Laser 3 Laser irradiated part 4 Plating solution 5 Plating

Claims (17)

1 to 30 parts by weight of a laser direct structuring additive, 1 to 30 parts by weight of zinc borate, and 10 to 150 parts by weight of inorganic fiber, relative to 100 parts by weight of polyamide resin,
A polyamide resin composition for laser direct structuring, wherein the content of the flame retardant is 5 parts by weight or less with respect to 100 parts by weight of the polyamide resin, and 100% by weight or less of the content of the zinc borate. The polyamide resin composition for laser direct structuring according to claim 1, wherein the inorganic fibers are glass fibers. The polyamide resin composition for laser direct structuring according to claim 1 or 2, wherein the laser direct structuring additive contains at least one of copper, antimony and tin. The polyamide resin composition for laser direct structuring according to any one of claims 1 to 3, wherein the polyamide resin is a semi-aromatic polyamide resin. At least one of the polyamide resins is composed of a constitutional unit derived from a diamine and a constitutional unit derived from a dicarboxylic acid, and 70 mol% or more of the constitutional unit derived from the diamine is derived from xylylenediamine, and a constitutional unit derived from a dicarboxylic acid. 70 mol% or more of the above is derived from an α,ω-straight chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and the polyamide resin composition for laser direct structuring according to any one of claims 1 to 3. .. The polyamide resin composition for laser direct structuring according to any one of claims 1 to 5, which contains 10 to 30 parts by weight of the zinc borate with respect to 100 parts by weight of the polyamide resin. Further, the polyamide resin composition for laser direct structuring according to any one of claims 1 to 6, further comprising 0.1 to 200 parts by weight of talc with respect to 100 parts by weight of the laser direct structuring additive. The polyamide resin composition for laser direct structuring according to any one of claims 1 to 7, wherein a melting point of the polyamide resin is 200 to 330°C. The polyamide resin composition for laser direct structuring according to any one of claims 1 to 8, comprising 20 to 80 parts by weight with respect to 100 parts by weight of the polyamide resin. A resin molded product obtained by molding the polyamide resin composition for laser direct structuring according to any one of claims 1 to 9. The resin molded product according to claim 10, wherein a surface roughness Ra of a part of the resin molded product is 4.0 μm or more and a surface roughness Ra of another part of the resin molded product is 1.0 μm or less. The resin molded product according to claim 10 or 11, wherein the surface of the resin molded product is plated. The resin molded product according to claim 12, wherein the plating has a performance as an antenna. The resin molded product according to any one of claims 10 to 13, which is a mobile electronic device component. A metal is applied to the surface of a resin molded product obtained by molding the polyamide resin composition for laser direct structuring according to any one of claims 1 to 9 after applying a laser to form a plating. A method for producing a plated resin molded article, including: The method for producing a plated resin molded article according to claim 15, wherein the plating is copper plating. A method of manufacturing a portable electronic device component having an antenna, including the method of manufacturing the plated resin molded product according to claim 15 or 16.