JP2018119043A - Polyamide resin composition for laser direct structuring, resin molded article, method for producing resin molded article with plating and method for manufacturing portable electric equipment component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition for laser direct structuring capable of providing a resin molded article comprising plating which is hard to peeling and has a high plating growth rate, a resin molded article using the resin composition, a method for producing a resin molded article with plating, and a method for manufacturing a portable electric equipment component.SOLUTION: The polyamide resin composition for laser direct structuring is provided which includes 1-30 pts.wt. of a laser direct structuring addition agent, 1-30 pts.wt. of zinc borate and 10-150 pts.wt. of an inorganic fiber with respect to 100 pts.wt. of a polyamide resin, and in which a content of a flame retardant is 5 pts.wt. or less with respect to 100 pts.wt. of the polyamide resin and is 100 pt.% or less of content of the zinc borate.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyamide resin composition for laser direct structuring, 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 by irradiating a surface of a resin molded product containing an LDS additive by irradiating a laser and applying a metal to the activated portion. 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 Document 1, for example. Specifically, Patent Document 1 includes (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) 2-30 parts by weight of a laser direct structuring additive having a reflectance at a wavelength of 450 nm of 25% or more, (C) 30-150 parts by weight of titanium oxide, and (D) 5.5% by weight of a phosphorus flame retardant. A thermoplastic resin composition containing at least a part is disclosed.

Japanese Patent Laying-Open No. 2015-25127

  In recent years, with the advancement of LDS technology, it has been demanded that the polyamide resin composition for LDS is hard to peel off and the plating growth rate is high. The present invention solves such a problem, and is a polyamide resin composition for LDS capable of providing a resin molded product that is difficult to peel off and has a high plating growth rate, and a resin using the resin composition. It aims at providing the manufacturing method of a molded article, the resin molded article with plating, and the manufacturing method of portable electronic device components.

As a result of investigations by the inventor under the above problems, it has been found that the above problems can be solved by blending zinc borate. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <17>.
<1> 100 parts by weight of polyamide resin, 1-30 parts by weight of laser direct structuring additive, 1-30 parts by weight of zinc borate and 10-150 parts by weight of inorganic fiber, The polyamide resin composition for laser direct structuring which is 5 parts by weight or less and 100% by weight or less of the content of the zinc borate with respect to 100 parts by weight of the polyamide resin.
<2> The polyamide resin composition for laser direct structuring according to <1>, wherein the inorganic fiber is a 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 of the polyamide resins is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, 70 mol% or more of the structural unit derived from the diamine is derived from xylylenediamine, and derived from a dicarboxylic acid The laser direct structuring according to any one of <1> to <3>, wherein 70 mol% or more of the structural unit is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Polyamide resin composition.
<6> The polyamide resin composition for laser direct structuring according to any one of <1> to <5>, wherein the zinc borate is included in an amount of 10 to 30 parts by weight 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 comprising 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>, wherein the inorganic fiber is contained in an amount of 20 to 80 parts by weight 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 surface roughness Ra of the resin molded product is 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>, wherein the surface of the resin molded product is plated.
<13> The resin molded product according to <12>, wherein the plating has performance as an antenna.
<14> The resin molded product according to any one of <10> to <13>, which is a portable electronic device component.
<15><1> to <9> After applying the laser to the surface of the resin molded product formed by molding the polyamide resin composition for laser direct structuring according to any one of the above, a metal is applied, A method for producing a resin-molded article with plating, comprising forming plating.
<16> The method for producing a resin-molded product with plating 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>.

  According to the present invention, a polyamide resin composition for laser direct structuring capable of providing a resin molded product in which plating is difficult to peel off and has a high plating growth rate, and a resin molded product and a plated resin using the resin composition It has become possible to provide a method for manufacturing a 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 polyamide resin composition for laser direct structuring of the present invention (hereinafter sometimes referred to as “resin composition of the present invention”) is 1 to 30 parts by weight of a laser direct structuring additive with respect to 100 parts by weight of the polyamide resin. Including 1 to 30 parts by weight of zinc borate and 10 to 150 parts by weight of inorganic fiber, 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 the zinc borate It is characterized by being 100% by weight or less of the amount. By adopting such a configuration, it becomes possible to provide a resin molded product in which the plating is difficult to 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 easily roughened. The roughened resin molded product is presumed to have an anchor effect on plating. Furthermore, it is presumed that the glass fiber exposed when the resin on the surface of the resin molded product is carbonized also enters the plating side by adding the glass fiber, and further, the adhesion of plating of the resin molded product is improved. .
Furthermore, the growth rate of plating can be improved by using the resin composition of the present invention. This is presumably because the surface area of the LDS active region increases due to the roughening of the surface, and the metal seeds necessary for copper plating to grow increase.

<Polyamide resin>
The polyamide resin used in the present invention is not particularly defined, and a known polyamide resin can be used. For example, as the polyamide resin, descriptions in paragraphs 0011 to 0013 of JP2011-132550A can be referred to.
The polyamide resin may be a crystalline polyamide resin or an amorphous polyamide resin, but a crystalline polyamide resin is preferred. When the crystalline polyamide resin is used, the resin molded product can be hardened more quickly, so that the unevenness can be more effectively formed on the surface of the resin molded product. For this reason, the adhesiveness of a resin molded product and plating can be improved more.

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

In the polyamide resin used in the present invention, at least one kind 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 xylylenediamine, and dicarboxylic acid A polyamide resin in which 70 mol% or more of the derived structural unit is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (hereinafter sometimes referred to as “xylylenediamine-based polyamide resin”) preferable.
The structural unit derived from diamine of the xylylenediamine 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. 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.
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 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. .

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.
Melting | fusing point is measured in accordance with the method as described in the Example mentioned later.

  In the polyamide resin, the lower limit of the number average molecular weight (Mn) is preferably 6,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, and 15,000 or more. Is more preferably 20,000 or more, and further preferably 22,000 or more. The upper limit of the 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, the 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 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.

  The resin composition of the present invention may or may not contain a thermoplastic resin other than the polyamide resin. In the resin composition of the present invention, the content of the thermoplastic resin other than the polyamide resin is preferably 5% by weight or less, more preferably 3% by weight or less, and more preferably 1% by weight of the resin composition of the present invention. More preferably, it is as follows.

<Laser direct structuring additive (LDS additive)>
The resin composition of the present invention contains a laser direct structuring (LDS) additive. The LDS additive in the present invention is 10 parts by weight of an additive considered to be an LDS additive with respect to 100 parts by weight of a polyamide resin, and a YAG laser having a wavelength of 1064 nm is used. The output is 10 W, the frequency is 80 kHz, and the speed is 3 m / s. The subsequent plating process is performed in an electroless MacDermid M-Copper 85 plating tank, and refers to a compound that can form plating when a metal is applied to the laser irradiated surface. 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 weight of copper. Moreover, it is preferable that 15-50 weight% 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 having a content of metal oxide other than copper chromium oxide of 10% by weight 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 weight 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 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 were doped. 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 weight. In the LDS additive containing antimony and tin oxide, the content of antimony is preferably 1 to 20% by weight. In the LDS additive containing phosphorus, antimony and tin oxide, the phosphorus content is preferably 0.5 to 10% by weight, and the antimony content is preferably 0.5 to 10% by weight.

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 lower limit, For example, 1 * 10 < ¹ > ohm * cm or more may be sufficient, and 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 kinds of 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 weight or more of the metal component contained in the LDS additive is composed of the group n metal content and the group n + 1 metal 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.), group 14 (germanium, tin, etc.), group 15 (arsenic, antimony, etc.), and group 16 (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, and calcium. These metals may exist as oxides. The content 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 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. By setting it as such an average particle diameter, the surface of 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. It is. 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. As will be described later, by combining with talc, plating can be formed 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, when plating is formed on a resin molded product, the plating is difficult to peel off, 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 can be achieved only when zinc borate is used without being exhibited by other flame retardant aids (for example, magnesium hydroxide and zinc stannate).
In this invention, 1-30 weight part of zinc borate is included with respect to 100 weight part of polyamide resins. 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 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 to zinc borate is preferably 0.1 to 3.0 with respect to the LDS additive 1, and preferably 1.0 to 3.0. Is more preferable, and it is more preferable that it is 1.5-2.6. 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 an embodiment of the present invention, another flame retardant aid is exemplified by a form in which the amount of zinc borate is 5% by weight or less, further 3% by weight or less, particularly 1% by weight or less.

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

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 converged and cut to a predetermined length is preferable. .
The inorganic 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 inorganic 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 inorganic 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 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.
In addition, 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 semicircles are combined on both short sides of the rectangle, or an eyebrow shape, 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.
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 even more preferably 7.5 μm or less. By using inorganic fibers having a number average fiber diameter in such a range, a resin molded article having excellent 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. In addition, the number average fiber diameter of the inorganic fiber is obtained by randomly extracting the glass fiber to be measured for the fiber diameter from the image obtained by observation with an electron microscope and measuring the fiber diameter 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.

Next, the glass fiber preferably used in the present invention will be described.
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, it can be used as long as it can be made into glass fiber, and 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 The adhesion amount of the surface treatment agent is preferably 0.01 to 1% by weight of the 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, T286H, T56H, T289H, Owens Corning, DEFT2A, PPG, HP3540, Nittobo, CSG3PA820, and the like.

The content of inorganic fibers in the resin composition of the present invention has a lower limit of 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 still more preferably 70 parts by weight or less.
The resin composition of the present invention may contain only one kind of inorganic fiber, or may contain two or more kinds. When 2 or more types are included, the total amount is preferably within the above range.

  In the resin composition of the present invention, the total amount of the polyamide resin and the inorganic fibers preferably occupies 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 blending talc, dimensional stability and product appearance can be improved, and by blending talc, the plating growth rate can be further increased. Furthermore, by blending talc, 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, the adhesion amount of the siloxane compound in talc is preferably 0.1 to 5% by weight 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.

When blended, 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, further preferably 100 parts by weight of polyamide resin. 5 to 20 parts by weight.
When blended, the content of talc in the resin composition of the present invention is preferably 0.1 to 200 parts by weight and more preferably 1 to 150 parts by weight with respect to 100 parts by weight of the LDS additive. Preferably, it is 20-120 weight part, More preferably, it is 80-120 weight part. 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 mold release agent is mainly used for improving the productivity at the time of molding the resin composition. Examples of the release agent include aliphatic carboxylic acid amides, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oils, and the like. Can be mentioned. Among these release agents, carboxylic acid amide compounds are particularly preferable.

Examples of the aliphatic carboxylic acid amide system include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and / or a polybasic acid and a diamine.
Details of the mold release agent can be referred to the descriptions in paragraphs 0037 to 0042 of JP-A-2006-196563 and paragraphs 0048 to 0058 of JP-A-2006-078318, the contents of which are incorporated herein. .

  The content of the release agent, when blended, is preferably 0.001% by weight or more, more preferably 0.01% by weight or more with respect to the resin composition, and the upper limit is Preferably it is 2 weight% or less, More preferably, it is 1.5 weight% 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 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 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 contained, the content of the heat stabilizer is preferably 0.01 to 5 parts by weight, and 0.03 to 4 parts by weight, with respect to 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 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 resin composition of the present invention may contain an organic and / or inorganic light stabilizer.
Examples of 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 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 to 5 parts by weight and more preferably 0.01 to 4 parts by weight with respect to 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 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.
In the resin composition of the present invention, the alkali content depends on the type of LDS additive and the type of alkali, but is preferably 0.01 to 20% by weight, more preferably the content of the LDS additive. Is 0.05 to 15% by weight.

<Other additives>
The resin composition of the present invention may contain other components in addition to the above. Other components include elastomers, fillers other than inorganic fibers, titanium oxide, antioxidants, hydrolysis resistance improvers, matting agents, UV absorbers, nucleating agents, plasticizers, dispersants, antistatic agents, coloring Examples thereof include an inhibitor, an antigelling agent, and a colorant. 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 weight or less of the resin composition. Each of these components may be used alone or in combination of two or more.
In the resin composition of the present invention, 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. 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 the zinc borate. More preferably, the flame retardant content in the resin composition is substantially zero. Examples of the flame retardant include a phosphorus-based flame retardant and a halogen-based flame retardant.

<Method for producing resin composition>
Arbitrary methods are employ | adopted as a manufacturing method of the resin composition of this invention.
For example, a method of mixing polyamide resin, inorganic fiber, LDS additive, etc. using a mixing means such as a V-type blender to prepare a batch blend, and then melt-kneading with a vented extruder to pelletize. . Alternatively, as a two-stage kneading method, components other than inorganic fibers, etc., are mixed in advance and then melt-kneaded with a vented extruder to produce pellets, and then the pellets and inorganic fibers are mixed and then vented The method of melt-kneading with an extruder is mentioned.
Further, a component in which components other than the inorganic fibers are sufficiently mixed with a V-type blender is prepared in advance, and is supplied from the first chute of the twin screw extruder with a vent. A method of supplying from two chutes and melt-kneading and pelletizing can be mentioned.

As for the screw configuration of the kneading zone of the extruder, it is preferable that the element that promotes kneading is arranged on the upstream side, and the element having a boosting ability is arranged on the downstream side.
Examples of elements that promote kneading include a progressive kneading disk element, an orthogonal kneading disk element, a wide kneading disk element, and a progressive mixing screw element.

  The heating temperature at the time of melt kneading can be appropriately selected from the range of usually 180 to 360 ° C. If the temperature is too high, decomposition gas tends to be generated, which may cause extrusion failure such as strand breakage. 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 resin composition of the present invention. The resin molded product of the present invention preferably has a partial surface roughness Ra of 4.0 μm or more, more preferably 4.2 μm or more, and even more preferably 5.0 μm or more. The upper limit value of the surface roughness Ra is, for example, 7.0 μm or less, and may be 6.5 μm or less. Thus, a part with 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. Thus, by increasing the surface roughness only in a part of the region irradiated with the laser, a resin molded product having excellent appearance and high adhesion to the plating can be obtained.

  The method for producing a resin molded product in the present invention 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 resin composition of the present invention is preferably used as a resin molded product with plating 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 includes forming a plating by applying a metal to the surface of a resin-molded article obtained by molding the resin composition of the present invention after laser irradiation is disclosed. 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 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 YAG 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, plating (circuit) having an interval of a width of 1 mm or less, further 150 μm or less (the lower limit is not particularly defined, but 30 μm or more, for example) can be formed. In order to suppress corrosion and deterioration of the formed plating (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.

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

  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.

The following raw materials were used.
<Synthesis of polyamide resin PXD10>
8950 g (44.25 mol) of sebacic acid (made by Ito Oil Co., Ltd., Sebacic acid TA) precisely weighed in a reaction vessel equipped with a stirrer, a condenser, a cooler, a thermometer, a dropping device and a nitrogen introduction 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 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, and the pressure was reduced to 0.08 MPa over 20 minutes. 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, and the polymer was taken out from the strand die in a strand shape at a reaction vessel internal temperature of 301 ° C. and a resin temperature of 301 ° C., and cooled with 20 ° C. cooling water, and pelletized. The melting point of the obtained polyamide resin was 290 ° C.

<< Measurement of melting point >>
The melting point was measured as the peak top temperature of the endothermic peak at the time of temperature rise observed by DSC (Differential Scanning Calorimetry).
For the measurement, a DSC measuring instrument was used, the sample amount was about 1 mg, nitrogen was flowed at 30 mL / min as the atmospheric gas, and the rate of temperature increase was from room temperature to a temperature higher than the expected melting point at 10 ° C./min. The melting point was determined from the temperature at the peak top of the endothermic peak observed when heated and melted.
As the DSC measuring instrument, DSC-60 manufactured by 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 full condenser, a thermometer, a dropping funnel and a nitrogen introducing tube, and a strand die, 12,135 g (60 mol) of sebacic acid precisely weighed, sodium hypophosphite monohydrate (NaH ₂ PO ₂ .H ₂ O) 3.105 g (phosphorus atom concentration in the polyamide resin 50 ppm by weight) and 1.61 g of sodium acetate were sufficiently substituted with nitrogen, and then 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.
To this, 7,172 g (60 mol) of a 7: 3 mixed diamine of metaxylylenediamine and paraxylylenediamine was added dropwise with stirring, and the system was continuously heated while removing the condensed water produced. . After completion of the dropwise addition of the mixed metaxylylenediamine, the melt polymerization reaction was continued for 40 minutes at an internal temperature of 260 ° C.
Thereafter, the inside of the system was pressurized with nitrogen, the polymer was taken out from the strand die, and pelletized. The resulting polyamide had a melting point of 215 ° C.

<Synthesis of polyamide resin MP6>
In a reaction vessel equipped with a stirrer, a partial condenser, a full condenser, a thermometer, a dropping funnel and a nitrogen introduction tube, and a strand die, 7.22 kg (49.4 mol) of adipic acid (Rodia) and sodium acetate / next After charging 11.66 g of sodium phosphite monohydrate (molar ratio = 1 / 1.5) and thoroughly replacing with nitrogen, heat to 170 ° C while stirring the system under a small amount of nitrogen. Melted.
6.647 kg of mixed xylylenediamine having a molar ratio of metaxylylenediamine and paraxylylenediamine of 70/30 (34.16 mol of metaxylylenediamine, 14.64 mol of paraxylylenediamine, manufactured by Mitsubishi Gas Chemical Company), The mixture was added dropwise to the melt in the reaction vessel with stirring, and the internal temperature was continuously raised to 240 ° C. over 2.5 hours while discharging the generated condensed water out of the system.
After completion of the dropping, the internal temperature was raised, and when the temperature reached 250 ° C., the pressure in the reaction vessel was reduced, and the internal temperature was further raised to continue the melt polycondensation reaction at 270 ° C. for 20 minutes. Thereafter, the inside of the system was pressurized with nitrogen, and the obtained polymer was taken out of the strand die and 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)
CP5C: antimony-doped tin oxide (95% by weight of tin oxide, 5% by weight of antimony oxide) (manufactured by Keeling & Walker)

<Zinc borate or alternatives>
Zinc borate: Firebrake ZB, manufactured by Borax Magnesium hydroxide: manufactured by Junsei Kagaku, special grade zinc stannate: Flametard-S, manufactured by Nippon Light Metal Co., Ltd.

<Flame Retardant>
Phosphazene FB-110: 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 (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, blended with a tumbler, except for glass fiber, and charged from the root of a twin-screw extruder (Toshiki Machine Co., Ltd., TEM26SS), After melting, glass fibers were side fed to produce pellets. The temperature setting of the twin screw extruder was 300 ° C.

<Surface roughness Ra>
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 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 the irradiation, Ra of the laser irradiation part was measured according to JIS B 0601. In the measurement, SURFCOM 3000A-3DF-STD manufactured by Tokyo Seimitsu Co., Ltd. was used. The results are shown in Table 1.
Moreover, it measured similarly about Ra of a laser unirradiated part.

<Plating peel strength>
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 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. The test piece was degreased with sulfuric acid and then treated with Kizai, THP Alkali Acti and THP Alkali Ax, and subjected to copper plating with a SEL copper made by Kizai. The integrated average value was calculated from the detected load when the obtained copper plating pattern was peeled 10 mm at a speed of 20 mm / min by a 90-degree peel test. For the measurement, a load cell 2 kN manufactured by Instron was used. The results are shown in Table 1.

<Plating growth rate>
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 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. The test piece was degreased with sulfuric acid and then treated with Kizai, THP Alkali Acti and THP Alkali Ax, and subjected to copper plating with a SEL copper made by Kizai. 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 locations.
About the film thickness of each Example and the comparative example, it was ratio with the film thickness of the 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, it changed as described in Table 1 or Table 2, and performed others similarly. The results are shown in Table 1 or Table 2.

As apparent 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 plating peeling strength can be increased and the plating can be made difficult to peel off.
Furthermore, the plating growth rate can be increased.
In contrast, when zinc borate is not added (Comparative Examples 1 and 2), when zinc borate is not added, and a compound known as a known flame retardant aid is blended instead (comparison) In Examples 4 and 5), the peeling strength of the plating decreased, and the plating was easily peeled off.
Further, when the amount of zinc borate exceeded the range of the present invention (Comparative Example 3), extrusion was difficult.
Further, even when zinc borate was added, when the flame retardant was also blended (Comparative Example 6), the plating peel strength was reduced and the plating was easily peeled off.

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

Claims (17)

Including 100 parts by weight of polyamide resin, 1-30 parts by weight of laser direct structuring additive, 1-30 parts by weight of zinc borate and 10-150 parts by weight of inorganic fiber,
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 structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, 70 mol% or more of the structural unit derived from the diamine is derived from xylylenediamine, and a structural unit derived from a dicarboxylic acid The polyamide resin composition for laser direct structuring according to any one of claims 1 to 3, wherein 70 mol% or more of is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. . The polyamide resin composition for laser direct structuring according to any one of claims 1 to 5, comprising 10 to 30 parts by weight of the zinc borate with respect to 100 parts by weight of the polyamide resin. Furthermore, the polyamide resin composition for laser direct structuring of any one of Claims 1-6 which contains 0.1-200 weight part with respect to 100 weight part of laser direct structuring additives. The polyamide resin composition for laser direct structuring according to any one of claims 1 to 7, wherein the polyamide resin has a melting point of 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 of the inorganic fiber with respect to 100 parts by weight of the polyamide resin. The resin molded product formed by shape | molding the polyamide resin composition for laser direct structuring of any one of Claims 1-9. The resin molded product according to claim 10, wherein a part of the surface roughness Ra of the resin molded product is 4.0 μm or more and another part of the surface roughness Ra is 1.0 μm or less. The resin molded product according to claim 10 or 11, wherein the surface of the resin molded product has plating. The resin molded product according to claim 12, wherein the plating retains performance as an antenna. The resin molded product according to any one of claims 10 to 13, which is a portable electronic device component. Applying a metal 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, and then forming a plating. The manufacturing method of the resin molded product with plating containing. The manufacturing method of the resin molded product with plating of Claim 15 whose said plating is copper plating. The manufacturing method of the portable electronic device component which has an antenna including the manufacturing method of the resin molded product with plating of Claim 15 or 16.