JP6131151B2 - Polyamide resin composition, resin molded product, and method for producing resin molded product with plating layer - Google Patents

Description

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

  In recent years, techniques for providing various electronic device parts (plated layers) such as conductive circuits on the surface of resin molded products have been widely studied. As such a technique, a laser direct structuring (hereinafter, sometimes referred to as “LDS”) technique has attracted attention. In the LDS technique, for example, the surface of a resin molded product containing an LDS additive is irradiated with a laser, only a portion irradiated with the laser is activated, and a plating layer is formed by applying a metal to the activated portion. Technology. Such LDS technology is disclosed in, for example, Patent Documents 1 to 3 and the like.

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

  Here, it has been found that when a conductive circuit is provided on the surface of a resin molded product containing the LDS additive, there may be a problem in conduction. Further examination by the present inventor has revealed that one of the causes of this poor conduction is the adhesion between the resin molded product and the conductive circuit (plated layer). In particular, it has been found that there is a problem in adhesion when placed in a humid atmosphere or at a high temperature. The present invention aims to solve such problems, and provides a resin molded product with a plated layer that can form a plated layer appropriately and has excellent adhesion between the resin molded product and the plated layer. An object of the present invention is to provide a polyamide resin composition that can be used.

Under such circumstances, as a result of investigations by the present inventors, it has been found that the above-mentioned problems can be solved by employing a specific polyamide resin. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <15>.
<1> 20 to 150 parts by weight of glass fiber and laser with respect to 100 parts by weight of polyamide resin component containing 50% by weight or more of polyamide resin (A) having a saturated water absorption rate of 4% by weight or less when immersed in water A polyamide resin composition comprising 1 to 30 parts by weight of a direct structuring additive.
<2> The polyamide resin composition according to <1>, wherein the polyamide resin (A) includes an aromatic ring in a molecule, and a ratio of carbon atoms constituting the aromatic ring to the molecule is 30 mol% or more.
<3> The polyamide resin composition according to <1> or <2>, containing 0.1 to 20 parts by weight of talc with respect to 100 parts by weight of the polyamide resin composition.
<4> The plate filler having an aspect ratio of 3 or more and an average particle size of 50 μm or less is contained in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin composition, according to any one of <1> to <3>. Polyamide resin composition.
<5> The polyamide resin composition according to any one of <1> to <4>, wherein a cross section of the glass fiber is a longitudinal glass fiber having a flatness ratio of 2.5 or more according to the following formula.
Flatness ratio = glass fiber major axis D2 / glass fiber minor axis D1
<6> The polyamide resin (A) is a polyamide resin in which 70 mol% or more of diamine structural units are derived from xylylenediamine units and 50 mol% or more of dicarboxylic acid structural units are derived from sebacic acid, The range amine unit is a polyamide resin containing 20 to 100 mol% of a paraxylylenediamine-derived unit and 0 to 80 mol% of a metaxylylenediamine-derived unit, according to any one of <1> to <5>. Polyamide resin composition.
<7> The polyamide resin component according to any one of <1> to <6>, wherein 90% by weight or more of the polyamide resin component is a polyamide resin (A) having a saturated water absorption rate of 4% by weight or less when immersed in water. Polyamide resin composition.
<8> The polyamide resin composition according to any one of <1> to <7>, wherein the laser direct structuring additive contains copper.
<9> A resin molded product obtained by molding the polyamide resin composition according to any one of <1> to <8>.
<10> The resin molded product according to <9>, further having a plating layer on the surface.
<11> The resin molded product according to <9> or <10>, which is a portable electronic device part.
<12> The resin molded product according to <10> or <11>, wherein the plated layer has performance as an antenna.
<13> Forming a plating layer by applying a metal to a surface of a resin molded product obtained by molding the thermoplastic resin composition according to any one of <1> to <8>, after irradiating a laser. The manufacturing method of the resin molded product with a plating layer containing.
<14> The method for producing a resin molded product with a plating layer according to <13>, wherein the plating layer is a copper plating layer.
<15> A method for manufacturing a portable electronic device component having an antenna, including the method for manufacturing a resin-molded article with a plated layer according to <13> or <14>.

  According to the present invention, it is possible to provide a resin molded product with a plated layer that can form a plated layer appropriately and has excellent adhesion between the resin molded product and the plated layer.

It is the schematic which shows the process of providing plating on the surface of a resin molded product. In FIG. 1, 1 indicates a resin molded product, 2 indicates a laser, 3 indicates a portion irradiated with the laser, 4 indicates a plating solution, and 5 indicates a plating layer.

  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 of the present invention contains 50% by weight or more of a polyamide resin (A) (hereinafter sometimes referred to as “polyamide resin (A)”) having a saturated water absorption of 4% by weight or less when immersed in water. Further, it is characterized by containing 20 to 150 parts by weight of glass fiber and 1 to 30 parts by weight of LDS additive with respect to 100 parts by weight of the polyamide resin component.
By adopting such a polyamide resin composition, it is possible to appropriately form a plating layer, and a resin molded product with a plating layer is subjected to high humidity (after saturation in water) or high temperature (after heating and cooling). In this case, the adhesion between the plating layer and the resin molded product can be maintained. Details of the present invention will be described below.

<Polyamide resin>
The polyamide resin used in the present invention has a saturated water absorption of 4% by weight or less when 50% by weight or more is immersed in water. By adopting such a polyamide resin (A), due to the reason (mechanism) that the water absorption dimensional change after molding becomes small, it is possible to appropriately form a plating, and even after saturation in water or after heating and cooling, It becomes possible to maintain the adhesion between the plating layer and the resin molded product. Here, the saturated water absorption rate when immersed in water refers to the water absorption rate measured by the method described in Examples described later. The saturated water absorption of the polyamide resin (A) used in the present invention is preferably 3.5% by weight or less.
In the polyamide resin used in the present invention, the proportion of the polyamide resin (A) is 50% by weight or more, preferably 90% by weight or more, and more preferably 99% by weight or more. The polyamide resin (A) may be only one type or two or more types. In the case of two or more types, the total amount is in the above range.

  The polyamide resin (A) used in the present invention is not particularly defined as long as the saturated water absorption rate when immersed in water is 4% by weight or less. However, the polyamide resin (A) contains an aromatic ring in the molecule and has carbon atoms constituting the aromatic ring. The ratio in the molecule is preferably 30 mol% or more. By using such a polyamide resin, the water absorption is reduced, and it is possible to maintain the adhesion between the resin molded product and the plating layer after saturation of the resin molded product with a plating layer in water at a higher level. Become. The ratio of the aromatic ring is preferably 30 to 80 mol%, and more preferably 30 to 50 mol%.

  In the polyamide resin (A), 70 mol% or more of the diamine structural unit is derived from xylylenediamine units, more preferably 80 mol% or more, and 50 mol% or more, more preferably 70 mol% or more of the dicarboxylic acid structural unit. A polyamide resin derived from sebacic acid is preferred. Furthermore, the xylylenediamine unit preferably contains 20 to 100 mol% of paraxylylenediamine-derived units and 0 to 80 mol% of metaxylylenediamine-derived units, and 25 to 100 mol of paraxylylenediamine-derived units. %, Metaxylylenediamine-derived units are further preferably contained in an amount of 0 to 75 mol%.

Among the polyamide resin components contained in the polyamide resin composition of the present invention, the type of polyamide resin other than the polyamide resin (A) is not particularly defined, and a known polyamide resin can be used. Only one type of other polyamide resin may be used, or two or more types may be used.
As other polyamide resin, description of paragraph number 0011-0013 of Unexamined-Japanese-Patent No. 2011-132550 can be referred. Preferably, 50 mol% or more of the diamine structural unit (structural unit derived from diamine) is a polyamide resin derived from xylylenediamine. More than 50 mol% of the diamine is derived from xylylenediamine and is a xylylenediamine-based polyamide resin polycondensed with a dicarboxylic acid.
Preferably, 70 mol% or more, more preferably 80 mol% or more of the diamine structural unit is derived from metaxylylenediamine and / or paraxylylenediamine, and preferably a dicarboxylic acid structural unit (a structural unit derived from dicarboxylic acid). Is a xylylenediamine system derived from an α, ω-linear aliphatic dicarboxylic acid having 50 mol% or more, more preferably 70 mol% or more, particularly 80 mol% or more, preferably having 4 to 20 carbon atoms. Polyamide resin. Adipic acid, sebacic acid, suberic acid, dodecanedioic acid, eicodioic acid and the like can be preferably used as the 4-20 α, ω-linear aliphatic dibasic acid.

  The amount of the polyamide resin component (the total of the polyamide resin (A) and the other polyamide resin) in the polyamide resin composition of the present invention is preferably 50 to 100% by weight, and preferably 70 to 100% by weight. Is more preferable.

<Glass fiber>
The polyamide resin composition of the present invention preferably contains 20 to 150 parts by weight of glass fiber and 35 to 110 parts by weight with respect to 100 parts by weight of the polyamide resin component. Only one type of glass fiber may be used, or two or more types may be used. In the case of two or more types, the total amount is in the above range. By including such glass fibers, it is possible to improve the mechanical strength of the resin molded product, to reduce the linear expansion coefficient, and to maintain high adhesion even after heating and cooling.
Here, the glass fiber refers to glass whose appearance is fibrous.

  The glass fiber preferably used in the present invention preferably has an average diameter of 20 μm or less, and further 1 to 15 μm further increases the balance of physical properties (strength, rigidity, heat-resistant rigidity, impact strength) and molding. This is preferable in that the warpage is further reduced. In general, a glass fiber having a circular cross section is generally used, but in the present invention, a flat fiber is particularly preferably used. By using a flat product, the linear expansion coefficient in the direction perpendicular to the flow direction of the obtained molded product and the water absorption dimensional change are reduced, so that the resin molded product with a plating layer is saturated in water. It is possible to maintain the adhesion of the plating layer at a higher level.

  The length of the glass fiber is not specified and can be selected from a long fiber type (roving), a short fiber type (chopped strand), or the like. In this case, the number of focusing is preferably about 100 to 5000. Further, if the average length of the glass fiber in the polyamide resin composition after kneading the polyamide resin composition can be obtained with an average of 0.1 mm or more, so-called milled fiber, a pulverized product of strands called glass powder may be used, It may be a continuous single fiber sliver. The composition of the raw material glass is preferably non-alkali, and examples thereof include E glass, C glass, and S glass. In the present invention, E glass is preferably used.

  The glass fiber is preferably surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. The adhesion amount is usually 0.01 to 1% by weight of the glass fiber weight. Furthermore, if necessary, a lubricant such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin or a urethane resin, a resin having a film forming ability and a heat. What was surface-treated with a mixture of a stabilizer, a flame retardant, etc. can also be used.

In the present invention, glass fibers having a flat cross section can be preferably employed. By adopting a flat cross-section, the linear expansion coefficient in the direction perpendicular to the flow direction of the obtained molded product and the water absorption dimensional change are reduced, so that the resin after saturating the resin molded product with a plating layer in water It becomes possible to maintain the adhesion between the molded product and the plated layer at a higher level.
As the glass fiber having a flat cross section, a glass fiber having a longitudinal shape with a flatness ratio of 2.5 or more (hereinafter sometimes referred to as “flat cross section glass fiber”) is preferable. Here, the flat cross section is a non-circular cross section whose cross section is not a normal circular shape, such as a rectangle, an oval close to a rectangle, an ellipse, or a saddle type with a narrowed central portion in the longitudinal direction. What is shown by FIG. 1 of the Kaihei 7-41670 gazette etc. is mentioned. The flatness in the present invention is expressed as follows when the major axis is D2, the minor axis is D1, and the degree of flatness of the reinforcing fibers is the flatness.
Flatness ratio = glass fiber major axis D2 / glass fiber minor axis D1

  The major axis (D2) and minor axis (D1) of the glass fiber cross-section for calculating the flatness ratio are specifically used if there is a nominal value according to the above definition of the manufacturer, but if there is no cross-section, It is obtained by measuring the actual size from the photomicrograph.

  The flatness ratio (D2) / (D1) of the flat cross-section glass fiber used in the polyamide resin composition of the present invention is more preferably 2.5 to 10, still more preferably 3 to 10, and particularly preferably 3.1 to 6. . Further, since the glass fiber is crushed by a load applied to the glass fiber during mixing, kneading, and molding with a resin or the like, and the actual flatness in the molded product may be reduced, the flatness need not be so high.

  In the present invention, the major axis (D2) and minor axis (D1) of the cross section of the flat glass fiber are arbitrary, but the major axis (D2) is 1.25 to 300 μm and the minor axis (D1) is 0.5 to 25 μm. It is preferable that By making the major axis and minor axis within the above ranges, it is preferable because spinning of the glass fiber is facilitated, and the contact area between the resin and the glass fiber surface is reduced and the strength of the molded product can be suppressed from being lowered. In the present invention, it is more preferable that the minor axis (D1) is 3 μm or more, and it is particularly preferable that the minor axis (D1) is 3 μm or more and the major axis (D2) / minor axis (D1) is larger than 3. .

  The flat cross-section glass fiber in the present invention can be produced by using a method described in, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775. In particular, in an orifice plate having a large number of orifices on the bottom surface, an outer peripheral portion of an orifice plate surrounding a plurality of orifice outlets and having a convex edge extending below the bottom surface of the orifice plate, or a nozzle tip having one or more orifice holes Flat cross-section glass fibers manufactured using a modified cross-section glass fiber spinning nozzle tip provided with a plurality of convex edges extending downward from the tip are preferred.

<Laser direct structuring additive>
The polyamide resin composition of the present invention contains an LDS additive. The compounding amount of the LDS additive in the polyamide resin composition of the present invention is 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 10 to 18 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. Only one type of LDS additive may be used, or two or more types may be used in combination. In the case of two or more types, the total amount is in the above range.

  The LDS additive in the present invention is obtained by adding 4 parts by weight of an additive considered to be an LDS additive to 100 parts by weight of PA-MP6 (PAMP6 synthesized in Examples described later), and a YAG laser having a wavelength of 1064 nm. , With an output of 10 W, a frequency of 80 kHz, and a scanning speed of 3 m / s. After that, the plating process was performed in an electroless MacDermid MIDCopper100XB Strike plating tank, and metal was applied to the laser irradiation surface. Refers to a compound capable of forming a plating. The LDS additive used in the present invention may be a synthetic product or a commercial product. Moreover, as long as the commercially available product satisfies the requirements for the LDS additive in the present invention, it may be a material sold for other uses as well as those marketed as LDS additives.

The LDS additive used in the present invention preferably contains copper. Of the metal components in the LDS additive, the copper content is preferably 20 to 95% by weight. Preferable examples of the LDS additive containing copper include Cu ₃ (PO ₄ ) ₂ Cu (OH) ₂ and CuCr ₂ O ₄ . When the LDS additive containing copper is used, the adhesion between the resin molded product and the plating layer is excellent, so the adhesion between the resin molded product and the plating layer after saturation of the resin molded product with a plating layer in water is higher. It becomes possible to maintain at. In particular, when the blending amount of the LDS additive is 10 parts by weight or more with respect to 100 parts by weight of the polyamide resin component, the effect becomes more remarkable.

The polyamide resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include talc, plate filler, heat stabilizer, light stabilizer, alkali, mold release agent, other resin components, antioxidant, ultraviolet absorber, flame retardant, dye pigment, fluorescent whitening Agents, anti-dripping agents, antistatic agents, anti-fogging agents, lubricants, anti-blocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like.
Moreover, these components may use only 1 type and may use 2 or more types together.

<Talc>
The polyamide resin composition of the present invention may contain talc. In the present invention, the addition of talc can be added because the plating property is improved.
The blending amount of talc in the polyamide resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin composition. Preferably, it is 0.3-5 weight part. Only one type of talc may be used, or two or more types may be used in combination. In the case of two or more types, the total amount is in the above range.

<Plate filler>
The polyamide resin composition of the present invention may contain a plate-like filler. In the polyamide resin composition of the present invention, the amount of the plate-like filler is preferably 1 to 150 parts by weight, more preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the polyamide resin composition. More preferably, it is 20-70 weight part. Only one type of plate-like filler may be used, or two or more types may be used in combination. In the case of two or more types, the total amount is in the above range.

Here, the plate-like filler means inorganic or organic flat fine particles.
The average particle diameter of the plate-like filler is a flat plate structure, preferably 50 μm or less, more preferably 5 to 30 μm.
Further, the aspect ratio of the plate filler is preferably 3 or more, and more preferably 5-20.
By using a plate-like filler that satisfies the above average particle diameter and aspect ratio, the linear expansion coefficient in the flow perpendicular direction of the obtained molded product, and the water absorption dimensional change are reduced, so that the resin molded product with a plating layer is submerged in water. It becomes possible to maintain the adhesion between the resin molded product after saturation and the plating layer at a higher level.

  Examples of the plate filler include glass flake, mica, talc, clay, graphite, sericite, montmorillonite, plate calcium carbonate, plate alumina and the like. Among these, glass flakes, mica, and talc are preferred from the viewpoint of the balance of bending characteristics, impact resistance, dimensional stability, fluidity, and product appearance. Since portable electronic device parts are often required to have particularly high impact resistance, it is most preferable to use glass flakes having the highest impact resistance.

As glass flakes suitable as a plate-like filler, those having an E glass composition and a C glass composition are available as general commercial products. The average particle diameter varies depending on the grade of each company, but is preferably a flat glass having a size of 50 μm or less. Moreover, you may use together 2 or more types of glass flakes from which an average particle diameter differs.
Furthermore, the surface treatment is preferably performed with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like. The amount is usually 0.01% by weight or more of the glass flake weight.

<Heat stabilizer>
The polyamide resin composition of the present invention may further contain an organic and / or inorganic heat stabilizer, and more preferably contains an organic 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.
One type of heat stabilizer may be used, or two or more types may be used in combination.

  Although it does not specifically limit as a phenolic compound, For example, a hindered phenolic compound can be mentioned. Examples of the hindered phenol compound include N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), pentaerythrityl-tetrakis. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) , Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl-4-hydroxy- 5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3,5-di-tert-butyl-4- Roxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and 1,3,5-tris (4 -T-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid and the like.

  The phosphite compound is not particularly limited, and examples thereof include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, phenyl diisodecyl phosphite, phenyl diphosphite. (Tridecyl) phosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) ) Phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylpheny) -Tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, 4,4'-isopropylidenebis (2-t-butylphenyl) .di (nonylphenyl) Phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite, tetra (tridecyl) -4, 4'-butylidenebis (3-methyl-6-t-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tris (mono, dimixed nonylphenyl) phosphite 4,4′-isopropylidenebis (2-t-butylphenyl) · di (noni Ruphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t-butyl-4-hydroxyphenyl) Phosphite, hydrogenated-4,4′-isopropylidene diphenyl polyphosphite, bis (octylphenyl) · bis (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl)), 1,6- Hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) diphosphite, tris (4,4′-isopropylidenebis (2-tert-butyl) Phenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2,2-methylenebis (4,6-di-t) Butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) ) -4,4′-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite.

  Although it does not specifically limit as a phosphite type compound, For example, a pentaerythritol type phosphite compound can also be mentioned. Examples of pentaerythritol-type phosphite compounds include 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl Methyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl, 2-ethylhexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl isodecyl, Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl isotridecyl pentaerythritol diphos Phyto, 2,6-di-t-butyl-4-methylphenyl stearyl Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl benzyl pentaerythritol diphos Phyto, 2,6-di-t-butyl-4-methylphenyl / ethylcellosolve / pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl / butylcarbitol / pentaerythritol diphosphite 2,6-di-t-butyl-4-methylphenyl octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl nonylphenyl pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) Intererythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2,6-di- t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2,4-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t -Butyl-4-methylphenyl · 2,4-di-t-octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2-cyclohexylphenyl · pentaerythritol diphosphite 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol diphosphite, bis (2 , 6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite, and the like.

  Pentaerythritol phosphite compounds include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-butyl-4-ethylphenyl). Pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite Phosphite and the like are preferable, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferable.

  The hindered amine compound is not particularly limited, and examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetra Methylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetra Methylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetra Tilpiperidine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) Oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6 , 6-Tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis 2,2,6,6-tetramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2 , 2,6,6-tetramethyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate , Tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene -1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5 -Di-t-butyl-4-hydroxy Phenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β , Β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol and the like.

Although it does not specifically limit as a triazine type compound, For example, hydroxyphenyl triazine is mentioned.
Examples of the hydroxyphenyltriazines include 2,4,6-tris (2′-hydroxy-4′-octyloxy-phenyl) -1,3,5-triazine, 2- (2′-hydroxy-4′- Hexyloxy-phenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2′-hydroxy-4′-octyloxyphenyl) -4,6-bis (2 ′, 4′-dimethylphenyl) ) -1,3,5-triazine, 2- (2 ′, 4′-dihydroxyphenyl) -4,6-bis (2 ′, 4′-dimethylphenyl) -1,3,5-triazine, 2,4 -Bis (2'-hydroxy-4'-propyloxy-phenyl) -6- (2 ', 4'-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) ) -4,6-bis (4′-methyl) Phenyl) -1,3,5-triazine, 2- (2′-hydroxy-4′-dodecyloxyphenyl) -4,6-bis (2 ′, 4′-dimethylphenyl) -1,3,5-triazine 2,4,6-tris (2′-hydroxy-4′-isopropyloxyphenyl) -1,3,5-triazine, 2,4,6-tris (2′-hydroxy-4′-n-hexyloxy) Phenyl) -1,3,5-triazine, 2,4,6-tris (2′-hydroxy-4′-ethoxycarbonylmethoxyphenyl) -1,3,5-triazine and the like.

  Although it does not specifically limit as a sulfur type compound, For example, pentaerythrityl tetrakis (3-lauryl thiopropionate), dilauryl-3,3'- thiodipropionate, dimyristyl-3,3'- Examples thereof include thiodipropionate and distearyl 3,3′-thiodipropionate.

  As an example of the inorganic heat stabilizer, a metal hydroxide is preferable, and magnesium hydroxide, calcium hydroxide, and antimony trioxide are exemplified. In particular, when an alkali is added as an inorganic heat stabilizer when the LDS additive is an acidic substance, it can also serve as an alkali component for making the color of the LDS additive described later uniform. Moreover, such an alkali may also work as a heat stabilizer.

  The content of the heat stabilizer is preferably 0.01 parts by weight to 5 parts by weight and more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the polyamide resin composition of the present invention. 0.03 to 2 parts by weight 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 polyamide resin composition of the present invention preferably contains an organic and / or inorganic light stabilizer, and more preferably contains an organic 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 the light stabilizer, one kind may be used, or two or more kinds may be used in combination.

  The benzophenone-based compound is not particularly limited, and examples thereof include 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4, Examples include 4′-dimethoxybenzophenone, 2,2′4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone.

  The salicylate-based compound is not particularly limited, and examples thereof include phenyl salicylate, pt-butylphenyl salicylate, and p-octylphenyl salicylate.

  Although it does not specifically limit as a benzotriazole type compound, For example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-) Hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) Benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butyl) Phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-aminophenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 '' , 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl} benzotriazole, 2,2-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H— Benzotriazol-2-yl) phenol}, 6- (2-benzotriazolyl) -4-t-octyl-6′-t-butyl-4′-methyl-2,2′-methylenebisphenol, etc. It is done.

  The cyanoacrylate compound is not particularly limited, and examples thereof include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate and ethyl-2-cyano-3,3′-diphenyl acrylate. Can be mentioned.

  Although it does not specifically limit as a hindered amine type compound, For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4) -Piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-t-butyl-4-hydroxybenzyl malonate, 1- (2-hydroxyethyl) -2,2 , 6,6-Tetramethyl-4-hydroxypiperidine and succinic acid condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine And a linear or cyclic condensate of 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) -bis (3,3, 5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2, 2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-t-butylbenzyl) malonate, 3-n-octyl-7,7,9,9 -Tetramethyl-1,3,3 8-Triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6, 6-tetramethylpiperidyl) succinate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide, N, N′-bis (2,2 , 6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6 A condensate of bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 2- Chloro-4,6 Condensation product of di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) ethane 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2 , 6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione , A mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa Methylenediamine and 4-cyclohexyl Condensates of Mino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4 -Condensate of butylamino-2,2,6,6-tetramethylpiperidine (CAS registry number [136504-96-6]); 1,6-hexanediamine and 2,4,6-trichloro-1,3 5-triazine and condensate of N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [192268-64-7]); N- (2,2, 6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7, 7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1- Reaction product of oxa-3,8-diaza-4-oxo-spiro [4.5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyl Oxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N′-bis-formyl-N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4 A diester of methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4 -Piperidyl)] siloxa Reaction product of maleic anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2 , 4-Bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -N-butylamino] -6- (2-hydroxyethyl) amino-1,3 5-triazine, 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5- (2-ethylhexanoyl) oxymethyl-3, 3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Registry Number [106917-31-1]), 5- ( -Ethylhexanoyl) oxymethyl-3,3,5-trimethyl-2-morpholinone, 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino]- The reaction product of 6-chloro-s-triazine and N, N′-bis (3-aminopropyl) ethylenediamine), 1,3,5-tris (N-cyclohexyl-N- (2,2,6,6) -Tetramethylpiperidin-3-one-4-yl) amino) -s-triazine, 1,3,5-tris (N-cyclohexyl-N- (1,2,2,6,6-pentamethylpiperazine-3) -On-4-yl) amino) -s-triazine, N, N ', N ", N' ''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) ami ) -Triazin-2-yl) -4,7-diazadecane-1,10 diamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2, 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like, Among them, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide, N, N ', N ", N '' '-Tetrakis- (4,6-bis- (butyl -(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10 diamine and the like.

  Although it does not specifically limit as a hindered phenol type compound, For example, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, N, N- Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide, triethylene glycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [ 5,5] undecane, 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4 Examples include 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (4-t-butyl-3hydroxy-2,6-dimethylbenzyl) isocyanate. .

  The content of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the polyamide resin composition of the present invention. 0.03 to 2 parts by weight is more preferable.

<Alkali>
The polyamide 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 one type of alkali may be used, or two or more types may be used in combination.
The blending amount of alkali in the polyamide resin composition of the present invention is preferably 0.01 to 10% by weight of the blending amount of the LDS additive, although it depends on the kind of LDS additive and the kind of alkali. Preferably it is 0.05-5 weight%.

<Release agent>
The polyamide resin composition of the present invention may contain a release agent.
Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like.

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

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

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

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

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.

  The content of the release agent is preferably 0.001 to 2 parts by weight, and more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the total of the polyamide resin and the glass fiber. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

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

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

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

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

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

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

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

As the resin molded product 1 in the present invention, a portable electronic device component is preferable. Portable electronic device parts have both high impact resistance, rigidity, and excellent heat resistance, as well as low anisotropy and low warpage. PDAs such as electronic notebooks and portable computers, pagers, and mobile phones. It is extremely effective as an internal structure and case such as a telephone and PHS. In particular, the molded product is suitable for flat-plate-shaped portable electronic device parts whose average thickness excluding ribs is 1.2 mm or less (the lower limit is not particularly defined, for example, 0.4 mm or more). Particularly suitable as a housing.
Returning to FIG. 1 again, in the method for producing a resin molded product with a plated layer of the present invention, the resin molded product 1 is irradiated with a laser 2.

  The laser 2 is not particularly limited, and can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and electromagnetic radiation, and a YGA laser is particularly preferable. Further, the wavelength of the laser 2 is not particularly limited. The wavelength range of the preferable laser 2 is 200 nm to 1200 nm, and particularly preferably 800 to 1200 nm.

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

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

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

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

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

<Polyamide resin>
<Production Example 1>
(Synthesis of polyamide (PAMP6))
After adipic acid is heated and dissolved in a reactor under a nitrogen atmosphere, the contents are stirred and paraxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) While gradually adding a mixed diamine having a molar ratio of 3: 7 under pressure (0.35 Mpa) so that the molar ratio of diamine and adipic acid (manufactured by Rhodia) is about 1: 1, Was raised to 270 ° C. After completion of the dropping, the pressure was reduced to 0.06 MPa and the reaction was continued for 10 minutes to adjust the amount of the component having a molecular weight of 1,000 or less. Thereafter, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain polyamide. Hereinafter, it is referred to as “PAMP6”.

<Production Example 2>
(Synthesis of polyamide (PAMP10))
After heating and dissolving sebacic acid in a reactor under a nitrogen atmosphere, while stirring the contents, paraxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) The temperature was raised to 235 ° C. while gradually adding a mixed diamine having a molar ratio of 3: 7 under pressure (0.35 Mpa) so that the molar ratio of diamine to adipic acid was about 1: 1. I let you. After completion of the dropping, the reaction was continued for 60 minutes to adjust the amount of the component having a molecular weight of 1,000 or less. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain polyamide. Hereinafter, it is referred to as “PAMP10”.

<Production Example 3>
(Synthesis of polyamide (PAP10))
A sebacic acid (made by Ito Oil Co., Ltd., product name Sebacin) precisely weighed in a reaction vessel having an internal volume of 50 liters equipped with a stirrer, a condenser, a cooler, a thermometer, a dropping device and a nitrogen introduction tube, and a strand die Acid TA) 8950 g (44.25 mol), calcium hypophosphite 12.54 g (0.074 mol), and sodium acetate 6.45 g (0.079 mol) were weighed and charged. After sufficiently purging the inside of the reaction vessel with nitrogen, the pressure was increased to 0.4 MPa with nitrogen, the temperature was raised from 20 ° C. to 190 ° C. with stirring, and sebacic acid was uniformly melted in 55 minutes. Next, 5960 g (43.76 mol) of paraxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) was added dropwise over 110 minutes with stirring. During this time, the internal temperature of the reaction vessel was continuously increased to 293 ° C. In the dropping step, the pressure was controlled to 0.42 MPa, and the generated water was removed from the system through a partial condenser and a cooler. The temperature of the partial condenser was controlled in the range of 145 to 147 ° C. After completion of dropwise addition of paraxylylenediamine, the polycondensation reaction was continued for 20 minutes at a reaction vessel internal pressure of 0.42 MPa. During this time, the temperature inside the reaction vessel was raised to 296 ° C. Thereafter, the internal pressure of the reaction vessel was reduced from 0.42 MPa to 0.12 MPa over 30 minutes. During this time, the internal temperature rose to 298 ° C. Thereafter, the pressure was reduced at a rate of 0.002 MPa / minute, the pressure was reduced to 0.08 MPa over 20 minutes, and the amount of the component having a molecular weight of 1,000 or less was adjusted. The temperature in the reaction vessel at the time of completion of decompression was 301 ° C. Thereafter, the inside of the system was pressurized with nitrogen, the temperature in the reaction vessel was 301 ° C., the resin temperature was 301 ° C., the polymer was taken out from the strand die into a strand shape, cooled with 20 ° C. cooling water, pelletized, and about 13 kg. A polyamide resin was obtained. The cooling time in cooling water was 5 seconds, and the strand take-up speed was 100 m / min. Hereinafter, it is referred to as “PAP10”.

<Measurement method of saturated water absorption rate when polyamide resin is immersed in water>
A plate test piece of 100 × 100 mm and a thickness of 2 mm was immersed in hot water at 80 ° C., and the plate weight was measured every 24 hours. At that time, water on the plate surface was sufficiently blown away by air blow. The immersion was terminated when the weight change was saturated, and the weight change rate relative to the initial weight was calculated as the saturated water absorption rate.

<Polyamide resin>
PAMP6: synthesized as described above, saturated water absorption 6.8% by weight when immersed in water
PAMP10: synthesized as described above, saturated water absorption 3% by weight when immersed in water
PAP10: synthesized as described above, saturated water absorption 3% by weight when immersed in water
PA12: Polyamide 12 (trade name: L20G, manufactured by EMS), saturated water absorption 1.8% by weight when immersed in water

<Glass fiber>
Glass fiber 1: 03T-296GH (manufactured by Nippon Electric Glass)
Glass fiber 2: flat glass fiber (manufactured by Nittobo, 3PA-810S, flat rate: 4)

<Plate filler>
Glass flake: REFG313 (manufactured by Nippon Sheet Glass), aspect ratio: 3.2, average particle size: 160 μm

<LSD additive>
Black 1G: CuCr ₂ O ₄ (manufactured by Shepherd color company)
Black 30C965: CuCr ₂ O ₄ (manufactured by Shepherd color company)

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

<Compound>
Each component is weighed so as to have the composition shown in the following table, which will be described later, components other than the glass filler are blended with a tumbler, charged from the root of a twin-screw extruder (Toshiki Machine Co., Ltd., TEM26SS), and melted. After that, glass pellets were made by side-feeding the glass filler. The temperature setting of the extruder was uniformly the same temperature, and the setting was changed depending on the type of resin. PAMP6, PAMP10, and PA12 were performed at 280 ° C., and PAP10 was performed at 300 ° C.

<Preparation of plate specimen>
The mold was performed by filling a resin composition from a fan gate having a width of 100 mm and a thickness of 0.8 mm into a cavity of 100 mm × 100 mm and a thickness of 2 mm. The gate portion was cut to obtain a plate test piece.

<Platting appearance>
A laser irradiation device (a YAG laser maximum output of 15 W at a wavelength of 1064 nm) manufactured by Trumpf is used in a range of 40 mm (vertical direction of the plate test piece) × 80 mm (lateral direction of the plate test piece) of the obtained plate test piece. Irradiation was performed at an output of 80%, a frequency of 60 kHz, and a scanning speed of 3 m / s. The subsequent plating process was carried out in an electroless Enthone, ENPLATE LDS CU 400 PC 48 ° C. plating bath. For the plating performance, the thickness of copper (plating layer) plated for 20 minutes was judged visually.
Evaluation was performed as follows. The results are shown in the table below.
○: Good appearance △: Plating is on board but slightly thin (practical level)
×: No plating at all

<Preparation of plate for adhesion evaluation>
The plated layer of the plate test piece on which the plated layer was formed was cut into a 2 mm square grid to produce two 10 squares × 10 squares.

<Underwater saturation test>
The plate for evaluating the adhesion was adjusted according to a method for measuring the saturated water absorption rate when the polyamide resin was immersed in water. Then, the cellophane adhesive tape was sufficiently bonded to the grid on the plate, and the work was peeled off while keeping the angle between the painted surface and the adhesive tape at about 45 degrees, and the state of the grid remaining on the plate was observed and evaluated.
Evaluation was performed as follows. The results are shown in the table below.
○: None of the cells showed any separation. Δ: Partial separation was observed in one or more cells, but there were no cells completely separated. ×: One or more cells were completely separated. Oops

<Temperature cooling test>
The plate for evaluation of adhesion was heated to 170 ° C. using a reflow bath, held for 60 seconds, and then cooled to room temperature. This process was performed three times. Then, the cellophane adhesive tape was sufficiently bonded to the grid on the plate, and the work was peeled off while keeping the angle between the painted surface and the adhesive tape at about 45 degrees, and the state of the grid remaining on the plate was observed and evaluated.
In addition, PA12 (Example 3) was not evaluated because plate deformation under a 170 ° C. environment was significant.
Evaluation was performed as follows. The results are shown in the table below.
○: No separation was found in any of the cells. Δ: Partial separation was observed in some of the cells, but there were no completely separated cells. ×: Some of the cells were completely separated.

As is apparent from the above table, when the polyamide resin composition of the present invention was used (Examples 1 to 9), the plating appearance was excellent, and the adhesion was kept high even when the underwater saturation test and the heating / cooling test were performed. I found out. On the other hand, when the saturated water absorption in the polyamide resin exceeds 4% by weight (Comparative Example 1), the adhesion after the water saturation test was significantly inferior. Moreover, when there were few compounding quantities of the LDS additive (comparative example 2), the plating layer was not able to be formed. Furthermore, when there are few compounding quantities of glass fiber (comparative example 3), the adhesiveness after a temperature rising cooling test was inferior. In Comparative Example 2, since plating did not occur, neither an underwater saturation test nor a heating / cooling test was performed.
Moreover, when talc was mix | blended in the composition of this invention (Example 4), the adhesiveness after an underwater saturation test improved further. When a plate-like filler (glass flake) was blended in the composition of the present invention (Example 5), the adhesion after the water saturation test was further improved. When flat glass fibers were blended as glass fibers in the composition of the present invention (Example 6), the adhesion after the underwater saturation test was further improved. When the blending amount of the LDS additive was increased (Example 8), the adhesion after the water saturation test was further improved.

Claims (13)

20 to 150 parts by weight of glass fiber and laser direct structuring with respect to 100 parts by weight of polyamide resin component containing 50% by weight or more of polyamide resin (A) having a saturated water absorption of 4% by weight or less when immersed in water A polyamide resin composition comprising 1 to 30 parts by weight of an additive ,
The laser direct structuring additive comprises CuCr ₂ O ₄ ;
Furthermore, the polyamide resin composition which contains 1-150 weight part of glass flakes with respect to 100 weight part of polyamide resin compositions. The polyamide resin (A) contains an aromatic ring in the molecule, and the ratio of carbon atoms constituting the aromatic ring in the molecule is 30 mol% or more based on the total number of carbon atoms in the molecule. The polyamide resin composition described in 1. The polyamide resin composition of Claim 1 or 2 which contains 0.1-20 weight part of talc with respect to 100 weight part of polyamide resin compositions. The polyamide resin composition according to any one of claims 1 to 3 , wherein a cross-section of the glass fiber is a longitudinal glass fiber having a flatness ratio of 2.5 or more according to the following formula.
Flatness ratio = glass fiber major axis D2 / glass fiber minor axis D1 The polyamide resin (A) is a polyamide resin in which 70 mol% or more of diamine structural units are derived from xylylenediamine units and 50 mol% or more of dicarboxylic acid structural units are derived from sebacic acid, The polyamide resin according to any one of claims 1 to 4 , which is a polyamide resin containing 20 to 100 mol% of paraxylylenediamine-derived units and 0 to 80 mol% of metaxylylenediamine-derived units. Composition. The polyamide resin composition according to any one of claims 1 to 5 , wherein 90% by weight or more of the polyamide resin component is a polyamide resin (A) having a saturated water absorption of 4% by weight or less when immersed in water. object. The resin molded product formed by shape | molding the polyamide resin composition of any one of Claims 1-6 . Furthermore, the resin molded product of Claim 7 which has a plating layer on the surface. The resin molded product according to claim 8 , wherein the plated layer retains performance as an antenna. The resin molded product according to any one of claims 7 to 9 , which is a portable electronic device component. Plating including forming a plating layer by applying a metal to a surface of a resin molded product obtained by molding the polyamide resin composition according to any one of claims 1 to 6 after laser irradiation. Manufacturing method of resin molded product with layer. The manufacturing method of the resin molded product with a plating layer of Claim 11 whose said plating layer is a copper plating layer. A method for manufacturing a portable electronic device part having an antenna, comprising the method for manufacturing a resin molded product with a plated layer according to claim 11 or 12 .

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