JP6363885B2 - Thermoplastic resin composition, resin molded product, and method for producing resin molded product with plating layer - Google Patents

Description

  The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition for laser direct structuring. Furthermore, the present invention relates to a resin molded product formed by molding the thermoplastic resin composition and a method for producing a resin molded product with a plated layer in which a plated layer is formed on the surface of the resin molded product.

In recent years, new light sources such as light-emitting diodes (LEDs) and organic ELs have been increasing in demand as lighting, display elements and the like by taking advantage of low power and long life. In particular, LEDs are used in various applications such as mobile communication devices such as mobile phones, displays, automobile console panels, signal devices, and other household appliances. Such electrical and electronic equipment products are increasingly becoming lighter, thinner, and smaller due to demands for design and portability.
Surface mounting technology (SMT) has become widespread as a key technology for realizing such miniaturization, and is used in many electrical and electronic equipment products. As a result, the mounting density of the electronic substrate has been dramatically improved, and a light, thin, and small size that has not been realized in the past has been achieved.

  When SMT is applied, in order to solder the entire component mounted on the electronic substrate, the material can only be used if it can withstand the soldering temperature (230 to 240 ° C.). A heat-resistant resin composition is known as a material that can be used for such applications (for example, Patent Document 1).

  Here, a laser direct structuring (hereinafter, also referred to as “LDS”) technique has attracted attention as one of the techniques for directly forming a plating that can be three-dimensionally designed on an LED or the like. LDS technology, for example, irradiates the surface of a resin molded product containing an LDS additive with a laser, activates only the portion irradiated with the laser, and forms a plating layer by applying metal to the activated portion. Technology. A feature of this technique is that a metal structure can be manufactured on the surface of a resin base material without using an adhesive or the like. Such LDS technology is disclosed in, for example, Patent Documents 2 to 4.

Japanese Patent Laid-Open No. 2004-075994 Special table 2000-503817 Special table 2004-534408 gazette International Publication WO2009 / 141800 Pamphlet

The LED is generally composed of a semiconductor part that emits light, a lead wire, a reflector that also serves as a housing, and a transparent sealing agent that seals the semiconductor. Of these, the reflector part has been commercialized with various materials such as ceramics and heat-resistant resin compositions, but with ceramics the productivity is high, with heat-resistant resin compositions the injection molding process, the sealant thermosetting process, In an actual use environment, a decrease in light reflectance due to discoloration is a problem. Further, in recent years, such resin compositions are also required to have flame retardancy. However, in a thermoplastic resin composition containing an LDS additive, there is a concern that if the additive is blended, the plating property is lowered.
The present invention aims to provide a resin composition that satisfies the above-mentioned requirements and solves the problems, and has high reflectivity while maintaining heat resistance and flame retardancy, and plating characteristics ( It is an object to provide a thermoplastic resin composition excellent in (plating appearance).

Under such circumstances, the inventors have studied and found that the above problems can be solved by the following means <1>, preferably <2> to <23>.
<1> (A) With respect to 100 parts by weight of a crystalline thermoplastic resin having a melting point measured by differential scanning calorimetry (DSC) at a temperature rising rate of 10 ° C./min. A thermoplastic resin containing 2 to 30 parts by weight of a laser direct structuring additive having a content of 25% or more, (C) 30 to 150 parts by weight of titanium oxide, and (D) 5.5 parts by weight or more of a phosphorus-based flame retardant Composition.
<2> The thermoplastic resin composition according to <1>, further comprising 10 to 90 parts by weight of a glass filler with respect to 100 parts by weight of the crystalline thermoplastic resin (A).
<3> The thermoplastic resin composition according to <1> or <2>, further comprising zinc borate.
<4> (D) The phosphorous flame retardant is selected from (a) a reaction product of melamine and phosphoric acid, (b) (di) phosphinate and (c) phosphazene compound, 3> The thermoplastic resin composition according to any one of the above.
<5> (A) The thermoplastic resin composition according to any one of <1> to <4>, wherein the crystalline thermoplastic resin is a polyamide resin.
<6> (C) The thermoplastic resin composition according to any one of <1> to <5>, wherein the laser direct structuring additive contains antimony and tin.
<7> (C) The laser direct structuring additive contains antimony and tin, and the content of tin is higher than that of antimony, according to any one of <1> to <6> Thermoplastic resin composition.
<8> The thermoplastic resin composition according to any one of <1> to <7>, wherein the halogen atom ratio in the thermoplastic resin composition is 0.1% by weight or less.
<9> The thermoplastic resin composition according to any one of <1> to <8>, further comprising talc at a ratio of 0.1 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.
<10> (D) The thermoplastic resin composition according to any one of <1> to <9>, wherein the titanium oxide has an average primary particle size of 1 μm or less.
<11> (D) The thermoplastic resin composition according to any one of <1> to <10>, wherein the titanium oxide is a rutile type.
<12> (B) The thermoplastic resin composition according to any one of <2> to <11>, wherein the glass filler is at least one selected from chopped strands, milled fibers, flakes, beads, and balloons.
<13> (B) The thermoplastic resin composition according to any one of <2> to <12>, wherein the glass filler is E glass.
<14> (A) The crystalline thermoplastic resin is a polyamide resin containing an aromatic ring in the molecule, and a ratio of carbon atoms constituting the aromatic ring to the polyamide resin molecule is 30 mol% or more. <1> ~ The thermoplastic resin composition according to any one of <13>.
<15> A resin molded product obtained by molding the thermoplastic resin composition according to any one of <1> to <14>.
<16> The resin molded product according to <15>, which is a light-emitting diode device part.
<17> The resin molded product according to <16>, wherein the light-emitting diode device part has a function as a reflector.
<18> The resin molded product according to any one of <15> to <17>, further having a plating layer on the surface.
<19> The resin molded product according to <18>, wherein the plating layer retains performance as a conductive circuit.
<20> 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 <19>, after irradiating a laser. The manufacturing method of the resin molded product with a plating layer containing.
<21> The method for producing a resin-molded article with a plating layer according to <20>, wherein the plating includes at least one of copper, nickel, silver, and gold.
<22> The method for producing a resin-molded article with a plating layer according to <21>, wherein the plating is used in a multilayer structure.
<23> A method for producing a light-emitting diode device component having a conductive circuit, comprising the method for producing a resin-molded article with a plated layer according to any one of <20> to <22>.

  According to the present invention, it is possible to provide a thermoplastic resin composition having high reflectivity and excellent plating characteristics (plating appearance) while maintaining heat resistance and flame retardancy.

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. Unless otherwise stated, the reflectance in this specification refers to the reflectance at a wavelength of 450 nm.

The thermoplastic resin composition of the present invention comprises (A) 100 parts by weight of a crystalline thermoplastic resin having a melting point of 250 ° C. or higher measured by differential scanning calorimetry (DSC) at a temperature rising rate of 10 ° C./min. B) 2 to 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 to 150 parts by weight of titanium oxide, and (D) 5.5 parts by weight of a phosphorus-based flame retardant It is characterized by including the above. By adopting such a configuration, it is possible to provide a thermoplastic resin composition having high reflectance and excellent plating characteristics (plating appearance) while maintaining heat resistance and flame retardancy.
Hereinafter, each component of the present invention will be described.

<(A) Crystalline thermoplastic resin>
The thermoplastic resin composition of the present invention has a melting point measured by differential scanning calorimetry (DSC) at a rate of temperature increase of 10 ° C./min of 250 ° C. or more, and the melting point is 255 ° C. or more. preferable. The upper limit is not particularly defined, but is usually 350 ° C. or lower. By adopting such a resin, the product dimensions during the reflow soldering process are more effectively maintained.

  A crystalline thermoplastic resin is a thermoplastic resin that has a distinct crystal structure or crystallizable molecular structure and exhibits non-glass-like properties, and has a measurable heat of fusion and a distinct melting point. Say. The melting point and heat of fusion can be measured using a differential scanning calorimeter, for example, DSC-II manufactured by PERKIN-ELMER. That is, a resin having a heat of fusion of 1 calorie / gram or more measured using this apparatus is defined as a crystalline thermoplastic resin. The melting point is determined by using a differential scanning calorimeter and heating the sample to a temperature above the expected melting point at a rate of 10 ° C. per minute, and then lowering the sample at a rate of 10 ° C. per minute. The temperature can be measured by cooling to 20 ° C., leaving it for about 1 minute, and then heating again at a rate of 10 ° C. per minute.

  Specific examples of the crystalline thermoplastic resin include polyolefin resin, polyester resin, polyacetal resin, polyphenylene sulfide resin, polyamide resin, liquid crystal polymer, and the like, and polyamide resin is preferable.

As the polyester resin, the description of paragraph numbers 0013 to 0016 in JP2010-174223A can be referred to.
As the polyacetal resin, description of paragraph number 0011 of JP-A-2003-003041 and paragraph numbers 0018 to 0020 of JP-A-2003-220667 can be referred to.

As the polyamide resin, the description in paragraph numbers 0011 to 0013 of JP2011-132550A can be referred to. 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.
In the present invention, a polyamide resin containing an aromatic ring in the molecule and having a ratio of carbon atoms constituting the aromatic ring to the polyamide resin molecule is preferably 30 mol% or more. By adopting such a resin, the water absorption rate is reduced, and as a result, the water absorption dimensional change is more effectively suppressed.

The glass transition point of the crystalline thermoplastic resin used in the present invention is preferably 40 to 180 ° C, and more preferably 60 to 130 ° C.
The number average molecular weight of the crystalline thermoplastic resin used in the present invention is preferably 5,000 to 45,000, and more preferably 10,000 to 25,000.

  The compounding amount of the crystalline thermoplastic resin in the thermoplastic resin composition of the present invention is preferably 50 to 95% by weight, and more preferably 60 to 90% by weight. The crystalline thermoplastic resin may be a single type or a mixture of two types of resins. When two or more types are included, the total amount is preferably within the above range.

<(B) Laser direct structuring additive>
The LDS additive contained in the thermoplastic resin composition of the present invention is characterized in that the reflectance at a wavelength of 450 nm is 25% or more, the reflectance is preferably 50 to 100%, and the reflectance is 60 to More preferably, it is 100%. Only one type of LDS additive may be used, or two or more types may be used in combination.

The LDS additive in the present invention is 4 parts by weight of an additive considered to be an LDS additive with respect to 100 parts by weight of PAMP6 manufactured by Mitsubishi Gas Chemical Co., Ltd. (PAMP6 synthesized in Examples described later), and has a wavelength of 1064 nm. Using a YAG laser, irradiate at an output of 10W, a frequency of 80kHz, and a speed of 3m / s. The subsequent plating process was performed in an electroless MacDermid M-Copper85 plating tank, and metal was applied to the laser irradiation surface. Refers to a compound that can form a plating. For example, if an additive is added to the resin, the absorption of the YAG laser is poor and the surface of the resin cannot be burned cleanly. In order to burn the surface with the laser, 10 to 40 parts by weight of titanium oxide is added and evaluated. Also good.
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. Although many known LDS additives are black, in the present invention, non-black LDS additives can also be widely used, so that it becomes possible to color resin molded products.

The LDS additive used in the present invention preferably contains at least one of copper, tin and antimony, more preferably contains antimony and tin, contains antimony and tin, and the content of tin is higher than that of antimony. More preferably, it contains antimony and tin oxide, and it is particularly preferable that the content of tin is higher than that of antimony. Moreover, the aspect which contains an antimony oxide and a tin oxide and tin has more content than an antimony is illustrated preferably.
When antimony and tin are included, the weight ratio is preferably 3.5: 96.5 to 25:75, and more preferably 7.5: 92.5 to 20:80.

  Furthermore, the LDS additive used in the present invention has a composition having a reflectance of 50% or more at a wavelength of 450 nm as a central portion, and contains at least one of copper, tin, and antimony in part or all of the surface of the central portion. It is preferable that the composition is coated. More preferably, a composition having a reflectivity of 50% or more in the center is coated with a composition containing at least one of copper, tin and antimony in an area of 60% or more of the surface area of the center. is there. By adopting such a configuration, the ratio of the composition containing at least one of copper, tin and antimony to the surface increases, and even a composition containing a small amount of at least one of copper, tin and antimony has a high LDS. It becomes possible to show the effect. Moreover, the high reflectance of the thermoplastic resin composition of this invention can be achieved by employ | adopting a composition with a reflectance of 50% or more for the composition which comprises center part.

The reflectance of the composition constituting the central part is more preferably 80% or more.
The composition constituting the central portion and having a reflectance of 50% or more preferably contains a metal oxide, more preferably contains at least one of silicon dioxide, mica and titanium oxide, and contains titanium dioxide. Further preferred. As an embodiment of the present invention, a composition having a reflectance of 50% or more constituting the central portion is an embodiment in which 20% by weight or more of the composition is composed of a metal oxide (preferably substantially only a metal oxide). Is mentioned. Such metal oxide is preferably titanium oxide.

The composition containing at least one of copper, tin and antimony to be coated is preferably a composition containing antimony and tin. The composition contains antimony and tin, and the content of tin is higher than that of antimony. More preferably, the composition contains antimony and tin oxide, and more preferably a composition containing more tin than antimony. Further, a composition containing antimony oxide and tin oxide, in which the content of tin is higher than that of antimony is also preferably exemplified.
When antimony and tin are included, the weight ratio is preferably 3.5: 96.5 to 25:75, and more preferably 7.5: 92.5 to 20:80.

  The LDS additive has a composition having a reflectance of 50% or more as a central part, and a part or all of the surface of the central part is coated with a composition containing at least one of copper, tin and antimony. In some cases, the weight ratio of the composition at the center and the composition at the coating portion is preferably 40 to 90:60 to 10, more preferably 70 to 90:30 to 10.

  As the LDS additive used in the present invention, antimony-doped tin, antimony-doped tin oxide and antimony oxide-doped tin oxide, and one of these has a reflectance of 50% or more A composition coated with the surface of the above composition at the center can be preferably used.

  The average particle size of the LDS additive is preferably 0.01 to 50 μm, and more preferably 0.05 to 30 μm. By adopting such a configuration, the uniformity of the plating surface state tends to be good when plating is applied.

In the thermoplastic resin composition of the present invention, the amount of the LDS additive is 2 to 30 parts by weight, preferably 3 to 25 parts by weight, more preferably 100 parts by weight of the crystalline thermoplastic resin. It is 5 to 22 parts by weight, and more preferably 8 to 20 parts by weight. Only one type of LDS additive may be used, or two or more types may be used in combination. When two or more types are used, the total amount falls within the above range.
In particular, when blending talc described later, the effects of the present invention can be more effectively exhibited even if the blending amount of the LDS additive is reduced.

<(C) Titanium oxide>
The thermoplastic resin composition of the present invention contains (C) at least one titanium oxide.
As titanium oxide, it is preferable to use titanium oxide containing 80% by weight or more of titanium oxide from the viewpoint of whiteness and hiding properties among those commercially available.
Examples of the titanium oxide used in the present invention include titanium monoxide (TiO), titanium trioxide (Ti ₂ O ₃ ), titanium dioxide (TiO ₂ ), and any of these may be used. Titanium dioxide is preferred. Further, as the titanium oxide, those having a rutile type crystal structure are preferably used.

  The average primary particle diameter of titanium oxide is preferably 1 μm or less, more preferably in the range of 0.001 to 0.5 μm, and still more preferably in the range of 0.002 to 0.1 μm. . By setting the average particle diameter of titanium oxide in such a range and the blending amount in the above range, a thermoplastic resin composition giving a molded product having high whiteness and high surface reflectance can be obtained.

As the titanium oxide, a surface-treated one may be used. As the surface treatment agent, inorganic materials and / or organic materials are preferable. Specific examples include metal oxides such as silica, alumina, and zinc oxide, silane coupling agents, titanium coupling agents, organic materials such as organic acids, polyols, and silicones.
Moreover, what is marketed can be used as a titanium oxide. Furthermore, it is also possible to use a material obtained by pulverizing a lump-shaped material or a material having a large average particle size, and classifying the material with a sieve or the like as necessary to obtain the above-mentioned average particle size.

  The blending amount of (C) titanium oxide in the thermoplastic resin composition of the present invention is 30 to 150 parts by weight, preferably 30 to 145 parts by weight, with respect to 100 parts by weight of (A) crystalline thermoplastic resin. More preferably, it is 35 to 110 parts by weight. Titanium oxide may contain only 1 type and may contain 2 or more types. When two or more types are included, the total amount falls within the above range.

<(D) Phosphorus flame retardant>
The (D) phosphorus flame retardant used in the present invention is a flame retardant containing a phosphorus atom. For example, (a) a reaction product of melamine and phosphoric acid, (b) (di) phosphinic acid salt, (C) A phosphazene compound can be mentioned.
(D) The compounding amount of the phosphorus flame retardant is 5.5 parts by weight or more, preferably 6 to 60 parts by weight with respect to 100 parts by weight of the (A) crystalline thermoplastic resin. Preferably it is 7-30 weight part, More preferably, it is 8-20 weight part, Especially preferably, it is 8-15 weight part. The phosphorous flame retardant may contain only one type or two or more types. When two or more types are included, the total amount falls within the above range.
More specifically, (b) (di) phosphinic acid salt is preferably 10 to 40 parts by weight, and 15 to 35 parts by weight with respect to 100 parts by weight of (A) crystalline thermoplastic resin. Is more preferable.
More specifically, (c) the phosphazene compound is preferably 5.5 to 25 parts by weight and more preferably 7 to 20 parts by weight with respect to 100 parts by weight of (A) the crystalline thermoplastic resin. preferable.

(A) The reaction product of melamine and phosphoric acid means a product obtained from a substantially equimolar reaction product of melamine or a condensation product of melamine and phosphoric acid, pyrophosphoric acid, or polyphosphoric acid. However, there are no particular restrictions on the production method. Usually, mention may be made of melamine polyphosphate (chemical formula “(C ₃ H ₆ N ₆ .HPO ₃ ) _n ” (where n represents the degree of condensation)) obtained by heat condensation of melamine phosphate under a nitrogen atmosphere. it can.

Specific examples of phosphoric acid constituting melamine phosphate include orthophosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid. Melamine polyphosphate obtained by condensing an adduct with acid and melamine using pyrophosphoric acid has a high effect as a flame retardant and is preferable. In particular, from the viewpoint of heat resistance, the condensation degree n of the melamine polyphosphate is preferably 5 or more.
In addition, melamine polyphosphate may be an equimolar addition salt of polyphosphoric acid and melamine, and is not limited to those in which all of polyphosphoric acid and melamine form an addition salt, and may be a mixture thereof. Good. That is, as polyphosphoric acid forming an addition salt with melamine, chain polyphosphoric acid or cyclic polymetaphosphoric acid called so-called condensed phosphoric acid may be used. The condensation degree n of these polyphosphoric acids is not particularly limited and is usually from 3 to 50. From the viewpoint of heat resistance of the resulting polyphosphate melamine addition salt, the condensation degree n of polyphosphoric acid used here is preferably 5 or more. The melamine polyphosphate addition salt is prepared by, for example, forming a mixture of melamine and polyphosphoric acid into a water slurry, mixing well to form both reaction products into fine particles, and then filtering, washing, and drying the slurry. Further, it is a powder obtained by firing if necessary and pulverizing the obtained solid.
The melamine polyphosphate may be an addition salt of phosphoric acid and a melamine condensation product, and is not limited to those in which all of the phosphoric acid and melamine condensation product form an addition salt. It may be a mixture. Examples of melamine condensation products that form addition salts with phosphoric acid include melem, melam, and melon.

  In the present invention, it is preferable to use a powder pulverized so that the weight average particle diameter of melamine polyphosphate is preferably 100 μm or less, more preferably 50 μm or less, from the viewpoint of mechanical strength and appearance of the molded product. In particular, use of a powder of 0.5 to 20 μm is more preferable because not only high flame retardancy is exhibited but also the strength of the molded product is remarkably improved. The melamine polyphosphate is not necessarily completely pure, and some unreacted melamine, melamine condensate, phosphoric acid or polyphosphoric acid may remain. Further, the content of phosphorus atoms in the melamine polyphosphate is 8 to 18% by weight, which is particularly preferable because there is little phenomenon that contaminants adhere to the molding die during molding.

  (B) (Di) phosphinic acid salt used in the present invention is a phosphinic acid salt represented by the following formula (I) and / or a diphosphinic acid salt represented by the following formula (II). Examples thereof include those produced in an aqueous medium using an acid and a metal carbonate, a metal hydroxide, or a metal oxide. The (di) phosphinate is essentially a monomeric compound, but depending on the reaction conditions, it may be a polymeric phosphinate having a degree of condensation of 1 to 3 depending on the environment.

（一般式（Ｉ）および（ＩＩ）において、Ｒ¹およびＲ²は、それぞれ、線状もしくは分枝状の炭素数１〜６（「Ｃ₁〜Ｃ₆」と記載する。以下同様）のアルキル基および／またはＣ₆〜Ｃ₁₀のアリール基、Ｒ³は線状もしくは分枝状のＣ₁〜Ｃ₁₀のアルキレン基、Ｃ₆〜Ｃ₁₀のアリーレン基、Ｃ₇〜Ｃ₁₀のアルキルアリーレン基またはＣ₇〜Ｃ₁₀のアリールアルキレン基、ＭはＣａ、Ｍｇ、Ａｌおよび／またはＺｎ、ｍはＭの価数を表し、２ｎ＝ｍｘであり、ｎは１または３、ｘは１または２である。）
ここで、ｍまたはｎが２以上の場合、それぞれの、Ｒ¹〜Ｒ³は同一であっても良いし異なっていても良い。

(In the general formulas (I) and (II), R ¹ and R ² are each linear or branched alkyl having 1 to 6 carbon atoms (described as “C _{1 to} C ₆ ”). Group and / or C ₆ -C ₁₀ aryl group, R ³ is linear or branched C ₁ -C ₁₀ alkylene group, C ₆ -C ₁₀ arylene group, C ₇ -C ₁₀ alkylarylene group Or C _{7 to} C ₁₀ arylalkylene group, M represents Ca, Mg, Al and / or Zn, m represents the valence of M, 2n = mx, n is 1 or 3, x is 1 or 2 is there.)
Here, when m or n is 2 or more, R ^{1 to} R ³ may be the same or different.

  Examples of phosphinic acid include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4-di (methylphosphinic acid), methylphenyl Examples include phosphinic acid and diphenylphosphinic acid. Examples of the metal component (M) include calcium ions, magnesium ions, aluminum ions and / or zinc ions.

Examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, Calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, methyl-n -Zinc propylphosphinate, calcium methylphenylphosphinate, magnesium phenylphenylphosphinate , Aluminum methylphenyl phosphinate, methyl phenyl phosphinate, zinc, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinate, and zinc diphenyl phosphinate and the like.
Diphosphinic acid salts include methandi (methylphosphinic acid) calcium, methandi (methylphosphinic acid) magnesium, methandi (methylphosphinic acid) aluminum, methandi (methylphosphinic acid) zinc, benzene-1,4-di (methylphosphinic acid) Examples include calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-di (methylphosphinic acid) aluminum, and benzene-1,4-di (methylphosphinic acid) zinc.
Among these (di) phosphinic acid salts, aluminum ethylmethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are particularly preferable from the viewpoints of flame retardancy and electrical properties.

  In the present invention, in view of the mechanical strength and appearance of the molded product, it is preferable to use a powder pulverized so that the weight average particle diameter of the (di) phosphinate is preferably 100 μm or less, more preferably 80 μm or less. preferable. In particular, the use of a powder of 0.5 to 50 μm is more preferable because it not only exhibits high flame retardancy but also significantly improves the strength of the molded product. Further, the proportion of phosphorus atoms in the (di) phosphinate is preferably 5 to 40% by weight because there is little phenomenon that contaminants adhere to the molding die during molding. The (di) phosphinic acid salt acts as a flame retardant, but (a) when used in combination with a reaction product of melamine and phosphoric acid, can exhibit excellent flame retardancy and excellent electrical properties.

（一般式（ＩＩＩ）において、ｍは３〜２５の整数であり、Ｐｈはフェニル基を示す。） The (c) phosphazene compound used in the present invention is an organic compound having a —P═N— bond in the molecule, preferably a cyclic phenoxyphosphazene represented by the following general formula (III), and represented by the following general formula (IV). A chain phenoxyphosphazene, and at least one phenoxyphosphazene selected from the group consisting of the following general formula (III) and the following general formula (IV) is crosslinked by a crosslinking group represented by the following general formula (V) And at least one compound selected from the group consisting of crosslinked phenoxyphosphazene compounds. (C) The phosphazene compound has a high flame retarding effect, and in particular, when used in combination with a metal borate described later, excellent flame retardancy can be exhibited even with a small content. This is preferable because it tends to suppress the reduction of the mechanical strength and the generation of gas.

(In General Formula (III), m is an integer of 3 to 25, and Ph represents a phenyl group.)

（一般式（ＩＶ）において、Ｘ¹は−Ｎ＝Ｐ（ＯＰｈ）₃基、または、−Ｎ＝Ｐ（Ｏ）ＯＰｈ基であり、Ｙ¹は−Ｐ（ＯＰｈ）₄基、または、−Ｐ（Ｏ）（ＯＰｈ）₂基であり、ｎは３〜１００００の整数であり、Ｐｈはフェニル基を示す。）

(In General Formula (IV), X ¹ is —N═P (OPh) ₃ group or —N═P (O) OPh group, Y ¹ is —P (OPh) ₄ group, or —P (O) (OPh) ₂ group, n is an integer of 3 to 10,000, and Ph represents a phenyl group.)

（一般式（Ｖ）において、Ａは−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−、または−Ｏ−であり、ｑは０または１である。）

(In the general formula (V), A is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and q is 0 or 1.)

  As the cyclic phenoxyphosphazene compound represented by the general formula (III), for example, a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Cyclic chlorophosphazenes such as cyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, etc. are taken out and then substituted with phenoxy groups. Phenoxycyclotriphosphazenes, octaphenoxycyclotetraphosphazenes, decaffenoxycyclopentaphosphazenes And the like. The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (III) is an integer of 3 to 8.

  As the chain phenoxyphosphazene compound represented by the general formula (IV), for example, hexachlorocyclotriphosphazene obtained by the above method is subjected to reduction polymerization at a temperature of 220 to 250 ° C., and the degree of polymerization obtained is 3 to 10,000. And a compound obtained by substituting the linear dichlorophosphazene with a phenoxy group. N of general formula (IV) of this linear phenoxyphosphazene compound becomes like this. Preferably it is 3-1000, More preferably, it is 3-100, More preferably, it is 3-25.

  Examples of the crosslinked phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned. The content of the phenylene group in the crosslinked phenoxyphosphazene compound is the number of all phenyl groups and phenylene groups in the cyclic phosphazene compound represented by the general formula (III) and / or the chain phenoxyphosphazene compound represented by the general formula (IV). Is usually from 50 to 99.9%, preferably from 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  Examples of the cyclic phenoxyphosphazene compound and the chain phenoxyphosphazene compound include H.I. R. Allcook, “Phosphorus-Nitrogen Compounds (Academic Press, (1972))”, J. Am. E. Mark, H.C. R. Allcook, R.A. It can be synthesized by the method described in “Inorganic Polymers (Prentice-Hall International, Inc. (1992))” by West.

Phosphorus flame retardants, particularly phosphazenes, may be formulated as a masterbatch. In addition, the flame retardant described in the pamphlet of International Publication No. WO2009 / 141799 can also be preferably used, and the contents thereof are incorporated herein.
The thermoplastic resin composition of the present invention includes flame retardants other than (D) phosphorus-based flame retardants, such as triazine-based, metal hydrate-based, and silicone-based flame retardants, as long as the object of the present invention is not impaired. A flame retardant can be blended. The content of these other flame retardant components is preferably 0.5 to 10% by weight in the thermoplastic resin composition of the present invention when added. Moreover, it is preferable that the thermoplastic resin composition of the present invention does not substantially contain a halogen-based flame retardant. For example, it is preferably 0.1% by weight or less of the thermoplastic resin composition of the present invention. By setting it as such a structure, it can be set as an environmentally friendly composition. Furthermore, in the thermoplastic resin composition of the present invention, if a halogen-based flame retardant is used instead of the phosphorus-based flame retardant, the plating property is inferior. In particular, a combination of a halogen-based flame retardant and antimony trioxide tends to have poor plating properties. Furthermore, it is preferable that the thermoplastic resin composition of the present invention does not substantially contain a halogen atom. For example, it is preferably 0.1% by weight or less of the entire thermoplastic resin composition of the present invention. .

<Flame retardant aid>
In the thermoplastic resin composition of the present invention, a flame retardant aid may be blended in order to enhance flame retardancy. Examples of the flame retardant aid include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, magnesium oxide, zinc sulfide, iron oxide, boron oxide, zinc stannate, metal borate and the like. Among these, water Magnesium oxide and metal borate are preferable, and zinc borate is particularly preferable. By incorporating zinc borate into the composition of the present invention, water is released when the composition is heated. This water has a cooling effect and further improves the flame retardancy. Such an additive may lower the plating performance, but zinc borate is highly valuable in that it can maintain high plating properties.

In the present invention, the boric acid metal salt that may be used as a flame retardant aid is preferably one that is stable under normal processing conditions and has no volatile components. Examples of the boric acid metal salt include alkali metal salts of boric acid (sodium tetraborate, potassium metaborate, etc.) or alkaline earth metal salts (calcium borate, magnesium orthoborate, barium orthoborate, zinc borate, etc.). Among these, a hydrated zinc borate salt represented by 2ZnO · 3B ₂ O ₃ · xH ₂ O (x = 3.3 to 3.7) is preferable, and 2ZnO · 3B ₂ O ₃ · 3. It is represented by 5H ₂ O, more preferably stable up to a temperature of 260 ° C. or higher.
In the present invention, the metal borate has a weight average particle size of preferably 30 μm or less, more preferably 20 μm or less, from the viewpoint of mechanical strength of the molded product and appearance of the molded product. In particular, it is preferable to use a powder of 1 to 20 μm because the mechanical strength is stabilized.

  The content of the flame retardant aid is preferably, for example, 10% by weight or less in the thermoplastic resin composition of the present invention (however, the total of all components is 100% by weight). By setting the content to 10% by weight or less, decomposition of the resin during molding can be suppressed. From the viewpoint of the balance between flame retardancy, electrical properties, and mechanical properties, it is more preferably 1 to 9% by weight, still more preferably 2 to 8% by weight.

<Glass filler>
The thermoplastic resin composition of the present invention preferably contains a glass filler. The glass filler is at least one selected from chopped strands, milled fibers, flakes, beads, and balloons, and chopped fibers, milled fibers, and flakes are preferable.

The chopped strand is obtained by cutting glass fibers into 1 to 10 mm, and the milled fiber is obtained by pulverizing glass fibers to a length of about 10 to 500 μm. The glass fiber is commercially available from Nippon Electric Glass Co., Ltd. and can be easily obtained.
The glass flake is a scale-like one having a thickness of 1 to 20 μm and a side length of 0.05 to 1.0 mm. For example, it is commercially available from Nippon Sheet Glass Co., Ltd. under the trade name “Fureka”. Is available.
Further, the glass beads are spherical ones having an outer diameter of 10 to 100 μm, and are, for example, commercially available from Toshiba Barotini under the trade name “EGB731” and are easily available.
The balloon is a hollow glass bead, which is commercially available from Tokai Kogyo under the trade name “PZ6000” and is easily available.

  The composition of the raw glass is preferably alkali-free, and examples thereof include E glass, C glass, S glass, and R glass. In the present invention, E glass is preferably used.

  The glass filler may be surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like. The amount is usually from 0.01 to 1% by weight of the glass filler. 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.

The blending amount of the glass filler in the thermoplastic resin composition of the present invention is preferably 10 to 100 parts by weight, more preferably 15 to 90 parts by weight with respect to 100 parts by weight of the crystalline thermoplastic resin. Preferably it is 20-80 weight part.
In the thermoplastic resin composition of the present invention, the crystalline thermoplastic resin and the glass filler usually occupy 70% by weight or more of all components.

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

<Talc>
The thermoplastic resin composition of the present invention may contain talc. In this invention, it exists in the tendency which the plating performance of the part irradiated with the laser improves more by mix | blending a talc.
The blending amount of talc in the thermoplastic resin composition of the present invention is preferably 0.1 to 50 parts by weight, and 0.5 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition. Is more preferably 1 to 15 parts by weight, and particularly preferably 1 to 10 parts by weight.

<Heat stabilizer>
The thermoplastic resin composition of the present invention may further contain an organic and / or inorganic heat stabilizer, and more preferably contains an organic heat stabilizer.
It is preferable that the heat stabilizer used in the present invention does not substantially contain copper. “Substantially” means below the detection limit. Thus, it becomes possible to suppress discoloration by reducing the compounding quantity of copper.
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, metal hydroxide is preferable, and magnesium hydroxide, calcium hydroxide, and antimony trioxide are exemplified. From the viewpoint of further improving the plating property, magnesium hydroxide and calcium hydroxide are exemplified. Is preferred. 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 to 5 parts by weight and more preferably 0.03 to 4 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. 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 thermoplastic 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 radicals such as benzophenone compounds, salicylate compounds, benzotriazole compounds, and cyanoacrylate compounds, and compounds that have an ultraviolet absorption effect, and 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 and more preferably 0.01 to 4 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. preferable.

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

<Release agent>
The thermoplastic 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 thermoplastic resin and the glass filler. By setting the content of the release agent to 0.001 part by weight or more, the effect of release property is more effectively exhibited, and by setting it to 2 parts by weight or less, the hydrolysis resistance is lowered and injection molding is performed. The mold contamination at the time is effectively suppressed.

<Method for producing thermoplastic resin composition>
Arbitrary methods are employ | adopted as a manufacturing method of the thermoplastic resin composition of this invention.
For example, a method of mixing a thermoplastic resin, a glass filler, an LDS additive, etc. using a mixing means such as a V-type blender, adjusting a batch blend, and then melt-kneading with a vented extruder to form a pellet. It is done. Alternatively, as a two-step kneading method, after mixing components, etc. other than glass filler, in advance, melt-kneading with a vented extruder to produce pellets, mixing the pellets and glass filler, and then venting The method of melt-kneading with an extruder is mentioned.
In addition, the components other than the glass filler, etc., mixed sufficiently with a V-type blender, etc. are prepared in advance, and supplied from the first chute of the vented twin-screw extruder. 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 is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation. In order to suppress decomposition during kneading or molding in the subsequent process, it is desirable to use an antioxidant or a heat stabilizer.

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

  Next, the process of providing plating on the surface of a resin molded product obtained by molding the thermoplastic resin composition of the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing a process of forming plating on the surface of a resin molded product 1 by a laser direct structuring technique. In FIG. 1, the resin molded product 1 is a flat substrate. However, the resin molded product 1 is not necessarily a flat substrate, and may be a resin molded product having a partially or entirely curved surface. The obtained resin molded product with a plated layer is not limited to the final product, and includes various parts.

Returning again to FIG. 1, the resin molded product 1 is irradiated with a laser 2. The laser here is not particularly defined, and can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and electromagnetic radiation, and a YGA laser is preferable. Further, the wavelength of the laser is not particularly defined. A preferable wavelength range is 200 nm to 1200 nm. Especially preferably, it is 800-1200 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, the plating layer in the present invention preferably has a metal component 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 layer 5 is formed only in the portion irradiated with the laser.
In the method of the present invention, it is possible to form a line interval (a lower limit value is not specifically defined, for example, 30 μm or more) having a width of 1 mm or less, and further 150 μm or less. In order to suppress corrosion and deterioration of the formed circuit, the plating can be further protected with nickel or gold after performing electroless plating, for example. Similarly, a necessary film thickness can be formed in a short time by using electroplating after electroless plating.

Molded articles obtained from the thermoplastic resin composition of the present invention include, for example, electronic parts such as connectors, switches, relays and conductive circuits, reflectors such as lamp reflectors, sliding parts such as gears and cams, air intakes, and the like. It can be used for various parts such as automobile parts such as manifolds, water-borne parts such as sinks, various decorative parts, or films, sheets, and fibers.
Although the thermoplastic resin composition of the present invention depends on the molding method, it gives a molded product having high whiteness and excellent reflectance. The whiteness (Hunter type) of the molded product obtained from the thermoplastic resin composition of the present invention is usually 92 or more, preferably 94 or more. In addition, the molded product obtained from the thermoplastic resin composition of the present invention is excellent in heat resistance and light stability in an actual use environment. Therefore, the molded product obtained from the thermoplastic resin composition of the present invention functions as a component having a function of reflecting light, particularly a light emitting diode (LED) device component, preferably an LED reflector or a conductive circuit. Only one layer may be sufficient as a plating layer, and a multilayered structure may be sufficient as it.

  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.

<Thermoplastic resin>
(1) Polyamide resin PAP10 was synthesized by the following method.
(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”. The melting point was 290 ° C.
(2) The polyamide resin MP6 was synthesized by the following method.
(Synthesis of polyamide (MP6))
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 “MP6”. The melting point was 257 ° C.
The melting point is determined by using a DSC-II manufactured by PERKIN-ELMER and heating the sample to a temperature above the expected melting point at a rate of temperature increase of 10 ° C. per minute. The temperature was lowered at a rate of 10 ° C. per minute, cooled to 20 ° C., allowed to stand for about 1 minute, and then heated and heated again at a rate of 10 ° C. per minute.

<LDS additive>
(1) CP5C: Made of Keeling & Walker, made of antimony-doped tin oxide (95% by weight of tin oxide, 5% by weight of antimony oxide, 0.02% by weight of lead oxide, 0.004% by weight of copper oxide). Reflectance 61.7%
(2) Minatec 40CM: Mica + SiO ₂ (total 57% by weight) (Merck) coated with a composition comprising (Sb / Sn) O ₂ (43% by weight), reflectivity 51.1%
(3) Black 1G: CuCr ₂ O ₄ (manufactured by Shepherd color company), reflectance 7.2%

  The reflectance is measured using a UV-3100PC made by placing LDS additive powder in a polyethylene bag having a thickness of about 100 μm and using a visible ultraviolet spectrometer, Shimadzu Corporation.

<Titanium oxide>
CR-63: manufactured by Ishihara Sangyo, rutile type, average primary particle size of 0.21 μm

<Glass filler>
03T-296GH: Nippon Electric Glass, E glass

<Heat stabilizer>
Irganox 1098: hindered phenol heat stabilizer, manufactured by BASF

<Flame Retardant>
Method for producing PME90FR After dry blending 34.7% by weight of polyphenylene ether resin, 0.3% by weight of maleic anhydride, 35% by weight of phosphazene and 30% by weight of zinc borate, using “TEX-30α” manufactured by Toshiba Machine Co., Ltd. The mixture was melt-kneaded under the conditions of a barrel set temperature of 280 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 20 kg / h to obtain phosphazene master batch pellets.
<< Raw materials used for masterbatch production >>
Polyphenylene ether resin: Manufacturer: manufactured by Mitsubishi Engineering Plastics, product number: PX100L
Phosphazene: Manufacturer: manufactured by Otsuka Chemical Co., Ltd., product number: SPS-100
ZnB: Manufacturer: manufactured by RIO TINTO, product number: Fire Break ZB

<Other flame retardants>
OP-1230: manufacturer: manufactured by Clariant Japan, product number: EXOLIT OP-1230
HP3010: Halogen flame retardant, Albemarle

<Flame retardant aid>
ZnB: Manufacturer: manufactured by RIO TINTO, product number: Fire Break ZB
Sb ₂ O ₃ : Manufactured by: Nippon Seiko Co., Ltd., Product Number: PATOX

<Alkali>
Ca (OH) ₂

<Talc>
MW5000S: Hayashi Kasei

<Release agent>
CS-8CP: Manufacturer: Nitto Kako, Product number: CS-8CP

<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 300 ° C.

<Reflectance (450 nm)>
A test piece of 60 mm × 60 mm × 2 mmt was produced by injection molding. The reflectance (unit:%) at a wavelength of 450 nm was measured using a visible ultraviolet spectrometer, manufactured by Shimadzu Corporation, UV-3100PC. 450 nm is a wavelength region of a blue light emitting diode. If the molded product has an initial reflectance of 50% or more, it is judged that the reflectance is good, and it can be judged that there is a possibility that it can be used for applications requiring reflectance.

<Flame retardance>
A test piece having a thickness of 1.5 mm was produced by injection molding.
According to the UL-94 test, the flame retardancy at a thickness of 1.5 mm was evaluated as follows. The results are shown in the table below.
A: V-0 was achieved.
B: The level was V-1 or less.

<Plating properties (plating appearance)>
Molding was performed by filling a cavity of 60 mm × 60 mm and a thickness of 2 mm as a mold from a fan gate having a side of 60 mm and a thickness of 1.5 mm. The gate portion was cut to obtain a plate test piece.
Using an LP-Z SERIES laser irradiation device (YAG laser maximum output 13 W at a wavelength of 1064 nm) manufactured by SUNX Co., Ltd., in an area of 10 × 10 mm of the obtained plate test piece, output 80%, pulse period 20 μs (microseconds) ) And irradiation at a speed of 4 m / s. The subsequent plating process was performed in a plating bath at 60 ° C. using a non-electrolytic MacDermid product, MIDCopper100XB Strike. The plating performance was determined by visual observation of the thickness of copper plated for 15 minutes.
Evaluation was performed as follows. The results are shown in the table below.
A: Good appearance (confirmed that the copper color is dark and the plating is thick)
B: Plating is hardly confirmed

<Solder heat resistance>
The test piece of the said plate test piece (0.8mmt) was produced, the test piece was immersed for 1 minute using the soldering bath of 240 degreeC, and the degree of deformation | transformation was confirmed visually. Evaluation was performed as follows.
A: Deformation did not occur even when immersed for 1 minute. B: Deformation was slightly observed at the corner of the test piece within 1 minute. C: The test piece was reliably deformed within 1 minute.

  As is clear from the above table, it was found that the thermoplastic resin composition of the present invention was excellent in solder heat resistance and flame retardancy, had high reflectance, and had high plating properties (Examples 1 to 12). When the blending amount of the phosphorus flame retardant is small or not blended (Comparative Examples 1 to 3), the flame retardancy is inferior. Further, when a flame retardant other than the phosphorus flame retardant was used (Comparative Example 4), the plating property and the solder heat resistance were inferior. Moreover, when the reflectance of the LDS additive was low (Comparative Example 5), the reflectance was poor. When the compounding amount of the LDS additive was small (Comparative Example 6), the plating property was inferior.

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

Claims (23)

(A) With respect to 100 parts by weight of a crystalline thermoplastic resin having a melting point of 250 ° C. or higher measured by differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min, (B) the reflectance at a wavelength of 450 nm is 25%. A thermoplastic resin composition comprising 2 to 30 parts by weight of the above laser direct structuring additive, (C) 30 to 150 parts by weight of titanium oxide, and (D) 5.5 parts by weight or more of a phosphorus-based flame retardant. Furthermore, the thermoplastic resin composition of Claim 1 which contains 10-90 weight part of glass fillers with respect to 100 weight part of said (A) crystalline thermoplastic resins. The gas Rasufira is at least one selected chopped strands, milled fibers, flakes, from beads and balloons, thermoplastic resin composition according to claim 2. The gas Rasufira is E glass, thermoplastic resin composition according to claim 2 or 3. Furthermore, the thermoplastic resin composition of any one of Claims 1-4 containing a zinc borate. (D) a phosphorus-based flame retardant, (a) a reaction product of melamine with phosphoric acid is selected from (b) (di) phosphinic acid salt and (c) phosphazene compound, claim 1-5 2. The thermoplastic resin composition according to item 1. (A) The thermoplastic resin composition according to any one of claims 1 to 6 , wherein the crystalline thermoplastic resin is a polyamide resin. (B) Laser Direct Structuring additives, characterized in that it comprises antimony and tin, the thermoplastic resin composition according to any one of claims 1-7. The thermoplastic resin according to any one of claims 1 to 8 , wherein ( B ) the laser direct structuring additive contains antimony and tin, and the content of tin is higher than that of antimony. Composition. The thermoplastic resin composition according to any one of claims 1 to 9 , wherein a proportion of halogen atoms in the thermoplastic resin composition is 0.1% by weight or less of the whole. Furthermore, the thermoplastic resin composition of any one of Claims 1-10 which contains a talc in the ratio of 0.1-20 weight part with respect to 100 weight part of thermoplastic resin compositions. ( C ) The thermoplastic resin composition according to any one of claims 1 to 11 , wherein the average primary particle diameter of titanium oxide is 1 µm or less. ( C ) The thermoplastic resin composition according to any one of claims 1 to 12 , wherein the titanium oxide is a rutile type. (A) The crystalline thermoplastic resin is a polyamide resin containing an aromatic ring in the molecule and having a ratio of carbon atoms constituting the aromatic ring to the polyamide resin molecule of 30 mol% or more. The thermoplastic resin composition according to any one of the above. The resin molded product formed by shape | molding the thermoplastic resin composition of any one of Claims 1-14. The resin molded product according to claim 15, which is a light-emitting diode device part. The resin molded product according to claim 16, wherein the light emitting diode device component has a function as a reflector. Furthermore, the resin molded product of any one of Claims 15-17 which has a plating layer on the surface. The resin molded product according to claim 18, wherein the plated layer retains performance as a conductive circuit. Including applying a metal to the surface of a resin molded product obtained by molding the thermoplastic resin composition according to any one of claims 1 to 14 and then applying a metal to form a plating layer. Manufacturing method of resin molded product with plating layer. The manufacturing method of the resin molded product with a plating layer of Claim 20 with which the said plating contains at least 1 sort (s) of copper, nickel, silver, and gold | metal | money. The method for producing a resin molded product with a plating layer according to claim 21, wherein the plating is used in a multilayer structure. The manufacturing method of the light emitting diode apparatus component which has a conductive circuit including the manufacturing method of the resin molded product with a plating layer of any one of Claims 20-22.

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