JP6147107B2 - 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. Furthermore, it is related with the manufacturing method of the resin molded product formed by shape | molding this thermoplastic resin composition, and the resin molded product with a plating layer which formed the plating layer on the surface of this resin molded product.

  In recent years, with the development of mobile phones including smartphones, various methods for manufacturing antennas inside mobile phones have been studied. In particular, there is a need for a method of manufacturing an antenna that can be three-dimensionally designed for a mobile phone. As one of the techniques for forming such a three-dimensional antenna, a laser direct structuring (hereinafter, also referred to as “LDS”) technique has attracted attention. 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 such as an antenna can be manufactured directly on the surface of the resin base material without using an adhesive or the like. Such LDS technology is disclosed in Patent Documents 1 to 4, for example.

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

  Here, if a large amount of LDS additive is added to the thermoplastic resin composition for LDS, it can be expected that the plating property is improved. However, since the ratio of the resin in the resin molded product is reduced, the appearance of the resin molded product tends to be inferior. In particular, in the formulation in which glass fiber is blended, the appearance of the resin molded product tends to be a problem. The present invention aims to solve such problems, and provides a thermoplastic resin composition capable of appropriately forming plating on the surface of a resin molded product while maintaining the appearance of the resin molded product. For the purpose.

Based on the above problems, the present inventors conducted extensive studies, and as a result, by optimizing the amount of LDS additive even when using a crystalline thermoplastic resin having a high crystallization temperature, However, the present inventors have found that the appearance of the resin molded product can be improved and a resin composition excellent in plating properties can be obtained, and the present invention has been completed.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <12>.
<1> 20 to 40 parts by weight of a laser direct structuring additive and 10 to 150 parts by weight of glass fiber are included with respect to 100 parts by weight of a crystalline thermoplastic resin having a melting point by differential scanning calorimetry (DSC) of 250 ° C. or higher. Thermoplastic resin composition.
<2> The thermoplastic resin composition according to <1>, wherein the blending amount of the laser direct structuring additive is more than 20 parts by weight and 40 parts by weight or less with respect to 100 parts by weight of the crystalline thermoplastic resin.
<3> The thermoplastic resin composition according to <1> or <2>, wherein the laser direct structuring additive includes an oxide containing copper and chromium.
<4> The thermoplastic resin composition according to any one of <1> to <3>, further including talc.
<5> The thermoplastic resin composition according to any one of <1> to <4>, wherein the crystalline thermoplastic resin is a polyamide resin.
<6> A resin molded product obtained by molding the thermoplastic resin composition according to any one of <1> to <5>.
<7> The resin molded product according to <6>, further having a plating layer on the surface.
<8> The resin molded product according to <6> or <7>, which is a portable electronic device part.
<9> The resin molded product according to <7> or <8>, wherein the plated layer has performance as an antenna.
<10> Forming a plating layer by applying a metal to the surface of a resin molded product obtained by molding the thermoplastic resin composition according to any one of <1> to <5>, after irradiating a laser. The manufacturing method of the resin molded product with a plating layer containing.
<11> The method for producing a resin molded article with a plating layer according to <10>, wherein the plating layer is a copper plating layer.
<12> A method for manufacturing a portable electronic device part having an antenna, including the method for manufacturing a resin molded product with a plating layer according to <10> or <11>.

  It has become possible to provide a thermoplastic resin composition containing glass fibers that can appropriately form a plating on the surface of a resin molded product while maintaining the appearance of the resin molded product.

It is the schematic which shows the process of providing plating on the surface of a resin molded product.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  The thermoplastic resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is obtained by adding 100 parts by weight of a crystalline thermoplastic resin having a melting point of 250 ° C. or higher by differential scanning calorimetry (DSC). On the other hand, it contains 20 to 40 parts by weight of laser direct structuring additive and 10 to 150 parts by weight of glass fiber. With such a configuration, it is possible to appropriately form plating on the surface of the resin molded product while maintaining the appearance of the resin molded product. Hereinafter, the details of the composition of the present invention will be described.

<Crystalline thermoplastic resin having a melting point of 250 ° C. or higher by differential scanning calorimetry (DSC)>
The crystalline thermoplastic resin used in the present invention has a melting point measured by differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min. Is preferred. 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. However, in a prescription in which a thermoplastic resin having a high crystallization temperature is used and glass fiber is blended, the appearance of the resin molded product may be inferior. In particular, the LDS additive is a substance necessary for exerting the plating property, but the addition of the LDS additive tends to affect other performances. In the present invention, even if a crystalline thermoplastic resin having a high crystallization temperature is used, by optimizing the amount of the LDS additive, the appearance of the resin molded product can be improved even in a prescription containing glass fiber, and plating. It is highly valuable in that a resin composition having excellent properties can be obtained.

  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. Unless otherwise specified, the crystalline thermoplastic resin in the present specification means “crystalline thermoplastic resin having a melting point of 250 ° C. or higher by differential scanning calorimetry (DSC)”.

  Specific examples of the crystalline thermoplastic resin used in the present invention include polyolefin resin, polyester resin, polyacetal resin, polyphenylene sulfide resin, polyamide resin, liquid crystal polymer and the like, and polyamide resin is preferable. The crystalline thermoplastic resin may be a single type or a mixture of two types of resins.

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 composition of the present invention is preferably 10 to 80% by weight, and more preferably 30 to 70% by weight.

<Glass fiber>
The composition of the present invention comprises glass fibers. 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, glass fibers having a circular cross-sectional shape are generally used in many cases. However, in the present invention, there is no particular limitation. For example, a glass fiber having a cross-sectional shape of an eyebrow shape, an oval shape, or a rectangular shape can also be used.

  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 composition after kneading the composition of the present invention is 0.1 mm or more, a so-called milled fiber, a pulverized product of strands called glass powder may be used. A continuous single fiber sliver may also be used. 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.

The compounding amount of the glass fiber in the composition of the present invention is 10 to 150 parts by weight, preferably 10 to 130 parts by weight, more preferably 20 parts by weight or more with respect to 100 parts by weight of the crystalline thermoplastic resin. Less than 100 parts by weight.
In the composition of the present invention, the crystalline thermoplastic resin and glass fiber usually occupy 60% by weight or more of all components.

<Laser direct structuring additive>
The composition of the present invention includes an LDS additive.
In the LDS additive of the present invention, 4 parts by weight of an additive considered to be an LDS additive is added to 100 parts by weight of the resin (1) (PAP10) resin synthesized in Examples described later, and YAG having a wavelength of 1064 nm is added. Using a laser, irradiation was performed at an output of 10 W, a frequency of 80 kHz, and a speed of 3 m / s, and the subsequent plating process was performed in an electroless MacDermid M-Copper85 plating tank, and a metal was applied to the laser irradiation surface. Sometimes it refers to a compound that can form 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. 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 compounding amount of the LDS additive in the composition of the present invention is 20 to 40 parts by weight, preferably more than 20 parts by weight and 40 parts by weight or less, more preferably 100 parts by weight of the crystalline thermoplastic resin. Is 25 to 40 parts by weight, particularly preferably more than 30 parts by weight and 40 parts by weight or less, and particularly preferably 32 to 40 parts by weight. Only one type of LDS additive may be used, or two or more types may be used in combination. When using 2 or more types, it is preferable that the total amount becomes the said range.

  Hereinafter, preferred embodiments of the LDS additive used in the present invention will be described. By using the LDS additive of such an embodiment, the effects of the present invention tend to be more effectively exhibited. However, it goes without saying that the present invention is not limited to these embodiments.

The first embodiment of the LDS additive used in the present invention is an LDS additive containing copper. The LDS additive used in the first embodiment is preferably an oxide containing copper, and more preferably an oxide containing copper and chromium (copper chromium oxide). Examples of such an LDS additive include CuCr ₂ O ₄ and Cu ₃ (PO ₄ ) ₂ Cu (OH) ₂ , and CuCr ₂ O ₄ is particularly preferable. Thus, the effect of the present invention tends to be exhibited more effectively by using an oxide containing copper as an LDS additive. The copper content in the LDS additive used in the first embodiment is preferably 20 to 95% by mass.

The Mohs hardness of the LDS additive used in the first embodiment is preferably 5.5 or more, and more preferably 5.5 to 6.5. By setting it as such a range, the mechanical strength of a resin molded product can be improved more.
The LDS additive used in the first embodiment preferably has an average particle size of 0.01 to 50 μm, and more preferably 0.05 to 30 μm. By setting it as such an average particle diameter, it exists in the tendency for the effect of this invention to be exhibited more effectively.

  A second embodiment of the LDS additive used in the present invention is an LDS additive containing antimony and / or tin. Of the metal components in the LDS additive containing only one of antimony or tin as the metal component, the content of antimony or tin is preferably 1 to 95% by weight, and 1.5 to 60% by weight, respectively. More preferred. In the embodiment containing both antimony and tin, the total amount of antimony and tin in the metal component of the LDS additive is preferably 90% by weight or more, and more preferably 90 to 100% by weight.

In the second embodiment of the LDS additive, an LDS additive containing antimony and tin is preferably exemplified. In the present embodiment, an aspect that includes both antimony and tin and that has a higher tin content than antimony is more preferable, includes both antimony and tin, and includes antimony oxide and / or tin oxide. And the aspect with more tin content than antimony is still more preferable.
Examples of the LDS additive used in the present invention include tin doped with antimony, tin oxide doped with antimony, and tin oxide doped with antimony oxide.

<Alkali>
The 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. For example, the above-described LDS additive containing copper (Cu ₃ (PO ₄ ) ₂ Cu (OH) ₂ ) corresponds to the LDS additive of an acidic substance.
The blending amount of the alkali in the composition of the present invention is preferably 0.01 to 3% by weight of the blending amount of the LDS additive, more preferably, although it depends on the kind of the LDS additive and the kind of the alkali. 0.05 to 1% by weight. Only one type of alkali may be used, or two or more types may be used in combination. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Inorganic pigment>
The composition of the present invention may contain an inorganic pigment. In the present invention, the resin molded product can be colored by adding an inorganic pigment. As the inorganic pigment, an inorganic pigment having an L ^* value of 80 or more in CIELab and a Mohs hardness of 5.0 or less is preferable. The L ^* value is more preferably 50-100.
The blending amount of the inorganic pigment in the composition of the present invention is preferably 0.1 to 20 parts by weight, and more preferably 0.3 to 15 parts by weight with respect to 100 parts by weight of the composition of the present invention. More preferably, it is 0.5 to 12 parts by weight. Only one type may be used, or two or more types may be used in combination. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Talc>
The composition of the present invention may contain talc. In this invention, by mix | blending talc, the plating characteristic of a resin molded product can be made more favorable, and suitable plating can be formed in a resin molded product. As the talc, one having a surface treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes may be used. In this case, the adhesion amount of the siloxane compound in talc is preferably 0.1 to 5% by weight of talc.

  The amount of talc in the composition of the present invention is preferably 0.01 to 10 parts by weight, and 0.05 to 8 parts by weight with respect to 100 parts by weight of the crystalline thermoplastic resin used in the present invention. More preferably, the amount is 1.0 to 5 parts by weight. Moreover, when the talc is surface-treated with a siloxane compound, the blending amount of the talc surface-treated with the siloxane compound is preferably within the above range. Only one type of talc may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<Release agent>
The composition of the present invention may further contain a release agent. The mold release agent is mainly used for improving the productivity at the time of molding the composition of the present invention. Examples of the release agent include aliphatic carboxylic acid amides, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oils, and the like. Can be mentioned. Among these release agents, carboxylic acid amide compounds are particularly preferable.

  Examples of the aliphatic carboxylic acid amide system include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and / or a polybasic acid and a diamine.

  The higher aliphatic monocarboxylic acid is preferably a saturated aliphatic monocarboxylic acid or hydroxycarboxylic acid having 16 or more carbon atoms, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. .

  Examples of polybasic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid and azelaic acid, aromatic dicarboxylic acids such as phthalic acid and terephthalic acid, cyclohexanedicarboxylic acid, and cyclohexylsuccinic acid. Examples include alicyclic dicarboxylic acids such as acids.

  Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine.

  As the carboxylic acid amide compound, a compound obtained by polycondensation of stearic acid, sebacic acid and ethylenediamine is preferable, and a compound obtained by polycondensation of 2 mol of stearic acid, 1 mol of sebacic acid and 2 mol of ethylenediamine is more preferable. In addition to bisamide compounds obtained by reacting diamines with aliphatic carboxylic acids such as N, N′-methylenebisstearic acid amide and N, N′-ethylene bisstearic acid amide, N, N′— Dicarboxylic acid amide compounds such as dioctadecyl terephthalic acid amide can also be suitably used.

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

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, 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 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. The number average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less.

  The content of the release agent is preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more, and preferably 2 parts by weight or less, with respect to 100 parts by weight of the crystalline thermoplastic resin. More preferably, it is 1.5 parts by weight or less. By making the content of the release agent 0.001 part by weight or more with respect to 100 parts by weight of the crystalline thermoplastic resin, the release property can be improved. In addition, by making the content of the release agent 2 parts by weight or less with respect to 100 parts by weight of the crystalline thermoplastic resin, it is possible to prevent degradation of hydrolysis resistance, and at the time of injection molding Mold contamination can be prevented. Only one type of release agent may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<Other additives>
The 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 flame retardants, titanium oxide, alkalis, heat stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, dyes and pigments, fluorescent whitening agents, anti-dripping agents, antistatic agents, and anti-fogging agents. Agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. These components may use only 1 type and may use 2 or more types together.

<Method for producing thermoplastic resin composition>
Any method can be adopted as a method for producing the composition of the present invention. For example, a crystalline thermoplastic resin, an LDS additive, and glass fibers are mixed using a mixing means such as a V-type blender to prepare a batch blended product, and then melt-kneaded with a vented extruder to be pelletized. A method is 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, you may use antioxidant and a heat stabilizer from a viewpoint of suppressing the decomposition | disassembly at the time of kneading | mixing or a back process.

  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.

<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 process of providing plating on the surface of the resin molded product formed of the 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.

  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 known plating solution can be widely used, and preferably contains at least one of copper, nickel, gold, silver and palladium as a metal component. 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, 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. 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.
Furthermore, in the method of the present invention, the amount of energy 2000~100000Wμs / mm ² per unit area provided by the laser irradiation, and further, even 4000~10000Wμs / mm ^2, can be formed appropriately plated. That is, the composition of the present invention has an advantage that the laser irradiation conditions that can form plating are wide. As a result, plating can be appropriately formed even in regions where uniform laser irradiation is difficult, such as molded products having corners.

  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.

<Production Example 1>
(Synthesis of Resin (1) (MP10))
After sebacic acid (Ito Oil Co., Ltd.) was heated and dissolved in a reactor under a nitrogen atmosphere, the molar ratio of paraxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine was stirred while the contents were stirred. While the 7: 3 mixed diamine was gradually added dropwise so that the molar ratio of diamine to dicarboxylic acid was 1: 1, the temperature was raised. After completion of the dropping, stirring and reaction were continued until a predetermined viscosity was reached, and then the contents were taken out in a strand shape and pelletized with a pelletizer to obtain a polyamide resin (MP10). The melting point was 253 ° C.

<Production Example 2>
(Synthesis of Resin (2) (MP6))
After adipic acid (made by Rhodia) was heated and dissolved in a reaction vessel under a nitrogen atmosphere, the molar ratio of paraxylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Inc.) and metaxylylenediamine was 4 while stirring the contents. The temperature was increased while gradually adding dropwise the mixed diamine of 6: 6 so that the molar ratio of diamine to dicarboxylic acid was 1: 1. After completion of the dropping, stirring and reaction were continued until a predetermined viscosity was reached, and then the contents were taken out in a strand shape and pelletized with a pelletizer to obtain a polyamide resin (MP6). The melting point was 269 ° C.

PAMXD6: Polyamide PAMXD6 resin, manufactured by Mitsubishi Gas Chemical Co., Ltd., melting point 243 ° C.
LDS additive: copper chromium oxide (CuCr ₂ O ₄ ), Black 1G, Shepherd Japan glass fiber (1): E glass, 03T-286GH, circular cross section, Nippon Electric Glass glass fiber (2): E glass, 3PA -810S, flat cross section, Nitto Boseki talc: Micron White 5000S, Hayashi Kasei mold release agent: Calcium montanate, CS-8CP, Nitto Kasei Kogyo

<Compound>
Each component is weighed so as to have the composition shown in the following table, and the components other than glass fiber are blended with a tumbler, charged from the root of a twin-screw extruder (TEM 26SS, manufactured by Toshiba Machine Co., Ltd.), and melted After that, glass pellets were made by side-feeding the glass filler. The temperature setting of the extruder was 290 ° C.

<Plate molding>
After drying the obtained pellets at 80 ° C. for 12 hours, a molding machine (manufactured by FANUC, 100iα, mold clamping pressure 100 t) was used, and the conditions were 100 mm × 100 mm × 2 mm under conditions of a cylinder temperature of 300 ° C. and a mold temperature of 130 ° C. It was made to flow with a film gate from one side in thickness and injection molded. The filling time was 0.5 seconds, the holding pressure was 600 kg / cm ² , the holding pressure time was 10 seconds, and the cooling time was 12 seconds.

<Appearance of plate>
The plate obtained above was judged visually.
A: A uniform and glossy surface was confirmed. B: Floating filler was confirmed (practical level).
C: Check that the filler is floating and rough

<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 a laser irradiation device of LP-Z SERIES manufactured by SUNX Co., Ltd. (maximum output of 13 YAG laser with a wavelength of 1064 nm) in the range of 10 × 10 mm of the obtained plate test piece, the output (unit:%) shown in the table and Irradiation was performed at a speed of 4 m / s with a pulse period (unit: μs). The subsequent plating process was performed in a 60 ° C. plating tank using an electroless MacDermid MIDCopper100XB Strike. The plating performance was determined by visual observation of the thickness of copper plated at the times shown in the table below.
Evaluation was performed as follows.

<< Plating property >>
A: Plated on one side and good appearance confirmed B: Partially plated but practical level C: No plated or partial plated, not practical level

<Solder heat resistance>
A test piece of 126 × 12.6 mm × 0.8 mmt was prepared, and a test bath was immersed in a length of 30 mm from the end at a 45 ° angle for 30 seconds using a 230 ° C. solder bath, and the degree of deformation was visually confirmed. Evaluation was performed as follows.
A: No deformation and good appearance B: Some deformation is observed in the test piece C: The test piece is reliably deformed or partially melted

As is clear from the above results, the composition of the present invention was able to appropriately form plating on the surface of the resin molded product while maintaining its appearance in the resin molded product containing glass fiber (Examples 1 to 3). ). On the other hand, when the compounding amount of the LDS additive was less than 20 parts by weight with respect to 100 parts by weight of the crystalline thermoplastic resin (Comparative Examples 1 to 3), the plating property was inferior. On the other hand, when the compounding amount of the LDS additive was more than 40 parts by weight with respect to 100 parts by weight of the crystalline thermoplastic resin (Comparative Example 4), the appearance of the resin molded product was inferior. Further, when the melting point of the thermoplastic resin used was less than 250 ° C. (243 ° C.), the solder heat resistance was inferior. When the blending amount of the glass fiber exceeded 150 parts by weight with respect to 100 parts by weight of the crystalline thermoplastic resin (Comparative Example 6), the compound could not be made.
Furthermore, when the composition of this invention was used, it turned out that the laser conditions which can form plating are wide. In particular, it was found that plating can be appropriately formed even in a short time with a low output by setting the amount of the LDS additive to more than 30 parts by weight with respect to 100 parts by weight of the crystalline thermoplastic resin.

1 resin molded product, 2 laser, 3 laser irradiated part, 4 plating solution, 5 plating layer

Claims (10)

To differential scanning calorimetry (DSC) by melting point measured at heating rate 10 ° C. / min or more 250 ° C. Crystalline thermoplastic resin 100 parts by weight of a laser direct structuring additive 2 5 to 40 wt parts, the glass fibers 10 to 150 parts by weight seen containing further comprises talc, the thermoplastic resin composition. The thermoplastic resin composition according to claim 1, wherein the laser direct structuring additive includes an oxide containing copper and chromium. The thermoplastic resin composition according to claim 1 or 2 , wherein the crystalline thermoplastic resin is a polyamide resin. The resin molded product formed by shape | molding the thermoplastic resin composition of any one of Claims 1-3 . The resin molded product according to claim 4 , which is a portable electronic device part. Furthermore, the resin molded product of Claim 4 or 5 which has a plating layer on the surface. The resin molded product according to claim 6 , wherein the plating layer retains performance as an antenna. 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 3 and 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 8 whose said plating layer is a copper plating layer. A method for producing a portable electronic device part having an antenna, comprising the method for producing a resin molded product with a plated layer according to claim 8 or 9 .

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