WO2017110458A1

WO2017110458A1 - Composition for forming laser direct structuring layer, kit, and method for manufacturing resin molded article having plating layer

Info

Publication number: WO2017110458A1
Application number: PCT/JP2016/086254
Authority: WO
Inventors: 尚秀杉山; 達也菊地; 山中　康史
Original assignee: 三菱エンジニアリングプラスチックス株式会社
Priority date: 2015-12-24
Filing date: 2016-12-06
Publication date: 2017-06-29

Abstract

The present invention makes it possible to form a plating layer on the surface of a resin molded article even without mixing a laser direct structuring (LDS) additive into a thermoplastic resin composition. Disclosed are: a composition for forming an LDS layer, the composition including a curable compound, an organic solvent, and an LDS additive; and a kit including the composition, or a method for manufacturing a resin molded article having a plating layer by using the composition.

Description

Composition for forming laser direct structuring layer, kit, and method for producing resin molded product with plating layer

The present invention relates to a composition for forming a laser direct structuring layer. Furthermore, it is related with the kit which has the said composition for laser direct structuring layer formation, and a thermoplastic resin composition. Moreover, it is related with the manufacturing method of the resin molded product with a plating layer using the composition for laser direct structuring layer formation.

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, for example, Patent Documents 1 to 4.
Patent Document 5 discloses a non-conductive substrate material comprising a metal nucleus produced by crushing a fine non-conductive metal compound contained in a substrate material by use of electromagnetic radiation, and subsequently a metallized product applied thereto. In the conductor track structure provided above, the non-conductive metal compound is a high oxide that is thermally stable, durable in an acidic or alkaline aqueous metallization bath, and has a spinel structure. Formed from an insoluble inorganic oxide which is a simple d-metal oxide or a mixture thereof or a mixed metal oxide similar to a spinel structure and the non-conductive metal compound is in an unirradiated region The above conductor track structure is disclosed, characterized in that it remains unchanged. In addition, US Pat. No. 6,057,059 applies a non-conductive high oxide as a coating on a structural member, releases heavy metal nuclei by electromagnetic radiation in the region of the conductor track structure to be manufactured, and this region is then chemically treated. The reduction and metallization is described.

International publication WO2011 / 095632 pamphlet International Publication WO2011 / 076729 Pamphlet International Publication WO2011 / 077630 Pamphlet International Publication WO2012 / 128219 Pamphlet JP-T-2004-534408

However, when the LDS technology is used, if a LDS additive is blended with a thermoplastic resin, a large amount of LDS additive is required. The LDS additive is useful for forming the plating layer, but becomes a foreign substance in the final resin molded product. In particular, depending on the type of LDS additive, various performances may be adversely affected, and other additives blended in the thermoplastic resin composition may adversely affect the ability of the LDS additive to form a plating layer. is there.
On the other hand, Patent Document 5 describes that a non-conductive high oxide is coated on a substrate body material and applied, and heavy metal nuclei are released by electromagnetic radiation, and this region is chemically reduced to be metallized. Has been. However, there is no specific description as to how to coat the non-conductive high oxide on the substrate body material.
An object of the present invention is to solve such a problem, and it is possible to form a plating layer on the surface of a resin molded product without adding an LDS additive to a thermoplastic resin composition. And

As a result of investigation by the present inventors under such problems, a thermoplastic resin composition is formed by forming a layer containing a curable compound, an organic solvent, and an LDS additive on the surface of a resin molded product. It has been found that a plating layer can be appropriately formed on the surface of a resin molded product without blending an LDS additive, and the present invention has been completed.
Specifically, it has been found that the above problems can be solved by the following means <1>, preferably by <2> to <24>.
<1> A composition for forming a laser direct structuring layer, comprising a curable compound, an organic solvent, and a laser direct structuring additive.
<2> The composition for forming a laser direct structuring layer according to <1>, wherein the curable compound is a resin.
<3> The composition for forming a laser direct structuring layer according to <1> or <2>, wherein the curable compound is an ultraviolet curable compound or a thermosetting compound.
<4> The laser direct structure according to any one of <1> to <3>, comprising 0.05 to 70 parts by weight of a laser direct structuring additive with respect to 100 parts by weight of the total of the curable compound and the organic solvent. A composition for forming a ring layer.
<5> The composition for forming a laser direct structuring layer according to any one of <1> to <4>, wherein the composition for forming a laser direct structuring layer contains 20 to 80% by weight of the curable compound. .
<6> A kit comprising the composition for forming a laser direct structuring layer according to any one of <1> to <5> and a thermoplastic resin composition containing a thermoplastic resin.
<7> The kit according to <6>, wherein the thermoplastic resin composition does not substantially contain a laser direct structuring additive.
<8> The kit according to <6> or <7>, wherein the thermoplastic resin is a crystalline resin.
<9> The kit according to <8>, wherein the crystalline resin is a polyamide resin.
<10> The kit according to <8>, wherein the crystalline resin is a thermoplastic polyester resin.
<11> The kit according to <6> or <7>, wherein the thermoplastic resin is an amorphous resin.
<12> The kit according to <11>, wherein the amorphous resin is a polycarbonate resin.
<13> The kit according to any one of <6> to <12>, wherein the thermoplastic resin composition includes a dye / pigment and / or a flame retardant composition.
<14> The kit according to any one of <6> to <12>, wherein the thermoplastic resin composition includes a pigment and / or a flame retardant composition.
<15> The kit according to any one of <6> to <14>, wherein the thermoplastic resin composition contains a black dye / pigment.
<16> The kit according to any one of <6> to <15>, wherein the thermoplastic resin composition contains at least one of an antimony flame retardant and an antimony flame retardant aid.
<17> The kit according to any one of <6> to <16>, wherein the thermoplastic resin composition contains a halogen-based flame retardant.
<18> The kit according to any one of <6> to <15>, wherein the thermoplastic resin composition contains a phosphorus-based flame retardant.
<19> The kit according to <18>, wherein the phosphorus-based flame retardant is a condensed phosphate ester and / or a phosphazene compound.
<20> The kit according to any one of <6> to <15>, wherein the thermoplastic resin composition contains an organometallic salt flame retardant.
<21> The composition for forming a laser direct structuring layer according to any one of <1> to <5> is applied to the surface of a thermoplastic resin molded article, cured, and then irradiated with a laser to form a plating layer The manufacturing method of the resin molded product with a plating layer including the process of forming.
<22> The method for producing a resin molded product with a plating layer according to <21>, wherein the thermoplastic resin molded product includes a crystalline resin.
<23> The method for producing a resin molded product with a plating layer according to <21>, wherein the thermoplastic resin molded product includes an amorphous resin.
<24> A method for producing a resin-molded article with a plating layer according to any one of <21> to <23>, wherein the kit according to any one of <6> to <20> is used.

It is now possible to form a plating layer on the surface of a resin molded product without adding an LDS additive to the thermoplastic resin composition.

It is the schematic which shows the process of forming a plating layer on the surface of the conventional resin molded product. It is the schematic which shows the process of forming a plating layer on the surface of the resin molded product in this invention.

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. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Furthermore, in the case of a group having a limited number of carbon atoms, the carbon number means a number including the carbon number of the substituent.
The solid, liquid and the like in the present invention are those at 25 ° C. unless otherwise specified.

The present invention is characterized in that a composition for forming an LDS layer containing a curable compound, an organic solvent, and an LDS additive is used separately from the resin molded product. By setting it as such a structure, even if it does not mix | blend an LDS additive with a thermoplastic resin composition, it becomes possible to form a plating layer on the surface of a resin molded product.
This point will be described with reference to the drawings. FIG. 1 shows a process of forming a plating layer on the surface of a conventional resin molded product. In FIG. 1, 11 indicates a molded article of the thermoplastic resin composition, and 12 indicates an LDS additive. In the conventional method, an LDS additive is blended and molded into the thermoplastic resin composition. Then, as shown in FIG. 1 (1), when only the part where the plating layer is to be formed is irradiated with the laser (the part indicated by the arrow in FIG. 1 (1)), the LDS additive in the part irradiated with the laser is activated. (FIG. 1 (2)). When a plating solution is applied to the surface of the resin molded product in this activated state, the plating layer 13 is formed only on the laser-irradiated portion of the resin molded product (FIG. 1 (3)).
Although this conventional method is a useful method, when the LDS additive is blended with the thermoplastic resin, the blending amount of the LDS additive with respect to the resin molded product is relatively increased. That is, the LDS additive only needs to be present on the surface of the resin molded product forming the plating layer. However, when added to the thermoplastic resin composition, the LDS additive is added to the resin molded product as shown in FIG. Since it exists in a dispersed state, an LDS additive in an amount more than that necessary for forming a plating layer is blended. However, some LDS additives are expensive and it is desirable to reduce the amount of LDS additive in the resin molded product. The LDS additive is useful for forming a plating layer, but becomes a foreign substance in the final resin molded product. In particular, depending on the type of LDS additive, various performances may be adversely affected. Specifically, the LDS additive damages the glass fiber and the mechanical strength is not exhibited. Moreover, in the resin composition which mix | blended additives, such as a flame retardant composition and a pigment, even if it mix | blends an LDS additive, a plating layer may not be formed appropriately.

On the other hand, FIG. 2 is a schematic view showing a step of forming a plating layer on the surface of the resin molded product in the present invention. In FIG. 2A, 21 indicates a resin molded product, 22 indicates an LDS layer, and 23 indicates an LDS additive.
That is, when the composition for forming an LDS layer of the present invention is applied (for example, applied) to the surface of the resin molded article 21, a thin LDS layer 22 in which the LDS additive 23 is uniformly dispersed can be formed (FIG. 2 (1)). .

Next, after the LDS layer 22 is cured, a laser beam is irradiated on a portion necessary for forming the plating layer (FIG. 2 (1)). Then, the LDS additive in the portion irradiated with the laser is activated. In this activated state, a plating solution is applied to the surface of the resin molded product. In the resin molded product after applying the plating solution, the plating layer 24 is formed only in the portion irradiated with the laser (FIG. 2 (4)). As a result, it is possible to form a plating layer on the surface of the resin molded product without adding an LDS additive to the thermoplastic resin composition. In the present invention, the plating layer is preferably formed in an atmosphere of, for example, 10 to 50 ° C., more preferably 15 to 45 ° C., particularly 20 to 40 ° C. In particular, it is preferable that no heating is performed other than the heat accompanying laser irradiation.

In order to form a uniform plating layer, the composition for forming an LDS layer is required to be able to form an LDS layer in which the LDS additive is substantially uniformly dispersed on the surface of the resin molded product. In the present invention, since an LDS additive is dispersed in a composition containing a curable compound and an organic solvent, an LDS layer in which the LDS additive is substantially uniformly dispersed is formed on the surface of the resin molded product. it can. In such an LDS layer, when the curable compound is cured, the LDS additive remains on the surface of the resin molded product in a state of being dispersed on the surface of the resin molded product. In particular, a composition for forming an LDS layer in which an LDS additive is blended in a paint has an advantage that it is difficult to easily peel off after curing. Further, in a resin molded product using an amorphous resin such as a polycarbonate resin, the surface is likely to be uneven due to laser irradiation at the time of plating layer formation. In the method of the present invention, such unevenness is relatively Less.
Hereinafter, the composition for forming an LDS layer of the present invention, a kit, and a method for producing a resin molded product with a plating layer will be described in detail.

<Composition for forming laser direct structuring layer>
The composition for forming a laser direct structuring layer includes a curable compound, an organic solvent, and a laser direct structuring additive. By setting it as such a structure, even if it does not mix | blend an LDS additive with a thermoplastic resin composition, it becomes possible to form a plating layer on the surface of a resin molded product.

<< Curable compound >>
The curable compound used in the present invention is preferably a substance that can be dissolved or dispersed in an organic solvent, and more preferably a substance that can be dissolved in an organic solvent. The temperature at the time of dissolution or dispersion is not particularly defined, but is preferably room temperature (for example, 25 ° C.).

The curable compound may be a low molecule, but is preferably a resin.
The curable compound used in the present invention is preferably, for example, a curable compound that cures with moisture in the air at room temperature (room temperature curable compound), an ultraviolet curable compound, or a thermosetting compound. More preferably, it is a curable compound or a thermosetting compound. By using a curable compound that is cured by ultraviolet rays or heat, there is an advantage that handling at room temperature is improved as compared with a room temperature curable compound that needs to be stored at a low temperature.

Examples of the curable compound include urethane resin, epoxy resin, polyester resin, silicon resin, acrylic resin, and polyvinyl chloride resin.

In the composition for forming an LDS layer of the present invention, the content of the curable compound is preferably 20 to 80% by weight, more preferably 25 to 75% by weight in the composition for forming an LDS layer. The curable compound may contain only one type, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Organic solvent >>
The composition for forming an LDS layer contains an organic solvent. By including the organic solvent, the LDS additive can be uniformly dispersed in the composition for forming an LDS layer, and as a result, an LDS layer in which the LDS additive is uniformly dispersed can be formed.
The organic solvent is not particularly limited as long as it is a substance that can dissolve or disperse the curable compound, and examples thereof include thinner and solvent naphtha.
The compounding amount of the organic solvent in the composition for forming an LDS layer of the present invention is preferably 20 to 80% by weight, and more preferably 25 to 75% by weight. Moreover, in order to make it easy to apply | coat the composition for LDS layer formation of this invention to a resin molded product, you may adjust the compounding quantity of an organic solvent and may adjust a viscosity. The viscosity of the composition for forming an LDS layer is preferably 0.01 to 200 Pa · s, more preferably 0.1 to 150 Pa · s at 25 ° C. from the viewpoint of applicability.

<< Paint >>
In this invention, a well-known coating material can be used as a composition containing a sclerosing | hardenable compound and an organic solvent. As the paint, a resin paint is preferable. Specific examples of resin coatings that can be used in the present invention include: Kansai Paint Co., Ltd., Retan PG80III Clear, Origin Denki, Origin Plate Z Meta Silver, Nippon Iupika, Neopole 8476, Nippon Paint, nax Mighty Rack Various paints such as G-II KB type clear, cashew, high metal KD2850 silver, cashew, 6110 clear, Kansai paint, Million clear, Kansai paint, Binibon 100 clear can be used.
In addition to the paint in which the main agent and the organic solvent are already mixed, there are paints composed of the main agent and the organic solvent, which are mixed at the time of use, and any aspect can be preferably used in the present invention. Furthermore, a curing agent may be included. In the present invention, the main agent and the curing agent correspond to the curable compound.
The composition for forming an LDS layer of the present invention is excellent in production suitability in that it can be made into a composition for forming an LDS layer by adding an LDS additive to a commercially available paint. Moreover, the adhesiveness of a resin molded product and a LDS layer can be improved by using the resin coating material.

<< LDS additive >>
The composition for forming an LDS layer contains an LDS additive.
The LDS additive in the present invention uses 10 parts by weight of an additive considered to be an LDS additive to 100 parts by weight of a thermoplastic resin (for example, polyamide resin and / or polycarbonate resin), and uses a YAG laser having a wavelength of 1064 nm. Irradiation at an output of 13 W, a frequency of 20 kHz, a scanning speed of 2 m / s, and the subsequent plating process was performed in an electroless MacDermid, MIDCopper100XB Strike plating tank, and when the metal was applied to the laser irradiation surface, A compound that can form a plating layer.
The LDS additive used in the present invention may be a synthetic product or a commercial product. In addition to those that are commercially available as LDS additives, commercially available products may be substances that are sold for other uses as long as they satisfy the requirements of the LDS additive in the present invention. Only one type of LDS additive may be used, or two or more types may be used in combination.
Hereinafter, preferred embodiments of the LDS additive used in the present invention will be described, but it goes without saying that the present invention is not limited thereto. In the present invention, the LDS additive of the first embodiment and the second embodiment is preferable.

The first embodiment of the LDS additive used in the present invention is a compound containing copper and chromium. The LDS additive of the first embodiment preferably contains 10 to 30% by weight of copper. Further, it is preferable to contain 15 to 50% by weight of chromium. The LDS additive in the first embodiment is preferably an oxide containing copper and chromium.

As the copper and chromium content, a spinel structure is preferable. The spinel structure is one of the typical crystal structure types found in double oxide AB ₂ O ₄ type compounds (A and B are metal elements).

The LDS additive of the first embodiment may contain a trace amount of other metals in addition to copper and chromium. Examples of other metals include antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, calcium, and the like, and manganese is preferable. These metals may exist as oxides.
A preferred example of the LDS additive of the first embodiment is an LDS additive having a content of metal oxide other than copper chromium oxide of 10% by weight or less.

A second embodiment of the LDS additive used in the present invention is an oxide containing antimony and / or phosphorus and tin, preferably an oxide containing antimony and tin.

The LDS additive of the second embodiment is more preferably one in which the amount of tin is greater than the amount of phosphorus and / or antimony, and the amount of tin with respect to the total amount of tin, phosphorus and antimony is 80% by weight or more It is more preferable that

In particular, the LDS additive of the second embodiment is preferably an oxide containing antimony and tin, more preferably the amount of tin added is greater than the amount of antimony, and tin relative to the total amount of tin and antimony. More preferably, the amount is 80% by weight or more.

More specifically, as the LDS additive of the second embodiment, tin oxide doped with antimony, tin oxide doped with antimony oxide, tin oxide doped with phosphorus, doped with phosphorous oxide Examples thereof include tin oxide, tin oxide doped with antimony and tin oxide doped with antimony oxide are preferable, and tin oxide doped with antimony oxide is more preferable. For example, in an LDS additive containing phosphorus and tin oxide, the phosphorus content is preferably 1 to 20% by weight. In the LDS additive containing antimony and tin oxide, the content of antimony is preferably 1 to 20% by weight. Further, in the LDS additive containing phosphorus, antimony and tin oxide, the phosphorus content is preferably 0.5 to 10% by weight, and the antimony content is preferably 0.5 to 10% by weight.

The third embodiment of the LDS additive used in the present invention preferably contains a conductive oxide containing at least two kinds of metals and having a resistivity of 5 × 10 ³ Ω · cm or less. The resistivity of the conductive oxide is preferably 8 × 10 ² Ω · cm or less, more preferably 7 × 10 ² Ω · cm or less, and further preferably 5 × 10 ² Ω · cm or less. Although there is no restriction | limiting in particular about a minimum, For example, it can be set to 1 * 10 < ¹ > ohm * cm or more, Furthermore, it can be set to 1 * 10 < ² > ohm * cm or more.
The resistivity of the conductive oxide in the present invention usually refers to the powder resistivity, and 10 g of the fine powder of the conductive oxide is charged into a cylinder having an inner diameter of 25 mm and subjected to Teflon (registered trademark) processing on the inner surface. Te 100 kg / cm ² pressurized (filling rate 20%) can be measured by Yokogawa of "3223 Model" tester.

The LDS additive used in the third embodiment is not particularly limited as long as it contains a conductive oxide having a resistivity of 5 × 10 ³ Ω · cm or less, but preferably contains at least two kinds of metals. Specifically, it preferably includes a metal of group n (n is an integer of 3 to 16) and a metal of group n + 1 of the periodic table. n is preferably an integer of 10 to 13, and more preferably 12 or 13.
In the LDS additive, the LDS additive used in the third embodiment is 100 mol in total of the content of the group n metal (n is an integer of 3 to 16) and the metal content of the group n + 1 in the periodic table. %, The content of one metal is preferably 15 mol% or less, more preferably 12 mol% or less, and particularly preferably 10 mol% or less. Although there is no restriction | limiting in particular about a minimum, It is 0.0001 mol% or more. By setting the content of two or more kinds of metals in such a range, the plating property can be improved. In the present invention, an n group metal oxide doped with an n + 1 group metal is particularly preferable.
Further, in the LDS additive used in the third embodiment, 98% by weight or more of the metal component contained in the LDS additive is composed of the group n metal content and the group n + 1 metal of the periodic table. It is preferable.

Examples of the metal of group n in the periodic table include group 3 (scandium, yttrium), group 4 (titanium, zirconium, etc.), group 5 (vanadium, niobium, etc.), group 6 (chromium, molybdenum, etc.), group 7 ( Manganese, etc.), group 8 (iron, ruthenium, etc.), group 9 (cobalt, rhodium, iridium, etc.), group 10 (nickel, palladium, platinum), group 11 (copper, silver, gold etc.), group 12 (zinc, Cadmium, etc.), group 13 (aluminum, gallium, indium, etc.), group 14 (germanium, tin, etc.), group 15 (arsenic, antimony, etc.), group 16 (selenium, tellurium, etc.), and metal oxides thereof. It is done. Among them, a Group 12 (n = 12) metal or metal oxide is preferable, and zinc is more preferable.

Examples of the metal of group n + 1 of the periodic table include group 4 (titanium, zirconium, etc.), group 5 (vanadium, niobium, etc.), group 6 (chromium, molybdenum, etc.), group 7 (manganese, etc.), group 8 (iron). , Ruthenium, etc.), group 9 (cobalt, rhodium, iridium, etc.), group 10 (nickel, palladium, platinum), group 11 (copper, silver, gold, etc.), group 12 (zinc, cadmium, etc.), group 13 (aluminum) Gallium, indium, etc.), group 14 (germanium, tin, etc.), group 15 (arsenic, antimony, etc.), group 16 (selenium, tellurium, etc.), and metal oxides thereof. Among them, a Group 13 (n + 1 = 13) metal or metal oxide is preferable, aluminum or gallium is more preferable, and aluminum is further preferable.

The LDS additive used in the third embodiment may contain a metal other than the conductive metal oxide. Examples of the metal other than the conductive oxide include antimony, titanium, indium, iron, cobalt, nickel, cadmium, silver, bismuth, arsenic, manganese, chromium, magnesium, and calcium. These metals may exist as oxides. The content of these metals is preferably 0.01% by weight or less with respect to the LDS additive.
The LDS additive used in the third embodiment preferably has an antimony content of 3% by weight or less with respect to the LDS additive from the viewpoint of improving the L value, and is 1% by weight or less. More preferably, it is more preferable that it is 0.01 weight% or less, and it is especially preferable not to contain substantially. “Substantially free” means not contained within a range that affects the effects of the present invention.

The average particle size of the LDS additive used in the present invention is preferably 0.01 to 100 μm, more preferably 0.05 to 30 μm, and further preferably 0.05 to 15 μm. By setting such an average particle diameter, the LDS additive can be uniformly dispersed in the composition for forming an LDS layer, and the plating property tends to be further improved, which is preferable.

The blending amount of the LDS additive in the composition for forming an LDS layer is preferably 0.01 to 50% by weight. Moreover, it is preferable that it is 0.05 weight part or more with respect to a total of 100 weight part of the said sclerosing | hardenable compound and an organic solvent, It is more preferable that it is 0.3 weight part or more, It is 1 weight part or more. More preferred is 3 parts by weight or more. Further, it is preferably 70 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 40 parts by weight or less, based on 100 parts by weight of the total of the curable compound and the organic solvent. It is even more preferable that the amount is not more than parts by weight. By setting it as such a range, a Platting appearance can be improved more.
The present invention is highly valuable in that the amount of the LDS additive in the final resin molded product with a plated layer can be reduced.

<< Other components of composition for forming LDS layer >>
The composition for forming an LDS layer used in the present invention may comprise only a curable compound, an organic solvent and an LDS additive, but may contain other components. Examples of other components include components that are generally blended in paints and curable compounds, among which dispersants, sensitizers, compatibilizers, and dyes / pigments. As a preferred embodiment of the composition for forming an LDS layer in the present invention, a composition for forming an LDS layer substantially consisting of a curable compound, an organic solvent and an LDS additive is exemplified. Or the composition for LDS layer formation which consists only of a coating material and a LDS additive substantially is illustrated. The term “substantially” means that the other components than the above are 5% by weight or less of the amount of the LDS additive, preferably 3% by weight or less, and 1% by weight or less. Is more preferable, and it is still more preferable that it is 0.1 weight% or less.

<< Characteristics of LDS Layer Forming Composition >>
The composition for forming an LDS layer is a dispersion in which an LDS additive is dispersed. The curable compound may be dissolved or dispersed in an organic solvent, but is preferably dissolved as described above. By applying such a composition for forming an LDS layer to the surface of a resin molded product, an LDS layer in which the LDS additive is uniformly dispersed can be formed. Therefore, the composition for forming the LDS layer may be a dispersion in which the LDS additive is dispersed immediately before being applied to the surface of the resin molded product, and it is not necessarily required to be dispersed even after standing for a long time. Absent.
In the present invention, the weight ratio of the curable compound to the solvent is preferably 20:80 to 80:20, and more preferably 25:75 to 75:25. Such a range is preferable because the dispersibility of the LDS additive is excellent and the plating property tends to be improved.

<Kit>
The kit of the present invention has a composition for forming a laser direct structuring layer and a thermoplastic resin composition containing a thermoplastic resin. By using such a kit, it is possible to form a plating layer on the surface of the resin molded product without blending the LDS additive into the thermoplastic resin composition.
In particular, in the present invention, the amount of the LDS additive contained in the composition for forming an LDS layer can be 3.0% by weight or less of the amount of the thermoplastic resin contained in the thermoplastic resin composition, Furthermore, it can be set to 2.0% by weight or less, and particularly 1.5% by weight or less. The lower limit of the amount of the LDS additive added can be, for example, 0.5% by weight or more.

<< LDS layer forming composition >>
As the composition for forming an LDS layer, the above-described composition for forming an LDS layer can be used, and the preferred range is also the same.

<< Thermoplastic resin composition containing a thermoplastic resin >>
The thermoplastic resin composition in the present invention contains a thermoplastic resin. The kind of the thermoplastic resin is not particularly defined, and may be a crystalline resin or an amorphous resin.
Conventionally, when a resin composition containing an amorphous resin and an LDS additive is used, the surface may be uneven due to laser irradiation. However, when the composition for forming an LDS layer of the present invention is used, Even when a crystalline resin is used, the surface can be made uniform. Specific examples of the thermoplastic resin include polycarbonate resin, a mixture of polycarbonate resin and polystyrene resin, an alloy of polyphenylene ether resin and polystyrene resin, an alloy of polyphenylene ether resin and polyamide resin, thermoplastic polyester resin, methyl methacrylate / acrylonitrile / Examples thereof include butadiene / styrene copolymer resin, methyl methacrylate / styrene copolymer resin, methyl methacrylate resin, rubber-reinforced methyl methacrylate resin, polyamide resin, polyacetal resin, polylactic acid resin, polyolefin resin, and polyphenylene sulfide resin. In the present invention, it is preferable to include at least one of a polycarbonate resin, a mixture of a polycarbonate resin and a polystyrene resin, a thermoplastic polyester resin, and a polyamide resin, and at least one of a polycarbonate resin, a mixture of a polycarbonate resin and a polystyrene resin, and a polyamide resin. It is more preferable that a polyamide resin is included.
Moreover, as a crystalline resin, a polyamide resin and a thermoplastic polyester resin are preferable. As the amorphous resin, a polycarbonate resin is preferable.
A preferred embodiment will be described below.

Embodiment with Polycarbonate Resin as Main Component As a first embodiment of the thermoplastic resin in the present invention, there is a case where the thermoplastic resin contains a polycarbonate resin as a main component. In the first embodiment, the proportion of the polycarbonate resin in all resin components is preferably 30 to 100% by weight, more preferably 50 to 100% by weight, and further preferably 80 to 100% by weight.

Polycarbonate resin The polycarbonate resin used in the present invention is not particularly limited, and any of an aromatic polycarbonate, an aliphatic polycarbonate, and an aromatic-aliphatic polycarbonate can be used. Of these, an aromatic polycarbonate is preferable, and a thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is more preferable.

As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxydiphenyl and the like are preferable, and bisphenol A is preferable. Furthermore, for the purpose of preparing a composition having a high flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound, or a polymer containing both terminal phenolic OH groups having a siloxane structure or Oligomers and the like can be used.

Preferred examples of polycarbonate resins used in the present invention include polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds A polycarbonate copolymer derived from

The molecular weight of the polycarbonate resin is preferably 14,000 to 30,000 in terms of viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and 15,000 to 28,000. More preferably, it is 16,000 to 26,000. It is preferable for the viscosity average molecular weight to be in the above range since the mechanical strength becomes better and the moldability becomes better.

The method for producing the polycarbonate resin is not particularly limited, and the present invention also uses a polycarbonate resin produced by any method such as the phosgene method (interfacial polymerization method) and the melting method (transesterification method). can do. Moreover, in this invention, after passing through the manufacturing process of a general melting method, you may use the polycarbonate resin manufactured through the process of adjusting the amount of OH groups of a terminal group.

Furthermore, the polycarbonate resin used in the present invention may be not only a polycarbonate resin as a virgin raw material but also a polycarbonate resin regenerated from a used product, a so-called material recycled polycarbonate resin.

In addition, with respect to the polycarbonate resin used in the present invention, for example, the description in paragraph numbers 0018 to 0066 of JP2012-072338A can be referred to, and the contents thereof are incorporated in the present specification.

The thermoplastic resin composition used in the present invention may contain only one type of polycarbonate resin or two or more types.

The aspect containing a polycarbonate resin and a styrene resin As a 2nd embodiment, the case where a thermoplastic resin contains a polycarbonate resin and a styrene resin is mentioned. Specifically, it is more preferable to include 40% by weight or more and less than 100% by weight of the polycarbonate resin, and a resin component including more than 0% by weight and less than 60% by weight of the styrene resin. More preferably, the resin contains 60 to 10% by weight, more preferably 60 to 80% by weight of polycarbonate resin and 40 to 20% by weight of styrene resin.
For the details of the polycarbonate resin, the description of the first embodiment can be referred to.

Styrene resin Styrene resin is a styrene polymer composed of styrene monomers, a copolymer of styrene monomers and other copolymerizable vinyl monomers, and the presence of rubbery polymers. Below, it means at least one polymer selected from the group consisting of styrene monomers or copolymers obtained by polymerizing styrene monomers and other copolymerizable vinyl monomers.

Specific examples of the styrenic monomer include styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, ethylvinylbenzene, dimethylstyrene, pt-butylstyrene, bromostyrene, and dibromostyrene. Among them, styrene is preferable. In addition, these can also be used individually or in mixture of 2 or more types.

As vinyl monomers copolymerizable with the above styrenic monomers, vinylcyan compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, octyl acrylate and cyclohexyl acrylate, methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate and cyclohexyl methacrylate Acrylic esters, phenyl acrylate, benzyl acrylate, etc. Methacrylic acid aryl esters such as acid aryl esters, phenyl methacrylate and benzyl methacrylate, epoxy group-containing acrylic acid esters or methacrylic acid esters such as glycidyl acrylate and glycidyl methacrylate, maleimides such as N, N-methylmaleimide and N-phenylmaleimide Examples thereof include α-, β-unsaturated carboxylic acids such as acrylic monomers, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid, or anhydrides thereof.

Further, rubbery polymers that can be copolymerized with styrene monomers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene random copolymers and block copolymers, acrylonitrile. -Butadiene copolymers, copolymers of alkyl acrylates or alkyl methacrylates and butadiene, polybutadiene-polyisoprene diene copolymers, ethylene-isoprene random copolymers and block copolymers, ethylene-butene randoms Copolymers of ethylene and α-olefins such as copolymers and block copolymers, ethylene-methacrylate copolymers, ethylene-butyl acrylate copolymers and the like of ethylene and α, β-unsaturated carboxylic acid esters Copolymer, Ethylene-propylene-non-conjugated diene terpolymers such as tylene-vinyl acetate copolymer, ethylene-propylene-hexadiene copolymer, acrylic rubber, composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate or methacrylate rubber, etc. Can be mentioned.

Such styrene resins include, for example, high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. Polymer (MABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), styrene-methyl methacrylate copolymer (MS resin), styrene -Maleic anhydride copolymer and the like.

The styrene resin is produced by a method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or bulk / suspension polymerization. In the present invention, the styrene resin or styrene random copolymer is used. In the case of a polymer or block copolymer, those produced by bulk polymerization, suspension polymerization, or bulk / suspension polymerization are suitable. In the case of a styrene-based graft copolymer, bulk polymerization, bulk / suspension polymerization or Those produced by emulsion polymerization are preferred.

In the present invention, acrylonitrile-butadiene-styrene copolymer (ABS resin) which is particularly preferably used is a thermoplastic graft copolymer obtained by graft copolymerization of acrylonitrile and styrene with a butadiene rubber component, and a copolymer of acrylonitrile and styrene. It is a mixture of The butadiene rubber component is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, and particularly preferably 13 to 25% by weight, in 100% by weight of the ABS resin component. The rubber particle size is preferably 0.1 to 5 μm, more preferably 0.2 to 3 μm, further 0.3 to 1.5 μm, and particularly preferably 0.4 to 0.9 μm. The distribution of the rubber particle size may be either a single distribution or a plurality of distributions of two or more peaks.

The thermoplastic resin composition used in the present invention may contain only one type of styrenic resin, or may contain two or more types.
Moreover, resin components other than polycarbonate resin and styrene resin may be included. However, in this embodiment, these components are preferably 5% by weight or less of the total resin components.

Embodiment with Polyamide Resin as Main Component A third embodiment of the thermoplastic resin in the present invention includes a case where the thermoplastic resin contains a polyamide resin. When the polyamide resin is contained, the polyamide resin is more preferably contained in an amount of 80% by weight or more, more preferably 90% by weight or more, further preferably 95% by weight or more, and particularly preferably 99% by weight or more. The upper limit when the thermoplastic resin includes a polyamide resin is 100% by weight or less. In addition, when a polyamide resin is included, the other resin component may be included. However, the other resin is preferably 5% by weight or less of the total resin components.

Polyamide resin The polyamide resin is a polymer having a repeating unit of acid amide obtained by ring-opening polymerization of lactam, polycondensation of aminocarboxylic acid, and polycondensation of diamine and dibasic acid. Specifically, polyamide 6 11, 12, 46, 66, 610, 612, 6I, 6/66, 6T / 6I, 6 / 6T, 66 / 6T, 66 / 6T / 6I, polyamide MX, polytrimethylhexamethylene terephthalamide, polybis (4 -Aminocyclohexyl) methane dodecamide, polybis (3-methyl-4-aminocyclohexyl) methane dodecamide, polyundecamethylene hexahydroterephthalamide and the like. In addition, said "I" shows an isophthalic acid component and "T" shows a terephthalic acid component.
As the polyamide resin used in the present invention, an appropriate polyamide resin is selected in consideration of various properties of these polyamide resins and the intended use of the molded product.

Among the above-mentioned polyamide resins, the semi-aromatic polyamide having an aromatic ring as a raw material dicarboxylic acid component, the polyamide MX having an aromatic ring as a raw material diamine component, or a polyamide resin obtained by mixing these is a glass fiber and a carbon fiber that increase strength. This is preferable because a compound containing a relatively large amount of filler such as can be easily obtained.
Specific examples of the semi-aromatic polyamide include 6I, 6T / 6I, 6 / 6T, 66 / 6T, 66 / 6T / 6I, and the like.
A polyamide MX resin obtained by polycondensation of xylylenediamine having an aromatic ring in the diamine component and α, ω-dibasic acid is particularly preferable because a high-strength resin composition can be obtained. More preferably, it is a polyamide resin obtained by polycondensation of paraxylylenediamine and / or metaxylylenediamine with an α, ω-linear aliphatic dibasic acid or aromatic dibasic acid having 6 to 12 carbon atoms. Particularly preferred are polyamide MX resins using sebacic acid and / or adipic acid as the dicarboxylic acid component, and particularly preferred is polymetaxylylene adipamide.
A mixture of a polyamide resin having an aromatic ring and an aliphatic polyamide resin (for example, polyamide 6, polyamide 66, etc.) is also preferably used. Even when the aliphatic polyamide resin alone is blended with a large amount of filler, the appearance and physical properties are improved by mixing with the above polyamide resin having an aromatic ring even when the appearance and physical properties are not sufficient. In the case of a mixture of a polyamide resin having an aromatic ring and an aliphatic polyamide resin, the weight ratio is preferably 100: 1 to 100: 20.

Embodiment with Thermoplastic Polyester Resin as Main Component As a fourth embodiment of the thermoplastic resin in the present invention, there is a case where the thermoplastic resin contains a thermoplastic polyester resin as a main component. In the fourth embodiment, the ratio of the thermoplastic polyester resin in the total resin components is preferably 51 to 100% by weight, more preferably 80 to 100% by weight, and further 90 to 100% by weight. preferable.

Thermoplastic polyester resin As the thermoplastic polyester resin, the description in paragraphs 0013 to 0016 of JP 2010-174223 A can be referred to.
As the polyester resin, a polybutylene terephthalate resin or a mixture containing 60% by weight or more, preferably 80% by weight or more of polybutylene terephthalate resin is usually used. For example, a mixture of a polybutylene terephthalate resin and a polyethylene terephthalate resin, the former occupying 60% by weight or more, and further 80% by weight or more, is one of the preferable polyester resins used in the present invention. In the mixture of the polybutylene terephthalate resin and the polyethylene terephthalate resin, the polyethylene terephthalate resin is preferably contained in an amount of 10 to 40% by weight, and more preferably 20 to 40% by weight.
As is well known, polybutylene terephthalate resin and polyethylene terephthalate resin are produced on a large scale by the reaction of terephthalic acid or its ester with 1,4-butanediol or ethylene glycol, and are distributed in the market. In the present invention, these resins available on the market can be used. Some commercially available resins contain a copolymer component other than a terephthalic acid component and a 1,4-butanediol component or an ethylene glycol component. However, in the present invention, a small amount of a copolymer component is usually used. What contains 10 weight% or less, Preferably it is 5 weight% or less can also be used.
The intrinsic viscosity of the polybutylene terephthalate resin is usually 0.5 to 1.5 dl / g, particularly preferably 0.6 to 1.3 dl / g. If it is less than 0.5 dl / g, it is difficult to obtain a resin composition having excellent mechanical strength. On the other hand, if it is larger than 1.5 dl / g, the fluidity of the resin composition is lowered, and the moldability may be lowered. Moreover, it is preferable that the amount of terminal carboxyl groups is 30 meq / g or less. Further, the content of tetrahydrofuran derived from 1,4-butanediol is preferably 300 ppm or less.
The intrinsic viscosity of the polyethylene terephthalate resin is usually 0.4 to 1.0 dl / g, particularly preferably 0.5 to 1.0 dl / g. If the intrinsic viscosity is less than 0.4, the mechanical properties of the resin composition are likely to be lowered, and if it exceeds 1.0, the fluidity is likely to be lowered. In addition, any intrinsic viscosity is a measured value in 30 degreeC in a phenol / tetrachloroethane (weight ratio 1/1) mixed solvent.
The thermoplastic resin composition used in the present invention may contain only one kind of thermoplastic polyester resin, or may contain two or more kinds.
In the present embodiment, a resin component other than the thermoplastic polyester resin may be included. However, the other resin is preferably 5% by weight or less of the total resin components.

Embodiment with Polyacetal Resin as Main Component As a fifth embodiment of the thermoplastic resin in the present invention, there is a case where the thermoplastic resin contains a polyacetal resin. When the polyacetal resin is included, the polyacetal resin is more preferably contained in an amount of 80% by weight or more, and the upper limit is 100% by weight or less. In addition, when a polyacetal resin is included, the other resin component may be included. However, the other resin is preferably 5% by weight or less of the total resin components.

Polyacetal Resin As for the polyacetal resin, description in paragraph Nos. 0011 of JP2003-003041A and paragraph Nos.0018 to 0020 of JP2003-220667A can be referred to.
Examples of the polyphenylene sulfide resin include paragraphs 0014 to 0016 in JP-A-10-292114, paragraphs 0011 to 0013 in JP-A-10-279800, and paragraphs 0011 to 0013 in JP2009-30030. The description of 0015 can be considered.

In the thermoplastic resin composition used in the present invention, 40% by weight or more of the total composition is preferably a resin component, more preferably 50% by weight or more is a resin component, and 60% by weight or more is a resin component. More preferably. When blending fibers (for example, glass fillers described later), it is preferable to occupy 80% by weight or more in total of fibers and resin components.

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The thermoplastic resin composition used in the present invention may contain fibers such as glass filler and various additives in addition to the thermoplastic resin.
In a thermoplastic resin composition containing a conventional LDS additive, the LDS additive may damage the glass filler, which may reduce the mechanical strength originally exhibited by the glass filler. However, in the present invention, since the LDS additive is blended separately from the thermoplastic resin composition, such a problem can be avoided.
In addition, when a dye / pigment or a flame retardant composition is blended with a conventional thermoplastic resin composition containing an LDS additive, the plating layer may not be formed properly even if the LDS additive is blended. However, in the present invention, since the LDS additive is blended separately from the thermoplastic resin composition, such a problem can be avoided.
In addition, the thermoplastic resin composition used in the present invention has a configuration that does not substantially contain an LDS additive. “The LDS additive is not substantially contained” means that the LDS additive is not blended in an amount capable of forming a plating layer, for example, 0.01 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. That means.

Glass Filler The thermoplastic resin composition used in the present invention may contain a glass filler. Examples of the glass filler include glass fiber, plate-like glass, glass beads, and glass flakes. Among these, glass fiber is preferable.

A glass filler consists of glass compositions, such as A glass, C glass, E glass, and S glass, and since E glass (an alkali free glass) does not have a bad influence on polycarbonate resin especially, it is preferable.
Glass fiber refers to a fiber having a fiber-like outer shape with a cross-sectional shape cut at right angles to the length direction and having a perfect circle or polygonal shape.

The glass fiber used for the thermoplastic resin composition used in the present invention may be a single fiber or a single fiber twisted together.
The form of the glass fiber is “glass roving” in which single fibers or a plurality of twisted strands are continuously wound, “chopped strand” trimmed to a length of 1 to 10 mm, and pulverized to a length of about 10 to 500 μm. Any of "Mildo fiber" etc. may be sufficient. Such glass fibers are commercially available from Asahi Fiber Glass under the trade names of “Glasslon Chopped Strand” and “Glasslon Milled Fiber” and are easily available. Glass fibers having different forms can be used in combination.

In the present invention, glass fibers having an irregular cross-sectional shape are also preferable. This irregular cross-sectional shape means that the flatness indicated by the long diameter / short diameter ratio (D2 / D1) when the long diameter of the cross section perpendicular to the length direction of the fiber is D2 and the short diameter is D1, is, for example, 1. It is preferably 5 to 10, more preferably 2.5 to 10, more preferably 2.5 to 8, and particularly preferably 2.5 to 5. Regarding such flat glass, the description of paragraph numbers 0065 to 0072 of JP-A-2011-195820 can be referred to, and the contents thereof are incorporated herein.

Glass beads are spherical ones having an outer diameter of 10 to 100 μm, and are commercially available, for example, under the trade name “EGB731” from Potters Barotini. Glass flakes are flakes having a thickness of 1 to 20 μm and a side length of 0.05 to 1 mm. For example, they are commercially available from Nippon Sheet Glass under the trade name “Fureka”. Are readily available.

The compounding amount of the glass filler in the thermoplastic resin composition used in the present invention is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and further 15 parts by weight or more with respect to 100 parts by weight of the resin component. preferable. Moreover, depending on a use, it can also be 30 weight part or more, Furthermore, it can also be 40 weight part or more. On the other hand, the upper limit is preferably 200 parts by weight or less, and more preferably 150 parts by weight or less. Depending on the application, it may be 60 parts by weight or less, further 50 parts by weight or less, and particularly 20 parts by weight or less.
The thermoplastic resin composition used in the present invention may contain only one type of glass filler, or may contain two or more types. When two or more types are included, the total amount falls within the above range. By blending a glass filler, mechanical strength can be improved and plating properties tend to be improved.

Bundling agent The glass filler blended in the thermoplastic resin composition used in the present invention is preferably coated with a sizing agent. The type of sizing agent is not particularly defined. A sizing agent may be used alone or in combination of two or more. Examples of the sizing agent include polyolefin resin, silicone resin, epoxy resin, and urethane resin.

The blending amount of the sizing agent in the thermoplastic resin composition used in the present invention is preferably 0.1 to 5.0% by weight of the glass filler, and more preferably 0.2 to 2.0% by weight. . The thermoplastic resin composition used in the present invention may contain only one type of sizing agent or two or more types. When two or more types are included, the total amount falls within the above range.

Titanium oxide The thermoplastic resin composition may contain titanium oxide. Examples of the titanium oxide include titanium monoxide (TiO), titanium trioxide (Ti ₂ O ₃ ), titanium dioxide (TiO ₂ ), and any of these may be used, but titanium dioxide is preferred. . Further, as the titanium oxide, those having a rutile type crystal structure are preferably used.

The average primary particle size 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-described range, a resin 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.

Also, commercially available titanium oxide may be used. Further, a lump-shaped material or a material having a large average particle diameter may be appropriately pulverized and classified by sieving or the like as necessary to obtain the above-mentioned average particle diameter.

When blended, the blending amount of titanium oxide in the thermoplastic resin composition is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the resin component. More preferably, it is at least part. Moreover, as an upper limit, 80 weight part or less is preferable, 20 weight part or less is preferable, 12 weight part or less is more preferable, and 8 weight part or less is further more preferable.
The thermoplastic resin composition may contain only one type of titanium oxide, or may contain two or more types. When two or more types are included, the total amount falls within the above range.

Elastomer The thermoplastic resin composition used in the present invention may contain an elastomer. By containing an elastomer, the impact resistance of the obtained resin molded product can be improved. Examples of the elastomer used in the present invention include methyl methacrylate-butadiene-styrene copolymer (MBS resin), styrene-butadiene triblock copolymer called SBS, SEBS, and hydrogenated products thereof, SPS, SEPS, Examples thereof include styrene-isoprene triblock copolymers and hydrogenated products thereof, olefinic thermoplastic elastomers, polyester elastomers, siloxane rubbers, and acrylate rubbers called TPO. As the elastomer, elastomers described in paragraph numbers 0075 to 0088 of JP2012-251061A, elastomers described in paragraph numbers 0101 to 0107 of JP2012-1777047A, and the like can be used. Incorporated herein.
The elastomer used in the present invention preferably has an acrylonitrile / butadiene / styrene copolymer content of less than 10% by weight, more preferably 5% by weight or less, and more preferably 3% by weight or less. Further preferred.

The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

The rubber component generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .

Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

The graft copolymer obtained by copolymerizing the rubber component is preferably a core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by weight or more of rubber component, more preferably 60% by weight or more. Moreover, what contains 10 weight% or more of (meth) acrylic acid is preferable. The core / shell type in the present invention does not necessarily have to be clearly distinguishable between the core layer and the shell layer, and widely includes compounds obtained by graft polymerization of a rubber component around the core portion. The purpose.

Preferred examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic / butadiene rubber copolymer, methyl methacrylate-acrylic / butadiene rubber- Styrene copolymer, methyl methacrylate- (acryl / silicone IPN rubber) copolymer, silicone-acrylic composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate Polyorganosiloxane polyalkyl (meth) silicone containing acrylate - acrylic composite rubber and methyl methacrylate - butadiene copolymer (MB) is particularly preferred. Such rubbery polymers may be used alone or in combination of two or more.

As such an elastomer, for example, “Paraloid (registered trademark, same applies hereinafter) EXL2602,” “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid EXL2311”, “Paraloid EXL2313” manufactured by Rohm and Haas Japan, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same applies hereinafter) C-223A” manufactured by Mitsubishi Rayon, “Metabrene E-901”, “Metabrene S-2001” ”,“ Metabrene SRK-200 ”,“ Metabrene S-2030 ”“ Kane Ace (registered trademark, the same applies hereinafter) M-511 ”,“ Kane Ace M-600 ”,“ Kane Ace M-400 ”,“ Kane Ace M- ” 5 0 "," Kane Ace M-711 "," Kane Ace MR-01 ", manufactured by Ube Industries, Ltd. of" UBESTA XPA ", and the like.

When blended, the amount of the elastomer is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, and further preferably 2 to 10 parts by weight with respect to 100 parts by weight of the resin component.
The thermoplastic resin composition used in the present invention may contain only one type of elastomer or two or more types. When two or more types are included, the total amount falls within the above range.

Flame retardant composition The thermoplastic resin composition used in the present invention may contain a flame retardant composition. As a flame retardant composition, it may consist only of a flame retardant, and the combination of a flame retardant and a flame retardant adjuvant may be sufficient. Each of the flame retardant and the flame retardant aid may be only one type or two or more types.

Examples of the flame retardant and / or flame retardant aid contained in the flame retardant composition of the present invention include halogen flame retardants, organometallic salt flame retardants, phosphorus flame retardants, silicone flame retardants, antimony flame retardants and flame retardants. Examples of the flame retardant can be exemplified. When a polyamide resin or a polyester resin is used as the thermoplastic resin, it is preferable to blend a halogen flame retardant or a phosphorus flame retardant. Moreover, when using polycarbonate resin as a thermoplastic resin, a phosphorus flame retardant and an organometallic salt flame retardant are preferable.

Preferable specific examples of the halogen-based flame retardant include brominated flame retardants, such as brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, glycidyl. Examples include brominated bisphenol A, pentabromobenzyl polyacrylate, and brominated imide. Among them, brominated polycarbonate, brominated polystyrene resin, glycidyl brominated bisphenol A, and pentabromobenzyl polyacrylate suppress the decrease in impact resistance. This is more preferable.

Examples of the phosphorus flame retardant include ethyl phosphinic acid metal salt, diethyl phosphinic acid metal salt, melamine polyphosphate, condensed phosphate ester, phosphazene compound, etc. Among them, condensed phosphate ester or phosphazene is preferable. Moreover, in order to suppress the generation | occurrence | production of the gas at the time of shaping | molding, a mold deposit, and the bleed-out of a flame retardant, you may mix | blend the thermoplastic resin excellent in a miscibility with a phosphorus flame retardant. Such a thermoplastic resin is preferably a polyphenylene ether resin, a polycarbonate resin, or a styrene resin.

The condensed phosphate ester is preferably a compound represented by the following general formula (10).
General formula (10)

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or an organic group, except that R ₁ , R ₂ , R ₃ and R ₄ are all hydrogen atoms. X represents a divalent organic group, p is 0 or 1, q represents an integer of 1 or more, and r represents 0 or an integer of 1 or more.)

In the above general formula (10), examples of the organic group include an alkyl group, a cycloalkyl group, and an aryl group having a substituent or not having a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a halogen atom, and a halogenated aryl group. Further, a group in which these substituents are combined, or a group in which these substituents are combined by combining with an oxygen atom, a sulfur atom, a nitrogen atom, or the like may be used. The divalent organic group refers to a divalent or higher group formed by removing one carbon atom from the above organic group. Examples thereof include an alkylene group, a phenylene group, a substituted phenylene group, and a polynuclear phenylene group derived from bisphenols.

Specific examples of the condensed phosphate ester represented by the general formula (10) include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, Tricresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) Phosphate, bis (2,3-dibromopropyl) -2,3-dichlorophosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A tetraphenyl phosphate Over DOO, bisphenol A tetra cresyl diphosphate, bisphenol A tetra xylylene distearate phosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetra cresyl phosphate, various ones such as hydroquinone tetra xylylene distearate phosphate are exemplified.
Examples of commercially available condensed phosphate esters include “CR733S” (resorcinol bis (diphenyl phosphate)), “CR741” (bisphenol A bis (diphenyl phosphate)), “PX-200” from Daihachi Chemical Industry Co., Ltd. (Resorcinol bis (dixylenyl phosphate)), “Adekastab FP-700” (2,2-bis (p-hydroxyphenyl) propane / trichlorophosphine oxide polycondensate (polymerization degree 1 to 4) from Asahi Denka Kogyo Co., Ltd. It is sold under the trade name such as 3) phenol condensate and is readily available.

The phosphazene compound is an organic compound having —P═N— bond in the molecule, preferably a cyclic phosphazene compound represented by the following general formula (1), a chain phosphazene represented by the following general formula (2) A compound, and at least one selected from the group consisting of a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of the following general formula (1) and the following general formula (2) is crosslinked by a crosslinking group It is this compound.

In the general formula (1), a is an integer of 3 to 25, and R ¹ and R ² may be the same or different and are an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an allyloxy group, an amino group , A hydroxy group, an aryl group or an alkylaryl group.

In the general formula (2), b is an integer of 3 to 10000, R ³ and R ⁴ may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an allyloxy group, an amino group , A hydroxy group, an aryl group or an alkylaryl group.
R ⁵ is selected from —N═P (OR ³ ) ₃ groups, —N═P (OR ⁴ ) ₃ groups, —N═P (O) OR ³ groups, and —N═P (O) OR ⁴ groups. R ⁶ represents at least one type, and R ⁶ represents —P (OR ³ ) ₄ group, —P (OR ⁴ ) ₄ group, —P (O) (OR ³ ) ₂ group, —P (O) (OR ⁴ ) ₂ At least one selected from the group is shown.

In the general formulas (1) and (2), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, A decyl group, a dodecyl group, etc., and an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, and a hexyl group is preferable. Particularly preferred are alkyl groups having 1 to 4 carbon atoms such as ethyl group and propyl group.

Examples of the cycloalkyl group include a cycloalkyl group having 5 to 14 carbon atoms such as a cyclopentyl group and a cyclohexyl group, and a cycloalkyl group having 5 to 8 carbon atoms is preferable.

Examples of the alkenyl group include alkenyl groups having 2 to 8 carbon atoms such as vinyl group and allyl group. Examples of the cycloalkenyl group include cycloalkenyl groups having 5 to 12 carbon atoms such as a cyclopentyl group and a cyclohexyl group.

Examples of the alkynyl group include an alkynyl group having an aryl group such as an alkynyl group having 2 to 8 carbon atoms such as an ethynyl group and a propynyl group and an ethynylbenzene group as a substituent.

Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl (ie, tolyl) group, a dimethylphenyl (ie, xylyl) group, a trimethylphenyl group, and a naphthyl group. However, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

Examples of the alkylaryl group include aralkyl groups having 6 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group. Among them, aralkyl groups having 7 to 10 carbon atoms are preferable, and benzyl group is particularly preferable. .

Among these, those in which R ¹ and R ² in the general formula (1) and R ³ and R ⁴ in the general formula (2) are an aryl group and an arylalkyl group are preferable. By using such an aromatic phosphazene, the thermal stability of the thermoplastic resin composition can be effectively increased. From such a viewpoint, R ¹ , R ² , R ³ and R ⁴ are more preferably aryl groups, and particularly preferably phenyl groups.

Examples of the cyclic and / or chain phosphazene compounds represented by the general formula (1) and the general formula (2) include phenoxyphosphazene, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene and the like. (Poly) xylyloxyphosphazenes such as (poly) tolyloxyphosphazene, o, m-xylyloxyphosphazene, o, p-xylyloxyphosphazene, m, p-xylyloxyphosphazene, o, m, p-trimethyl (Poly) phenoxytolyloxyphosphazenes such as phenyloxyphosphazene, phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxyphosphazene, phenoxy p-tolyloxyphosphazene, phenoxy o, m-xylyloxyphosphazene, phenoxyo, -Xylyloxyphosphazene, phenoxy m, p-xylyloxyphosphazene, etc. (poly) phenoxytolyloxyxylyloxyphosphazene, phenoxy o, m, p-trimethylphenyloxyphosphazene, etc. can be exemplified, preferably cyclic and / or chain Phenoxyphosphazene and the like.

As the cyclic phosphazene compound represented by the general formula (1), cyclic phenoxyphosphazene in which R ¹ and R ² are phenyl groups is particularly preferable. Examples of such cyclic phenoxyphosphazene compounds include hexachlorocyclotriphosphazene, octachlorochloromethane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by taking out cyclic chlorophosphazenes such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and replacing them with phenoxy groups . The cyclic phenoxyphosphazene compound is preferably a compound in which a in the general formula (1) is an integer of 3 to 8, and may be a mixture of compounds having different a.

The average a is preferably 3 to 5, more preferably 3 to 4. Among them, a mixture of compounds in which a = 3 is 50% by weight or more, a = 4 is 10 to 40% by weight, and a = 5 or more is 30% by weight or less is preferable.

As the chain phosphazene compound represented by the general formula (2), chain phenoxyphosphazene in which R ³ and R ⁴ are phenyl groups is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above method to reversion polymerization at a temperature of 220 to 250 ° C., and obtaining a linear dichlorophosphazene having a polymerization degree of 3 to 10,000. Examples include compounds obtained by substitution with a phenoxy group. In the general formula (2), b in the linear phenoxyphosphazene compound is preferably 3 to 1000, more preferably 3 to 100, and still more preferably 3 to 25.

Examples of the bridged phosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (that is, a bisphenol S residue), and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene group, such as compounds having a crosslinked structure of 4,4′-oxydiphenylene group, and compounds having a crosslinked structure of 4,4′-thiodiphenylene group Etc.

In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound in which R ¹ and R ² are phenyl groups in the general formula (1) is crosslinked by the above-mentioned crosslinking group, or the above general formula (2) In the above, a crosslinked phenoxyphosphazene compound in which a chain phenoxyphosphazene compound in which R ³ and R ⁴ are phenyl groups is crosslinked by the crosslinking group is preferable from the viewpoint of flame retardancy, and the cyclic phenoxyphosphazene compound is crosslinked by the crosslinking group. A crosslinked phenoxyphosphazene compound is more preferable.
The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (1) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (2) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

In the present invention, the phosphazene compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (1) and the cyclic phenoxyphosphazene compound represented by the general formula (1) with a crosslinking group. From the viewpoint of flame retardancy and mechanical properties of the thermoplastic resin composition, at least one selected from the group consisting of phosphazene compounds is preferred.
Examples of commercially available phosphazene compounds include FP-110 and Fushimi Pharmaceutical Co., Ltd.

As the organic metal salt flame retardant, an organic alkali metal salt compound or an organic alkaline earth metal salt compound is preferable (hereinafter, the alkali metal and the alkaline earth metal are referred to as “alkali (earth) metal”). Examples of the organic metal salt flame retardant include sulfonic acid metal salt, carboxylic acid metal salt, boric acid metal salt, and phosphoric acid metal salt. To sulfonic acid metal salts are preferable, and perfluoroalkanesulfonic acid metal salts are particularly preferable.

Examples of metal sulfonates include lithium sulfonate (Li), sodium sulfonate (Na), potassium sulfonate (K), rubidium sulfonate (Rb), cesium sulfonate (Cs), and magnesium sulfonate. (Mg) salt, calcium sulfonate (Ca) salt, strontium sulfonate (Sr) salt, barium sulfonate (Ba) salt, and the like. Among these, sodium sulfonate (Na) salt, potassium sulfonate (K ) Salt is preferred.

Examples of such sulfonic acid metal salts include diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, paratoluenesulfonic acid. Sodium, (branched) sodium dodecylbenzenesulfonate, sodium trichlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, (branched) potassium dodecylbenzenesulfonate, Potassium trichlorobenzenesulfonate, cesium benzenesulfonate, cesium (poly) styrenesulfonate, cesium p-toluenesulfonate, (branched) dodecylbenzenesulfone Perfluoroalkane sulfonic acid metal salts (alkanes), such as cesium, alkali (earth) metal sulfonate compounds such as cesium trichlorobenzene sulfonate, alkali metal perfluoroalkane sulfonates such as potassium perfluorobutane sulfonate The number of carbon atoms is preferably 2 to 6). Among these, diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium paratoluenesulfonate, potassium paratoluenesulfonate, and potassium perfluorobutanesulfonate are transparent and flame retardant. In particular, a perfluoroalkanesulfonic acid metal salt such as potassium perfluorobutanesulfonate is preferable.

The antimony flame retardant or flame retardant aid is a compound containing antimony and a compound that contributes to flame retardancy. Specific examples include antimony oxide such as antimony trioxide (Sb ₂ O ₃ ), antimony tetroxide, and antimony pentoxide (Sb ₂ O ₅ ), sodium antimonate, and antimony phosphate. Of these, antimony oxide is preferable because of its excellent resistance to moist heat. More preferably, antimony trioxide is used.

In addition to the above, flame retardant aids include copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, zirconium oxide, tin oxide, iron oxide, titanium oxide, aluminum oxide, zinc borate and the like. Among these, zinc borate is preferable from the viewpoint of more excellent flame retardancy.
The content of the flame retardant aid is preferably 0.3 to 1.1 (weight ratio) with respect to the flame retardant, preferably 0.4 to 1.0. Is more preferable.

In particular, the flame retardant composition used in the present invention includes a combination of a halogen flame retardant and an antimony flame retardant or a flame retardant aid. That is, as a result of investigation by the present inventors, it has been found that when an antimony flame retardant or a flame retardant aid is blended with a resin composition containing an LDS additive, a plating layer may not be formed properly. Antimony flame retardants or flame retardant aids are useful as flame retardants for thermoplastic resins, etc., and technology to appropriately form plating layers on thermoplastic resin molded articles containing antimony flame retardants or flame retardant aids Is required. Here, in the present invention, by using the composition for forming an LDS layer separately from the thermoplastic resin composition, a plating layer is appropriately applied to the surface of the resin molded product while using an antimony flame retardant or a flame retardant aid. It has succeeded in forming.
When contained, the content of the antimony-based flame retardant or flame retardant aid is preferably 0.1 to 25 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the thermoplastic resin. .
Further, the content of the antimony flame retardant or the flame retardant aid is preferably 1: 0.3 to 1.1 (weight ratio) with respect to the halogen flame retardant, and is preferably 1: 0.4 to More preferably, the ratio is 1.0.

The blending amount of the flame retardant composition is preferably 0.01 to 40 parts by weight, more preferably 1 to 40 parts by weight, still more preferably 5 to 50 parts by weight, more preferably 6 to 35 parts per 100 parts by weight of the resin component. Part by weight is particularly preferred, and 7 to 30 parts by weight is even more preferred. When the flame retardant composition is blended with the thermoplastic resin composition containing the LDS additive, the plating property (plating appearance) may be deteriorated. However, in the present invention, since the thermoplastic resin composition and the LDS layer forming composition are used separately, the plating layer can be appropriately formed also on the surface of the resin molded product containing the flame retardant composition.
In particular, when an organic metal salt flame retardant is used as the flame retardant composition, it is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the resin component.

Anti-dripping agent The thermoplastic resin composition used in the present invention may contain an anti-dripping agent. As the anti-drip agent, polytetrafluoroethylene (PTFE) is preferable, has a fibril-forming ability, easily disperses in the resin composition, and shows a tendency to form a fibrous material by bonding the resins together. is there. As specific examples of polytetrafluoroethylene, for example, “Teflon (registered trademark) 6J” or “Teflon (registered trademark) 30J” marketed by Mitsui / Dupont Fluorochemical, and products marketed by Daikin Chemical Industries, Ltd. Examples include the name “Polyflon” or the product name “Fullon” marketed by Asahi Glass.
The content ratio of the dripping inhibitor is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin. By setting the anti-dripping agent to 0.1 parts by weight or more, flame retardancy is further improved, and by setting it to 20 parts by weight or less, the appearance tends to be improved. The content ratio of the anti-dripping agent is more preferably 0.05 to 10 parts by weight, preferably 0.08 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

Silicate mineral The thermoplastic resin composition used in the present invention may contain a silicate mineral. In the present invention, by adding a silicate mineral, it is possible to improve the notched Charpy impact strength. The silicate mineral is not particularly limited as long as it contains silicon Si and oxygen O, but talc and / or mica is preferable, and talc is more preferable.
The silicate mineral used in the present invention is preferably in the form of particles, and the average particle diameter is preferably 1 to 30 μm, and more preferably 2 to 20 μm.
Further, the silicate mineral used in the present invention may be a silicate mineral surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. It is preferable not to be done.
When blended, the blending amount of the silicate mineral is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the resin component, and 3 parts by weight or more. More preferably, it is 3.5 parts by weight or more, particularly preferably 4.0 parts by weight or more. The upper limit is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less, and can be 9 parts by weight or less, and 8 parts by weight. It can also be as follows.
The thermoplastic resin composition used in the present invention may contain only one type of silicate mineral or two or more types. When two or more types are included, the total amount falls within the above range. When the silicate mineral is surface-treated, the total amount of the surface-treated is preferably within the above range.

Dye and Pigment The thermoplastic resin composition used in the present invention may contain a dye and pigment other than titanium oxide. In the present invention, the resin molded product can be colored by adding a dye / pigment. The dye / pigment is preferably a pigment.
Examples of the dye / pigment include white pigments containing ZnS or ZnO and black dye / pigment such as carbon black (particularly black pigment). In particular, when black dyes and pigments are blended, the black dyes and pigments absorb the heat during laser irradiation, the surface of the resin molded product made of the thermoplastic resin composition melts, and the adhesion with the LDS additive is improved. Can be made.
Also, phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green, azo dyes such as nickel azo yellow, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, quinophthalone, etc. Examples thereof include condensed polycyclic dyes, anthraquinone, heterocyclic, and methyl dyes.
When dyes and pigments are blended with a thermoplastic resin composition containing an LDS additive, the plating property may be lowered. However, in the present invention, since the thermoplastic resin composition and the LDS layer forming composition are used separately, a plating layer is appropriately formed on the surface of the resin molded product using the thermoplastic resin composition containing the dye / pigment. it can. In particular, when a white pigment is used, the present invention is effective because the plating property is easily damaged.

When the thermoplastic resin composition used in the present invention contains a dye / pigment, the amount of the dye / pigment is preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin component. More preferably, it is a part.
The thermoplastic resin composition used in the present invention may contain only one type of dye / pigment, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

Phosphorus Stabilizer The thermoplastic resin composition used in the present invention preferably contains a phosphorus stabilizer. As the phosphorus stabilizer, phosphate ester and phosphite ester are preferable.

As the phosphate ester, a compound represented by the following general formula (3) is preferable.
General formula (3)
O = P (OH) _m (OR) _3-m (3)
(In general formula (3), R is an alkyl group or an aryl group, which may be the same or different. M is an integer of 0 to 2.)
R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and an alkyl group having 2 to 25 carbon atoms, a phenyl group, a nonylphenyl group, an atarylphenyl group, 2, 4 -Di-tert-butylphenyl group, 2,4-ditert-butylmethylphenyl group, and tolyl group are more preferable.

Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, tetrakis (2,4-di-). tert-butylphenyl) -4,4-diphenylene phosphonite.

As the phosphite, a compound represented by the following general formula (4) is preferable.
General formula (4)

(In general formula (4), R ′ is an alkyl group or an aryl group, and each may be the same or different.)
R ′ is preferably an alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 12 carbon atoms. When R ′ is an alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable. When R ′ is an aryl group, an aryl group having 6 to 30 carbon atoms is preferable.

Examples of phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctyl phosphite , Trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite Bis (2.6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, etc. Triesters of acid, diesters, monoesters, and the like.

When the thermoplastic resin composition used in the present invention contains a phosphorus stabilizer, the amount of the phosphorus stabilizer is 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin component, and 0.02 to 2 Part by weight is more preferred.
The thermoplastic resin composition used in the present invention may contain only one type of phosphorus-based stabilizer, or may contain two or more types. When two or more types are included, the total amount falls within the above range.

Antioxidant The thermoplastic resin composition used in the present invention may contain an antioxidant. As the antioxidant, a phenolic antioxidant is preferable, and more specifically, 2,6-di-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) Isocyanurate, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-hydroxy-5-methylphenyl) propionate], and 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl Ethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N ′ hexamethylene bis [3- (3,5-di-tert-butyl-4 (-hydroxyphenyl) propion Amide), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. Among them, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′hexamethylene bis [3- (3,5-di-t-butyl-4 (-hydroxy) Phenyl) propionamide) and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.
When the thermoplastic resin composition used in the present invention contains an antioxidant, the amount of the antioxidant is 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin component, and 0.05 to 3 parts by weight. Is more preferable.
The thermoplastic resin composition used in the present invention may contain only one kind of antioxidant or two or more kinds. When two or more types are included, the total amount falls within the above range.

Hydrolysis resistance improver The thermoplastic resin composition used in the present invention may contain a hydrolysis resistance improver. In particular, it is useful when a polyester resin is included as the thermoplastic resin. As the hydrolysis resistance improver, known ones can be used, and examples thereof include carbodiimide compounds, epoxy compounds, oxazoline compounds, and oxazine compounds.

The carbodiimide compound, which is a hydrolysis resistance improver used in the present invention, is a compound having at least two carbodiimide groups (—N═C═N—) in one molecule, for example, an isocyanate in the molecule. A polyvalent isocyanate compound having at least two groups can be produced by performing a carbon dioxide condensation reaction (carbodiimidization reaction) in the presence of a carbodiimidization catalyst. The carbodiimidization reaction can be carried out by a known method. Specifically, the isocyanate is dissolved in an inert solvent, or phosphorene is used without a solvent in a stream of inert gas such as nitrogen or bubbling. By adding a carbodiimidization catalyst such as an organic phosphorus compound typified by oxides and heating and stirring in a temperature range of 150 to 200 ° C., a condensation reaction (carbodiimidization reaction) accompanied by decarbonation can be advanced. .

As a preferable polyvalent isocyanate compound, a bifunctional isocyanate having two isocyanate groups in the molecule is particularly suitable, but an isocyanate compound having three or more isocyanate groups can also be used in combination with diisocyanate. The polyvalent isocyanate compound may be any of aliphatic isocyanate, alicyclic isocyanate, and aromatic isocyanate. Specific examples of the polyvalent isocyanate include hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (H6XDI), xylylene diisocyanate (XDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), 1,12- Diisocyanate dodecane (DDI), norbornane diisocyanate (NBDI), 2,4-bis- (8-isocyanate octyl) -1,3-dioctylcyclobutane (OCDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), tetramethylxyl Range isocyanate (TMXDI), isophorone diisocyanate (IPDI), 2,4,6-triisopropylphenyl diisocyanate (TIDI), 4,4'-diphenylmethane diisocyanate Over preparative (MDI), tolylene diisocyanate (TDI), but hydrogenated tolylene diisocyanate (HTDI) and the like, but is not limited thereto.

As the carbodiimide compound used in the present invention, a carbodiimide compound obtained from HMDI or MDI is preferably used, or a commercially available “carbodilite” (manufactured by Nisshinbo Co., Ltd.) or “stabakuzol P” (manufactured by Rhein Chemie) is used. It may be used.

Next, as an epoxy compound used as a hydrolysis resistance improver in the present invention, bisphenol A type epoxy compound, bisphenol F type epoxy compound, resorcin type epoxy compound, novolac type epoxy compound, alicyclic compound type epoxy compound, glycidyl Ethers, epoxidized polybutadiene, and more specifically, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, resorcin type epoxy compounds, novolac type epoxy compounds, vinylcyclohexene dioxide, dicyclopentadiene oxide, and the like An epoxy compound is mentioned. As the epoxy compound, a novolac type epoxy resin having an epoxy equivalent of 150 to 280 g / eq or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 g / eq is preferably used from the viewpoint of chemical resistance and dispersion in the resin. More preferred is a novolak type epoxy resin having an epoxy equivalent of 180 to 250 g / eq and a molecular weight of 1000 to 6000, or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 g / eq and a molecular weight of 1200 to 6000. Catalog values are used for epoxy equivalent and molecular weight.

Examples of the compound having an oxazoline group (ring) include oxazolines, alkyloxazolines (C1-4 alkyloxazolines such as 2-methyloxazoline and 2-ethyloxazoline), and bisoxazoline compounds. Examples of bisoxazoline compounds include 2,2′-bis (2-oxazoline), 2,2′-bis (alkyl-2-oxazoline) [2,2′-bis (4-methyl-2-oxazoline), 2, 2,2'-bis (C1-6 alkyl-2-oxazoline) such as 2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4-dimethyl-2-oxazoline), etc. ], 2,2'-bis (aryl-2-oxazoline) [2,2'-bis (4-phenyl-2-oxazoline) etc.], 2,2'-bis (cycloalkyl-2-oxazoline) [2 2,2′-bis (4-cyclohexyl-2-oxazoline), etc.], 2,2′-bis (aralkyl-2-oxazoline) [2,2′-bis (4-benzyl-2-oxazoline), etc.], 2 , 2'-alkylenebis (2 Oxazoline) [2,2'-C1-10 alkylenebis (2-oxazoline) such as 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline)], 2 , 2'-alkylenebis (alkyl-2-oxazoline) [2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4-dimethyl-2-oxazoline) 2,2'-C1-10 alkylene bis (C1-6 alkyl-2-oxazoline) etc.], 2,2'-arylene bis (2-oxazoline) [2,2 '-(1,3-phenylene) -Bis (2-oxazoline), 2,2 '-(1,4-phenylene) -bis (2-oxazoline), 2,2'-(1,2-phenylene) -bis (2-oxazoline), 2, 2 -Diphenylenebis (2-oxazoline), etc.], 2,2'-arylenebis (alkyl-2-oxazoline) [2,2 '-(1,3-phenylene) -bis (4-methyl-2-oxazoline) 2,2′-phenylene-bis (C1-6 alkyl-2-oxazoline) such as 2,2 ′-(1,4-phenylene) -bis (4,4-dimethyl-2-oxazoline)], 2 2,2′-aryloxyalkanebis (2-oxazoline) [2,2′-9,9′-diphenoxyethanebis (2-oxazoline) etc.], 2,2′-cycloalkylenebis (2-oxazoline) [ 2,2′-cyclohexylenebis (2-oxazoline) etc.], N, N′-alkylenebis (2-carbamoyl-2-oxazoline) [N, N′-ethylenebis (2-carbamoyl-2-o) Xazoline), N, N′-tetramethylenebis (2-carbamoyl-2-oxazoline), etc., N, N′-C1-10 alkylenebis (2-carbamoyl-2-oxazoline) etc.], N, N′-alkylene Bis (2-carbamoyl-alkyl-2-oxazoline) [N, N'-ethylenebis (2-carbamoyl-4-methyl-2-oxazoline), N, N'-tetramethylenebis (2-carbamoyl-4,4 N, N′-C1-10 alkylene bis (2-carbamoyl-C 1-6 alkyl-2-oxazoline) such as dimethyl-2-oxazoline), N, N′-arylene bis (2-carbamoyl-2- Examples include oxazoline) [N, N′-phenylenebis (2-carbamoyl-oxazoline) and the like]. The compound having an oxazoline group also includes a vinyl polymer containing an oxazoline group [manufactured by Nippon Shokubai Co., Ltd., Epocros RPS series, RAS series, RMS series, etc.]. Of these oxazoline compounds, bisoxazoline compounds are preferred.

Examples of the compound having an oxazine group (ring) include oxazine and bisoxazine compounds. Examples of bisoxazine compounds include 2,2'-bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-bis (alkyl-5,6-dihydro-4H-1,3-oxazine ) [2,2'-bis (4-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-bis (4,4-dimethyl-5,6-dihydro-4H-1 , 3-oxazine), 2,2′-bis (4,5-dimethyl-5,6-dihydro-4H-1,3-oxazine) and the like, 2,2′-bis (C1-6 alkyl-5,6) -Dihydro-4H-1,3-oxazine)], 2,2'-alkylenebis (5,6-dihydro-4H-1,3-oxazine) [2,2'-methylenebis (5,6-dihydro- 4H-1,3-oxazine), 2,2'-ethylenebis (5,6-dihydro 4H-1,3-oxazine), 2,2′-hexanemethylenebis (5,6-dihydro-4H-1,3-oxazine) and the like 2,2′-C1-10 alkylenebis (5,6-dihydro) -4H-1,3-oxazine), etc.], 2,2'-arylenebis (5,6-dihydro-4H-1,3-oxazine) [2,2 '-(1,3-phenylene) -bis ( 5,6-dihydro-4H-1,3-oxazine), 2,2 '-(1,4-phenylene) -bis (5,6-dihydro-4H-1,3-oxazine), 2,2'- (1,2-phenylene) -bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2 '-Diphenylenebis (5,6-dihydro-4H-1,3-oxadi Etc.], N, N′-alkylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine) [N, N′-ethylenebis (2-carbamoyl-5,6-dihydro-4H) -1,3-oxazine), N, N'-tetramethylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine) and other N, N'-C1-10 alkylenebis (2- Carbamoyl-5,6-dihydro-4H-1,3-oxazine)], N, N′-alkylenebis (2-carbamoyl-alkyl-5,6-dihydro-4H-1,3-oxazine) [N, N'-ethylenebis (2-carbamoyl-4-methyl-5,6-dihydro-4H-1,3-oxazine), N, N'-hexamethylenebis (2-carbamoyl-4,4-dimethyl-5, 6-dihydr N, N′-C1-10 alkylenebis (2-carbamoyl-C1-6alkyl-5,6-dihydro-4H-1,3-oxazine) etc.], N , N′-arylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine) [N, N′-phenylenebis (2-carbamoyl-oxazine) etc.] and the like. Of these oxazine compounds, bisoxazine compounds are preferred.

The blending amount of the hydrolysis resistance improving agent is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

Release agent The thermoplastic resin composition used in the present invention may contain a release agent. The release agent is preferably at least one compound selected from an aliphatic carboxylic acid, an aliphatic carboxylic acid ester, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000, and a polyolefin compound. Among these, at least one compound selected from polyolefin compounds, aliphatic carboxylic acids, and aliphatic carboxylic acid esters is more preferably used.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. In the present specification, the term “aliphatic carboxylic acid” is used to include alicyclic carboxylic acids. Among the aliphatic carboxylic acids, mono- or dicarboxylic acids having 6 to 36 carbon atoms are preferable, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellic acid, and tetrariacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Of these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.
Examples of the polyolefin compound include compounds selected from paraffin wax and polyethylene wax. Among them, the weight average molecular weight is 700 to 10,000, and more preferably 900 to 8 from the viewpoint of good dispersion of the polyolefin compound. 1,000 polyethylene waxes are preferred.

When the thermoplastic resin composition used in the present invention contains a release agent, the compounding amount of the release agent is 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin component, and 0.05 to 3 parts by weight. Is more preferable. The thermoplastic resin composition used in the present invention may contain only one type of release agent, or may contain two or more types. When two or more types are included, the total amount falls within the above range.

The thermoplastic resin composition used in the present invention may contain other components without departing from the spirit of the present invention. Other components include stabilizers other than phosphorus stabilizers, ultraviolet absorbers, inorganic fillers other than those mentioned above, white pigments other than titanium oxide, fluorescent whitening agents, anti-dripping agents, antistatic agents, antifogging agents. , Lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. Two or more of these may be used in combination.
With respect to these components, descriptions in JP 2007-314766 A, JP 2008-127485 A, JP 2009-51989 A, and JP 2012-72338 A can be referred to, and the contents thereof are described in this specification. Embedded in the book.

<Method for producing thermoplastic resin composition and method for producing resin molded product>
The method for producing the thermoplastic resin composition used in the present invention is not particularly defined, and a wide variety of known methods for producing a thermoplastic resin composition can be employed. Specifically, each component is mixed in advance using various mixers such as a tumbler or Henschel mixer, and then melt kneaded with a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. By doing so, a resin composition can be produced.

In addition, for example, it is also possible to produce a thermoplastic resin composition without mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading. it can.
Furthermore, for example, a resin composition obtained by mixing some components in advance, supplying them to an extruder and melt-kneading is used as a master batch, and this master batch is mixed with the remaining components again and melt-kneaded. A thermoplastic resin composition can also be produced.

The method for producing a resin molded product from the thermoplastic resin composition is not particularly limited, and a molding method generally employed for thermoplastic resins, that is, a general injection molding method, an ultra-high speed injection molding method, an injection Compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, molding method using rapid heating mold, foam molding (including supercritical fluid), insert molding An IMC (in-mold coating molding) molding method, an extrusion molding method, a sheet molding method, a thermoforming method, a rotational molding method, a lamination molding method, a press molding method and the like can be employed. A molding method using a hot runner method can also be selected.

<Method for producing resin molded product with plating layer>
As shown in FIG. 2, the method for producing a resin molded product with a plated layer of the present invention is applied to the surface of the resin molded product 21 with the composition for forming a laser direct structuring layer of the present invention and cured, It includes a step of forming a plating layer 24 by irradiating a laser.
By setting it as such a structure, even if it does not mix | blend an LDS additive with a thermoplastic resin composition, it becomes possible to form a plating layer on the surface of a resin molded product.

The method for applying the composition for forming an LDS layer to the surface of the resin molded product is not particularly defined, but is preferably applied. The application includes not only a method using a brush or the like but also so-called hand coating. In this invention, it is preferable to stir before applying the composition for LDS layer formation to the surface of a resin molded product. By stirring, an LDS layer in which the LDS additive is more uniformly dispersed can be formed.
The composition for forming an LDS layer is preferably applied so that the average film thickness of the LDS layer after drying is 0.1 to 1000 μm, and more preferably 0.5 to 300 μm.

The resin molded product in the present invention may be a flat substrate, but may be a resin molded product that is partially or entirely curved. Moreover, the surface of the part where the plating of the resin molded product is formed may have roughness, but may be a smooth surface. In the conventionally known plating formation method, the surface of the resin molded product is roughened and then the plating is formed. However, in the present invention, the plating can be formed even if the surface of the resin molded product is smooth. Is advantageous.
Further, the resin molded product is not limited to the final product, and includes various parts. The resin molded product in the present invention is preferably used for parts of portable electronic devices, vehicles and medical devices, and electronic parts including other electric circuits. In particular, resin molded products have both high impact resistance, rigidity, and excellent heat resistance, as well as low anisotropy and low warpage, so PDAs and pockets for electronic notebooks, portable computers, etc. It is extremely effective as an internal structure and casing such as a bell, a mobile phone, and a PHS. In particular, the resin molded product is suitable for flat plate-like parts having an average thickness excluding ribs of 1.2 mm or less (the lower limit is not particularly defined, for example, 0.4 mm or more). Particularly suitable as a housing.
Furthermore, the surface of the resin molded product may be roughened, but may not be roughened. In particular, unlike the known plating layer forming method, the present invention is advantageous in that plating can be formed on the surface of a resin molded product that has not been roughened while achieving high adhesion. Examples of the surface roughening treatment include filing and primer treatment with a solvent.

Returning again to FIG. 2, the composition for forming an LDS layer is applied to the surface of the resin molded product 21, and then the curable compound is cured by means such as ultraviolet irradiation or heating. By curing the curable compound, the LDS additive is also fixed.
Next, in the present invention, the LDS layer 22 provided on the surface of the resin molded product 21 is irradiated with a laser. 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 preferred wavelength range is 200 nm to 1200 nm. Particularly preferred is 800 to 1200 nm. When an ultraviolet curable compound is used as the curable compound, it is preferable to irradiate a laser with a wavelength of 800 to 1200 nm so that plating is not formed by ultraviolet rays.
When the laser is irradiated, the LDS additive 23 is activated only in the portion irradiated with the laser. In this activated state, the resin molded product 21 having the LDS layer 22 is applied to the plating solution. The plating solution is not particularly defined, and a wide variety of known plating solutions can be used. A metal component in which copper, nickel, gold, silver, and palladium are mixed is preferable, and copper is more preferable.
The method of applying the resin molded product 21 having the LDS layer 22 to the plating solution is not particularly defined, but for example, a method of putting it in a solution containing the plating solution can be mentioned. In the resin molded product after applying the plating solution, the plating layer 24 is formed only in the portion irradiated with the laser.
In the method of the present invention, a circuit interval having a width of 1 mm or less and further 150 μm or less (the lower limit is not particularly defined, but for example, 30 μm or more) can be formed. Such a circuit is preferably used as an antenna of a portable electronic device component. That is, as an example of a preferred embodiment of the resin molded product, 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 given.
The resin molded article with a plated layer of the present invention is preferably produced using the kit of the present invention.

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.

<Resin>
PAMXD6: Polymetaxylylene adipamide, S6007, Amilan (registered trademark) CM3001-N manufactured by Mitsubishi Gas Chemical, CM3001-N: Polyamide resin, PC resin made by Toray, Iupilon S-3000, PBT manufactured by Mitsubishi Engineering Plastics: Polybutylene terephthalate resin , 5008 / F, Mitsubishi Chemical <Glass fiber>
03T-296GH: Nippon Electric Glass T-571: Nippon Electric Glass T-127: Nippon Electric Glass <talc>
Micron white 5000S: Hayashi Kasei <release agent>
Hostamont NAV101, Hoechst Hoechst wax E powder, Clariant Japan CS-8CP: Nitto Kasei PE520: Polyethylene wax, Clariant Japan <Flame Retardant>
PATOX-M: Antimony trioxide, Nippon Seiki Great Lakes PDBS-80: Polydibromostyrene, Great Lakes Chemical Corporation KFBS: Potassium perfluorobutanesulfonate, Mitsubishi Materials PTFE-6J: Polytetrafluoroethylene, DuPont fluoro Chemical PX-200: Resorcinol bis-2,6-xylenyl phosphate, Daihachi Chemical Industries FP-110: Phenoxyphosphazene compound, Fushimi Pharmaceutical

<Hydrolysis resistance improver>
Adeka Sizer EP-17, manufactured by Adeka <Antioxidant>
IRGANOX-1010, manufactured by BASF <Pigment>
CB-1: Carbon black, # 45, Mitsubishi Chemical ZnS: Zinc sulfide, Sacritus HD, Satris RB948G: Carbon black, Koshigaya Kasei CB-2: Carbon black, # 650B, Mitsubishi Chemical

<Paint>
Paint 1: Urethane-based thermosetting paint: Retan PG80III Clear, manufactured by Kansai Paint As a curable compound, 10 parts by weight of a curing agent and 100 parts by weight of thinner as an organic solvent were used for 100 parts by weight of a urethane resin. .
Paint 2: Acrylic urethane-based thermosetting paint: nax Mighty-lac G-II KB type clear, manufactured by Nippon Paint As a curable compound, 100 parts by weight of acrylic urethane resin, 25 parts by weight of curing agent, thinner 125 as an organic solvent A part by weight was blended and used.
Paint 3: Urethane-based thermosetting paint: High Metal KD2850 Silver, manufactured by Cashew As a curable compound, 100 parts by weight of urethane-based resin was blended with 150 parts by weight of thinner as an organic solvent.
Paint 4: Urethane-based UV curable paint: 6110 clear, 50% by weight of thinner as an organic solvent was mixed with 100% by weight of urethane-based resin as a curable compound made from cashew.
Paint 5: Epoxy thermosetting paint: Million Clear, manufactured by Kansai Paint As a curable compound, 20 parts by weight of a curing agent and 50 parts by weight of thinner as an organic solvent were blended with 80 parts by weight of an epoxy resin.
Paint 6: Polyvinyl chloride paint (room temperature curing type): 100% by weight of polyvinyl chloride as a curable compound, 100 parts by weight of polyvinyl chloride as a curable compound was used by blending 80 parts by weight of thinner.

<LDS additive>
Black 1G: Shepherd CP5C: 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) (manufactured by Keeling & Walker)
23K: manufactured by Hakusuitec, aluminum-doped zinc oxide, resistivity (product standard value) 100 to 500 Ω · cm

<Compound of thermoplastic resin composition>
Each component is weighed so as to have the composition shown in the table to be described later, components other than glass fibers are blended with a tumbler, charged from the root of a twin screw extruder (manufactured by Toshiba Machine, TEM26SS), and melted. Then, glass fibers were side-fed to produce resin pellets (thermoplastic resin composition). The set temperature of the extruder was 280 ° C. for Examples 1 to 18 and Comparative Examples 1 to 8. Examples 19 to 22, Examples 25 to 31, Comparative Examples 9 to 12, Comparative Example 14, and Reference Example were performed at 290 ° C. About Example 23, 24 and the comparative example 13, it implemented at 260 degreeC.

<Specimen plate>
Molding was performed by filling a cavity of 60 × 60 mm and a thickness of 2 mm as a mold with a resin melted 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 test piece plate. The color of the obtained test piece was visually observed.

<Bending strength>
The resin pellets obtained by the above production method were dried at 120 ° C. for 4 hours, and then an ISO tensile test piece having a thickness of 4 mm was injection molded using SG125-MII manufactured by Sumitomo Heavy Industries.
Cylinder temperature and mold temperature were 280 ° C. and 130 ° C. for Examples 1 to 18, Comparative Examples 1 to 8, and 260 ° C. and 80 ° C. for Examples 23 and 24 and Comparative Example 13, respectively. -22, Examples 25-31, Comparative Examples 10-12, Comparative Example 14, and Reference Example were carried out at 280 ° C. and 80 ° C.
Based on ISO178, the bending strength (unit: MPa) was measured at a temperature of 23 ° C. using the ISO tensile test piece (4 mm thickness).

<Charpy impact strength>
Using the ISO tensile test piece (4 mm thickness) obtained above, the notched and notched Charpy impact strength (unit: KJ / m ² ) was measured at 23 ° C. according to ISO 179.

<Preparation of composition for forming LDS layer and application to test piece plate>
<< Examples 1 to 17, Comparative Example 2 >>
A composition for forming an LDS layer (coating material for forming an LDS layer) was prepared by mixing the coating material and an LDS additive with a spoonful so as to have a composition shown in a table to be described later. After degreasing the surface of the test piece plate obtained above with isopropyl alcohol, the composition for forming an LDS layer was spray-coated on the surface of the test piece plate. After fixing for 10 minutes for fixing, baking treatment was performed at 80 ° C. for 30 minutes.
<< Comparative Examples 1, 3 to 8 >>
The composition for forming the LDS layer was not applied, and the surface of the test piece plate obtained above was degreased with isopropyl alcohol as it was.
<< Example 18 >>
Example 18 was the same as in Example 1 except that the fixing time was 20 minutes, and pre-drying treatment was allowed to stand at 40 ° C. for 20 minutes, followed by baking at 70 ° C. for 50 minutes.

<< Examples 19 to 21, Comparative Example 9, Example 25, Examples 27 to 30, Examples 32 to 39 >>
A composition for forming an LDS layer (coating material for forming an LDS layer) was prepared by mixing a coating material, a thinner, and an LDS additive with a spoonful so as to have a composition shown in a table to be described later. The surface of the test piece plate obtained above was washed with a neutral detergent and further washed with methanol. The composition for LDS layer formation was apply | coated to the test piece using the brush. It was cured by heating at 70 ° C. for 10 minutes.
<< Example 22, Comparative Example 10, Example 26, Example 31, Examples 40 to 42 >>
A composition for forming an LDS layer (coating material for forming an LDS layer) was prepared by mixing a coating material, a thinner, and an LDS additive with a spoonful so as to have a composition shown in a table to be described later. The surface of the test piece plate obtained above was washed with a neutral detergent and further washed with methanol. The composition for LDS layer formation was apply | coated to the test piece using the brush. After preheating at 60 ° C. for 5 minutes, it was cured by ultraviolet irradiation at an exposure amount of 1000 mJ / cm ² .
<< Comparative Examples 11 and 12, Reference Example, Comparative Example 14 >>
The composition for forming the LDS layer was not applied, and the surface of the test piece plate obtained above was washed with a neutral detergent and further washed with methanol.
<< Example 23 >>
A composition for forming an LDS layer (coating material for forming an LDS layer) was prepared by mixing the coating material and an LDS additive with a spoonful so as to have a composition shown in a table to be described later. The surface of the test piece plate obtained above was degreased with isopropyl alcohol, and then the LDS layer forming composition obtained above was spray-coated uniformly on the surface of the test piece plate. After fixing for 20 minutes for fixing, baking and drying treatment was performed at 100 ° C. for 30 minutes.
<< Example 24 >>
A composition for forming an LDS layer (coating material for forming an LDS layer) was prepared by mixing the coating material and an LDS additive with a spoonful so as to have a composition shown in a table to be described later. The surface of the test piece plate obtained above was degreased with isopropyl alcohol, and then the LDS layer forming composition obtained above was spray-coated uniformly on the surface of the test piece plate. It left still at 23 degreeC for 48 hours.
<< Comparative Example 13 >>
The surface of the test piece plate obtained above was degreased with isopropyl alcohol and then used as it was.

<Platting appearance (plating properties)>
Using a laser irradiation apparatus (manufactured by SUNX, LP-Z SERIES (maximum output of YAG laser with a wavelength of 1064 nm, 13 W)) in the range of 55 × 40 mm of the obtained specimen plate, output 100, 80, 60, 40%, pulse period Irradiation was at 50 and 20 microseconds at a speed of 2 m / s. The subsequent plating layer forming step was carried out in a plating bath at 70 ° C. using an electroless MacDermid product, MIDCopper100XB Strike. The plating performance was determined by visual observation of the thickness of the plating layer in 10 minutes.
Of the 10 square samples, the evaluation was based on the number of squares on which no irregularities were found on the surface and a good appearance could be confirmed.
A: 9 to 10 squares (no irregularities are observed on the surface of the 10 square samples as a whole, and a good appearance is confirmed)
B: 7 to 8 squares C: 4 to 6 squares D: 2 to 3 squares E: 0 to 1 square (the entire sample of 10 squares has irregularities on its surface, and the appearance is poor)

<Flame retardance>
The resin pellets obtained by the above production method were dried at 120 ° C. for 4 hours and then injection molded using a J50-EP type injection molding machine manufactured by Nippon Steel, Ltd., and the length was 125 mm, the width was 13 mm, and the thickness was A 1.6 mm UL test specimen was molded. Cylinder temperature and mold temperature were 280 ° C. and 130 ° C. for Examples 1 to 18, Comparative Examples 1 to 8, and 260 ° C. and 80 ° C. for Examples 23 and 24 and Comparative Example 13, respectively. -22, Examples 25-42, Comparative Examples 10-12, Comparative Example 14, and Reference Example were carried out at 280 ° C. and 80 ° C.

The flame retardancy of each resin composition was evaluated by conditioning the test piece for UL test obtained by the above-mentioned method for 48 hours in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50%, and US Underwriters Laboratories. The test was conducted in accordance with the UL94 test (combustion test of plastic materials for equipment parts) defined by (UL). UL94V is a method for evaluating flame retardancy from the afterflame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in the following table.

Here, the afterflame time is the length of time for which the test piece continues to burn with flame after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Furthermore, if any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) as not satisfying V-2.

As is apparent from the above results, when the composition for forming an LDS layer of the present invention was used, good plating could be formed on the surface of the resin molded product without adding an LDS additive to the thermoplastic resin composition. . In particular, the plating has high adhesiveness with the resin molded product and cannot be easily removed.
On the other hand, when the composition for forming an LDS layer is not used (Comparative Examples 1, 3 to 8, 11 to 14), mechanical strength is not achieved even though glass fibers are blended, or LDS is added. Despite blending the agent, plating properties were not achieved.
Further, in Comparative Examples 2, 9, and 10 in which no LDS additive was used, plating could not be formed.

11 Resin Molded Product 12 LDS Additive 13 Plating Layer 21 Resin Molded Product 22 LDS Layer 23 LDS Additive 24 Plating Layer 25 Unirradiated LDS Layer

Claims

A composition for forming a laser direct structuring layer, comprising a curable compound, an organic solvent, and a laser direct structuring additive.
The composition for forming a laser direct structuring layer according to claim 1, wherein the curable compound is a resin.
The composition for forming a laser direct structuring layer according to claim 1, wherein the curable compound is an ultraviolet curable compound or a thermosetting compound.
The laser direct structuring layer formation according to any one of claims 1 to 3, comprising 0.05 to 70 parts by weight of a laser direct structuring additive with respect to a total of 100 parts by weight of the curable compound and the organic solvent. Composition.
The composition for forming a laser direct structuring layer according to any one of claims 1 to 4, wherein the composition for forming a laser direct structuring layer contains 20 to 80% by weight of the curable compound.
A kit comprising the composition for forming a laser direct structuring layer according to any one of claims 1 to 5 and a thermoplastic resin composition containing a thermoplastic resin.
The kit of claim 6, wherein the thermoplastic resin composition is substantially free of laser direct structuring additives.
The kit according to claim 6 or 7, wherein the thermoplastic resin is a crystalline resin.
The kit according to claim 8, wherein the crystalline resin is a polyamide resin.
The kit according to claim 8, wherein the crystalline resin is a thermoplastic polyester resin.
The kit according to claim 6 or 7, wherein the thermoplastic resin is an amorphous resin.
The kit according to claim 11, wherein the amorphous resin is a polycarbonate resin.
The kit according to any one of claims 6 to 12, wherein the thermoplastic resin composition comprises a dye / pigment and / or a flame retardant composition.
The kit according to any one of claims 6 to 12, wherein the thermoplastic resin composition comprises a pigment and / or a flame retardant composition.
The kit according to any one of claims 6 to 14, wherein the thermoplastic resin composition contains a black dye / pigment.
The kit according to any one of claims 6 to 15, wherein the thermoplastic resin composition contains at least one of an antimony flame retardant and an antimony flame retardant aid.
The kit according to any one of claims 6 to 16, wherein the thermoplastic resin composition contains a halogen-based flame retardant.
The kit according to any one of claims 6 to 15, wherein the thermoplastic resin composition contains a phosphorus-based flame retardant.
The kit according to claim 18, wherein the phosphorus-based flame retardant comprises at least one selected from a condensed phosphate ester and a phosphazene compound.
The kit according to any one of claims 6 to 15, wherein the thermoplastic resin composition contains an organometallic salt flame retardant.
A laser direct structuring layer forming composition according to any one of claims 1 to 5 is applied to the surface of a thermoplastic resin molded article, cured, and then irradiated with a laser to form a plating layer. The manufacturing method of the resin molded product with a plating layer including a process.
The method for producing a resin molded product with a plating layer according to claim 21, wherein the thermoplastic resin molded product contains a crystalline resin.
The method for producing a resin molded product with a plating layer according to claim 21, wherein the thermoplastic resin molded product contains an amorphous resin.
The method for producing a resin molded product with a plating layer according to any one of claims 21 to 23, wherein the kit according to any one of claims 6 to 20 is used.