JP2022157658A - Resin composition, resin molding, and method for manufacturing plated resin molding - Google Patents

Abstract

To provide a resin composition, a resin molding and a method for manufacturing a plated resin molding which can provide a resin molding that can be plated and has low dielectric property.SOLUTION: A resin composition for low dielectric laser direct structuring contains a thermoplastic resin, a laser direct structuring additive, and polyolefin, where the thermoplastic resin contains at least one of a polycarbonate resin, a polyphenylene ether resin, a polyester resin and a polyamide resin, and contains 4.0-30.0 pts.mass of polyolefin with respect to 100 pts.mass of the thermoplastic resin.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a resin composition, a resin molded article, and a method for producing a plated resin molded article.

2. Description of the Related Art In recent years, with the development of mobile phones including smart phones, various methods of manufacturing antennas inside mobile phones have been investigated. In particular, there is a need for a method of manufacturing an antenna that allows three-dimensional design for mobile phones. As one of techniques for forming such a three-dimensional antenna, a laser direct structuring (hereinafter sometimes referred to as "LDS") technique is attracting attention. The LDS technique is, for example, a technique of forming a plating by irradiating the surface of a resin molded article containing an LDS additive with a laser to activate it and applying a metal to the activated portion. A feature of this technology is that it enables the production of a metal structure such as an antenna directly on the surface of a resin molded product without using an adhesive or the like. Such LDS techniques are disclosed, for example, in Patent Documents 1-3.

JP 2013-144767 A JP 2014-043549 A WO2017/102930

Here, as the use of LDS technology spreads, a resin composition for LDS with low dielectric properties is also required. In order to reduce the dielectric properties of the resin composition, alloying a thermoplastic resin with a resin having relatively low dielectric properties is conceivable. However, as a result of investigation by the present inventor, it was found that in a resin composition containing an LDS additive, even if a resin having low dielectric properties was alloyed, the relative dielectric constant or dielectric loss tangent did not decrease in some cases. .
An object of the present invention is to solve such problems, and a resin composition, a resin molded product, and a plated resin molded product that can be plated and can provide a low-dielectric resin molded product. The object is to provide a manufacturing method.

Based on the above-mentioned problems, the present inventor conducted a study and found that the above-mentioned problems can be solved by blending a predetermined thermoplastic resin with a polyolefin together with an LDS additive. . Specifically, the above problems have been solved by the following means.
<1> A thermoplastic resin, a laser direct structuring additive, and a polyolefin, wherein the thermoplastic resin includes at least one of a polycarbonate resin, a polyphenylene ether resin, a polyester resin, and a polyamide resin; A resin composition for low dielectric laser direct structuring, containing 4.0 to 30.0 parts by mass of polyolefin with respect to 100 parts by mass of plastic resin.
<2> The resin composition according to <1>, wherein the thermoplastic resin contains a polyamide resin.
<3> The resin composition according to <2>, wherein the polyamide resin contains a semi-aromatic polyamide resin.
<4> At least one of the polyamide resins contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, and is derived from the dicarboxylic acid. The resin composition according to <2>, wherein 70 mol% or more of the structural units of are derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
<5> The resin composition according to any one of <1> to <4>, which contains 1.0 to 30.0 parts by mass of the laser direct structuring additive with respect to 100 parts by mass of the thermoplastic resin. .
<6> The resin composition according to any one of <1> to <5>, wherein the laser direct structuring additive contains at least one of copper, antimony, tin, aluminum and zinc.
<7> The resin composition according to any one of <1> to <5>, wherein the laser direct structuring additive contains copper chromium copper oxide and/or an oxide containing antimony and tin.
<8> The resin composition according to any one of <1> to <7>, wherein the laser direct structuring additive has a resistivity of more than 5×10 ³ Ω·cm.
<9> The resin composition according to any one of <1> to <8>, wherein the polyolefin comprises an acid-modified polyolefin.
<10> The resin composition according to any one of <1> to <9>, wherein the polyolefin contains polyethylene.
<11> The resin composition according to any one of <1> to <10>, further comprising 10.0 to 150.0 parts by mass of inorganic fibers with respect to 100 parts by mass of the thermoplastic resin.
<12> The resin composition according to <11>, wherein the inorganic fiber has a dielectric constant of 7 or less.
<13> The resin composition according to <11> or <12>, wherein the inorganic fibers include glass fibers.
<14> The glass fiber contains 65 to 85% by mass of SiO ₂ , 15 to 30% by mass of B ₂ O ₃ , and 0 to 4% by mass of sodium oxide (Na ₂ O) and/or potassium oxide (K ₂ O) and 0 to 4% by mass of other components, according to <13>.
<15> The resin composition according to any one of <11> to <14>, containing 20.0 to 80.0 parts by mass of the inorganic fiber with respect to 100 parts by mass of the thermoplastic resin.
<16> The resin composition according to any one of <1> to <15>, further comprising 0.1 to 200.0 parts by mass of talc with respect to 100.0 parts by mass of the laser direct structuring additive. thing.
<17> The resin composition according to any one of <1> to <16>, wherein the resin composition has a dielectric constant of 3.60 or less at a frequency of 2.45 GHz.
<18> A resin molded article formed from the resin composition according to any one of <1> to <17>.
<19> The resin molded article according to <18>, wherein the surface of the resin molded article is plated.
<20> The resin molded article according to <19>, wherein the plating has performance as an antenna.
<21> The resin molded product according to any one of <18> to <20>, which is a mobile electronic device component.
<22> The surface of the resin molded article formed from the resin composition according to any one of <1> to <17> is irradiated with a laser, and then metal is applied to form plating. , a method for manufacturing a plated resin molded product.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition, a resin molded article, and a method for manufacturing a plated resin molded article, which can form a plating and provide a low-dielectric resin molded article.

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

EMBODIMENT OF THE INVENTION Hereinafter, the form (only henceforth "this embodiment") for implementing this invention is demonstrated in detail. In addition, the following embodiment is an example for explaining the present invention, and the present invention is not limited only to this embodiment.
In this specification, the term "~" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.
In the present specification, the number average molecular weight is a polystyrene equivalent value measured by GPC (gel permeation chromatography) method.
In this specification, various physical property values and characteristic values are at 23° C. unless otherwise specified.
If the standards shown in this specification differ from year to year in terms of measurement methods, etc., the standards as of January 1, 2021 shall be used unless otherwise specified.

The resin composition of the present embodiment contains a thermoplastic resin, a laser direct structuring additive, and a polyolefin, and the thermoplastic resin is at least one of a polycarbonate resin, a polyphenylene ether resin, a polyester resin, and a polyamide resin. A resin composition containing 4.0 to 30.0 parts by mass of polyolefin with respect to 100 parts by mass of thermoplastic resin, which has low dielectric properties and is used for laser direct structuring be.
By adding a polyolefin and an LDS additive to at least one thermoplastic resin selected from a polycarbonate resin, a polyphenylene ether resin, a polyester resin, and a polyamide resin, the platability of the resin molded product obtained from the resin composition is maintained. At the same time, the dielectric properties of the resin composition can be lowered.
It was thought that blending a resin having relatively low dielectric properties with a thermoplastic resin could lower the dielectric properties of the resin composition. However, for example, when polyphenylene sulfide was blended with polyamide resin, the dielectric loss tangent of the resin composition was slightly lowered, but the relative dielectric constant remained almost unchanged, and plating could not be formed. As a result of investigations by the present inventors, it was found that by using polyolefin as a resin for reducing the dielectric properties of thermoplastic resins, it is possible to sufficiently reduce the dielectric properties while maintaining plating properties.

<Thermoplastic resin>
The resin composition of the present embodiment contains at least one of a polycarbonate resin, a polyphenylene ether resin, a polyester resin, and a polyamide resin as a thermoplastic resin, and preferably contains a polyamide resin. By combining such a thermoplastic resin and polyolefin, it becomes possible to form plating on the obtained resin molding while sufficiently reducing the dielectric properties.

A preferable example of the thermoplastic resin in the present embodiment is to contain a polycarbonate resin, and 90% by mass or more (preferably 95% by mass or more) of the resin composition is the polycarbonate resin.
Another preferred example of the thermoplastic resin in the present embodiment is to contain a polyphenylene ether resin, and 90% by mass or more (preferably 95% by mass or more) of the thermoplastic resin contained in the resin composition is a polyphenylene ether resin. It is to be.
Another preferred example of the thermoplastic resin in the present embodiment is to contain a polyester resin (preferably polybutylene terephthalate resin), and 90% by mass or more (preferably 95% by mass) of the thermoplastic resin contained in the resin composition. mass % or more) is polyester resin (preferably polybutylene terephthalate resin).
Another preferred example of the thermoplastic resin in the present embodiment is to contain a polyamide resin (preferably a xylylenediamine-based polyamide resin described later), and 90% by mass or more of the thermoplastic resin contained in the resin composition. (preferably 95% by mass or more) is a polyamide resin (preferably a xylylenediamine-based polyamide resin described later).

<<Polycarbonate Resin>>
The polycarbonate resin is not particularly limited, and any of an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin can be used. Among them, aromatic polycarbonate resins are preferable, and aromatic polycarbonate resins obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid are more preferable, and bisphenol A-type polycarbonate resins and/or bisphenol C-type polycarbonate resins are preferable. , a blend of bisphenol A-type polycarbonate resin and bisphenol C-type polycarbonate resin is more preferred.

Examples of aromatic dihydroxy compounds include 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A), tetramethylbisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -dihydroxydiphenyl, preferably bisphenol A. Furthermore, for the purpose of preparing a highly flame-retardant resin composition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the aromatic dihydroxy compound, or a polymer containing phenolic OH groups at both ends having a siloxane structure Alternatively, oligomers and the like can be used.

The method for producing the polycarbonate resin is not particularly limited, and in the present embodiment, a polycarbonate resin produced by any method such as a phosgene method (interfacial polymerization method) and a melting method (transesterification method) can be used. can be used. Further, in the present embodiment, a polycarbonate resin produced through a step of adjusting the amount of OH groups of terminal groups after undergoing a production step of a general melting method may be used.

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

The molecular weight of the polycarbonate resin that can be used in the present embodiment is the viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 10,000 or more, more preferably 15, 000 or more. Also, the viscosity average molecular weight is preferably 32,000 or less, more preferably 28,000 or less. When the content is equal to or higher than the lower limit, the mechanical properties of the molded product tend to be improved, and when the content is equal to or lower than the upper limit, the workability during injection molding tends to be improved.
Two or more kinds of polycarbonate resins having different viscosity-average molecular weights may be mixed and used, and in this case, polycarbonates having viscosity-average molecular weights outside the above preferred range may be mixed.
Here, the viscosity average molecular weight [Mv] means using methylene chloride as a solvent and using an Ubbelohde viscometer to determine the intrinsic viscosity [η] (unit dL / g) at a temperature of 25 ° C., Schnell's viscosity formula, That is, it means a value calculated from η=1.23×10 ⁻⁴ Mv ^0.83 . In addition, the intrinsic viscosity [η] is a value calculated from the following formula by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g/dL).

In addition, for the polycarbonate resin used in the present embodiment, for example, the description of paragraphs 0018 to 0066 of JP-A-2012-072338 and the description of paragraphs 0011 to 0018 of JP-A-2015-166460 can be considered, and the contents thereof is incorporated herein.

<<Polyphenylene ether resin>>
In the present embodiment, a known polyphenylene ether resin can be used, for example, a polymer having a structural unit represented by the following formula in its main chain (preferably, the structural unit represented by the following formula excludes a terminal group Polymers occupying 90 mol % or more of all structural units) are exemplified. Polyphenylene ether resins may be either homopolymers or copolymers.

（式中、２つのＲ^aは、それぞれ独立に、水素原子、ハロゲン原子、第１級もしくは第２級アルキル基、アリール基、アミノアルキル基、ハロゲン化アルキル基、炭化水素オキシ基、またはハロゲン化炭化水素オキシ基を表し、２つのＲ^bは、それぞれ独立に、水素原子、ハロゲン原子、第１級もしくは第２級アルキル基、アリール基、ハロゲン化アルキル基、炭化水素オキシ基、またはハロゲン化炭化水素オキシ基を表す。ただし、２つのＲ^aがともに水素原子になることはない。）

(In the formula, two R ^a are each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a halogenated alkyl group, a hydrocarbonoxy group, or a halogenated represents a hydrocarbonoxy group, and two R ^b are each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a halogenated alkyl group, a hydrocarbonoxy group, or a halogenated hydrocarbon; represents a hydrogen oxy group, provided that both R ^a are not hydrogen atoms.)

R ^a and R ^b are each independently preferably a hydrogen atom, a primary or secondary alkyl group, or an aryl group. Preferred examples of primary alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, 2,3-dimethylbutyl, 2 -, 3- or 4-methylpentyl groups or heptyl groups. Suitable examples of secondary alkyl groups include, for example, isopropyl, sec-butyl and 1-ethylpropyl groups. In particular, R ^a is preferably a primary or secondary alkyl group having 1 to 4 carbon atoms or a phenyl group. R ^b is preferably a hydrogen atom.

Suitable polyphenylene ether resin homopolymers include, for example, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene ether), poly(2, 6-dipropyl-1,4-phenylene ether), poly(2-ethyl-6-methyl-1,4-phenylene ether), poly(2-methyl-6-propyl-1,4-phenylene ether), etc. ,6-dialkylphenylene ether polymers. Copolymers include 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol/2,3,6-triethylphenol copolymer, 2,6-diethylphenol /2,3,6-trimethylphenol copolymer, 2,6-dialkylphenol/2,3,6-trialkylphenol copolymer such as 2,6-dipropylphenol/2,3,6-trimethylphenol copolymer Polymer, graft copolymer obtained by grafting styrene to poly(2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer to styrene and a graft copolymer obtained by graft polymerization.

Poly(2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol/2,3,6-trimethylphenol random copolymer are particularly preferable as the polyphenylene ether resin in the present embodiment. In addition, polyphenylene ether resins in which the number of terminal groups and the copper content are specified as described in JP-A-2005-344065 can also be preferably used.

The polyphenylene ether resin preferably has an intrinsic viscosity of 0.2 to 0.8 dL/g, more preferably 0.3 to 0.6 dL/g, measured in chloroform at 30°C. When the intrinsic viscosity is 0.2 dL/g or more, the mechanical strength of the resin composition tends to be further improved. tends to be easier. Also, two or more polyphenylene ether resins having different intrinsic viscosities may be used in combination to set the intrinsic viscosity within this range.

The method for producing the polyphenylene ether resin used in the present embodiment is not particularly limited, and according to a known method, for example, a monomer such as 2,6-dimethylphenol is oxidatively polymerized in the presence of an amine copper catalyst. A method can be employed in which the intrinsic viscosity can be controlled within the desired range by selecting the reaction conditions. Control of intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, amount of catalyst, and the like.

<<polyester resin>>
As the polyester resin, a known thermoplastic polyester resin can be used, preferably containing polyethylene terephthalate resin and/or polybutylene terephthalate resin, more preferably containing at least polybutylene terephthalate resin.
Polyethylene terephthalate resin and polybutylene terephthalate resin are, as is well known, produced on a large scale by reaction of terephthalic acid or ester with ethylene glycol or 1,4-butanediol and distributed on the market. These commercially available resins can be used in this embodiment. Some resins available on the market contain a copolymer component other than a terephthalic acid component and an ethylene glycol component or a 1,4-butanediol component. Those containing up to 40% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 25% by mass can also be used.

The intrinsic viscosity of the polyethylene terephthalate resin is usually 0.4-1.0 dL/g, preferably 0.5-1.0 dL/g. When the intrinsic viscosity is at least the above lower limit, the mechanical properties of the resin composition are less likely to deteriorate, and when it is at most the above upper limit, fluidity is easily maintained.
The intrinsic viscosity of the polybutylene terephthalate resin is usually 0.5 to 1.5 dL/g, preferably 0.6 to 1.3 dL/g. It becomes easy to obtain the resin composition excellent in mechanical strength as it is more than the said lower limit. Moreover, when it is the above upper limit or less, the fluidity of the resin composition is not lost, and the moldability tends to be excellent.
In addition, the intrinsic viscosity of any polyester resin is also a measured value at 30° C. in a phenol/tetrachloroethane (mass ratio 1/1) mixed solvent.
The terminal carboxyl group content of the polyester resin (preferably polybutylene terephthalate resin) is usually 60 eq/ton or less, preferably 50 eq/ton or less, and preferably 30 eq/ton or less. By making it 60 eq/ton or more, alkali resistance and hydrolysis resistance are improved, and gas is less likely to be generated during melt molding of the resin composition. Although the lower limit of the amount of terminal carboxyl groups is not particularly defined, it is usually 10 eq/ton in consideration of the productivity of polyester resin production.
The terminal carboxyl group content of the polyester resin can be determined by dissolving 0.5 g of the resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol/L benzyl alcohol solution of sodium hydroxide.

The polybutylene terephthalate resin may be a polybutylene terephthalate resin modified by copolymerization. Specific preferred copolymers thereof include polyester ether obtained by copolymerizing polyalkylene glycols, particularly polytetramethylene glycol. Examples thereof include resins, dimer acid-copolymerized polybutylene terephthalate resin, and isophthalic acid-copolymerized polybutylene terephthalate resin. In addition, these copolymers refer to those having a copolymerization amount of 1 mol % or more and less than 50 mol % in all segments of the polybutylene terephthalate resin. Among them, the copolymerization amount is preferably 2 to 50 mol %, more preferably 3 to 40 mol %, particularly preferably 5 to 20 mol %. These details can be referred to paragraphs 0014 to 0022 of Japanese Patent Application Laid-Open No. 2019-006866, the contents of which are incorporated herein.

As for the polyester resin, in addition to the above, descriptions in paragraphs 0013 to 0016 of JP-A-2010-174223 can be referred to, the contents of which are incorporated herein.

<<polyamide resin>>
The type of the polyamide resin used in the present embodiment is not particularly specified, and may be an aliphatic polyamide resin or a semi-aromatic polyamide resin. As the polyamide resin, for example, paragraphs 0011 to 0013 of JP-A-2011-132550 can be referred to, the contents of which are incorporated herein.
The polyamide resin used in this embodiment preferably contains a semi-aromatic polyamide resin. For example, it is more preferable that 90% by mass or more of the polyamide resin contained in the resin composition of the present embodiment is a semi-aromatic polyamide resin. Here, the semi-aromatic polyamide resin is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, and 20 to 80 mol% of the total structural units of the diamine-derived structural units and dicarboxylic acid-derived structural units are A structural unit containing an aromatic ring. By using such a semi-aromatic polyamide resin, the mechanical strength of the resulting resin molded product can be increased. Examples of semi-aromatic polyamide resins include terephthalic acid-based polyamide resins (polyamide 6T, polyamide 9T, and polyamide 10T), xylylenediamine-based polyamide resins described later, and the like.

At least one of the polyamide resins used in the present embodiment contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, and is derived from a dicarboxylic acid. It is preferable that 70 mol % or more of the constitutional units are derived from α,ω-straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Hereinafter, such a polyamide resin may be referred to as a xylylenediamine-based polyamide resin.
The diamine-derived structural unit of the xylylenediamine-based polyamide resin is more preferably 75 mol% or more, still more preferably 80 mol% or more, still more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more of is derived from xylylenediamine. The dicarboxylic acid-derived structural unit of the xylylenediamine-based polyamide resin is more preferably 75 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more. It is derived from α,ω-straight-chain aliphatic dicarboxylic acids with numbers from 4 to 20.

Examples of diamines other than meta-xylylenediamine and para-xylylenediamine that can be used as raw material diamine components for xylylenediamine-based polyamide resins include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, and heptamethylene. Aliphatic diamines such as diamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3- bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-amino cyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane and other alicyclic diamines, bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene and other aromatic rings can be exemplified, and can be used alone or in combination of two or more.

Examples of α,ω-straight-chain aliphatic dicarboxylic acids having 4 to 20 carbon atoms that are preferable for use as the starting dicarboxylic acid component of the xylylenediamine-based polyamide resin include succinic acid, glutaric acid, pimelic acid, suberic acid, and azelaine. Aliphatic dicarboxylic acids such as acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid can be exemplified, and one or a mixture of two or more thereof can be used. Adipic acid or sebacic acid is more preferred, and sebacic acid is even more preferred, since it is in the appropriate range for .

Examples of dicarboxylic acid components other than the α,ω-straight-chain aliphatic dicarboxylic acids having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3 -naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Naphthalenedicarboxylic acid isomers such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid can be exemplified, and one or a mixture of two or more thereof can be used.

In the xylylenediamine-based polyamide resin in the present embodiment, 0 to 100 mol% of the diamine-derived structural units are derived from para-xylylenediamine, 100 to 0 mol% are derived from meta-xylylenediamine, and dicarboxylic acid-derived Preferably, 70 mol % or more (preferably 80 mol % or more, more preferably 90 mol % or more) of the structural units are derived from sebacic acid and/or adipic acid.
As a more preferred embodiment A of the xylylenediamine-based polyamide resin, 70 mol% or more (preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more) of the structural units derived from diamine is para Examples thereof include those derived from xylylenediamine and having 70 mol % or more (preferably 80 mol % or more, more preferably 90 mol % or more) of structural units derived from dicarboxylic acid derived from sebacic acid.
Further, as a more preferred embodiment B of the xylylenediamine-based polyamide resin, 30 to 90 mol% (preferably 60 to 80 mol%) of the structural units derived from diamine are derived from meta-xylylenediamine, and 70 to 10 mol% (preferably 40 to 20 mol%) is derived from paraxylylenediamine, and 70 mol% or more (preferably 80 mol% or more, more preferably 90 mol% or more) of the structural units derived from dicarboxylic acid is derived from sebacic acid Polyamide resins are exemplified.
As a more preferred embodiment C of the xylylenediamine-based polyamide resin, 70 mol% or more (preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more) of the structural units derived from diamine is meta. Examples thereof include those derived from xylylenediamine and having 70 mol % or more (preferably 80 mol % or more, more preferably 90 mol % or more) of structural units derived from dicarboxylic acid derived from adipic acid.
In the resin composition of this embodiment, embodiment A is particularly preferred.
In any of the above embodiments, the total amount of diamine-derived structural units does not exceed 100 mol %, and the total amount of dicarboxylic acid-derived structural units does not exceed 100 mol %.

In addition, although it is composed mainly of structural units derived from diamine and structural units derived from dicarboxylic acid, it does not completely exclude structural units other than these, and lactams such as ε-caprolactam and laurolactam, aminocaproic acid , aminoundecanoic acid, and other structural units derived from aliphatic aminocarboxylic acids. The term "main component" as used herein means that among the constituent units constituting the xylylenediamine-based polyamide resin, the total number of constituent units derived from diamine and constituent units derived from dicarboxylic acid is the largest among all constituent units. In the present embodiment, the sum of diamine-derived structural units and dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin preferably accounts for 90% or more of all structural units, more preferably 95% or more. Preferably, it accounts for 98% or more.

The melting point of the polyamide resin is preferably 150 to 350°C, more preferably 180 to 330°C, even more preferably 200 to 300°C.
The melting point can be measured according to JIS K7121 and K7122 according to differential scanning calorimetry.

Polyamide resin, the lower limit of the number average molecular weight (Mn) is preferably 6,000 or more, more preferably 8,000 or more, more preferably 10,000 or more, 15,000 or more more preferably, 20,000 or more, and even more preferably 22,000 or more. The upper limit of Mn is preferably 35,000 or less, more preferably 30,000 or less, even more preferably 28,000 or less, and even more preferably 26,000 or less. Within such a range, heat resistance, elastic modulus, dimensional stability, and moldability are improved.

The content of the thermoplastic resin in the resin composition of the present embodiment is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and 45% by mass. % or more is more preferable. By making it equal to or higher than the lower limit, the mechanical strength of the molded product tends to be improved. The content of the thermoplastic resin in the resin composition of the present embodiment is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. By making the content equal to or less than the above upper limit, there is a tendency that the mechanical strength of the molded product can be maintained.
The resin composition of the present embodiment may contain only one type of each thermoplastic resin, or may contain two or more types thereof. When two or more types are included, the total amount is preferably within the above range.

<Laser direct structuring additive>
The resin composition of this embodiment contains a laser direct structuring additive (LDS additive). By including the LDS additive, it becomes possible to form a plating on the resulting resin molded product.
The LDS additive in the present embodiment is obtained by adding 10 parts by mass of an additive that is considered to be an LDS additive to 100 parts by mass of any of polycarbonate resin, polyphenylene ether resin, polyester resin, and polyamide resin. It refers to a compound that can selectively form plating only at laser-irradiated areas when irradiated with a YAG laser at an output of 10 W, a frequency of 80 kHz, and a speed of 3 m/s, and immersed in an electroless plating bath as the subsequent plating step. The LDS additive used in this embodiment may be a synthetic product or a commercially available product. In addition, the commercially available product may be a substance sold for other uses as long as it satisfies the requirements of the LDS additive in this embodiment, in addition to the substance sold as an LDS additive. Only one kind of LDS additive may be used, or two or more kinds thereof may be used in combination.

The LDS additive used in this embodiment preferably contains at least one of copper, antimony, tin, aluminum and zinc, and more preferably contains copper chromium copper oxide and/or an oxide containing antimony and tin. More preferably, it contains copper chromium copper oxide.
Moreover, the LDS additive used in the present embodiment preferably has a resistivity of more than 5×10 ³ Ω·cm. By using an LDS additive having such a high resistivity, a resin composition having lower dielectric properties can be obtained.

More specifically, a first embodiment of the LDS additive used in this embodiment is a compound containing copper and chromium. The LDS additive of the first embodiment preferably contains 10 to 30% by mass of copper. Also, it preferably contains 15 to 50% by mass of chromium. The LDS additive in the first embodiment is preferably an oxide containing copper and chromium (copper chromium oxide).

A spinel structure is preferable as the form of containing copper and chromium. The spinel structure is one of the typical crystal structure types seen in AB ₂ O ₄ -type compounds (A and B are metal elements) in multiple oxides.

In addition to copper and chromium, the LDS additive of the first embodiment may contain minor amounts of other metals. Other metals include antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium and calcium, with manganese being preferred. These metals may be present as oxides.
A preferred example of the LDS additive of the first embodiment is an LDS additive in which the content of metal oxides other than copper chromium oxide is 10% by mass or less.

A second embodiment of the LDS additive used in this embodiment is an oxide containing at least one of antimony and phosphorus and tin, preferably an oxide containing antimony and tin.

The LDS additive of the second embodiment preferably contains more tin than phosphorus and antimony, and the amount of tin with respect to the total amount of tin, phosphorus, and antimony is 80% by mass or more. is more preferred.

In particular, as the LDS additive of the second embodiment, an oxide containing antimony and tin is preferable, and an oxide containing more tin than antimony is more preferable. Oxides in which the amount of tin is 80% by mass or more are more preferable.
More specifically, the LDS additives of the second embodiment include antimony doped tin oxide, antimony oxide doped tin oxide, phosphorus doped tin oxide, phosphorus oxide doped Tin oxides may be mentioned, with antimony doped tin oxide and antimony oxide doped tin oxide being preferred, with antimony oxide doped tin oxide being more preferred.

The number average particle size of the LDS additive used in this embodiment is preferably 0.01 to 100 μm, more preferably 0.05 to 30 μm, and even more preferably 0.05 to 15 μm. By setting it as such a number average particle diameter, the surface of plating can be made more uniform.

The content of the LDS additive in the resin composition of the present embodiment is preferably 1.0 parts by mass or more, more preferably 2.0 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin. , more preferably 3.0 parts by mass or more, still more preferably 4.0 parts by mass or more, and even more preferably 5.0 parts by mass or more. By making it more than the said lower limit, there exists a tendency for plating property to improve more. In addition, the content of the LDS additive in the resin composition of the present embodiment is preferably 30.0 parts by mass or less, and preferably 25.0 parts by mass or less, with respect to 100 parts by mass of the thermoplastic resin. It is more preferably 20.0 parts by mass or less, even more preferably 15.0 parts by mass or less, and even more preferably 10.0 parts by mass or less. By making it equal to or less than the upper limit, the resin composition tends to exhibit a lower dielectric.
The resin composition of the present embodiment may contain only one type of LDS additive, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Polyolefin>
The resin composition of the present embodiment contains 4.0 to 30.0 parts by mass of polyolefin with respect to 100 parts by mass of thermoplastic resin. By containing the polyolefin, it is possible to provide the obtained resin molded product with a low dielectric property while imparting plateability.
Preferred polyolefins are homopolymers and/or copolymers of α-olefins such as ethylene, propylene and butene.

Preferred homopolymers are polyethylene and polypropylene, and more preferred is polyethylene.
On the other hand, as the copolymer, a polymer of at least two of ethylene, propylene and butene, or a copolymer of at least one of ethylene, propylene and butene and a monomer that can be copolymerized therewith is used. be able to. Examples of monomers that can be copolymerized with at least one of ethylene, propylene and butene include α-olefins, styrenes, dienes, cyclic compounds, oxygen atom-containing compounds and the like. Particularly preferred copolymers include ethylene/butene copolymers and ethylene/propylene copolymers, with ethylene/butene copolymers being preferred.
Details of α-olefins, styrenes, dienes, cyclic compounds, and oxygen atom-containing compounds can be referred to paragraph 0044 of WO 2017/094564, the contents of which are incorporated herein.
The copolymer may be any of alternating copolymerization, random copolymerization, and block copolymerization.

As polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), etc. can be used. is preferred.

In this embodiment, the polyolefin is preferably acid-modified polyolefin. Acid-modified polyolefins are acid-modified polyolefins with carboxylic acid and/or derivatives thereof, and acid-modified with carboxylic acids and/or derivatives thereof, and polyamides via functional groups introduced into the molecule by acid modification. Graft-bonded polyolefins are preferred. By using an acid-modified polyolefin, it is possible to introduce a functional group having an affinity for the thermoplastic resin into the molecule, which tends to further improve the dispersibility of the polyolefin in the thermoplastic resin. In particular, it is effective when a polyamide resin is used as the thermoplastic resin.

Compounds capable of acid-modifying polyolefins include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene- 1,2-dicarboxylic acid, endobicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, ethyl acrylate , butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itacon anhydride acid, citraconic anhydride, endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacryl Amide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconate and the like are preferred. These can be used singly or in combination of two or more. Among these, maleic anhydride is preferable from the viewpoint of melt-mixability with other resins.

In the present embodiment, particularly preferably used acid-modified polyolefins include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and maleic anhydride-modified ethylene/butene copolymer from the viewpoint of elastic modulus, flexibility and impact resistance. coalescence is mentioned. Among them, maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene are particularly preferably used.

In addition, the description of paragraphs 0042 to 0056 of WO 2017/094564 can be referred to for details of the polyolefin, and the contents thereof are incorporated herein.

The content of the polyolefin in the resin composition of the present embodiment is 4.0 parts by mass or more, preferably 6.0 parts by mass or more, and 8.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is more preferably 10.0 parts by mass or more, still more preferably 12.0 parts by mass or more, and even more preferably 14.0 parts by mass or more. By setting the amount to the above lower limit or more, there is a tendency that the dielectric properties of the resin composition can be further reduced. In addition, the content of polyolefin in the resin composition of the present embodiment is 30.0 parts by mass or less, preferably 28.0 parts by mass or less, and 26.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is even more preferably not more than 24.0 parts by mass, and more preferably not more than 22.0 parts by mass. By adjusting the content to be equal to or less than the above upper limit, it is possible to suppress significant deterioration of the mechanical properties and thermal properties inherent in the thermoplastic resin.
The resin composition of the present embodiment may contain only one type of polyolefin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

In the resin composition of the present embodiment, the mass ratio of polyolefin and LDS additive (LDS/polyolefin) is preferably 0.1 or more, more preferably 0.2 or more, and more preferably 0.3 It is more preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.1 or less, and 0.9 or less. More preferred. By setting it as such a range, there exists a tendency for the effect of this invention to be exhibited more effectively.

<Inorganic fiber>
The resin composition of the present embodiment may further contain 10.0 to 150.0 parts by mass of inorganic fibers with respect to 100 parts by mass of the thermoplastic resin. By including inorganic fibers, the mechanical strength of the obtained resin molding can be further improved.
Carbon fibers and glass fibers are exemplified as inorganic fibers, and glass fibers are preferably included.

The inorganic fiber in the present embodiment means a fibrous inorganic material, more specifically, a chopped shape in which 1,000 to 10,000 inorganic fibers are bundled and cut to a predetermined length. preferable.
The inorganic fibers in this embodiment preferably have a number average fiber length of 0.5 to 10 mm, more preferably 1 to 5 mm. By using inorganic fibers having such a number average fiber length, the mechanical strength can be further improved. The number average fiber length is obtained by randomly extracting inorganic fibers to measure the fiber length from the image obtained by optical microscope observation, measuring the long side, and calculating the number average fiber length from the obtained measurement value. calculate. The magnification of observation is 20 times, and the number of lines to be measured is 1,000 or more. It roughly corresponds to the cut length.
The cross-section of the inorganic fiber may be circular, elliptical, oval, rectangular, semicircular on both short sides of a rectangle, cocoon-shaped, etc., but circular is preferred. The circular here is intended to include what is usually called circular in the technical field of the present embodiment, in addition to circular in the mathematical sense.
The lower limit of the number average fiber diameter of the inorganic fibers is preferably 4.0 μm or more, more preferably 4.5 μm or more, and even more preferably 5.0 μm or more. The upper limit of the number average fiber diameter of the inorganic fibers is preferably 15.0 μm or less, more preferably 12.0 μm or less. By using inorganic fibers having a number-average fiber diameter within such a range, it is possible to obtain a resin molded article having excellent plating properties even after being subjected to moist heat. Furthermore, high plating properties can be maintained even when the resin molded product is stored for a long period of time or heat-treated for a long period of time. The number average fiber diameter of the inorganic fibers is obtained by randomly extracting the glass fibers whose fiber diameter is to be measured from the image obtained by observation with an electron microscope, and measuring the fiber diameter near the center. calculated from the measured values obtained. The magnification of observation is 1,000, and the number of lines to be measured is 1,000 or more. The number average fiber diameter of glass fibers having a non-circular cross section is the number average fiber diameter when converted to a circle having the same area as the cross section.

Next, the glass fiber preferably used in this embodiment will be described.
Glass fibers include commonly supplied E glass (electrical glass), C glass (chemical glass), A glass (alkali glass), S glass (high strength glass), D glass, R glass, and alkali-resistant glass. Fibers obtained by melt-spinning glass are used. A preferred example of this embodiment is E-glass, and to achieve a lower dielectric, D-glass is also preferred.

The inorganic fiber in the present embodiment is preferably a low-dielectric inorganic fiber, more preferably a low-dielectric glass fiber, in order to lower the dielectric properties of the resin composition.
A low dielectric inorganic fiber means an inorganic fiber having a low dielectric constant and a low dielectric loss tangent, and examples thereof include inorganic fibers having a dielectric constant of 7 or less. The dielectric constant here is a value measured according to ASTM D150.
Such low dielectric glass fibers include, for example, 65-85 mass % SiO ₂ , 15-30 mass % B ₂ O ₃ , 0-4 mass % sodium oxide (Na ₂ O) and/or or glass fibers composed of potassium oxide (K ₂ O) and 0 to 4% by weight of other components (the total amount here does not exceed 100% by weight, preferably 100% by weight in total). be). Glass fibers with such a large amount of B ₂ O ₃ are known as glass fibers with a low dielectric constant.

The glass fibers used in this embodiment are treated with a surface treatment agent such as a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane. It is preferably treated. The adhesion amount of the surface treatment agent is preferably 0.01 to 1 mass % of the glass fiber. Furthermore, if necessary, lubricants such as fatty acid amide compounds, silicone oils, antistatic agents such as quaternary ammonium salts, resins having film-forming properties such as epoxy resins and urethane resins, resins having film-forming properties and heat It is also possible to use those surface-treated with a mixture of stabilizers, flame retardants, and the like.

The content of inorganic fibers (preferably glass fibers) in the resin composition of the present embodiment is preferably 10.0 parts by mass or more, and is 20.0 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin. It is more preferably 30.0 parts by mass or more, and may be 40.0 parts by mass or more, particularly 50.0 parts by mass or more. When the content is equal to or higher than the above lower limit, the mechanical strength of the obtained resin molded product tends to be further improved. In addition, the content of inorganic fibers (preferably glass fibers) in the resin composition of the present embodiment is preferably 150.0 parts by mass or less, and 120.0 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. is more preferably 100.0 parts by mass or less, even more preferably 80.0 parts by mass or less, and even more preferably 70.0 parts by mass or less. By adjusting the content to the above upper limit or less, there is a tendency that the dielectric properties of the resin composition can be further reduced.
In addition, the content of inorganic fibers (preferably glass fibers) in the resin composition of the present embodiment is preferably 10.0% by mass or more in the resin composition, and is preferably 15.0% by mass or more. More preferably, it is 18.0% by mass or more. When the content is equal to or higher than the above lower limit, the mechanical strength of the obtained resin molded product tends to be further improved. In addition, the content of inorganic fibers (preferably glass fibers) in the resin composition of the present embodiment is preferably 50.0% by mass or less, and preferably 45.0% by mass or less in the resin composition. More preferably, it is 40.0% by mass or less, even more preferably 35.0% by mass or less, and even more preferably 34.0% by mass or less. By adjusting the content to the above upper limit or less, there is a tendency that the dielectric properties of the resin composition can be further reduced.
The resin composition of the present embodiment may contain only one kind of inorganic fiber, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.

<Talc>
The resin composition of the present embodiment may further contain 0.1 to 200.0 parts by mass of talc with respect to 100 parts by mass of the laser direct structuring additive. By containing talc, the dimensional stability and appearance of the product can be improved, and the plating growth rate can be increased. Furthermore, by including talc, the plating property of the resin molded product can be improved even if the content of the LDS additive is reduced.
Talc may be surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. In this case, the amount of the siloxane compound attached to the talc is preferably 0.1 to 5% by mass of the talc.
The number average particle size of talc is preferably 1 to 50 μm, more preferably 2 to 25 μm. Talc is usually scaly, and the length of the longest part is taken as the average particle size. The number-average particle size of talc is calculated from the measured value obtained by randomly extracting talc to be measured for particle size from an image obtained by observation with an electron microscope, measuring the particle size. The magnification of observation is 1,000 times, and the number of measurements is 1,000 or more.

The content of talc in the resin composition of the present embodiment is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, with respect to 100.0 parts by mass of the laser direct structuring additive. It is more preferably 10.0 parts by mass or more, even more preferably 60.0 parts by mass or more, and even more preferably 100.0 parts by mass or more. By making it more than the said lower limit, there exists a tendency for plating property to improve more. In addition, the content of talc in the resin composition of the present embodiment is preferably 200.0 parts by mass or less, more preferably 180.0 parts by mass or less with respect to 100 parts by mass of the laser direct structuring additive. It is more preferably 170.0 parts by mass or less, even more preferably 160.0 parts by mass or less, and even more preferably 150.0 parts by mass or less. By setting the content to the above upper limit or less, the mechanical properties of the resulting molded product can be improved more effectively.
In addition, the content of talc in the resin composition of the present embodiment, when blended, is preferably 0.1 parts by mass or more, and 1.0 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin. is more preferably 4.5 parts by mass or more, preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less, and 12.0 parts by mass or less is more preferable.
The resin composition of the present embodiment may contain only one type of talc, or may contain two or more types of talc. When two or more types are included, the total amount is preferably within the above range.

<Release agent>
The resin composition of the present embodiment may further contain a release agent. A mold release agent is mainly used to improve productivity during molding of a resin composition. Examples of release agents include aliphatic carboxylic acid amides, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. mentioned.

Details of the release agent can be referred to paragraphs 0037 to 0042 of JP-A-2016-196563 and paragraphs 0048-0058 of JP-A-2016-078318, the contents of which are incorporated herein. .

When the content of the release agent is blended, the lower limit is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, with respect to the resin composition, and the upper limit is It is preferably 2.0% by mass or less, more preferably 1.5% by mass or less. By setting it to such a range, it is possible to improve the releasability when performing molding using a mold such as injection molding, and it is possible to effectively suppress mold contamination. . The release agents may be used alone or in combination of two or more. When two or more are used, the total amount is preferably within the above range.

<Other additives>
The resin composition of the present embodiment may contain other components in addition to those mentioned above. Other ingredients include light stabilizers, heat stabilizers, alkalis, elastomers, titanium oxide, antioxidants, hydrolysis resistance improvers, matting agents, UV absorbers, nucleating agents, plasticizers, dispersants, and electrification agents. Examples include inhibitors, anti-coloring agents, anti-gelling agents, coloring agents, flame retardants and the like. These details can be referred to paragraphs 0130 to 0155 of Japanese Patent No. 4894982, and the contents thereof are incorporated herein. The total content of these components is preferably 20% by mass or less of the resin composition. Each of these components may be used alone or in combination of two or more.
In the resin composition of the present embodiment, the total amount of the thermoplastic resin, the polyolefin, the LDS additive, and the inorganic fiber, release agent, and talc blended as necessary is 95% by mass or more of the resin composition. , more preferably 98% by mass or more, and even more preferably 99% by mass or more.
Moreover, it is preferable that the resin composition of this embodiment does not contain calcium copper titanate.

<Method for producing resin composition>
Any method is employed as the method for producing the resin composition of the present embodiment.
For example, thermoplastic resins, polyolefins, LDS additives, inorganic fibers, etc. are mixed using a mixing means such as a V-type blender to prepare a batch blended product, which is then melted and kneaded with a vented extruder to pelletize. is mentioned. Alternatively, as a two-step kneading method, after thoroughly mixing components other than inorganic fibers in advance, melt-kneading them with a vented extruder to produce pellets, then mix the pellets with the reinforcing filler and then add them with a vent. A method of melt-kneading with an extruder can be mentioned.
Furthermore, components other than inorganic fibers are sufficiently mixed with a V-type blender or the like, and are prepared in advance. A method of supplying from two chutes, melt-kneading, and pelletizing can be used.

The screw configuration of the kneading zone of the extruder is preferably arranged such that an element that promotes kneading is arranged on the upstream side and an element capable of increasing pressure is arranged on the downstream side.
Elements that promote kneading include progressive kneading disc elements, orthogonal kneading disc elements, wide kneading disc elements, progressive mixing screw elements, and the like.

The heating temperature for melt-kneading can be appropriately selected from the range of 180 to 360°C. If the temperature is too high, decomposition gas is likely to be generated, which may cause extrusion defects such as strand breakage. Therefore, it is desirable to select a screw structure in consideration of shear heat generation and the like. In order to suppress decomposition during kneading and subsequent molding, it is desirable to use antioxidants and heat stabilizers.

<Physical properties of the resin composition>
The resin composition of the present embodiment preferably has low dielectric properties, and particularly preferably has a low relative dielectric constant. For example, when comparing the resin composition of the present embodiment with a resin composition obtained by removing polyolefin from the resin composition of the present embodiment, if the resin composition of the present embodiment has a lower dielectric constant, the dielectric I would say the rate is low.
For example, the dielectric constant of the resin composition of the present embodiment at a frequency of 2.45 GHz can be 3.60 or less, and can be 3.50 or less. Ideally, the lower limit of the relative dielectric constant is 0, but for example, 1.00 or more, or even 2.80 or more satisfies the required performance. In particular, when a polyamide resin is used as the thermoplastic resin, the above range is preferred.
The resin composition of the present embodiment preferably has a low dielectric loss tangent.
For example, the specific inductive tangent of the resin composition of the present embodiment at a frequency of 2.45 GHz can be 0.020 or less, and can be 0.015 or less. The lower limit value is ideally 0, but for example, 0.001 or more, or even 0.008 or more satisfies the required performance. In particular, when a polyamide resin is used as the thermoplastic resin, the above range is preferred.

The resin composition of the present embodiment preferably has a bending strength conforming to ISO 178 of 140 MPa or more, more preferably 145 MPa or more, and even more preferably 150 MPa or more when molded to a thickness of 4 mm. . Although the upper limit of the bending strength is not particularly defined, for example, 270 MPa or less, further 260 MPa or less, and particularly 250 MPa or less is practical. In particular, when a polyamide resin is used as the thermoplastic resin, the above range is preferred.
The resin composition of the present embodiment preferably has a flexural modulus of 5.0 GPa or more, more preferably 5.5 GPa or more, and more preferably 6.0 GPa or more according to ISO 178 when molded to a thickness of 4 mm. is more preferable. Although the upper limit of the bending elastic modulus is not particularly defined, for example, 15 GPa or less, further 14 GPa or less, and particularly 13 GPa or less is practical. In particular, when a polyamide resin is used as the thermoplastic resin, the above range is preferred.

The resin composition of the present embodiment preferably has a notched Charpy impact strength conforming to the ISO179 standard of 2 kJ/m ² or more when molded to a thickness of 4 mm. Although the upper limit of the notched Charpy impact strength is not particularly defined, for example, 15 kJ/m ² or less is practical. In particular, when a polyamide resin is used as the thermoplastic resin, the above range is preferable.

The dielectric constant, dielectric loss tangent, flexural strength, flexural modulus, and notched Charpy impact strength are each measured according to the methods described in Examples below.

<Resin molded product>
This embodiment also discloses a resin molded article formed from the resin composition of this embodiment.
In the present embodiment, the method for producing the resin molded article is not particularly limited, and any molding method commonly used for resin compositions can be employed. Examples include injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, hollow molding such as gas assist, molding using heat insulating molds, and rapid heating molds. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, A blow molding method and the like can be mentioned. A molding method using a hot runner system can also be used.

A resin molded article formed from the resin composition of the present embodiment is preferably used as a resin molded article having plating on the surface of the resin molded article. It is preferable that the plating in the resin molded product of the present embodiment retains performance as an antenna.

<Method for manufacturing plated resin molded product>
Next, a method for producing a plated resin molded product is disclosed, which includes forming a plating by applying a metal after irradiating the surface of the resin molded product formed from the resin composition of the present embodiment with a laser. do.
FIG. 1 is a schematic diagram showing a process of plating the surface of a resin molded product 1 by laser direct structuring technology. In FIG. 1, the resin molded product 1 is a flat substrate, but it does not necessarily have to be a flat substrate, and may be a resin molded product having a partially or wholly curved surface. In addition, the obtained plated resin molded product is intended to include not only the final product but also various parts.

Returning to FIG. 1 again, the resin molded product 1 is irradiated with the laser 2 . The laser here is not particularly defined, and can be appropriately selected from known lasers such as YAG laser, excimer laser, and electromagnetic radiation, and YAG laser is preferable. Also, the wavelength of the laser is not particularly defined. A preferred wavelength range is 200 nm to 1200 nm, more preferably 800 to 1200 nm.
When the laser is irradiated, the resin molded product 1 is activated only at the portion 3 irradiated with the laser. In this activated state, the resin molding 1 is applied to the plating solution 4 . The plating liquid 4 is not particularly defined, and a wide range of known plating liquids can be employed. Electrolytic plating solution) is preferred, plating solution comprising one or more of copper, nickel, silver and gold (especially electroless plating solution) is more preferred, and plating solution containing copper (especially electroless plating solution ) is more preferred. That is, it is preferable that the metal component of the plating in this embodiment is at least one of the above metals.
The method of applying the resin molded product 1 to the plating solution 4 is also not particularly defined, but for example, a method of putting the resin molded product 1 into a solution mixed with the plating solution can be mentioned. In the resin molded product after applying the plating solution, plating 5 is formed only on the laser-irradiated portions.
According to the method of the present embodiment, a plating (circuit) having a width of 1 mm or less, further 150 μm or less (the lower limit is not specifically defined, but is 30 μm or more, for example) can be formed. In order to suppress corrosion and deterioration of the formed plating (circuit), the plating can be further protected with nickel or gold after electroless plating, for example. Similarly, electrolytic plating can be used after electroless plating to form a required film thickness in a short time.
Moreover, the method for manufacturing a plated resin molded product is preferably used as a method for manufacturing a mobile electronic device component having an antenna, including the method for manufacturing a plated resin molded product.

Resin molded articles obtained from the resin composition of the present embodiment include, for example, electronic components such as sensors, connectors, switches, relays, conductive circuits, and antennas (particularly, mobile electronic device components, communication base stations, personal computer peripherals), and the like. It can be used for various purposes.

In addition, within the scope of the present embodiment, JP 2011-219620, JP 2011-195820, JP 2011-178873, JP 2011-168705, JP 2011-148267 The description in the publication can be taken into consideration.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.
If the measuring instruments and the like used in the examples are discontinued and difficult to obtain, other instruments having equivalent performance can be used for measurement.

The following raw materials were used in this example.

In Table 1 above, MAH stands for maleic anhydride, HDPE for high density polyethylene, PP for polypropylene, LDPE for low density polyethylene, PTFE for polytetrafluoroethylene, and PPS for polyphenylene sulfide. .

Examples 1 to 10, Comparative Examples 1 to 4
<Compound>
Each component was weighed so that the composition shown in Tables 2 to 4 (the unit of each component in Tables 2 to 4 is parts by mass), and the components other than inorganic fibers (glass fibers) were removed in a tumbler. After blending at the bottom of a twin-screw extruder (TEM26SS manufactured by Shibaura Kikai Co., Ltd.) and melting, inorganic fibers (glass fibers) were side-fed to prepare a resin composition (pellets). The temperature setting of the twin-screw extruder was 300°C. Each component in Tables 2 to 4 is shown by mass ratio.

<Bending strength and bending elastic modulus>
After drying the pellets obtained by the above production method at 120 ° C. for 4 hours, an injection molding machine (manufactured by Shibaura Machine Co., Ltd., "EC75SX") was used at a cylinder temperature of 300 ° C., a mold temperature of 130 ° C., and a molding cycle of 50. ISO tensile specimens (4 mm thick) were injection molded under conditions of seconds.
Flexural strength (unit: MPa) and flexural modulus (unit: GPa) were measured at a temperature of 23° C. according to ISO178.

<Notched Charpy impact strength>
After drying the pellets obtained by the above production method at 120 ° C. for 4 hours, an injection molding machine (manufactured by Shibaura Machine Co., Ltd., "EC75SX") was used at a cylinder temperature of 300 ° C., a mold temperature of 130 ° C., and a molding cycle of 50. ISO tensile specimens (4 mm thick) were injection molded under conditions of seconds.
Using the ISO tensile test piece (4 mm thick) obtained above, Charpy impact strength (notched) was measured at a temperature of 23° C. according to the ISO 179 standard.
The unit is kJ/m ² .

<Deflection temperature under load (DTUL)>
After drying the pellets obtained by the above production method at 120 ° C. for 4 hours, an injection molding machine (manufactured by Shibaura Machine Co., Ltd., "EC75SX") was used at a cylinder temperature of 300 ° C., a mold temperature of 130 ° C., and a molding cycle of 50. ISO multi-purpose test specimens (4 mm thick) were injection molded under conditions of seconds.
Using the ISO multi-purpose test piece (4 mm thick) obtained above, it was processed into a shape based on ISO75-1 and ISO75-2, and the deflection temperature under load (unit: ° C.) was measured based on ISO75-1 and ISO75-2. , and a load of 1.80 MPa.

<Relative permittivity/dielectric loss tangent>
The dielectric constant and dielectric loss tangent were measured by cavity resonator perturbation method at a frequency of 2.45 GHz on a flat test piece of 100 mm×100 mm×2 mm formed from the resin composition.
Specifically, after drying the pellets obtained by the above production method at 120 ° C. for 4 hours, an injection molding machine (manufactured by Shibaura Kikai Co., Ltd., "EC75SX") was used at a cylinder temperature of 300 ° C. and a mold temperature of 130. °C and a molding cycle of 50 seconds to mold a flat test piece of 100 mm x 100 mm x 2 mm.
After obtaining a flat test piece of 100 mm × 1 mm × 2 mm in the longitudinal direction with the flow direction from the obtained flat test piece by cutting, the relative permittivity and dielectric loss tangent at the set frequency were measured by the cavity resonator perturbation method. .
For the measurement, a network analyzer manufactured by KEYSIGHT and a cavity resonator manufactured by Kanto Denshi Applied Development Co., Ltd. were used.

<Plating property>
In the range of 10 × 10 mm of the ISO multi-purpose test piece (4 mm thick) obtained above, a Trumpf VMc1 laser irradiation device (YAG laser maximum output 15 W at a wavelength of 1064 nm) was used. (Frequency) Laser irradiation was performed at a frequency of 80 kHz and a speed of 2 m/s. The subsequent plating process was carried out for 10 minutes in a 65° C. plating bath (set temperature: 68° C.) of Electroless Copper 100XB manufactured by MacDermid.
A: Plating was formed B: Plating was not formed

As is clear from the above results, the resin compositions of the present invention were able to achieve low dielectric properties, particularly low dielectric constants, while maintaining plating properties (Examples 1 to 10).
In contrast, when no polyolefin was blended (Comparative Example 1), the dielectric constant did not decrease. Also, when a resin other than polyolefin was alloyed (Comparative Examples 2 and 3), the dielectric constant did not decrease.
On the other hand, when the LDS additive was not blended (Comparative Example 4), although the dielectric constant was low, plating could not be formed.

1 resin molded product 2 laser 3 portion irradiated with laser 4 plating solution 5 plating

Claims (22)

a thermoplastic resin;
a laser direct structuring additive;
polyolefin and
The thermoplastic resin contains at least one of polycarbonate resin, polyphenylene ether resin, polyester resin, and polyamide resin,
4.0 to 30.0 parts by mass of polyolefin with respect to 100 parts by mass of the thermoplastic resin,
Resin composition for low dielectric laser direct structuring. 2. The resin composition of claim 1, wherein said thermoplastic resin comprises a polyamide resin. 3. The resin composition of claim 2, wherein said polyamide resin comprises a semi-aromatic polyamide resin. At least one of the polyamide resins contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, and the dicarboxylic acid-derived structural unit. The resin composition according to claim 2, wherein 70 mol% or more of is derived from the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. The resin composition according to any one of claims 1 to 4, comprising 1.0 to 30.0 parts by mass of the laser direct structuring additive with respect to 100 parts by mass of the thermoplastic resin. The resin composition according to any one of claims 1 to 5, wherein the laser direct structuring additive comprises at least one of copper, antimony, tin, aluminum and zinc. The resin composition according to any one of claims 1 to 5, wherein the laser direct structuring additive comprises copper chromium copper oxide and/or an oxide containing antimony and tin. The resin composition according to any one of claims 1 to 7, wherein the resistivity of the laser direct structuring additive is greater than ⁵ x 103 Ω-cm. The resin composition according to any one of claims 1 to 8, wherein the polyolefin comprises an acid-modified polyolefin. The resin composition according to any one of claims 1 to 9, wherein said polyolefin comprises polyethylene. The resin composition according to any one of claims 1 to 10, further comprising 10.0 to 150.0 parts by mass of inorganic fibers with respect to 100 parts by mass of the thermoplastic resin. 12. The resin composition according to claim 11, wherein the inorganic fiber has a dielectric constant of 7 or less. The resin composition according to claim 11 or 12, wherein the inorganic fibers contain glass fibers. The glass fibers comprise 65-85% by weight SiO ₂ , 15-30% by weight B ₂ O ₃ and 0-4% by weight sodium oxide (Na ₂ O) and/or potassium oxide (K ₂ O). and 0 to 4% by mass of other components, the resin composition according to claim 13. The resin composition according to any one of claims 11 to 14, comprising 20.0 to 80.0 parts by mass of the inorganic fiber with respect to 100 parts by mass of the thermoplastic resin. The resin composition according to any one of claims 1 to 15, further comprising 0.1 to 200.0 parts by mass of talc with respect to 100.0 parts by mass of the laser direct structuring additive. The resin composition according to any one of claims 1 to 16, wherein the resin composition has a dielectric constant of 3.60 or less at a frequency of 2.45 GHz. A resin molded article formed from the resin composition according to any one of claims 1 to 17. 19. The resin molded product according to claim 18, having plating on the surface of said resin molded product. 20. The resin molded article according to claim 19, wherein said plating has performance as an antenna. 21. The resin molded product according to any one of claims 18 to 20, which is a portable electronic device component. After irradiating the surface of the resin molded article formed from the resin composition according to any one of claims 1 to 17 with a laser, applying a metal to form a plating, resin molding with plating. method of manufacturing the product.

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