JP2021014549A - Thermoplastic resin composition for laser direct structuring and molded article - Google Patents

Abstract

To provide a thermoplastic resin composition for laser direct structuring and a molded article having excellent plating property and low dielectric characteristics.SOLUTION: There is provided a thermoplastic resin composition comprising a cyclic polyolefin (A) and a laser direct structuring additive (B), wherein the cyclic polyolefin (A) is composed of a hydrogenated block copolymer which is a hydrogenation product of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit, the hydrogenated block copolymer has a hydrogenated aromatic vinyl polymer block unit which is a hydrogenation product of a polymer block composed of an aromatic vinyl monomer unit and a hydrogenated conjugated diene polymer block unit which is a hydrogenation product of a polymer block composed of a conjugated diene polymer unit and the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit.SELECTED DRAWING: None

Description

The present invention is a thermoplastic resin composition for laser direct structuring and molding, which is excellent in plating property and low dielectric property, by a three-dimensional circuit forming technique (Laser-Direct-Structuring; hereinafter may be referred to as "LDS method"). Regarding the body.

For plating formation by the LDS method, which has been put into practical use in recent years and can easily form fine circuits, a substrate material made of polybutylene terephthalate or the like containing a metal oxide capable of forming a single metal nucleus by electromagnetic beam irradiation is preferably used. (Patent Document 1).
When polycarbonate is used as the substrate material used in the LDS method, there is a problem that the polycarbonate is decomposed by the metal oxide, the melt stability is lowered, and the processing becomes difficult. In order to solve this, it has been proposed to blend a rubber-like polymer such as acrylonitrile-butadiene-styrene (ABS) (Patent Document 2). Further, it is described here that it is desirable to add titanium dioxide to polycarbonate in order to increase the amount of plating deposited and the adhesion strength.

Japanese Patent Publication No. 2004-534408 Special Table 2010-536947

By the way, the speed and capacity of communication are increasing year by year. In related parts such as circuits of communication equipment, antennas, sensors, covers, connectors, and casings, it is known that the dielectric loss of the materials used reduces the communication efficiency. In order not to reduce the communication efficiency, the material used for the related parts is required to have a low dielectric constant, particularly a low dielectric loss. However, the materials proposed in Patent Documents 1 and 2 all have a high dielectric constant and are not suitable for parts for high-speed communication equipment.

Therefore, the present invention has been made in view of the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a thermoplastic resin composition and a molded product for laser direct structuring, which are excellent in plating property and low dielectric property.

As a result of diligent studies, the present inventor has made a hydrogenated block which is a hydride of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit as a substrate material for plating formation by the LDS method. It has been found that by using a cyclic polyolefin composed of a copolymer and a laser direct structuring additive, it is excellent in plating property and low dielectric property, and can be suitably used as a substrate material for high-speed communication equipment for plating formation by the LDS method.

That is, the present invention has the following features.
[1] A thermoplastic resin composition containing a cyclic polyolefin (A) and a laser direct structuring additive (B), wherein the cyclic polyolefin (A) contains at least one aromatic vinyl monomer unit and It is composed of a hydride block copolymer which is a hydride of a block copolymer containing at least one conjugated diene monomer unit, and the hydride block copolymer is a hydride of a polymer block composed of the aromatic vinyl monomer unit. It has an aromatic vinyl polymer block unit and a hydride conjugated diene polymer block unit which is a hydride of the polymer block composed of the conjugated diene monomer unit, and the hydride block copolymer is the hydride aromatic vinyl polymer block unit. A thermoplastic resin composition having at least two of the above and at least one of the hydrogenated conjugated diene polymer block units.

[2] The thermoplastic resin composition according to [1], which contains 3 to 30 parts by mass of the laser direct structuring additive (B) with respect to 100 parts by mass of the resin component in the thermoplastic resin composition. ..
[3] The thermoplastic resin composition according to [1] or [2], wherein the laser direct structuring additive (B) is at least one selected from copper chromium oxide and antimony-containing tin oxide.
[4] The hydrogenated aromatic vinyl polymer block unit has a hydrogenation level of 90% or more, and the hydrogenated conjugated diene polymer block unit has a hydrogenation level of 95% or more [1] to [3]. ] The thermoplastic resin composition according to any one item.

[5] Any one of [1] to [4], wherein the hydrogenated aromatic vinyl polymer block unit is made of polystyrene hydride and the content in the cyclic polyolefin (A) is 30 to 99 mol%. The thermoplastic resin composition according to.
[6] The item according to any one of [1] to [5], wherein the hydrogenated conjugated diene polymer block unit is made of hydrogenated polybutadiene, and the content in the cyclic polyolefin (A) is 1 to 70 mol%. The thermoplastic resin composition according to the above.
[7] The heat according to any one of [1] to [6], which further contains 0 to 50 parts by mass of the acid-modified cyclic polyolefin (C) with respect to 100 parts by mass of the cyclic polyolefin (A). Plastic resin composition.
[8] The thermoplastic resin composition according to any one of [1] to [7], which is a thermoplastic resin composition for laser direct structuring.

[9] A molded product obtained by molding the thermoplastic resin composition according to any one of [1] to [7].
[10] The molded product according to [9], which has plating on its surface.
[11] The molded product according to [10], wherein the plating retains the performance as an antenna.
[12] The molded product according to any one of [9] to [11], which is a portable electronic device component.
[13] A method for producing a plated molded product, wherein a copper-plated layer is formed after irradiating the surface of the molded product according to [9] with a laser.
[14] A method for manufacturing a portable electronic device component having an antenna, which comprises the method for manufacturing a plated molded product according to [13].

According to the present invention, by using a thermoplastic resin composition having a specific cyclic polyolefin and a laser direct structuring additive as a substrate material for performing plating formation by the LDS method, it is excellent in plating property and low dielectric property. It has been found that it can be suitably used as a substrate material for high-speed communication equipment for plating formation by the LDS method.
Further, since the molded product made of this thermoplastic resin composition has excellent low dielectric properties, it can be used for interior parts and exterior parts of portable electronic devices.

The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as the gist of the present invention is not exceeded. It can be arbitrarily modified and carried out without departing from the gist of the invention.
In the following, when a numerical value or a physical property value is inserted before and after using "~", it is used as including the values before and after that.

The invention according to the present application is an invention for a thermoplastic resin composition containing a cyclic polyolefin (A) and a laser direct structuring additive (B), particularly a thermoplastic resin composition for laser direct structuring.

<Cyclic polyolefin (A)>
The cyclic polyolefin (A) of the present invention comprises a hydrogenated block copolymer which is a hydride of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit.
The hydrogenated block copolymer is a hydrogenated product of a hydrogenated aromatic vinyl polymer block unit, which is a hydride of a polymer block composed of the aromatic vinyl monomer unit, and hydrogen, which is a hydride of a polymer block composed of the conjugated diene monomer unit. It has a modified conjugated diene polymer block unit.
Further, the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit.

The cyclic polyolefin (A) of the present invention is preferably made of the hydrogenated block copolymer from the viewpoint of low dielectric properties and weather resistance.
As will be described later, the term "block" as used herein refers to a polymerized segment of a copolymer that represents microlayer separation from polymerized segments that are structurally or compositionally different from each other. For this reason, for example, "having at least two block units" means that the hydrogenated block copolymer has at least two polymerized segments of the copolymer representing microlayer separation from structurally or structurally different polymerized segments. Say that.

The aromatic vinyl monomer used as a raw material for the aromatic vinyl monomer unit is a monomer represented by the general formula (1).

Here, R is a hydrogen or an alkyl group, Ar is a phenyl group, a halophenyl group, an alkylphenyl group, an alkylhalophenyl group, a naphthyl group, a pyridinyl group, or an anthrasenyl group.

The alkyl group may be a mono- or multiple-substituted alkyl group with a functional group such as a halo group, a nitro group, an amino group, a hydroxy group, a cyano group, a carbonyl group, and a carboxyl group. The alkyl group preferably has 1 to 6 carbon atoms.
Further, the Ar is preferably a phenyl group or an alkylphenyl group, and more preferably a phenyl group.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene (including all isomers, particularly p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, and vinyl. Anthracene (all isomers), and mixtures thereof.

The conjugated diene monomer used as a raw material for the conjugated diene monomer unit may be a monomer having two conjugated double bonds, and is not particularly limited.
Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3 pentadiene and similar compounds, and mixtures thereof.

Polybutadiene, which is a polymer of 1,3-butadiene, has either an 1,2 configuration that gives an equivalent of 1-butene repeating units by hydrogenation, or a 1,4 configuration that gives an equivalent of ethylene repeating units by hydrogenation. Can be included.

The hydrogenated block copolymer composed of the aromatic vinyl monomer and the conjugated diene monomer containing 1,3-butadiene is included in the hydrogenated block copolymer used in the present invention. Preferably, the hydrogenated block copolymer is a functional group-free block copolymer.
In addition, "without functional groups" means that there are no functional groups in the block copolymer, that is, groups containing elements other than carbon and hydrogen.

Preferable examples of the hydrogenated aromatic vinyl polymer block unit include polystyrene hydride, and preferred examples of the hydrogenated conjugated diene polymer block unit include hydrogenated polybutadiene.
A preferred embodiment of the hydrogenated block copolymer is a hydrogenated triblock or pentablock copolymer of styrene and butadiene, preferably free of any other functional group or structural modifier.
A "block" is defined as a polymerization segment of a copolymer that represents microlayer separation from structurally or compositionally different polymerization segments of the copolymer. Microlayer separation occurs due to the immiscibility of the polymerized segments in the block copolymer.
It should be noted that microlayer separation and block copolymers are widely discussed in "Block Copolymers-Designer Soft Materials", February 1999, pp. 32-38 of PHYSICS TODAY.

The content of the hydrogenated aromatic vinyl polymer block unit is preferably 30 to 99 mol%, more preferably 40 to 90 mol% with respect to the cyclic polyolefin (A).
If the ratio of hydrogenated aromatic vinyl polymer block units is at least the above lower limit value, the rigidity is not lowered, and if it is at least the above upper limit value, brittleness is not deteriorated.

The content of the hydrogenated conjugated diene polymer block unit is preferably 1 to 70 mol%, more preferably 10 to 60 mol% with respect to the cyclic polyolefin (A).
If the ratio of hydrogenated conjugated diene polymer block units is at least the above lower limit value, brittleness does not deteriorate, and if it is at least the above upper limit value, rigidity does not decrease.

As described above, the polyolefin according to the present invention is a "cyclic polyolefin", and the "cyclic" is an alicyclic formed by hydrogenation of an aromatic ring possessed by the hydrogenated aromatic vinyl polymer block unit. It refers to the formula structure.

The hydrogenated block copolymers of the present invention are triblocks, multiblocks, taper blocks such as SBS, SBSBS, SIS, SISIS, and SISBS (where S stands for polystyrene, B stands for polybutadiene, I stands for polyisoprene). , And block copolymers, including star block copolymers, are produced by hydrogenation.

The hydrogenated block copolymers of the present invention contain a segment consisting of an aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer of the present invention will have at least two hydrogenated aromatic vinyl polymer block units. Then, at least one hydrogenated conjugated diene polymer block unit will be provided between the two hydrogenated aromatic vinyl polymer block units.

The pre-hydrogenation block copolymer constituting the hydrogenation block may contain several additional blocks, which may be attached to any position on the triblock polymer backbone. Thus, the linear block includes, for example, SBS, SBSB, SBBSS, and SBBSSB. The copolymer may be branched and the polymerization chain may be attached at any position along the backbone of the copolymer.

The lower limit of the weight average molecular weight (Mw) of the hydrogenated block copolymer is preferably 30,000 or more, more preferably 40,000 or more, still more preferably 45,000 or more, and particularly preferably 50,000 or more. The upper limit of Mw is preferably 120,000 or less, more preferably 100,000 or less, further preferably 95,000 or less, particularly preferably 90,000 or less, most preferably 85,000 or less, and extremely preferably 80. It is less than 000.
If Mw is at least the above lower limit value, the mechanical strength does not decrease, and if it is at least the above upper limit value, the moldability does not deteriorate.
The Mw herein is determined using gel permeation chromatography (GPC).

The hydrogenation level of the block copolymer is preferably 90% or more for the hydrogenated aromatic vinyl polymer block unit, 95% or more for the hydrogenated conjugated diene polymer block unit, and more preferably 95% or more for the hydrogenated aromatic vinyl polymer block unit. % Or more, the hydrogenated conjugated diene polymer block unit is 99% or more, more preferably the hydrogenated aromatic vinyl polymer block unit is 98% or more, and the hydrogenated conjugated diene polymer block unit is 99.5% or more, particularly. Preferably, the hydrogenated aromatic vinyl polymer block unit is 99.5% or more, and the hydrogenation-conjugated diene polymer block unit is 99.5% or more.
The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the rate at which the aromatic vinyl polymer block unit is saturated by hydrogenation, and the hydrogenation level of the hydrogenation-conjugated diene polymer block unit is the conjugated diene. Shows the rate at which a polymer block unit is saturated by hydrogenation. Such high levels of hydrogenation are preferred in order to reduce dielectric loss.

The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit and the hydrogenation level of the hydrogenated conjugated diene polymer block unit are determined by using proton NMR.

The melt flow rate (MFR) of the cyclic polyolefin (A) of the present invention is not particularly limited, but is usually 0.1 g / 10 minutes or more, and is preferably 0.2 g / 10 from the viewpoint of the molding method and the appearance of the molded product. More than a minute. Further, it is usually 200 g / 10 minutes or less, preferably 100 g / 10 minutes or less, and more preferably 50 g / 10 minutes or less from the viewpoint of material strength.
The MFR was measured according to ISO 1133 under the conditions of a measurement temperature of 230 ° C. and a measurement load of 2.16 kg.

As the cyclic polyolefin (A), one type may be used alone, or two or more types having different composition and physical properties of each monomer unit may be used in combination.
As the cyclic polyolefin (A) of the present invention, a commercially available product can be used. Specifically, Mitsubishi Chemical Corporation: Zelas (registered trademark) can be mentioned.

<Laser direct structuring additive (B)>
The laser direct structuring additive (B) is an additive having a characteristic that when a laser beam is irradiated, metal atoms contained in the additive (B) are activated and a metal layer is formed on the surface. is there.
Hereinafter, the "laser direct structuring additive (B)" may be referred to as "LDS additive (B)".

Examples of the LDS additive (B) include heavy metal composite oxide spinels such as copper chromium oxide (CuCr ₂ O ₄ ); copper hydroxide phosphate, copper phosphate, copper sulfate, copper thiocyanate and the like. Copper salt; antimony-containing tin oxide such as antimon-doped tin oxide; metal oxides such as metal oxides and metal compounds such as metal salts, and other metal-containing metal compounds in which a different metal is doped in a part of the metal compound, etc. Can be mentioned. Among these, copper chromium oxide and antimony-containing tin oxide are preferable.
Since copper chromium oxide also functions as a black pigment, it is suitable for obtaining a black molded body, and antimony-containing tin oxide can be used as a white pigment, so that it can be used as a white molded body or with pigments of other colors. It can also be applied in combination as a desired color variation.

The particle size of the LDS additive (B) is preferably 0.01 to 50 μm, more preferably 0.05 to 30 μm. With such a particle size, the uniformity of the plating surface state when plating is applied tends to be good.

The LDS additive (B) may be used alone or in combination of two or more.
As the LDS additive (B) of the present invention, a commercially available product can be used. Specific examples thereof include Black1G manufactured by Shepherd and CP5C manufactured by Keeling & Walker.

<Acid-modified cyclic polyolefin (C)>
The thermoplastic resin composition of the present invention preferably further contains an acid-modified cyclic polyolefin (C) in addition to the above components (A) and (B).
The acid-modified cyclic polyolefin (C) can exhibit high compatibility performance with the component (A) and an inorganic substance such as the component (B).

The acid-modified cyclic polyolefin (C) is a modified cyclic polyolefin obtained by graft-modifying the above-mentioned cyclic polyolefin (A) with an unsaturated carboxylic acid and / or a derivative thereof.
The cyclic polyolefin (A) to be subjected to modification may be one kind or two or more kinds having different composition and physical properties of each monomer unit.
For the graft modification treatment with an unsaturated carboxylic acid and / or a derivative thereof, any commonly used method can be adopted, and the method is not particularly limited.

For example, as a solution modification method, a cyclic polyolefin (A), an unsaturated carboxylic acid and / or a derivative thereof, and a radical polymerization initiator, if necessary, are added to an organic solvent, and the temperature is usually 60 to 350 ° C., preferably. Examples thereof include a method of reacting at a temperature of 80 to 250 ° C. for usually 0.5 to 15 hours, preferably 1 to 10 hours.
As a melt modification method, the cyclic polyolefin (A) and the unsaturated carboxylic acid and / or its derivative are melted at 170 to 290 ° C. using an extruder or the like and usually reacted for 0.5 to 10 minutes. The method can be mentioned.

Among these, from the viewpoint of hygiene, a melt modification method that does not use a solvent is preferable, and modification using an extruder is more preferable. In order to modify efficiently, it is preferable to modify in the presence of a radical polymerization initiator.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and endosis-bicyclo [2.2.1] hept-5-en-2. , 3-Dicarboxylic acid.
Examples of the unsaturated carboxylic acid derivative include acid anhydrides, esters, amides, imides, and metal salts. Specifically, acid anhydrides such as maleic anhydride, hymicic anhydride, itaconic anhydride, and citraconic anhydride; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, monoethyl maleate. Esters such as esters, maleic acid diethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester; acrylamide, methacrylic acid, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide. , Maleic acid-N, N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, etc. Amides; imides such as maleimide, N-butyl maleimide, N-phenylmaleimide; metal salts such as sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like can be mentioned.

As the unsaturated carboxylic acid and / or its derivative, one type may be used alone, or two or more types may be used in combination.
Among these, maleic acid and maleic anhydride are particularly preferable.

As the radical polymerization initiator, an organic peroxide or an azo compound is preferable, and an organic peroxide is more preferable.
Specifically, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, 2,5-dimethyl. -2,5-di (t-butylperoxy) hexin-3,1,4-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl- 4,4-bis (t-butylperoxy) ballet, 2,2-bis (4,5-t-butylperoxycyclohexyl) propane, 2,2-bis (t-butylperoxy) butane, 1,1 Dialkyl peroxides such as -bis (t-butylperoxy) cyclododecane; t-butylperoxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylper Oxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, t-butylperoxymaleic acid, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di ( Peroxyesters such as benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexin-3, 2,5-dimethyl-2,5-di (toluylperoxy) hexane; Diacyl peroxides such as di-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, dibenzoyl peroxide; t-butylhydroperoxide, cumenehydroperoxide, diisopropylbenzenehydroperoxide, p- Hydroperoxides such as mentan hydroperoxide and 2,5-dimethyl-2,5-di (hydroperoxy) hexane; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide can be mentioned.
One type of radical polymerization initiator may be used alone, or two or more types may be used in combination.

As the radical polymerization initiator, among the above-mentioned examples, those having a decomposition temperature of 100 ° C. or higher having a half-life of 1 minute are preferable from the viewpoint of modification efficiency.
Specifically, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (). Dialkyl peroxides such as t-butylperoxy) hexin-3; t-butylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5 Peroxy esters such as −di (benzoyl peroxy) hexin-3 are preferred.

The amount of the radical polymerization initiator used is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the cyclic polyolefin (A) as a raw material.

The content of the structural unit derived from the unsaturated carboxylic acid and / or its derivative in the acid-modified cyclic polyolefin (C) (hereinafter, may be referred to as “modification rate”) is the content of the acid-modified cyclic polyolefin (C). 0.25 to 5.0% by mass is preferable, 0.30 to 4.0% by mass is more preferable, and 0.50 to 3.0% by mass is further preferable with respect to the whole.
If the modification rate is within the above range, the compatibility tends to be sufficient.

The bonding position of the structural unit derived from the unsaturated carboxylic acid and / or its derivative in the acid-modified cyclic polyolefin (C) is not particularly limited, and at least one of the main chain end and the side chain of the acid-modified cyclic polyolefin (C). It should be introduced in.
The modification rate of the acid-modified cyclic polyolefin (C) can be measured by, for example, the following method.

First, a sheet-shaped press sample having a thickness of 0.1 to 0.4 mm is prepared from the acid-modified cyclic polyolefin (C) using a compression molding machine or the like.
Next, a spectrum of 2000 to 1600 cm ^-1 of the sample was measured with a Fourier transform infrared spectrophotometer, and the absorption peculiar to unsaturated carboxylic acid and / or its derivative (C = O stretching vibration band, that is, carbonyl). It can be obtained from characteristic absorption.).

More specifically, the obtained spectrum, pull the baseline between 1950cm ^-1 and 1665 cm ^-1, calculates the peak area S between 1827~1665cm ^-1.
Using the obtained peak area S, the content rate Xm of the structural unit derived from the unsaturated carboxylic acid and / or its derivative is calculated based on the following formula (1).
In the modification of the acid-modified cyclic polyolefin (C), an unreacted unsaturated carboxylic acid and / or a derivative thereof may remain, but the modification rate in the present specification refers to the acid-modified cyclic polyolefin (C) as described above. C) shall mean the value when measured by the above method.
Xm = k ・ S / t ・ ρ ・ ・ ・ (1)
(In the formula, k represents a coefficient obtained based on the NMR quantitative value of the methyl esterified product of the thermoplastic resin containing an unsaturated carboxylic acid, t (mm) represents the thickness of the sample, and ρ represents the thickness of the sample. It represents the density (g / cm ³ ).)

As the acid-modified cyclic polyolefin (C), one type may be used alone, or two or more types may be used in combination.
As the acid-modified cyclic polyolefin (C) of the present invention, a commercially available product can be used. Specifically, Mitsubishi Chemical Corporation: "Zeras (registered trademark) MC940AP" can be mentioned.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains a cyclic polyolefin (A) and an LDS additive (B).
The thermoplastic resin composition of the present invention may further contain an acid-modified cyclic polyolefin (C).
In addition, the thermoplastic resin composition of the present invention may further contain a resin component (resin component other than the components (A) and (C)) and an elastomer component described later.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition for laser direct structuring that can be suitably used for laser direct structuring applications.

The thermoplastic resin composition of the present invention preferably contains 3 to 30 parts by mass of the LDS additive (B) with respect to 100 parts by mass of the resin component in the thermoplastic resin composition.
The content of the LDS additive (B) is preferably 5 parts by mass or more. Further, 25 parts by mass or less is preferable, and 20 parts by mass or less is more preferable.

When the content of the component (B) is at least the above lower limit value, the plating property due to the inclusion of the component (B) is effectively exhibited. Further, if it is not more than the above upper limit value, the low dielectric property can be effectively obtained.

Here, the "resin component" in the thermoplastic resin composition refers to the component (A) when only the component (A) is used as the resin.
When the components (A) and (C) are used as the resin, it refers to the components (A) + (C).
When the components (A), (C) and other resins are used as the resin, it refers to the components (A) + (C) + other resins.

The thermoplastic resin composition of the present invention can contain 0 to 50 parts by mass of the acid-modified cyclic polyolefin (C) with respect to 100 parts by mass of the cyclic polyolefin (A). The content of the component (C) is preferably 0.2 to 20 parts by mass.
By containing the component (C), high compatibility performance with respect to inorganic substances can be exhibited, but if the content is too large, the dielectric property tends to deteriorate. Therefore, the content of the component (C) is preferably not more than the above upper limit value.

<Other ingredients>
As other components, the thermoplastic resin composition of the present invention may contain a compounding agent commonly used in the resin composition as long as the effects of the present invention are not impaired.
Examples of such a compounding agent include a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an antioxidant, a crystal nucleating agent, a rust preventive, an inorganic filler, a glass fiber, a foaming agent, and a pigment. Can be mentioned.
Of these, it is preferable to contain an antioxidant, particularly a phenol-based, sulfur-based or phosphorus-based antioxidant.
The antioxidant is preferably contained in an amount of 0.01 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention.

Further, a resin component or an elastomer component other than the component (A) and the component (C) may be contained as long as the effect of the present invention is not impaired.
Examples of such resin components include polyethylene resin, polypropylene resin, ethylene-α-olefin copolymer resin, propylene-α-olefin copolymer resin, ethylene-vinyl acetate copolymer resin, and ethylene-acrylic acid ester copolymer resin. , Ethylene- (meth) acrylic acid copolymer resin, polystyrene resin, polyvinyl chloride resin, polyester resin, polyamide resin, ethylene-vinyl alcohol copolymer, acrylic resin, and petroleum resin styrene-conjugated diene block Copolymerized resin can be mentioned.

These other components may be added by kneading them into the component (A) by the kneading method commonly used for melt-kneading the thermoplastic resin, or they may be dissolved together with the component (A) in an organic solvent. You may mix them.

<Manufacturing method of thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains components (A) and (B), and if necessary, component (C) and other components in a normal extruder, Banbury mixer, roll, lavender plastograph, kneaderb. It can be produced by kneading with a conventional method using lavender or the like.
Among these manufacturing methods, it is preferable to use an extruder, particularly a twin-screw extruder.

When the thermoplastic resin composition of the present invention is kneaded and kneaded with an extruder or the like, it can be produced by melt-kneading while heating to 180 to 300 ° C., preferably 220 to 280 ° C.

<Molded body>
The surface of the molded product obtained by molding the thermoplastic resin composition of the present invention is irradiated with a laser beam in a desired pattern such as an antenna circuit. As a result, an activated metal layer is formed on the surface of the molded product only in the region where the circuit pattern is provided. Also, an advantageous surface structure is generated due to the subsequent metal plating.
The molded body is immersed in a plating solution, and copper, nickel, gold, etc. are plated on the surface of the molded body by electroless plating (or electric field plating), particularly on the surface of the activated metal layer portion of the surface of the molded body. Is applied to form a circuit pattern.

<Molding method>
The thermoplastic resin composition of the present invention can be molded by using an ordinary injection molding method or, if necessary, various molding methods such as a gas injection molding method, an injection compression molding method, and a short shot foam molding method. It can be a molded product. As a result, it can be used as various communication equipment members for laser direct structuring.
In particular, it is preferable that the thermoplastic resin composition of the present invention is injection-molded to form a molded product, and the molding conditions for performing injection molding are as follows.
The molding temperature is usually 200 to 300 ° C, preferably 220 to 280 ° C. The injection pressure is usually 5 to 100 MPa, preferably 10 to 80 MPa. The mold temperature is usually 0 to 100 ° C, preferably 30 to 95 ° C.

<Use>
As described above, the molded product of the thermoplastic resin composition of the present invention can be made into a plated molded product by irradiating a laser beam in a desired pattern such as an antenna circuit and plating the surface thereof. .. Then, the plating of this plated molded product can retain the performance as an antenna. Therefore, the irradiated and plated molded product can be used as a portable electronic device component having an antenna.

Hereinafter, the content of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable ranges are the above-mentioned upper limit or lower limit values and the following. It may be in the range specified by the value of Examples or the combination of the values of Examples.

[Physical characteristics]
<Melt flow rate (MFR)>
・ Equipment: "Melt Indexer" manufactured by Toyo Seiki Seisakusho Co., Ltd.
・ Temperature: 230 ℃
・ Orifice hole diameter: 2 mm
・ Load: 2.16kg

<Ratio of polymer blocks>
[Measurement by carbon NMR]
-Device: Bruker's "AVANCE400 spectrometer"
-Solvent: Orthodichlorobenzene-h ₄ / para-dichlorobenzene-d ₄ mixed solvent-Concentration: 0.3 g / 2.5 mL
-Measurement: ¹³ C-NMR
・ Resonance frequency: 400MHz
・ Number of integrations: 1536
・ Flip angle: 45 degrees ・ Data acquisition time: 1.5 seconds ・ Pulse repetition time: 15 seconds ・ Measurement temperature: 100 ° C
・¹ H irradiation: Complete decoupling

<Hydrogenation level of hydrogenated aromatic vinyl polymer block unit, hydrogenation conjugated diene polymer block unit>
[Measurement by proton NMR]
・ Equipment: "400YH spectrometer" manufactured by JASCO Corporation
-Solvent: Deuterated chloroform-Concentration: 0.045 g / 1.0 mL
・ Measurement: ^{1 1} H-NMR
・ Resonance frequency: 400MHz
・ Number of integrations: 8
-Measurement temperature: 18.5 ° C
-Hydrogenated aromatic vinyl polymer block unit hydrogenation level: 6.8 to 7.5 ppm integrated value reduction rate-Hydrogen conjugated diene polymer block unit hydrogenation level: 5.7 to 6.4 ppm integrated value reduction rate

<Dissipation factor>
Using the obtained thermoplastic resin composition for laser direct structuring, an in-line screw type injection molding machine (“J110AD” manufactured by JSW) was used at an injection pressure of 50 MPa, a cylinder temperature of 270 ° C, and a mold temperature of 95 ° C. A test piece having a thickness of 2 mm, a width of 120 mm, and a length of 120 mm was molded.
This was cut into a thickness of 1.5 mm, a width of 1.5 mm, and a length of 80 mm to obtain a test piece for dielectric loss tangent.
Using a PNA-L network analyzer N5230A (manufactured by Agilent Technologies, Ltd.), the dielectric loss tangent, which is an index of low dielectric characteristics, was measured at a frequency of 10 GHz and a measurement temperature of 23 ° C. in accordance with IEC62810.
The dielectric loss tangent of the thermoplastic resin composition for laser direct structuring of the present invention is preferably 0.002 or less, more preferably 0.0015 or less.

<Plating property>
Using the obtained thermoplastic resin composition for laser direct structuring, an in-line screw type injection molding machine (“J110AD” manufactured by JSW) was used at an injection pressure of 50 MPa, a cylinder temperature of 270 ° C, and a mold temperature of 95 ° C. A test piece having a thickness of 2 mm, a width of 120 mm, and a length of 120 mm was molded.
This was cut into a thickness of 2 mm, a width of 60 mm, and a length of 60 mm to obtain a test piece for a plating test.
Irradiation was performed with a laser irradiation device (“LP-Z SERIES” manufactured by SUNX) at a wavelength of 1064 nm, YAG lasers 4W, 8W and 12W, an output of 40%, and 2 m / s.
Then, using an electroless MacDermid MIDCoper100XB Strike, a plating layer forming treatment was carried out at 65 ° C. for 30 minutes in a plating tank, and the plating state was visually judged.
In each laser output, the plated state was marked with ◯, and the unplated state was marked with x. A state plated with any laser output is preferable, and a state plated with all laser outputs is more preferable.

[material]
<Cyclic polyolefin (A-1)>
"Zeras (registered trademark) MC930" manufactured by Mitsubishi Chemical Corporation
-Density (ASTM D792): 0.94 g / cm ³
-MFR (230 ° C, 2.16 kg): 1 g / 10 minutes-Hydrogenated aromatic vinyl polymer block Unit: Hydrogenated polystyrene with a content of 67 mol% and hydrogenation level of 99.5% or more-Hydrogenated conjugated diene polymer block Unit: Hydrogenated polybutadiene block structure: pentablock structure, total hydrogenation level: 99.5% or more, content rate 33 mol%, hydrogenation level 99.5% or more

<Laser direct structuring additive (B-1)>
Black1G manufactured by Shepherd: Copper-chromium (III) composite oxide <Laser direct structuring additive (B-2)>
Keeling & Walker CP5C: Antimony-containing tin oxide (95% by mass of tin oxide, 5% by mass of antimony oxide, 0.02% by mass of lead oxide, 0.004% by mass of copper oxide)

<Acid-modified cyclic polyolefin (C-1)>
"Zeras (registered trademark) MC940AP" manufactured by Mitsubishi Chemical Corporation
-Density (ASTM D792): 0.94 g / cm ³
-MFR (230 ° C, 2.16 kg): 3 g / 10 minutes-Hydrogenated aromatic vinyl polymer block Unit: Hydrogenated polystyrene with a content of 67 mol% and hydrogenation level of 99.5% or more-Hydrogenated conjugated diene polymer block Unit: Hydrogenated polybutadiene block structure: pentablock structure, total hydrogenation level: 99.5% or more, maleic acid modification rate: 1.2% by mass, content rate 33 mol%, hydrogenation level 99.5% or more

[Example 1]
100 parts by mass of component (A-1) and 11 parts by mass of component (B-1) are charged at a speed of 5 kg / h with a twin-screw extruder (HK25D Φ25, L / D = 41 manufactured by Parka Corporation) in the same direction. Then, the temperature was raised in the range of 240 ° C. and melt-kneaded to produce a thermoplastic resin composition.
The obtained pellets were used for evaluation. The results are shown in Table 1.

[Examples 2 to 8, Comparative Example 1]
Pellets of the thermoplastic resin composition were obtained in the same manner as in Example 1 except that the formulations shown in Table 1 were used.
The obtained pellets were used for evaluation in the same manner as in Example 1. The results are shown in Table 1.

<Evaluation result>
From Table 1, it was found that Examples 1 to 8 corresponding to the present invention were excellent in low dielectric property and plating property.
The larger the amount of the component (B) added, the better the plating property. On the other hand, Comparative Example 1 containing no component (B) was inferior in plating property.

The thermoplastic resin composition for laser direct structuring and the molded product of the present invention are excellent in plating property and low dielectric property, and are very useful as a substrate material for high-speed communication equipment for plating formation by the LDS method, and are used for interior and exterior parts. Can be used.

Claims (14)

A thermoplastic resin composition containing a cyclic polyolefin (A) and a laser direct structuring additive (B).
The cyclic polyolefin (A) comprises a hydrogenated block copolymer which is a hydride of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit.
The hydrogenated block copolymer is a hydrogenated product of a hydrogenated aromatic vinyl polymer block unit, which is a hydride of a polymer block composed of the aromatic vinyl monomer unit, and a hydride of a polymer block composed of the conjugated diene monomer unit. Has a conjugated diene polymer block unit,
The hydrogenated block copolymer is a thermoplastic resin composition having at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit. The thermoplastic resin composition according to claim 1, which contains 3 to 30 parts by mass of the laser direct structuring additive (B) with respect to 100 parts by mass of the resin component in the thermoplastic resin composition. The thermoplastic resin composition according to claim 1 or 2, wherein the laser direct structuring additive (B) is at least one selected from copper chromium oxide and antimony-containing tin oxide. Any one of claims 1 to 3, wherein the hydrogenated aromatic vinyl polymer block unit has a hydrogenation level of 90% or more, and the hydrogenated conjugated diene polymer block unit has a hydrogenation level of 95% or more. The thermoplastic resin composition according to the section. The thermoplastic according to any one of claims 1 to 4, wherein the hydrogenated aromatic vinyl polymer block unit is made of polystyrene hydride and the content in the cyclic polyolefin (A) is 30 to 99 mol%. Resin composition. The thermoplastic resin according to any one of claims 1 to 5, wherein the hydrogenated conjugated diene polymer block unit is made of hydrogenated polybutadiene, and the content in the cyclic polyolefin (A) is 1 to 70 mol%. Composition. The thermoplastic resin composition according to any one of claims 1 to 6, further containing 0 to 50 parts by mass of the acid-modified cyclic polyolefin (C) with respect to 100 parts by mass of the cyclic polyolefin (A). The thermoplastic resin composition according to any one of claims 1 to 7, which is a thermoplastic resin composition for laser direct structuring. A molded product obtained by molding the thermoplastic resin composition according to any one of claims 1 to 7. The molded product according to claim 9, which has a plating on the surface. The molded product according to claim 10, wherein the plating retains the performance as an antenna. The molded product according to any one of claims 9 to 11, which is a portable electronic device component. A method for producing a plated molded product, wherein a copper-plated layer is formed on the surface of the molded product according to claim 9 after irradiating the surface with a laser. A method for manufacturing a portable electronic device component having an antenna, which comprises the method for manufacturing a plated molded product according to claim 13.