WO2014163243A1

WO2014163243A1 - Laser direct structuring method

Info

Publication number: WO2014163243A1
Application number: PCT/KR2013/006713
Authority: WO
Inventors: 김한주; 손정철
Original assignee: Kim Han Joo
Priority date: 2013-04-02
Filing date: 2013-07-26
Publication date: 2014-10-09
Also published as: CN104995334B; CN104995334A; KR101339640B1; JP2016516903A

Abstract

The purpose of the present invention is to provide an improved laser direct structuring method capable of reforming an area to be plated on the surface of a resin structure by means of laser radiation, thereby making the area suitable for plating, without using a nucleation agent. An example of implementation of a laser direct structuring method according to an aspect of the present invention comprises a step of forming trench lines of lattice pattern arrangement by radiating lasers to an area to be plated on the surface of a resin structure.

Description

Laser Direct Structuring Method

The present invention relates to a method of forming a metal layer on the surface of a nonconductive resin molded article, and more particularly, to a laser direct structuring method.

In order to plate the metal layer on at least part of the surface of the resin molded body, a laser direct structuring process may be used. The laser direct structuring process is a process performed before the plating step, and means a process of modifying the plating target region on the surface of the resin molding to have properties suitable for plating by irradiating a laser to the plating target region on the surface of the resin molding. For this purpose, the resin molded body should contain a "laser direct structuring nucleating agent (hereinafter simply referred to as" nucleating agent ")" capable of forming a metal nucleus by a laser. The nucleating agent contained in the resin molded body generates metal nuclei while decomposing upon receiving a laser. In addition, the plating target region to which the laser is irradiated has surface roughness. Due to the presence of such metal nuclei and surface roughness, the region to be laser modified is suitable for plating.

Using a laser direct structuring process, it is possible to quickly and economically form an electric / electronic circuit on the three-dimensional shape of the resin molded body. For example, the laser direct structuring process may be utilized to manufacture antennas, RFID antennas, and the like of portable electronic devices.

The resin composition for a laser direct structuring process refers to a composition for producing a resin molded body whose surface can be modified as described above by a laser direct structuring process. Thus, the resin composition for the laser direct structuring process contains a nucleating agent.

Examples of the nucleating agent of the conventional composition for laser direct structuring process include metal oxides having a spinel structure (Patent 10-0716486, Published Patent 10-2010-0055474); Heavy metal composite oxide spinel such as copper chromium oxide spinel (Patent 10-2011-0009684); Copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate, or cuprous thiocyanate (published patent 10-2011-0009684, published patent 10-2011-0018319); and the like are known.

However, the copper chromium oxide of the spinel structure is so dark that it is also used as a black pigment. Therefore, the copper chromium oxide of the spinel structure is applicable only when the color required for the resin molded body is black or gray. When various colors other than black and gray are required for the resin molded body, when the spinel structure copper chromium oxide is applied as a nucleation agent, it is very difficult to obtain a resin molded body of a desired color.

Copper phosphate compounds generally have a pale green or blue based color. Therefore, when green or blue-based color is required for the resin molded body, it may be considered to apply a copper phosphate compound as a nucleation agent. However, a copper phosphate compound (for example, Cu2P2O7 * H2O, 4CuO * P2O5 * H2O, etc.) can discharge | release crystal water under the temperature and pressure of a resin molding process. The released crystal water may react with other components such as the resin or the additive in the composition, or may remain in the resin molded body even after molding. Accordingly, the physical properties of the resin molded body may be reduced, or the color or surface state of the resin molded body may be reduced. In particular, this problem may occur more seriously if the composition contains moisture sensitive polymers such as, for example, polycarbonate, polyamide, polybutylene terephthalate and the like.

The copper hydroxide phosphate compound is a compound in which copper phosphate and copper hydroxide are bonded. Copper hydroxide phosphate contains copper hydroxide instead of crystal water, so that even during the molding process of the resin molded body, water is not released. In addition, copper hydroxide phosphate does not lower the color reproducibility of the colorant contained in the resin molded body, whereby it becomes very easy to obtain a resin molded body of a desired color.

However, colorants such as pigments and dyes contained in the resin molded body in order to impart the desired color to the resin molded body exhibit color by reflecting or absorbing incident light rays. Laser electromagnetic radiation irradiated to the resin molded body in the LDS process is also reflected or absorbed by the colorant. Therefore, in the presence of a colorant, the depth at which laser electromagnetic radiation is transmitted into the resin molded body is reduced, and as a result, the reaction efficiency of the nucleating agent (for example, copper hydroxide phosphate) by the laser electromagnetic radiation is significantly reduced. Can be.

It is an object of the present invention to provide an improved laser direct structuring method capable of modifying a region to be plated on a resin structure surface to be suitable for plating by irradiating a laser without using a nucleating agent.

One embodiment of the laser direct structuring method according to an aspect of the present invention includes the step of irradiating a laser to the plating target region of the surface of the resin structure to form a trench line of the grid pattern arrangement.

According to another aspect of the present invention, in a resin structure having a region to be plated, there is provided a resin structure in which a trench line having a lattice pattern formed by laser irradiation is formed in the region to be plated.

According to another aspect of the invention,

(a) A resin structure having a region to be plated, comprising: a resin structure in which a trench line of a lattice pattern formed by laser irradiation is formed in the region to be plated; And

(b) a metal layer attached to the plating target region of the resin structure;

A resin structure having a conductor portion is provided.

In an embodiment of the laser direct structuring method of the present invention, the plurality of first trench lines and the plurality of second trench lines formed by laser irradiation intersect each other, so that the first trench lines and the second trench lines cross each other. Trenchs of a lattice pattern are formed in the plating target region of the structure surface.

According to the present invention, the trench of the lattice pattern formed by laser irradiation promotes the adhesion of the metal layer to the plating target region on the surface of the resin structure by plating. Furthermore, according to the present invention, the trench of the lattice pattern formed by laser irradiation enhances the adhesion between the metal layer and the resin structure attached to the plating target region on the surface of the resin structure by plating.

By using an embodiment of the laser direct structuring method of the present invention, even if the resin structure does not contain a nucleation agent, it is possible to attach the metal layer to the plating target region on the surface of the resin structure by plating. On the other hand, the metal layer is not attached to the region where the trench in the lattice pattern arrangement by the laser irradiation is not formed.

By using an embodiment of the laser direct structuring method of the present invention that does not require the use of a nucleating agent, problems associated with the use of the nucleating agent in the conventional laser direct structuring method can be solved fundamentally.

Hereinafter, an embodiment of the laser direct structuring method according to an aspect of the present invention will be described in more detail. One embodiment of the laser direct structuring method includes irradiating a laser to a region to be plated on the surface of a resin structure to form trench lines having a lattice pattern.

The resin structure may include an thermoplastic resin, a thermosetting resin, or a blend thereof. For example, the resin structure may include an acrylonitrile butadiene styrene copolymer (ABS) resin, a polycarbonate resin, a polyamide resin, a polybutylene terephthalate resin, a polyethylene terephthalate resin, a polyvinyl chloride (PVC) resin, and a polyphthalamide (PPA). Resins, polyphenylene sulfide (PPS) resins, polyester resins, liquid crystal polymer (LCP) resins, or blends thereof.

The resin structure may further include glass fibers. In the case where the resin structure further includes glass fibers, the trench of the lattice pattern formed by laser irradiation more effectively promotes the adhesion of the metal layer to the plating target region on the surface of the resin structure by plating. In addition, the glass fibers may reinforce the mechanical strength of the resin structure or compensate for structural defects of the resin structure. The content of the glass fibers in the resin structure may be, for example, about 5 parts by weight to about 45 parts by weight based on 100 parts by weight of the resin.

The resin structure may further include ceramic filler powder. In the case where the resin structure further includes ceramic filler powder, the trench of the lattice pattern formed by laser irradiation promotes the metal layer on the surface to be plated on the surface of the resin structure by plating more effectively. The content of the ceramic filler in the resin structure may be, for example, about 0.1 part by weight to about 15 parts by weight based on 100 parts by weight of the resin. The ceramic filler can be, for example, alumina, titanium dioxide, or a combination thereof.

The resin structure may further include an antioxidant. In the case where the resin structure further includes an antioxidant, the trenches in the lattice pattern formed by laser irradiation further promote the adhesion of the metal layer to the plating target region on the surface of the resin structure by plating. The content of the antioxidant in the resin structure may be, for example, about 0.1 part by weight to about 5 parts by weight based on 100 parts by weight of the resin.

The resin structure may further include an acrylonitrile styrene acrylate component, or a resin component derived from acrylonitrile styrene acrylate. When the resin structure further comprises an acrylonitrile styrene acrylate component or a resin component derived from acrylonitrile styrene acrylate, the metal layer is plated on the surface of the resin structure by plating the trenches of the lattice pattern formed by laser irradiation. More effectively promote attachment to the target area. The content of the acrylonitrile styrene acrylate component or the resin component derived from acrylonitrile styrene acrylate in the resin structure may be, for example, about 5 parts by weight to about 35 parts by weight based on 100 parts by weight of the resin.

The resin structure may further include a phosphate ester component. When the resin structure further contains a phosphate ester component, the trench of the lattice pattern formed by laser irradiation promotes the metal layer more effectively to adhere to the plating target region on the surface of the resin structure by plating. The content of the phosphate ester component in the resin structure may be, for example, about 0.5 parts by weight to about 15 parts by weight based on 100 parts by weight of the resin.

The resin structure may further include a bisphenol A diphosphate component. When the resin structure further includes a bisphenol A diphosphate component, the trench of the lattice pattern formed by laser irradiation more effectively promotes the adhesion of the metal layer to the plating target region on the surface of the resin structure by plating. The content of the bisphenol A diphosphate component in the resin structure may be, for example, about 6 parts by weight to about 20 parts by weight based on 100 parts by weight of the resin.

The resin structure may further include a colorant. In the present invention, since it is not necessary to use a nucleating agent, the phenomenon of lowering the color reproducibility of the colorant by the nucleating agent can be prevented at all. The content of the colorant in the resin structure may be, for example, about 0.1 part by weight to about 5 parts by weight based on 100 parts by weight of the resin. The colorant can be, for example, a pigment or a dye. The pigment can be, for example, an inorganic pigment or an organic pigment. As an inorganic pigment, For example, Metal oxide or composite metal oxide, such as zinc oxide, titanium dioxide, iron oxide, etc .; Sulfides such as zinc sulfide and the like; Aluminate; Sodium sulfosilicates; Sulfates; Chromate; Carbon black; Zinc ferrite; Ultramarine blue; Pigment brown 24; Pigment red 101; Pigment yellow 119; And the like can be used. Examples of the organic pigments include azo, diazo, quinacridone, perylene, naphthalene tetracarboxylic acid, flavantron, isoindolinone, tetrachloroisoindoleone, anthraquinone, ananthrone, dioxazine, Phthalocyanine, Azo Lake, Pigment Blue 60, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Green 7, Pigment Yellow 147, Pigment Yellow 150, and the like can be used. Alternatively, a mixture containing two or more of these pigments may be used as the pigment. As dyes, for example, coumarin 460 (blue), coumarin 6 (green), nile red, lanthanide complexes, hydrocarbons and substituted hydrocarbon dyes, polycyclic aromatic hydrocarbons, scintillation dyes (preferably oxazoles and oxadiazoles) ), Aryl- or heteroaryl-substituted poly (2-8 olefins), carbocyanine dyes, phthalocyanine dyes, oxazine dyes, carbostyryl dyes, porphyrin dyes, acridine dyes, anthraquinone dyes, arylmethane dyes , Azo dyes, diazonium dyes, nitro dyes, quinone imine dyes, tetrazolium dyes, thiazole dyes, perylene dyes, perinone dyes, bis-benzoxazolylthiophene (BBOT), xanthene dyes, fluorescent dyes (e.g. For example, anti-stokes transition dyes that absorb at near infrared wavelengths and emit at visible wavelengths, luminescent dyes (eg, 5-amino-9-diethyliminobenzophenoxazonium perchlorate), 7 - Amino-4-methylcarbostyryl, 7-amino-4-methylcoumarin, 3- (2'-benzimidazolyl) -7-N, N-diethylaminocoumarin, 3- (2'-benzothiazolyl ) -7-diethylaminocoumarin; 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2- (4-biphenyl) -6-phenylbenzoxazole-1,3 ; 2,5-bis- (4-biphenylyl) -1,3,4-oxadiazole; 2,5-bis- (4-biphenylyl) -oxazole; 4,4'-bis- (2-butyloctyloxy) -p-quaterphenyl; p-bis (o-methylstyryl) -benzene; 5,9-diaminobenzo (a) phenoxazonium perchlorate; 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran; 1,1'-diethyl-2,2'-carbocyanide iodide; 3,3'-diethyl-4,4 ', 5,5'-dibenzothiatricarbocyanide iodide; 7-diethylamino-4-methylcoumarin; 7-diethylamino-4-trifluoromethylcoumarin; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 7-ethylamino-6-methyl-4-trifluoromethylcoumarin; 7-ethylamino-4-trifluoromethylcoumarin; Nile red; Rhodamine 700; Oxazine 750; Rhodamine 800; IR 125; IR 144; IR 140; IR 132; IR26; IR5; Diphenylhexatriene; Diphenylbutadiene; Tetraphenylbutadiene; naphthalene; anthracene; 9,10-diphenylanthracene; Pyrene; Chrysene; Rubrene; Coronene; Phenanthrene and the like can be used. Or as a dye, a mixture comprising two or more of these dyes may be used.

The resin structure may be substantially free of a nucleating agent. Examples of the nucleating agent of the conventional composition for laser direct structuring process include metal oxides having a spinel structure (Patent 10-0716486, Published Patent 10-2010-0055474); Heavy metal composite oxide spinel such as copper chromium oxide spinel (Patent 10-2011-0009684); Copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate, or cuprous thiocyanate (published patent 10-2011-0009684, published patent 10-2011-0018319); and the like are known. In the present invention, since the trench of the lattice pattern formed by laser irradiation promotes adhesion of the metal layer to the plating target region on the surface of the resin structure by plating, even if the resin structure does not contain a nucleating agent, It is possible to attach a metal layer to the plating target area on the surface of the resin structure. In the conventional laser direct structuring process, the amount of the nucleating agent used was about 4 parts by weight or more based on 100 parts by weight of the resin. In an embodiment of the invention, the resin structure is substantially free of a nucleating agent, wherein the content of the nucleating agent in the resin structure is less than about 4 parts by weight, preferably 0.1 parts by weight based on 100 parts by weight of the resin. It means less than wealth. More preferably, in another embodiment of the present invention, the content of the nucleating agent in the resin structure may be about 0 parts by weight to about 0.05 parts by weight based on 100 parts by weight of the resin.

Irradiating a laser beam to the plating target region on the surface of the resin structure to form trench lines in a lattice pattern arrangement may be performed by irradiating a laser to the plating target region on the surface of the resin structure.

As a medium of laser electromagnetic radiation, for example, yttrium aluminum garnet (YAG), yttrium orthovanadate (YVO 4), ytterbium (YB), CO ₂ , or the like may be used. As the wavelength of the laser electromagnetic radiation, for example, 532 nm, 1064 nm, 1090 nm, 9.3 μm, 10.6 μm, or the like may be used. When processing with laser electromagnetic radiation, an algorithm that recognizes and processes a three-dimensional shape (for example, recognizes a three-dimensional shape part with a 3D recognition program and divides it into ten steps for each height to control the processing height of the laser) Can be. Laser electromagnetic radiation can be used to further process the outer line for uniformity of plating on the processed surface (plated surface) and the unprocessed surface. The output value of the laser electromagnetic radiation may be, for example, about 2 W to about 30 W.

The trench lines of the grid pattern arrangement may include, for example, a plurality of first trench lines not crossing each other and a plurality of second trench lines not crossing each other. The first trench line and the second trench line are formed to cross each other.

On the other hand, when processing the trench line when processing the continuous trench line, the heat generated in the resin by the laser may be difficult to implement the desired grid pattern trench line. In this case, by dividing the odd number and even number when processing the trench line and jumping at the time of machining, it is possible to prevent the uneven portion from being recessed by the processing heat.

The plurality of first trench lines formed by laser irradiation do not cross each other. The spacing between adjacent first trench lines may be, for example, about 0.02 mm to about 0.10 mm. When the spacing between adjacent first trench lines is less than about 0.02 mm, the lattice structure of the lattice structure is difficult to achieve due to the spot size of the laser (typically about 40 to about 80 μm), and adhesion during plating This may not come out. When the spacing between adjacent first trench lines is greater than about 0.10 mm, even when the trench line spacing is large, the shape of the trench lines of the lattice structure may be difficult and adhesion may not be produced during plating.

The plurality of second trench lines formed by the laser irradiation do not cross each other. The spacing between adjacent second trench lines may be, for example, about 0.02 mm to about 0.10 mm. If the spacing between adjacent second trench lines is less than about 0.02 mm, the lattice structure of the lattice structure is difficult to achieve due to the spot size of the laser (typically about 40 to about 80 μm), and adhesion during plating This may not come out. When the spacing between adjacent second trench lines is greater than about 0.10 mm, even when the trench line spacing is large, the shape of the trench lines of the lattice structure may be difficult and adhesion may not be produced during plating.

The plurality of first trench lines and the plurality of second trench lines formed by laser irradiation are formed so as to intersect each other with the first trench line and the second trench lines, so that the lattice pattern is arranged in the plating target region of the surface of the resin structure. To form a trench. The angle at which the first trench line and the second trench line cross each other does not necessarily have to be at right angles. For example, an angle at which the first trench line and the second trench line cross each other may be greater than about 0 ° and less than or equal to about 90 °. Preferably, the angle at which the first trench line and the second trench line cross each other may be about 60 ° to about 90 °.

The cross-sectional shape of the trench lines may be U-shaped or V-shaped, for example. Preferably, the cross-sectional shape of the trench line may be V-shaped. When the cross-sectional shape of the trench line is V-shaped, a pyramidal or square-shaped island may be formed in the plating target region by forming the trench in the lattice pattern. When a pyramidal or square-shaped island is formed in the plating target region, the adhesion between the metal plating layer and the plating target region of the resin structure can be increased even more remarkably.

The width of the first trench line and the second trench line may be, for example, about 40 μm to about 80 μm. Even if the width of the trench line is too small or too large, it may be difficult to form trench lines having a lattice structure and adhesion may not be produced during plating.

The depth of the first trench line and the second trench line may be, for example, about 5 μm to about 50 μm. The deeper the trench line, the greater the adhesion. On the other hand, if it is too deep, it may be impossible to use due to problems in appearance and performance when used as an intenna and electronic products.

Another embodiment of the laser direct structuring method of the present invention may further include forming a metal layer by plating in a region to be plated on the surface of the resin structure in which the trench lines of the lattice pattern are formed by laser irradiation. have. Plating may be carried out, for example, in an electroless plating manner. In the present invention, there is no significant change in plating conditions according to the type of resin.

The metal layer forming step by plating may include, for example, applying a catalyst to a region to be plated on the surface of the resin structure in which the trench lines in the lattice pattern are formed; And striking the metal in an electroless manner to the plating target region to which the catalyst is applied.

The catalyst applying step is to promote the formation / attach of the metal layer to the plating target region in the subsequent electroless metal strike step by applying the catalyst particles to the trench lines of the lattice pattern of the plating target region. As the catalyst, for example, palladium can be used. As the palladium source, for example, palladium chloride or palladium sulfate can be used. The catalyst imparting step may be, for example, immersing the resin structure in the catalyst solution for about 1 minute to about 5 minutes at a temperature of about 30 ° C to about 40 ° C, and then at about 30 ° C to about 60 ° C It can be carried out by soaking in the catalyst activation solution for 1 to about 3 minutes. The treating solution for catalyzing may be, for example, an aqueous solution containing palladium chloride and hydrochloric acid. The amount of palladium chloride used in the aqueous solution is, for example, about 10 ml to about 450 based on 1 liter of deionized water used. may be ml; The amount of hydrochloric anhydride in the aqueous solution may be, for example, about 150 ml to about 300 ml based on 1 liter of deionized water usage. The catalyst activating solution may be, for example, an aqueous solution containing acidic ammonium fluoride: The content of acidic ammonium fluoride in this aqueous solution may be, for example, from about 70 g / L to about 150 g / L.

In the electroless metal strike step, the metal layer is plated in an electroless manner on the plating target region of the surface of the resin structure to which the catalyst is applied. The metal layer may be copper, nickel, gold, silver, or a combination thereof. The metal layer may be a single layer or a laminated structure. In the laminated structure, each layer may be a different metal or the same metal as each other.

For example, when striking a copper layer, the resin structure to which the catalyst was provided is immersed in the plating liquid for electroless copper strikes. For example, an aqueous electroplating solution for electroless copper strikes may contain about 55 ml to about 65 ml of copper bath / supplement, about 55 ml to about 65 ml of alkali supplement, and about 15 ml of complexing agent based on 1 liter of deionized water. About 20 ml, about 0.1 ml to about 0.2 ml of stabilizer, and about 8 ml to about 10 ml of formaldehyde. The bath / supplement agent is, for example, about 6 parts by weight to about 12 parts by weight of copper sulfate, about 1 part by weight to about 1.5 parts by weight of polyethylene glycol, about 0.01 part by weight to about 0.02 parts by weight of stabilizer, and about 78 parts by weight of water. To about 80 parts by weight. The alkaline supplement may, for example, contain about 40 parts by weight to about 50 parts by weight sodium hydroxide, about 0.01 parts by weight to about 0.02 parts by weight stabilizer, and about 50 parts by weight to about 60 parts by weight of water. The complexing agent may contain, for example, about 49 to about 50 parts by weight sodium hydroxide, about 0.01 to about 0.02 parts by weight stabilizer, and about 50 to about 51 parts by weight water. Stabilizers include, for example, about 0.2 parts by weight to about 0.3 parts by weight of potassium selenocyanate, about 5 parts by weight to about 6 parts by weight of potassium cyanide, about 0.3 parts by weight to about 0.4 parts by weight of sodium hydroxide, and about 92 parts by weight of water. It may contain from about 100 parts by weight to about 93 parts by weight. For example, in order to strike a copper layer, the resin structure to which the catalyst was given was immersed in the plating liquid for electroless copper strikes at the precipitation rate of about 0.5 to about 0.7 micrometer / 10min at about 41 degreeC to about 55 degreeC. Wash with water.

In another specific example, when the nickel layer is strike, the resin structure to which the catalyst is applied is dipped in the plating solution for electroless nickel strike. For example, the aqueous plating solution for electroless nickel strike may contain about 55 ml to about 60 ml of the first nickel plating solution, and about 140 ml to about 150 ml of the second nickel plating solution, based on 1 liter of deionized water. The first nickel plating solution may contain, for example, about 15 parts by weight to about 30 parts by weight of nickel sulfate, about 1 part by weight to about 10 parts by weight of the stabilizer, and about 70 parts by weight to about 80 parts by weight of water. The second nickel plating solution may be, for example, about 1 part by weight to about 10 parts by weight of ammonia, about 10 parts by weight to about 20 parts by weight of hypophosphite, about 10 parts by weight to about 20 parts by weight, and about 70 parts by weight to about 80 parts by weight of water. It may contain parts by weight. Stabilizers include, for example, about 0.2 parts by weight to about 0.3 parts by weight of potassium selenocyanate, about 5 parts by weight to about 6 parts by weight of potassium cyanide, about 0.3 parts by weight to about 0.4 parts by weight of sodium hydroxide, and about 92 parts by weight of water. It may contain from about 100 parts by weight to about 93 parts by weight. The temperature of the aqueous plating solution for electroless nickel strike may be, for example, about 55 ° C to about 70 ° C. The pH of the aqueous plating solution for electroless nickel strikes may be, for example, about 5.5 to about 6.0. The nickel metal concentration in the aqueous plating solution for electroless nickel strikes may be, for example, about 5.0 to about 6.0 g / L. The phosphorus concentration in the aqueous plating solution for electroless nickel strike may be about 3 to about 6 weight percent. For example, in order to strike the nickel layer, the resin structure provided with the catalyst is immersed in a plating solution for electroless nickel strike at a deposition rate of about 5 to about 6 mu m / hr, and then washed with water.

As another example, the step of applying a catalyst to the plating target region; And striking the metal in an electroless manner in the plating target region to which the catalyst is applied, thereby forming a stacked metal layer.

According to another aspect of the present invention, in a resin structure having a region to be plated, there is provided a resin structure in which a trench line having a lattice pattern formed by laser irradiation is formed in the region to be plated. The trench lines of the grid pattern include, for example, a plurality of first trench lines not crossing each other and a plurality of second trench lines not crossing each other, wherein the first trench lines and the first trench lines The two trench lines may be formed to cross each other. For example, the spacing between the first trench lines may be 0.02 mm to 0.10 mm, and the spacing between the second trench lines may be 0.02 mm to 0.10 mm.

According to another aspect of the invention,

(b) a metal layer attached to the plating target region of the resin structure;

A "resin structure having a conductor portion" is provided.

The trench lines of the grid pattern include, for example, a plurality of first trench lines not crossing each other and a plurality of second trench lines not crossing each other, wherein the first trench lines and the first trench lines The two trench lines may be formed to cross each other.

For example, the spacing between the first trench lines may be 0.02 mm to 0.10 mm, and the spacing between the second trench lines may be 0.02 mm to 0.10 mm.

The metal layer may be, for example, Cu, Ni, Au, Ag, an alloy thereof, or a laminate thereof. The thickness of the metal layer may be, for example, about 6 to about 18 μm.

The "resin structure having a conductor part" according to another aspect of the present invention is, for example, an antenna for a portable electronic device, an antenna for an RFID, automotive electronics, or white household appliances. It can be used as NFC antenna, cable replacement part, semiconductor IC composite part, etc.

Example 1

In Example 1, a resin molded body (smartphone antenna base) that was injection molded using a polycarbonate resin for injection molding (LUPOY SC1004A, LG Chemical) was used as the resin structure. In the resin structure used in Example 1, no nucleation agent was used.

A laser beam was irradiated to the plating target region (antenna pattern) on the surface of this resin structure to form trench lines in a lattice pattern arrangement. Laser processing conditions were as shown in Table 1 below.

Table 1

Item	Condition
Laser medium	YVO4
Laser wavelength	1064 nm
Laser power	20 W
Laser moving speed	1000 mm / min
First and second trench line spacing	0.06 mm
Trench line width	0.06 mm
Trench line depth	0.04 mm
Angle formed by the first and second trench lines	90 °

Then, a plating process was performed on the resin structure thus treated. First, the resin structure was pretreated with ultrasonic waves to remove dust and bubbles from the surface of the resin structure. The sonication process conditions are shown in Table 2 below.

TABLE 2

Item	Condition
Ultrasonic medium	95 parts by weight of deionized water + 5 parts by weight of triethanolamine
Ultrasonic medium temperature	60 ℃
Ultrasonic treatment time	1 min

Then, the resin structure was immersed in the treating solution for catalyzing, and the catalyzing process was performed. The conditions of the catalyst application process are shown in Table 3 below.

TABLE 3

Item		Condition
Treatment liquid preparation composition for catalysis	Deionized water	1 liter
	Palladium chloride	380 mg
	Hydrochloric anhydride	200 ml
Treatment liquid temperature for catalyst		35 ℃
Dipped time		4 mins

The resin structure was then immersed in a catalyst activation solution to activate the catalyst. The conditions of the catalyst activation process are shown in Table 4 below.

Table 4

Item		Condition
Catalyst Activation Solution Preparation Composition	Deionized water	1 liter
	Acid Ammonium Fluoride (NH4HF2)	120 g
Catalyst Activation Solution Temperature		60 ℃
Dipped time		2 mins

Then, the resin structure was immersed in the plating liquid for electroless copper strike to form a copper layer. The conditions of the copper layer forming process are shown in Table 5 below.

Table 5

Item		Condition
Aqueous Plating Solution for Electroless Copper Strike	Deionized water	1 liter
	Copper bath / supplement	100 ml
	Alkali supplements	80 ml
	Complexing agent	50 ml
	stabilizator	1 ml
	Formaldehyde	6 g
Copper bath / supplement manufacturing composition	Copper sulfate	8 parts by weight
	Polyethylene Glycol (PEG 20000)	1 part by weight
	stabilizator	0.02 parts by weight
	Deionized water	80 parts by weight
Alkali Supplement Manufacturing Composition	Sodium hydroxide	40 parts by weight
	stabilizator	0.02 parts by weight
	Deionized water	60 parts by weight
Complexing agent	Sodium hydroxide	50 parts by weight
	stabilizator	0.02 parts by weight
	Deionized water	50 parts by weight
stabilizator	Potassium Selenocyanate	0.2 parts by weight
	Potassium Cyanide	6 parts by weight
	Sodium hydroxide	0.4 parts by weight
	Deionized water	93 parts by weight
Plating solution temperature		48 ℃
Plating speed and time		0.5 μm / 10 min, 220 min

The "resin structure having a conductor portion" thus prepared was washed with deionized water, and then the plating state was observed by an X-shaped cutting test (X-shaped cutting method: cutting along the lines of a lattice arrangement of 2 mm intervals in the plated layer. Draw the line, stick the adhesive tape on it, and then lift the adhesive tape in the vertical direction, if it sticks to the adhesive tape and the piece of plating layer is not peeled off at all, then pass). Moreover, the part which is not plated among the plating object areas was not found. From this, it was confirmed that the copper layer was firmly plated only in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 2

Example 2 was the same as Example 1 except that a resin molded body (smartphone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GF EH-3104HF, Cheil Industries) was used as the resin structure. A "resin structure having a conductor portion" was produced by the method. In the resin structure used in Example 2, no nucleation agent was used. The "resin structure having a conductor portion" thus prepared was washed with deionized water, and then the plating state was observed by an X-shaped cutting test. Moreover, the part which is not plated among the plating object areas was not found. From this, it was confirmed that the copper layer was firmly plated only in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 3

Example 3 was the same as Example 1 except that a resin molded body (smartphone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GF EH-3200HF, Cheil Industries) was used as the resin structure. A "resin structure having a conductor portion" was produced by the method. In the resin structure used in Example 3, no nucleation agent was used. The "resin structure having a conductor portion" thus prepared was washed with deionized water, and then the plating state was observed by an X-shaped cutting test. Moreover, the part which is not plated among the plating object areas was not found. From this, it was confirmed that the copper layer was firmly plated only in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 4

Example 4 has the "conductor portion" in the same manner as in Example 1, except that a resin molded body (smartphone antenna base) injection molded using polycarbonate resin (HF-1023IM, Cheil Industries) was used as the resin structure. Resin structure ". In the resin structure used in Example 4, no nucleation agent was used. The "resin structure having a conductor portion" thus prepared was washed with deionized water, and then the plating state was observed by an X-shaped cutting test. Moreover, the part which is not plated among the plating object areas was not found. From this, it was confirmed that the copper layer was firmly plated only in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 5

Example 5 was the same as Example 1 except that a resin molded body (smartphone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GF HF-3201GL, Cheil Industries) was used as the resin structure. A "resin structure having a conductor portion" was produced by the method. In the resin structure used in Example 5, no nucleation agent was used. The "resin structure having a conductor portion" thus prepared was washed with deionized water, and then the plating state was observed by an X-shaped cutting test. Moreover, the part which is not plated among the plating object areas was not found. From this, it was confirmed that the copper layer was firmly plated only in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 6

Example 6 has the "conductor portion" in the same manner as in Example 1, except that a resin molded body (smartphone antenna base) injection molded using polycarbonate resin (EH-1050, Cheil Industries) was used as the resin structure. Resin structure ". In the resin structure used in Example 6, no nucleation agent was used. The "resin structure having a conductor portion" thus prepared was washed with deionized water, and then the plating state was observed by an X-shaped cutting test. Moreover, the part which is not plated among the plating object areas was not found. From this, it was confirmed that the copper layer was firmly plated only in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 1

In Comparative Example 1, a “resin structure having a conductor portion” was manufactured in the same manner as in Example 1, except that the laser processing conditions were applied as shown in Table 6 below.

Table 6

Item	Condition
Laser medium	YVO4
Laser wavelength	1064 nm
Laser power	8 W
Laser moving speed	2000 mm / min
Laser irradiation pattern	The entire area to be plated was cut to a uniform depth without forming trench lines in a lattice arrangement.

As a result of visually observing the plating state in Comparative Example 1, it was found that the unplated portion of the plating target region was found, and the adhesion of the plated portion was also significantly weak. From this, in Comparative Example 1, it was confirmed that the copper layer was not plated effectively on the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 2

In Comparative Example 2, the same resin composition as Comparative Example 1 was used except that a resin molded body (smartphone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GF EH-3104HF, Cheil Industries) was used as the resin structure. A "resin structure having a conductor portion" was produced by the method. As a result of visually observing the plating state in Comparative Example 2, it was found that the unplated portion of the plating target region was found, and the adhesion of the plated portion was also significantly weak. From this, in Comparative Example 2, it was confirmed that the copper layer was not plated effectively on the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 3

Comparative Example 3 was the same as Comparative Example 1 except that a resin molded body (smartphone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GF EH-3200HF, Cheil Industries) was used as the resin structure. A "resin structure having a conductor portion" was produced by the method. As a result of visually observing the plating state in Comparative Example 3, it was found that the unplated portion of the plating target region was found, and the adhesion of the plated portion was also significantly weak. From this, in Comparative Example 3, it was confirmed that the copper layer was not effectively plated in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 4

In Comparative Example 4, the same method as in Comparative Example 1 was used except that a resin molded product (smartphone antenna base) injection-molded using polycarbonate resin (HF-1023IM, Cheil Industries) was used as the resin structure. Resin structure ". As a result of visually observing the plating state in Comparative Example 4, it was found that the unplated portion of the plating target region was found, and the adhesion of the plated portion was also significantly weak. From this, in Comparative Example 4, it was confirmed that the copper layer was not effectively plated in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 5

Comparative Example 5 was the same as Comparative Example 1 except that a resin molded body (smartphone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GF HF-3201GL, Cheil Industries) was used as the resin structure. A "resin structure having a conductor portion" was produced by the method. As a result of visually observing the plating state in Comparative Example 5, the unplated portion of the plating target region was found, it was confirmed that the adhesion of the plated portion was also significantly weak. From this, in Comparative Example 5, it was confirmed that the copper layer was not effectively plated on the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 6

In Comparative Example 6, "the conductor portion was formed in the same manner as in Comparative Example 1, except that a resin molded body (smartphone antenna base) injection molded using polycarbonate resin (EH-1050, Cheil Industries) was used as the resin structure. Resin structure ". As a result of visually observing the plating state in Comparative Example 6, it was found that the unplated portion of the plating target region was found, and the adhesion of the plated portion was also significantly weak. From this, in Comparative Example 6, it was confirmed that the copper layer was not effectively plated in the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

The "resin structure having a conductor portion" of the present invention is, for example, an antenna for a portable electronic device, an antenna for RFID, automotive electrical appliances, or white household electrical appliances. It can be used as NFC antenna, cable replacement part, semiconductor IC composite part, etc.

Claims

Irradiating a laser to the plating target region on the surface of the resin structure to form trench lines in a lattice pattern.
The method of claim 1, wherein the forming of the trench lines in the lattice arrangement comprises forming a plurality of first trench lines not crossing each other and a plurality of second trench lines not crossing each other, wherein the first trenches are formed. And the second trench line is formed to intersect with each other.
The method of claim 2, wherein the spacing between the first trench lines is between 0.02 mm and 0.10 mm, and the spacing between the second trench lines is between 0.02 mm and 0.10 mm.
The method of claim 1, wherein the resin structure is ABS (acrylonitrile butadiene styrene copolymer) resin, polycarbonate resin, polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, PVC (poly vinyl chloride) resin, PPA ( A laser direct structuring method comprising a polyphthalamide (PPS) resin, a polyphenylene sulfide (PPS) resin, a polyester resin, a liquid crystal polymer (LCP) resin, or a blend thereof.
The method of claim 1, wherein the resin structure further comprises a glass fiber.
The laser direct structuring method according to claim 5, wherein the content of the glass fiber in the resin structure is 5 parts by weight to 45 parts by weight based on 100 parts by weight of the resin.
The method of claim 1, wherein the resin structure further comprises a ceramic filler powder.
8. The laser direct structuring method of claim 7, wherein the content of the ceramic filler in the resin structure is 0.1 to 15 parts by weight based on 100 parts by weight of the resin.
8. The method of claim 7, wherein the ceramic filler is alumina, titanium dioxide, or a combination thereof.
The method of claim 1, wherein the resin structure further comprises an antioxidant.
The laser direct structuring method according to claim 10, wherein the content of the antioxidant in the resin structure is 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the resin.
The laser direct structuring method of claim 1, wherein the resin structure further comprises an acrylonitrile styrene acrylate component or a resin component derived from acrylonitrile styrene acrylate.
The content of the acrylonitrile styrene acrylate component or the resin component derived from acrylonitrile styrene acrylate in the resin structure is 5 parts by weight to 35 parts by weight based on 100 parts by weight of the resin. Laser direct structuring method.
The method of claim 1, wherein the resin structure further comprises a phosphate ester component.
15. The method of claim 14, wherein the content of the phosphate ester component in the resin structure is 0.5 to 15 parts by weight based on 100 parts by weight of the resin.
The method of claim 1, wherein the resin structure further comprises a bisphenol A diphosphate component.
The laser direct structuring method according to claim 16, wherein the content of the bisphenol A diphosphate component in the resin structure is 6 parts by weight to 20 parts by weight based on 100 parts by weight of the resin.
The method of claim 1, wherein the resin structure further comprises a colorant.
20. The method of claim 19, wherein the content of the colorant in the resin structure is 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the resin.
The method of claim 1, wherein said resin structure is substantially free of a nucleating agent.
The laser direct structuring method of claim 1, wherein an angle at which the first trench line and the second trench line cross each other is 60 ° to 90 °.
The laser direct structuring method of claim 1, wherein the widths of the first trench line and the second trench line are each independently 0.02 μm to 0.1 μm.
The method of claim 1, wherein the depths of the first trench line and the second trench line are each independently 0.02 mm to 0.1 mm.
The laser direct structuring method of claim 1, further comprising forming a metal layer in the plating target region of the surface of the resin structure by plating.
The method of claim 24, wherein the forming of the metal layer by plating,

Applying a catalyst to a region to be plated on the surface of the resin structure in which the trench lines of the lattice pattern are formed; And

And striking a metal in an electroless manner on the plating target region to which the catalyst is applied.
27. The method of claim 25 wherein the catalyst is palladium.
27. The method of claim 25, wherein the metal layer is copper, nickel, gold, silver, or a combination thereof.
26. The method of claim 25, further comprising: applying a catalyst to the region to be plated; And striking the metal in an electroless manner in the plating target region to which the catalyst is applied. By repeating the above method, a layered metal layer is formed.
The resin structure which has a plating object area | region, WHEREIN: The resin structure in which the trench line of the grid pattern array formed by laser irradiation is formed in the said plating object area | region.
30. The method of claim 29, wherein the trench lines of the grid pattern include a plurality of first trench lines that do not cross each other and a plurality of second trench lines that do not cross each other, wherein the first trench lines and the The second trench lines are formed to intersect with each other, the spacing between the first trench lines is 0.02 mm to 0.10 mm, and the spacing between the second trench lines is 0.02 mm to 0.10 mm. Structure.
(a) A resin structure having a region to be plated, comprising: a resin structure in which a trench line of a lattice pattern formed by laser irradiation is formed in the region to be plated; And

(b) a metal layer attached to the plating target region of the resin structure;

Resin structure having a conductor portion.
32. The method of claim 31, wherein the trench lines of the grid pattern include a plurality of first trench lines that do not cross each other and a plurality of second trench lines that do not intersect each other, wherein the first trench lines and the The second trench lines are formed to cross each other, the spacing between the first trench lines is 0.02 mm to 0.10 mm, the spacing between the second trench lines is 0.02 mm to 0.10 mm, Resin structure having a conductor portion.