JP2016516903A - Laser direct structuring method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improved direct laser structuring method capable of modifying a plating target region on a resin structure surface by laser irradiation so as to be compatible with plating without using a nucleating agent. To do. A laser direct structuring method including a step of irradiating a region to be plated on a surface of a resin structure with a laser to form trench lines in a lattice arrangement. [Selection figure] None

Description

  The present invention relates to a method of forming a metal layer on the surface of a non-conductive resin molded body, and more particularly to a laser direct structuring (LDS) method.

  In order to plate the metal layer on at least a part of the resin molded body surface, a laser direct structuring process is used. The laser direct structuring process is a process executed before the plating step, and by irradiating the plating target area on the surface of the resin molded body with a laser, the plating target area on the surface of the resin molded body is modified and plated. It means a process with suitable properties. For this purpose, the resin molded body must contain a “nucleating agent for direct laser structuring (hereinafter abbreviated as“ nucleating agent ”)” which forms a metal nucleus by a laser. The nucleating agent contained in the resin molded body generates metal nuclei while being decomposed when irradiated with a laser. Further, the plating target area irradiated with the laser has surface roughness. Due to the presence of such metal nuclei and surface roughness, the plating target region modified by the laser is suitable for plating.

  By using the laser direct structuring process, it is possible to quickly and economically form an electric / electronic circuit on the three-dimensional shape of the resin molding. As a specific example, the direct laser structuring process is used for manufacturing antennas for portable electronic devices, RFID antennas, and the like.

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

  As a nucleating agent of a conventional composition for laser direct structuring process, metal oxide having a spinel structure (Patent Documents 1 and 2); heavy metal complex oxide spinel such as copper chromium oxide spinel (Patent Document 3); Copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate or cuprous thiocyanate (Patent Documents 3 and 4) are known.

  However, the color of spinel copper chrome oxide is so black that it is used for black pigments. Therefore, the copper chromium oxide having a spinel structure can be applied only when the color required for the resin molding is black or gray. When various colors other than black and gray are required for the resin molded body, it is difficult to obtain a resin molded body having a desired hue if copper chrome oxide having a spinel structure is applied as a nucleating agent.

Copper phosphate compounds typically have a light green or blue color. Accordingly, when a green or blue color is required for the resin molded body, application as a nucleating agent of a copper phosphate compound can be considered. However, copper phosphate compounds (for example, Cu ₂ P ₂ O ₇ · H ₂ O, 4CuO · P ₂ O ₅ · H ₂ O, etc.) release crystal water under the temperature and pressure during the molding process of resin moldings. To do. The released crystal water reacts with other components such as a resin or additive in the composition, or remains in the resin molded body even after molding. Thereby, the physical property of a resin molding may fall, or the color or surface state of a resin molding may fall. In particular, such a problem may occur even more severely when the composition contains a moisture-sensitive polymer such as polycarbonate, polyamide, or polybutylene terephthalate.

  A copper hydroxide phosphate compound is a compound in which copper phosphate and copper hydroxide are combined. Copper hydroxide phosphate contains copper hydroxide, not crystal water, and does not release moisture even during the molding process of the resin molding. Moreover, copper hydroxide phosphate does not reduce the color reproducibility of the colorant contained in the resin molded product, whereby a resin molded product having a desired hue can be obtained very easily.

  However, in order to add a desired hue to the resin molded body, colorants such as pigments and dyes contained in the resin molded body reflect or absorb incident light and exhibit a hue. During the LDS process, the laser electromagnetic radiation applied to the resin molding is also reflected or absorbed by the colorant. Thereby, in the presence of the colorant, the depth at which the laser electromagnetic radiation is transmitted to the inside of the resin molding is reduced, that is, the reaction efficiency of the nucleating agent (for example, copper hydroxide phosphate) by the laser electromagnetic radiation is remarkable. descend.

Korean Registered Patent No. 10-0716486 Korean Published Patent 10-2010-0055474 Korean Published Patent 10-2011-0009684 Korean Published Patent No. 10-2011-0018319

  The problem to be solved by the present invention is an improvement in which an area to be plated on the surface of a resin structure can be modified to be suitable for plating by laser irradiation without using a nucleating agent. It is to provide a laser direct structuring method.

  One embodiment of a method for direct laser structuring according to an aspect of the present invention includes a step of irradiating a region to be plated on a surface of a resin structure with a laser to form trench lines in a grid pattern.

  According to another aspect of the present invention, there is provided a resin structure having a plating target region, wherein the plating target region is formed with a grid-like array of trench lines formed by laser irradiation.

  According to still another aspect of the present invention, (a) in a resin structure having a plating target region, a resin structure in which trench lines in a grid pattern formed by laser irradiation are formed in the plating target region; (b) A resin structure having a conductor portion including a metal layer attached to the plating target region of the resin structure is provided.

  In the 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 are such that the first trench lines and the second trench lines intersect with each other. A grid-arranged trench is formed in a plating target region on the surface of the structure.

  According to the present invention, the grid-arranged trenches formed by laser irradiation promote the adhesion of the metal layer to the plating target region on the surface of the resin structure by plating. In addition, according to the present invention, the grid-arranged trenches formed by laser irradiation enhance the adhesive force 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 nucleating agent, the metal layer can be adhered to the plating target region on the surface of the resin structure by plating. On the other hand, the metal layer does not adhere to the region where the grid-arranged trenches formed by laser irradiation are 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, the problems caused by the use of the nucleating agent in the conventional direct laser structuring method can be basically solved. it can.

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

  The resin structure includes a thermoplastic resin, a thermosetting resin, or a mixture thereof. Specifically, the resin structure includes ABS (acrylonitrile butadiene styrene copolymer) resin, polycarbonate resin, polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, PVC (poly vinyl chloride) resin, PPA (poly phthal amide) resin, PPS. (poly phenylene sulfide) resin, polyester resin, LCP (liquid crystal polymer) resin, or a mixture thereof.

  The resin structure can further include glass fibers. When the resin structure further includes glass fibers, the grid-arranged trenches formed by laser irradiation further effectively promote the adhesion of the metal layer to the plating target region of the resin structure surface by plating. Further, the glass fiber can reinforce the mechanical strength of the resin structure or can complement the structural defect of the resin structure. The content of the glass fiber in the resin structure is, 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 a ceramic filler powder. When the resin structure further includes a ceramic filler powder, the grid-arranged trenches formed by laser irradiation further effectively 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 ceramic filler in the resin structure is, for example, about 0.1 to about 15 parts by weight based on 100 parts by weight of the resin. The ceramic filler is, for example, alumina, titanium dioxide, or a combination thereof.

  The resin structure can further contain an antioxidant. When the resin structure further includes an antioxidant, the grid-arranged trenches formed by laser irradiation further effectively 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 is, for example, about 0.1 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 includes an acrylonitrile styrene acrylate component or a resin component derived from acrylonitrile styrene acrylate, the grid-arranged trenches formed by laser irradiation are connected to the plating target region of the resin structure surface of the metal layer by plating. Promotes adhesion more effectively. The content of the acrylonitrile styrene acrylate component or the resin component derived from acrylonitrile styrene acrylate in the resin structure is, 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 can further include a phosphate ester component. When the resin structure further includes a phosphate ester component, the grid-arranged trenches formed by laser irradiation further effectively 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 phosphate ester component in the resin structure is, for example, about 0.5 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 grid-arranged trenches formed by laser irradiation further effectively promote the adhesion of the metal layer to the plating target region of the resin structure surface by plating. . The content of the bisphenol A diphosphate component in the resin structure is, 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 can further include a colorant. In the present invention, since it is not necessary to use a nucleating agent, the color reproducibility reduction phenomenon of the colorant due to the nucleating agent is basically prevented. The content of the colorant in the resin structure is, 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 is, for example, a pigment or a dye. The pigment is, for example, an inorganic pigment or an organic pigment. Examples of inorganic pigments include metal oxides such as zinc oxide, titanium dioxide, and iron oxide, or composite metal oxides; sulfides such as zinc sulfide; aluminates; sodium sulfosilicates; sulfates; chromates; Ferrite; Ultramarine Blue; Pigment Brown 24; Pigment Red 101; Pigment Yellow 119 and the like are used. Examples of organic pigments include azo, diazo, quinacridone, perylene, naphthalenetetracarboxylic acid, flavantron, isoindolinone, tetrachloroisoindolone, anthraquinone, anthrone, dioxazine, phthalocyanine, azo lake (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 are used. Alternatively, a mixture containing two or more of such pigments is used as the pigment. Examples of the dye include coumarin 460 (blue), coumarin 6 (green), Nile red, lanthanide complex, hydrocarbon and substituted hydrocarbon dye, polycyclic aromatic hydrocarbon, scintillation dye (preferably oxazole 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 (for example, absorb at near infrared wavelengths, Emit at visible wavelengths Anti-stokes transfer dyes), luminescent dyes (e.g., 5-amino-9-diethyliminobenzophenoxazonium perchlorate), 7-amino-4-methylcarbostyril, 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-quarterphenyl; 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; -Diethylamino-4-trifluoromethylcoumarin; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 7-ethylamino-6-methyl-4-trifluoromethylcoumarin; -Ethylamino-4-trifluoromethylcoumarin; Nile Red; rhodamine 700; oxazine 750; rhodamine 800; IR 125; IR 144; IR 140; IR 132; IR26; IR5; diphenylhexatriene; Naphthalene, anthracene, 9,10-diphenylanthracene, pyrene, chrysene, rubrene, coronene, phenanthrene, and the like are used. Alternatively, a mixture containing two or more of such dyes is used as the dye.

  The resin structure contains substantially no nucleating agent. As a nucleating agent of a conventional composition for laser direct structuring process, metal oxides having a spinel structure (Korea registered patent 10-0716486, Korean published patent 10-2010-0055474), and copper chromium oxide Heavy metal composite oxide spinels such as spinel (Korea published patent 10-2011-0009684) and copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate, or cuprous thiocyanate (Korea published patent 10 -2011-0009684, Korean Published Patent No. 10-2011-0018319) and the like are known. In the present invention, the grid-arranged trenches formed by laser irradiation promote the adhesion of the metal layer to the plating target region on the surface of the resin structure by plating, so that the resin structure does not contain a nucleating agent. The metal layer can be attached to the plating target area on the surface of the resin structure by plating. In the conventional direct laser structuring process, the amount of 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 present invention, the fact that the resin structure does not substantially contain a nucleating agent means that the content of the nucleating agent in the resin structure is less than about 4 parts by weight based on 100 parts by weight of the resin. Desirably, it means less than 0.1 parts by weight. More preferably, in another embodiment of the present invention, the content of the nucleating agent in the resin structure is about 0 to about 0.05 parts by weight based on 100 parts by weight of the resin.

  The step of irradiating the region to be plated on the surface of the resin structure with the laser to form the trench lines in the lattice arrangement is performed by irradiating the region to be plated on the surface of the resin structure with the laser.

As a medium for laser electromagnetic radiation, for example, YAG (yttrium aluminum garnet), YVO4 (yttrium orthovanadate), YB (ytterbium), CO ₂ or the like is used. As the wavelength of the laser electromagnetic wave radiation, for example, 532 nm, 1064 nm, 1090 nm, 9.3 μm, 10.6 μm, and the like are used. An algorithm that recognizes and processes 3D shapes when processing with laser radiation (for example, 3D recognition parts are recognized by a 3D recognition program, and the laser processing height is controlled by dividing the height into 10 levels. System) is used. With the laser electromagnetic radiation, it is possible to additionally carry out contour line processing for processing surface (plating surface) and non-processing and surface plating uniformity. The output value of the laser electromagnetic radiation is, for example, about 2W to about 30W.

  The grid-arranged trench lines may include, for example, a plurality of first trench lines that do not intersect with each other and a plurality of second trench lines that do not intersect with each other. The first trench line and the second trench line are formed to cross each other.

  On the other hand, when a continuous trench line is processed during the processing of the trench line, heat may be generated in the resin by a laser and it may be difficult to implement a desired lattice-shaped trench line. In this case, when the trench line is processed, the odd-numbered portion and the even-number portion are divided, and the jump is performed at the time of processing, so that the depression of the uneven portion due to the processing row can be prevented.

  The plurality of first trench lines formed by laser irradiation do not intersect each other. An interval between adjacent first trench lines is, for example, about 0.02 mm to about 0.10 mm. If the distance between adjacent first trench lines is less than about 0.02 mm, the laser spot size (usually about 40 to about 80 μm) makes it difficult to implement a trench shape with a lattice structure, and adhesion during plating is difficult. I can't get it. When the interval between adjacent first trench lines is larger than about 0.10 mm, even when the trench line interval is large, it is difficult to form a trench line having a lattice structure, and adhesion cannot be obtained during plating.

  The plurality of second trench lines formed by laser irradiation do not intersect each other. An interval between adjacent second trench lines is, for example, about 0.02 mm to about 0.10 mm. If the distance between adjacent second trench lines is less than about 0.02mm, it is difficult to implement a trench structure with a lattice structure depending on the laser spot size (usually about 40 to about 80μm), and adhesion can be obtained even during plating. Absent. When the interval between adjacent second trench lines is larger than about 0.10 mm, it is difficult to form a trench line having a lattice structure even when the trench line interval is large, and an adhesion force cannot be obtained during plating.

  The plurality of first trench lines and the plurality of second trench lines formed by laser irradiation are formed so that the first trench lines and the second trench lines intersect with each other, thereby subjecting the resin structure surface to plating. A grid-arranged trench is formed in the region. The angle at which the first trench line and the second trench line intersect with each other is not necessarily a right angle. For example, the angle at which the first trench line and the second trench line intersect each other is about 0 ° or more and about 90 ° or less. Preferably, the angle at which the first trench line and the second trench line intersect each other is about 60 ° to about 90 °.

  The cross-sectional shape of the trench line is, for example, U-shaped or V-shaped. Preferably, the cross-sectional shape of the trench line is V-shaped. When the cross-sectional shape of the trench line is V-shaped, a pyramid-shaped or quadrangular pyramid-shaped island is formed in the plating target region by forming the lattice-shaped trench. If a pyramid-shaped or quadrangular pyramid-shaped island is formed in the plating target region, the adhesion force between the metal plating layer and the plating target region of the resin structure further increases.

  The width of the first trench line and the second trench line is, for example, about 40 μm to about 80 μm. Even when the width of the trench line is excessively small or excessively large, it is difficult to form a trench line having a lattice structure, and adhesion cannot be obtained during plating.

  The depth of the first trench line and the second trench line is, for example, about 5 μm to about 50 μm. The adhesion increases as the depth of the trench line increases. On the other hand, when it is excessively deep, it may not be used due to problems in appearance and performance when used as an antenna or electronic product.

  According to another embodiment of the laser direct structuring method of the present invention, the method further includes a step of forming a metal layer by plating in a plating target region on the surface of the resin structure where the trench lines in a grid pattern are formed by laser irradiation. be able to. The plating is performed by, for example, an electroless plating method. The present invention is characterized in that the change in the plating conditions by the type of the resin and thereby is not large.

  The metal layer forming step by plating includes, for example, a step of applying a catalyst to the plating target region on the surface of the resin structure where the grid-like trench lines are formed, and an electroless method to apply the metal to the plating target region to which the catalyst is applied. Striking.

  The catalyst application step is to promote formation / attachment of the metal layer to the plating target region in the subsequent electroless metal strike step by applying catalyst particles to the trench lines in the grid-like arrangement of the plating target region. For example, palladium is used as the catalyst. As the palladium supply source, for example, palladium chloride or palladium sulfate is used. The catalyst application step includes, for example, immersing the resin structure in a catalyst application treatment solution at a temperature of about 30 ° C. to about 40 ° C. for about 1 minute to about 5 minutes, and then about 1 ° C. at a temperature of about 30 ° C. to about 60 ° C. Performed by immersing in the catalyst activation solution for from about 3 minutes to about 3 minutes. The catalyst application treatment liquid is, for example, an aqueous solution containing palladium chloride and hydrochloric acid. The amount of palladium chloride used in this aqueous solution is, for example, about 10 ml to about 450 ml, based on the amount of deionized water used of 1 liter. The amount of anhydrous hydrochloric acid used in this aqueous solution is, for example, about 150 ml to about 300 ml based on the amount of deionized water used of 1 liter. The catalyst activation solution is, for example, an aqueous solution containing ammonium acid fluoride. The content of acidic ammonium fluoride in this aqueous solution is, for example, about 70 g / L to about 150 g / L.

  In the electroless metal strike stage, the metal layer is plated by an electroless method on the plating target area on the surface of the resin structure provided with the catalyst. The metal layer is copper, nickel, gold, silver, or a combination thereof. The metal layer is a single layer or a laminated structure. In the laminated structure, each layer may be a different metal or the same metal.

  As a specific example, when striking a copper layer, a resin structure provided with a catalyst is immersed in a plating solution for electroless copper strike. For example, an aqueous plating solution for electroless copper strike is based on 1 liter of deionized water, with a copper bath / replenisher of about 55 ml to about 65 ml, an alkali replenisher of about 55 ml to about 65 ml, and a complexing agent of about 15 ml to about 65 ml. 20 ml, stabilizers from about 0.1 ml to about 0.2 ml, and formaldehyde from about 8 ml to about 10 ml. Copper baths / replenishers include, for example, about 6 to about 12 parts by weight copper sulfate, about 1 to about 1.5 parts by weight polyethylene glycol, about 0.01 to about 0.02 parts by weight stabilizer, and about 78 parts by weight water. Part by weight to about 80 parts by weight can be contained. The alkaline replenisher can contain, for example, about 40 to about 50 parts by weight of sodium hydroxide, about 0.01 to about 0.02 parts by weight of stabilizer, and about 50 to about 60 parts by weight of water. The complexing agent can contain, for example, about 49 to about 50 parts by weight of sodium hydroxide, about 0.01 to about 0.02 parts by weight of stabilizer, and about 50 to about 51 parts by weight of water. Stabilizers include, for example, about 0.2 to about 0.3 parts by weight potassium selenocyanate, about 5 to about 6 parts by weight potassium cyanide, about 0.3 to about 0.4 parts by weight sodium hydroxide, and about 92 to about 92 parts by weight water. About 93 parts by weight can be contained. For example, in order to strike a copper layer, a resin structure provided with a catalyst is applied to a plating solution for electroless copper strike at a deposition rate of about 0.5 to about 0.7 μm / 10 min at about 41 ° C. to about 55 ° C. After soaking, rinse with water.

  As another specific example, when striking a nickel layer, a resin structure provided with a catalyst is immersed in a plating solution for electroless nickel strike. For example, the electroless nickel strike aqueous plating solution 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 to about 30 parts by weight of nickel sulfate, about 1 to about 10 parts by weight of stabilizer, and about 70 to about 80 parts by weight of water. The second nickel plating solution is, for example, about 1 to about 10 parts by weight of ammonia, about 10 to about 20 parts by weight of hypophosphite, about 10 to about 20 parts by weight of stabilizer, and about 70 parts by weight of water. To about 80 parts by weight. Stabilizers include, for example, about 0.2 to about 0.3 parts by weight potassium selenocyanate, about 5 to about 6 parts by weight potassium cyanide, about 0.3 to about 0.4 parts by weight sodium hydroxide, and about 92 to about 92 parts by weight water. About 93 parts by weight can be contained. The temperature of the electroless nickel strike aqueous plating solution is, for example, about 55 ° C. to about 70 ° C. The pH of the electroless nickel strike aqueous plating solution is, for example, about 5.5 to about 6.0. The nickel metal concentration in the electroless nickel strike aqueous plating solution is, for example, about 5.0 to about 6.0 g / L. The phosphorus concentration in the electroless nickel strike aqueous plating solution is about 3 to about 6% by weight. For example, in order to strike a nickel layer, a resin structure provided with a catalyst is immersed in an electroless nickel strike plating solution at a deposition rate of about 5 to about 6 μm / hr, and then washed with water.

  As another example, a multilayer metal layer is formed by repeating a step of applying a catalyst to a plating target region and a step of striking a metal in an electroless manner to the plating target region to which the catalyst is applied. can do.

  According to another aspect of the present invention, there is provided a resin structure having a plating target region, wherein the plating target region is formed with a grid-like array of trench lines formed by laser irradiation. The grid-arranged trench lines include, for example, a plurality of first trench lines that do not intersect with each other and a plurality of second trench lines that do not intersect with each other, and the first trench lines and the second trench lines intersect with each other. Is formed. For example, the distance between the first trench lines is 0.02 mm to 0.10 mm, and the distance between the second trench lines is 0.02 mm to 0.10 mm.

According to yet another aspect of the invention,
(a) In the resin structure having an area to be plated, the resin structure in which trench lines in a grid-like arrangement formed by laser irradiation are formed in the area to be plated;
(b) A “resin structure having a conductor portion” is provided, including a metal layer attached to the plating target region of the resin structure.

  The grid-arranged trench lines include, for example, a plurality of first trench lines that do not intersect with each other and a plurality of second trench lines that do not intersect with each other, and the first trench lines and the second trench lines intersect with each other. Is formed.

  For example, the distance between the first trench lines is 0.02 mm to 0.10 mm, and the distance between the second trench lines is 0.02 mm to 0.10 mm.

  The said metal layer is Cu, Ni, Au, Ag, those alloys, or those laminated bodies, for example. The metal layer has a thickness of about 6 to about 18 μm, for example.

The “resin structure having a conductor” according to still another aspect of the present invention includes, for example, portable electronic device antennas, RFID antennas, automotive electrical components, white home appliances, NFC antennas, cable replacement parts, semiconductors, etc. Used for IC composite parts.
<Example>

Example 1
In Example 1, a resin molded body (smart phone antenna base) that was injection molded using a polycarbonate resin for injection molding (LUPOYSC1004A, LG Chemical) was used as the resin structure. In the resin structure used in Example 1, no nucleating agent is used.

Such a plating target region (antenna pattern) on the surface of the resin structure was irradiated with a laser to form trench lines in a grid pattern. The laser process conditions are as shown in Table 1 below.

Subsequently, the plating process was performed with respect to the resin structure processed in this way. First, the resin structure was pretreated with ultrasonic waves to remove dust and bubbles on the surface of the resin structure. The ultrasonic treatment process conditions are as shown in Table 2 below.

Next, the resin structure was immersed in a catalyst application treatment solution, and a catalyst application step was performed. The conditions for the catalyst application step are as shown in Table 3 below.

Next, the resin structure was immersed in a catalyst activation solution to activate the catalyst. The conditions for the catalyst activation step are as shown in Table 4 below.

Next, the resin structure was immersed in a plating solution for electroless copper strike to form a copper layer. The conditions for the copper layer forming step are as shown in Table 5 below.

  After the thus-prepared "resin structure with conductor part" was washed with deionized water, the plating state was observed by the X-shaped cutting test method (X-shaped cutting test method: grid pattern with 2 mm intervals on the plating layer) Draw a cutting line along the line of the array.After applying the adhesive tape on it, remove the adhesive tape vertically.The adhesive tape is acceptable if no plating layer strip is peeled off). Moreover, it was not possible to find an unplated portion in the plating target area. This confirmed that the copper layer was firmly plated only on the plating target area (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 2
In Example 2, it was carried out except that a resin molded body (smartphone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GFEH-3104HF, first woolen) was used as the resin structure. A “resin structure having a conductor” was produced in the same manner as in Example 1. In the resin structure used in Example 2, no nucleating agent is used. The thus produced “resin structure having a conductor” was washed with deionized water, and then the plating state was observed by an X-shaped cutting test method. Moreover, the part which is not plated among the areas to be plated could not be found. This confirmed that the copper layer was firmly plated only on the plating target area (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 3
In Example 3, as the resin structure, except that a resin molded body (smart phone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GFEH-3200HF, first woolen) was used, A “resin structure having a conductor” was manufactured in the same manner as in Example 1. In the resin structure used in Example 3, no nucleating agent is used. The thus produced “resin structure having a conductor” was washed with deionized water, and then the plating state was observed by an X-shaped cutting test method. Moreover, the part which is not plated among the plating object area | regions was not found. This confirmed that the copper layer was firmly plated only on the plating target area (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 4
In Example 4, the resin structure was the same as Example 1 except that a resin molded body (smartphone antenna base) injection molded using a polycarbonate resin (HF-1023IM, first woolen) was used. The “resin structure having a conductor” was manufactured by the method. In the resin structure used in Example 4, no nucleating agent is used. The thus produced “resin structure having a conductor” was washed with deionized water, and then the plating state was observed by an X-shaped cutting test method. Moreover, the part which is not plated among the plating object area | regions was not found. This confirmed that the copper layer was firmly plated only on the plating target area (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 5
In Example 5, except that a resin molded body (smart phone antenna base) injection molded using polycarbonate / glass fiber resin (PC / GFHF-3201GL, first woolen) was used as the resin structure, A “resin structure having a conductor” was manufactured in the same manner as in Example 1. In the resin structure used in Example 5, no nucleating agent is used. The thus produced “resin structure having a conductor” was washed with deionized water, and then the plating state was observed by an X-shaped cutting test method. Moreover, the part which is not plated among the plating object area | regions was not found. From this, it was confirmed that the copper layer was firmly plated only on the plating target area (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Example 6
In Example 6, the resin structure was the same as Example 1 except that a resin molded body (smartphone antenna base) injection molded using a polycarbonate resin (EH-1050, first woolen) was used. The “resin structure having a conductor” was manufactured by the method. In the resin structure used in Example 6, no nucleating agent is used. The thus produced “resin structure having a conductor” was washed with deionized water, and then the plating state was observed by an X-shaped cutting test method. Moreover, the part which is not plated among the plating object area | regions was not found. This confirmed that the copper layer was firmly plated only on the plating target area (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 produced in the same manner as in Example 1 except that the laser process conditions were applied as shown in Table 6 below.

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

Comparative Example 2
In Comparative Example 2, except that a resin molded body (smartphone antenna base) that was injection molded using a polycarbonate / glass fiber resin (PC / GFEH-3104HF, first woolen) was used as the resin structure, A “resin structure having a conductor” was produced in the same manner as in Comparative Example 1. As a result of observing the plating state in Comparative Example 2 with the naked eye, an unplated portion was found in the plating target region, and it was confirmed that the adhesion of the plated portion was also significantly weak. Thereby, in Comparative Example 2, it was confirmed that the copper layer was not efficiently plated on the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 3
In Comparative Example 3, except that a resin molded body (smart phone antenna base) that was injection molded using a polycarbonate / glass fiber resin (PC / GFEH-3200HF, first woolen) was used as the resin structure, A “resin structure having a conductor” was produced in the same manner as in Comparative Example 1. As a result of observing the plating state in Comparative Example 3 with the naked eye, an unplated portion was found in the plating target region, and it was confirmed that the adhesion of the plated portion was also significantly weak. Thereby, in Comparative Example 3, it was confirmed that the copper layer was not efficiently plated on the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 4
Comparative Example 4 is the same as Comparative Example 1 except that a resin molded body (smartphone antenna base) injection molded using a polycarbonate resin (HF-1023IM, first woolen) is used as the resin structure. The “resin structure having a conductor” was manufactured by the method. As a result of observing the plating state in Comparative Example 4 with the naked eye, an unplated portion was found in the plating target region, and it was confirmed that the adhesion of the plated portion was also significantly weak. Thereby, in Comparative Example 4, it was confirmed that the copper layer was not efficiently plated on the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Comparative Example 5
In Comparative Example 5, except that a resin molded body (smart phone antenna base) injection molded using a polycarbonate / glass fiber resin (PC / GFHF-3201GL, first woolen) was used as the resin structure, A “resin structure having a conductor” was produced in the same manner as in Comparative Example 1. As a result of observing the plating state in Comparative Example 5 with the naked eye, an unplated portion was found in the plating target region, and it was confirmed that the adhesion of the plated portion was also significantly fragile. Thereby, in Comparative Example 5, it was confirmed that the copper layer was not efficiently 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 same method as Comparative Example 1 except that a resin molded body (smartphone antenna base) injection molded using a polycarbonate resin (EH-1050, first woolen) as the resin structure was used. Produced a "resin structure having a conductor". As a result of observing the plating state in Comparative Example 6 with the naked eye, an unplated portion was found in the plating target region, and it was confirmed that the adhesion of the plated portion was also significantly fragile. Thereby, in Comparative Example 6, it was confirmed that the copper layer was not efficiently plated on the plating target region (antenna pattern) on the surface of the resin structure (smartphone antenna base).

Claims (32)

  A laser direct structuring method including a step of irradiating a region to be plated on a surface of a resin structure with a laser to form trench lines in a lattice arrangement.   The step of forming the grid-arranged trench lines is a step of forming a plurality of first trench lines that do not intersect with each other and a plurality of second trench lines that do not intersect with each other, wherein the first trench lines and the second trenches are formed. The laser direct structuring method according to claim 1, further comprising forming the lines so as to intersect each other.   3. The laser direct structuring according to claim 2, wherein an interval between the first trench lines is 0.02 mm to 0.10 mm, and an interval between the second trench lines is 0.02 mm to 0.10 mm. Method.   The resin structure includes ABS (acrylonitrile butadiene styrene copolymer) resin, polycarbonate resin, polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, PVC (poly vinyl chloride) resin, PPA (poly phthal amide) resin, PPS (poly phenylene). The laser direct structuring method according to claim 1, comprising a sulfide) resin, a polyester resin, a LCP (liquid crystal polymer) resin, or a mixture thereof.   The laser direct structuring method according to claim 1, wherein the resin structure further includes glass fiber.   6. The laser direct structuring method according to claim 5, wherein the glass fiber content in the resin structure is 5 to 45 parts by weight based on 100 parts by weight of the resin.   The laser direct structuring method according to claim 1, wherein the resin structure further includes a ceramic filler powder.   The laser direct structuring method according to 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.   The laser direct structuring method according to claim 7, wherein the ceramic filler is alumina, titanium dioxide, or a combination thereof.   The laser direct structuring method according to claim 1, wherein the resin structure further includes an antioxidant.   The method according to claim 10, wherein the content of the antioxidant in the resin structure is 0.1 to 5 parts by weight based on 100 parts by weight of the resin.   The laser direct structuring method according to claim 1, wherein the resin structure further includes 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 to 35 parts by weight based on 100 parts by weight of the resin. The laser direct structuring method described.   The laser direct structuring method according to claim 1, wherein the resin structure further includes a phosphate ester component.   The laser direct structuring method according to 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 laser direct structuring method according to claim 1, wherein the resin structure further includes 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 to 20 parts by weight based on 100 parts by weight of the resin.   The laser direct structuring method according to claim 1, wherein the resin structure further includes a colorant.   The laser direct structuring method according to claim 18, wherein the content of the colorant in the resin structure is 0.1 to 5 parts by weight based on 100 parts by weight of the resin.   The laser direct structuring method according to claim 1, wherein the resin structure does not substantially contain a nucleating agent.   The laser direct structuring method according to claim 2, wherein an angle at which the first trench line and the second trench line intersect each other is 60 ° to 90 °.   3. The laser direct structuring method according to claim 2, wherein widths of the first trench line and the second trench line are each independently 0.02 μm to 0.1 μm.   3. The laser direct structuring method according to claim 2, wherein the depths of the first trench line and the second trench line are each independently 0.02 mm to 0.1 mm.   2. The laser direct structuring method according to claim 1, further comprising a step of forming a metal layer on the plating target area on the surface of the resin structure by plating. The metal layer forming step by plating includes:
Providing a catalyst to the plating target region on the surface of the resin structure in which the trench lines in the grid-like arrangement are formed;
25. The laser direct structuring method according to claim 24, further comprising: striking a metal in an electroless manner on a plating target area provided with the catalyst.   26. The laser direct structuring method according to claim 25, wherein the catalyst is palladium.   26. The laser direct structuring method according to claim 25, wherein the metal layer is copper, nickel, gold, silver, or a combination thereof.   The multilayer metal layer is formed by repeating a step of applying a catalyst to the plating target region and a step of striking a metal in an electroless manner to the plating target region to which the catalyst is applied. Item 26. The laser direct structuring method according to Item 25.   The resin structure which has a plating object area | region, The resin structure body by which the trench line of the grid | lattice-like arrangement | sequence formed by laser irradiation is formed in the said plating object area | region.   The grid-arranged trench lines 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, and the first trench lines and the second trench lines are formed so as to cross each other. The distance between the first trench lines is 0.02 mm to 0.10 mm, and the distance between the second trench lines is 0.02 mm to 0.10 mm. Resin structure. In the resin structure having a plating target region, a resin structure in which the grid target trench lines formed by laser irradiation are formed in the plating target region; and
A resin structure having a conductor portion including a metal layer attached to the plating target region of the resin structure. The grid-arranged trench lines 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, and the first trench lines and the second trench lines are formed so as to cross each other. The conductor according to claim 31, wherein a distance between the first trench lines is 0.02 mm to 0.10 mm, and a distance between the second trench lines is 0.02 mm to 0.10 mm. Resin structure having parts.