KR102010472B1 - Method for forming conductive pattern by direct radiation of electromagnetic wave - Google Patents
Method for forming conductive pattern by direct radiation of electromagnetic wave Download PDFInfo
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- KR102010472B1 KR102010472B1 KR1020150102615A KR20150102615A KR102010472B1 KR 102010472 B1 KR102010472 B1 KR 102010472B1 KR 1020150102615 A KR1020150102615 A KR 1020150102615A KR 20150102615 A KR20150102615 A KR 20150102615A KR 102010472 B1 KR102010472 B1 KR 102010472B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0275—Photolithographic processes using lasers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
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- H01L51/0007—
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Optics & Photonics (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The present invention provides a method of forming a conductive pattern by direct irradiation of electromagnetic waves, which makes it possible to form a better fine conductive pattern on a variety of polymer resin products or resin layers, without including a special inorganic additive in the polymer resin itself. It is about.
The method of forming a conductive pattern by direct irradiation of electromagnetic waves may include forming a soluble polymer coating layer soluble on a polymer resin substrate in a solvent or a polar organic solvent; Selectively irradiating the polymer resin substrate with electromagnetic waves to remove the soluble polymer coating layer of the first region while forming a first region having a predetermined surface roughness; Forming a conductive seed on the polymer resin substrate; Plating a polymer resin substrate on which a conductive seed is formed to form a metal layer; And removing the soluble polymer coating layer and the metal layer in the second region of the polymer resin substrate not irradiated with electromagnetic waves by treating the polymer resin substrate having the metal layer formed thereon with a solvent or a polar organic solvent.
Description
The present invention provides a method of forming a conductive pattern by direct irradiation of electromagnetic waves, which makes it possible to form a better fine conductive pattern on a variety of polymer resin products or resin layers, without including a special inorganic additive in the polymer resin itself. It is about.
In recent years, with the development of fine electronic technology, there is an increasing demand for a structure in which a fine conductive pattern is formed on the surface of polymer resin substrates (or products) such as various resin products or resin layers. The conductive patterns and structures on the surface of the polymer resin substrate may be applied to form various objects such as antennas, various sensors, MEMS structures, or RFID tags integrated in a mobile phone case such as a smartphone.
In particular, recent portable devices such as smartphones need to be equipped with near field communication functions such as communication, Bluetooth, Wi-Fi, or electronic payment, unlike conventional mobile phones. Therefore, various antennas can be mounted together in one smartphone. There is a need. However, since the beautiful design aspects of portable devices such as smartphones are emphasized, conductive patterns that can serve as various antennas on the surface of the polymer resin substrate such as the case of the portable device are formed to satisfy these requirements simultaneously. How to do this is constantly being proposed and studied.
As such, as the interest in the technology of forming the conductive pattern on the surface of the polymer resin substrate increases, some techniques related thereto have been proposed. For example, a polymer resin substrate is formed by blending and molding a special inorganic additive (for example, CuCr 2 O 4 having a spinel structure) containing a transition metal such as copper or chromium on a polymer resin chip, and forming a predetermined region. After directly irradiating electromagnetic waves such as a laser to a metal layer, a method of forming a conductive pattern on the polymer resin substrate has been proposed by forming a metal layer by plating in a laser irradiation region. In this method, the metal additive and the conductive pattern may be formed by exposing the inorganic additive-derived component in the laser irradiation region to act as a seed for a kind of plating.
However, in such a conductive pattern forming method, since a large amount of expensive special inorganic additives must be used, there is a disadvantage that the overall process cost increases. In addition, since the inorganic additive needs to be blended onto the polymer resin chip itself, such an inorganic additive may reduce physical properties such as the polymer resin substrate or the mechanical properties of the resin product formed therefrom. In addition, special inorganic additives such as CuCr 2 O 4 having the spinel structure often have a very dark color by themselves, and thus may be an inhibitory factor in implementing a polymer resin substrate or a resin product including the same as a desired color. have. For example, in order to implement a polymer resin substrate including such an inorganic additive in a desired color, it is necessary to use a larger amount of pigment, and furthermore, it is not easy to implement white.
Due to these shortcomings, there has been a continuous demand for the development of a technology capable of forming fine conductive patterns on a variety of polymer resin products or resin layers in a simplified process without including a special inorganic additive in the polymer resin itself. .
As one of the technologies capable of satisfying such a requirement, the polymer resin in the region is irradiated with electromagnetic waves such as a laser to the region to form the conductive pattern to have a surface roughness of a predetermined level or higher, and the conductivity to promote plating on the polymer resin. After forming the seed, a technique of selectively forming a metal layer through electroless plating in such a region has been proposed. According to this, since the surface roughness of the polymer resin in the electromagnetic wave irradiation region, the conductive pattern having excellent adhesion can be formed well, while in the non-electromagnetic wave irradiation region, the metal layer cannot be properly attached to the smooth polymer resin surface and can be easily removed. It becomes Thus, fine conductive patterns can be formed in desired areas of various polymer resin products or resin layers without the use of special inorganic additives.
However, in such a conventional method of forming a conductive pattern by electromagnetic wave irradiation, when it is desired to form a conductive pattern on a polymer resin product or a resin layer having a constant surface curvature or surface roughness, the surface characteristics of the polymer resin product or the like itself have As a result, it is difficult to completely remove the metal layer from the non-electromagnetic wave irradiation area, or a part of the metal layer is removed from the electromagnetic wave irradiation area. In other words, the conventional conductive pattern forming method attempts to form a conductive pattern by selectively leaving a metal layer in the electromagnetic radiation irradiation region only by the surface roughness of the electromagnetic radiation irradiation and unirradiated regions and the difference in adhesion thereto. All remaining), due to the surface properties of the polymer resin product, etc., it is difficult to form a good conductive pattern selectively in the desired region only by such a difference in surface roughness.
In addition, in the conventional conductive pattern forming method, a separate process for removing the metal layer from the non-electromagnetic wave irradiation area also needs to be carried out, and surface characteristics of the polymer resin product or the like itself (particularly, surface properties in the non-electromagnetic wave irradiation area) ), Even though such a separate process proceeds, there is a disadvantage in that it is difficult to selectively remove the metal layer in the non-irradiated region of electromagnetic waves. Therefore, not only the whole process has to be performed at once, but also there is a problem that it is difficult to selectively form a good conductive pattern only in the electromagnetic wave irradiation region.
The present invention provides a method for forming a conductive pattern by direct irradiation of electromagnetic waves, which makes it possible to selectively form a better fine conductive pattern on various polymer resin products or resin layers without including a special inorganic additive in the polymer resin itself. It is.
The present invention comprises the steps of forming a soluble polymer coating layer soluble in a solvent or a polar organic solvent on the polymer resin substrate;
Selectively irradiating an electromagnetic wave to the polymer resin substrate to remove the soluble polymer coating layer of the first region while forming a first region having a predetermined surface roughness;
Forming a conductive seed on the polymer resin substrate;
Stabilizing the conductive seed by drying a polymer resin substrate at a temperature of 20 ° C. or higher;
Treating the polymer resin substrate with a solvent or a polar organic solvent to remove the soluble polymer coating layer and the conductive seed in the second region of the polymer resin substrate not irradiated with electromagnetic waves; And
It provides a method of forming a conductive pattern by direct irradiation of electromagnetic waves comprising the step of plating a polymer resin substrate to selectively form a metal layer on the polymer resin substrate of the first region.
In the conductive pattern forming method, the first region of the polymer resin substrate may have a surface roughness defined by a centerline surface roughness Ra of about 500 nm or more, and the second region may have a smaller centerline surface roughness Ra than the first region. )
Moreover, this invention is a resin structure for conductive pattern formation corresponding to the intermediate | middle product of the above-mentioned conductive pattern formation method, Comprising: The 1st area | region which has surface roughness defined by centerline surface roughness Ra of 500 nm or more, and smaller than a 1st area | region. A polymer resin substrate in which a second region having a surface roughness defined by a centerline surface roughness Ra is defined; And it provides a resin structure for forming a conductive pattern comprising a conductive seed selectively formed only in the first region of the polymer resin substrate.
According to the present invention, even if expensive special inorganic additives are not included in the polymer resin substrate itself, the surface roughness of the region where the conductive pattern is to be formed by electromagnetic wave irradiation such as a laser, the selective formation of the conductive seed, the adhesion to the metal layer, etc. By controlling, the conductive pattern can be formed on the polymer-based substrate in a simplified process.
Therefore, the unit cost of the conductive pattern forming process may be lowered, and the special inorganic additive may minimize the risk of physical property degradation such as the mechanical properties of the polymer resin substrate or the product. In addition, since the desired fine conductive pattern can be formed on the polymer resin substrate without using the special inorganic additive, it becomes easier to express the color of the resin itself and the color of the polymer resin substrate or the product in the desired color.
Particularly, in the present invention, the stabilized conductive seed remains only in the electromagnetic radiation irradiated region, and the polymer coated layer and conductive seed remain in the electromagnetic irradiated region through the process of forming a soluble polymer coating layer, forming and stabilizing a conductive seed, and removing the polymer coating layer. Can be left out. Therefore, irrespective of the surface state of the polymer resin substrate on which the conductive pattern is to be formed, the metal layer by plating may not be formed in the non-electromagnetic wave irradiation region, and a good metal layer may be formed only in the electromagnetic wave irradiation region. Therefore, in a desired process on various polymer resin products or resin layers having various surface states and shapes, a better fine conductive pattern can be selectively formed in a simplified process without the removal process of the metal layer.
As a result, the conductive pattern for antennas, RFID tags, various sensors, MEMS structures, etc., on various resin products such as smartphone cases can be formed very effectively using the conductive pattern forming method of the present invention.
1 is a schematic diagram schematically showing an example of a method of forming a conductive pattern by direct irradiation of electromagnetic waves according to an embodiment of the present invention in the order of processes.
2 is XRD analysis results of the polycarbonate resin substrates used in Examples 1 and 2, and Comparative Examples 2 and 3. FIG.
3 is a view showing a result of surface roughness evaluation of a laser irradiation area in Example 1. FIG.
4A and 4B are photographs showing SEM EDS analysis results of the resin substrates in the laser irradiation region and the unirradiated region, respectively, before forming the metal layer in the laser irradiation region in Example 1. FIG.
FIG. 5A is a photograph showing a state after forming a metal layer by electroless plating in a laser irradiation region in Example 1, and FIG. 5B is a metal layer not formed at all because plating is not performed in the laser unirradiated region in Example 1 It is a photograph showing.
FIG. 6 is a photograph showing the whole state (laser irradiation area and non-irradiation area) after forming a metal layer by electroless plating in the laser irradiation area in Example 2. FIG.
7 is an XRD pattern showing the presence of an inorganic additive in the polymer resin substrate in Comparative Example 1.
FIG. 8 is a photograph showing the whole state (laser irradiation area and non-irradiation area) after forming a metal layer by electroless plating in Comparative Example 2. FIG.
FIG. 9 is a photograph showing a state in which a coating layer and a conductive seed are not properly removed from the laser unirradiated region in Comparative Example 3 in which the conductive seed stabilization process is not performed, and a plating and a metal layer are partially formed.
FIG. 10 is a photograph showing a result of evaluating adhesive force through a cross-cut test on the metal layer (conductive pattern) of Example 1 in Test Example 1. FIG.
Hereinafter, a method of forming a conductive pattern by direct irradiation of electromagnetic waves according to a specific embodiment of the present invention will be described.
According to one embodiment of the invention, forming a soluble polymer coating layer soluble in a water-soluble solvent or a polar organic solvent on the polymer resin substrate; Selectively irradiating an electromagnetic wave to the polymer resin substrate to remove the soluble polymer coating layer of the first region while forming a first region having a predetermined surface roughness; Forming a conductive seed on the polymer resin substrate; Stabilizing the conductive seed by drying a polymer resin substrate at a temperature of 20 ° C. or higher; Treating the polymer resin substrate with a solvent or a polar organic solvent to remove the soluble polymer coating layer and the conductive seed in the second region of the polymer resin substrate not irradiated with electromagnetic waves; And plating a polymer resin substrate to selectively form a metal layer on the polymer resin substrate of the first region. The method of forming a conductive pattern by direct irradiation of electromagnetic waves is provided.
According to the method of the embodiment of the present invention, first, a predetermined soluble polymer coating layer is formed on the polymer resin substrate, and then electromagnetic waves such as a laser are irradiated to the first region to form the conductive pattern. By the electromagnetic wave irradiation, the soluble polymer coating layer is removed in the first region, and at the same time, an uneven form, a constant pattern form or an amorphous form surface structure, etc. are formed on the polymer resin substrate of the first region, thereby providing a predetermined surface roughness. Will have In this first region, the adhesion between the surface of the polymer resin substrate and the metal layer to be formed by plating may be further improved due to a predetermined surface roughness. On the other hand, in the second region not irradiated with electromagnetic waves such as a laser, the soluble polymer coating layer remains as it is, and due to the original surface roughness of the polymer resin substrate itself, it exhibits poor adhesion with the metal layer relative to the first region. Can be.
Subsequently, when the conductive seed for promoting the plating is formed on the polymer resin substrate and stabilized, the stabilized conductive seed remains on the polymer resin substrate having a predetermined surface roughness in the first region, and in the second region, Stabilized conductive seeds remain on the polymer coating layer. Subsequently, when the polymer resin substrate is treated with a predetermined solvent to dissolve and remove the soluble polymer coating layer of the second region, the conductive seed of the second region is closely bonded to the polymer coating layer in a stabilized state. All together can be removed. On the contrary, since the conductive seed of the first region is closely bonded to the polymer resin substrate itself in a stabilized state, the conductive seed of the first region is not substantially removed upon removal of the polymer coating layer, and remains in the first region.
Therefore, when the subsequent plating process is carried out, the conductive seed remains, the plating proceeds only in the first region where excellent adhesion to the metal layer is secured by a predetermined surface roughness, and thus a good metal layer may be selectively formed. On the contrary, in the second region, both the polymer coating layer and the conductive seed for promoting plating are removed, and since the surface shows poor adhesion with the metal layer due to the small surface roughness, the plating does not proceed substantially. No metal layer is formed.
As a result, a good metal layer can be selectively formed only in the first region to which the electromagnetic wave is irradiated, so that a better metal layer can be selectively formed in a desired region more simply without removing the metal layer with respect to the second region.
If the conductive seed is not stabilized, the conductive seed of the second region may not be completely removed or even a part of the conductive seed of the first region may be removed when the polymer coating layer is removed. A process may be required or it may be difficult to form a good metal layer in the desired area.
In addition, by the progress of the stabilization process of the conductive seed, the transfer or storage of the polymer resin substrate having a stabilized conductive seed is free, and the process proceeds through various methods and routes. In addition, by the progress of the stabilization process of the conductive seed, the range of the component applicable to the conductive seed is further expanded to allow easier process progress as a whole.
As a result, according to the exemplary embodiment of the present invention, a better conductive pattern may be selectively formed in a desired region of the polymer resin substrate through the above-described soluble polymer coating layer and its removing step, and stabilizing the conductive seed. In particular, the remaining regions of the conductive seeds can be effectively controlled to selectively form better fine conductive patterns in desired regions on various polymer resin products or resin layers having more varied surface states and shapes. In addition, the metal layer removing process of the non-electromagnetic wave irradiated region is not necessary during the process, and the overall process can be further simplified.
In addition, in the method of this embodiment, a good conductive pattern can be formed on various polymer hand substrates in a simpler process without using expensive special inorganic additives such as, for example, spinel structure CuCr 2 O 4 . have.
On the other hand, in the following, the conductive pattern forming method by direct irradiation of the electromagnetic wave according to an embodiment with reference to the drawings will be described in more detail in each step step. 1 is a schematic diagram schematically showing an example of a method of forming a conductive pattern by direct irradiation of electromagnetic waves according to an embodiment of the present invention in the order of processes.
As shown in ① and ② of FIG. 1, in the conductive pattern forming method of the embodiment, first, a soluble polymer coating layer soluble in a water soluble solvent or a polar organic solvent is formed on the polymer resin substrate.
In this case, the polymer resin substrate may be formed using any thermosetting resin or thermoplastic resin. Specific examples of polymer resins such as thermosetting resins or thermoplastic resins capable of forming such polymer resin substrates include polyalkylene terephthalate resins such as ABS resins, polybutylene terephthalate resins, and polyethylene terephthalate resins, and polycarbonate resins. , Polypropylene resin or polyphthalamide resin, and the like, and in addition, various polymer resins can be used to form the polymer resin substrate.
And, the polymer resin substrate may be formed only of the above-described polymer resin, but if necessary, additives commonly used to form polymer resin products, such as UV stabilizers, heat stabilizers, impact modifiers, titanium dioxide or carbon black It may further include an infrared absorption auxiliary material such as. Such additives may be included in an appropriate amount of about 2% by weight or less, or about 0.01 to 2% by weight, based on the weight of the entire polymeric resin substrate. However, the polymer resin substrate does not need to include a special inorganic additive, for example, CuCr 2 O 4 having a spinel structure, which has been used for the formation of a conductive pattern by electromagnetic wave irradiation previously known.
In addition, the soluble polymer coating layer may be suitably coated and formed on the entire surface of the polymer resin substrate, the polymer coating layer exhibits excellent coating properties for the polymer resin substrate, a water-soluble solvent such as water or a polar organic such as ethanol It can be formed using any soluble polymer that exhibits other good solubility in the solvent and is readily removable in subsequent processes.
The type of the soluble polymer may be appropriately selected by those skilled in the art in consideration of the type of the polymer resin substrate, the solubility in the aqueous solvent or the polar organic solvent, and the like, and is not particularly limited. However, specific examples of such soluble polymers include acrylic polymers such as polyacrylic acid (PAA), polyalkylene glycol polymers such as polyethylene glycol (PEG), and polyvinylpyrrolidone (PVP) -based polymers. And at least one selected from the group consisting of polymers, polyoxazoline polymers, and polyvinyl alcohol polymers.
In addition, the soluble polymer may have a weight average molecular weight of about 1000 to 60000 in consideration of coating property on the polymer resin substrate, solubility in various solvents, and the like.
In addition, the soluble polymer coating layer may be coated on the polymer substrate by a conventional coating method, for example, dip coating, spin coating, or spray coating, in a solution obtained by dissolving the above-described soluble polymer in a solvent or a polar organic solvent. It can be dried and formed.
On the other hand, after the soluble polymer coating layer is formed, as shown in ③ of FIG. 1, the polymer resin substrate may be selectively irradiated with electromagnetic waves to form a first region having a predetermined surface roughness. By irradiation of the electromagnetic waves, the polymer resin substrate has a predetermined surface roughness in the first region, while the soluble polymer coating layer is destroyed by the electromagnetic waves and can be removed.
In the electromagnetic wave irradiation process, a relatively standard pattern or irregularities such as holes or mesh patterns are formed in the first region, or an amorphous surface structure in which a plurality of irregular holes, patterns or irregularities are formed in combination. Due to such various surface shapes or structures, the polymer resin substrate of the first region may have a predetermined surface roughness.
In one example, the first region of the polymer resin substrate may be about 500 nm or more, or about 1 μm or more, to secure excellent adhesion between the metal layer (conductive pattern) to be formed in the first region and the surface of the polymer resin substrate. The second region, which has a surface roughness defined by a centerline surface roughness Ra of about 1 to 3 μm, and the electromagnetic wave is not irradiated, has a centerline surface roughness Ra smaller than the first region, for example, about 400 nm. Or a surface roughness defined by a centerline surface roughness Ra of about 100 nm or less, or about 0 to 90 nm. However, the surface roughness of the second region may vary depending on the surface properties of the original polymer resin substrate.
When the polymer coating layer of the first region is removed by electromagnetic wave irradiation of the laser or the like, and the polymer resin substrate of the first region has the above-described surface roughness, the metal layer is formed on the first region in a subsequent plating process. In addition, the metal layer may be formed and maintained with excellent adhesion on the polymer resin substrate, thereby forming a good conductive pattern. Compared with the first region, the polymer resin substrate of the second region, which is not irradiated with electromagnetic waves, such as a laser, has a relatively small surface roughness, and thus exhibits low adhesion with the metal layer. As it is removed, plating may not proceed substantially and the metal layer may not be formed in the second region. As a result, according to one embodiment, a good conductive pattern may be selectively formed on the polymer resin substrate of the first region.
On the other hand, electromagnetic waves, such as a laser, can be irradiated under the predetermined conditions mentioned later so that the polymer resin base material of a 1st area | region can show the surface roughness mentioned above.
First, in the electromagnetic wave irradiation step, laser electromagnetic waves may be irradiated, for example, about 248 nm, about 308 nm, about 355 nm, about 532 nm, about 585 nm, about 755 nm, about 1064 nm, about 1070 nm, about 1550 nm, about 2940 nm Or laser electromagnetic waves having a wavelength of about 10600 nm. In another example, laser electromagnetic waves having a wavelength in the infrared (IR) region may be irradiated.
In addition, the specific conditions during the laser electromagnetic wave irradiation may be adjusted or changed according to the resin type, physical properties, thickness of the polymer resin substrate, the type or thickness of the metal layer to be formed, or the level of appropriate adhesive force considering the same. However, under irradiation conditions of, for example, about 0.1 to 50 W, or about 1 to 30 W, or about 5 to 25 W, so that the polymer resin substrate of the first region may have the predetermined surface roughness described above, It can proceed by irradiating laser electromagnetic waves.
In addition, the laser electromagnetic wave irradiation may be irradiated once with relatively strong power, but may be irradiated twice or more with relatively low power. As the number of times of irradiation of laser electromagnetic waves increases, surface roughness increases, and structures such as irregularities formed on the surface may change from hole-shaped patterns to mesh patterns or amorphous surface structures. By adjusting the number of times, it is possible to form an appropriate surface structure on the polymer resin substrate of the first region and to have an appropriate degree of surface roughness and thereby excellent adhesion to the metal layer.
In the laser electromagnetic wave irradiation, on the polymer resin substrate according to the irradiation interval, for example, a trace of electromagnetic wave irradiation may be formed in a hole shape or the like. By the way, although not particularly limited, in order for the polymer resin substrate of the first region to have the appropriate surface roughness already described above, the interval between the centers of the electromagnetic wave irradiation traces or the electromagnetic wave irradiation interval is about 20 µm or more, or about 20 It may be appropriate to irradiate the laser electromagnetic wave so that it is from about 70㎛. Through this, the polymer resin substrate of the first region may have an appropriate surface roughness, and together with the polymer resin substrate and the metal layer may have an appropriate adhesion.
Meanwhile, as described above, after irradiating electromagnetic waves such as a laser to the first region, a conductive seed may be formed on the polymer resin substrate as shown in ④ of FIG. 1. Such a conductive seed may serve as a seed that enables the progress of plating by reducing / precipitating and growing upon plating on the polymer resin substrate and may serve to promote formation of a metal layer. Through this, a better metal layer and a conductive pattern can be appropriately formed on the polymer resin substrate of the first region.
However, in the second region, since the conductive seed may be removed together with the polymer coating layer in a subsequent process, plating does not proceed substantially and no metal layer is formed.
Meanwhile, the conductive seed may include metal nanoparticles, metal ions, or metal complex ions. In addition, the metal ions or metal complex ions are not only as such, but also in the form of a metal containing compound or a metal complex containing a metal complex in which metal ions including them are bound, furthermore, in the form of particles of the metal containing compound or metal complex, etc. Of course, it can also be used as.
The kind of metal element that can be included in such a conductive seed is not particularly limited as long as it can exhibit conductivity, for example, copper (Cu), platinum (Pt), palladium (Pd), silver (Ag), gold (Au) , Nickel (Ni), tungsten (W), titanium (Ti), chromium (Cr), aluminum (Al), zinc (Zn), tin (Sn), lead (Pb), magnesium (Mg), manganese (Mn) , Bismuth (Bi) and iron (Fe) may include one or more metals selected from the group consisting of ions or complex ions thereof.
And, in order to form the conductive seed on the polymer resin substrate, a dispersion or solution containing the above-mentioned conductive seed, for example, metal nanoparticles, metal ions or metal complex ions, is applied on the polymer resin substrate, and precipitated. The method of forming a conductive seed in a desired form, for example, in the form of particles, may be carried out by a method such as drying and / or reduction. More specifically, when the dispersion or the like contains metal nanoparticles, it is possible to form a conductive seed in the form of particles by depositing it using the difference in solubility, the dispersion or the like is a metal ion or a metal complex ion (or Including metal compounds or complexes; for example, metal compounds or complexes such as AgNO 3 , Ag 2 SO 4 , KAg (CN) 2, and the like), and reducing them to suitably form conductive seeds in the form of particles. Can be.
At this time, the reduction of the metal ions or metal complex ions is conventional reducing agents, for example, alcohol-based reducing agents such as ethanol or ethylene glycol, aldehyde-based reducing agents such as formaldehyde, hypophosphite-based such as sodium hypophosphite or its hydrate At least one reducing agent selected from the group consisting of a reducing agent, a hydrazine-based reducing agent such as hydrazine or a hydrate thereof, sodium borohydride and lithium aluminum hydride can be used.
The dispersion or solution may be an aqueous polymer solution (eg, a solution such as polyvinylpyrrolidone-based polymer) or a metal ion or metal complex ion which may improve adhesion between the polymer resin substrate and the conductive seed as a liquid medium. A water-based complexing agent (for example, NH 3 , EDTA or Rotsel salt, etc.) that can be stabilized may be appropriately included.
In addition, the application of the dispersion or the solution of the conductive seed may proceed to the general process for applying the liquid composition to the polymer resin substrate, for example, may be carried out by a method such as dipping (dipping), spin coating or spraying.
The conductive seed formed in this manner may be formed on the entire surface of the polymer resin substrate, including between surface irregularities, patterns, or surface structures formed in the first region.
Meanwhile, referring to FIG. 1, after the conductive seed is formed on the polymer resin substrate, the polymer resin substrate is dried at a temperature of 20 ° C. or higher, or 20 to 90 ° C., or 40 to 80 ° C. A step of stabilizing the conductive seed is performed. In this stabilization process, in the first region, the conductive seed may be seated on the polymer resin substrate (more specifically, between the pattern or the structure having the surface roughness by electromagnetic wave irradiation) to be closely coupled. In addition, in the second region, the conductive seed may be seated on the polymer coating layer to be intimately coupled. Thus, in subsequent processes, the conductive seed in the second region may optionally be completely removed along with the polymer coating layer.
As already described above, if the stabilization process of the conductive seed is not carried out, the conductive seed of the second region may not be completely removed or part of the conductive seed of the first region may be removed upon the subsequent removal of the polymer coating layer. A separate metal layer removal process may be required or it may be difficult to form a good metal layer in the desired area.
In addition, by this stabilization process, as the conductive seed is more effectively stabilized and reduced, it is possible to apply a metal having a relatively low reducing power or a (complex) ion thereof as the conductive seed. That is, as the range of metals applicable as conductive seeds increases, relative process ease and process freedom can be further improved.
Meanwhile, the stabilizing step of the conductive seed may further include applying a reducing agent solution after the drying step in consideration of the type or form (ion or complex ion) of the metal included in the conductive seed. . In this case, the reducing agent solution may be used in the conductive seed forming process, for example, a reducing agent as described above, for example, an alcohol-based reducing agent such as ethanol or ethylene glycol, an aldehyde-based reducing agent such as formaldehyde, sodium hypophosphite or a hydrate thereof, and the like. Or a reducing agent selected from the group consisting of a hypophosphite reducing agent, a hydrazine reducing agent such as hydrazine or a hydrate thereof, sodium borohydride and lithium aluminum hydride.
In the conductive seed stabilization process, further application of such a reducing agent solution reduces and stabilizes the conductive seeds in the first and second regions more effectively, so that the conductive seeds are not removed in the subsequent process and are substantially removed. All can be maintained, and the second region can be more effectively removed with the polymer coating layer.
On the other hand, after stabilizing the conductive seeds, as shown in ⑤ of FIG. 1, the polymer resin substrate is treated with a solvent or a polar organic solvent to dissolve and remove the soluble polymer coating layer in the second region where electromagnetic waves are not irradiated. At this time, the conductive seed stabilized on the polymer coating layer is removed together.
As described above, since the conductive seed is bonded and maintained in the stabilized state on the polymer resin substrate and the polymer coating layer in the first and second regions, respectively, the conductive seed is selectively conductive only in the second region when the polymer coating layer is removed by the above process. The seed may be removed and the conductive seed may remain intact in the first region without being substantially removed. Therefore, when the subsequent plating process is performed, plating may be selectively performed on the first region where the conductive seed is present to form a metal layer, and the metal layer may not be formed on the second region.
When the polymer coating layer is removed, a first region having a surface roughness defined by a centerline surface roughness Ra of 500 nm or more, and a second region having a surface roughness defined by a centerline surface roughness Ra smaller than the first region. Polymer resin base material which is defined; And a (stabilized) conductive seed selectively formed only in the first region of the polymer resin substrate. In such a resin structure, the conductive seed may be stably present in a chemically reduced stabilized form, for example, in the form of reduced solid metal particles that are well adhered to the polymer resin substrate of the first region.
Accordingly, the resin structure is an intermediate product present only in the first region in a form in which the conductive seed is stabilized, and thus stable transport and storage are possible. Therefore, it is possible to secure process freedom using these intermediate products, and it is possible to form conductive patterns by various process combinations and subjects (for example, the above intermediate products are supplied to cell phone companies, and cell phone companies, etc. It is possible to form the desired conductive pattern.
On the other hand, in the step of removing the polymer coating layer and the conductive seed, the soluble polymer may proceed by appropriately selecting any solvent or polar organic solvent exhibiting high solubility. Specific examples of such a solvent or a polar organic solvent include water solvents such as alcohol solvents such as ethanol, ketone solvents such as acetone, carboxylic acid solvents such as acetic acid, and the like, and various other solvents can be used. For example, when the soluble polymer coating layer is formed of a PVP-based polymer, the removing of the polymer coating layer may be performed by washing or rinsing the polymer resin substrate with water or ethanol.
Further, in order to more effectively remove the soluble polymer coating layer and the conductive seed by treatment with such a solvent or polar solvent, the treatment with the solvent or polar organic solvent may be performed by ultrasonication, air blowing, taping and It can proceed while applying a physical force by a method selected from the group consisting of brushing. In a more specific example, the soluble polymer coating layer and the conductive seed of the second region may be selectively removed by washing or rinsing under ultrasonic irradiation in water for a predetermined time.
Referring to ⑥ of FIG. 1, after removing the polymer coating layer and the conductive seed, a metal layer may be formed by plating the polymer resin substrate. The metal layer forming step may be performed by electroless plating a conductive metal on the polymer resin substrate, and the method and conditions of the electroless plating step may be in accordance with conventional methods and conditions.
As described above, when the plating process is performed, the conductive seed remains and plating proceeds only in the first region in which excellent adhesion to the metal layer is secured by a predetermined surface roughness, thereby forming a good metal layer. . On the contrary, in the second region, both the polymer coating layer and the conductive seed are removed, and because the surface roughness is less than that of the first region, the adhesion is poor with the metal layer, so that the plating does not proceed substantially and the metal layer is not formed. Do not. Therefore, unlike the existing process, even if a separate process for removing the metal layer in the second region is not performed, a good conductive pattern can be selectively formed in the desired first region.
In the meantime, the plating process may be performed by using a plating solution including a conductive metal constituting the metal layer, for example, a metal source such as copper, a complexing agent, a pH adjuster, a reducing agent, and the like. In this case, the metal layer may be formed on the conductive seed while the aforementioned conductive seed is grown.
The resin structure having the conductive pattern formed by the above-described method includes a polymer resin substrate having a first region formed to have a predetermined surface roughness and a second region having a surface roughness smaller than the first region; And a conductive seed and a metal layer selectively formed in the first region of the polymer resin substrate.
In this case, since the surface roughness of the first and second regions is sufficiently described above with respect to the method of the exemplary embodiment, further description thereof will be omitted. As described above, the first region may correspond to an electromagnetic wave irradiation region such as a laser.
The resin structure described above may be various resin products or resin layers such as a smart phone case having a conductive pattern for an antenna, or various resin products or resin layers having conductive patterns such as other RFID tags, various sensors or MEMS structures.
As described above, according to the embodiment of the invention, even if expensive special inorganic additives are not included in the polymer resin substrate itself, the surface roughness of the region where the conductive pattern is to be formed by electromagnetic wave irradiation such as a laser and the adhesion to the metal layer By controlling, the conductive pattern can be formed on the polymer hand-based substrate in a simpler process.
Therefore, the unit cost and raw material cost of the conductive pattern forming process may be lowered, and the special inorganic additive may minimize the risk of physical property degradation such as the mechanical properties of the polymer resin substrate or the product. In addition, since the desired fine conductive pattern can be formed on the polymer resin substrate without the use of the special inorganic additive, the color of the resin itself can be utilized and the color of the polymer resin substrate or the product can be easily expressed in the desired color.
In addition, through the above-described process, it is possible to selectively form a better fine conductive pattern in a desired region, regardless of the surface state of the polymer resin substrate on which the conductive pattern is to be formed. As a result, embodiments of the invention can form good fine conductive patterns on a wider variety of resin products or resin layers even at a lower cost and simplified process, and thus include new resin products and the like that have not been proposed before. It can greatly contribute to realizing resin products of various colors and shapes.
Hereinafter, the operation and effect of the invention will be described in more detail with reference to specific examples. However, this is presented as an example of the invention, whereby the scope of the invention is not limited in any sense.
Example 1 Formation of Conductive Pattern by Laser Direct Irradiation
A polycarbonate resin substrate was prepared containing less than 2% by weight of UV stabilizers, heat stabilizers and impact modifiers in total, and no other inorganic additives. The XRD analysis result for this resin substrate is shown in FIG. 2. 2, it is confirmed that a special inorganic additive including CuCr 2 O 4, etc. is not included in the polycarbonate resin substrate.
On this polycarbonate resin substrate, a coating solution containing polyvinylpyrrolidone (Mw: average 10,000) at a concentration of 1% by weight was applied for 1 minute, and dried at 60 to 80 ° C for 1 to 5 minutes, A polyvinylpyrrolidone coating layer was formed.
After forming a polyvinylpyrrolidone coating layer on the entire surface of the polycarbonate resin substrate, using a Nd-YAG laser device in a predetermined region of the resin substrate, a laser of 1064nm wavelength under irradiation conditions of an average power of 21.4W, One survey was made. At this time, by adjusting the laser irradiation interval, the interval between the center of the laser irradiation trace of the polycarbonate resin substrate was adjusted to about 35㎛.
Through this, the laser was formed to have a constant surface roughness on a predetermined region of the irradiated polycarbonate resin substrate. At this time, it was confirmed that the polyvinylpyrrolidone coating layer of the region is removed together.
Moreover, the result of surface roughness evaluation in the said laser irradiation area is shown in FIG. For reference, the surface roughness was measured using an optical profiler (Nano view E1000, Nanosystem, Korea) equipment, the center line average roughness (Ra) of 0.2 mm X 0.3 mm area. More specifically, in FIG. 3, the color change according to the height was shown using the optical profiler in the laser irradiation area of Example 1 (right), and the picture showing the three-dimensionalization (left) thereof was also shown. In addition, the surface roughness measured at this time is also shown. The measured average surface roughness value measured the surface roughness of six different points of the laser irradiation area, and then averaged these measured values. As a result of this measurement, the centerline surface roughness Ra of the laser irradiation area was found to be about 1.58 μm.
Thereafter, the polycarbonate resin substrate was immersed in an aqueous solution containing Pd ions for about 5 minutes to form a conductive seed including Pd on the substrate. Thereafter, a drying process was performed at a temperature of 70 ° C. to stabilize the conductive seed. Subsequently, the substrate was immersed in deionized water and ultrasonically irradiated for 20 minutes, thereby dissolving and removing the polyvinylpyrrolidone coating layer of the unirradiated region of the laser, and simultaneously removing the conductive seeds of the unirradiated region of the laser.
After removal of the conductive seeds, SEM EDS analysis results for the resin substrates in the laser irradiated and unirradiated regions are shown in FIGS. 4A and 4B, respectively. 4A and 4B, while the conductive seed remains stably fixed on the resin substrate in the laser irradiation area (FIG. 4A), the conductive seed is completely removed together with the polyvinylpyrrolidone coating layer in the non-laser irradiation area. It is confirmed that no more remains (FIG. 4B).
Meanwhile, after removing the conductive seed and the coating layer of the second region, electroless plating was performed using copper as the conductive metal. In the electroless plating, the plating solution used was copper sulfate as a copper source, a lotel salt as a complexing agent, an aqueous solution of sodium hydroxide as a pH adjusting agent, and formaldehyde as a reducing agent, and the metal layer was subjected to electroless plating at room temperature for about 1 hour. Formed.
After the metal layer was formed in this way, photographs of the laser irradiation area and the unirradiated area are shown in FIGS. 5A and 5B, respectively. Referring to FIG. 5A, a good metal layer was formed in the laser irradiation area, and referring to FIG. 5B, it was confirmed that the plating and the formation of the metal layer did not proceed at all as the conductive seed itself did not remain in the laser unirradiated area. .
Example 2: Formation of Conductive Pattern by Laser Direct Irradiation
A metal layer and a conductive pattern including the same were formed by the same method and condition as Example 1 except that the polyacrylic acid coating layer was formed instead of the polyvinylpyrrolidone coating layer.
The polyacrylic acid coating layer was coated with a reagent (Poly (acrylic acid), 63 wt% solution in water; Mw 2,000) containing H 2 O, and coated with a coating solution containing the same at a concentration of 10% by weight for 1 minute. It formed by drying for 5 minutes at ° C.
After the process was performed in the same manner and in the same manner as in Example 1 to form a metal layer, the entire photograph including the laser irradiated region and the unirradiated region is shown in FIG. 6. Referring to FIG. 6, it was confirmed that a good metal layer was formed in the laser irradiation area, and plating and formation of the metal layer did not proceed at all as the conductive seed itself did not remain in the non-laser irradiation area.
Comparative Example 1: Formation of a Conductive Pattern by Laser Direct Irradiation
To the polycarbonate resin was added an inorganic additive of CuCr 2 O 4 in less than about 10% by weight. In addition, the UV stabilizer, heat stabilizer and impact modifier were mixed in less than 2% by weight in total, and blended by extrusion at 260 to 280 ° C, to prepare a resin composition in the form of pellets, the resin composition of the pellet form A resin substrate was prepared by injection molding into a 100 mm diameter, 2 mm thick substrate at about 260 to 280 ° C. The XRD measurement results of the polycarbonate resin substrate including the CuCr 2 O 4 and the XRD measurement results of the CuCr 2 O 4 inorganic additives were compared and illustrated in FIG. 7. Through this, it was confirmed that the inorganic additive of CuCr 2 O 4 remains in the polycarbonate resin substrate as it may affect the physical properties of the resin substrate.
On the other hand, the Nd-YAG laser apparatus was used to irradiate the surface of the resin substrate prepared above by irradiating a laser of 1064 nm wavelength under the conditions of 40 kHz and 10 W.
Subsequently, an electroless plating process was performed on the resin substrate whose surface was activated by the laser irradiation in the same manner and in the same manner as in Example 1. This confirmed that the metal layer and the conductive pattern were formed in the laser irradiation area on the polycarbonate resin substrate.
Comparative example 2: formation of a conductive pattern by laser direct irradiation
The same polycarbonate resin substrate as in Example 1 was prepared. The laser of 1064 nm wavelength was irradiated to the fixed area | region of this polycarbonate resin substrate once under the irradiation conditions of the average output of 21.4W. At this time, by adjusting the laser irradiation interval, the interval between the center of the laser irradiation trace of the polycarbonate resin substrate was adjusted to about 35㎛. Through this, the laser was formed to have a constant surface roughness on a predetermined region of the irradiated polycarbonate resin substrate.
Thereafter, the polycarbonate resin substrate was immersed in an aqueous solution containing Pd ions for about 5 minutes to form a conductive seed including Pd on the substrate. The substrate was then washed with deionized water and electroless plating was carried out using copper as the conductive metal. In the electroless plating, the plating solution used was copper sulfate as a copper source, a lotel salt as a complexing agent, an aqueous solution of sodium hydroxide as a pH adjusting agent, and formaldehyde as a reducing agent. Formed. The photograph after such a metal layer formation is shown in FIG.
Thereafter, the substrate was immersed in deionized water and ultrasonically irradiated for 20 minutes, and then gas blown to selectively remove the metal layer of the non-irradiated region of the laser. Referring to FIG. 8, in Comparative Example 2, as the plating and the metal layer were partially formed in the non-laser region, it was confirmed that a separate metal layer removal process was required.
Comparative example 3: Formation of conductive pattern by laser direct irradiation
A conductive pattern was formed under the same conditions and methods as in Example 1 except that the drying process was performed at a temperature of 70 ° C. to omit the stabilization of the conductive seed. 9 is a photograph of a laser unirradiated region immediately after forming a metal layer by plating. Referring to FIG. 9, in Comparative Example 3, as a part of plating and metal layer formation proceeded even in the unirradiated region (the conductive seed of the region did not seem to be properly removed), it was confirmed that a separate metal layer removal process was required. .
Test Example 1: Evaluation of the adhesion of the conductive pattern
After forming the conductive pattern in Example 1 at all times, in the region where the metal layer and the conductive pattern were formed, using a tape (3M Scotch tape # 371) having an adhesive strength of 4.0 to 6.0 N / 10 mm width by the standard method of ISO 2409, the cross- Cut test was performed. At this time, the metal layer was cut into 10 × 10 grids (about 2 mm or less), and the adhesive force or adhesion between the substrate and the metal layer was evaluated by measuring the area of the metal layer peeled off from the tape when the metal layer was cut with the tape.
As a result of this evaluation, the peeled area of the conductive pattern was evaluated under the following ISO class criteria.
1.
2.
3.
4. class 3 grade: The peeling area of the conductive pattern is more than 15% and 35% or less of the conductive pattern area to be evaluated;
5. class 4 grade: The peeling area of the conductive pattern is more than 35% and 65% or less of the conductive pattern area to be evaluated;
6. Class 5: The peeling area of the conductive pattern is more than 65% of the conductive pattern area to be evaluated.
This evaluation result is shown in FIG. Referring to FIG. 10, in Example 1, it was confirmed that a good conductive pattern showing excellent adhesion to
Claims (17)
Selectively irradiating an electromagnetic wave to the polymer resin substrate to remove the soluble polymer coating layer of the first region while forming a first region having a predetermined surface roughness;
Forming a conductive seed on the polymer resin substrate;
Stabilizing the conductive seed by drying a polymer resin substrate at a temperature of 20 ° C. or higher;
Treating the polymer resin substrate with a solvent or a polar organic solvent to remove the soluble polymer coating layer and the conductive seed in the second region of the polymer resin substrate not irradiated with electromagnetic waves; And
Plating the polymer resin substrate to selectively form a metal layer on the polymer resin substrate of the first region,
The soluble polymer coating layer includes at least one soluble polymer selected from the group consisting of an acrylic polymer, a polyalkylene glycol polymer, a polyvinylpyrrolidone (PVP) polymer, a polyoxazoline polymer and a polyvinyl alcohol polymer. ,
The removing of the soluble polymer coating layer and the conductive seed in the second region may include treating the polymer resin substrate in the second region with a solvent or a polar organic solvent to dissolve the polymer coating layer. Is a method of forming a conductive pattern by direct irradiation of electromagnetic waves proceeding while applying a physical force by a method selected from the group consisting of ultrasonication, air blowing, taping, and brushing.
Applying a dispersion or solution comprising metal nanoparticles, metal ions or metal complex ions on the polymeric resin substrate; And
Precipitating the metal nanoparticles, or reducing the metal ions or metal complex ions to form a conductive seed in the form of particles comprising a conductive pattern by direct irradiation of electromagnetic waves.
A method of forming a conductive pattern by direct irradiation of electromagnetic waves in which a metal layer is selectively formed only on the polymer resin substrate of the first region in which the conductive seed remains.
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| JP2001308497A (en) * | 2000-04-27 | 2001-11-02 | Sankyo Kasei Co Ltd | Stereoscopic circuit board and method for manufacturing the same |
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