WO2016064192A1 - 전자기파 조사에 의한 도전성 패턴 형성용 조성물, 이를 사용한 도전성 패턴 형성 방법과, 도전성 패턴을 갖는 수지 구조체 - Google Patents
전자기파 조사에 의한 도전성 패턴 형성용 조성물, 이를 사용한 도전성 패턴 형성 방법과, 도전성 패턴을 갖는 수지 구조체 Download PDFInfo
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- WO2016064192A1 WO2016064192A1 PCT/KR2015/011155 KR2015011155W WO2016064192A1 WO 2016064192 A1 WO2016064192 A1 WO 2016064192A1 KR 2015011155 W KR2015011155 W KR 2015011155W WO 2016064192 A1 WO2016064192 A1 WO 2016064192A1
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- WIPO (PCT)
- Prior art keywords
- electromagnetic wave
- conductive pattern
- forming
- composition
- inorganic additive
- Prior art date
Links
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Classifications
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C25D5/024—Electroplating of selected surface areas using locally applied electromagnetic radiation, e.g. lasers
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- H01L21/02107—Forming insulating materials on a substrate
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- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
- H01L21/02348—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to UV light
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- H05K1/00—Printed circuits
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
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- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/146—Mixed devices
- H01L2924/1461—MEMS
Definitions
- the present invention makes it possible to form a fine conductive pattern on a variety of polymer resins including polycarbonate resins or resin layers by a simple method of electromagnetic wave irradiation and plating, and also to improve the physical properties of the resin product or resin layer by the electromagnetic wave irradiation. It relates to a composition for forming a conductive pattern by electromagnetic wave irradiation, which can further reduce the decrease, a method of forming a conductive pattern using the same, and a resin structure having a conductive pattern.
- a method of forming a conductive pattern by forming a metal layer on the surface of the polymer resin substrate and then applying photolithography or printing a conductive paste may be considered.
- a polymer resin substrate is formed by blending and molding a special inorganic additive (eg, Sb doped Sn0 2, etc.) including a ' transition metal such as antimony or tin on a polymer resin chip, After directly irradiating electromagnetic waves such as a laser to a predetermined region, a metal layer is formed by plating in the laser irradiation region, thereby forming a conductive pattern on the polymer resin substrate.
- a special inorganic additive eg, Sb doped Sn0 2, etc.
- a metal layer is formed by plating in the laser irradiation region, thereby forming a conductive pattern on the polymer resin substrate.
- such inorganic additives may be used for the physical properties of the polymer resin substrate, the mechanical properties of the resin product formed therefrom, and the dielectric constant. It can lower, and cause dielectric loss.
- a means such as reducing its content or minimizing its particle size is applied, it exhibits sufficient absorption and sensitivity in the irradiation region of electromagnetic waves such as a laser. In this case, even if the plating is carried out after the electromagnetic wave irradiation, a good conductive pattern becomes difficult, and the conductive pattern often does not exhibit sufficient adhesive force to the polymer resin substrate, and is often easily dropped.
- a method of increasing the irradiation conditions of electromagnetic waves such as lasers, for example, average power for irradiating electromagnetic waves, and the like may be considered.
- the resin substrate itself may be excessively damaged and its mechanical properties and the like may be degraded.
- electromagnetic wave irradiation under severe commercially unfavorable conditions is required, the economics of the overall process may also be greatly degraded. Can be.
- the present invention makes it possible to form a fine conductive pattern well on a variety of polymer resin products or resin layers including polycarbonate resins by a simple method of electromagnetic wave irradiation and plating, and also the physical properties of the resin product or resin layer by the electromagnetic wave irradiation. It is to provide a composition for forming a conductive pattern by electromagnetic wave irradiation which can further reduce the decrease, and a conductive pattern forming method using the same.
- the present invention also provides a resin structure having a conductive pattern formed from the above-mentioned composition for forming a conductive pattern.
- the present invention is a polymer resin including a polycarbonate resin; And an electromagnetic wave absorbing inorganic additive, which absorbs electromagnetic waves having a wavelength in the infrared region, and which satisfies a characteristic in which the laser sensitivity Ls defined by Equation 1 is about 1.6 ⁇ -log (Ls) ⁇ 6.0.
- compositions for pattern formation :
- wt is a value representing the content (weight) of the electromagnetic wave absorbing inorganic additive as a weight fraction of the total composition when the total content (weight) of the composition for forming a conductive pattern is 1,
- the polymer resin further includes at least one resin selected from the group consisting of ABS resin, polyalkylene terephthalate resin, polypropylene resin and polyphthalamide resin, in addition to polycarbonate resin. It may include.
- the electromagnetic wave absorbing inorganic additive may include one or more conductive metal elements, and may include a non-conductive metal compound in which a cation and an anion are included and chemically bonded to each other. Can be. More specific examples of the electromagnetic wave absorbing inorganic additive having the form of such a non-conductive metal compound include CuCr0 2 , NiCr0 2 , AgCr0 2 .
- the electromagnetic wave absorbing inorganic additive may satisfy a characteristic in which the laser sensitivity Ls is about 1.6 ⁇ -log (Ls) ⁇ 5.6, and at the same time, By absorbing the electromagnetic wave having a wavelength in the infrared region can exhibit a property of generating a metal core containing the conductive metal element or its ions.
- the electromagnetic wave absorbing inorganic additive may be used as a single material stratifying these two properties together, and specific examples of such inorganic additives include the non-conductive metal compounds listed above.
- the electromagnetic wave absorbing inorganic additive may only stratify the laser sensitivity Ls of about 1.6 ⁇ -log (Ls) ⁇ 5.6, in this case, if necessary.
- Ls laser sensitivity
- a conductive seed former that generates a metal nucleus containing a conductive metal element or its silver may be additionally used.
- the conductive seed former may be applied and formed on the surface of the polymer resin
- the electromagnetic wave absorbing inorganic additive is Fe 3 (P0 4 ) 2 , Zn 3 (P0 4 ) 2 , ZnFe 2 ( It may include one or more selected from the group consisting of P 4 4 2 , NbOx and MoOx.
- the conductive seed former is copper (Cu), platinum (Pt), palladium (Pd), silver (Ag), gold (Au), nickel (Ni), tungsten (W), titanium 1 type selected from the group consisting of (Ti), chromium (Cr), aluminum (A1), zinc (Zn), tin (Sn), lead (Pb), magnesium (Mg), manganese (Mn) and iron (Fe) It may contain the above conductive metal, ions or complex ions thereof.
- the electromagnetic wave absorbing adjuvant may aid in the absorbent for the electromagnetic radiation representing the electromagnetic wave absorptive inorganic additive. This allows higher absorption and sensitivity in the electromagnetic radiation region even when electromagnetic absorbing inorganic additives are used, which exhibit relatively low laser sensitivities, e.g., about 5.6 ⁇ -log (Ls) ⁇ 6.0. have. Accordingly, the range of the electromagnetic wave absorbing inorganic additive applicable to form a good conductive pattern in the electromagnetic wave irradiation region can be further extended.
- the electromagnetic wave absorbing inorganic additive may be included in about 0.05 to 30% by weight, or about 0.1 to 20% by weight based on the total composition.
- the composition for forming a conductive pattern the laser electromagnetic wave having a wavelength of about 100nm to 1200nm, typically about 1064nm is irradiated with an average power of about 1 to 20W, black is about 1.5 to 20W, the irradiation region of the laser electromagnetic wave
- the plating may be carried out to form a composition applied to form a conductive pattern.
- the electromagnetic wave absorbing inorganic additive may be included as a particle having an average particle diameter of about 0.05 to 20 /, or about 0.1 to 15 zm.
- electromagnetic wave absorption aid about 0.01 to 20 weight percent of the composition.
- carbon-based black pigments such as carbon black may be included in about 0.01 to 5% by weight black is about 0.1 to 2% by weight
- titanium dioxide may be included in about 0.1 to 20% by weight, or about 5 to 10% by weight. have.
- composition for forming a conductive pattern is, in addition to each component described above, in the group consisting of thermal stabilizers, UV stabilizers, flame retardants, lubricants, antioxidants, inorganic layering agents, color additives, lamellar reinforcing agents, flow modifiers and functional reinforcing agents
- the at least one additive selected may further comprise from about 0.01 to 30 weight percent of the total composition.
- the present invention also comprises the steps of forming a resin worm by molding the above-mentioned composition for forming a conductive pattern into a resin product, or by applying to another product; Irradiating an electromagnetic wave having a wavelength of an infrared ray region to a predetermined region of the resin product or the resin layer; And forming a conductive metal layer by plating the irradiation region of the electromagnetic wave, thereby providing a method of forming a conductive pattern by direct irradiation of the electromagnetic wave.
- the present invention also provides a polymer resin substrate comprising a polycarbonate resin; An electromagnetic wave absorbing inorganic additive dispersed in the polymer resin substrate, absorbing electromagnetic waves having a wavelength in the infrared region, and satisfying a characteristic in which the laser sensitivity Ls defined by Equation 1 is 1.6 ⁇ -log (Ls) ⁇ 6.0; And it provides a resin structure having a conductive pattern comprising a conductive metal worm formed on a predetermined region of the polymer resin substrate.
- a predetermined region in which the conductive metal layer is formed may be applied to a region in which electromagnetic waves having a wavelength of an infrared region are irradiated onto the polymer resin substrate.
- the electromagnetic radiation region even if electromagnetic radiation in the infrared region is irradiated with a relatively low content of a special inorganic additive exhibiting electromagnetic wave absorption, and gentle irradiation conditions (e.g., low average power) which is commercially and generally applied, the electromagnetic radiation region
- a special inorganic additive exhibiting electromagnetic wave absorption
- gentle irradiation conditions e.g., low average power
- FIG. 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 another embodiment of the present invention in the order of processes.
- FIG. 2 shows the -log (Ls) value (X-axis) of the respective compositions and good conductive patterns when the conductive patterns are formed on the polycarbonate resin substrate using the conductive pattern forming compositions of Examples 1 to 17.
- FIG. This graph shows the relationship between the required laser electromagnetic wave and minimum power condition (Y axis).
- FIG. 3 shows -log (Ls) of each composition when a conductive pattern is formed on a polycarbonate resin substrate using the composition for forming a conductive pattern of Examples 18 to 34 (different from laser irradiation conditions from Examples 1 to 17). ) Is a graph showing the relationship between the value (X axis) and the minimum power condition (Y axis) of laser electromagnetic waves necessary for forming a good conductive pattern.
- FIG. 5 illustrates the formation of a good conductive pattern when the conductive pattern is formed on the polycarbonate resin substrate by using the composition for forming the conductive pattern of Example 17 and Example 52, wherein titanium dioxide is additionally used. Required This photo shows the progress of the test to determine the minimum power condition of the laser electromagnetic wave.
- composition for forming a conductive pattern according to a specific embodiment of the present invention, a method of forming a conductive pattern using the same, and a resin structure having a conductive pattern will be described.
- a polymer resin including a polycarbonate resin; And an electromagnetic wave absorbing inorganic additive that absorbs electromagnetic waves having a wavelength in the infrared region and that satisfies a characteristic in which the laser sensitivity Ls defined by Equation 1 is 1.6 ⁇ -log (Ls) ⁇ 6.0.
- a composition for formation is provided: [Formula 1]
- the effective radius of the electromagnetic wave absorbing inorganic additive calculated by the formula
- ⁇ I a value expressed as a weight fraction of the total content (weight) of the electromagnetic wave absorbing inorganic additive when the total content (weight) of the composition for forming a conductive pattern is 1,
- a method of forming a conductive pattern on a resin substrate such as a polymer resin product or a resin layer including a polycarbonate resin using a composition for forming a conductive pattern according to an embodiment of the present invention is as follows. After extruding and / or extruding the composition for forming the conductive pattern and molding it into a resin product or a resin layer, and irradiating electromagnetic waves such as a laser having a wavelength in the infrared region to the region to form the conductive pattern, Electromagnetic wave absorbing inorganic additives that are uniformly dispersed in the polymer resin substrate may cause these electromagnetic waves to be above a certain level. Will be absorbed.
- the surface of the polymer resin substrate in the electromagnetic wave irradiation region may have a certain level or more roughness.
- the electromagnetic wave absorbing inorganic additive absorbs electromagnetic waves having a wavelength in the infrared region, and generates, for example, a metal nucleus in the electromagnetic wave irradiation region, including a conductive metal element included in the inorganic additive, or the like. You can.
- the metal nucleus is coated at the time of the electromagnetic nucleus irradiation region, that is, the portion where the metal nucleus is generated with a certain level of surface roughness.
- the plating can be uniformly and well performed in one row, and the conductive metal layer formed by the plating can be attached with a relatively high adhesion to the surface of the polymer resin substrate to form a conductive pattern.
- the plating itself does not proceed properly due to the formation of the metal nucleus (ie, the conductive metal layer itself is not formed properly), and even if some plating proceeds, the adhesion of the conductive metal layer to the surface of the polymer resin substrate that is smooth is not achieved. Cannot be represented. Therefore, the conductive metal layer itself is not formed in the non-electromagnetic wave irradiation region, or even if some plating proceeds, the conductive metal layer by such plating can be removed very easily. Accordingly, the conductive metal layer remains selectively in only the electromagnetic wave irradiation region, thereby forming a fine conductive pattern having a desired shape on the polymer resin substrate.
- the metal nucleus is sufficiently formed and the seed can be good and uniform plating by seeding, By the surface roughness of a predetermined level or more, the conductive metal layer formed by the plating exhibits excellent adhesion, and thus a good conductive pattern can be formed.
- the metal nucleus serving as a seed during the plating may not be sufficiently formed to be uniform.
- the fine shape of the desired shape on the polymer resin substrate by the above-described method In order to form the conductive pattern better (to have higher adhesion to the polymer resin substrate surface) by uniform plating, in the electromagnetic radiation region, the electromagnetic wave absorbing inorganic additive may exhibit higher electromagnetic wave absorbing and / or sensitivity. Thus, it was confirmed that it is very important to sufficiently generate a metal nucleus serving as the seed, and to make the surface of the polymer resin substrate have a surface roughness of a predetermined level or more.
- the polymer resin substrate in particular, basically excellent physical properties when the irradiation conditions are darkened, such as simply increasing the content of the inorganic additive or increasing the electromagnetic wave irradiation power.
- Various physical properties such as mechanical properties of the polycarbonate-based resin substrate known to have can be greatly reduced.
- the laser electromagnetic wave having a wavelength in the infrared region of about 100 to 1200 nm for example, mild conditions that are commercially and generally applied to the electromagnetic radiation irradiation conditions without greatly increasing the content of the inorganic additives, For example, even when irradiated under mild conditions with an average power of about 1.5 to 15 W or about 1.5 to 20 W, it is possible to perform uniform plating on the surface of the polymer resin substrate in the electromagnetic wave irradiation region and to form a good conductive pattern showing excellent adhesion.
- compositions and related technologies that can be made.
- the present inventors continue to research to solve this technical request, and as a result, by controlling the type, content, shape and size of the electromagnetic wave absorbing inorganic additives, it is defined by the formula (1) represented by these inorganic additives It was confirmed that the physical property value of the laser sensitivity Ls could be adjusted. Furthermore, the inventors have found that such laser sensitivity Ls is approximately 1.6 ⁇ -log (Ls) ⁇ 6.0, more suitably approximately 1.6 ⁇ -log (Ls) ⁇ 5.6, or 2.0 ⁇ -log (Ls) ⁇ 5.0.
- Ls laser sensitivity Ls
- the inventors have found that such laser sensitivity Ls is approximately 1.6 ⁇ -log (Ls) ⁇ 6.0, more suitably approximately 1.6 ⁇ -log (Ls) ⁇ 5.6, or 2.0 ⁇ -log (Ls) ⁇ 5.0.
- the resin substrate including the inorganic additive exhibits low sensitivity to electromagnetic waves such as lasers, and thus the surface roughness that can achieve the excellent adhesion can be achieved.
- electromagnetic waves need to be irradiated with very strong power conditions of about 20 W or more. For this reason, the fall of the physical property of a polycarbonate resin base material can appear large.
- the electromagnetic radiation irradiation in these dark conditions is beyond the commercial and general application range, and the overall process cost can also be greatly increased.
- the minimum laser power, such as the minimum laser, required to cause denaturation of the resin substrate becomes about 1.0 W
- the type and content of -log (Ls) of about 1.6 or less Even if inorganic additives are used, it is difficult to adjust the electromagnetic wave irradiation conditions to an average power of less than about LOW.
- the use of the inorganic additive having the -log (Ls) of about 1.6 or less may result in deterioration of the physical properties of the resin substrate, depending on the economical efficiency of the overall process or the increase of the content of the inorganic additive. It can be difficult.
- the inventors When the electromagnetic wave is irradiated, the inventors have confirmed that the electromagnetic wave absorbing inorganic additives in the polymer resin substrate exhibit scattering properties due to the surface shape and size of the particles, together with the absorbency against the electromagnetic wave.
- the measured value of the BET specific surface area A (m 2 / g) is assumed to be 4 K Re 2 (m 2 ) / weight (g), the density B (g / cm 3 ) was assumed to be 3/4 [(weight ( g )) / (Re 3 (cm 3 ))], from which the effective radius was calculated.
- the radius Re was derived.
- the BET specific surface area A (m 2 / g) can be measured according to the conventional method for measuring the specific surface area of the inorganic particles
- the density B (g / cm 3 ) is the kind of material constituting the electromagnetic wave absorbing inorganic additives. Can be determined accordingly.
- the wt of the equation (1) is, as a factor to consider the content of the electromagnetic wave absorptive inorganic additive, the content at the time of the total amount (weight) of the above-mentioned conductive pattern forming composition to 1, the electromagnetic wave absorptive inorganic additive ( Weight) can be a value expressed as a weight fraction of the total composition (e.g., when the total composition of the inorganic additive is 3% by weight, wt is 0.03 which is a weight fraction of the total content of the composition 1). ).
- the Iaa is a constant for the electromagnetic wave absorbency exhibited by a particular inorganic additive, according to the type of the electromagnetic wave absorbing inorganic additive, the predetermined infrared region measured using a UV-vis-IR spectrum for the inorganic additive
- the absorbance of the electromagnetic wave absorbing inorganic additive calculated by the formula of absorbance ⁇ (from ⁇ ⁇ ⁇ ⁇ ) for an electromagnetic wave having a wavelength (for example, a wavelength of about 100 to 1200 nm, typically a wavelength of about 1064 nm).
- the present inventors calculated the property values of Ls from Re- 14 , wt and Iaa measured and calculated as described above, and as described above, these property values are about 1.6 ⁇ -log (Ls).
- the above-described relationship of about 1.6 ⁇ -log (Ls) ⁇ 6.0 is determined in consideration of physical properties of the polycarbonate-based resin among various polymer resin substrates, and in the composition for forming a conductive pattern of the embodiment, the polymer resin Includes a polycarbonate resin.
- the polycarbonate resin in consideration of the type of the polymer resin substrate such as the resin product or the resin layer to be obtained using the composition of one embodiment, in addition to the polycarbonate resin may further include additional polymer resins such as various thermoplastic resins or thermosetting resins. Of course.
- additional polymer resins include ABS resins, polyalkylene terephthalate resins, polypropylene resins, or polyphthalamide resins, which may be used with two or more selected resins or other polycarbonate resins. Various known resins may be further included.
- the electromagnetic wave absorbing inorganic additive contains, for example, at least one conductive metal element such as Cu, Ag, or Ni, and includes a cation and an anion, which are chemically ionically and selectively covalently bonded to each other.
- a non-conductive metal compound When a non-conductive metal compound having such a form is irradiated with an electromagnetic wave such as a laser, a metal nucleus containing the conductive metal element or the (ion) ion thereof from the non-conductive metal compound This metal nucleus can be selectively exposed in a predetermined region irradiated with electromagnetic waves to form an adhesive active surface of the surface of the polymer resin substrate.
- the sensitivity of electromagnetic waves is improved by satisfying the relationship of about 1.6 ⁇ -log (Ls) ⁇ 6.0, it is better formed. Can.
- this metal core and bonding the active surface it may proceed well, a uniform coating to a see d, in the electromagnetic wave irradiation area having a more satisfactory good adhesion to the substrate surface a polymer resin A conductive pattern can be formed.
- electromagnetic wave absorbing inorganic additive in the form of the non-conductive metal compound described above include CuCr0 2 , NiCr0 2 , AgCr0 2 CuMo0 2 , NiMo0 2 , .AgMo0 2 , NiMn0 2 , AgMn0 2 , NiFe0 2 , AgFe0 2 , CuW0 2 , AgW0 2 , NiW0 2 , AgSn0 2 , NiSn0 2 , CuSn0 2 , CuA10 2 , CuGa0 2 , Culn0 2 , CuT10 2 , CuY0 2 , CuSc0 2 , CuLa0 2 , CuLu0 2 , NiA10 2 , NiGa0 2 , Niln0 2 , NiT10 2 , NiY0 2 , NiSc0 2 , NiLa0 2 , NiLu0 2 , AgA10 2 , AgGa0 2 , Agl
- the non-conductive metal compounds exemplified above exhibit better absorption for electromagnetic waves having a wavelength in the infrared region, for example, wavelengths of about 100 nm to 1200 nm, typically about 1064 nm, thus providing about 1.6 ⁇ -log described above. (Ls) ⁇ 6.0 can be achieved.
- the non-conductive metal compounds may facilitate the reduction / precipitation of the conductive metal (for example, Cu, etc.) or ions thereof contained therein, and thus the metal nucleus, and the formation of an adhesive active surface. Therefore, by using these non-conductive metal compounds as an electromagnetic wave absorbing inorganic additive, it is possible to easily form a better conductive pattern having excellent adhesion to the polymer resin substrate in the electromagnetic wave irradiation region.
- the electromagnetic wave absorbing inorganic additive may satisfy the characteristic that the laser sensitivity Ls is about 1.6 ⁇ -log (Ls) ⁇ 5.6, At the same time, it is possible to exhibit a property of sufficiently forming the above-described metal nucleus and the adhesive active surface.
- the electromagnetic wave absorbing inorganic additive may be used as a single material that satisfies these two properties. Examples of such a single material may include the non-conductive metal compounds shown as the examples described above, and more preferably Cu-containing. Non-conductive metal compounds may be mentioned.
- the electromagnetic wave absorbing inorganic additive may satisfy only a characteristic in which the laser sensitivity Ls is about 1.6 ⁇ -log (Ls) ⁇ 5.6.
- Ls the laser sensitivity
- a conductive seed former that generates a metal nucleus may be further included in the composition of the above embodiment.
- examples of the electromagnetic wave absorbing inorganic additive may include at least one selected from the group consisting of Fe 3 (P0 4 ) 2 , Zn 3 (P0 4 ) 2 , ZnFe 2 (P0 4 ) 2 , NbOx, and MoOx. Can be mentioned.
- the conductive seed forming agent may be additionally used in order to form a metal nucleus and an adhesive active surface including the same to form a better conductive pattern.
- the conductive seed forming agent may be included in the polymer resin together with the electromagnetic wave absorbing inorganic additive, or may be applied and formed in the form of a solution or dispersion on the surface of the polymer resin substrate.
- a conductive seed is formed on the polymer resin substrate in the region irradiated with electromagnetic waves, and the conductive seed can grow during plating. As a result, it can play a role in facilitating good and uniform plating to enable formation of a good conductive metal layer.
- Such conductive seed formers include copper (Cu), platinum (Pt), palladium (Pd), silver (Ag), gold (Au), nickel (Ni), tungsten (W), titanium (Ti), chromium (Cr) At least one conductive metal selected from the group consisting of aluminum (A1), zinc (Zn), tin (Sn), lead (Pb), magnesium (Mg), manganese (Mn) and iron (Fe), or ions thereof It may include complex ions. More specifically, the conductive seed forming agent may be not only such a conductive metal, its ions or complex silver itself, but may be in any form such as metal nanoparticles, metal compounds or metal complexes containing them. . In addition, the conductive seed former may be provided and used in the form of a solution or dispersion containing the conductive metal, ions or complex ions thereof, or metal nanoparticles, metal compounds or metal complex compounds containing them.
- the group consisting of carbon black, smoke, flexible, lamp black, channel black, farnes black and acetylene black At least one carbon-based pigment pigment selected from; Or electromagnetic waves such as titanium dioxide (Ti0 2 ), which is a kind of white pigment. It may further comprise an absorption aid. Such electromagnetic wave absorption aid may be further improved by assisting the absorbency and / or sensitivity to the electromagnetic wave represented by the above-mentioned electromagnetic wave absorbing inorganic additive.
- the electromagnetic wave absorbing inorganic additive may be included in about 0.05 to 30% by weight, or about 0.1 to 20% by weight based on the total composition.
- the specific inorganic additives described above can be used in such amounts to reduce the physical property degradation of the polycarbonate-based resin substrate with the addition of the inorganic additives, so that the characteristics of about 1.6 ⁇ -log (Ls) ⁇ 6.0 It may be easier to achieve.
- electromagnetic wave absorption aid may be included in about 0.01 to 20% by weight based on the total composition.
- the carbon-based dark pigments such as carbon black, may be included in about 0.01 to 5% by weight, black is about 0.1 to 2% by weight ⁇ 3 ⁇ 4, titanium dioxide is about ⁇ to 20% by weight, black is about 0.5 to 10% by weight It may be included as.
- the electromagnetic wave absorbing inorganic additive may have a large spherical particle form, and may be included as a particle form having an average particle diameter of about 0.05 to 20, or about 0.1 to 15.
- the effective radius Re may be appropriately adjusted to be one factor that makes it easier to achieve a characteristic of about 1.6 ⁇ -log (Ls) ⁇ 6.0.
- the electromagnetic wave absorbing inorganic additive having the average particle diameter and particle shape may have an effective radius Re of about 0.1 to 1500, depending on the type and density of the material forming the same.
- the conductive pattern forming composition may have a laser electromagnetic wave having a wavelength of about 100 nm to about 1200 nm, typically about 1064 nm, about 1 to 20 W, or The composition may be irradiated with an average power of about 1.5 to 20 W, and the plating may be applied to the irradiation region of the laser electromagnetic wave to form a composition applied to form a conductive pattern.
- These electromagnetic radiation irradiation conditions are commercial, generally gentle irradiation conditions, when applying the composition of one embodiment, even under such irradiation conditions, in the electromagnetic wave irradiation region, achieve excellent electromagnetic sensitivity, constant on the polymer resin substrate
- the composition for forming a conductive pattern of the embodiment described above in addition to each component described above, a group consisting of a heat stabilizer, UV stabilizer, flame retardant, lubricant, antioxidant, inorganic filler, color additives, impact modifier, flow modifier and functional reinforcement
- One or more additives selected from may further comprise from about 0.01 to 30 weight « 3 ⁇ 4 of the total composition.
- an inorganic layering agent such as glass fiber may be included in an amount of about 0.5 to 30% by weight based on the total composition
- other additives such as impact modifiers, flame retardants, and flow modifiers may be included in an amount of 01 to 5% by weight of the total composition. May contain%.
- a method of forming a conductive pattern by direct irradiation of electromagnetic waves using the composition for forming a conductive pattern of the embodiment described above may include forming a resin layer by molding the composition for forming a conductive pattern of the above-described embodiment into a resin product or by applying it to another product; Irradiating an electromagnetic wave having a wavelength of an infrared ray region to a predetermined region of the resin product or the resin layer; And plating the irradiation area of the electromagnetic wave to form a conductive metal layer.
- FIG. 1 an example of the method of forming the conductive pattern is shown in a simplified step by step.
- the above-described composition for forming a conductive pattern may be molded into a resin product or applied to another product to form a resin layer.
- a product molding method or a resin layer forming method using a conventional polymer resin composition is particularly limited.
- the composition for forming the conductive pattern is extruded and engraved, and then formed into pellets or particles, and then injection molded into a desired form to prepare various polymer resin products. Can be.
- the polymer resin product or the resin layer thus formed may have a form in which the above-mentioned electromagnetic wave absorbing inorganic additive is uniformly dispersed on the resin substrate formed from the polymer resin.
- the above-mentioned electromagnetic wave absorbing inorganic additive may be uniformly dispersed throughout the entire area on the resin substrate and maintained in a non-conductive state.
- Electromagnetic waves can be irradiated.
- a surface roughness of a predetermined level or more may be formed on the surface of the polymer resin substrate in such an irradiation area, and the conductive metal element or its ions are reduced / precipitated from the electromagnetic wave absorbing inorganic additive or the like to form a metal core including the same.
- Can be generated see second figure in FIG. 1).
- the electromagnetic radiation irradiation region that is, the metal core is generated, has a surface roughness of a predetermined level or more.
- uniform plating proceeds well, and the conductive metal layer formed by the plating adheres to the surface of the polymer resin substrate with a relatively high adhesive force to form a conductive pattern.
- the plating itself does not proceed properly (ie, the conductive metal layer itself is not formed properly) due to the non-formation of the metal nucleus, and even if some plating proceeds, the adhesion to the surface of the polymer resin substrate having the conductive metal layer is smooth. Cannot be represented. Therefore, the conductive metal worm itself is not formed in the non-irradiated region of the electromagnetic wave, or even if some plating is performed, the conductive metal layer by the plating can be removed very easily.
- the conductive metal layer of the non-electromagnetic wave irradiated region is removed as necessary, the conductive metal layer remains selectively in the electromagnetic wave irradiated region to form a fine conductive pattern of a desired shape on the polymer resin substrate. It can be formed favorably.
- the laser electromagnetic wave having a wavelength corresponding to the infrared region for example, wavelengths of about 100 nm to 1200 nm, or about 1060 nm to 1070 nm, or about .1064 nm, is irradiated with an average power of about 1 to 20 W.
- the conductive metal layer may be formed by plating the electromagnetic wave irradiation area.
- a conductive metal layer exhibiting excellent adhesion to the polymer resin substrate may be formed in the electromagnetic radiation irradiation region, and the conductive metal layer may be easily removed in the remaining regions. Accordingly, a fine conductive pattern may be selectively formed only in a predetermined region on the polymer resin substrate.
- the polymer resin substrate may be treated with an electroless plating solution containing a reducing agent and a conductive metal ion.
- the conductive metal ions contained in the electroless plating solution may be chemically reduced to form a conductive pattern, and in particular, the conductive pattern may be well formed with excellent adhesion in the electromagnetic wave irradiation region.
- the conductive pattern may be better formed by using the seed as a seed.
- a resin structure having a conductive pattern obtained by the above-described composition for forming a conductive pattern and a conductive pattern forming method is provided.
- a resin structure includes a polymer resin substrate including a polycarbonate resin; An electromagnetic wave absorbing inorganic additive dispersed in the polymer resin substrate, absorbing electromagnetic waves having a wavelength in the infrared region, and stratifying a characteristic in which the laser sensitivity Ls defined by Equation 1 is 1.6 ⁇ -log (Ls) ⁇ 6.0; And a conductive metal layer formed on a predetermined region of the polymer resin substrate.
- a predetermined region in which the conductive metal layer is formed may be applied to a region in which electromagnetic waves having a wavelength of an infrared region are irradiated onto the polymer resin substrate.
- the resin structure described above may be made of various resin products or resin layers such as mobile phone cases having conductive patterns for antennas, other RFID tags, various sensors, or MEMS.
- Various resin products or resin layers which have conductive patterns, such as a structure, can be used.
- 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.
- Spherical non-conductive metal compound powders of 0 "0 2 were used with the polycarbonate resin.
- thermal stabilizers IR1076, PEP36
- UV stabilizers UV 32 9
- lubricants EP184 which are additives for processing and stabilization
- S2001 layered reinforcement
- the extruded pellet-like resin composition was injection molded into a substrate having a diameter of 100 mm and a thickness of 2 mm at about 260 to 280 ° C.
- the plating solution was prepared by dissolving 3 g of copper sulfate, 14 g of Rotsel salt, and 4 g of sodium hydroxide in 100 ml of deionized water. To 40 ml of the plating solution prepared, 1.6 ml of formaldehyde was added as a reducing agent. The resin substrate whose surface was activated with a laser was immersed in the plating solution for 3 to 5 hours, and then washed with distilled water. Through this process, a conductive pattern having a thickness of 10 or more Formed.
- the adhesion performance of the formed conductive pattern (or plated layer) was evaluated using the ISO 2409 standard method. In this evaluation, a 3M scotch # 371 tape having an adhesive force of 4.9 N / 10 mm width was used, and a cross cut test of a 10 X 10 grid was applied to the conductive pattern. It was evaluated under the ISO class of:
- class 1 grade peeling area of the conductive pattern is greater than 0% and 5% or less of the conductive pattern area to be evaluated;
- Class 2 Class: Peel Area of Conductive Pattern
- class 4 peeling area of the conductive pattern o 'More than 35% of the conductive pattern area to be evaluated 65% or less;
- Class 5 Peeling area of conductive pattern 0 'More than 65% of the area of the conductive pattern to be evaluated.
- Example 1 while increasing the average power for irradiating the laser within the range of 1 to 30W, the formation of the above-described conductive pattern and the evaluation of its adhesion strength was repeated, and according to the result is necessary for good conductive pattern formation
- the minimum power condition of the laser was calculated and the results are shown in Table i below.
- a conductive pattern was formed in the same manner as in Example 1, except that the kind of the non-conductive metal compound, the BET specific surface area (change in particle size), and its content (wt) were changed as summarized in Table 1 below.
- the physical properties of the electrically conductive metal compound and the conductive pattern (Iaa, wt, Re, and one log (Ls), and the minimum power condition of the laser electromagnetic wave required for forming a good conductive pattern) are collectively shown in Table 1 below.
- LGD additive 1 CuCr0 2 ; LGD additive 2: CuA10 2 LGD additive 3: CuS0 4 ; LGD additive 4: Cul; LGD additive 5: CuSn 2 (P0 4 ) 3 .
- a conductive pattern was formed by the same composition and method as in Examples 1 to 17, except that the laser irradiation condition was changed to the condition of Laser condition 2 below.
- LGD additive 1 CuCr0 2 ; LGD additive 2: CuA10 2 LGD additive 3: CuS0 4 ; LGD additive 4: Cul; LGD additive 5: CuSn 2 (P0 4 ) 3 .
- Examples 35 to 51 Formation of Conductive Patterns by Laser Direct Irradiation Conductive patterns were formed in the same composition and method as in Examples 1 to 17, except that carbon black having a weight of ⁇ 3/4 was added to Examples 1 to 17 and the content of polycarbonate resin was reduced by that amount.
- a conductive pattern was formed in the same composition and method as in Example 17, except that 5 wt% titanium dioxide was added to Example 17, and the polycarbonate resin content was reduced by that amount.
- Example 52 the general properties (Iaa, wt, Re, and -log (Ls)) of the non-conductive metal compound are the same as those of Example 17, and the minimum power condition of the laser electromagnetic wave necessary for forming a good conductive pattern is It was determined by repeated testing according to the same method as 17, in particular the method shown in FIG. As a result, it was confirmed that a good conductive pattern could be formed under a minimum power of 14.3 W (for Example 17, a good conductive pattern was not obtained until 14.3 W, and the minimum power was determined to be 17.4 W).
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US15/510,967 US10837114B2 (en) | 2014-10-23 | 2015-10-21 | Composition for forming conductive pattern by irradiation of electromagnetic waves, method for forming conductive pattern using same, and resin structure having conductive pattern |
CN201580056626.7A CN107075239B (zh) | 2014-10-23 | 2015-10-21 | 通过电磁波辐射形成导电图案的组合物、形成导电图案的方法以及具有导电图案的树脂结构 |
PCT/KR2015/011155 WO2016064192A1 (ko) | 2014-10-23 | 2015-10-21 | 전자기파 조사에 의한 도전성 패턴 형성용 조성물, 이를 사용한 도전성 패턴 형성 방법과, 도전성 패턴을 갖는 수지 구조체 |
EP15852488.4A EP3176792B1 (en) | 2014-10-23 | 2015-10-21 | Composition for forming conductive pattern by electromagnetic wave radiation, method for forming conductive pattern using same, and resin structure having conductive pattern |
JP2017513795A JP6389326B2 (ja) | 2014-10-23 | 2015-10-21 | 電磁波照射による導電性パターン形成用組成物、これを用いた導電性パターン形成方法と、導電性パターンを有する樹脂構造体 |
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KR10-2014-0144490 | 2014-10-23 | ||
PCT/KR2015/011155 WO2016064192A1 (ko) | 2014-10-23 | 2015-10-21 | 전자기파 조사에 의한 도전성 패턴 형성용 조성물, 이를 사용한 도전성 패턴 형성 방법과, 도전성 패턴을 갖는 수지 구조체 |
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KR101717753B1 (ko) * | 2013-11-29 | 2017-03-17 | 주식회사 엘지화학 | 도전성 패턴 형성용 조성물, 이를 사용한 도전성 패턴 형성 방법과, 도전성 패턴을 갖는 수지 구조체 |
KR101774041B1 (ko) | 2014-09-17 | 2017-09-01 | 주식회사 엘지화학 | 도전성 패턴 형성용 조성물 및 도전성 패턴을 가지는 수지 구조체 |
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Cited By (8)
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WO2018178020A1 (de) * | 2017-03-30 | 2018-10-04 | Chemische Fabrik Budenheim Kg | Verwendung von kristallwasserfreien fe(ii)-verbindungen als strahlungsabsorber |
CN110475815A (zh) * | 2017-03-30 | 2019-11-19 | 化学制造布敦海姆两合公司 | 无结晶水Fe(II)化合物作为辐射吸收剂的用途 |
US10793437B2 (en) | 2017-03-30 | 2020-10-06 | Chemische Fabrik Budenheim Kg | Method for the manufacture of Fe(II)P/Fe(II)MetP compounds |
TWI758432B (zh) * | 2017-03-30 | 2022-03-21 | 德商坎斯菲立克布登漢兩合公司 | 無結晶水Fe(II)化合物作為輻射吸收劑的用途 |
US11536880B2 (en) | 2017-03-30 | 2022-12-27 | Chemische Fabrik Budenheim Kg | Use of crystal water-free Fe(II) compounds as radiation absorbers |
US11718727B2 (en) | 2017-03-30 | 2023-08-08 | Chemische Fabrik Budenheim Kg | Method for manufacturing electrically conductive structures on a carrier material |
CN108295868A (zh) * | 2018-03-06 | 2018-07-20 | 湖北文理学院 | AgCrO2-CuCr2O4复合材料、其制备方法及应用 |
CN108295868B (zh) * | 2018-03-06 | 2020-11-06 | 湖北文理学院 | AgCrO2-CuCr2O4复合材料、其制备方法及应用 |
Also Published As
Publication number | Publication date |
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CN107075239B (zh) | 2019-07-05 |
KR101722744B1 (ko) | 2017-04-03 |
EP3176792A1 (en) | 2017-06-07 |
EP3176792B1 (en) | 2020-06-17 |
JP2017535028A (ja) | 2017-11-24 |
JP6389326B2 (ja) | 2018-09-12 |
KR20160047931A (ko) | 2016-05-03 |
EP3176792A4 (en) | 2018-03-28 |
CN107075239A (zh) | 2017-08-18 |
US10837114B2 (en) | 2020-11-17 |
US20170275764A1 (en) | 2017-09-28 |
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