WO2016043542A1 - Composition for forming conductive pattern and resin structure having conductive pattern - Google Patents

Composition for forming conductive pattern and resin structure having conductive pattern Download PDF

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Publication number
WO2016043542A1
WO2016043542A1 PCT/KR2015/009786 KR2015009786W WO2016043542A1 WO 2016043542 A1 WO2016043542 A1 WO 2016043542A1 KR 2015009786 W KR2015009786 W KR 2015009786W WO 2016043542 A1 WO2016043542 A1 WO 2016043542A1
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resin
conductive pattern
conductive
composition
non
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PCT/KR2015/009786
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French (fr)
Korean (ko)
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정한나
박치성
이하나
박철희
김재현
전신희
성은규
이수정
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주식회사 엘지화학
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Abstract

The present invention relates to a composition for forming a conductive pattern and a resin structure having a conductive pattern, wherein the composition makes it possible to form a fine conductive pattern on various polymer resin products or resin layers through a simple process, and can more effectively meet needs of the art, such as displaying various colors. The composition for forming a conductive pattern, comprises: a polymer resin; and a non-conductive metal compound having a predetermined chemical structure, and may be a composition for forming a conductive pattern through electromagnetic irradiation, by which a metal nucleus is formed from the non-conductive metal compound.

Description

【Specification】

[Name of the Invention

Resin structure having a composition and a conductive pattern for conductive pattern forming

- mutual quotation of the related application (s);

This application claims the benefit of priority based on the September 17 issue of Korea Patent Application No. 10-2014-0123893 and No. 16 dated September 2015 Korea Patent Application No. 10-2015-0130984, 2014, and of the Korea Patent Application everything described in the literature are included as part of the specification.

[Technology]

The present invention compositions and for conductive pattern forming, which can be able to form a fine conductive pattern in a simplified process for the various polymer resin products or resin layer, and than charged and effectively the needs of the art, such as various colors ^ It relates to a resin structure having a conductive pattern.

[Background Art]

As microelectronic technology advances in recent years, there has been increasing demand for various types of resin products or resin layer such as a polymer resin base material (or product) fine conductive pattern is formed on the structure surface. Conductive pattern of such a polymer resin base material surface can be applied to form a variety of objects in the antenna, and various sensors, MEMS structure or a RFID tag incorporated in an electronic device case.

In this way, there have been proposed and growing interest in technology for forming a conductive pattern on a substrate surface a polymer resin, a few techniques relating thereto. However, the method still can more effectively take advantage of these technologies to a situation that is not being offered.

Can be, for example, according to the technique previously known, considered a method of forming a conductive pattern by applying a photolithography after forming a metal layer on the substrate surface a polymer resin, or forming the conductive pattern by printing a conductive paste. However, in the case of forming a conductive pattern according to this technique, or the necessary process equipment or too complicated, there is a good and even the drawback to be difficult to form a fine conductive pattern.

The more simplified process development of the technology capable of forming fine conductive patterns on the polymeric resin substrate surface more effectively with this has been required before. As one of technologies to meet the needs of this art, to include a special inorganic additive in the resin, proceed to investigate the laser or the like electromagnetic radiation to a portion to form the conductive pattern, plating to such an electromagnetic wave irradiation. Area polymeric resin It may bar a method for easily forming a conductive pattern on a substrate surface is known.

By the way, in this conductive pattern forming method, since the kinds of things the proposed the inorganic additives before extremely limited, various needs in the art, for example, it is difficult to cheungjok the requirements such as various colors. Therefore, it is necessary for the development of each variety of inorganic additives to meet the various needs of the industry.

[Contents of the present invention;

- to solve problems;

The present invention provides a simplified process with a fine electrically conductive and able to form patterns, various colors, such as the composition for the conductive pattern formed to be able to better meet the needs of the art in the various polymer resin products or resin layer to.

The invention also from such a composition for the conductive pattern forming, provide a resin structure having a conductive pattern formed by a conductive pattern forming method.

[Solving means of a problem]

The present invention is a polymeric resin; And to be represented by the general formula 1, Cu or M of five oxygen atoms are distorted square non-conductive metal compounds having the structure surrounding the has the structure or Cu or M surrounded by a pyramid with six oxygen atoms are distorted octa head Ron form the inclusion, and by electromagnetic wave irradiation, provides a composition for forming a conductive pattern by electromagnetic wave irradiation are the non-metal core formed from a conductive metal compound.

Formula 1

Figure imgf000004_0001

In formula 1, and M is at least one metal selected from the group consisting of Zn, Mg, Ca, Sr and Ba, X satisfies the condition of 0≤x <2.

Such non-three-dimensional structure of the non-conductive metal compounds may be determined according to the kind of X and / or M of the formula (I). Specifically, X is 0 Cu 2 P 2 0 7 may have a structure to surround the Cu in the five oxygen is distorted square pyramids (di storted square pyramid) shape. On the other hand, if X is greater than 0, the structure M is Zn black is Mg If the non-conductive metal compounds of the formula 1 Cu or M of six oxygen atoms are distorted octa head Ron (di storted octahedron), enclosed in the form to have, and the M is Ca, Sr or Ba is a non-conductive metal compounds of the formula (1) can have the structures surrounding the Cu or M to the square pyramid shape with five oxygen is distorted.

On the other hand, in the above-mentioned conductive pattern forming composition, the polymer resin may be a thermosetting resin or a thermoplastic resin, and specific examples include, ABS (Acryloni ti le poly-butadiene styrene) resin, polyalkylene terephthalate resin more thereof , there may be mentioned a polycarbonate resin, polypropylene resin and poly one or more selected from the group consisting of a phthalamide resin.

And, in the above-mentioned conductive pattern forming composition, the non-conductive metal compounds may be included as about 0. 1 to 15% by weight of the total composition.

Further, for the conductive pattern forming composition may further comprise a flame retardant, a heat stabilizer, UV stabilizer, a lubricant, an antioxidant, an inorganic layer assumption, color additives, one or more additives selected from the group consisting of an impact modifier and a functional modifier.

The present invention also provides a resin structure is formed by using the above-described composition for the conductive pattern forming a conductive metal layer (conductive pattern) on the surface of the substrate polymer resin. Resin structure having the conductive pattern is a polymer resin base material; And is dispersed in a polymer resin base material, is represented by the formula 1, Cu or M 5 oxygen atoms surround the structure or Cu or M surrounded by a distorted square pyramid with six oxygen atoms are distorted octa head Ron form a non-conductive metal compounds having the structure; Bonding an active surface containing a metal nucleus exposed to the polymeric resin substrate surface having a predetermined area; And it may include a conductive metal layer formed on the adhesion surface activity.

In this resin structure having a conductive pattern, a predetermined region is the active adhesive surface and the conductive metal layer may correspond to the electromagnetic wave irradiation area on the polymeric resin base.

[Effect of the Invention] According to the invention, the composition for the conductive pattern formed to be on the polymeric resin substrate, such as various polymer resin products or resin layer, to form a fine conductive pattern in a very simplified step of irradiating an electromagnetic wave such as a laser and, the resin structure is provided with a conductive pattern formed therefrom.

In particular, the use of the above-mentioned conductive pattern forming composition, while still resin structure cheungjok the needs of the industry more effectively party to implement various colors in the (various polymer resin products or resin layer and the like), a good conductive pattern on such a resin structure It can be easily formed.

Accordingly, via the use of such a composition for forming a conductive pattern, it is possible to form such as a mobile phone or tablet PC case such as an antenna conductive pattern, on the RFID tags for various resin products, various sensors, MEMS structure very effectively.

[Brief description of drawings]

1 is Cu 2 contained in the composition for forming a conductive pattern according to one embodiment - a graph showing the absorbance of the wavelength (nm) of the x Zn x P 2 0 7.

2 is a view showing a simplified example of a method of forming a conductive pattern by using a composition according to one embodiment in step-by-step process.

3 is a view showing a XRD pattern of the non-conductive metal compounds synthesized in Example 3.

4 is a view showing a XRD pattern of the non-conductive metal compounds synthesized in Example 4.

5 is a view showing a XRD pattern of the non-conductive metal compounds prepared in Example 5.

6 is a view showing a XRD pattern of the non-conductive metal compounds synthesized in Example 6.

Figure 7 is exemplary. A diagram showing a 'XRD pattern of the non-conductive metal compounds synthesized in seven.

- specific information for carrying out the invention;

According to the specific implementation of the invention hereinafter it will be described the resin or the like structure having the conductive pattern formed for the conductive pattern forming composition therefrom. According to one embodiment of the invention, the polymeric resin; And to be represented by the general formula 1, Cu or M of five oxygen atoms are distorted square non-conductive metal compounds having the structure surrounding the has the structure or Cu or M surrounded by a pyramid with six oxygen atoms are distorted octa head Ron form the inclusion, and by electromagnetic wave irradiation, electromagnetic wave irradiation is a metal nucleation from the non-conductive metal compounds for conductive pattern forming compositions are provided by the.

Formula 1

Cu 2 - x M x P 2 0 7

In formula 1, and M is at least one metal selected from the group consisting of Zn, Mg, Ca, Sr and Ba, X satisfies the condition of 0≤x <2.

Although described in more detail below, the use for conductive pattern forming compositions these non comprises a conductive metal compound and then forming the polymer resin products or resin layer, the electromagnetic radiation of about 700nm to 3000nm range (near infrared to infrared range) in a predetermined area When irradiated, the non-it can be a metal core formed from a conductive metal compound. In the non-conductive metal compounds are chemically stable in a typical environment, the areas exposed to electromagnetic waves such as near-infrared wavelengths, and may be the metal nucleation easier. Accordingly, in order to easily form the conductive pattern by the irradiation of electromagnetic waves directly to the composition for forming the conductive pattern may include a non-conductive metal compounds showing a high absorbance in the near infrared region.

Optical properties of the compounds generally containing a transition metal is related to the energy level of the d- orbitals. The transition metal is the transition metal of the d- orbitals are all if the energy level equal gajina ligand present energy level of the d- orbitals of the transition metal according to the metal atom and local symmetry (local symmetry) make up the ligand, if present free reactor It is divided into multiple parts (crystal field theory). At this time, all of the d- orbitals of the transition metal atom filled with electron-not a state, the transition which is available in the energy level E is higher in a low energy level, is known as the transition dd (dd transi t ion) of the transition metal .

Since the non-conductive metal compound of Chemical Formula 1 include Cu 2+ electrons filled in a part of the d orbital, non-conductive metal compounds of the formula I may exhibit the optical properties due to dd transition. In particular, the transition between the energy level caused by the unique three-dimensional structure described above of the non-conductive metal compounds represented by the above formula (1) contains less of a visible light region (from about 300nm to about 700nm), a near infrared to infrared region (from about 700nm to about 3000nm ) because it contains a large part, the absorption of near-infrared region of the non-conductive metal compounds of the formula (1) is related to the energy level of the d- orbitals. Specifically, the number of ligand of the Cu or M according to the X and / or the type of M of the general formula (1); And the structure is Cu or M and the ligand forms can be modified.

In one embodiment X satisfies the condition of 0 <x <2 in the formula (I) and M is Ca, Sr or and at least one metal selected from the group consisting of Ba; Or for the case where X is 0, the non-conductive metal compounds of formula (1) include the structures surrounding the central atom is Cu or M of the local symmetry (local symmetry) to five oxygen atoms are distorted square pyramids (distorted square pyramid) shape can.

Further, if at least one metal selected from the group satisfies a condition of X is 0 <x <2 Formula 1 In another example one, and M is made of Zn and Mg, the non-conductive metal compounds of the formula I is localized symmetry (local symmetry) surround the central atom is Cu or M of six oxygen atoms are distorted octa head Ron (distorted octahedral) forms may comprise the structure.

D- orbital energy level of Cu 2+ in the structure as described above can be formed to absorb the electromagnetic radiation of near-infrared region. Thus, the non-conductive metal compounds of formula (I) can easily form a metal nuclei by the electromagnetic wave of the near infrared region.

In particular, existing in the center of a distorted square pyramids Cu 2+ can be located in the area (non- centrosymmetric site) does not have a center of symmetry Laporte allowed transition (Laporte allowed transition) in the d- orbitals of Cu 2+ . As a result, either X is 0 in the formula (1); Or when X is, but satisfies the condition of 0 <x <2 M is Ca, the at least one metal selected from the group consisting of Sr and Ba, the non-conductive metal compounds of formula (I) is a near infrared region showed a strong absorption band in the near infrared region more easily by the electromagnetic waves that it is possible to form a metal nuclei. ,

Typically, the non-conductive metal compounds showing a high absorbance in the near infrared region is not appropriate to implement the polymeric resin products or resin layer of different color to show a high absorbance in the visible light region. For example, compounds such as CuCr 2 0 4 having a spinel structure are difficult to implements the polymer resin products or resin layer of various colors according to represent the dark hoksaek (dark black). On the other hand, the non-conductive metal compound of Formula 1 has a low absorbance in the visible light range, showing a high absorbance in the near infrared to infrared region can be implemented a polymeric resin products or resin layer of various colors.

Figure 1 shows one example of a non-conductive metal compound of Formula 1 Cu 2 - shows the absorbance (Absorbance) of x Zn x P 2 0 7. Absorbance is calculated as expression 1, in accordance with the Kubelka Munk equation eu, R is a di f ref lectance fuse that can be measured by a UV-Vi s spectroscopy * ible.

[Equation 1]

Absorbance (Absorbance) = (1-R ) 2 / 2R = reflectance)

Specifically, the spectrum of Figure 1 is an average particle size of 0.1 to lum of Cu 2 - and x Zn x P 2 0 7 of the compound absorbance measurements results, shows the absorbance results of the X value of the formula (I). Referring to Figure 1, the non-conductive metal compounds of formula (1) represents a low absorbance in the visible region (300nm to about 700nm), it is confirmed refers to high absorbance in the near infrared to infrared region (from about 700nm to 3000nm). Accordingly, the non-conductive metal compounds of the formula I may suitably be used to implement a variety of fine conductive. Polymer resin products or resin layer of the color pattern is formed.

In particular, the absorption of visible light is viewed becomes lower as the value of X is increased in FIG. This means that by controlling the content of M can provide a brighter color of the resin structure, even if a small amount of pigment in the composition may implement the white polymer or resin product or resin layer of the desired color. However, the present invention is Cu 2 - x Zn x P 2 is not limited to 0 to 7, it can be implemented by the general formula (I) of the M and the polymer resin products or resin layer of the light color by controlling the X.

These non After use for conductive pattern forming composition comprising a conductive metal compound forming the polymer resin products or resin layer, when irradiated with a laser beam, such as an electromagnetic wave in a predetermined area, the non-can be a metal core formed from a conductive metal compound. One of the non-conductive metal compounds are chemically stable under normal circumstances, in the region exposed to electromagnetic radiation of near-infrared light or the like, can be a non-metal nuclear easily formed from conductive metal compound. The thus formed metal nuclei is selectively exposed in a predetermined area of ​​the electromagnetic wave it is irradiated to form the adhesive polymer resin, the active surface of the substrate surface. Then, the chemical reduction process to metal nuclei, etc., or may be by it to the seed when the electroless plating to the plating solution including a conductive metal ions, a conductive metal layer formed on the active surface adhesive, which includes the metal core. In particular, as a ^, a non-conductive by the structural features of the metal compound, when the non-electromagnetic wave is irradiated to the near infrared region of the conductive metal compounds, may also be easy to form a metal core with a low power electromagnetic wave. Also, the metal core can be easily forming a conductive pattern by plating it, for reducing, or plating method, for example, electroless Cu-.

On the other hand, in the one embodiment the composition, the non-conductive metal compounds are chemically also a solution which not only exhibit a non-conductive before the electromagnetic wave irradiation in the near infrared region, having the polymer resin and a good compatibility, used for the reduction, or plating stable and has the property of maintaining the non-conductive.

Thus, in such non-conductive metal compounds are regions that are not irradiated with the electromagnetic wave, is kept chemically stable in a uniformly dispersed state in the polymer resin base material can exhibit a non-conductive. On the other hand, in the electromagnetic wave of the near infrared wavelength of the irradiated predetermined area easily metal nucleation in the previously described principle from the non-conductive metal compounds, and thus it can easily form a fine conductive pattern.

Thus, using the example composition of the above-described one embodiment, on a polymer resin base material such as various polymer resin products or resin charge, it is possible to form a fine conductive pattern in a very simplified step of irradiating an electromagnetic wave such as a laser, in particular, near IR a low power electromagnetic wave due to the high absorbance region can also be very easily form a metal nuclei which promote the formation of the conductive pattern. In addition, the more effectively the needs in the art that the non-conductive metal compounds are to implement a variety of colors such as various polymer resin products only relative to the use of small color additives do not substantially colored with the colors of various polymer resin products or resin layer cheungjok can. On the other hand, in the composition embodiment the conductive pattern formed one above, as the polymer resins can be used without limitation any of the thermosetting resin or thermoplastic resin that can form a variety of polymeric resin product or resin. In particular, a specific non-conductive metal compounds described above may exhibit a wide range of polymer resins with good compatibility and uniform dispersibility, one embodiment the composition can be molded into a variety of resin products or resin layer, including a variety of polymeric resin . Specific examples of such polymer resin, (Acryl oni tile poly-but di ene styrene) ABS resin, polybutylene terephthalate resin or polyethylene terephthalate resin, and the like of the polyalkylene terephthalate resin, polycarbonate resin, polypropylene resin, or and the like polyphthalamide resin, and in addition may comprise a different polymer resin.

Further, in the above-mentioned conductive pattern forming composition, the non-conductive metal compound of Chemical Formula 1 may be included as about 0. 1 to 15 parts by weight, or from about 1 to 10 parts by weight ¾ for the entire composition, may contain the polymer resin of the remaining content have. According to this content range, while properly maintaining the basic properties such as mechanical properties of the polymer resin products or resin layer formed from the composition can be preferably exhibit a characteristic of forming a conductive pattern on a predetermined area by the electromagnetic wave irradiation.

Further, for the conductive pattern forming composition comprises in addition to a polymer resin and a predetermined non-described conductive metal compounds, flame retardants, heat stabilizers, UV stabilizers, lubricants, antioxidants, inorganic fillers, color additives, from the group consisting of cheunggyeok reinforcing agents and functionality adjuvant It may further include at least one selected more additives. By addition of such additives, it is possible to appropriately enhance the physical properties of the resin structure, resulting from one embodiment the composition. Such additives of, for the color additives, for example, in the case of a pigment, etc., is included in an amount of about 0.1 to 10% by weight, it is possible to give a desired color to the resin structure.

Representative examples of such additives include color pigments, ZnO, ZnS, Tal c, Ti0 2,

Sn0 and a white pigment, such as 2, or BaS0 4, can be used in addition to color additives, and a variety of colors and pigments are known to be available in the polymer resin composition from before, of course.

The flame retardant may be one containing a phosphorus-based flame retardant and inorganic flame retardant. More specifically, the phosphorus-based flame retardant include triphenyl phosphate (tr iphenyl phosphate, TPP), the tree-party Ile carbonyl phosphate (tr ixylenyl phosphate, TXP), tricresyl phosphate (tr i cresyl phosphate, TCP), or triisopropyl phenyl phosphate, phosphoric acid ester-based flame retardant, or the like (tr ii sophenyl phosphate, RE0F0S); Aromatic polyphosphate (aromat ic polyphosphate) flame retardants; Polyphosphate-based flame retardant; Or you can use the red phosphorus-based flame retardant and the like, may be used in addition to all of the various phosphorus-based flame retardant known to be usable in the resin composition without limitation. Further, the inorganic flame retardant is aluminum hydroxide, magnesium hydroxide, zinc borate, molybdenum oxide (Mo0 3), molybdenum peroxide salts (Mo 2 0 7 2_), calcium-zinc molybdate phosphate, antimony trioxide (Sb 2 0 3) , or antimony pentoxide (Sb 2 0 5), and the like. However, it is the example of the inorganic flame retardant is not limited to this, it is possible to use all without limitation in the use of various inorganic flame retardants are known to be available in other resin compositions.

In the case of cheunggyeok reinforcing agents, thermal stabilizers, such as UV stabilizers, lubricants or antioxidants, about 0.01 to 5% by weight, or is included in an amount of about 0.05 to 3% by weight, it can suitably express the desired physical properties to the resin structure have.

On the other hand, in the following it will be described a method of forming a conductive pattern by the phase polymeric resin substrate, such as by using the composition for example a conductive pattern implement one described above formed, a resin product or resin layer, the electromagnetic waves directly investigated in detail . The process for forming a conductive pattern, or molding the composition for the above-described conductive pattern forming the resin product, can be applied to other product forming a resin layer; Generating a metal core from a non-conductive metal compound particles of the general formula (1) by irradiating an electromagnetic wave in a predetermined area of ​​the resin product or resin; And then reducing, or plating an area that caused the metal nucleus by chemical may include a step of forming a conductive metal layer.

Reference to the accompanying drawings, a method of forming such conductive patterns is described as follows for each phase. For reference, Figure shows a simplified example of the conductive pattern forming method as a process step in the second.

In the conductive pattern forming method, first, it is possible to form a resin layer forming the above-described composition for the conductive pattern forming the resin, or by coating on the other products. At forming the resin layer or molding of such a resin product, a product is molded using a conventional polymer resin composition or the resin layer forming method can be applied without limitation. For example, according as the use of the composition forming the resin product, and forming the above-mentioned conductive pattern forming composition by extrusion and a nyaenggak after pellet or particle form, which was injection-molded into the desired shape to produce a wide range of polymeric resin product can.

The thus formed polymer resin products or resin layer on the resin base material formed from the polymeric resin, may have the above-described particular non-conductive metal compounds are uniformly dispersed form. In particular, the non-conductive metal compound of the formula (1) can be held in a state having a so have a good compatibility and chemical stability and a variety of polymeric resin, were uniformly dispersed over the entire area on the non-conductive resin base. After forming such a polymeric resin products or resin layer, it can be a predetermined region of the resin product or resin layer to form a conductive pattern as shown in the first drawing of Figure 2, examine an electromagnetic wave such as a laser . When such an electromagnetic wave irradiation, can generate the non-conductive metal nuclei from the metal compound (as shown in the second diagram of Fig. 2).

More specifically, performing the metal nucleation step by the electromagnetic wave irradiation, and a portion of the non-conductive metal compounds of the formula (1) is a metal core therefrom occurs while exposing a predetermined surface area of ​​the resin product or resin, and more It may form an activated adhesive active surface so as to have a high adhesion. According to this bonding the active surface is selectively formed only in a certain area of ​​the electromagnetic wave is irradiated, and when Garachine the plating step to be described later, wherein the conductive metal layer can be selectively formed on the polymer resin base material in a predetermined area. More specifically, when the electroless plating at the time of plating, a conductive metal ion contained in the metal plating solution and the nucleus acts as a kind of seed to be chemically reduced, it is possible to form these strong bonds. As a result, the conductive metal layer more easily, and can be selectively formed.

In the other hand, generating the above-mentioned metal core phase, may be among the electromagnetic waves, the laser electromagnetic wave irradiation, for example, a laser electromagnetic radiation having about 755nm, about 1064 皿, a wavelength of about 1550nm, or from about near-infrared (NIR) region of 2940nm It may be examined. In another example, there is a laser electromagnetic radiation having an infrared (IR) region of the wavelength to be irradiated. Further, the electromagnetic wave laser may be irradiated under typical conditions or power.

By the irradiation of this laser, it is possible to more effectively cause the metal core from the non-conductive metal compounds of formula (I), may. Be selectively generated, and exposing the active adhesive surface of a predetermined region including this.

On the other hand, after proceeding the above-mentioned metal nucleation step is, as shown in the third diagram of Fig. 2, by reduction, or plating an area that caused the metal nucleus by chemical may be carried out the step of forming a conductive metal layer . After a proceed to this reduction, or plating i steps, can optionally be a conductive metal layer formed in the metal core and adhesion of the active surface is exposed to a predetermined area and the other area, to maintain as a non-stable chemically-conductive metal compound non-conductive can. Accordingly, a fine conductive pattern selectively only to predetermined areas on the polymeric resin substrate can be formed.

More particularly, the forming of the conductive metal layer may be electroless plating conducted by plating, whereby the good conductivity metal layer on the adhesion surface activity can be formed. In particular, the non-adhesive active surface formed from a conductive metal compound of Chemical Formula 1 can be rapidly form a fine conductive pattern having a good adhesion by electroless plating Cu-.

In one example, in such a reduction or plating step can process resin product or resin layer of a predetermined area caused by the metal core with an acidic or basic solution containing a reducing agent, such a solution as the reducing agent, formaldehyde, hypophosphite, dimethyl may include amino borane (DMAB), 1 or more kinds selected from the group consisting of diethylamino borane (DEAB), and hydrazine. In the reduction, or plating step, to the electroless plating by including the above-described reducing agent, and a conductive metal ion treated with the plating solution or the like to form a conductive metal layer by plating.

In the same progression of the reduction or plating step, a conductive metal ion contained in the electroless plating solution to this as seed in the region where the metal core formed by chemical reduction, a selectively good conductive pattern in a predetermined area can be formed . In this case, the metal nuclei and the active adhesive surface can form a conductive metal ion and a strong bond is reduced with the chemical, and as a result may alternatively be a conductive pattern is formed more easily in a predetermined area.

Further, the remaining area is the conductive pattern is not formed, the non-conductive metal compound of Formula 1 wherein the resin has a structure are uniformly dispersed. Meanwhile, according to another embodiment of the invention, there is provided a resin structure having a conductive pattern obtained by the composition and the conductive pattern forming method for the above-described conductive pattern forming. The resin structure is a polymer resin base material; And is dispersed in a polymer resin base material, to be represented by the general formula 1, Cu, or M is a five oxygen atoms are distorted square surrounding the has the structure or Cu or M surrounded by a pyramid with six oxygen atoms are distorted octa head Ron form a non-conductive metal compounds having the structure; Bonding an active surface containing a metal nucleus exposed to the polymeric resin substrate surface having a predetermined area; And it can contain a conductive metal layer formed on the adhesion surface activity.

Formula 1

Cu 2 - x M x P 2 0 7

In formula 1, and M is at least one metal selected from the group consisting of Zn, Mg, Ca, Sr and Ba, X satisfies the condition of 0≤x <2.

In this resin structure, a predetermined region is the active adhesive surface and the conductive metal layer may correspond to the electromagnetic wave irradiation area on the polymeric resin base. Further, the metal or the metal ion contained in the nucleus of the activated adhesive surface may be that derived from a non-conductive metal compounds of the formula (I). On the other hand, the conductive metal layer may be that derived from the metal included in the non-conductive metal compounds of formula (I), or electroless comes from a conductive metal ions contained in the plating solution. Moreover, the resin structure, the non-may further include a residue derived from a conductive metal compound. These residues are at least in part the emission of the metal contained in the non-conductive metal compounds, may have a structure vacancy is formed on at least a portion of the spot.

The above-described resin structure can be in a variety of resin products or resin layer having a conductive pattern, such as a mobile phone or tablet PC case, etc., or in a variety of resin products or resin layer, other RFID tags, various sensors or MEMS structure having a conductive pattern for an antenna have.

According to, the implementation of the invention as described above, it is possible to examine the electromagnetic wave such as laser to form the even and improve the variety of resin products having a very simplified method for reducing or plating, various kinds of fine conductive patterns easy. Operation of the invention through a specific embodiment of the invention hereinafter, will be described the effect in more detail. However, it is not limited thereto whatsoever that any means the scope of the invention set forth by way of illustration of the invention. Example 1: formation of conductive pattern by electromagnetic direct irradiation

With using a base resin a polycarbonate resin and, Cu 2 P 2 0 7 with the structure surrounding the Cu as the non-conductive metal compounds of five oxygen atoms are distorted square pyramid form and with the additives for the process and the stabilization a composition for the conductive pattern formed by the electromagnetic wave irradiation was prepared.

As the additive was used as the thermal stabilizer (IR1076, PEP36), UV stabilizers (UV329), a lubricant (EP184), impact modifier (S2001).

The polycarbonate resin of 90% by weight, Cu 2 P 2 0 7 5% by weight, and other additives were combined to obtain a 5% by weight of common composition, it was extruded through an extruder at 260 to 280 ° C temperature. The composition of the extruded pellet form from about 260 to 270 ° C lOOran horizontal, vertical in 100隱, injection molding was in the form of a substrate having a thickness of 2隨.

With respect to the injection-molded test specimens, 40kHz eu by irradiating laser having a 1064 12W 皿 wavelength under conditions to activate the surface, was subjected to the plating process, electroless plating, as follows:

Plating solution was prepared by dissolving 4g of copper sulfate 3g, Lot saelyeom 14g, sodium hydroxide in 100ml of deionized water ■. Formaldehyde 1.6ml was added as a reducing agent in the prepared plating solution 40ml. After the laser structure of the resin surface is activated by carrying a plating solution for 4 to 5 hours, washed with distilled water.

Thus, the electroless the surface was activated by irradiating a laser of 12W to form a good conductive pattern (copper metal layer) through a plating. Example 2: formation of conductive pattern by electromagnetic direct irradiation

Example 1 of the conductive as a pigment in the pattern forming composition for Ti0 2 5 resin structure having a conductive pattern, and Example 1 in the same manner except that 85 wt% of a polycarbonate resin and further added to the weight% the form. Example 3: formation of conductive pattern by electromagnetic direct irradiation

CuO, ZnO, and the (NH 4) 2 HP0 4 1 : heunhap were in a molar ratio of 2: 1. Then, heat treatment was a common compound obtained at 950 ° C for 10 hours. The XRD pattern showing the determination of properties of CuZnP 2 0 7 synthesized under these conditions are shown in FIG. CuZnP 2 0 7 synthesized under the above conditions had a structure is surrounding the Cu or Zn to six oxygen atoms are distorted octa head Ron form.

To form a resin structure having a conductive pattern in the same manner as in Example 1, except for using the CuZnP 2 0 7 - in Example 1 as the non-conductive metal compounds synthesized in place of the Cu 2 P 2 0 7. Example 4: formation of conductive pattern by electromagnetic direct irradiation

Of CuO, MgO and (N¾) 2 HP0 4 1: heunhap were in a molar ratio of 2: 1. Then, heat treatment was a common compound obtained at 950 ° C for 10 hours. This showed XRD patterns indicating the determined characteristic of the CuM g P 2 0 7 synthesized under the same conditions in Figure 4. CuMgP 2 0 7 synthesized under the above conditions had a structure is surrounding the Cu or Mg to the six oxygen atoms are distorted octa head Ron form.

In Example 1 as the non-conductive metal compound to form a resin structure having a conductive pattern in the same manner as in Example 1, except for using a eu CuMgP 2 0 7 prepared in place of Cu 2 P 2 0 7. Example 5: formation of conductive pattern by electromagnetic direct irradiation

CuO, CaO and the (NH 4) 2 HP0 4 1 : heunhap were in a molar ratio of 2: 1. Then, heat treatment was a common compound obtained at 950 ° C for 10 hours. The determination of properties of the CuCaP 2 0 7 synthesized under the same conditions exhibited the XRD pattern shown in Figure 5 all. The CuCaP synthesized in morning 20 7 had a structure is surrounding the Cu or Ca in the form of a square pyramid to five oxygen atoms eu distortion.

To form a resin structure having a conductive pattern in the same manner as in Example 1, except for using the CuCaP 2 0 7 - in Example 1 as the non-conductive metal compounds synthesized in place of the Cu 2 P 2 0 7. Example 6: formation of conductive pattern by electromagnetic direct irradiation

The CuO, SrC0 3 and (NH 4) 2 HP0 4 1 : heunhap were in a molar ratio of 2: 1. The "hitting, and heat treating the common compound obtained in the 500 ° C for 5 hours in the heat-treated again, 950 ° C 10 hours. Synthesized in this condition it is shown the XRD pattern showing the determination of properties of CuSrP 2 0 7 in Fig. The CuSrP synthesized in Condition 2 0 7 had a structure is surrounding the Cu or Sr in the form of a square pyramid to five oxygen atoms are distorted.

In Example 1 as the non-conductive metal compounds to form a Souza structure having a conductive pattern in the same manner as in Example 1, except for using a eu CuSrP 2 0 7 prepared in place of Cu 2 P 2 0 7. Example 7: formation of conductive pattern by electromagnetic direct irradiation

CuO, the Ba (C 2 ¾0 2) 2 and (NH 4) 2 HP0 4 1 : heunhap were in a molar ratio of 2: 1. Then, after the heat treatment of the common compounds obtained in the 500 ° C for 5 hours, it was heat-treated again 10 hours at 850 ° C. The XRD pattern showing the determination of properties of CuBaP 2 0 7 prepared in this condition is shown in Fig 7. The CuBaP synthesized in Condition 2 0 7 had a structure is surrounding the Cu or Ba as a square pyramid shape with five oxygen atoms are distorted.

In Example 1 as the non-conductive metal compound to form a resin structure having a conductive pattern in the same manner as in Example 1, except for using a -CuBaP 2 0 7 prepared in place of Cu 2 P 2 0 7. Comparative Example 1: formation of conductive pattern by electromagnetic direct irradiation

In Example 1 as the non-conductive metal compound to form a resin structure having a conductive pattern in the same manner as in Example 1, except for using the CuCr 2 0 4 instead of Cu 2 P 2 0 7. Comparative Example 2: formation of conductive pattern by electromagnetic direct irradiation

In the first embodiment the non as the conductive metal compound Cu 2 P 2 0 7 instead of the combined polycarbonate resin and a non-conductive metal compounds, and other additives as in Example 1, except for using the CuF 2 common to obtain a composition, 260 at 280 ° C temperature was extruded through an extruder. However, the polycarbonate resin is decomposed by the CuF 2 were unable to find a composition of pellet form. Also, CuF 2 and the polycarbonate resin is a polycarbonate resin ttuina a light color was black sides and heunhap 2 and CuF. As a result, CuF 2 this could not be obtained a uniformly dispersed resin composition prepared by the resin structure to form a conductive pattern in a desired region. Comparative Example 3: formation of conductive pattern by electromagnetic direct irradiation

In the first embodiment the non as the conductive metal compound Cu 2 P 2 0 7 instead of Cu 2 P 2 except for using 0r 3H 2 0, and in Example 1, a polycarbonate resin and a non-combined non-conductive metal compounds, and other additives common as to obtain a composition, and 260 to 2.801: was extruded through an extruder at a temperature. However, the polycarbonate resin by the Cu 2 P 2 0 7 '3¾0 at high temperatures is decomposed was unable to find a composition of pellet form. As a result, Cu 2 P 2 0 3H 2 0 is not possible to obtain a uniformly dispersed resin composition could not be prepared the resin structure to form a conductive pattern in a desired region. Comparative Example 4: formation of conductive pattern by electromagnetic direct irradiation

For synthesizing the CuFeP 2 0 7, the CuO, Fe 2 0 3 and (NH 4) 2 HP0 4 1 : heunhap were in a molar ratio of 2: 0.5. Then, heat treatment was a common compound obtained at 950 ° C for 10 hours. As a result, CuFeP 2 0 7 was not synthesized, copper phosphate and iron phosphate were synthesized, respectively. Thus, Cu 2 P 2 0 7 in the metal, which may be doped is limited, it is confirmed that the same may provide a non-conductive metal compounds having a specific three-dimensional structure as long as the scope of the general formula M 1 suggested in the present invention. Test Example: Evaluation of a resin structure having a conductive pattern

(1) In accordance with the examples and the comparative examples to the case, which is optionally a conductive pattern formed as expressed as "0" in Table 1. However, the non-conductive metal compounds were shown as 'X' for the case optionally forming a conductive pattern that is not or not to a polymeric resin heunhap Table 1. (2) Examples and Comparative Examples, the resin conductive pattern colorimeter according to ASTM 2244 standard for the area that is not formed of a structure made in accordance with the; using the (color imeter color eye 7000A, Xr i te) oblique incidence of standard light source D65 It turned on. And to measure the color coordinates in L, a * and b * reference sample material and the chromaticity difference from the International Commission on Illumination (CIE) color space is defined. And, it exhibited the L * value associated with the brightness of the colors in Table 1.

(3) In the adhesion of the conductive pattern (or coating layer) formed in accordance with Examples and Comparative Examples were evaluated in the Cross-cut test according to ISO 2409 standard method. cl ass to 0 rating means, and cl ass 1 rating that the separation area of ​​the conductive pattern on the target evaluation 0¾ conductive pattern area means the area of ​​the peeling of the conductive pattern evaluation object area of ​​conductive pattern> than 5% or less. The class 2 rating refers to greater than 5% to 15% of the peeled area of ​​the conductive pattern evaluation conductive pattern area. cl ass to 3 grade is meant 15% or less than 35% of the peeled area of ​​the conductive pattern evaluation conductive pattern area. cl ass to 4 rating refers to greater than 35% less than 65% of the peeled area of ​​the conductive pattern evaluation conductive pattern area. c to lass 5 rating refers to greater than 65% of the peeled area of ​​the conductive pattern evaluation conductive pattern area.

(4) Examples and Comparative Examples, the resin MFR (Mel t Flow Rate) of the structure was prepared according to the silver is measured at 300 ° C and 1.2kg of hajeung method according to ASTMD1238.

[Table 11

Whether the conductive pattern forming the CIE color coordinates (L *) ISO c lass MFR [g / 10min] Example 1 10 84.38 16.4

Example 20 92. 17 1 17.7

Example 30 16.5 87.21 1

Example 40 16.6 84.08 1

Example 50 16.5 83.07 1

Example 60 16.4 81.49 1

Example 70 16.8 76.69 1

Comparative Example 10 35.11 17.8 1

Comparative Example 2 X eu - - Comparative Example 3 X - - - Comparative Example 4, a non-conductive metal compounds are not synthesized

Claims

[Claims] [Claim 1] a polymer resin; And to be represented by the general formula 1, Cu or M of five oxygen atoms are distorted square non-conductive metal compounds having the structure surrounding the has the structure or Cu or M surrounded by a pyramid with six oxygen atoms are distorted octa head Ron form the inclusion, and by electromagnetic wave irradiation, the non-conductive pattern and from the conductive metal compound in the electromagnetic wave irradiation is a metal nucleation forming composition: [formula 1] in the Cu2-xMxP207 formula (I) M is Zn, Mg, Ca, Sr and is at least one metal selected from the group consisting of Ba, X satisfies the condition of 0≤x <2. [Claim 2] 2. The method of claim 1 wherein said polymeric resin is a composition for the conductive pattern formed by the electromagnetic wave irradiation comprising a thermosetting resin or a thermoplastic resin. According to [Claim 3] of claim 1, wherein the electromagnetic wave irradiated to the polymer resin comprises an ABS resin, polyalkylene terephthalate resin, polycarbonate resin, polypropylene resin and poly one or more selected from the group consisting of a phthalamide resin of the composition for the conductive pattern formed. [Claim 4] The method of claim 1 wherein the non-conductive metal compounds are the composition for the conductive pattern formed by the electromagnetic wave irradiation contained in 0.1 to 15% by weight of the total composition. _ 5. The method of claim 1, wherein a flame retardant, heat stability to, UV stabilizers, lubricants, antioxidants, inorganic layer assumption, color additives, electromagnetic wave further comprises at least one additive selected from the group consisting of cheunggyeok reinforcing agents and functionality adjuvant the composition for conductive pattern formation by the irradiation. 6. The polymer resin base material; and the ^ minutes to a polymer resin base material, to be represented by the general formula 1, Cu or M to surround a square pyramid shape with five oxygen atoms distortion architecture or Cu or M of six oxygen atoms non having the structure enclosed in a distorted form octa head Rhone-conductive metal compound; Bonding an active surface containing a metal nucleus exposed to the polymeric resin substrate surface having a predetermined area; And resin structure having a conductive pattern including a conductive metal layer formed on the adhesion surface activity:
Formula 1
Cu 2 - x M x P 2 0 7
In formula 1, and M is at least one metal selected from the group consisting of Zn, Mg, Ca, Sr and Ba, X satisfies the condition of 0≤x <2. [7.]
7. The method of claim 6 wherein the surface active adhesive, and a conductive metal layer is formed in a predetermined area is a resin structure having a conductive pattern that Daewoong in the electromagnetic wave irradiation area on the polymeric resin substrate.
PCT/KR2015/009786 2014-09-17 2015-09-17 Composition for forming conductive pattern and resin structure having conductive pattern WO2016043542A1 (en)

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CN 201580046641 CN106605272B (en) 2014-09-17 2015-09-17 A conductive pattern forming composition and the resin structure having a conductive pattern
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100716486B1 (en) * 2001-07-05 2007-05-10 엘피케이에프 레이저 앤드 일렉트로닉스 악티엔게젤샤프트 Conductor track structures and method for the production thereof
KR20110112860A (en) * 2009-12-17 2011-10-13 비와이디 컴퍼니 리미티드 Surface metallizing method, method for preparing plastic article and plastic article made therefrom
US20130106659A1 (en) * 2011-10-31 2013-05-02 Ticona Llc Thermoplastic Composition for Use in Forming a Laser Direct Structured Substrate
US20130136869A1 (en) * 2010-01-26 2013-05-30 Macdermid Acumen, Inc. Method for Improving Plating on Non-Conductive Substrates
KR101434423B1 (en) * 2013-04-02 2014-08-26 전자부품연구원 Curved surface polymer material and method of conductive pattern using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100716486B1 (en) * 2001-07-05 2007-05-10 엘피케이에프 레이저 앤드 일렉트로닉스 악티엔게젤샤프트 Conductor track structures and method for the production thereof
KR20110112860A (en) * 2009-12-17 2011-10-13 비와이디 컴퍼니 리미티드 Surface metallizing method, method for preparing plastic article and plastic article made therefrom
US20130136869A1 (en) * 2010-01-26 2013-05-30 Macdermid Acumen, Inc. Method for Improving Plating on Non-Conductive Substrates
US20130106659A1 (en) * 2011-10-31 2013-05-02 Ticona Llc Thermoplastic Composition for Use in Forming a Laser Direct Structured Substrate
KR101434423B1 (en) * 2013-04-02 2014-08-26 전자부품연구원 Curved surface polymer material and method of conductive pattern using the same

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