KR20200041170A - Methallic glass-resin laminate, and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a metallic glass-resin bonded body having high bonding strength with a resin layer by using metallic glass which is surface-treated with a laser, and a manufacturing method thereof. The metallic glass-resin bonded body of the present invention comprises: a metallic glass layer; and the resin layer.

Description

Metallic glass-resin conjugate, and manufacturing method therefor {METHALLIC GLASS-RESIN LAMINATE, AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a metallic glass-resin assembly capable of realizing excellent durability and adhesion characteristics through high adhesion, and a method for manufacturing the same.

In general, bonding between dissimilar materials (materials) such as metals and resins is often not easy because the physical and chemical properties and surface conditions of each material are different. Techniques that can be attempted for bonding between these dissimilar materials can be broadly classified into bonding using adhesives, mechanical tightening, welding, and insert injection.

Among them, the method using an adhesive or an adhesive film has the advantage that the method of use is simple, and is most frequently used as a representative and classic method used for bonding between dissimilar materials in electronic products. In the case of using an adhesive film, after cutting the adhesive film to a size and placing it between metal-plastics, by applying heat and pressure using a jig and cooling for a certain period of time, the adhesive is cured to generate a bonding force. To use.

In addition, the mechanical tightening is performed using a mechanical fastening tool such as a screw or rivet. In this process, self-piercing rivet, clinching, which is slightly modified in the general mechanical joining process to be effective in joining dissimilar materials, is used. Processes such as (clinching) are being introduced.

The adhesive and mechanical tightening process enables the bonding of dissimilar materials with a relatively easy approach, but since different materials are inserted between dissimilar materials or the joints are exposed on the exterior, new technologies have been proposed for pure bonding between the two base materials. have.

There are various technologies for bonding between different materials, but in the case of the adhesive film method, a process using relatively high heat and pressure is required compared to the process of applying the adhesive, and the deterioration rate due to moisture increases under a high temperature and high humidity environment. Therefore, there is a disadvantage that the strength loss of the joint may increase.

In addition, when an adhesive is used for bonding different materials, the bonding temperature is low compared to the temperature used at the time of application or the adhesive film method, so that the joint is not deteriorated by heat, and the high rigidity and airtightness of the joint can be simultaneously obtained. However, since the wetting phenomenon occurring between the adhesive and the base material has a great influence on the adhesive strength, the adhesive bonding improves the wettability between the adhesive and the base material surface through proper surface treatment on the metal or plastic surface. The process must be carried out as essential, and for this, there is also a hassle of increasing the surface energy of the base material or reducing the surface tension of the adhesive.

The method of using a mechanical fastening tool such as a screw or rivet is also a classic method, and the mechanical fastening tool is generally heavy and has a high cost required for use, which has a problem of not meeting the trend of light weight of related technologies.

Since the conventional method for bonding different materials has the above-mentioned problems, it is necessary to study a method capable of improving the bonding strength between different materials through a relatively simple process while solving the above problems.

The present invention relates to a metallic glass-resin assembly capable of realizing excellent durability and adhesion characteristics through high adhesion.

In addition, the present invention is to provide a method of manufacturing the above metallic glass-resin assembly.

In order to solve the above problems, in the present specification, a metallic glass layer including an etching groove on at least one surface; And a resin layer bonded to one surface including the grooves of the metallic glass layer, wherein the ratio of the etch groove inlet width: the etch groove intermediate width is 10: 1 to 1: 1, or 5: 1 to 1: Metallic glass-resin conjugates of 1 or 2: 1 to 1: 1 are provided.

In this specification, further, by irradiating a laser on the surface of the metallic glass, forming an etching groove on the surface of the metallic glass; And forming a resin layer on one surface of the metallic glass in which the etching groove is formed; wherein the ratio of the entrance width of the etching groove: the middle width of the etching groove is 10: 1 to 1: 1, or 5: 1 to A method of manufacturing a metallic glass-resin conjugate, in which 1: 1 or 2: 1 to 1: 1 is provided.

Hereinafter, a metallic glass-resin conjugate according to a specific embodiment of the present invention and a method of manufacturing the same will be described in more detail.

Ⅰ. Metallic glass-resin assembly

According to an embodiment of the invention, at least one side of the metallic glass layer includes an etching groove; And a resin layer bonded to one surface including the grooves of the metallic glass layer, wherein the ratio of the etching groove inlet width to the intermediate width of the etching groove is 10: 1 to 1: 1, and the metallic glass-resin assembly Can be provided.

The present inventors, as in the metallic glass-resin bonding body of the above embodiment, form an etching groove on one surface of the metallic glass layer and bond it with the resin, thereby increasing the surface area and improving the bonding force between the metallic glass-resin through the anchoring effect. It was confirmed through experiments and the invention was completed.

When the metallic glass was not pre-treated, it was not bonded at the time of insert injection and was not effective at the time of sand blasting, but exhibited excellent bonding strength when forming an etching groove according to the laser irradiation peculiar to the present invention.

In particular, when the laser is irradiated with respect to the metallic glass, the mechanical properties are superior to general crystalline metals such as aluminum, and the moldability is excellent, so it can be more easily applied as an exterior material.

The metallic glass-resin assembly may be applied as an exterior material of various articles, for example, an exterior material of an electronic product, and more specifically, may be used as a rear case of a mobile phone.

(1) metallic glass layer

According to an exemplary embodiment of the present invention, it is preferable to use the metallic glass layer that is easy to form a pattern by laser irradiation and has excellent thermal conductivity. The metallic glass contained in the metallic glass layer heats a metal or alloy composed of metal elements to a high temperature to form a high temperature liquid with an irregular structure, and rapidly cools it to maintain an irregular structure at room temperature. Refers to a metastable substance, and may have amorphousness.

During the cooling, in order to suppress nucleation and growth of the crystal phase in the supercooled liquid section between the melting point of the metallic glass and the glass transition temperature, it is preferable to cool at a sufficient rate from the temperature above the melting point of the metallic glass to the glass transition temperature. .

The example of the metallic glass is not particularly limited, and various known metallic glass materials may be used. Specific examples of the metallic glass, palladium (Pd) -based alloy, zirconium (Zr) -based alloy, copper (Cu) -based alloy, magnesium (Mg) -based alloy, iron (Fe) -based alloy, cobalt (Co) -based alloy , Titanium (Ti) -based alloys, calcium (Ca) -based alloys, platinum (Pt) -based alloys, and the like.

The palladium (Pd) based alloy, zirconium (Zr) based alloy, copper (Cu) based alloy, magnesium (Mg) based alloy, iron (Fe) based alloy, cobalt (Co) based alloy, titanium (Ti) based alloy, Calcium (Ca) -based alloys and platinum (Pt) -based alloys refer to metal elements having the highest molar ratio among the metal elements included in each alloy.

More preferably, a zirconium (Zr) -based alloy may be used as the metallic glass, and an alloy represented by Formula 1 below may be mentioned as a specific example of the zirconium (Zr) -based alloy.

[Formula 1]

A _a B _b C _c D _d

In Chemical Formula 1, A is Zr, B is a group 11 element, C is a group 10 element, D is a group 13 element, and the ratio of a: b is 2: 1 to 10: 1, and c: d of The ratio is 1.1: 1 to 5: 1.

More specifically, in Formula 1, A is Zr, B is Cu, C is Ni, D is Al, and the ratio of a: b is 4: 1 to 5: 1, and the ratio of c: d is 1.2: 1 to 2: 1. The a may be 60 to 70, the b may be 10 to 20, the c may be 5 to 15, and the d may be 5 to 10.

Preferred examples of the metallic glass represented by Chemical Formula 1 include Zr _67.5 Cu ₁₅ Ni ₁₀ Al _7.5 .

Examples of the palladium (Pd) -based alloy may include Pd ₄₀ Ni ₄₀ P ₂₀ , Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ . Examples of the copper (Cu) -based alloy include Cu ₄₆ Zr ₄₂ Al ₇ Y ₅ and Cu ₄₉ Hf ₄₂ Al ₉ .

Examples of the magnesium (Mg) -based alloy may include Mg ₅₄ Cu _26.5 Ag _8.5 Gd ₁₁ , Mg ₆₅ Cu _7.5 Ni _7.5 Zn ₅ Ag ₅ Y ₅ Gd ₅ .

Examples of the iron (Fe) -based alloy is Fe ₄₈ Cr ₁₅ Mo ₁₄ Er ₂ C ₁₅ B ₆ , (Fe _44.3 Cr ₅ Co ₅ Mo _12.8 Mn _11.2 C _15.8 B _5.9 ) _98.5 Y _1.5 , Fe ₄₁ Co ₇ Cr1 ₅ Mo ₁₄ C ₁₅ B ₆ Y ₂ .

Examples of the cobalt (Co) -based alloys include Co ₄₈ Cr ₁₅ Mo ₁₄ C ₁₅ B ₆ Er ₂ .

Examples of the titanium (Ti) -based alloy is Ti ₄₀ Zr ₂₅ Cu ₁₂ Ni ₃ Be ₂₀ .

Examples of the calcium (Ca) -based alloy may include Ca ₆₅ Mg ₁₅ Zn ₂₀ .

Examples of the platinum (Pt) -based alloy include Pt _42.5 Cu ₂₇ Ni _9.5 P ₂₁ .

The metallic glass has a strength of 3 to 10 times and an elastic strain limit of 5 to 10 times, a surface hardness of 2 to 3 times, and a corrosion resistance of tens of thousands of times that of stainless steel. It is possible to achieve an excellent effect that is difficult to implement.

According to an exemplary embodiment of the present invention, the shape of the metallic glass layer can be applied without any particular limitation, as long as it can be laser etched and can be smoothly joined with a resin, for example, a flat surface or a curved surface. It may be a cylindrical and polyhedral containing.

According to an exemplary embodiment of the present invention, the metallic glass layer may include two or more etching grooves.

The etch groove inlet width: the ratio of the etch groove intermediate width is 10: 1 to 1: 1, or 5: 1 to 1: 1, or 2: 1 to 1: 1, or 1.6: 1 to 1: 1, or It may be 1.5: 1 to 1: 1, or 10: 1 to 1.5: 1, or 5: 1 to 1.5: 1, or 2: 1 to 1.5: 1. In the above range, the resin layer can be sufficiently filled in the etching groove, thereby improving the bonding force between the metallic glass layer and the resin layer.

That is, in the metallic glass-resin assembly of the embodiment, the etch groove inlet width is greater than or equal to the etch groove middle width. On the contrary, when the etch groove inlet width is narrower than the middle width of the etch groove, in the case of a resin having poor flowability, it is difficult to fill the groove in a short time and thereby the bonding strength may be deteriorated.

According to an exemplary embodiment of the present invention, the etching groove inlet width may mean a width of the etching groove on an extension line of the surface of the metallic glass layer on which the etching groove is formed. The etching groove depth may mean a maximum distance from the lowest point of the one etching groove to the intersection of the extension line of the metallic glass layer and the central axis of the one etching groove. The middle width of the etching groove may mean a maximum distance between the etching grooves at a point that is half the depth of the etching groove.

The etching groove inlet width may be 10 μm or more and 30 μm or less. According to an exemplary embodiment of the present invention, the intermediate width of the etching groove may be 15 μm or more and 25 μm or less.

The ratio of the depth of the etching groove to the etching groove entrance width is 10: 1 to 1: 1, or 5: 1 to 1: 1, or 5: 1 to 1: 1, or 4: 1 to 1.2: 1, or Or 3.5: 1 to 1.4: 1. The depth of the etching groove may be 3 μm or more and 20 μm or less.

Meanwhile, the metallic glass-resin assembly may further include two or more burrs provided on the surface of the metallic glass layer adjacent to the etching groove.

The protrusion may be provided in a direction away from the etching groove. The protrusion may be continuously or continuously discontinuous depending on the direction of the etching groove.

According to an exemplary embodiment of the present invention, since the protrusion is provided in a direction away from the etching groove, and the metal layer includes two or more etching grooves, the protrusion provided in a direction away from one etching groove, and the one etching The protrusion provided in a direction away from the other etching groove adjacent to the groove may be provided in a form facing each other.

According to an exemplary embodiment of the present invention, a portion of the metallic glass layer may be melted in a direction away from the central axis of the etching groove on the surface of the metallic glass layer to include the protrusion.

According to an exemplary embodiment of the present invention, the protrusion may be provided at an acute angle or at a right angle to the surface of the metallic glass layer. Specifically, the angle formed by the surface of the metallic glass layer and the protrusion provided in a direction away from the etching groove may be an acute angle or a right angle.

According to an exemplary embodiment of the present invention, the angle formed by the protrusion relative to the surface of the metallic glass layer is 30 ° or more and 90 ° or less, or 30 ° or more and 70 ° or less, 35 ° or more and 90 ° or less, or 35 ° or more and 70 ° or less.

In the above range, the resin layer can be sufficiently filled between the protrusions, the resin layer can be sufficiently fixed to the metallic glass layer, and the bonding force between the metallic glass layer and the resin layer can be maximized.

According to an exemplary embodiment of the present invention, the length from one end to the other end of the protrusion may be 0.1 μm or more and 30 μm or less, or 5 μm or more and 30 μm or less, or 11 μm or more and 26 μm or less. Further, according to an exemplary embodiment of the present invention, the height of the protrusion may be 0.1 μm or more and 25 μm or less, or 5 μm or more and 25 μm or less, or 8 μm or more and 22 μm or less.

In the range of the length of the protrusion and the height of the protrusion, the resin layer may be sufficiently supplied to be fixed to the metallic glass layer with sufficient bonding force. In addition, in the above range, the tensile value of the metallic glass-resin joint can be maintained high, the structure of the protrusion can be easily controlled, and airtightness and water tightness of the joint can be secured.

On the other hand, the metallic glass layer may include two or more etching grooves, and the plurality of etching grooves may independently form a dot pattern, or may be continuously connected to form a linear pattern or a crosshatch pattern. have.

According to an exemplary embodiment of the present invention, a scanning electron microscope image of a surface of a metallic glass layer provided with an etching groove and a protrusion is shown in FIG. 1. According to FIG. 1, the surface of the metallic glass layer may exhibit an etched groove shape having a linear structure. Specifically, in the etching groove of the linear structure, a traveling direction of one etching groove and a traveling direction of the other etching groove may be parallel.

In this case, the distance between the central axes of the etching groove may be 50 μm or more and 2,000 μm or less, or 100 μm or more and 1000 μm or less, or 150 μm or more and 850 μm or less, or 200 μm or more and 800 μm or less. By preventing the phenomenon that the protrusions facing each other in the above range are merged, it is possible to prevent the formation of an empty space structure in which the resin layer is not supplied, and the bonding area between the structure formed by the etching groove and the protrusion and the resin layer is Relatively increased, it is possible to form a sufficient bonding force.

In the present specification, the distance between the central axes of the etching grooves may mean a distance from the end of one etching groove to the end of the other etching groove where the depth of the etching groove is maximum.

(2) Resin layer

The resin layer contains polyphenyl sulfide resin (PPS), polycarbonate (PC), polycarbonate / ABS resin, polypropylene (PP) resin, polyamide (PA) resin, polyphenylene oxide (PPO) resin, and reinforcing material It may be composed of one or more selected from the group consisting of resin, but the type is not limited.

In addition, the reinforcing material may be at least one selected from the group consisting of glass fiber, talc, and carbon fiber, but the type is not limited.

The resin layer may be filled inside the etching groove and on the surface of the metallic glass layer to be fixed to the metallic glass layer. In addition, the resin layer may be filled between and the protrusion. Specifically, the resin layer may be filled in a fence made of the inside of the etching groove and the protrusion and fixed to the metallic glass layer. Accordingly, a more solid anchoring effect may occur.

(3) Metallic glass-resin assembly

The bonding force between the metallic glass layer and the resin layer is 60 kgf / cm ² or more and 150 kgf / cm ² or less, or 65 kgf / cm ² or more and 120 kgf / cm ² or less, or 66 kgf / cm ² or more and 113 kgf / cm ² It may be the following, the bonding force of the metallic glass layer and the resin layer may be different depending on the type of the resin layer.

In this specification, the bonding force between the metallic glass layer and the resin layer may mean tensile strength and / or shear strength of the resin layer to the metallic glass layer.

Ⅱ. Method for manufacturing metallic glass-resin joints

According to another embodiment of the present invention, by irradiating a laser on the surface of the metallic glass, forming an etching groove on the surface of the metallic glass; And forming a resin layer on one surface of the metallic glass in which the etching groove is formed; wherein the ratio of the entrance width of the etching groove: the middle width of the etching groove is 10: 1 to 1: 1, or 5: 1 to Provided is a method for producing a metallic glass-resin conjugate with 1: 1 or 2: 1 to 1: 1.

When using the metallic glass-resin bonding method according to an exemplary embodiment of the present invention, while the resin layer at the interface between the metallic glass layer and the resin layer is melted, the resin layer is etched metallic as well as the surface of the metallic glass layer. A more solid anchoring effect may be generated by being introduced into the etching groove of the glass layer and the inside of the fence-shaped burr formed according to the etching groove.

In addition, according to an exemplary embodiment of the present invention, unlike the conventional metallic glass-resin bonding method, there is no possibility of problems such as environmental pollution caused by chemical harmful substances or difficult to manage mass production processes, and also, by minimizing the process steps It is possible to provide a metallic glass-resin assembly capable of improving operational efficiency and realizing airtightness and watertightness.

In the step of forming an etching groove on the surface of the metallic glass by irradiating a laser on the surface of the metallic glass, the contents of the metallic glass, the resin layer, the etching groove, and the protrusions are all described in the above embodiment. Includes.

The laser irradiated on the surface of the metallic glass layer is irradiated on the surface of the metallic glass to form a pattern by an etching groove on the surface of the metallic glass.

Specifically, when the laser is irradiated to the surface of the metallic glass, an etching groove may be formed according to the traveling direction of the laser. That is, the traveling direction of the laser and the traveling direction of the etching groove may coincide.

For example, when a linear pattern as shown in FIG. 1 is formed on the surface of the metallic glass, two or more lasers may be irradiated on the surface of the metallic glass layer, and the two or more laser traveling directions may be parallel. You can. Specifically, the traveling direction of the one first laser and the traveling direction of the other second laser may be parallel.

In addition, depending on the laser irradiation, the protrusion may be continuously or partially discontinuously.

The wavelength of the laser can be freely selected from 300 nm to 1100 nm. Preferably, a wavelength of 300 nm to 400 nm with a high absorption rate can be applied, and the deformation after injection is minimized by using a picosecond laser capable of minimizing thermal effects.

The output of the laser may be 3 W or more and 200 W or less, or 3 W or more and 10 W or less, or 5 W or more and 10 W or less, or 7 W or more and 10 W or less.

The frequency of the laser may be 30 kHz or more and 600 kHz or less, or 100 kHz or more and 600 kHz, or 200 kHz or more and 400 kHz or less. The frequency of the laser may mean the frequency per second of the pulse laser.

The scan speed of the laser is 100 mm / s or more and 1000 mm / s or less, or 100 mm / s or more and 400 mm / s or less, or 100 mm / s or more and 300 mm / s or less, or 150 mm / s or more and 250 mm / s s or less. The scan speed of the pulse laser may mean a speed that moves from one point to another point of the irradiated laser.

The number of irradiation of the laser may be 1 or more and 10 or less, or 1 or more and 8 or less, or 1 or more and 4 or less.

The pulse width of the laser may be 1 ps or more and 10 ps or less. The spot size of the laser may be 15 μm to 50 μm, 25 μm to 50 μm, 30 μm to 50 μm, or 35 μm to 50 μm. The spot size (or beam size) may mean a maximum distance from one end of the focus of the pulse laser to the other end.

The pulse energy of the laser may be 0.1 mJ to 2 mJ, 0.1 mJ to 1 mJ, 0.5 mJ to 2 mJ, or 0.5 mJ to 1 mJ.

The shape in which the laser is irradiated is the same as the pattern shape formed in the metallic glass layer, and various types of laser irradiation may be applied according to the shape of the pattern. For example, the laser may be irradiated in the same way as a dot pattern, a line pattern, or a crosshatch pattern shape.

For a more specific example, when the surface of the metallic glass layer has a linear pattern, the laser is 50 μm or more and 2000 μm or less, or 100 μm or more and 1000 μm or less, or 150 μm or more and 850 μm or less, or 200 μm or more 800 It may be irradiated in parallel at intervals of µm or less. By preventing the phenomenon that the protrusions facing each other in the above range are merged, it is possible to prevent the formation of an empty space structure in which the resin layer is not supplied, and the bonding area between the structure formed by the etching groove and the protrusion and the resin layer is Relatively increased, it is possible to form a sufficient bonding force.

Under the irradiation conditions of the laser, the etching groove depth, the etching groove inlet width, the etching groove intermediate width, the length of the protrusion, the height of the protrusion and the angle range formed by the surface of the protrusion and the metallic glass layer can be implemented. It is possible to increase the bonding force between the metallic glass layer and the resin layer.

Specifically, the ratio of the etch groove inlet width to the etch groove intermediate width is 10: 1 to 1: 1, or 5: 1 to 1: 1, or 2: 1 to 1: 1, or 1.6: 1 to 1: It may be 1, or 1.5: 1 to 1: 1, or 10: 1 to 1.5: 1, or 5: 1 to 1.5: 1, or 2: 1 to 1.5: 1. In the above range, the resin layer can be sufficiently filled in the etching groove, thereby improving the bonding force between the metallic glass layer and the resin layer.

Specifically, the energy condition of the laser can be re-condensation of the material evaporated at the wall of the etching groove and the entrance of the etching groove, and the protrusion protruding from the metallic glass layer can be formed relatively roughly, and accordingly, the metallic glass An area capable of bonding the layer to the resin layer and an anchoring structure may be formed.

According to an exemplary embodiment of the present invention, the laser may be irradiated in the depth direction of the etching groove, and a part of the metallic glass layer may be central axis of the etching groove on the surface of the metallic glass layer according to the irradiation of the laser It may be melted in a direction away from it to have the protrusion.

Meanwhile, the step of forming a resin layer on one surface of the metallic glass in which the etching groove is formed may be performed by supplying resin to each surface of the metallic glass layer, the etching groove, and the protrusions. Specifically, the step of forming the resin layer is performed by a method of bonding the resin layer to the mold by applying a pressure to the metal glass layer with the surface etched as a mold, supplying the resin layer to the mold, and applying pressure (insert injection) ).

The method, equipment, etc. specific to the insert injection can be applied without limitation various contents known in the injection molding field.

According to the present invention, a metallic glass-resin assembly capable of realizing excellent durability and adhesion characteristics through high adhesion, and a method for manufacturing the same can be provided.

1 is a surface SEM image of the metallic glass substrate of Preparation Example 1.
2 is a cross-sectional SEM image of the metallic glass substrates of Production Example 1 and Production Example 2.
3 is a cross-sectional SEM image of the metallic glass substrate of Preparation Example 3.
Figure 4 shows a cross-sectional SEM image of the metallic glass substrate of Comparative Production Example 2.

The invention is described in more detail in the following examples. However, the following examples are only illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Production Example and Comparative Production Example: Preparation of a metallic glass substrate>

Preparation Examples 1-3

A patterned metallic glass was prepared by irradiating and etching a pulse laser having the conditions shown in Table 1 below on one surface of a 20 mm x 60 mm x 220-260 μm metallic glass (Zr _67.5 Cu ₁₅ Ni ₁₀ Al _7.5 ) substrate Did.

As shown in FIG. 1, the etching was performed so that the etching grooves continuously formed a pattern of a linear structure in a direction parallel to the vertical direction of the metallic glass, and the etching grooves and the patterns of the linear structures were shown in Table 1 below. I had a gap.

division Laser output (W) Wavelength (nm) Scan speed (mm / s) Frequency (kHz) Number of repetitions (times) Pattern spacing (㎛) Preparation Example 1 7 343 200 200 2 800 Preparation Example 2 7 343 200 200 2 400 Preparation Example 3 7 343 200 200 One 200

Comparative Production Example 1

A metallic glass (Zr _67.5 Cu ₁₅ Ni ₁₀ Al _7.5 ) substrate having a width of 20 mm x length of 60 mm x height of 220 to 260 μm was used.

Comparative Production Example 2

A patterned metallic glass was prepared by sandblasting a surface of a metallic glass (Zr _67.5 Cu ₁₅ Ni ₁₀ Al _7.5 ) substrate having a width of 20 mm x length of 60 mm x height of 220 to 260 µm.

<Examples and Comparative Examples: Preparation of metallic glass-resin conjugate>

Examples 1-3

The insert injection mold was introduced so that one surface of the patterned metallic glass substrates obtained in Preparation Examples 1 to 3 were exposed, and molten polyphenyl sulfide resin was injected on the patterned surface, so that the number of polyphenyl sulfides of 2 mm thickness could be obtained. A metallic glass-resin conjugate to which the layers were bonded was prepared.

Comparative Example 1

A metallic glass-resin assembly was prepared in the same manner as in Example 1, except that the metallic glass substrate obtained in Comparative Production Example 1 was used instead of the patterned metallic glass substrate obtained in Preparation Examples 1 to 3.

Comparative Example 2

A metallic glass-resin assembly was prepared in the same manner as in Example 1, except that the patterned metallic glass substrate obtained in Comparative Production Example 2 was used instead of the patterned metallic glass substrate obtained in Preparation Examples 1 to 3.

<Experimental Example>

Experimental Example 1

The cross-sections of the patterned metallic glass substrates obtained in Preparation Examples 1 to 3 and Comparative Production Example 2 are shown in FIGS. 2 to 4, respectively, by using a scanning electron microscope (SEM).

Each shape in 10 to 20 grooves per specimen (depth of etching groove, inlet width of etching groove, middle width of etching groove, length of protrusion (meaning the length from one end to the other end), and The average value of the measured value of the height of the protrusion) was calculated and recorded in Table 2 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Metallic glass Preparation Example 1 Preparation Example 2 Preparation Example 3 Comparative Production Example 1 Comparative Production Example 2 Depth of etching groove 13 13 6 - - Etching groove inlet width 19 19 20 - - Middle width of etching groove 19 19 13 - - Length of protrusion 26 26 11 - - Height of protrusion 22 22 8 - -

Experimental Example 2

The bonding force of the interface between the metallic glass-resin assembly of Examples and Comparative Examples was measured by the strength of the separation or fracture when shear was applied at a tensile speed of 10 mm / min using a UTM tensioner (INSTRON 5969). . The final bond strength was calculated by dividing the measured tensile strength value by the bonded area.

The bond strength was calculated from the five specimens and the average values are reported in Table 3 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Metallic glass Preparation Example 1 Preparation Example 2 Preparation Example 3 Comparative Production Example 1 Comparative Production Example 2 Bond strength (kgf / cm ² ) 66.1 110.6 112.1 Measurement impossible Measurement impossible

As shown in Table 3, the metallic glass-resin conjugates of Examples 1 to 3 in which the patterned metallic glass substrate and the resin layer were bonded using a laser had a high bonding strength of 66.1 kgf / cm ² to 112.1 kgf / cm ² Through this, it was confirmed that excellent durability can be realized. On the other hand, in Comparative Examples 1 to 2 in which patterning using a laser did not proceed, the bonding strength was not measured because the metallic glass and the resin layer were not bonded at all.

Claims (13)

A metallic glass layer including an etching groove on at least one surface; And
Including; a resin layer bonded to one surface containing the groove of the metallic glass layer;
A metallic glass-resin assembly, wherein the ratio of the etching groove inlet width to the intermediate width of the etching groove is 10: 1 to 1: 1.
According to claim 1,
The etching groove has a depth of 3 μm or more and 20 μm or less, and a metallic glass-resin assembly.
According to claim 1,
The ratio of the etching groove depth to the etching groove entrance width is 10: 1 to 1: 1, a metallic glass-resin assembly.
According to claim 1,
The metallic glass layer is palladium (Pd) -based alloy, zirconium (Zr) -based alloy, copper (Cu) -based alloy, magnesium (Mg) -based alloy, iron (Fe) -based alloy, cobalt (Co) -based alloy, titanium (Ti) ) -Based alloy, calcium (Ca) -based alloy, and platinum (Pt) -based alloy, a metal glass-resin assembly comprising at least one alloy selected from the group consisting of.
According to claim 4,
The zirconium-based metallic glass is represented by the following formula (1), a metallic glass-resin conjugate:
[Formula 1]
A _a B _b C _c D _d
In Chemical Formula 1,
A is zirconium,
B is an 11-membered element,
C is a 10-membered element,
D is a 13-membered element,
The ratio of a: b is 2: 1 to 10: 1,
The ratio of c: d is 1.1: 1 to 5: 1.
According to claim 1,
The metallic glass layer and the resin layer has a peel strength of 60 kgf / cm ² to 150 kgf / cm ² , a metallic glass-resin assembly.
According to claim 1,
A metallic glass-resin assembly further comprising two or more protrusions provided on the surface of the metallic glass layer adjacent to the etching groove.
The method of claim 7,
The protrusion is formed at an acute angle or a right angle to the surface of the metallic glass layer, the metallic glass-resin assembly.
The method of claim 7,
A metallic glass-resin assembly, wherein the length from one end of the protrusion to the other end is 0.1 μm or more and 30 μm or less, and the height of the protrusion is 0.1 μm or more and 25 μm or less.
According to claim 1,
The resin layer is filled in the surface of the metallic glass layer inside the etching groove, and fixed to the metallic glass layer.
According to claim 1,
The resin layer contains polyphenyl sulfide resin (PPS), polycarbonate (PC), polycarbonate / ABS resin, polypropylene (PP) resin, polyamide (PA) resin, polyphenylene oxide (PPO) resin, and reinforcing material A metallic glass-resin conjugate comprising at least one resin selected from the group consisting of resins.
Forming an etching groove on the surface of the metallic glass by irradiating a surface of the metallic glass with a laser; And
Including the step of forming a resin layer on one surface of the metallic glass in which the etching groove is formed;
Method of manufacturing a metallic glass-resin assembly, wherein the ratio of the etch groove inlet width: the etch groove intermediate width is 10: 1 to 1: 1.
The method of claim 12,
The laser is a metallic glass-resin irradiated with an output of 3 W or more and 200 W or less, a frequency of 30 kHz or more and 600 kHz or less, a scan speed of 100 mm / s or more and 1000 mm / s or less, and a number of irradiations of 1 or more and 10 or less. Method for manufacturing a conjugate.

Images