KR102498239B1 - 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 using metallic glass surface-treated with a laser, and a method for manufacturing the same.

Description

Metallic glass-resin junction, and manufacturing method thereof

The present invention relates to a metallic glass-resin bonded body capable of realizing excellent durability and adhesion characteristics through high adhesive strength, and a manufacturing method thereof.

In general, bonding between dissimilar materials (materials) such as metal and resin is not easy in most cases because the physical and chemical properties inherent in each material and the surface state are different. Techniques that can be attempted for bonding between dissimilar materials can be largely classified into bonding using an adhesive, mechanical fastening, welding, and insert injection.

Among them, a method using an adhesive or an adhesive film has the advantage of being simple in use, and thus is most commonly used as a representative and classic method used for bonding between dissimilar materials in electronic products. In the case of using an adhesive film, the adhesive is hardened and bonding force is created by cutting the adhesive film to size, placing it between metal and plastic, applying heat and pressure using a jig, and then cooling it for a certain period of time. Use

In addition, mechanical fastening is performed using mechanical fastening tools such as screws or rivets. In this process, self-piercing rivets slightly modified from general mechanical bonding processes to be effective for joining different materials, clinching A process such as clinching is being introduced.

The adhesive and mechanical tightening process enables the bonding of different materials with relatively easy access, but it is a process in which different materials are inserted between different materials or the joint is exposed as it is, so new technologies have recently been proposed for pure bonding between two base materials. there is.

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 an adhesive, and the deterioration rate due to moisture increases in high temperature and high humidity environments. As a result, there is a disadvantage in that strength loss of the joint may increase.

In addition, when using an adhesive for bonding different materials, since the bonding temperature is room temperature or lower than the temperature used when applying the adhesive film method, deterioration of the joint due to heat does not occur, and high stiffness and airtightness of the joint can be obtained at the same time. However, since the wetting phenomenon that occurs between the adhesive and the surface of the base material has a great effect on the adhesive strength, adhesive bonding is a method to improve the wettability between the adhesive and the base material surface through appropriate surface treatment on the metal or plastic surface. The process must be carried out as a necessity, and for this, there is the inconvenience of increasing the surface energy of the base material or reducing the surface tension of the adhesive.

The method using mechanical fastening tools such as screws or rivets is also a classic method, and mechanical fastening tools are generally heavy and expensive to use, which does not meet the trend of weight reduction in related technologies.

Since the conventional method of joining different materials has the above-mentioned problems, it is necessary to study a method that can improve 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 bonded body capable of realizing excellent durability and adhesion characteristics through high adhesive strength.

In addition, the present invention is to provide a method for manufacturing the above metallic glass-resin bonded body.

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 of the metallic glass layer including the groove, wherein the ratio of the entrance width of the etching groove to the middle width of the etching groove is 10:1 to 1:1, or 5:1 to 1:1. 1, or 2: 1 to 1: 1, a metallic glass-resin bonded body is provided.

In the present specification, 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 on which the etching grooves are formed, wherein the ratio of the entrance width of the etching groove to the middle width of the etching groove is 10:1 to 1:1, or 5:1 to 5:1. A method for manufacturing a 1:1, or 2:1 to 1:1, metallic glass-resin bonded body is provided.

Hereinafter, a metallic glass-resin bonded body and a manufacturing method thereof according to specific embodiments of the present invention will be described in more detail.

I. Metallic Glass-Resin Bonding

According to one embodiment of the invention, the metallic glass layer including an etching groove on at least one surface; and a resin layer bonded to one surface of the metallic glass layer including the groove, wherein the ratio of the entrance width of the etching groove to the middle width of the etching groove is in the range of 10:1 to 1:1. can be provided.

Like the metallic glass-resin bonded body of one embodiment, the present inventors form an etching groove on one surface of the metallic glass layer and bond it to the resin, thereby increasing the surface area and improving the bonding strength between the metallic glass-resin through an anchoring effect. It was confirmed through experiments that it could be done, and the invention was completed.

When the metallic glass is not subjected to pretreatment, bonding is not performed during insert injection and there is no effect during sandblasting treatment.

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

The metallic glass-resin bonding body can be applied as an exterior material for various products, and for example, it can be used as an exterior material for electronic products, more specifically, as a rear case for a mobile phone.

(1) metallic glass layer

According to an exemplary embodiment of the present invention, it is preferable to use a metallic glass layer that is easy to form a pattern by laser irradiation and has excellent thermal conductivity. The metallic glass included in the metallic glass layer heats a metal or alloy composed of metal elements to a high temperature to form a high-temperature liquid phase with an irregular structure, and then rapidly cools the metallic glass to maintain the irregular structure at room temperature. It refers to a metastable phase material that has a non-crystalline nature.

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

Examples of the metallic glass are not particularly limited, and various metallic glass materials known in the art may all be used. Specific examples of the metallic glass include palladium (Pd)-based alloys, zirconium (Zr)-based alloys, copper (Cu)-based alloys, magnesium (Mg)-based alloys, iron (Fe)-based alloys, and cobalt (Co)-based alloys. , 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, A calcium (Ca)-based alloy and a platinum (Pt)-based alloy refer to a metal element having the highest molar ratio among metal elements included in each alloy.

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

[Formula 1]

A _a B _b C _c D _d

In Formula 1, A is Zr, B is a group 11 element, C is a group 10 element, D is a group 13 element, the ratio of a:b is 2:1 to 10:1, and the ratio of c:d is 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, 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 include Pd ₄₀ Ni ₄₀ P ₂₀ and 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 include Mg ₅₄ Cu _26.5 Ag _8.5 Gd ₁₁ and Mg ₆₅ Cu _7.5 Ni _7.5 Zn ₅ Ag ₅ Y ₅ Gd ₅ .

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

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

Examples of the calcium (Ca)-based alloy 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 not only has a strength 3 to 10 times higher than that of crystalline metal, an elastic deformation limit 5 to 10 times higher, and a surface hardness 2 to 3 times higher than that of crystalline metal, but can also have corrosion resistance tens of thousands of times higher than that of stainless steel. It is possible to achieve excellent effects that are difficult to implement.

According to an exemplary embodiment of the present invention, the shape of the metallic glass layer may be applied without particular limitation as long as it can be laser etched and can be smoothly bonded to a resin. For example, a flat or curved surface can be applied. It may be a cylinder and a polyhedron, including.

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

The ratio of the entrance width of the etching groove to the middle width of the etching groove 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 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. Within the above range, the resin layer can sufficiently fill the inside of the etching groove, so that bonding strength between the metallic glass layer and the resin layer can be improved.

That is, in the metallic glass-resin assembly according to the embodiment, the width of the inlet of the etching groove is greater than or equal to the width of the middle of the etching groove. Conversely, when the width of the inlet of the etching groove is narrower than the middle width of the etching groove, it is difficult to quickly fill the groove in the case of a resin having poor flowability, and as a result, bonding strength may be deteriorated.

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

A width of the entrance of the etching groove may be greater than or equal to 10 μm and less than or equal to 30 μm. According to one embodiment of the present invention, the middle width of the etching groove may be 15 μm or more and 25 μm or less.

The ratio of the etching groove depth 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 a 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 protruding portion may be continuous or partly discontinuously connected along the direction of the etching groove.

According to one 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 groove. Protrusions provided in a direction away from another 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 a central axis of the etching groove on the surface of the metallic glass layer to form the protrusion.

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

According to one embodiment of the present invention, the angle formed by the protrusion with respect 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 more. may be less than or equal to °.

Within this range, the resin layer can sufficiently fill between the protrusions, the resin layer can be sufficiently fixed to the metallic glass layer, and bonding strength between the metallic glass layer and the resin layer can be maximized.

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

Within the range of the length of the protrusion and the height of the protrusion, the resin layer may be sufficiently supplied and fixed to the metallic glass layer with sufficient bonding strength. In addition, the tensile value of the metallic glass-resin assembly may be maintained high within the above range, the structure of the protruding part may be easily controlled, and airtightness and watertightness of the assembly may be secured.

Meanwhile, the metallic glass layer may include two or more etching grooves, and the plurality of etching grooves may independently form a dot pattern or be continuously connected to form a line pattern or a crosshatch pattern. there is.

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

In this case, the distance between the central axes of the etching grooves 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 merging of protrusions facing each other within the range, it is possible to prevent the formation of an empty space structure in which the resin layer cannot be supplied, and the bonding area between the structure formed by the etching groove and the protrusion and the resin layer is reduced. By relatively increasing, it is possible to form a sufficient binding force.

In the present specification, the distance between the central axes of the etching grooves may refer to a distance from an end of one etching groove having a maximum depth to an end of another etching groove.

(2) resin layer

The resin layer contains polyphenylsulfide resin (PPS), polycarbonate (PC), polycarbonate/ABS resin, polypropylene (PP) resin, polyamide (PA) resin, polyphenylene oxide (PPO) resin, and a 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 one or more selected from the group consisting of glass fiber, talc, and carbon fiber, but the type is not limited.

The resin layer may fill an inside of the etching groove and a surface of the metallic glass layer and be fixed to the metallic glass layer. In addition, the resin layer may be filled between the protrusions. Specifically, the resin layer may be fixed to the metallic glass layer by filling an inside of the etching groove and an enclosure formed of the protruding portion. Accordingly, a stronger anchoring effect may occur.

(3) metallic glass-resin junction

Bonding strength 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 or less, and bonding strength between the metallic glass layer and the resin layer may be different depending on the type of the resin layer.

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

II. Manufacturing method of metallic glass-resin junction

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 on which the etching grooves are formed, wherein the ratio of the entrance width of the etching groove to the middle width of the etching groove is 10:1 to 1:1, or 5:1 to 5:1. Provided is a method for manufacturing a 1:1, or 2:1 to 1:1, metallic glass-resin bonded body.

When the metallic glass-resin bonding method according to an exemplary embodiment of the present invention is used, as the resin layer at the interface between the metallic glass layer and the resin layer is melted, the resin layer is formed on the surface of the metallic glass layer as well as the etched metallic By flowing into the etching groove of the glass layer and the inner space of the fence-shaped burr formed along the etching groove, a stronger anchoring effect may occur.

In addition, according to one embodiment of the present invention, unlike the existing metallic glass-resin bonding method, there is no concern about problems such as environmental pollution caused by chemical hazardous substances or difficulty in managing the mass production process, and also, by minimizing process steps, It is possible to improve operational efficiency and provide a metallic glass-resin bond capable of realizing airtightness and watertightness.

In the step of irradiating the surface of the metallic glass with a laser to form an etching groove on the surface of the metallic glass, the contents of the metallic glass, the resin layer, the etching groove, and the protrusion are all the same as those described above in the embodiment. include

The laser irradiated to the surface of the metallic glass layer may form a pattern by etching grooves on the surface of the metallic glass by being irradiated to the surface of the metallic glass.

Specifically, as the laser is irradiated onto the surface of the metallic glass, etching grooves may be formed according to the direction in which the laser travels. 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 layer, two or more lasers may be irradiated to the surface of the metallic glass layer, and the two or more lasers may travel in parallel. can Specifically, the traveling direction of the one first laser and the traveling direction of the other second laser may be parallel.

Also, according to the laser irradiation, the protruding portion may be continuously connected or may be partially discontinuously connected.

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 high absorptivity can be applied and deformation after injection is minimized by using a picosecond laser that can minimize 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 to 600 kHz, or 100 kHz to 600 kHz, or 200 kHz to 400 kHz. The frequency of the laser may mean the number of oscillations per second of the pulsed laser.

The scanning 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 or less. s or less. The scan speed of the pulsed laser may mean a speed at which the irradiated laser beam moves from one point to another point.

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

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

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

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

For more specific example, when the surface of the metallic glass layer has a linear pattern, the laser beam is 50 μm to 2000 μm, or 100 μm to 1000 μm, or 150 μm to 850 μm, or 200 μm to 800 μm. It can be irradiated in parallel every interval of ㎛ or less. By preventing the merging of protrusions facing each other within the range, it is possible to prevent the formation of an empty space structure in which the resin layer cannot be supplied, and the bonding area between the structure formed by the etching groove and the protrusion and the resin layer is reduced. By relatively increasing, it is possible to form a sufficient binding force.

Under the irradiation condition of the laser, the etching groove depth, the etching groove entrance width, the etching groove middle width, the protruding portion length, the protruding portion height, and an angular range between the protruding portion and the surface of the metallic glass layer may be realized. Accordingly, bonding strength between the metallic glass layer and the resin layer may be increased.

Specifically, the ratio of the entrance width of the etching groove to the middle width of the etching groove 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 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. Within the above range, the resin layer can sufficiently fill the inside of the etching groove, so that bonding strength between the metallic glass layer and the resin layer can be improved.

Specifically, the energy condition of the laser enables recondensation of the material evaporated from the wall of the etching groove and the entrance of the etching groove, and can form a relatively rough protrusion protruding from the metallic glass layer. An area where the layer can be bonded to the resin layer and an anchoring structure can be formed.

According to an exemplary embodiment of the present invention, the laser may be irradiated in a depth direction of the etching groove, and a part of the metallic glass layer may move along a 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 the protruding portion.

Meanwhile, the forming of the resin layer on one surface of the metallic glass having the etching groove may be performed by supplying resin to each of the surface of the metallic glass layer, the etching groove, and the protrusion. Specifically, the resin layer forming step is performed by using a metallic glass layer whose surface is etched as a mold, supplying the resin layer to the mold, and bonding the resin layer to the mold by applying pressure (insert injection ) can be

Various methods and equipment known in the field of injection molding can be applied without limitation to the specific method and equipment for the insert injection.

According to the present invention, a metallic glass-resin bond that can realize excellent durability and adhesion characteristics through high adhesion, and a manufacturing method thereof can be provided.

1 shows a SEM image of the surface of a metallic glass substrate of Preparation Example 1.
2 shows cross-sectional SEM images of metallic glass substrates of Preparation Examples 1 and 2.
Figure 3 shows 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 Preparation Example 2.

The invention is explained in more detail in the following examples. However, the following examples are merely 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: Manufacturing of Metallic Glass Substrate>

Preparation Examples 1 to 3

Patterned metallic glass was manufactured by irradiating and etching one surface of a metallic glass (Zr _67.5 Cu ₁₅ Ni ₁₀ Al _7.5 ) substrate with a width of 20 mm x length of 60 mm x height of 220 to 260 μm by irradiating a pulse laser under the conditions shown in Table 1 below. did

As shown in FIG. 1, the etching was performed so that the etching grooves continuously form a pattern of a linear structure in a direction parallel to the length of the metallic glass. had a gap.

division Laser power (W) Wavelength (nm) Scanning 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 Manufacturing Example 1

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

Comparative Manufacturing Example 2

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

<Examples and Comparative Examples: Preparation of Metallic Glass-Resin Bonded Body>

Examples 1 to 3

Into the insert injection mold so that one side of the patterned metallic glass substrate obtained in Preparation Examples 1 to 3 is exposed, and molten polyphenylsulfide resin is injected on the patterned side to form a polyphenylsulfide solution having a thickness of 2 mm. A metallic glass-resin bonded body in which the stratum was bonded was prepared.

Comparative Example 1

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

<Experimental example>

Experimental example 1

Images taken using a scanning electron microscope (SEM) of the cross section of the patterned metallic glass substrate obtained in Preparation Examples 1 to 3 and Comparative Preparation Example 2 are shown in FIGS. 2 to 4, respectively.

Each shape in 10 to 20 grooves for each specimen (the depth of the etching groove, the entrance width of the etching groove, the middle width of the etching groove, the length of the protrusion (meaning the length from one end to the other end), and The average value of the measured values 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 Manufacturing Example 1 Comparative Manufacturing Example 2 Depth of etching groove 13 13 6 - - Entrance width of etching groove 19 19 20 - - Medium width of etch groove 19 19 13 - - length of overhang 26 26 11 - - height of overhang 22 22 8 - -

Experimental Example 2

The bonding strength of the interface portion of the metallic glass-resin bonding bodies of the above Examples and Comparative Examples was measured by the strength at which separation or breakage occurred when shear was applied at a tensile rate of 10 mm/min using a UTM tensile machine (INSTRON 5969). . The final joint strength was calculated by dividing the measured tensile strength value by the bonded area.

The bonding strength was recorded in Table 3 by calculating the average value from the five specimens.

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 Manufacturing Example 1 Comparative Manufacturing Example 2 Joint strength (kgf/cm ² ) 66.1 110.6 112.1 not measurable not measurable

As shown in Table 3, the metallic glass-resin composites of Examples 1 to 3 in which the patterned metallic glass substrate and the resin layer were bonded using a laser had high bonding strength of 66.1 kgf/cm ² to 112.1 kgf/cm ² On the other hand, in the case of Comparative Examples 1 and 2 in which patterning using a laser was not performed, measurement of bonding strength was impossible because the metallic glass and the resin layer were not bonded at all.

Claims (13)

a metallic glass layer having an etching groove on at least one surface thereof; and
A resin layer bonded to one surface of the metallic glass layer including the groove,
The ratio of the entrance width of the etching groove to the middle width of the etching groove is 10:1 to 1:1,
the resin layer fills the inside of the etching groove and the surface of the metallic glass layer and is fixed to the metallic glass layer;
A metallic glass-resin bonded body having a peel strength between the metallic glass layer and the resin layer of 60 kgf/cm ² to 150 kgf/cm ² .
According to claim 1,
The etching groove has a depth of 3 μm or more and 20 μm or less.
According to claim 1,
The ratio of the etching groove depth to the etching groove entrance width is 10: 1 to 1: 1, the metallic glass-resin assembly.
According to claim 1,
The metallic glass layer may include a palladium (Pd)-based alloy, a zirconium (Zr)-based alloy, a copper (Cu)-based alloy, a magnesium (Mg)-based alloy, an iron (Fe)-based alloy, a cobalt (Co)-based alloy, and a titanium (Ti A metallic glass-resin assembly comprising one or more alloys selected from the group consisting of )-based alloys, calcium (Ca)-based alloys, and platinum (Pt)-based alloys.
According to claim 4,
The zirconium-based metallic glass is represented by Formula 1 below, a metallic glass-resin composite:
[Formula 1]
A _a B _b C _c D _d
In Formula 1,
A is zirconium;
B is a group 11 element,
C is a group 10 element,
D is a group 13 element,
The ratio of a: b is 2: 1 to 10: 1,
The ratio of c:d is 1.1:1 to 5:1.
delete According to claim 1,
The metallic glass-resin assembly further comprises two or more protrusions provided on a surface of the metallic glass layer adjacent to the etching groove.
According to claim 7,
The protruding portion forms an acute angle or a right angle with respect to the surface of the metallic glass layer, the metallic glass-resin bonded body.
According to claim 7,
A length of the protrusion from one end to the other end is 0.1 μm or more and 30 μm or less, and a height of the protrusion is 0.1 μm or more and 25 μm or less.
delete According to claim 1,
The resin layer contains polyphenylsulfide resin (PPS), polycarbonate (PC), polycarbonate/ABS resin, polypropylene (PP) resin, polyamide (PA) resin, polyphenylene oxide (PPO) resin, and a reinforcing material. A metallic glass-resin junction comprising at least one resin selected from the group consisting of resins.
forming etching grooves on the surface of the metallic glass by irradiating a laser beam 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; includes,
The ratio of the entrance width of the etching groove to the middle width of the etching groove is 10:1 to 1:1,
the resin layer fills the inside of the etching groove and the surface of the metallic glass layer and is fixed to the metallic glass layer;
The method of manufacturing a metallic glass-resin bonded body, wherein the peel strength between the metallic glass layer and the resin layer is 60 kgf/cm ² to 150 kgf/cm ² .
According to 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 irradiation of 1 or more to 10 or less. Conjugate manufacturing method.

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