JPWO2019216440A1 - Metal molded body and roughening method of metal molded body - Google Patents

Abstract

Provision of a metal molded body that serves as a manufacturing intermediate between a metal molded body and another molded body. It is a metal molded body having a porous structure formed on the surface layer portion, and the average of the maximum height difference of the pore depth measured by the following method is in the range of 30 to 200 μm. In addition, the range of the maximum height difference on which the average maximum height difference is calculated is within ± 40% based on the average maximum height difference. (Measuring method of average maximum height difference) About the area area of 20 mm × 20 mm (the entire area area if it is less than 20 mm × 20 mm) in the porous structure part of the metal molded body, a maximum of 10 points in a length range of 500 μm are randomized. Select to, and measure the maximum height difference of the pores of the porous structure within the range of 500 μm in length at the maximum of 10 places from the cross-sectional photograph of SEM, and obtain the average value of the maximum height difference.

Description

The present invention relates to a metal molded body having a porous structure portion and a method for producing the metal molded body.

Background technology After continuously irradiating the surface of a metal molded product with a continuous wave laser beam to roughen it into a porous structure, it is joined to a resin molded product or another metal molded product via an adhesive layer to manufacture a composite molded product. (See Patent No. 5959689 (Patent Document 1) and Patent No. 5860190 (Patent Document 2)). The adhesive layer is formed by an adhesive that has penetrated into the roughened porous structure portion of the metal molded body. The more complicated the pore structure, the higher the bonding effect of the adhesive layer, and the same pores. In the case of a structure, it is considered that the deeper the hole depth, the higher the bonding strength due to the adhesive layer. Japanese Patent No. 5774246 discloses an invention of a method for roughening a metal molded body by continuously irradiating the surface of the metal molded body with a continuous wave laser beam.

Outline of the Invention In the present invention, the average maximum height difference of the pore depth of the porous structure portion of the metal molded body is made shallower than that of the prior art, and the hole depth (maximum height difference of the hole depth) varies. With a metal molded body having a porous structure portion, high bonding strength and durability can be obtained when a composite molded body of the metal molded body and another molded body such as a resin molded body is formed by reducing the size. An object is to provide the manufacturing method.

The present invention is a metal molded body having a porous structural portion formed on the surface layer portion.
The average of the maximum height difference of the pore depth measured by the following method in the porous structure is in the range of 30 μm to 200 μm, and the range of the maximum height difference on which the average maximum height difference is calculated is. Provided is a metal molded product, which is within the range of ± 40% based on the average maximum height difference.
(Measuring method of average maximum height difference)
For an area area of 20 mm × 20 mm (total area area if it is less than 20 mm × 20 mm) in the porous structure portion of the metal molded body, a maximum of 10 locations having a length of 500 μm were randomly selected, and a maximum of 10 locations were selected. The maximum height difference of the pores of the porous structure within the range of 500 μm in length is measured from the cross-sectional photograph of the SEM, and the average value of the maximum height difference is obtained.

The present invention is a method for producing the metal molded product.
When a continuous wave laser is used to continuously irradiate the surface of the metal molded body with laser light at an irradiation rate of 2000 mm / sec or more to form a porous structure portion on the surface layer portion, the following (a) to (d) ) Is provided, which comprises a step of continuously irradiating a laser beam so as to satisfy the requirements of).
(A) Output is 4W to 250W
(B) Spot diameter is 20 μm to 80 μm
(C) Energy density is 1 MW / cm ^{2 to} 100 MW / cm ²
(D) The number of repetitions is 1 to 10 times

The metal molded body of the present invention reduces the variation in the maximum height difference of the pore depth of the porous structure formed in the metal molded body, thereby increasing the bonding strength when the composite molded body is formed with another molded body. It can be enhanced, and the durability of the bonding strength including water resistance and moisture resistance can be enhanced.

The plan view of the roughened metal molded body of this invention. The conceptual diagram which shows the porous structure of the cross section between II and II of FIG. Top view of the aluminum plate irradiated with laser light in Examples and Comparative Examples. The figure for demonstrating the method of measuring the bonding strength of the complex obtained in Reference Examples 1 to 3 and Reference Comparative Example 1. SEM of a partial cross section in the thickness direction of an aluminum plate (composite of Reference Example 1 composed of two aluminum plates integrated via an adhesive layer) having a roughened surface to form a porous structure in Example 1. Photo. Partial cross section in the thickness direction of an aluminum plate (composite of Reference Comparative Example 1 composed of two aluminum plates integrated via an adhesive layer) having a roughened surface to form a porous structure in Comparative Example 1. SEM photo. (A) is an SEM photograph of a partial cross section in the thickness direction of the composite of Reference Example 3 composed of two aluminum plates integrated via an adhesive layer of Example 3, and (b) is a reference comparison. 6 is an SEM photograph of a partial cross section in the thickness direction of a composite composed of two aluminum plates integrated via an adhesive layer of Example 1. (A) and (b) have the same scale.

Form for carrying out the invention <Metal molded body>
The metal molded product of the present invention has a porous structural portion formed on the surface layer portion. The metal that can be used for the metal molded body is not particularly limited, and can be appropriately selected depending on the intended use. For example, iron, various stainless steels, aluminum, zinc, titanium, copper, brass, chrome-plated steel, magnesium and alloys containing them (excluding stainless steel), tungsten carbide, chromium carbide and other cermets can be selected. , These metals can be applied to those subjected to surface treatment such as alumite treatment and plating treatment.

The metal moldings of the present invention can also be implants used to bond with living tissue, including bone or teeth. Examples of the implant include an artificial hip joint (stem, cup), an artificial joint such as an artificial knee joint, a fracture fixing (plate, a screw), and an artificial tooth root. When the metal molded body of the present invention is used as an implant, a metal molded body made of a metal selected from titanium (pure titanium), a titanium alloy, a cobalt-chromium alloy, and tantalum is used. Titanium alloys and cobalt-chromium alloys are used as medical (including dental) titanium alloys and cobalt-chromium alloys. For example, as the cobalt-chromium alloy, ichrome (manufactured by IDS Co., Ltd.), premier cast hard (manufactured by Denken Hydental Co., Ltd.) and the like can be used.

The shape and size of the metal molded body can be set according to the application. The porous structure portion of the metal molded body is the same as the cross-sectional structure of the surface layer portion after roughening described in the inventions of Patent Documents 1 and 2, and is a trunk hole having an opening formed in the thickness direction. It has an opening hole formed of a branch hole formed in a direction different from that of the trunk hole from the inner wall surface of the trunk hole, and an internal space having no opening formed in the thickness direction, and further described above. It has a tunnel connecting path connecting the opening hole and the internal space, and a tunnel connecting path connecting the opening holes to each other.

In the metal molded product of the present invention, the average of the maximum height difference of the pore depth of the porous structure from the surface of the metal molded product measured by the following method is in the range of 30 to 200 μm, and the average maximum height difference is described above. The range of the maximum height difference on which the calculation is based is within ± 40% based on the average maximum height difference.
(Measuring method of average maximum height difference)
For an area area of 20 mm × 20 mm (total area area if it is less than 20 mm × 20 mm) in the porous structure portion of the metal molded body, a maximum of 10 locations having a length of 500 μm were randomly selected, and a maximum of 10 locations were selected. The maximum height difference of the pores of the porous structure within the range of 500 μm in length is measured from the cross-sectional photograph of the SEM, and the average value of the maximum height difference is obtained.

The above-mentioned method for measuring the average maximum height difference will be described with reference to FIGS. 1 and 2. FIG. 1 shows a state in which a part of the surface of the metal molded body 10 is roughened to form the porous structure portion 11. It can be considered that the roughened porous structure portion 11 has substantially the same cross-sectional structure as long as the roughening conditions are constant, and there is no difference depending on the position of the porous structure portion 11. Therefore, an area area (measurement area area) 12 of 20 mm × 20 mm is arbitrarily selected from the entire porous structure portion 11, and 10 cross-sectional structure photographs are taken of the measurement area area by SEM (scanning electron microscope).

FIG. 2 shows a porous structure portion, but this is for explaining a measurement method and does not show a specific form of the above-mentioned porous structure portion. For each of the 10 SEM photographs, the height difference (Hmax) between the highest peak portion 20a and the lowest portion (bottom portion) 21 was measured for a range of 500 μm in length as shown in FIG. Find the average value (average maximum height difference). The highest peak portion 20a and the other peak portions 20b to 20d indicate a state in which the metal molded body 10 is melted and raised. Since the thickness of the surface layer portion in the present invention is the distance from the highest peak portion 20a in FIG. 2 to the bottom 21 of the deepest hole, the thickness of the surface layer portion is the same as the maximum height difference Hmax.

When the roughened area is less than 20 mm × 20 mm, the total roughened area is measured. If the roughened area is less than 20 mm × 20 mm and it is very narrow and it is difficult to measure 10 points, the measurement is performed in the range of 1 to 9 points. Furthermore, even if the roughened area is very large, if the roughening conditions are the same, it is considered that there is no difference in the structure of the porous structure, so 20 mm × 20 mm at any one location. The area area (measurement area area) may be measured, but if necessary, 2 to 5 20 mm × 20 mm area areas (measurement area area) can be arbitrarily selected and measured.

The average maximum height difference of the porous structure portion 11 of the metal molded body 10 is in the range of 30 μm to 200 μm, preferably in the range of 40 μm to 150 μm, more preferably in the range of 60 μm to 125 μm, and further preferably in the range of 70 μm to 100 μm.

The range of the maximum height difference that was the basis for calculating the average maximum height difference is within ± 40% when the average maximum height difference is used as a reference (when the average maximum height difference is 100 μm, the range of the maximum height difference is It is in the range of 60 μm to 140 μm), preferably in the range of ± 35%, and more preferably in the range of ± 32%.

The metal molded product of the present invention can be used as an abrasive, an adsorbent, etc., and can also be used as a manufacturing intermediate for a composite molded product composed of the metal molded product and another molded product. it can. Examples of the other molded body include a metal molded body made of a metal different from the metal molded body, a resin molded body (thermoplastic resin molded body, thermosetting resin molded body, electron beam curable resin molded body), and rubber molded body. , Whichever is selected from the elastomer molded product can be used.

<Manufacturing method of metal molded body>
The method for producing the metal molded product of the present invention will be described. First, a continuous wave laser is used to continuously irradiate the surface of the metal molded body 10 with laser light at an irradiation speed of 2000 mm / sec or more to roughen the surface, thereby forming a porous structure portion on the surface layer portion. The method of continuously irradiating the laser beam with the continuous wave laser can be carried out in the same manner as the method described in Patent Documents 1 and 2, but so as to satisfy the following requirements (a) to (d). It is necessary to continuously irradiate the laser beam. By the roughening treatment in this step, the average of the maximum height difference of the pore depth of the porous structure from the surface of the metal molded body was in the range of 30 to 200 μm, and it was the basis for calculating the average maximum height difference. A porous structure portion is formed in which the range of the maximum height difference is within a range of ± 40% with respect to the average maximum height difference.

Requirements (a)
The output of the laser light is 4W to 250W, preferably 50W to 250W, more preferably 100W to 250W, and even more preferably 150W to 220W.

Requirement (b)
The spot diameter of the laser beam is 20 μm to 80 μm, preferably 20 μm to 50 μm, and more preferably 20 μm to 35 μm.

Requirement (c)
Energy density during the laser beam irradiation is ^{1MW / cm 2 ~100MW / cm 2} , preferably from ^{10MW / cm 2 ~80MW / cm 2} , more preferably from ^{20MW / cm 2 ~50MW / cm 2} . The energy density at the time of laser light irradiation is based on the laser light output (W) and the laser light (spot area (cm ² ) (π · [spot diameter / 2] ² ) by the following equation: laser light output / spot area. The requirement (c) is calculated from the requirement (a) and the requirement (b), and the requirement (c) is important for controlling the roughened state of the metal molded body. When the numerical value of the requirement (c) calculated from the numerical range of the a) and the numerical range of the requirement (b) deviates from the above range, the numerical range of the above requirement (c) takes precedence.

Requirement (d)
The number of repetitions during laser light irradiation is 1 to 10 times, preferably 1 to 8 times, and more preferably 2 to 8 times. The number of repetitions during laser light irradiation is the total number of times of irradiation to form one line (groove) when irradiating the laser light linearly. When repeatedly irradiating one line, bidirectional irradiation or unidirectional irradiation can be selected. In bidirectional radiation, when forming one line (groove), after irradiating the continuous wave laser light from the first end to the second end of the line (groove), the second end to the first end Is irradiated with a continuous wave laser beam, and then repeatedly irradiated with a continuous wave laser beam from the first end to the second end, from the second end to the first end, and so on. One-way irradiation is a method of repeating one-way continuous wave laser light irradiation from the first end portion to the second end portion.

The irradiation conditions of the laser beam excluding the requirements (a) to (d) are as follows.
The irradiation speed of the continuous wave laser light is preferably 2,000 to 20,000 mm / sec, more preferably 5,000 to 20,000 mm / sec, and even more preferably 8,000 to 20,000 mm / sec. When irradiating a continuous wave laser beam linearly, the distance (line spacing) between adjacent irradiation lines (grooves formed by adjacent irradiation) is preferably 0.01 to 0.2 mm, preferably 0.03 to 0. .15 mm is more preferred. The line spacing may be the same for all line spacings, or may be different for some or all of the line spacings.

The wavelength is preferably 300 to 1200 nm, more preferably 500 to 1200 nm.

The defocus distance is preferably −5 to +5 mm, more preferably −1 to + 1 mm, and even more preferably −0.5 to +0.1 mm. The defocusing distance may be laser irradiation with a constant set value, or laser light irradiation may be performed while changing the defocusing distance. For example, at the time of laser light irradiation, the defocusing distance may be gradually reduced, or periodically increased or decreased.

Known continuous wave lasers can be used, for example, YVO4 laser, fiber laser (preferably single mode fiber laser), excima laser, carbon dioxide gas laser, ultraviolet laser, YAG laser, semiconductor laser, glass laser, ruby. Lasers, He-Ne lasers, nitrogen lasers, chelate lasers, dye lasers can be used. Among these, a fiber laser is preferable, and a single mode fiber laser is particularly preferable because the energy density is increased.

Example Example 1, 2, 3, Comparative Example 1
For each of two aluminum plates (A5025) (length 100 mm, width 25 mm, thickness 3 mm) 10 using the following laser device, a roughened region (25 mm) to be the porous structure portion 11 shown in FIG. 3 is used. × 12.5 mm) 12 was continuously irradiated with laser light under the conditions shown in Table 1 to roughen the surface to produce a metal molded body having a porous structure.

(Laser device)
Oscillator: IPG-Yb fiber; YLR-300-SM (single mode fiber laser)
Galvano Mirror SQUIREEL (manufactured by ARGES)
Condensing system 1: fc = 80mm / fθ = 163mm
Condensing system 2: fc = 80mm / fθ = 100mm

Reference Examples 1 to 3, Reference Comparative Example 1
The roughened portion (porous structure portion) 11 of each of the two aluminum plates 10 manufactured in Examples 1, 2 and 3 and Comparative Example 1 was placed on a hot plate and preheated (50 ° C.). , 15 minutes). Next, an adhesive (EP106NL, an industrial one-component epoxy adhesive, manufactured by Cemedine Co., Ltd.) was applied to the roughened portion (porous structure portion) 11 of the aluminum plate 10, and the first composite was not heat-cured. I got a body. Next, for each example, as shown in FIG. 4, the adhesive-coated surfaces (adhesive layer of the first composite) of the two aluminum plates 10 were fixed together with a clip and held at 140 ° C. for 1 hour. The adhesive was cured to produce a second composite.

The second composites of Reference Examples 1, 2 and 3 (using the metal moldings of Examples 1, 2 and 3) and Reference Comparative Example 1 (using the metal moldings of Comparative Example 1) are shown in FIG. The shear test was carried out in this way to evaluate the shear joint strength. As shown in FIG. 4, the shear test was carried out by fixing the adhesive (second composite) of two aluminum plates with the chuck 100 of the testing machine via the spacer 101 of stainless steel (SUS304). Further, the second complex of Reference Examples 1, 2, 3 and Reference Comparative Example 1 was immersed in warm water at 50 ° C., and 7 days and 30 days after the immersion, a shear test was performed as shown in FIG. 4 for shearing. The joint strength was evaluated. The results are shown in Table 1.

(Shear test conditions)
Testing machine: Orientec Tencilon (UCT-1T)
Tensile rate: 5mm / min
Distance between chucks: 50 mm

Further, the second composite of Reference Examples 1 to 3 (using the metal molded product of Examples 1 to 3) and Reference Comparative Example 1 (using the metal molded product of Comparative Example 1) after the measurement test of the shear bonding strength is used. It was used and cut with an ultrasonic cutter in the direction perpendicular to the adhesive surface of the two aluminum 10 sheets, and SEM photographs of the cut surface (Reference Example 1 is FIG. 5, Reference Comparative Example 1 is FIG. 6, and Reference Example 3). For the comparison of Reference Comparative Example 1, FIG. 7) was taken. From FIGS. 5, 6 and 7, the average maximum height difference (average of 10 points) of the aluminum plates of Examples 1, 3 and Comparative Example 1 was measured, and the results are shown in Table 1. Table 1 also shows the range of the maximum height difference when the average maximum height difference is used as a reference. Although the SEM photograph of Example 2 is omitted, the measurement was carried out in the same manner.

In both FIGS. 5 and 6, the white portion indicates the porous structure portion of the aluminum plate, and the one adhered on the porous structure indicates the adhesive. FIG. 5 is 200 times, FIG. 6 is 100 times, and the difference in hole depth is clear from the comparison between FIGS. 5 and 6, but when FIG. 6 is 200 times, the difference in hole depth is clear. It turns out to be more prominent. 7A and 7B are SEM photographs of the cut surface of Reference Example 3 (Example 3), and FIG. 7B is an SEM photograph of the cut surface of Reference Comparative Example 1 (Comparative Example 1), shown at the same scale. There is. In FIGS. 7 (a) and 7 (b), circular or amorphous black portions are observed, but these are all bubbles existing in the adhesive layer between the two aluminum plates. It was confirmed that the bubbles in Reference Example 3 (Example 3) (FIG. 7 (a)) were much smaller than those in Reference Comparative Example 1 (Comparative Example 1) (FIG. 7 (b)). The results are shown in Table 1.

From the common general technical knowledge of those skilled in the art, it is considered that the larger the pore depth of the porous structure portion of the metal molded body, the deeper the adhesive penetrates, and therefore the higher the shear bonding strength. As is clear from the comparison between (using the metal molded body of Comparative Example 1) and Reference Comparative Example 1 (using the metal molded body of Comparative Example 1), the shear bonding strength is about the same despite the clear difference in the average maximum height difference. there were.

In addition, from the results of the hot water immersion test, the second composite of Reference Examples 1 to 3 (using the metal molded product of Examples 1 to 3) was compared with Reference Comparative Example 1 (using the metal molded product of Comparative Example 1). It was confirmed that the decrease in shear bonding strength was small as compared with that of the above, and that the durability including water resistance and moisture resistance was increased by producing the composite molded body using the metal molded bodies of Examples 1 to 3. Further, the difference between the hot water immersion test results in Reference Examples 1 to 3 (metal molded products of Examples 1 to 3) and Reference Comparative Example 1 (metal molded products of Comparative Example 1) remains in the adhesive layer described above. It is considered that the size of the bubbles (the outer diameter of each bubble and the total volume of the bubbles) has an effect. In Reference Examples 1 to 3 (metal molded bodies of Examples 1 to 3), the small size of the bubbles in the adhesive layer means that the average maximum height difference of the hole depths is small. It is considered that the ease of degassing contributes.

Reference example 4
The aluminum plate was roughened in the same manner as in Example 1 to form a porous structure. Next, the aluminum plate was placed in the mold (made of PTFE) so that the joint surface (the surface of the porous structure portion) was on top, and resin pellets were added on the joint surface. Then, the mold was sandwiched between iron plates and compressed under the following conditions to obtain a composite molded body composed of an aluminum plate and a resin plate.
Resin pellets: PA66 resin (2015B, manufactured by Ube Industries, Ltd.)
Temperature: 285 ° C
Pressure: 1MPa (preheated), 10MPa
Time: 2 minutes (when preheated), 3 minutes Molding machine: Compressor manufactured by Toyo Seiki Seisakusho (mini test press-10)

Reference example 5
The aluminum plate was roughened in the same manner as in Example 1 to form a porous structure. Silicone rubber (KE-880-U; manufactured by Shin-Etsu Chemical Co., Ltd.) contains 4 parts by mass of a curing agent (C-4; manufactured by Shin-Etsu Chemical Co., Ltd .; containing approximately 20% of jittery butyl peroxide). And kneaded to obtain a silicone rubber composition. A composite molded body composed of an aluminum plate and a silicone rubber plate by bringing the silicone rubber composition into contact with the joint surface (surface of the porous structure portion) of the aluminum plate and curing the silicone rubber by press molding under the following curing conditions. Got
Heating temperature: 170 ° C
Pressure: 5MPa
Heating time: 10 minutes Secondary heating temperature: 200 ° C
Secondary heating time: 120 minutes

Industrial availability The metal molded product of the present invention can be used as a manufacturing intermediate between a metal molded product and another molded product such as a resin molded product or a rubber molded product, as well as an implant. It can be used for use.

Description of code 10 Metal molded body 11 Roughened part (porous structure part)
12 Measurement area 20a to 20d Peak part of the porous structure part 21 Deepest bottom of the hole of the porous structure part

Claims (8)

It is a metal molded body having a porous structure formed on the surface layer portion.
The average of the maximum height difference of the pore depth measured by the following method in the porous structure is in the range of 30 μm to 200 μm, and the range of the maximum height difference on which the average maximum height difference is calculated is. , A metal molded product that is within the range of ± 40% based on the average maximum height difference.
(Measuring method of average maximum height difference)
For an area area of 20 mm × 20 mm (total area area if it is less than 20 mm × 20 mm) in the porous structure portion of the metal molded body, a maximum of 10 locations having a length of 500 μm were randomly selected, and a maximum of 10 locations were selected. The maximum height difference of the pores of the porous structure within the range of 500 μm in length is measured from the cross-sectional photograph of the SEM, and the average value of the maximum height difference is obtained. The average maximum height difference of the porous structure portion of the metal molded body is in the range of 40 μm to 150 μm, and the range of the maximum height difference on which the average maximum height difference is calculated is based on the average maximum height difference. The metal molded product according to claim 1, wherein the metal molded product is within the range of ± 35%. The average maximum height difference of the porous structure portion of the metal molded body is in the range of 60 μm to 125 μm, and the range of the maximum height difference on which the average maximum height difference is calculated is based on the average maximum height difference. The metal molded product according to claim 1, wherein the metal molded product is within the range of ± 35%. The average maximum height difference of the porous structure portion of the metal molded body is in the range of 70 μm to 100 μm, and the range of the maximum height difference on which the average maximum height difference is calculated is based on the average maximum height difference. The metal molded product according to claim 1, wherein the metal molded product is within the range of ± 35%. It is a manufacturing intermediate of a composite molded body composed of the metal molded body and another molded body, and the other molded body is a metal molded body, a resin molded body, a rubber molded body, an elastomer made of a metal different from the metal molded body. The metal molded product according to any one of claims 1 to 4, which is selected from the molded products. The method for producing a metal molded product according to any one of claims 1 to 5.
When a continuous wave laser is used to continuously irradiate the surface of the metal molded body with laser light at an irradiation rate of 2000 mm / sec or more to form a porous structure portion on the surface layer portion, the following (a) to (d) A method for manufacturing a metal molded body, which comprises a step of continuously irradiating a laser beam so as to satisfy the requirements of).
(A) Output is 4W to 250W
(B) Spot diameter is 20 μm to 80 μm
(C) Energy density is 1 MW / cm ^{2 to} 100 MW / cm ²
(D) The number of repetitions is 1 to 10 times The output of (a) is 50 W to 250 W, the spot diameter of (b) is 20 μm to 50 μm, the energy density of (c) is 10 MW / cm ^{2 to} 80 MW / cm ² , and the number of repetitions of (d) is 1 to 8 times. The method for producing a metal molded product according to claim 6. The output of (a) is 100 W to 250 W, the spot diameter of (b) is 20 μm to 35 μm, the energy density of (c) is 20 MW / cm ^{2 to} 50 MW / cm ² , and the number of repetitions of (d) is 2 to 8 times. The method for producing a metal molded product according to claim 6.

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