JP5774246B2 - Method of roughening a metal molded body - Google Patents

Description

  The present invention relates to a method for producing a composite molded body comprising a metal molded body and a resin molded body.

From the viewpoint of reducing the weight of various parts, resin molded bodies are used as metal substitutes, but it is often difficult to substitute all metal parts with resin. In such a case, it is conceivable to manufacture a new composite part by joining and integrating the metal molded body and the resin molded body.
However, a technique capable of joining and integrating a metal molded body and a resin molded body with an industrially advantageous method with high bonding strength has not been put into practical use.

Patent Document 1 discloses a laser on a metal surface for bonding to a different material (resin), including a step of laser scanning with respect to a metal surface in one scanning direction and a step of laser scanning in a scanning direction crossing the scanning direction. An invention of a processing method is described.
Patent Document 2 discloses an invention of a laser processing method in which the laser scanning is performed in a superposed manner a plurality of times in the invention of Patent Document 1.

However, since the inventions of Patent Documents 1 and 2 must always perform laser scanning in two crossing directions, there is room for improvement in that the processing time is too long.
Furthermore, since sufficient surface roughening treatment can be performed by laser scanning in the cross direction, it is considered that the bonding strength can be increased, but the surface roughness state is not uniform, and the directionality of the strength of the bonded portion between the metal and the resin There is a problem that may not be stable.
For example, one joined body has the highest shearing force and tensile strength in the X-axis direction, while the other joined body has the highest shearing force and tensile strength in the Y-axis direction different from the X-axis direction. There is a possibility that the bonded body of the above may have the highest shearing force and tensile strength in the Z-axis direction different from the X-axis and Y-axis directions.
Depending on the product (for example, a rotating body part in one direction or a reciprocating part in one direction), a metal / resin composite having high bonding strength in a specific direction may be required. In the invention of 2, the above-mentioned demand cannot be sufficiently met.

  In addition, when the joint surface has a complicated shape or a shape including a narrow portion (for example, a star shape, a triangle, or a dumbbell type), the surface is partially roughened by the laser scanning method in the cross direction. As a result of non-uniformity, it may be considered that sufficient bonding strength cannot be obtained.

Patent Document 3 describes a method of manufacturing an electrical / electronic component in which a metal surface is irradiated with laser light to form irregularities, and a resin, rubber, or the like is injection-molded on the irregularity formation site.
In Embodiments 1 to 3, it is described that the metal long coil surface is irradiated with laser to form irregularities. In paragraph No. 10, the surface of the long metal coil is roughened in a striped or satin shape. In paragraph No. 19, the surface of the long metal coil is striped, dotted, wavy, knurled, or satin. It is described.
However, as described in the effects of the inventions in paragraphs 21 and 22, the purpose of laser irradiation is to form fine irregular irregularities on the metal surface, thereby enhancing the anchor effect. In particular, since the object to be processed is a long metal coil, it is considered that any irregularities are inevitably formed into fine irregular irregularities.
Therefore, the invention of Patent Document 3 discloses the same technical idea as the invention of forming fine irregularities on the surface by laser irradiation in the cross direction as in Patent Documents 1 and 2.

  Patent Document 4 is an invention of a method for producing a composite molded body composed of a metal molded body and a resin molded body. It is a laser scanning process to form markings consisting of straight lines and / or curves in one direction or different directions with respect to the joint surface of the metal molded body, and the markings consisting of straight lines and / or curves do not intersect each other. Laser scanning step. FIGS. 6 to 9 show square, circular, elliptical, and triangular marking patterns.

Japanese Patent No. 4020957 JP 2010-167475 A JP-A-10-294024 International Publication No. 2012/090671

  Since all of the methods of the prior art are methods of irradiating a laser with a pulse wave (non-continuous wave), there has been a problem that the processing speed becomes slow.

  This invention makes it a subject to provide the manufacturing method of the composite molded object which can raise a processing speed and can also improve the joint strength of a different direction.

As a means for solving the problems, the present invention
A method for producing a composite molded body in which a metal molded body and a resin molded body are joined,
A step of continuously irradiating a laser beam at an irradiation speed of 2000 mm / sec or more using a continuous wave laser on the joint surface of the metal molded body;
Production of a composite molded body having a step of placing in a mold a portion including a joint surface of a metal molded body irradiated with laser light in the previous step and injection molding a resin to be the resin molded body Provide a method.
In addition, the present invention provides other means for solving the problems,
A method for producing a composite molded body in which a metal molded body and a resin molded body are joined,
A step of continuously irradiating a laser beam at an irradiation speed of 2000 mm / sec or more using a continuous wave laser on the joint surface of the metal molded body;
A step of placing the portion including the joint surface of the metal molded body irradiated with laser light in the previous step in the mold, and performing compression molding in a state where at least the joint surface and the resin to be the resin molded body are in contact with each other. A method for producing a composite molded body is provided.

  According to the method for producing a composite molded body of the present invention, the processing speed can be increased. As a result, the processing time can be shortened, and the bonding strength between the metal molded body and the resin molded body can be increased.

Sectional drawing (a partial enlarged view is included) of the thickness direction of the composite molded object of this invention. Sectional drawing of the thickness direction of the composite molded object which is other embodiment of this invention. Explanatory drawing of the continuous irradiation pattern of a laser beam. Explanatory drawing of the continuous irradiation pattern of the laser beam which is another embodiment. Furthermore, the explanatory drawing of the continuous irradiation pattern of the laser beam which is another embodiment. Explanatory drawing of the continuous irradiation pattern of the laser beam which is one Embodiment. (A) is sectional drawing when it sees from the arrow direction between DD shown in FIG. 6, (b) is sectional drawing of another embodiment when it sees from the arrow direction between DD shown in FIG. (A) is a cross-sectional view when viewed from the direction of the arrow between AA shown in FIG. 6, (b) is a cross-sectional view when viewed from the direction of the arrow between BB shown in FIG. 6, (c) Sectional drawing when it sees from the arrow direction between CC shown in FIG. Explanatory drawing of the manufacturing method of a composite molded object when implementing injection molding. The SEM photograph of the metal molded object surface after continuous laser irradiation in Example 1. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in Example 2. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in Example 3. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in Example 4. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in Example 5. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in Example 6. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in the comparative example 2. FIG. Explanatory drawing of the measuring method for measuring the shearing joint strength (S1) when it pulls in a direction parallel to a joining surface. Explanatory drawing of the manufacturing method of a composite molded object when implementing injection molding. The perspective view of the manufactured composite molded object. Explanatory drawing of the measuring method of the tensile joining strength (S2) of the composite molded object of FIG. Explanatory drawing of the manufacturing method of a composite molded object when implementing compression molding. The perspective view of the composite molded object manufactured by compression molding. Explanatory drawing of the measuring method for measuring the tensile joint strength (S2) when it pulls to a joining surface at a perpendicular direction. 4 is an SEM photograph of a cross section in the thickness direction of the composite molded body obtained in Example 10. FIG. 4 is an SEM photograph of a cross section in the thickness direction of the composite molded body obtained in Example 11. FIG. 4 is an SEM photograph of a cross section in the thickness direction of the composite molded body obtained in Example 12. FIG. 14 is an SEM photograph of a cross section in the thickness direction of the composite molded body obtained in Example 15. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in Example 16. FIG. 18 is a SEM photograph of a cross section in the thickness direction of the composite molded body obtained in Example 16. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in Example 17. FIG. The SEM photograph of the joint surface of the metal molded object after continuous laser irradiation in Example 21. The graph which shows the relationship between the energy density of Experimental example 1, and groove depth, and the SEM photograph of the thickness direction cross section of a composite molded object. The graph which shows the relationship between the energy density of Experimental example 1 and a groove width, and the SEM photograph of the joint surface of the metal molded object after continuous laser irradiation.

  As shown in FIG. 1, the composite molded body 1 obtained by the production method of the present invention is obtained by bonding a metal molded body 10 and a resin molded body 20 on a bonding surface 12 of the metal molded body.

Hereinafter, the manufacturing method of the composite molded object 1 is demonstrated for every process.
In the first step, a continuous wave laser is used to continuously irradiate the joining surface 12 of the metal molded body 10 with a laser beam at an irradiation speed of 2000 mm / sec or more.
In this step, the joining surface 12 can be roughened in a very short time by continuously irradiating the joining surface 12 with laser light at a high irradiation speed. The bonding surface 12 (partially enlarged view) in FIG. 1 is shown exaggerated in a roughened state.

The irradiation speed of the continuous wave laser is preferably 2000 to 20,000 mm / sec, more preferably 2,000 to 18,000 mm / sec, and further preferably 2,000 to 15,000 mm / sec.
When the irradiation speed of the continuous wave laser is within the above range, the processing speed can be increased (that is, the processing time can be shortened), and the bonding strength can be maintained at a high level.

In this step, it is preferable that the laser beam is continuously irradiated so that the processing time when the following requirements (A) and (B) are satisfied is in the range of 0.1 to 30 seconds.
(A) The irradiation speed of laser light is 2000-15000 mm / sec.
(B) The area of the joint surface of the metal molded body is 100 mm ²
When the processing time for requirements (A) and (B) is within the above range, the entire bonding surface 12 can be roughened (roughened).

For example, the following method can be applied to the continuous irradiation of the laser beam, but there is no particular limitation as long as the bonding surface 12 can be roughened.
(I) As shown in FIGS. 3 and 4, one straight line or curve is formed from one side (short side or long side) side of the joint surface (for example, a rectangle) 12 to the opposite side. The method of continuously irradiating and repeating this to form a plurality of straight lines or curves.
(II) Continuous irradiation so that a straight line or a curved line is continuously formed from one side of the joint surface to the opposite side, and this time a straight line or a curved line spaced in the opposite direction is formed. A method of repeating continuous irradiation.
(III) A method in which continuous irradiation is performed from one side of the joint surface to the opposite side, and this time continuous irradiation is performed in the orthogonal direction.
(IV) A method of continuously irradiating the joint surface randomly.

When carrying out the methods (I) to (IV), it is also possible to form a single straight line or a single curve by continuously irradiating a laser beam a plurality of times.
Under the same continuous irradiation conditions, the degree of roughening of the bonding surface 12 increases as the number of times of irradiation (number of repetitions) for forming one straight line or one curve increases.

In the methods (I) and (II), when forming a plurality of straight lines or a plurality of curves, each straight line or curve is equally spaced within a range of 0.005 to 1 mm (b1 interval shown in FIG. 3). The laser beam can be continuously irradiated so as to be formed.
The interval at this time is made larger than the beam diameter (spot diameter) of the laser beam, and the number of straight lines or curves at this time is adjusted according to the area of the joint surface of the metal molded body 10. Can do.

In the methods (I) and (II), when a plurality of straight lines or a plurality of curves are formed, the respective straight lines or curves are in the range of 0.005 to 1 mm (b1 interval shown in FIGS. 3 and 4). The laser beam can be continuously irradiated so as to be formed at equal intervals.
These plural straight lines or plural curves can be made into one group, and a plurality of groups can be formed.
At this time, the intervals between the groups can be equal to each other within a range of 0.01 to 1 mm (interval b2 shown in FIG. 4).
Instead of the continuous irradiation method shown in FIGS. 3 and 4, as shown in FIG. 5, a continuous irradiation method without interruption is also possible from the start of continuous irradiation to the end of continuous irradiation.

The continuous irradiation of the laser beam can be performed, for example, under the following conditions.
The output is preferably 4 to 4000 W, more preferably 50 to 2500 W, further preferably 100 to 2000 W, and further preferably 250 to 2000 W.
The beam diameter (spot diameter) is preferably 5 to 200 μm, more preferably 5 to 100 μm, further preferably 10 to 100 μm, and further preferably 11 to 80 μm.
Furthermore, the preferable range of the combination of the output and the spot diameter can be selected from the energy density (W / μm ² ) obtained from the laser output and the laser irradiation spot area (π · [spot diameter / 2] ² ).
Energy density (W / μm ²⁾ is preferably from 0.1 W / [mu] m ² or more, more preferably 0.2~10W / μm ^2, more preferably 0.2~6.0W / μm ^2.
When the energy density (W / μm ² ) is the same, the larger the output (W), the larger the spot area (μm ² ) can be irradiated with laser, so the processing speed (laser irradiation area per ^second ) ; Mm ² / sec) is increased, and the processing time can be shortened.
The wavelength is preferably from 300 to 1200 nm, more preferably from 500 to 1200 nm.
The focal position is preferably −10 to +10 mm, more preferably −6 to +6 mm.

A preferable relationship among the irradiation speed of the continuous wave laser, the laser output, the laser beam diameter (spot diameter) and the energy density is that the irradiation speed of the continuous wave laser is 2,000 to 15,000 mm / sec, and the laser output is 250 to 2000 W, the laser beam diameter (spot diameter) and is 10 to 100 [mu] m, the laser output and the spot area energy density obtained from ([pi · [spot diameter / 2] ²⁾ (W / [mu] m ²⁾ is 0.2~10W / Μm ² range.

The metal of the metal molded body 10 is not particularly limited, and can be appropriately selected from known metals according to applications. Examples thereof include those selected from iron, various stainless steels, aluminum or alloys thereof, copper, magnesium and alloys containing them.
The joining surface 12 of the metal molded body 10 may be a flat surface as shown in FIG. 1, a curved surface as shown in FIG. 2, or may have both a flat surface and a curved surface.

  A known continuous wave laser can be used, for example, YVO4 laser, fiber laser, excimer laser, carbon dioxide laser, ultraviolet laser, YAG laser, semiconductor laser, glass laser, ruby laser, He-Ne laser, nitrogen. Lasers, chelate lasers, and dye lasers can be used.

In the method for producing a composite molded body of the present invention, the laser beam is continuously irradiated to the joint surface 12 of the metal molded body using a continuous wave laser at an irradiation speed of 2000 mm / sec or more. The continuously irradiated part is roughened.
One embodiment of the state of the joint surface 12 of the metal molded body at this time will be described with reference to FIGS.
As shown in FIG. 6, laser light (for example, a spot diameter of 11 μm) is continuously irradiated to form a large number of lines (in the drawing, three lines 61 to 63 are shown. The interval between the lines is about 50 μm). Can be roughened. The number of times of irradiation on one straight line is preferably 1 to 10 times.
At this time, the surface layer portion of the metal molded body 10 including the roughened bonding surface 12 is as shown in FIGS. 7A and 8A to 8C. The “surface layer portion of the metal molded body 10” is a portion from the surface to the depth of an open hole (stem hole or branch hole) formed by roughening.
In addition, when the number of times of irradiation to one straight line is more than 10, the level of roughening can be further increased, and in the composite molded body 1, the metal molded body 10 and the resin molded body 20 are joined. The intensity can be increased, but the total irradiation time becomes longer. For this reason, it is preferable to determine the number of times of irradiation to one straight line in consideration of the relationship between the bonding strength of the target composite molded body 1 and the manufacturing time. When the number of times of irradiation to one straight line is more than 10 times, it is preferably more than 10 times to 50 times or less, more preferably 15 to 40 times, further preferably 20 to 35 times.

As shown in FIGS. 7 and 8, the surface layer portion of the metal molded body 10 including the roughened bonding surface 12 has an open hole 30 having an opening 31 on the bonding surface 12 side.
The opening hole 30 includes a trunk hole 32 having an opening 31 formed in the thickness direction, and a branch hole 33 formed in a direction different from the trunk hole 32 from the inner wall surface of the trunk hole 32. One or a plurality of branch holes 33 may be formed.
As long as the bonding strength between the metal molded body 10 and the resin molded body 20 can be maintained in the composite molded body 1, a part of the open hole 30 may be composed only of the trunk hole 32, and the branch hole 33 may not be provided.

As shown in FIGS. 7 and 8, the surface layer portion of the metal molded body 10 including the roughened bonding surface 12 has an internal space 40 having no opening on the bonding surface 12 side.
The internal space 40 is connected to the open hole 30 by a tunnel connection path 50.

As shown in FIG. 7B, the surface layer portion of the metal molded body 10 including the roughened bonding surface 12 may have an open space 45 in which a plurality of open holes 30 are integrated. The open space 45 may be formed by combining the open hole 30 and the internal space 40. One open space 45 has a larger internal volume than one open hole 30.
In addition, the many open holes 30 may be united and the groove-shaped open space 45 may be formed.

  Although not shown, two internal spaces 40 as shown in FIG. 8A may be connected by a tunnel connection path 50, or an open space 45 and an opening as shown in FIG. The hole 30, the internal space 40, and another open space 45 may be connected by a tunnel connection path 50.

  The internal space 40 is entirely connected to one or both of the open hole 30 and the open space 45 through the tunnel connection path 50, but the bonding strength between the metal molded body 10 and the resin molded body 20 in the composite molded body 1. May be a closed space in which a part of the internal space 40 is not connected to the open hole 30 and the open space 45.

The details of the formation of the open hole 30 and the internal space 40 as shown in FIGS. 7 and 8 when the laser beam is continuously irradiated are unknown, but the laser beam is continuously irradiated at a predetermined speed or more. In some cases, holes and grooves are formed once on the surface of the metal molded body, but as a result of the molten metal rising and capping or damming, an open hole 30, an internal space 40, and an open space 45 are formed. It is considered a thing.
Similarly, the details of the formation of the branch hole 33 and the tunnel connection path 50 of the open hole 30 are also unknown, but the side wall portion of the hole or groove is caused by the heat accumulated near the bottom of the hole or groove once formed. As a result of melting, the inner wall surface of the trunk hole 32 is melted to form the branch hole 33, and the branch hole 33 is further extended to form the tunnel connection path 50.
When a pulsed laser is used instead of a continuous wave laser, an open hole or groove is formed on the joint surface of the metal molded body, but there is no internal space that does not have an opening, and the open hole and the internal A connection passage connecting the spaces is not formed.

In the next step, the part including the joint surface 12 of the roughened metal molded body 10 and the resin molded body 20 are integrated.
In this process,
The part including the joint surface of the metal molded body irradiated with the laser beam in the previous process is placed in the mold and the resin to be the resin molded body is injection molded, or the laser beam is irradiated in the previous process. A step of placing a portion including the joint surface of the metal molded body in a mold and compression-molding in a state where at least the joint surface and the resin to be the resin molded body are in contact with each other;
Either method can be applied.
In addition, the well-known shaping | molding method used as a shaping | molding method of a thermoplastic resin and a thermosetting resin is also applicable.
When a thermoplastic resin is used, the resin is cooled and solidified after applying the pressure to the molten resin to enter the hole, groove or tunnel connection path formed in the metal molded body. Any method can be used as long as the composite molded body can be obtained. In addition to injection molding and compression molding, a molding method such as injection compression molding can also be used.
When a thermosetting resin is used, by applying pressure to the liquid or molten resin, the resin enters the hole, groove, or tunnel connection formed in the metal molded body, and then the resin is removed. What is necessary is just the shaping | molding method which can obtain a composite molded object by making it thermoset. In addition to injection molding and compression molding, molding methods such as transfer molding can also be used.

When the compression molding method is applied, for example, the metal molded body 10 is disposed in a state where the joint surface 12 is exposed in the mold (the joint surface is on the front side), and a thermoplastic resin, A method of compressing after adding a plastic elastomer and a thermosetting resin (however, a prepolymer) can be applied.
In addition, when a thermosetting resin (prepolymer) is used in the injection molding method and the compression molding method, it is cured by heating in a subsequent process.

The resin of the resin molded body used in this step includes thermoplastic elastomers as well as thermoplastic resins and thermosetting resins.
A thermoplastic resin can be suitably selected from well-known thermoplastic resins according to a use. For example, polyamide-based resins (aliphatic polyamides such as PA6 and PA66, aromatic polyamides), copolymers containing styrene units such as polystyrene, ABS resin, AS resin, polyethylene, copolymers containing ethylene units, polypropylene, propylene Examples thereof include copolymers containing units, other polyolefins, polyvinyl chloride, polyvinylidene chloride, polycarbonate resins, acrylic resins, methacrylic resins, polyester resins, polyacetal resins, and polyphenylene sulfide resins.

  A thermosetting resin can be suitably selected from well-known thermosetting resins according to a use. For example, urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane can be mentioned.

  A thermoplastic elastomer can be suitably selected from well-known thermoplastic elastomers according to a use. Examples thereof include styrene elastomers, vinyl chloride elastomers, olefin elastomers, urethane elastomers, polyester elastomers, nitrile elastomers, and polyamide elastomers.

These thermoplastic resins, thermosetting resins, and thermoplastic elastomers can be blended with known fibrous fillers.
Examples of known fibrous fillers include carbon fibers, inorganic fibers, metal fibers, and organic fibers.
Carbon fibers are well known, and PAN, pitch, rayon, lignin and the like can be used.
Examples of inorganic fibers include glass fibers, basalt fibers, silica fibers, silica / alumina fibers, zirconia fibers, boron nitride fibers, and silicon nitride fibers.
Examples of the metal fiber include fibers made of stainless steel, aluminum, copper and the like.
Examples of organic fibers include polyamide fibers (fully aromatic polyamide fibers, semi-aromatic polyamide fibers in which one of diamine and dicarboxylic acid is an aromatic compound, aliphatic polyamide fibers), polyvinyl alcohol fibers, acrylic fibers, polyolefin fibers, Synthetic fibers such as polyoxymethylene fibers, polytetrafluoroethylene fibers, polyester fibers (including wholly aromatic polyester fibers), polyphenylene sulfide fibers, polyimide fibers, liquid crystal polyester fibers, natural fibers (cellulosic fibers, etc.) and regenerated cellulose ( Rayon) fiber or the like can be used.

As these fibrous fillers, those having a fiber diameter in the range of 3 to 60 μm can be used, but among these, for example, open holes formed by roughening the joining surface 12 of the metal molded body 10 It is preferable to use one having a fiber diameter smaller than the opening diameter such as 30. The fiber diameter is more desirably 5 to 30 μm, and further desirably 7 to 20 μm.
When a fibrous filler having a fiber diameter smaller than the opening diameter such as the open hole 30 is used, composite molding in which a part of the fibrous filler is stuck inside the open hole 30 or the like of the metal molded body. A body is obtained, and the bonding strength between the metal molded body and the resin molded body is increased, which is preferable.
As for the compounding quantity of the fibrous filler with respect to 100 mass parts of a thermoplastic resin, a thermosetting resin, and a thermoplastic elastomer, 5-250 mass parts is preferable. More preferably, it is 25-200 mass parts, More preferably, it is 45-150 mass parts.

The composite molded body 1 obtained by the manufacturing method of the present invention includes an open hole 30, an internal space 40, a tunnel connection path 50, and an open space 45 included in the metal molded body 10 as shown in FIGS. 7 and 8. In addition, the resin forming body 20 is integrated in a state where the resin enters.
Resin enters the open space 45 and the open space 45 (the trunk hole 32 and the branch hole 33) from the respective open portions, and the open space 30 and the open portions of the open space 45 enter the internal space 40. The resin that has entered through the tunnel enters through the tunnel connection path 50.
For this reason, the composite molded body 1 obtained by the manufacturing method of the present invention has a metal molded body 10 and a resin molded body in FIG. 1 as compared with the composite molded body in which the resin enters only the open holes 30 and the open spaces 45. Shear bonding strength (S1) when the resin molded body 20 is pulled in the parallel direction (X direction in FIG. 1) with the end of the metal molded body 10 fixed to the bonding surface 12 of the metal, and metal molding Both the tensile bonding strength (S2) when pulled in the vertical direction (Y direction in FIG. 1) with respect to the bonding surface 12 of the body 10 and the resin molded body 20 are increased.

Examples 1-6, Comparative Examples 1-3
In Examples and Comparative Examples, laser light was continuously irradiated under the conditions shown in Table 1 on the entire bonding surface 12 (a range of 40 mm ² ) of a metal molded body (aluminum: A5052) shown in FIG.
Examples 1 to 5 and Comparative Examples 1 to 3 were continuously irradiated with laser light as shown in FIG. 3, and Example 6 was continuously irradiated with laser light as shown in FIG.
Next, the processed metal molded body was used for injection molding by the following method to obtain composite molded bodies shown in FIG. 17 of Examples and Comparative Examples.

FIG. 10 is a SEM photograph (100 times, 500 times, 700 times, 2500 times) of the joint surface of the metal molded body after continuous irradiation with the continuous wave laser of Example 1. It was confirmed that the joint surface was roughened and a small recess was formed.
FIG. 11 is an SEM photograph (100 times and 500 times) of the joint surface of the metal molded body after continuous irradiation with the continuous wave laser of Example 2. It was confirmed that the joint surface was roughened and a small recess was formed.
FIG. 12 is an SEM photograph (100 times and 500 times) of the joint surface of the metal molded body after continuous irradiation with the continuous wave laser of Example 3. It was confirmed that the joint surface was roughened and a small recess was formed.
FIG. 13 is a SEM photograph (100 times and 500 times) of the joint surface of the metal molded body after continuous irradiation with the continuous wave laser of Example 4. It was confirmed that the joint surface was roughened and a small recess was formed.
FIG. 14 is an SEM photograph (100 times and 500 times) of the joint surface of the metal molded body after continuous irradiation with the continuous wave laser of Example 5. It was confirmed that the joint surface was roughened and a small recess was formed.
FIG. 15 is an SEM photograph (100 times and 500 times) of the joint surface of the metal molded body after continuous irradiation with the continuous wave laser of Example 6. It was confirmed that the joint surface was roughened and a small recess was formed.
FIG. 16 is a SEM photograph (100 times and 500 times) of the joint surface of the metal molded body after continuous irradiation with the continuous wave laser of Comparative Example 2. Since the irradiation speed was 1000 mm / sec, the joint surface was not sufficiently roughened.

<Injection molding>
Resin: GF60% reinforced PA66 resin (Plastotron PA66-GF60-01 (L7): manufactured by Daicel Polymer Co., Ltd.), fiber length of glass fiber: 11 mm
Resin temperature: 320 ° C
Mold temperature: 100 ° C
Injection molding machine: FANUC ROBOSHOT S2000i100B)

[Tensile test]
Using the composite molded bodies shown in FIG. 17 of Examples and Comparative Examples, a tensile test was performed to evaluate the shear bonding strength (S1). The results are shown in Table 1.
The tensile test is performed in the X direction shown in FIG. 17 (the X direction in FIG. 1, and the bonding surface 12 until the metal molded body 10 and the resin molded body 20 break with the end on the metal molded body 10 side fixed. The maximum load until the joint surface 12 was broken when pulled in the parallel direction) was measured.
<Tensile test conditions>
Testing machine: Orientec Tensilon (UCT-1T)
Tensile speed: 5mm / min
Distance between chucks: 50mm

As can be confirmed from the comparison between Example 1 and Comparative Example 1, in Example 1, a composite molded body having higher bonding strength was obtained in 1/50 of the processing time.
Considering mass production on an industrial scale, the processing time can be shortened (that is, energy required for production can be reduced), and the industrial value of the production method of Example 1 is very large.
As can be confirmed from the comparison between Example 1 and Examples 2 and 3, the bonding strength can be increased by increasing the number of repetitions of laser irradiation as in Examples 2 and 3, but even in that case, Compared with Comparative Examples 1 to 3, the processing time could be shortened.
As can be confirmed from the comparison between Examples 1 to 3 and Examples 4 to 6, when the laser irradiation speed is increased as in Examples 4 to 6, the shear bond strength (S1) (X in FIGS. 1 and 17) is increased. Direction bonding strength).

Examples 7-9, Comparative Examples 4-6
In Examples and Comparative Examples, laser light was continuously irradiated under the conditions shown in Table 2 on the entire bonding surface 12 (90 mm ² wide range) of a metal molded body (aluminum: A5052) shown in FIG.
Then, it implemented similarly to Examples 1-6 and Comparative Examples 1-3, and obtained the composite molded object shown in FIG.
About the obtained composite molded object, the tensile bond strength (S2) corresponding to the Y direction (Y direction of FIG. 20) shown in FIG. 1 was measured with the following method.
As shown in FIG. 20, the tensile test is performed in the Y direction of FIG. 20 (the Y direction of FIG. 1) until the metal molded body 10 and the resin molded body 20 are broken while being fixed by the jig 70 on the metal molded body 10 side. The maximum load until the joint surface 12 was broken when it was pulled in the direction perpendicular to the joint surface 12 was measured.
<Tensile test conditions>
Testing machine: Orientec Tensilon (UCT-1T)
Tensile speed: 5mm / min
Distance between chucks: 50mm

Examples 7 to 9 in Table 2 (area 90 mm ^{2 of the} joining surface 12) correspond to Examples 1 to 3 (area 40 mm ² of the joining surface 12) in Table 1, but the area of the joining surface 12 is 2 .25 times.
However, as is clear from comparison with Comparative Examples 4 to 6 in Table 2, by applying the manufacturing method of the present invention, the joint surface 12 (area 90 mm ² ) of the metal molded body 10 and the resin molded body 20 is applied. It was confirmed that the tensile bond strength (S2) when pulled in the vertical direction (Y direction in FIG. 1) can be increased.

Examples 10-15, Comparative Examples 7-9
In Examples and Comparative Examples, a laser was continuously irradiated under the conditions shown in Table 3 on the entire joining surface 12 (a range of 40 mm ² ) of a metal molded body (aluminum: A5052) shown in FIG.
Examples 10 to 14 and Comparative Examples 8 and 9 were continuously irradiated with laser light as shown in FIG. 3, Example 15 was continuously irradiated with laser light as shown in FIG. 4, and Comparative Example 7 was shown in FIG. In this way, laser light was continuously irradiated.
Next, the processed metal molded body was used and compression molded by the following method to obtain composite molded bodies of Examples and Comparative Examples.

<Compression molding>
The metal molded body 10 was placed in the mold (made of Teflon) so that the bonding surface 12 was on top, and resin pellets were added on the bonding surface 12. Thereafter, the mold was sandwiched between iron plates and compressed under the following conditions to obtain a composite molded body shown in FIG.
Resin pellets: PA66 resin (2015B, manufactured by Ube Industries)
Temperature: 285 ° C
Pressure: 1 MPa (during preheating), 10 MPa
Time: 2 minutes (during preheating), 3 minutes Molding machine: Compressor manufactured by Toyo Seiki Seisakusho (mini test press-10)

[Tensile test]
Using the composite molded bodies of Examples and Comparative Examples, a tensile test was performed to evaluate the tensile bonding strength (S2). The results are shown in Table 3.
The tensile test was performed as follows.
As shown in FIG. 23, a jig 74a composed of an aluminum plate 72a and a tensile portion 73a fixed in a direction perpendicular to the surface of the resin molded body 20 of the composite molded body is bonded by an adhesive 71a. Stuck.
Similarly, as shown in FIG. 23, a jig 74b composed of an aluminum plate 72b and a fixing portion 73b fixed in a direction perpendicular to the surface of the exposed surface of the metal molded body 10 of the composite molded body is used as an adhesive. It was fixed by 71b.
With the fixing portion 73b fixed, the maximum load until the joint surface 12 was broken when the tensile portion 73a was pulled under the following conditions was measured.
<Tensile test conditions>
Testing machine: Tensilon Tensile speed: 5mm / min
Distance between chucks: 16mm

[How to observe the internal space]
The presence or absence of an internal space having no opening was confirmed. The method is shown below.
In the joint part including the joint surface 12 of the composite molded body, three points are randomly cut in the direction perpendicular to the laser irradiation direction (AA, BB, CC direction in FIG. 6), and the cross-sectional part of each surface layer part is scanned. Three points were randomly observed with an electron microscope (SEM).
When the presence or absence of an internal space was confirmed in the SEM observation photograph (500 times), the number was counted. Excluded were those whose maximum internal space diameter was 10 μm or less.
The number of internal spaces (average value at 9 locations) is shown (Table 3).
The internal space was analyzed by micro X-ray analysis (EDX), and it was confirmed that the resin had penetrated into the internal space.
SEM: Hitachi High-Technologies S-3400N
EDX analyzer: Apollo XP manufactured by Ametech (formerly Edax Japan)
Further, when the metal surface of the composite molded body is a curved surface as shown in FIG. 2, the same measurement can be performed by cutting the sample in a direction perpendicular to the tangent to the curved surface.
In addition, even if it uses a microscopic laser Raman spectroscopic measuring apparatus, it can confirm that resin has penetrate | invaded to internal space.

  In Examples 10 to 15, since the metal molded body 10 was continuously irradiated with laser light on the bonding surface 12 in the same manner as in Examples 1 to 6, the metal molded body 10 was bonded to the surface of the bonding surface 12. These are the same as the SEM photographs (FIGS. 10 to 15) shown in Examples 1 to 6, respectively.

24 is a SEM photograph of a cross section in the thickness direction of the composite molded body of Example 10 (cross-sectional views of A to C in FIG. 6).
The portion that appears relatively white is the metal molded body 10, and the portion that appears relatively black is the resin molded body 20.
From FIG. 24, a plurality of holes formed in the thickness direction and a plurality of independent spaces can be confirmed, and since they all appear black, it can be confirmed that the resin has entered.
The hole formed in the thickness direction is recognized as a hole corresponding to the trunk hole 32 of the open hole 30.
The independent space is recognized as a cross section of the branch hole 33 extending from the inner wall surface of the trunk hole 32 in a direction different from the formation direction of the trunk hole 32, or the internal space 40.
And if it is the internal space 40, since resin has penetrate | invaded inside, it is thought that it is connected with the open hole 30 and the tunnel connection path 50. FIG.
For this reason, the composite molded body of Example 10 has a high tensile bonding strength (S2) when pulled in the direction perpendicular to the bonding surface 12 (Y direction in FIG. 1).

25 is a SEM photograph of a cross section in the thickness direction of the composite molded body of Example 11 (cross-sectional views of A to C in FIG. 6).
The portion that appears relatively white is the metal molded body 10, and the portion that appears relatively black is the resin molded body 20.
From FIG. 25, a plurality of holes formed in the thickness direction and a plurality of independent spaces can be confirmed, and since they all appear black, it can be confirmed that the resin has entered.
The hole formed in the thickness direction is recognized as a hole corresponding to the trunk hole 32 of the open hole 30.
The independent space is recognized as a cross section of the branch hole 33 extending from the inner wall surface of the trunk hole 32 in a direction different from the formation direction of the trunk hole 32, or the internal space 40.
And if it is the internal space 40, since resin has penetrate | invaded inside, it is thought that it is connected with the open hole 30 and the tunnel connection path 50. FIG.
For this reason, the composite molded body of Example 11 has a high tensile bonding strength (S2) when pulled in the direction perpendicular to the bonding surface 12 (Y direction in FIG. 1).

FIG. 26 is an SEM photograph of a cross section in the thickness direction of the composite molded body of Example 12 (cross-sectional views of FIGS. 6A to 6C).
From FIG. 26, a plurality of holes formed in the thickness direction and a plurality of independent spaces can be confirmed, and since they all appear black, it can be confirmed that the resin has entered.
The hole formed in the thickness direction is recognized as a hole corresponding to the trunk hole 32 of the open hole 30.
The independent space is recognized as a cross section of the branch hole 33 extending from the inner wall surface of the trunk hole 32 in a direction different from the formation direction of the trunk hole 32, or the internal space 40.
And if it is the internal space 40, since resin has penetrate | invaded inside, it is thought that it is connected with the open hole 30 and the tunnel connection path 50. FIG.
For this reason, the composite molded body of Example 12 has a high tensile bonding strength (S2) when pulled in the direction perpendicular to the bonding surface 12 (Y direction in FIG. 1).

FIG. 27 is an SEM photograph of a cross section in the thickness direction of the composite molded body of Example 15.
The portion that appears relatively white is the metal molded body 10, and the portion that appears relatively black is the resin molded body 20.
It can be confirmed that a large number of open holes 30 are formed in the metal molded body 10.
For this reason, the composite molded body of Example 15 has a high tensile bonding strength (S2) when pulled in the direction perpendicular to the bonding surface 12 (Y direction in FIG. 1).

Examples 16-18
In the same manner as in Examples 7 to 9 (Table 2), Table 4 shows the entire joining surface 12 (90 mm ² wide range) of the metal molded body (metal shown in Table 4) shown in FIG. Laser light was continuously irradiated under the conditions.
Then, it implemented similarly to Examples 1-6 and Comparative Examples 1-3, and obtained the composite molded object shown in FIG.
About the obtained composite molded object, the tensile bond strength (S2) corresponding to the Y direction (Y direction of FIG. 20) shown in FIG. 1 was measured with the following method.
As shown in FIG. 20, the tensile test is performed in the Y direction of FIG. 20 (the Y direction of FIG. 1) until the metal molded body 10 and the resin molded body 20 are broken while being fixed by the jig 70 on the metal molded body 10 side. The maximum load until the joint surface 12 was broken when it was pulled in the direction perpendicular to the joint surface 12 was measured.
<Tensile test conditions>
Testing machine: Orientec Tensilon (UCT-1T)
Tensile speed: 5mm / min
Distance between chucks: 50mm

Examples 19-21
A laser was continuously irradiated under the conditions shown in Table 4 on the entire bonding surface 12 (width range of 40 mm ² ) of the metal molded body (metal shown in Table 4) shown in FIG.
The laser beam was continuously irradiated as shown in FIG.
Next, the processed metal molded body was used, and compression molded in the same manner as in Examples 10 to 15 to obtain a composite molded body.
The tensile test and the observation method of the internal space were carried out in the same manner as in Examples 10-15.

In Example 16, compared with Examples 7 to 9 in Table 2, since the number of repetitions was large, the processing time was long, but the tensile bond strength (S2) was high (FIGS. 28 and 29).
In Example 17 (SUS304), compared with Example 9 (aluminum) in Table 2, the laser irradiation speed was slowed and the processing time was increased, but the tensile bond strength (S2) was increased (FIG. 30). .
Example 18 (SUS304, PP with GF) was under the same conditions as Example 17 (SUS304, PA with GF), but the tensile bond strength (S2) was low.
In Example 19, compared with Examples 10 to 12 in Table 3, since the number of repetitions was large, the processing time was long, but the tensile bond strength (S2) was high.
In Example 20 (SUS304) and Example 21 (SUS304; FIG. 31), compared with Example 13 (aluminum) in Table 3, the laser irradiation speed was decreased and the number of repetitions was increased, so the processing time was longer. However, the tensile bond strength (S2) increased.

Experimental example 1
In the same manner as in Example 1, the relationship between energy density and groove depth when the aluminum surface was irradiated with laser (FIG. 32) and the relationship between energy density and groove width (FIG. 33) were tested.
As a result, a clear difference was observed when the energy density was around 0.3 W / μm ² .

Examples 22-35
In the same manner as in Examples 7 to 9 (Table 2), Table 5 shows the entire bonding surface 12 (90 mm ² wide range) of the metal molded body (metal shown in Table 5) shown in FIG. Laser light was continuously irradiated under the conditions.
Then, it implemented similarly to Examples 1-6 and Comparative Examples 1-3, and obtained the composite molded object shown in FIG.
About the obtained composite molded object, the tensile bond strength (S2) corresponding to the Y direction (Y direction of FIG. 20) shown in FIG. 1 was measured with the following method.
As shown in FIG. 20, the tensile test is performed in the Y direction of FIG. 20 (the Y direction of FIG. 1) until the metal molded body 10 and the resin molded body 20 are broken while being fixed by the jig 70 on the metal molded body 10 side. The maximum load until the joint surface 12 was broken when it was pulled in the direction perpendicular to the joint surface 12 was measured.
<Tensile test conditions>
Testing machine: Orientec Tensilon (UCT-1T)
Tensile speed: 5mm / min
Distance between chucks: 50mm

Examples 36-42
In the same manner as in Examples 7 to 9 (Table 2), Table 6 shows the entire bonding surface 12 (90 mm ² wide range) of the metal molded body (metal shown in Table 6) shown in FIG. Laser light was continuously irradiated under the conditions.
Then, it implemented similarly to Examples 1-6 and Comparative Examples 1-3, and obtained the composite molded object shown in FIG.
About the obtained composite molded object, the tensile bond strength (S2) corresponding to the Y direction (Y direction of FIG. 20) shown in FIG. 1 was measured with the following method.
As shown in FIG. 20, the tensile test is performed in the Y direction of FIG. 20 (the Y direction of FIG. 1) until the metal molded body 10 and the resin molded body 20 are broken while being fixed by the jig 70 on the metal molded body 10 side. The maximum load until the joint surface 12 was broken when it was pulled in the direction perpendicular to the joint surface 12 was measured.
<Tensile test conditions>
Testing machine: Orientec Tensilon (UCT-1T)
Tensile speed: 5mm / min
Distance between chucks: 50mm

DESCRIPTION OF SYMBOLS 1 Composite molded object 10 Metal molded object 12 Joint surface 20 Resin molded object

Claims (7)

  The surface of the metal molded body is roughened by continuously irradiating the surface of the metal molded body with laser light at an irradiation speed of 2000 mm / sec or more using a continuous wave laser. Method.   When a continuous wave laser is used to continuously irradiate the surface of the metal molded body with a laser beam at an irradiation speed of 2000 mm / sec or higher, a laser beam is formed so that a line composed of a straight line, a curve, and a combination thereof is formed. The roughening method of the metal molded object of Claim 1 which irradiates light continuously. When continuously irradiating the surface of the metal molded body with laser light at an irradiation speed of 2000 mm / sec or more using a continuous wave laser,
A laser beam is continuously irradiated so that a line composed of a straight line, a curved line and a combination thereof is formed,
The method for roughening a metal molded body according to claim 1, wherein the laser beam is continuously irradiated a plurality of times to form one straight line or one curved line. When continuously irradiating the surface of the metal molded body with laser light at an irradiation speed of 2000 mm / sec or more,
Laser light is continuously irradiated so that a line composed of a plurality of straight lines, a plurality of curves and combinations thereof is formed,
The roughening of the metal forming body of Claim 1 which continuously irradiates a laser beam so that the said several straight line or the said several curve may be formed at equal intervals in the range of 0.005-1 mm, respectively. Method. When continuously irradiating a laser beam at an irradiation speed of 2000 mm / sec or more to the joint surface of the metal molded body,
Laser light is continuously irradiated so that a line composed of a plurality of straight lines, a plurality of curves and combinations thereof is formed,
The plurality of straight lines or the plurality of curved lines are formed at equal intervals in the range of 0.005 to 1 mm, respectively, and each group is equally spaced in the range of 0.01 to 1 mm. The metal surface roughening method according to claim 1, wherein the laser beam is continuously irradiated so as to form a plurality of groups. 2. The step of continuously irradiating a laser beam so that the processing time is 0.1 to 30 seconds in the following conditions (A) and (B) when continuously irradiating the laser beam. The roughening method of the metal molded object of description.
(A) The irradiation speed of laser light is 2000-15000 mm / sec.
(B) The area of the joint surface of the metal molded body is 100 mm ² When continuously irradiating the laser beam,
The irradiation speed of the continuous wave laser is 2,000-15,000 mm / sec,
The laser output is 250 to 2000 W, the laser beam diameter (spot diameter) is 10 to 100 μm ,
Step energy density determined from the laser output and the spot area ([pi · [spot diameter / 2] ²⁾ (W / ^{μm 2)} is continuously irradiated with a laser beam to be in the range of 0.2～10W / [mu] m ² The metal surface roughening method according to claim 1, wherein