JP6276080B2 - Fiber reinforced thermoplastic resin composition, composite molded body using the same, and method for producing the same - Google Patents

Description

  The present invention relates to a fiber-reinforced thermoplastic resin composition used for manufacturing a composite molded body composed of a metal molded body and a resin molded body, a composite molded body using the composition, and a method for manufacturing the composite 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, there is a need for a technique that enables a metal molded body and a resin molded body to be joined and integrated with an industrially advantageous method with high bonding strength.

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.
The dissimilar material is described in paragraph 0061, and a thermoplastic resin added with glass fiber is also 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. Patent Document 2 describes the same dissimilar materials as Patent Document 1.

  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. However, there is no specific description about the resin and the composition containing it.

Patent Documents 4 and 5 disclose inventions having technical ideas different from Patent Documents 1 to 3, and Examples show that the bonding strength between a metal molded body and a resin molded body is high.
Patent Documents 4 and 5 describe a material of a resin molded body in which carbon fiber, inorganic fiber, metal fiber, and organic fiber are blended with thermoplastic resin, thermosetting resin, and thermoplastic elastomer. (Paragraph numbers 0090 and 0091 of Patent Document 4 and paragraph numbers 0051 and 0052 of Patent Document 5).

Japanese Patent No. 4020957 JP 2010-167475 A JP-A-10-294024 JP2013-52669A JP 2014-18995 A

The present invention is a composite molded body composed of a metal molded body and a resin molded body, and can be used as a material for producing a resin molded body that acts to increase the bonding strength between the metal molded body and the resin molded body. It is an object to provide a reinforced thermoplastic resin composition.
Furthermore, this invention makes it the other subject to provide the composite molded object which uses the said fiber reinforced thermoplastic resin composition, and its manufacturing method.

As a means for solving the problems, the present invention
A fiber-reinforced thermoplastic resin composition for producing the resin molded body of a composite molded body in which a metal molded body and a resin molded body are joined,
(A) thermoplastic resin,
(B) Reinforcing fiber (excluding milled fiber),
(C) a thermoplastic elastomer,
(D) A fiber-reinforced thermoplastic resin composition containing milled fibers is provided.

The present invention provides a solution to other problems.
A composite molded body in which a metal molded body and a resin molded body are joined,
The resin molded body is composed of the fiber-reinforced thermoplastic resin composition according to any one of claims 1 to 6,
The metal molded body has irregularities formed by irradiating the surface with laser light,
Provided is a composite molded body in which the metal molded body and the resin molded body are joined and integrated by entering a resin molded body into the irregularities, and a method for manufacturing the composite molded body.

  When the fiber reinforced thermoplastic resin composition of the present invention is used as a resin molding material of a composite molding comprising a metal molding and a resin molding, the bonding strength between the metal molding and the resin molding 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 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. The SEM photograph of the joint surface of the metal molded object of Example 1 after continuous laser irradiation on the conditions of Table 1. FIG.

<Fiber-reinforced thermoplastic resin composition>
The fiber-reinforced thermoplastic resin composition of the present invention is used as a material for producing the resin molded body of a composite molded body composed of a metal molded body and a resin molded body.
The composite molded body 1 is as shown in FIGS. 1 and 2, and a metal molded body 10 and a resin molded body 20 are joined and integrated at a contact surface (joint surface) 12.
The fiber-reinforced thermoplastic resin composition of the present invention contains components (A) to (D) and other components contained as necessary.

[(A) Thermoplastic resin]
The thermoplastic resin as the component (A) can be appropriately selected from known thermoplastic resins according to the application.
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.
Among these, those selected from polyamide resins and olefin resins are preferable.

(A) When using an olefin resin as a component, it is preferable to use acid-modified polyolefin together.
As the acid-modified polyolefin, maleic acid-modified polyolefin (maleic acid-modified polypropylene) and maleic anhydride-modified polyolefin (maleic anhydride-modified polypolypropylene) are preferable.

[(B) Reinforcing fiber]
As the reinforcing fiber (excluding milled fiber) as the component (B), those used in known fiber reinforced resins can be used.
Examples of the reinforcing fiber (B) include carbon fiber, inorganic fiber, metal fiber, and organic fiber.
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 etc. can be mentioned.

The reinforcing fiber of component (B) may be either a long fiber or a short fiber.
When the component (B) is a long fiber, the length is preferably 4 to 30 mm, more preferably 5 to 25 mm, and even more preferably 6 to 20 mm.
When the component (B) is a short fiber, the length is preferably 0.1 to 1.5 mm, more preferably 0.2 to 1.0 mm, and still more preferably 0.3 to 0.8 mm.
The fiber for reinforcing the component (B) has a fiber diameter of preferably 3 to 60 μm, more preferably 5 to 30 μm, and even more preferably 7 to 20 μm.

Examples of the thermoplastic elastomer of component (C) include urethane elastomers, polyester elastomers, olefin elastomers, polyamide elastomers, and styrene elastomers.
Among these, a styrene elastomer (a thermoplastic elastomer having a styrene unit) is preferable, and a hydrogenated thermoplastic elastomer having a styrene unit is more preferable.
As the component (C), styrene-butadiene copolymer (SBS), styrene-ethylene-butadiene-styrene copolymer (SEBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene-propylene-styrene. Copolymers (SEPS) and those obtained by modifying these copolymers with unsaturated carboxylic acids (such as maleic anhydride) or anhydrides thereof are preferred.

[(D) Milled fiber]
(D) The milled fiber of a component can mention what consists of carbon fiber, an inorganic fiber, a metal fiber, an organic fiber etc. similarly to (B) component.
The fiber diameter of the milled fiber (D) is preferably 5 to 23 μm, more preferably 6 to 17 μm, and even more preferably 7 to 13 μm.
(D) As for the average fiber length (weight average fiber length) of the milled fiber of a component, 30-150 micrometers is preferable, 40-100 micrometers is more preferable, 50-90 micrometers is more preferable.
The weight average fiber length is determined by, for example, a well-known calculation method described in JP-A-2002-5924 [0016] to [0017], JP-A-2006-274061 [0044], [0045], and the like. It is required.

The content ratios of the components (A) to (D) in the composition of the present invention are as follows.
The reinforcing fiber of the component (B) is preferably 8 to 220 parts by mass, more preferably 25 to 150 parts by mass, and still more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the component (A).
20-60 mass% is preferable, as for the content rate (mass%) in the composition of (B) component, 25-55 mass% is more preferable, and 30-50 mass% is further more preferable.
(C) As for the thermoplastic elastomer of a component, 1-20 mass parts is preferable with respect to 100 mass parts of (A) component, 3-15 mass parts is more preferable, and 5-10 mass parts is further more preferable.
Component (D) is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, and even more preferably 5 to 10 parts by weight with respect to 100 parts by weight of component (A).

  The composition of the present invention can be produced by a method of dry blending the components (A) to (D), a method of melt-kneading the dry blend and finally forming pellets, etc. It is preferable to include a resin-containing fiber bundle.

[Composition Comprising Resin-Containing Fiber Bundle Containing Component (A) and Component (B)]
(B) component reinforcing fiber bundles bundled in a state aligned in the length direction, containing (impregnated) molten (A) component and then integrating the resin-containing fiber bundles, A composition comprising component (C) and component (D).
The resin-containing fiber bundle is solidified in a state where the molten (A) component enters the fiber bundle of the (B) component.
The component (C) and the component (D) are not included in the resin-containing fiber bundle, but are added separately.
The (C) component and the (D) component can be blended as they are, but the (A) component thermoplastic resin, the (C) component, the (D) component mixed (masterbatch), the (A) component A thermoplastic resin, the component (C) and the component (D) are extruded with a melt kneader and pelletized (master batch pellets).
The thermoplastic resin used as the component (A) and the thermoplastic resin used as the masterbatch are preferably the same, but may be those that are compatible with each other even if they are not the same.
In addition, when (C) component and (D) component are used as a masterbatch containing (A) component, the quantity of (A) component contained in the said masterbatch is also the quantity of (A) component in a composition. include.

[Composition Comprising Resin-Containing Fiber Bundles Containing Components (A) to (D)]
Resin that has been cut after integrating (C) component, (D) component and molten (A) component into the reinforcing fiber bundle of component (B) bundled in a state aligned in the length direction A composition comprising a containing fiber bundle.
The resin-containing fiber bundle is a state in which the (C) component and the (D) component have entered together with the molten (A) component inside the fiber bundle of the (B) component, or one of the (C) component and the (D) component. It is solidified with the part attached to the surface of the fiber bundle.
The thermoplastic elastomer of component (C) may be in a molten state as in component (A) and enter the fiber bundle.

A method for producing a resin-containing fiber bundle is well known, and for example, it can be produced by applying a drawing method using a die described in paragraph No. 0011 of JP2012-99745A. More specifically, It can be produced in the same manner as in Production Example 1 (paragraph number 0030) of the publication.
In the resin-containing fiber bundle, the length of the reinforcing fiber (B) and the length of the resin-impregnated fiber bundle are the same.

<Composite molded body>
This will be described with reference to FIGS.
In the composite molded body 1 of the present invention, a metal molded body 10 and a resin molded body 20 are joined and integrated at a contact surface (joint surface) 12. The resin molded body 20 is made of the above-described fiber-reinforced thermoplastic resin composition.
The metal molded body 10 has irregularities on the surface of the bonding surface 12 before joining, and after joining, the resin molded body 20 enters the irregularities so that the metal molded body 10 and the resin molded body 20 are formed. Bonded and integrated.

  The unevenness formed on the bonding surface 12 is preferably formed by means selected from laser beam irradiation, etching, pressing, and blasting, and is formed by irradiation with continuous wave laser light or pulse wave laser light. Is more preferable.

  The metal forming the metal molded body 10 is not particularly limited, and can be appropriately selected from known metals according to the application. Examples thereof include those selected from iron, various stainless steels, aluminum or alloys thereof, copper, magnesium and alloys containing them.

<Method for producing composite molded body>
The manufacturing method of the composite molded object of this invention is demonstrated for every process.
Laser light is irradiated to the joint surface 12 of the metal molded body 10 having a desired shape according to the application.
In FIG. 1, the metal molded body 10 is a flat plate, but it may be a cube or a rectangular parallelepiped, or may have a curved surface such as the round bar of FIG.

Irradiation with a laser beam can use a continuous wave laser or a pulse wave laser.
When a pulse wave laser is used, Patent Document 1 (Japanese Patent No. 4020957), Patent Document 2 (Japanese Patent Laid-Open No. 2010-167475), Patent Document 3 (Japanese Patent Laid-Open No. 10-294024), and Patent Document 4 ( Irradiation can be performed in the same manner as described in JP 2013-52669 A) and Patent Document 5 (JP 2014-18995 A).

When a continuous wave laser is used, a method of continuously irradiating the joining surface 12 of the metal molded body 10 with laser light at an irradiation speed of 2000 mm / sec or more using a continuous wave laser can be applied.
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) of 10 to 100 [mu] m, the energy density obtained from the laser output and the spot area ([pi × [spot diameter / 2] ²⁾ (W / [mu] m ²⁾ is 0.2~10W / Μm ² range.

  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, when continuous light laser is used to continuously irradiate the joining surface 12 of the metal molded body with an irradiation speed of 2000 mm / sec or more, the laser light is 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 addition, it can replace with the process of irradiating a laser beam with respect to the above-mentioned joining surface 12 of the metal forming body 10, and the process of performing an etching process, a press process, and a blast process can be implemented.
For the etching process, a method in which a well-known etching solution corresponding to a metal and a masking member are used in combination can be applied.
For the press working, a method using a needle-like working tool capable of forming a concave portion of a predetermined size or a processing tool having a blade capable of forming a groove of a predetermined size can be applied.
As blasting, shot blasting, sand blasting, or the like can be used.

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,
In the previous step, the portion including the joint surface of the metal molded body irradiated with laser light in the previous step is placed in the mold, and the fiber reinforced thermoplastic resin composition to be the resin molded body is injection molded, or in the previous step The portion including the joint surface of the metal molded body irradiated with laser light is placed in the mold, and compression molding is performed with at least the joint surface and the fiber reinforced thermoplastic resin composition that becomes the resin molded body in contact with each other. The process of
Either method can be applied.
In addition, a known molding method used as a thermoplastic resin molding method can also be applied.
When a fiber reinforced thermoplastic resin composition is used, by applying pressure or the like to the molten composition containing the thermoplastic resin of component (A), holes, grooves and tunnel connection paths formed in the metal molded body (A) component thermoplastic resin, (C) component thermoplastic elastomer, and (D) component milled fiber, and then the composition is cooled and solidified to obtain a composite molded body. I just need it.
In addition to injection molding and compression molding, molding methods such as injection compression molding and 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 (with the joint surface on the front side) and melted therein (A). After putting the composition containing the component thermoplastic resin, a compression method can be applied.

  When the (B) component and the (D) component having a fiber diameter smaller than the opening diameter of the open hole 30 or the like, particularly the (D) component, the (D) component is placed inside the open hole 30 or the like of the metal molded body. This is preferable because a composite molded body in which the milled fiber is contained is obtained, and the bonding strength between the metal molded body and the resin molded body is increased.

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. The fiber reinforced thermoplastic resin composition forming the resin molded body 20 is integrated into a single body.
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 fiber reinforced thermoplastic resin composition that has entered from the inside passes through the tunnel connection path 50.

<Use ingredients>
(A) Component PP: PMB60A (manufactured by Sun Allomer Co., Ltd.)
PA6: UBE nylon 1013B (manufactured by Ube Industries)
PA66: UBE nylon 2015B (manufactured by Ube Industries)
MXD6: Reny 6002 (Mitsubishi Engineering Plastics)
(B) Component GF1: RS240QR-489 (manufactured by Nittobo) (fiber diameter 17.4μm)
GF2: RS240QR-483 (manufactured by Nittobo) (fiber diameter: 17.4μm)
(C) Component ER1: Tuftec H1041 (SEBS) (Asahi Kasei Chemical Co., Ltd.)
ER2: Tuftec M1913 (Maleic anhydride-modified SEBS) (Asahi Kasei Chemical Co., Ltd.)
(D) Component MF1: PF50E-401 (Nittobo) Average fiber length 60μm, Fiber diameter 10.5μm
MF2: EPH80M-10A (Nippon Electric Glass Co., Ltd.) average fiber length 80μm, fiber diameter 10.5μm
(Other)
MAH-PP: Maleic anhydride modified PP, OREVAC CA100 (manufactured by Arkema Co., Ltd.)
Talc: Micron White 5000S (manufactured by Hayashi Kasei Co., Ltd.)
Wollastonite: KAP-170 (Kansai Matec Co., Ltd.)

Example 1 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF1) through the crosshead die, the component (A) (PP (containing MAH-PP)) is melted from the 250 ° C. set temperature extruder into the crosshead die. Then, the continuous fiber was impregnated and taken up as a strand through a hook die.
After cooling, it was cut at right angles to the drawing direction to obtain a pellet having a pellet length of 11 mm (cylindrical fiber-reinforced thermoplastic resin composition).
In addition, (C) component (ER1) and (D) component (MF1) were supplied with the thermoplastic resin of the molten state. The pellet length and the glass fiber length of the component (B) are the same.

Examples 2 to 5 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA6) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 260 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition).
The component (C) (ER1 or ER2) and the component (D) (MF1 or MF2) were supplied together with the molten thermoplastic resin. The pellet length and the glass fiber length of the component (B) are the same.

Example 6 (Fiber-reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA6) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 260 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition).
In addition, (C) component (ER2) and (D) component (MF2) make a masterbatch pellet by using (A) component (PA6) as a base resin, and dry-blend the fiber-reinforced thermoplastic resin composition. Obtained.
The master batch pellet is manufactured by a single screw extruder at a set temperature of 240 ° C. after mixing at a blending ratio of (A) component: (C) component: (D) component = 4: 3: 3. The content of the component (A) includes the component (A) in the master batch pellet.
The pellet length and the glass fiber length of the component (B) are the same.

Example 7 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA66) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 290 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, it was cut at a right angle to the drawing direction to obtain a pellet having a pellet length of 7 mm (cylindrical fiber-reinforced thermoplastic resin composition).
In addition, (C) component (ER2) and (D) component (MF2) were supplied with the thermoplastic resin of the molten state. The pellet length and the glass fiber length of the component (B) are the same.

Example 8 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (A) (MXD6) is supplied to the crosshead die in a molten state from the extruder set at 270 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition).
In addition, (C) component (ER2) and (D) component (MF2) were supplied with the thermoplastic resin of the molten state. The pellet length and the glass fiber length of the component (B) are the same.

Comparative Example 1 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF1) through the crosshead die, the component (A) (PP (containing MAH-PP)) is melted from the 250 ° C. set temperature extruder into the crosshead die. Then, the continuous fiber was impregnated and taken up as a strand through a hook die.
After cooling, it was cut at right angles to the drawing direction to obtain a pellet having a pellet length of 11 mm (cylindrical fiber-reinforced thermoplastic resin composition). The pellet length and the glass fiber length of the component (B) are the same.

Comparative Example 2 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA6) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 260 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition). The pellet length and the glass fiber length of the component (B) are the same.

Comparative Example 3 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA66) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 290 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, it was cut at a right angle to the drawing direction to obtain a pellet having a pellet length of 7 mm (cylindrical fiber-reinforced thermoplastic resin composition). The pellet length and the glass fiber length of the component (B) are the same.

Comparative Example 4 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA6) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 260 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition).
In addition, (C) component (ER2) and (D) component (MF2) make a masterbatch pellet by using (A) component (PA6) as a base resin, and dry-blend the fiber-reinforced thermoplastic resin composition. Obtained.
The master batch pellets were mixed at a blending ratio of (A) component: (C) component: (D) component = 4: 3: 3, and then manufactured with a single screw extruder at 240 ° C. set temperature. The content of the component (A) includes the component (A) in the master batch pellet.
The pellet length and the glass fiber length of the component (B) are the same.

Comparative Example 5 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA6) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 260 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition). The pellet length and the glass fiber length of the component (B) are the same.

Comparative Example 6 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (A) (MXD6) is supplied to the crosshead die in a molten state from the extruder set at 270 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition). The pellet length and the glass fiber length of the component (B) are the same.

Comparative Example 7 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA6) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 260 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition).
In addition, (C) component (ER2) was supplied with the thermoplastic resin of the molten state. The pellet length and the glass fiber length of the component (B) are the same.

Comparative Example 8 (fiber reinforced thermoplastic resin composition)
(B) While pulling the continuous fiber to be the component (GF2) through the crosshead die, the component (PA6) is supplied to the crosshead die in a molten state from an extruder at a set temperature of 260 ° C. The fiber was impregnated and taken up as a strand through a cage die.
After cooling, the sample was cut at right angles to the drawing direction to obtain pellets having a pellet length of 9 mm (cylindrical fiber-reinforced thermoplastic resin composition).
In addition, (D) component (MF2) was supplied with the thermoplastic resin of the molten state. The pellet length and the glass fiber length of the component (B) are the same.

<Evaluation 1>
Using the compositions of Examples and Comparative Examples, Evaluation 1 tests shown in Tables 2 and 3 were performed.
(Method for producing ISO multipurpose test piece)
The following injection molding machine was used. The cylinder temperature and mold temperature were adjusted according to the type of component (A) used.
(Injection molding machine)
Injection molding machine: J150EII (Nippon Steel Works)
Screw: Screw for long fibers (temperature conditions)
PP: Cylinder temperature 250 ° C, mold temperature 50 ° C
PA6: Cylinder temperature 260 ° C, mold temperature 100 ° C
PA66: Cylinder temperature 290 ° C, mold temperature 100 ° C
MXD6: Cylinder temperature 270 ° C, mold temperature 140 ° C
(Measuring method)
Tensile test: according to ISO 527 Bending test: according to ISO 178 Charpy impact strength ISO 179 / 1eA (notched)

Examples 1 to 8 and Comparative Examples 1 to 10 (Manufacture of composite molded bodies using an injection molding method)
Examples and Comparative Examples are as shown in FIG. 3 under the conditions shown in Table 1 with respect to the entire bonding surface 12 (90 mm ² wide range) of the metal molded body (stainless steel: SUS304) shown in FIG. Laser light was continuously irradiated.

  Next, the metal molded body after laser light irradiation was used and injection molded by the following method to obtain composite molded bodies shown in FIG. 10 of Examples and Comparative Examples.

<Injection molding>
(Injection molding machine)
Injection molding machine: SE30S (manufactured by Sumitomo Heavy Industries)
It carried out on temperature conditions similarly to the preparation method of the above-mentioned ISO multipurpose test piece.

Using the composite molded bodies of Examples and Comparative Examples, a tensile test was performed, and the pull-out joint strength (joint strength 1) (Evaluation 2 in Tables 2 and 3) was measured by the following method.
As shown in FIG. 11, the tensile test is performed in the Y direction of FIG. 11 (the Y direction of FIG. 1) until the metal molded body 10 and the resin molded body 20 are broken with the jig 70 on the metal molded body 10 side fixed. 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, and the standard deviation (n = 5) was also obtained.
Bonding strength 1 (MPa) = Maximum load (N) / 60 (mm ² [bonding area (resin area)])
<Tensile test conditions>
Testing machine: Orientec Tensilon (UCT-1T)
Tensile speed: 5mm / min
Distance between chucks: 50mm

Examples 1 to 8 and Comparative Examples 1 to 10 (Manufacture of composite molded bodies using compression molding method)
In Examples and Comparative Examples, laser was continuously irradiated under the conditions shown in Table 1 on the entire bonding surface 12 (width range of 40 mm ² ) of the metal molded body (stainless steel: SUS304) shown in FIG.
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 a mold (made of Teflon) so that the joint surface 12 was on top, and a pulverized product of an ISO multipurpose test piece was added on the joint 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.
Temperature: It adjusted with the kind of thermoplastic resin contained in a composition.
PP: 220 ° C
PA6: 250 ° C
PA66: 280 ° C
MXD6: 260 ° 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 pull-out joint strength (joint strength 2) (Evaluation 2 in Tables 2 and 3). The results are shown in Tables 2 and 3.
The tensile test was performed as follows.
As shown in FIG. 14, 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. 14, a jig 74b comprising 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.
Bonding strength 2 (MPa) = Maximum load (N) / 40 (mm ² [Treatment area])
<Tensile test conditions>
Testing machine: Tensilon Tensile speed: 5mm / min
Distance between chucks: 16mm

As is clear from the comparison between the examples in Table 2 and Table 3 and the comparative example, the examples using the milled fiber of the component (D) are higher in both the joint strengths 1 and 2 and evaluated with the joint strength 1. It was confirmed that the variation was small.
This result is thought to be because the milled fiber of component (D) entered the hole formed in the joint surface of the metal molded body by laser light irradiation.

  The 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 1 is shown in FIG. It was confirmed that the joint surface was roughened and a small recess was formed. Since other examples and comparative examples were also irradiated with laser under the same conditions, similar SEM photographs were obtained.

Claims (9)

A fiber-reinforced thermoplastic resin composition for producing the resin molded body of a composite molded body in which a metal molded body and a resin molded body are joined,
(A) polypropylene or polyamide resin,
(B) Reinforcing fiber (excluding milled fiber),
(C) a thermoplastic elastomer,
(D) A fiber reinforced thermoplastic resin composition containing milled fibers having a fiber diameter of 5 to 23 μm and an average fiber length of 30 to 100 μm ,
(A) The fiber reinforced thermoplastic resin composition which is 1-20 mass parts of (C) component and 1-20 mass parts of (D) component with respect to 100 mass parts of component .   The fiber-reinforced thermoplastic resin composition according to claim 1, wherein the thermoplastic elastomer of component (C) is a hydrogenated thermoplastic elastomer having a styrene unit.   The component (A) and the component (B) are bundled in a state of being aligned in the length direction, and the fiber bundle for reinforcement of the component (B) is cut after the component (A) in the molten state is contained and integrated. The fiber-reinforced thermoplastic resin composition according to claim 1 or 2, comprising a resin-containing fiber bundle. With respect to the reinforcing fiber bundle of the component (B) bundled in a state where the components (A) to (D) are aligned in the length direction, the component (C), the component (D) and the molten state (A) The fiber-reinforced thermoplastic resin composition according to claim 1 or 2 , comprising a resin-containing fiber bundle that is cut after the components are contained and integrated. A composite molded body in which a metal molded body and a resin molded body are joined,
The said resin molding consists of the fiber reinforced thermoplastic resin composition of any one of Claims 1-4,
The metal molded body has irregularities on the surface,
A composite molded body in which the metal molded body and the resin molded body are joined and integrated by entering the resin molded body into the irregularities.   The composite molded body according to claim 5, wherein the irregularities on the surface of the metal molded body are formed by irradiating the surface of the metal molded body with continuous wave laser light or pulse wave laser light. A method for producing a composite molded article according to claim 5 or 6,
A step of irradiating the joint surface of the metal molded body with a laser beam, a step of using a continuous wave laser beam or a pulsed laser beam as the laser beam,
In the previous step, the method includes a step of placing a portion including a joint surface of a metal molded body irradiated with laser light in a mold and injection molding a fiber reinforced thermoplastic resin composition to be the resin molded body. A method for producing a composite molded body. A method for producing a composite molded article according to claim 5 or 6,
A step of irradiating the joint surface of the metal molded body with a laser beam, a step of using a continuous wave laser beam or a pulsed laser beam as the laser beam,
A state in which the portion including the joint surface of the metal molded body irradiated with laser light in the previous step is disposed in the mold, and at least the joint surface and the fiber-reinforced thermoplastic resin composition that becomes the resin molded body are in contact with each other The manufacturing method of the composite molded object which has the process of compression-molding in.   The method for producing a composite molded body according to claim 7 or 8, wherein the step of irradiating the laser beam is a step of continuously irradiating the laser beam at an irradiation speed of 2000 mm / sec or more using a continuous wave laser.