TWI832907B - Carbide-based non-magnetic ceramic shaped body with roughened surface structure and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a non-magnetic ceramic formed body with a roughened surface structure. It is a carbide-based non-magnetic ceramic formed body with a roughened surface structure, and the roughened structure has unevenness, which can be detected through a scanning electron microscope. When observed from a photograph (200 times or more), the cross-sectional shape in the thickness direction of the above-mentioned concave and convex parts is a curved surface, and the curved surface of the above-mentioned convex parts has wrinkle-like protrusions formed along the length direction, or the curved surface of the above-mentioned convex parts is formed along the length direction. A plurality of independent holes in a linear shape.

Description

Carbide-based non-magnetic ceramic shaped body with roughened surface structure and manufacturing method thereof

One aspect of the present invention relates to a carbide-based non-magnetic ceramic molded body having a roughened surface structure and a manufacturing method thereof.

It is known that non-magnetic ceramics are widely used in various molded products as daily necessities such as tableware, cups, vases, and engineering ceramics, and are processed to form uneven surfaces according to the intended use.

Japanese Patent Application Publication No. 2002-308683 discloses a ceramic component having a concave and convex structure formed by an acidic etching liquid. Japanese Patent No. 6032903 describes the invention of a baking bracket with a specific concave and convex structure (patent scope claimed). Examples of materials for the baking bracket include zirconium oxide, aluminum oxide, and magnesium oxide. , spinel, cordierite, etc. (paragraph number 0013).

WO2011/121808 A1 discloses an invention that includes a metal or ceramic base material, an impregnation layer provided by forming a recessed portion on the surface of the sliding side of the base material, and an impregnation layer impregnated with the A sliding member that covers the resin layer on the surface of the sliding side of the base material, and the recessed portion is formed by machining (patentable scope). It is described that the recessed portion is a plurality of linear grooves, and the maximum depth of the grooves is 200 to 2,000 μm (paragraph number 0026).

Examples of the above-mentioned mechanical processing include laser processing, wire cutting processing, etc. (paragraph number 0014), but specific processing conditions are not described. The examples only describe wire cutting processing of steel, and there is no specific description about ceramics. record.

Japanese Patent Application Publication No. 2015-109966 discloses a manufacturing method of medical device materials, which coats calcium phosphate on specific parts of medical device materials containing cubic zirconia, which is characterized by: including: a first step, The above-mentioned specific part is irradiated with ultra-short pulse laser to form concavities and convexities on the surface; and the second step is to evaporate or precipitate calcium phosphate particles smaller than the period of the above-mentioned concavities and convexities on the above-mentioned specific parts (patent application scope).

Japanese Patent No. 6111102 discloses a method for manufacturing a metal-ceramic bonded substrate, which is characterized in that a circuit pattern on at least one side of a ceramic substrate containing AlN or Al ₂ O ₃ as a main component has a planar shape that is substantially the same. A portion of the ceramic substrate is irradiated with laser light with a wavelength of 300 to 1500 nm, and an aluminum film is formed on a portion of the circuit pattern on at least one side of the ceramic substrate that is substantially the same as the planar shape. A copper plate is arranged on the aluminum film to form a eutectic of aluminum and copper. By heating at a temperature above the point and below 650°C, the copper plate is bonded to the ceramic substrate through the aluminum film.

Japanese Patent Application Laid-Open No. 2003-171190 discloses a ceramic member in which the surface of a base material composed of dense ceramics with a purity of 95% or more is formed with a first curvature unevenness with a surface roughness of Ra3 to 40 μm. , and the first uneven surface is formed into a curved second uneven surface with a surface roughness Ra of 0.1 to 2.9 μm. The figure shows that the second concave and convex cover the entire surface of the first concave and convex.

Japanese Patent Application Publication No. 2003-137677 and Japanese Patent Application Publication No. 2004-66299 disclose a technology for laser processing the surface of a ceramic body to form unevenness.

Japanese Patent No. 5774246 and Japanese Patent No. 5701414 disclose an invention, metal forming, which uses continuous wave laser to continuously irradiate laser light at an irradiation speed of 2,000 mm/sec or more to roughen the surface of a metal formed body. The method for manufacturing a composite molded body of a composite body and a resin molded body was invented, but there is no record about ceramics.

An object of one aspect of the present invention is to provide a nonmagnetic ceramic molded body having a roughened surface structure and a manufacturing method thereof.

One embodiment of the present invention provides a non-magnetic ceramic shaped body with a roughened surface structure, wherein The above-mentioned roughened structure has concavities and convexities. When observed through a scanning electron microscope photograph (200 times or more), the cross-sectional shape of the thickness direction of the above-mentioned concavities and convexities is a curved surface, and the curved surface of the above-mentioned convex portion has wrinkle-like protrusions formed along the length direction. , or the curved surface of the above-mentioned convex portion is formed into a plurality of linear independent holes along the length direction, and The above-mentioned non-magnetic ceramic formed body is a carbide-based non-magnetic ceramic formed body. Furthermore, another embodiment of the present invention provides a method for manufacturing such a non-magnetic ceramic formed body.

The non-magnetic ceramic shaped body according to the embodiment of the present invention has a roughened structure on the surface and can be used as an intermediate for manufacturing composite shaped bodies with other materials. Therefore, another aspect of the present invention is also suitable for the manufacturing method of such a composite molded article and the composite molded article.

According to the manufacturing method of the embodiment of the present invention, the surface of the originally hard and brittle carbide-based non-magnetic ceramic formed body can be roughened without being separated into two or more pieces due to cracking.

According to an embodiment of the present invention, the non-magnetic ceramic forming system with a roughened surface structure contains carbide-based non-magnetic ceramics. The carbide-based non-magnetic ceramic molded article may be a molded article containing carbide-based non-magnetic ceramics such as silicon carbide, titanium carbide, tungsten carbide, boron carbide, etc. Among these, the molded article may contain silicon carbide.

In addition to being composed solely of silicon carbide, silicon carbide can also be composed of a composite of silicon carbide and other non-magnetic ceramics, metals, and semi-metals as long as it meets the specified thermal shock temperature range. The composite of silicon carbide and metal may be one in which the porous interior of a porous silicon carbide body is impregnated with metal (for example, aluminum) or semimetal (for example, silicon). The content ratio of silicon carbide in such a composite is In a preferred aspect of the invention, it is 50% by mass or more, in another preferred aspect of the invention, it is 60% by mass or more, and in another preferred aspect of the invention, it is 70% by mass or more. .

The specified thermal shock temperature (JIS R1648: 2002) is in the range of 400 to 500°C in a preferred aspect of the present invention, and is in the range of 420 to 480°C in another preferred aspect of the invention.

Regarding the non-magnetic ceramic formed body containing silicon carbide, in order to prevent cracking during processing, in a preferred aspect of the invention, the thickness is 0.5 mm or more, and in another preferred aspect of the invention, the thickness is 1.0 mm. mm or more. In addition, "crack" in the present invention means that a part of the molded body is broken and divided into two or more pieces, and "cracks" are not included. In addition, "crack" also includes the following situation: although it does not break during processing by irradiation with laser light, the strength is significantly reduced, and it is divided into two or more pieces during subsequent movement and processing.

According to several embodiments of the present invention, the non-magnetic ceramic forming system with a roughened surface structure has unevenness. When observed through a scanning electron microscope photo (200 times or more), the thickness direction of the unevenness is The cross-sectional shape has a curved surface.

The cross-sectional shape in the thickness direction of the above-mentioned concavities and convexities may include a partial circle or a partial ellipse. Partial circles are semicircles, 1/3 circles, and other shapes that include a part of a circle. Partial ellipse is a shape that includes a part of an ellipse, such as a semi-ellipse or a 1/3 ellipse.

In the non-magnetic ceramic molding system with a roughened surface structure of the present invention, the concavities and convexities may be alternately formed with linear convex portions and linear concave portions, and the convex portions may be formed with wrinkles along the length direction of the curved surface. The protrusion or the curved surface of the above-mentioned convex portion is formed into a plurality of linear independent holes along the length direction.

According to one example, the wrinkle-like protrusions are portions that slightly protrude outward from the surface without wrinkle-like protrusions. For example, the corrugated protrusions may be formed continuously along the length direction, but may also have discontinuous portions. According to one example, the plurality of independent holes formed in a linear shape is a form in which a large number of independent holes are arranged in a linear manner. Regarding the corrugated protrusions and/or the plurality of independent holes formed in a linear shape, when the respective widths of the linear convex portions and the linear concave portions are 20 to 100 μm, the width may be 1 to 10 μm.

It is considered that if wrinkle-like protrusions and/or a plurality of linear independent holes are formed along the length direction of the surface (curved surface) of the convex portion to increase the surface area, for example, when a non-magnetic ceramic molded body is combined with other components (For example, resin molded objects) When joining, the contact area of the joining surface increases, so the joining strength can be improved.

In some examples of the non-magnetic ceramic molded body having a roughened surface structure according to the present invention, the concave portions in the concavities and convexities of the roughened structure are dispersed in an island shape, and the portions other than the concave portions are convex portions, and are formed on the convex portions. There are corrugated protrusions along the length direction and/or a plurality of linear independent holes formed in the curved surface of the protrusion along the length direction.

According to one example, the wrinkle-like protrusions are portions that slightly protrude outward from the surface without wrinkle-like protrusions. For example, the corrugated protrusions may be formed continuously along the length direction, but may also have discontinuous portions. According to one example, the plurality of independent holes formed in a linear shape is a form in which a large number of independent holes are arranged in a linear manner. Regarding the corrugated protrusions and/or the plurality of independent holes formed in a linear shape, when the respective widths of the linear convex portions and the linear concave portions are 20 to 100 μm, the width may be 1 to 10 μm.

If the surface (curved surface) of the convex portion is formed with corrugated protrusions along the length direction and/or the curved surface of the convex portion is formed into a plurality of linear independent holes along the length direction to increase the surface area, for example, When the non-magnetic ceramic molded body is joined to other members (such as resin molded bodies), the contact area of the joint surface is increased, so the joint strength can be improved.

According to some examples of the non-magnetic ceramic formed body of the present invention, the surface roughness (Ra) of the above-mentioned concavities and convexities is in the range of 2 to 100 μm in a preferred aspect of the present invention. In another preferred aspect of the present invention, In the sample, it is in the range of 5 to 80 μm, and in another preferred aspect of the present invention, it is in the range of 10 to 50 μm.

According to some examples of the non-magnetic ceramic formed body of the present invention, the height difference (Rz) between the convex and concave portions of the above-mentioned concave and convex portions is in the range of 10 to 200 μm in a preferred aspect of the present invention. In another aspect of the present invention, In a preferred aspect, it is in the range of 20 to 150 μm, and in yet another preferred aspect of the present invention, it is in the range of 20 to 100 μm.

Furthermore, according to some examples of the non-magnetic ceramic formed body of the present invention, Sa (arithmetic mean height), Sz (maximum height), and Str (aspect ratio of surface texture) of the roughened structural portion (concave-convex portion) can be as follows: Scope.

Sa (arithmetic mean height) is 2-100 μm in a preferred aspect of the invention, 5-80 μm in another preferred aspect of the invention, and is 5-80 μm in another preferred aspect of the invention. The sample is 10~50 μm.

Sz (maximum height) is 10-300 μm in a preferred aspect of the invention, 20-200 μm in another preferred aspect of the invention, and is 20-200 μm in another preferred aspect of the invention. Medium is 20~150 μm.

Sdr (interface development area ratio) is 0.1 to 3.0 in a preferred aspect of the present invention.

In addition, the surface roughness (Ra) of the convex portions of the above-mentioned concave and convex portions is in the range of 1 to 10 μm in a preferred aspect of the present invention, and in another preferred aspect of the present invention, the surface roughness (Ra) is in the range of 1.5 to 8 μm. The range is in the range of 2 to 8 μm in another preferred aspect of the present invention.

In this case, the height difference (Rz) between the convex and concave portions of the above-mentioned concave and convex is in the range of 5 to 50 μm in a preferred aspect of the present invention, and is 8 in another preferred aspect of the present invention. The range of ~40 μm is in the range of 10-30 μm in another preferred aspect of the present invention.

Furthermore, in this case, Sa (arithmetic mean height), Sz (maximum height), and Str (aspect ratio of surface texture) of the roughened structure portion (concave-convex portion) may be in the following ranges.

Sa (arithmetic mean height) is 1 to 10 μm in a preferred aspect of the invention, 1.5 to 8 μm in another preferred aspect of the invention, and is 1.5 to 8 μm in another preferred aspect of the invention. The sample is 2~8 μm.

Sz (maximum height) is 8-40 μm in a preferred aspect of the invention, 10-30 μm in another preferred aspect of the invention, and is 10-30 μm in another preferred aspect of the invention. Medium is 100~180 μm.

Sdr (interface development area ratio) is 0.01 to 2.0 in a preferred aspect of the present invention.

According to one embodiment of the present invention, the non-magnetic ceramic formed body can be used not only as a carrier that can hold liquid, powder, etc. in the roughened structure part, but also can be used to manufacture materials made of other materials (non-carbide-based materials). Manufacturing intermediates for composite moldings made of moldings made of materials other than magnetic ceramics).

<The first method of manufacturing a carbide-based non-magnetic ceramic molded body with a roughened surface structure> Next, a first method of manufacturing a carbide-based nonmagnetic ceramic molded body having a roughened surface structure according to one embodiment of the present invention will be described. The non-magnetic ceramic molded body according to one embodiment of the present invention can be produced by continuously irradiating the surface of the carbide-based non-magnetic ceramic molded body with laser light at an irradiation speed of 5,000 mm/sec or more using a continuous wave laser.

The shape, size, thickness, etc. of the carbide-based non-magnetic ceramic molded body used in the manufacturing method of one embodiment of the present invention are not particularly limited and can be selected according to the use and adjusted as necessary. For example, as the carbide-based non-magnetic ceramic molded body, in addition to flat plates, round rods, square rods (rods with polygonal cross-sections), tubes, cups, cubes, rectangular parallelepipeds, spheres or partial spheres (hemispheres, etc.), ellipses In addition to molded bodies such as spheres, partially elliptical spheres (semi-elliptical spheres, etc.), amorphous shapes, etc., existing non-magnetic ceramic products can also be used. In addition to the above-mentioned existing carbide-based non-magnetic ceramic products consisting only of carbide-based non-magnetic ceramics, they may also be composed of carbide-based non-magnetic ceramics and other materials (metals, resins, rubber, glass, composed of composites of wood, etc.).

According to one embodiment, when a continuous wave laser is used to continuously irradiate laser light on the surface of a carbide-based non-magnetic ceramic molded body at an irradiation speed of 5,000 mm/sec or more, straight lines can be formed in the same direction or in different directions. , curves and multiple lines composed of these combinations are continuously irradiated with laser light.

Furthermore, according to another embodiment, when a continuous wave laser is used to continuously irradiate the surface of the carbide-based non-magnetic ceramic molded body with an irradiation speed of 5,000 mm/sec or more, the laser light can be irradiated in the same direction or in different directions. Continuously irradiate laser light to form a plurality of lines composed of straight lines, curves and combinations thereof, and continuously irradiate laser light multiple times to form a straight line or a curve.

Furthermore, according to another embodiment, when a continuous wave laser is used to continuously irradiate the surface of the carbide-based non-magnetic ceramic molded body with an irradiation speed of 5,000 mm/sec or more, the laser light can be irradiated in the same direction or in different directions. Continuously irradiate laser light in a manner that forms a plurality of lines composed of straight lines, curves, and combinations thereof, and continuously irradiate laser light in a manner that the plurality of straight lines or the plurality of curves are spaced at equal intervals or at different intervals.

Regarding the irradiation speed of laser light, in order to roughen the carbide-based non-magnetic ceramic molded body, it can be 5,000 mm/sec or more, and in a preferred aspect of the present invention, it is 5,000 to 20,000 mm/sec. In the present invention, Another preferred aspect is 5,000 to 10,000 mm/sec. If the irradiation speed of laser light is less than 5,000 mm/sec, it will be difficult to form a roughened structure on the surface of the non-magnetic ceramic formed body.

The output of the laser is 50-4,000 W in a preferred aspect of the invention, 100-2,000 W in another preferred aspect of the invention, and is 100-2,000 W in another preferred aspect of the invention. It is 100~1,000 W. The roughening state can be adjusted by making the output of the laser light smaller when the irradiation speed of the laser light is slower within the above range, and by making the output of the laser light faster when the irradiation speed of the laser light is faster within the above range. The output becomes larger. For example, when the output of laser light is 100 W, in a preferred aspect of the present invention, the irradiation speed of laser light is 5,000-7,500 mm/sec. When the output of laser light is 500 W, in a preferred aspect of the present invention, In a preferred embodiment, the irradiation speed of laser light can be 7,500 to 10,000 mm/sec.

The spot diameter of the laser light is 10-100 μm in a preferred aspect of the invention, and is 10-75 μm in another preferred aspect of the invention.

The energy density during laser light irradiation is 3-1500 MW/cm ² in a preferred aspect of the present invention, and is 5-700 MW/cm ² in another preferred aspect of the present invention. The energy density during laser light irradiation is calculated from the laser light output (W) and the laser light spot area (cm ² ) (π・[spot diameter/2] ² ) according to the following formula: Laser light output /spot area.

The number of repetitions (number of passes) during laser light irradiation is 1 to 30 times in a preferred aspect of the present invention, 3 to 25 times in another preferred aspect of the present invention, and 3 to 25 times in another preferred aspect of the present invention. A preferred form is 5 to 20 times. The number of repetitions when irradiating laser light is the total number of irradiation times to form one line (groove) when irradiating laser light linearly.

When irradiating one line repeatedly, you can choose between bidirectional irradiation and unidirectional irradiation. Bidirectional irradiation is the following method. That is, when forming a line (trough), irradiate a continuous wave laser from the first end of the line (trough) to the second end, and then irradiate the continuous wave laser from the second end to the first end. The continuous wave laser is irradiated, and then the continuous wave laser is repeatedly irradiated from the first end to the second end and from the second end to the first end. The unidirectional irradiation is a method of repeatedly performing unidirectional continuous wave laser irradiation from the first end to the second end.

When laser light is irradiated linearly, the distance (line distance or pitch distance) between the middle positions of the widths of adjacent irradiation lines (adjacent grooves formed by irradiation) is 0.03 in a preferred aspect of the present invention. ~1.0 mm, in another preferred aspect of the present invention, it is 0.03~0.2 mm. Line spacing can be the same or different.

When irradiating laser light, it is also possible to perform bidirectional irradiation or unidirectional irradiation with the above-mentioned line intervals to form a plurality of grooves, and then perform bidirectional irradiation with the above-mentioned line intervals from a direction orthogonal or oblique to the plurality of grooves. Irradiation or cross-irradiation of one-way irradiation.

The wavelength of the laser light is 300-1200 nm in a preferred aspect of the invention, and is 500-1200 nm in another preferred aspect of the invention. The focus offset distance when irradiating laser light is -5 to +5 mm in a preferred aspect of the present invention, and is -1 to +1 mm in another preferred aspect of the present invention. Another preferred aspect is -0.5~+0.1 mm. The focus offset distance can be set to a fixed value and laser irradiation can be performed, or the focus offset distance can be changed and laser irradiation can be performed simultaneously. For example, during laser irradiation, the focus offset distance can also be made gradually smaller or periodically larger or smaller.

Continuous wave lasers can use well-known ones, for example: YVO ₄ laser, fiber laser (preferably single-mode fiber laser), excimer laser, carbon dioxide gas laser, ultraviolet laser, YAG laser, Semiconductor laser, glass laser, ruby laser, He-Ne laser, nitrogen laser, chelate laser, dye laser. Among these, fiber laser is preferred in terms of increasing energy density, and single-mode fiber laser is particularly preferred.

＜Second manufacturing method of carbide-based non-magnetic ceramic molded body having a roughened surface structure＞ The second manufacturing method of a carbide-based non-magnetic ceramic molded body having a roughened surface structure according to one embodiment of the present invention is the same as the above-mentioned first manufacturing method except for the irradiation form of laser light.

The second manufacturing method includes the step of continuously irradiating the surface of the carbide-based nonmagnetic ceramic molded body with laser light using a continuous wave laser at an irradiation speed of 5,000 mm/sec or more in the same manner as the first manufacturing method. In this method, when the surface of the carbide-based non-magnetic ceramic molded body to be roughened is irradiated with laser light, the irradiation is performed in such a manner that the irradiated portion and the non-irradiated portion of the laser light are alternately generated.

In the second manufacturing method, when laser light is irradiated in a straight line, a curve, or a combination of a straight line and a curve, the irradiation is performed in such a manner that the irradiated portion and the non-irradiated portion of the laser light are alternately generated. The so-called irradiation in such a manner that the irradiation part and the non-irradiation part of the laser light are alternately generated includes an embodiment in which irradiation is performed as shown in FIG. 1 . FIG. 1 shows a structure formed in a dotted line shape by alternately generating a laser light irradiation portion 11 of length L1 and a laser light non-irradiation portion 12 of length L2 between the adjacent laser light irradiation portions 11 of length L1. mode of irradiation. The above-mentioned dotted lines also include single-point chain lines, two-point chain lines and other chain lines.

When irradiating multiple times, the irradiated portions of the laser light can be made the same, or the irradiated portions of the laser light can be different (staggered) to roughen the entire carbide-based non-magnetic ceramic molded body. When the irradiated part of the laser light is irradiated multiple times with the same irradiation, it is irradiated in a dotted line shape, but if the irradiated part of the laser light is repeatedly staggered, the irradiated part of the laser light overlaps the part that was originally the non-irradiated part of the laser light. If the light is irradiated in a staggered manner, even if it is irradiated in a dotted line, it will eventually be irradiated into a solid line state. The number of repetitions can be set from 1 to 20 times.

If a carbide-based non-magnetic ceramic molded body is continuously irradiated with laser light, there is a risk that deformation such as cracking may occur in the molded body with a small thickness. However, if laser irradiation is performed in a dotted line shape as shown in FIG. 1 , the irradiated portion 11 of the laser light and the non-irradiated portion 12 of the laser light are alternately generated. Therefore, when the laser light is continued to be irradiated, the thickness becomes smaller. The molded body is also difficult to deform such as cracking. At this time, when the irradiation part of the laser light is made different (the irradiation part of the laser light is staggered) as described above, the same effect is obtained.

The laser light irradiation method may be, for example, a method of irradiating the surface of the metal formed body 20 in one direction as shown in FIG. 2(a) or a method of irradiating the surface of the metal molded body 20 in two directions as shown by the dotted line in FIG. 2(b). Alternatively, the laser light may be irradiated in such a manner that the irradiated portions of the dotted lines of laser light intersect. The interval b1 between the dotted lines after irradiation can be adjusted according to the irradiation target area of the metal formed body, etc., but can be set to the same range as the line interval in the first manufacturing method.

The length (L1) of the laser light irradiation part 11 and the length (L2) of the laser light non-irradiation part 12 shown in FIG. 1 can be adjusted so that it becomes the range of L1/L2=1/9-9/1. Regarding the length (L1) of the laser light irradiation part 11, in order to roughen it into a complex porous structure, it is 0.05 mm or more in a preferred aspect of the present invention, and is 0.1 in another preferred aspect of the present invention. ~10 mm, in another preferred aspect of the present invention, it is 0.3~7 mm.

In an exemplary embodiment of the second manufacturing method of the present invention, the laser light irradiation step uses an optical fiber connected to a laser power source by a modulation device of a direct modulation method that directly converts the driving current of the laser. The laser device adjusts the duty ratio to perform laser irradiation.

There are two types of laser excitation: pulse excitation and continuous excitation. The pulse wave laser obtained by pulse excitation is generally called a conventional pulse. Pulse wave laser can be generated even with continuous excitation. Pulse wave laser can be generated by the following method: Q-switching the laser oscillation that makes the pulse width (pulse ON time) shorter than the conventional pulse and correspondingly higher peak power. Pulse oscillation method, external modulation method that generates pulse wave laser by intercepting light in time using AOM or LN light intensity modulator, method of mechanically chopping and pulsing, operating galvanometer mirror Pulsing method is a direct modulation method that directly modulates the driving current of the laser to generate pulse wave laser. The method of operating the galvanometer mirror to pulse is to irradiate the laser light oscillated from the laser oscillator through the galvanometer mirror through the combination of the galvanometer mirror and the galvanometer controller. Specifically, it can be as follows Implement as described.

The self-check galvanometer controller periodically outputs the Gate signal ON/OFF, and uses the ON/OFF signal to turn the laser light oscillated by the laser oscillator ON/OFF, thereby preventing the energy density of the laser light from changing. Pulse. Thereby, the laser light can be irradiated in the following manner, that is, as shown in FIG. 1 , the irradiation part 11 of the laser light and the non-irradiation part 12 of the laser light between the adjacent laser light irradiation parts 11 are alternately generated, The whole is formed into a dotted line shape. The method of pulsing by operating the galvanometer mirror can adjust the working ratio without changing the oscillation state of the laser light itself, so the operation is simple.

Among these methods, as a method that can easily pulse without changing the energy density of the continuous wave laser (irradiate in such a way that the irradiated part and the non-irradiated part are alternately generated), a mechanical method can be used. The method of chopping and pulsing, the method of operating galvanometer mirror and pulsing, and the direct modulation method of directly modulating the driving current of the laser to generate pulse wave laser. In the exemplary embodiments described above, the laser can be continuously excited by using a fiber laser device in which a modulation device that directly converts the driving current of the laser is connected to a laser power source. And produce pulse wave laser.

The duty ratio is the ratio between the ON time and the OFF time of the laser light output, which is calculated according to the following formula. Working ratio (%) = ON time/(ON time + OFF time) × 100 The working ratio corresponds to L1 and L2 (ie, L1/[L1+L2]) shown in Figure 1, so it can be selected from the range of 10 to 90%, for example. By adjusting the duty ratio and irradiating laser light, it is possible to irradiate in a dotted line shape as shown in Figure 1 .

Several examples of manufacturing methods for composite shaped bodies when the non-magnetic ceramic shaped body having a roughened surface structure according to one embodiment of the present invention is used as an intermediate for manufacturing a composite shaped body that is manufactured from other materials will be described. A composite molded body made of molded materials (materials other than non-magnetic ceramics). The manufacturing methods of these composite shaped bodies and the manufactured composite shaped bodies are also included in the scope of the present invention.

(1) Method for manufacturing a composite molded article of a carbide-based non-magnetic ceramic molded article having a roughened structure and a resin molded article In the first step, a non-magnetic ceramic formed body having a roughened surface structure is produced by the above-mentioned first manufacturing method or second manufacturing method.

In the second step, the portion including the roughened structure of the carbide-based non-magnetic ceramic molded body having a roughened surface structure obtained in the first step is placed in a mold, and the resin that becomes the resin molded body is processed. Injection molding; or in the second step, the part including the roughened structure of the non-magnetic ceramic molded body irradiated with laser light in the first step is arranged in the mold, so that at least the part including the roughened structure becomes The above-mentioned resin molded article is compression molded in a state where the resins are in contact with each other.

The resin used in the second step includes thermoplastic elastomers in addition to thermoplastic resins and thermosetting resins. The thermoplastic resin can be appropriately selected from known thermoplastic resins according to the intended use. Examples include: polyamide-based resins (aliphatic polyamides, aromatic polyamides such as PA6 and PA66), polystyrene, ABS resin, AS resin and other copolymers containing styrene units, polyethylene, ethylene-containing copolymers Copolymers of units, polypropylene, copolymers containing propylene units, other polyolefins, polyvinyl chloride, polyvinylidene chloride, polycarbonate resins, acrylic resins, methacrylic resins, polyester resins , polyacetal resin, and polyphenylene sulfide resin.

The thermosetting resin can be appropriately selected from known thermosetting resins according to the intended use. Examples include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane. When using thermosetting resins, those in the form of prepolymers can be heated and cured in subsequent steps.

The thermoplastic elastomer can be appropriately selected from known thermoplastic elastomers according to the intended use. Examples include styrene elastomers, vinyl chloride elastomers, olefin elastomers, urethane elastomers, polyester elastomers, nitrile elastomers, and polyamide elastomers.

Known fibrous fillers can be blended into these thermoplastic resins, thermosetting resins, and thermoplastic elastomers. Examples of known fibrous fillers include carbon fibers, inorganic fibers, metal fibers, organic fibers, and the like.

Carbon fibers are publicly known, and PAN-based, pitch-based, rayon-based, lignin-based, etc. can be used. Examples of inorganic fibers include glass fiber, basalt fiber, silica fiber, silica aluminum fiber, zirconia fiber, boron nitride fiber, and silicon nitride fiber. Examples of metal fibers include fibers made of stainless steel, aluminum, copper, etc. As organic fibers, polyamide fibers (fully aromatic polyamide fibers, semi-aromatic polyamide fibers in which either diamine or dicarboxylic acid is an aromatic compound, or aliphatic polyamide fibers), Polyvinyl alcohol fiber, acrylic fiber, polyolefin fiber, polyoxymethylene fiber, polytetrafluoroethylene fiber, polyester fiber (including fully aromatic polyester fiber), polyphenylene sulfide fiber, polyimide fiber, liquid crystal polyester Synthetic fibers such as fiber, natural fibers (cellulose-based fibers, etc.) or regenerated cellulose (rayon) fibers, etc.

These fibrous fillers can use those with fiber diameters in the range of 3 to 60 μm. However, among these, for example, openings such as the open holes 30 formed by roughening the joint surface 12 of the metal formed body 10 can be used. Diameter. The fiber diameter is 5-30 μm in a preferred aspect of the invention, and is 7-20 μm in another preferred aspect of the invention. The blending amount of the fibrous filler relative to 100 parts by mass of the thermoplastic resin, thermosetting resin, or thermoplastic elastomer is 5 to 250 parts by mass in a preferred aspect of the invention, and in another preferred aspect of the invention In one aspect, it is 25-200 parts by mass, and in another preferred aspect of the present invention, it is 45-150 parts by mass.

(2-1) Method for manufacturing a composite molded body of a carbide-based non-magnetic ceramic molded body and a rubber molded body having a roughened structure In the first step, a nonmagnetic ceramic formed body having a roughened surface structure is produced by the first manufacturing method or the second manufacturing method. In the second step, the carbide-based nonmagnetic ceramic molded body and the rubber molded body obtained in the first step are integrated using a known molding method such as pressure molding or transfer molding.

When applying the pressure forming method, for example, a portion of a carbide-based nonmagnetic ceramic molded body containing a roughened structure is placed in a mold, and the portion containing the roughened structure is heated and pressurized. The unhardened rubber that becomes the rubber molded body is pressurized, cooled, and then taken out. When applying the transfer molding method, for example, the part containing the roughened structure of the carbide-based non-magnetic ceramic molded body is placed in a mold, unhardened rubber is injection molded into the mold, and then heated and pressurized. The portion including the roughened structure of the carbide-based nonmagnetic ceramic molded body is integrated with the rubber molded body, cooled, and then taken out.

Furthermore, depending on the type of rubber used, in order to mainly remove residual monomer, a second heating (secondary hardening) step may be performed using an oven or the like after being removed from the mold.

The rubber of the rubber molded body used in this step is not particularly limited, and known rubbers can be used, but thermoplastic elastomers are not included. As well-known rubbers, ethylene-propylene copolymer (EPM), ethylene-propylene-diene terpolymer (EPDM), ethylene-octene copolymer (EOM), ethylene-butylene copolymer (EBM) can be used , ethylene-octene terpolymer (EODM), ethylene-butene terpolymer (EBDM) and other ethylene-α-olefin rubber; Ethylene/acrylic rubber (EAM), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), styrene-butadiene rubber (SBR), alkylated chlorine Sulfonated polyethylene (ACSM), epichlorohydrin (ECO), polybutadiene rubber (BR), natural rubber (including synthetic polyisoprene) (NR), chlorinated polyethylene (CPE), brominated Polymethylstyrene-butylene copolymer, styrene-butadiene-styrene and styrene-ethylene-butadiene-styrene block copolymer, acrylic rubber (ACM), ethylene-vinyl acetate elastomer (EVM), and polysilicone rubber, etc.

The rubber may optionally contain a hardener corresponding to the type of rubber, and in addition, various known rubber additives may be blended. As additives for rubber, we can use: hardening accelerators, anti-aging agents, silane coupling agents, reinforcing agents, flame retardants, anti-odor oxidants, fillers, processing oils, plasticizers, adhesion-imparting agents, and processing aids. wait.

(2-2) Method for manufacturing a composite molded article (including an adhesive layer) of a carbide-based non-magnetic ceramic molded article with a roughened structure and a rubber molded article According to one embodiment, a method for manufacturing a composite molded body of a carbide-based non-magnetic ceramic molded body and a rubber molded body allows an adhesive layer to be interposed on the joint surface of the carbide-based non-magnetic ceramic molded body and the rubber molded body. .

In the first step, a continuous wave laser is used to roughen the carbide-based non-magnetic ceramic molded body in the same manner as the above method. In the second step, an adhesive (adhesive solution) is applied to the roughened structural surface of the carbide-based non-magnetic ceramic molded body to form an adhesive layer. At this time, the adhesive can also be pressed in. By applying the adhesive, the adhesive can be present in the roughened structural surface and internal pores of the non-magnetic ceramic.

The adhesive is not particularly limited, and known thermoplastic adhesives, thermosetting adhesives, rubber adhesives, etc. can be used. Examples of thermoplastic adhesives include: polyvinyl acetate, polyvinyl alcohol, polyvinyl formaldehyde, polyvinyl butyraldehyde, acrylic adhesives, polyethylene, chlorinated polyethylene, ethylene-vinyl acetate copolymer, ethylene - Vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ionomer, chlorinated polypropylene, polystyrene, polyvinyl chloride, plastisol, vinyl chloride-vinyl acetate copolymer, poly Vinyl ether, polyvinylpyrrolidone, polyamide, nylon, saturated amorphous polyester, and cellulose derivatives.

Examples of thermosetting adhesives include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinylurethane. Examples of rubber-based adhesives include natural rubber, synthetic polyisoprene, polychloroprene, nitrile rubber, styrene-butadiene rubber, styrene-butadiene-vinylpyridine ternary Copolymers, polyisobutylene-butyl rubber, polysulfide rubber, silicone RTV, chlorinated rubber, brominated rubber, cowhide rubber, block copolymers, and liquid rubber.

An example of this manufacturing method is to implement the following steps in the third step: a step of bonding a separately formed rubber molded body to the surface of the carbide-based non-magnetic ceramic molded body on which an adhesive layer has been formed in the previous step; or The portion containing the surface of the carbide-based non-magnetic ceramic molded body on which the adhesive layer was formed in the previous step is arranged in the mold, before the surface of the carbide-based non-magnetic ceramic molded body is formed into a rubber molded body. The hardened rubber is heated and pressurized while in contact with each other to integrate it. In the case of this step, in order to mainly remove the residual monomer, a step of secondary heating (secondary hardening) using an oven or the like can be added after the mold is taken out.

(3-1) Method for manufacturing a composite molded body of a carbide-based ceramic molded body and a metal molded body having a roughened structure In the first step, a carbide-based nonmagnetic ceramic molded body having a roughened structure is produced by the first manufacturing method or the second manufacturing method. In the second step, the roughened carbide-based nonmagnetic ceramic molded body is placed in the mold with the surface including the porous structure portion facing upward. Thereafter, for example, a known die casting method is used to flow the molten metal into the mold and then cool it.

The metal used is not limited as long as its melting point is lower than the melting point of the carbide-based non-magnetic ceramic constituting the carbide-based non-magnetic ceramic molded body. For example, metals such as iron, aluminum, aluminum alloys, gold, silver, platinum, copper, magnesium, titanium or alloys thereof, stainless steel, etc. that are suitable for the use of the composite formed body can be selected.

(3-2) Method for manufacturing a composite molded article (with an adhesive layer) of a carbide-based non-magnetic ceramic molded article with a roughened structure and a metal molded article The first step and the second step are the same as the above "(2-2) Manufacturing method of a composite molded article (including an adhesive layer) of a carbide-based non-magnetic ceramic molded article having a roughened structure and a rubber molded article" This was carried out to produce a carbide-based non-magnetic ceramic molded body having an adhesive layer.

In the third step, the metal formed body is pressed against the adhesive layer of the carbide-based non-magnetic ceramic formed body having an adhesive layer to be bonded and integrated. When the adhesive layer is made of a thermoplastic resin adhesive, it can be bonded to the bonding surface of the non-metal molded object in a state where the adhesive layer is softened by heating as necessary. Furthermore, when the adhesive layer is composed of a prepolymer of a thermosetting resin adhesive, the prepolymer is heated and hardened by placing it in a heating environment after adhesion.

(4) Method for manufacturing a composite molded article of a carbide-based non-magnetic ceramic molded article with a roughened structure and a UV curable resin molded article In the first step, a carbide-based nonmagnetic ceramic molded body having a roughened surface structure is produced by the first manufacturing method or the second manufacturing method.

In the next step, the monomer, oligomer, or mixture thereof that forms the UV curable resin layer is brought into contact with the portion including the roughened portion of the carbide-based nonmagnetic ceramic molded body (monomer, low polymer, etc.) polymer or mixture thereof). As the step of contacting a monomer, an oligomer, or a mixture thereof, the monomer, an oligomer, or a mixture thereof may be applied to the carbide-based nonmagnetic ceramic molded body including the roughened portion. Partial steps. The step of coating monomers, oligomers, or mixtures thereof may be brush coating, coating using a doctor blade, roller coating, casting, pouring, etc., either alone or in combination.

The step of contacting a monomer, an oligomer, or a mixture thereof may be carried out as follows: surrounding the portion including the roughened portion of the carbide-based nonmagnetic ceramic molded body with a mold frame, and injecting the monomer into the mold frame , oligomers or mixtures thereof. Furthermore, the step of contacting a monomer, an oligomer, or a mixture thereof may be performed by placing the carbide-based nonmagnetic ceramic molded body inside a mold with its roughened portion facing upward, and then placing the molded body into the mold. A monomer, an oligomer, or a mixture thereof is injected into the mold.

Through the contact step of the monomer, oligomer, or mixture thereof, the monomer, oligomer, or mixture thereof enters the pores of the roughened portion of the carbide-based nonmagnetic ceramic formed body. The form in which monomers, oligomers, or mixtures thereof enter into the pores, for example, includes monomers, oligomers, or mixtures thereof entering into more than 50% of all pores in a preferred aspect of the present invention. In another preferred aspect of the present invention, it reaches more than 70%. In yet another preferred aspect of the present invention, it reaches more than 80%. In yet another preferred aspect of the present invention, it reaches more than 90%. % or more. In addition, it also includes the form in which a mixture of monomers, oligomers, or the like enters the bottom of the hole. The mixture of monomers, oligomers, or the like enters the middle of the hole depth. A form in which monomers, oligomers, or mixtures thereof enter only near the entrance of the pores.

Monomers, oligomers, or mixtures thereof can be directly coated or injected when they are in the form of liquids (also including low-viscosity gels) or dissolved in solvents at room temperature. When they are solid (powder), they can be directly coated or injected. After being heated and melted, or dissolved in a solvent, it is coated or injected.

The monomer, oligomer, or mixture thereof used in the contacting step of the monomer, oligomer, or mixture thereof may be selected from the group consisting of radically polymerizable monomers and oligomers of radically polymerizable monomers, Alternatively, it may be selected from cationically polymerizable monomers and cationically polymerizable monomer oligomers of the above monomers, or a mixture of two or more types thereof.

(Radically polymerizable monomer) Examples of radically polymerizable compounds include one or more (meth)acrylyl groups, (meth)acryloxy groups, (meth)acrylamide groups, vinyl ether groups, and vinyl aryl groups in one molecule. , and vinyloxycarbonyl and other radically polymerizable compounds.

Examples of compounds having one or more (meth)acrylyl groups in one molecule include: 1-buten-3-one, 1-penten-3-one, 1-hexen-3-one, 4- Phenyl-1-buten-3-one, 5-phenyl-1-penten-3-one, etc., and their derivatives, etc.

Examples of compounds having one or more (meth)acryloxy groups in one molecule include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid n-butyl ester, (meth)acryloxy group ) Isobutyl acrylate, tertiary butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid n-Lauryl ester, n-stearyl (meth)acrylate, n-butoxyethyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate ) Acrylate, methoxypolyethylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, benzyl (meth)acrylate, benzene (meth)acrylate Oxyethyl ester, isocamphenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate )Dimethylaminoethyl acrylate, Diethylaminoethyl (meth)acrylate, Acrylic acid, Methacrylic acid, 2-(Meth)acryloxyethylsuccinic acid, 2-(Meth)acrylyl Oxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalate-2-hydroxypropyl ester, glycidyl (meth)acrylate, 2-(methyl)acrylic acid phosphate acrylic acid ethyl ester, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-butylene glycol Alcohol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, decane di(meth)acrylate, glycerol di(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-(methyl) Acryloxypropyl ester, dihydroxymethyltricyclodecane di(meth)acrylate, trifluoroethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, (meth)acrylic acid Isoamyl ester, isoteristyl (meth)acrylate, γ-(meth)acryloxypropyltrimethoxysilane, 2-(meth)acryloxyethyl isocyanate, isocyanic acid 1,1-bis(acryloxy)ethyl ester, 2-(2-(meth)acryloxyethoxy)ethyl isocyanate, 3-(meth)acryloxypropyltris Ethoxysilane, etc., and their derivatives, etc.

Examples of compounds having one or more (meth)acrylamide groups in one molecule include: 4-(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N ,N-diethyl(meth)acrylamide,N-methyl(meth)acrylamide,N-ethyl(meth)acrylamide,N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-n-butoxymethyl(meth)acrylamide, N-hexyl(meth)acrylamide Amine, N-octyl(meth)acrylamide, etc., and their derivatives, etc.

Examples of compounds having one or more vinyl ether groups in one molecule include: 3,3-bis(vinyloxymethyl)oxycyclobutane, 2-hydroxyethyl vinyl ether, and 3-hydroxypropyl vinyl ether. , 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether , 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclo Hexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol Monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol Alcohol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol Monovinyl ether, oligopropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, etc., and their derivatives.

Examples of compounds having one or more vinylaryl groups in one molecule include: styrene, divinylbenzene, methoxystyrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, acetic acid 4-vinylphenyl ester, (4-vinylphenyl)dihydroxyborane, N-(4-vinylphenyl)maleimide, etc., and their derivatives, etc.

Examples of compounds having one or more vinyloxycarbonyl groups in one molecule include isopropyl formate, isopropyl acetate, isopropyl propionate, isopropyl butyrate, isopropyl isobutyrate, and isopropyl caproate. Allyl ester, isopropyl valerate, isopropyl isovalerate, isopropyl lactate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl octanoate, vinyl laurate, meat Vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, trimethylvinyl acetate, vinyl octanoate, vinyl monochloroacetate, divinyl adipate, vinyl acrylate esters, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, etc., and their derivatives.

(Cationically polymerizable monomer) Examples of the cationically polymerizable monomer include cationically polymerizable groups other than oxycyclobutyl groups such as vinyl ether groups and vinyl aryl groups having one or more epoxy rings (oxyranyl groups) in one molecule. compounds, etc.

Examples of compounds having more than one epoxy ring in one molecule include: glycidyl methyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and brominated bisphenol. A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, Hydrogenated bisphenol S diglycidyl ether, (3,4-epoxy)cyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, 2-(3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy)cyclohexane-methyl-bis alkane, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3',4'- Epoxy-6'-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexyl ester, methylene bis(3,4-epoxycyclohexane), dicyclopentadienyl Ethylene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl) ether, ethylidene bis(3,4-epoxycyclohexanecarboxylate), epoxy hexahydro-phthalate Dioctyl dicarboxylate, di-2-ethylhexyl epoxy hexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glyceryl triglyceride Glyceryl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; by adding one or two aliphatic polyols such as ethylene glycol, propylene glycol, and glycerol. Polyglycidyl ethers of polyether polyols obtained from alkylene oxides; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; phenol, Cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these; and glycidyl esters of higher fatty acids, etc.

Examples of the compound having one or more vinyl ether groups in one molecule and the compound having one or more vinyl aryl groups in one molecule include the same compounds as those exemplified as the radically polymerizable compounds.

Examples of compounds having one or more oxycyclobutyl groups in one molecule include: 1,3-epoxypropane, 3,3-bis(vinyloxymethyl)oxycyclobutane, and 3-ethyl-3-hydroxy Methyloxycyclobutane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxycyclobutane, 3-ethyl-3-(hydroxymethyl)oxycyclobutane, 3-ethyl 3-[(phenoxy)methyl]oxycyclobutane, 3-ethyl-3-(hexyloxymethyl)oxycyclobutane, 3-ethyl-3-(chloromethyl)oxycyclobutane cyclobutane, 3,3-bis(chloromethyl)oxycyclobutane, 1,4-bis[(3-ethyl-3-oxocyclobutylmethoxy)methyl]benzene, bis{[1-ethyl methyl(3-oxocyclobutyl)]methyl}ether, 4,4'-bis[(3-ethyl-3-oxocyclobutyl)methoxymethyl]bicyclohexane, 1,4- Bis[(3-ethyl-3-oxobutyl)methoxymethyl]cyclohexane, and 3-ethyl-3{[(3-ethyloxybutan-3-yl)methoxy ]Methyl}oxycyclobutane, etc.

Examples of oligomers of radically polymerizable monomers and cationically polymerizable monomers include monofunctional or polyfunctional (meth)acrylic oligomers. You can use one type or a combination of two or more types. Examples of monofunctional or polyfunctional (meth)acrylic oligomers include (meth)acrylic urethane oligomer, epoxy (meth)acrylate oligomer, and polyether (meth)acrylate. Oligomers, and polyester (meth)acrylate oligomers, etc.

Examples of the (meth)acrylic urethane oligomer include polycarbonate-based (meth)acrylic urethane, polyester-based (meth)acrylic urethane, polyether-based (meth)acrylic urethane, and Caprolactone-based (meth)acrylic acid amine ester, etc. The (meth)acrylic urethane oligomer can be obtained by reacting an isocyanate compound obtained by reacting a polyol and a diisocyanate with a (meth)acrylate monomer having a hydroxyl group. Examples of the polyol include polycarbonate diol, polyester polyol, polyether polyol, and polycaprolactone polyol.

Epoxy (meth)acrylate oligomers are obtained, for example, through the esterification reaction of the ethylene oxide ring of low molecular weight bisphenol epoxy resin or novolak epoxy resin and acrylic acid. Polyether (meth)acrylate oligomers are obtained by dehydration condensation reaction of polyols to obtain polyether oligomers having hydroxyl groups at both ends, and then using acrylic acid to convert the hydroxyl groups at both ends. hydroxyl groups undergo esterification. The polyester (meth)acrylate oligomer is obtained, for example, by condensing a polycarboxylic acid and a polyol to obtain a polyester oligomer having hydroxyl groups at both ends, and then using acrylic acid to combine the two. The terminal hydroxyl group is esterified.

The weight average molecular weight of the monofunctional or polyfunctional (meth)acrylic oligomer is 100,000 or less in a preferred aspect of the invention, and is 500 to 50,000 in another preferred aspect of the invention.

When using the above-mentioned monomer, oligomer, or mixture thereof, 0.01 to 10 parts by mass of the photopolymerization initiator may be used with respect to 100 parts by mass of the above-mentioned monomer, oligomer, or mixture thereof.

In the next step, the monomer, oligomer, or mixture thereof in contact with the portion including the roughened portion of the carbide-based nonmagnetic ceramic molded body is irradiated with UV to harden it, thereby obtaining a curable resin. layered composite body.

(5) Composite moldings of carbide-based non-magnetic ceramic moldings with a roughened structure, or composite moldings of carbide-based non-magnetic ceramic moldings with a roughened structure and different types of non-magnetic ceramic moldings body manufacturing method A composite molded body of carbide-based non-magnetic ceramic molded bodies having a roughened structure can be produced, for example, by using a plurality of carbide-based non-magnetic ceramic molded bodies having a roughened structure in different shapes, and forming The adhesive layers on their joint surfaces are joined and integrated. The adhesive layer can be formed by applying an adhesive to a roughened structural portion of a carbide-based non-magnetic ceramic molded body. As the adhesive, the same adhesive as those used in the production of the other composite molded articles mentioned above can be used.

Furthermore, a composite molded body composed of a carbide-based non-magnetic ceramic molded body and a different type of non-magnetic ceramic molded body can also be produced in the same manner.

In this embodiment, in addition to the method of forming an adhesive layer on the roughened structural portion of the carbide-based non-magnetic ceramic molded body to join and integrate it with different types of non-magnetic ceramic molded bodies, different types of non-magnetic ceramic molded bodies can be integrated. The surface of the non-magnetic ceramic formed body also becomes a roughened structure and an adhesive layer is formed. Thereafter, the surface of the carbide-based non-magnetic ceramic formed body with the adhesive layer is bonded to the surface of the non-magnetic ceramic formed body of different types. The surfaces of the agent layer are bonded and integrated to produce a composite molded body.

Different types of non-magnetic ceramics include oxide series, nitride series, boride series, and silicide series. As a method for roughening the surface of non-magnetic ceramic molded bodies of different types, although the method or conditions differ depending on the type of non-magnetic ceramic, for example, the method of irradiating laser light as in the present invention can be applied, or by filing. Processing, blasting, etching, etc. are methods of roughening.

Each configuration and combination of the same in each embodiment is an example, and additions, omissions, substitutions, and other changes to the configuration may be made as appropriate without departing from the scope of the invention. The present invention is not limited by the embodiments but only by the scope of the patent application. [Example]

＜Thermal shock temperature (JIS R1648: 2002)＞ Thermal shock temperature is the temperature at which a heated test piece of a carbide-based non-magnetic ceramic molded body (4 x 35 x 3 mm thick) is destroyed when immersed in water at 30°C. When it is rapidly cooled, a temperature difference occurs between the interior and the surface, and the specimen is destroyed when the internal stress generated by the temperature difference exceeds the strength of the specimen.

Ra (arithmetic mean roughness): Draw 11 lines with a length of 1.5 mm on the surface of the roughened structural part of the carbide-based non-magnetic ceramic molded body, and measure it with a single-trigger 3D shape measuring machine (manufactured by Keyence) Wait for it.

Rz (maximum height): Draw 11 lines with a length of 1.5 mm on the surface of the roughened structural part of the carbide-based non-magnetic ceramic molded body, and measure them with a single-trigger 3D shape measuring machine (manufactured by Keyence) Rz.

Sa (arithmetic mean height): Sa measured in a 9 × 1.8 mm range on the surface of the roughened structure portion of the carbide-based non-magnetic ceramic molded body using a single-trigger 3D shape measuring machine (manufactured by Keyence).

Sz (maximum height): Sz in the 9 × 1.8 mm range of the surface of the roughened structural part of the carbide-based non-magnetic ceramic molded body was measured with a single-trigger 3D shape measuring machine (made by Keyence).

Str (aspect ratio of surface properties): represents the isotropy and anisotropy of surface properties, and is expressed in the range of 0 to 1. When Str is close to 0, it indicates stripes, and when Str is close to 1, it indicates that the surface does not depend on the direction. Str was measured with a single-trigger 3D shape measuring machine (manufactured by Keyence).

Examples 1 to 3, Comparative Example 1 The surface of the non-magnetic ceramic molded body (flat plate of 10×50×2 mm thickness) of the types shown in Table 1 was roughened by continuous irradiation of laser light using the following continuous wave laser device under the conditions shown in Table 1. . The trade name of the composite of 70 mass% silicon carbide/30 mass% aluminum in Example 2 is SA701 (JAPAN FINE CERAMICS Co., Ltd.). The trade name SS501 (JAPAN FINE CERAMICS Co., Ltd.) was used for the 50% by mass silicon carbide/50% by mass silicon composite in Example 3.

(laser device) Oscillator: IPG-Yb fiber; YLR-300-SM Galvanometer mirror SQUIREEL (manufactured by ARGES) Condensing system: fc=80 mm/fθ=100 mm

Furthermore, bidirectional irradiation is implemented as follows. Bidirectional irradiation: Repeat the following operation. After irradiating continuous wave laser light in a straight line to form a groove in one direction, irradiate continuous wave laser light in a straight line in the opposite direction with an interval of 0.05 mm. The 0.05 mm interval for bidirectional irradiation is the distance between the middle positions of the widths of adjacent grooves.

SEM photographs of the portions having a roughened structure of the nonmagnetic ceramic molded bodies of Examples 1 to 3 and Comparative Example 1 are shown in Figures 3 to 5 and 6 .

The nonmagnetic ceramic molded body having a roughened structure obtained in Examples 1 to 3 and Comparative Example 1 was used to produce a composite molded body with a resin molded body (a molded body of polyamide 66 containing 30% by mass of glass fiber). body (Figure 7).

Using the composite molded article obtained in Example 1, the joint strength of the nonmagnetic ceramic molded article and the resin molded article was measured. [Tensile test] A tensile test was performed using the composite molded body shown in Figure 7 to evaluate the shear joint strength (S1). The tensile test is based on ISO19095. With the end of the non-magnetic ceramic molded body 30 side fixed, it is stretched in the X direction shown in Figure 7 until the non-magnetic ceramic molded body 30 and the resin molded body 31 break. In this case, the maximum load until the joint surface is destroyed. The results are shown in Table 1. ＜Tensile test conditions＞ Testing machine: AUTOGRAPH AG-X plus (50 kN) manufactured by Shimadzu Corporation Stretching speed: 10 mm/min Distance between clamps: 50 mm

[Table 1] Example 1 Example 2 Example 3 Comparative example 1 non-magnetic ceramic silicon carbide Silicon carbide 70%/aluminum 30% Silicon carbide 50%/ silicon 50% silicon carbide Thermal shock temperature (℃) 450 - - 450 Irradiation speed (mm/sec) 10000 7500 7500 3000 Irradiation form Two-way Two-way Two-way Two-way Output(W) 280 280 280 280 Focus offset distance (mm) 0 0 0 0 Spacing interval (mm) 0.05 0.05 0.05 0.05 Number of passes (times) 10 10 10 10 Roughening state of concavity and convexity Ra（μm） 21.0 16.0 15.0 32.3 Rz(μm) 146 83 75 244 Sa (μm) 18.0 15 15 33 Sz(μm) 171 123 107 305 Sdr 1.3 1.3 1.4 1.9 SEM photo Figure 3 Figure 4 Figure 5 Figure 6 The roughened state of the convex part Ra（μm） 2.6 - - - Rz(μm) 13.8 - - - Sa (μm) 6.8 - - - Sz(μm) 36.4 - - - Sdr 0.55 - - - Is there any rupture? without without without None (surface defects) Bonding strength (MPa) 5 - - -

In the non-magnetic ceramic molded bodies containing silicon carbide of Examples 1 to 3, the cross-sectional shape in the thickness direction of the front end portion of the uneven structure of the roughened structure is a curved surface (partial circle). Example 1 (Fig. 3) has wrinkle-like protrusions that are continuous along the length direction. In Examples 2 and 3 (Figs. 4 and 5), a large number of independent holes are formed in a linear shape along the length direction. Comparative Example 1, in which the laser light irradiation speed was relatively slow, did not cause cracks, but partially caused defects. [Industrial availability]

The carbide-based non-magnetic ceramic molded body having a roughened surface structure of the present invention can be used as an intermediate for manufacturing composite molded bodies of carbide-based non-magnetic ceramic molded bodies and resins, rubbers, elastomers, metals, etc.

11:Irradiation part 12: Non-irradiated part 20: Metal formed body 30: Non-magnetic ceramic formed body 31: Resin molded body

FIG. 1 is a diagram showing an irradiation state of laser light according to an embodiment when performing a second manufacturing method according to an example of the present invention. 2 is a diagram showing the irradiation pattern of laser light when implementing the second manufacturing method according to an example of the present invention, in which (a) is the irradiation pattern in the same direction, and (b) is the irradiation pattern in both directions. Figure 3(a) is an SEM photograph (200 times) of the roughened structural part (top view) of the silicon carbide molded body of Example 1. Figure 3(b) is a cross-sectional SEM photograph in the thickness direction of Figure 3(a) (200 times). times). Figure 4 is an SEM photograph (200 times) of the roughened structural part (top view) of the silicon carbide/aluminum formed body of Example 2. Figure 5 is an SEM photograph (200 times) of the roughened structural part (top view) of the silicon carbide/silicon formed body of Example 3. Figure 6 is an SEM photograph (200 times) of the roughened structural part (top view) of the silicon carbide molded body of Comparative Example 1. 7 is a perspective view of the carbide-based ceramic molded article produced in the Example and a perspective view for explaining a test of the joint strength of a composite molded article using the carbide-based ceramic molded article and the resin molded article.

11:Irradiation part

12: Non-irradiated part

Claims (14)

A non-magnetic ceramic molded body, the surface of which has a roughened structure, and the roughened structure has unevenness, and the cross-sectional shape of the thickness direction of the unevenness is a curved surface when observed through a scanning electron microscope photograph (200 times or more), the above-mentioned The curved surface of the convex portion has wrinkle-like protrusions formed along the length direction, or the curved surface of the convex portion is formed into a plurality of linear independent holes along the length direction. The non-magnetic ceramic molded body is a carbide-based non-magnetic ceramic. Formed body. The non-magnetic ceramic formed body according to claim 1, wherein the thermal shock temperature (JIS R1648: 2002) of the carbide-based non-magnetic ceramic formed body is in the range of 400 to 500°C, and the thickness is 0.5 mm or more. The non-magnetic ceramic shaped body according to claim 2, wherein the carbide-based non-magnetic ceramic shaped body is a shaped body containing silicon carbide. The non-magnetic ceramic shaped body according to claim 1, wherein the carbide-based non-magnetic ceramic shaped body is a composite body in which the inside of the pores of porous silicon carbide is impregnated with metal or semi-metal, and the silicon carbide contains The ratio is 50% by mass or more. The nonmagnetic ceramic molded body according to any one of claims 1 to 4, wherein the cross-sectional shape in the thickness direction of the front end of the concave and convex convex portion is partially circular or partially elliptical. The nonmagnetic ceramic molded body according to any one of claims 1 to 4, wherein the unevenness is formed by alternately forming linear convex portions and linear concave portions, and the linear convex portions and linear concave portions are formed alternately. When the width of each of the linear recessed portions is 20 to 100 μm, the width of the corrugated protrusions formed along the length direction of the convex portion or the plurality of linear independent holes is 1 to 10 μm. The nonmagnetic ceramic molded body according to any one of claims 1 to 4, wherein the recessed portions among the recesses and convexities are dispersed in an island shape, and the portions other than the recessed portions are convex portions, When the width of the above-mentioned convex part is 20-100 μm, the width of the corrugated protrusions formed along the length direction of the above-mentioned convex part or the aggregate of linear independent holes is 1-10 μm. The non-magnetic ceramic molded body according to any one of claims 1 to 4, wherein the surface roughness (Ra) of the front end portion of the convex and concave portions is in the range of 5 to 40 μm, and the convex and concave portions of the concave and convex portions The height difference (Rz) is in the range of 50~200μm. The nonmagnetic ceramic molded body according to any one of claims 1 to 4, wherein the surface roughness (Ra) of the front end portion of the convex and concave portions is in the range of 10 to 30 μm, and the convex and concave portions of the concave and convex portions are in the range of 10 to 30 μm. The height difference (Rz) is in the range of 60~180μm. A method for manufacturing a non-magnetic ceramic formed body, which is a method for manufacturing a non-magnetic ceramic formed body having a roughened surface structure according to any one of claims 1 to 9, by using a continuous wave laser at a depth of 5,000 mm/ The surface of the non-magnetic ceramic molded body containing silicon carbide carbide is continuously irradiated with laser light at an irradiation speed of sec or more to roughen it. A method for manufacturing a non-magnetic ceramic formed body, which is a method for manufacturing a non-magnetic ceramic formed body with a roughened surface structure according to any one of claims 1 to 9, and has the method of using a continuous wave laser with a 5,000mm/ A step of continuously irradiating laser light to the surface of a non-magnetic ceramic molded body containing silicon carbide carbide at an irradiation speed of sec or more. The above-mentioned laser light irradiation step is to irradiate laser light to the surface of a metal molded body to be roughened. At this time, the irradiation step is performed in a manner that alternately generates the irradiated part and the non-irradiated part of the laser light. The method for manufacturing a non-magnetic ceramic formed body as described in claim 10 or 11, wherein a continuous wave laser is used to continuously irradiate the surface of the non-magnetic ceramic formed body with laser light at an irradiation speed of 5000 mm/sec or more. The laser light is continuously irradiated in the same direction or in different directions to form a plurality of lines composed of straight lines, curves and combinations thereof. The manufacturing method of the non-magnetic ceramic shaped body according to claim 10 or 11, which is based on using When a continuous wave laser is used to continuously irradiate the surface of the above-mentioned non-magnetic ceramic molded object with an irradiation speed of 5,000 mm/sec or more, a plurality of straight lines, curves and combinations thereof are formed in the same direction or in different directions. Continuously irradiate laser light in a line manner, and continuously irradiate laser light multiple times to form a straight line or a curve. The manufacturing method of the non-magnetic ceramic formed body as described in claim 10 or 11, which is when a continuous wave laser is used to continuously irradiate the surface of the non-magnetic ceramic formed body with laser light at an irradiation speed of 5,000 mm/sec or more, Continuously irradiating laser light in such a manner as to form a plurality of lines consisting of straight lines, curves and combinations thereof in the same direction or in different directions, and forming the plurality of straight lines or the plurality of curves at equal intervals or at different intervals. way of continuously irradiating laser light.

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