JP2020125239A - Method for producing carbide-based non-magnetic ceramic compact having roughened structure on the surface - Google Patents

Abstract

To provide a method for producing a non-magnetic ceramic compact having a roughened structure on a surface.SOLUTION: There is provided a method for producing a non-magnetic ceramic compact that has a roughened structure on a surface, and in which the non-magnetic ceramic compact is a carbide-based non-magnetic ceramic compact and the roughened surface is achieved by continuously radiating laser beam at a radiation speed of 5,000 mm/sec or more using a continuous wave laser to the surface of a silicon carbide-containing carbide-based non-magnetic ceramic compact.SELECTED DRAWING: None

Description

The present invention, in one of its aspects, relates to a carbide-based non-magnetic ceramic compact having a roughened structure on its surface and a method for producing the same.

Non-magnetic ceramics are commonly used in various molded articles such as tableware, cups, vase and other daily necessities, and engineering ceramics, and it is known to perform a treatment for forming irregularities on the surface according to the application.

Patent Document 1 (Japanese Patent Laid-Open No. 2002-308683) discloses a ceramic member having an uneven structure formed by an acidic etching solution. Patent Document 2 (Japanese Patent No. 6032903) describes an invention of a firing setter having a specific concavo-convex structure (claims), and as a material of the firing setter, zirconia, alumina, magnesia, Examples include spinel and cordierite (paragraph number 0013).

Patent Document 3 (WO2011/121808 A1) discloses that a base material made of metal or ceramics, an impregnation layer provided by forming a recess in the surface portion of the base material on the sliding side, and the impregnation layer Disclosed is an invention in which a resin layer that is impregnated and covers the surface of the base material on the sliding side is provided, and the concave portion is formed by machining (Claims). ). It is described that the recess 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 mechanical processing include laser processing and wire cutting processing (paragraph number 0014), but there is no description of specific processing conditions, and it is described that the steel was wire cut processing in the examples. There is no specific description about ceramics.

Patent Document 4 (JP-A-2015-109966) discloses a method for producing a medical device material, which comprises coating calcium phosphate on a specific site of a tetragonal zirconia-containing medical device material, wherein an ultrashort pulse is applied to the specific site. A first step of forming irregularities on the surface by irradiating a laser, and a second step of vapor depositing or precipitating calcium phosphate fine particles smaller than the period of the irregularities on the specific site, in a medical device material characterized by the following: A manufacturing method is disclosed (Claims).

In Patent Document 5 (Japanese Patent No. 6111102), a laser beam having a wavelength of 300 to 1500 nm is applied to a portion of a planar shape that is substantially the same as the circuit pattern on at least one surface of a ceramic substrate containing AlN or Al ₂ O ₃ as a main component. To form an aluminum film on a portion of the same planar shape as the circuit pattern on at least one surface of the ceramics substrate, and a copper plate is placed on the aluminum film to form a eutectic point of aluminum and copper or more. A method for manufacturing a metal/ceramic bonding substrate is disclosed in which a copper plate is bonded to a ceramic substrate via an aluminum film by heating at a temperature of 650° C. or lower.

In Patent Document 6 (Japanese Patent Laid-Open No. 2003-171190), the surface of a base material made of dense ceramics having a purity of 95% or more is formed into rounded first irregularities having a surface roughness Ra of 3 to 40 μm, and , A ceramic member in which the surface of the first unevenness is formed into a second unevenness having a roundness with a surface roughness Ra of 0.1 to 2.9 μm. It is shown that the second unevenness covers the entire surface of the first unevenness.

Patent Document 7 (Japanese Patent Laid-Open No. 2003-137677) and Patent Document 8 (Japanese Patent Laid-Open No. 2004-66299) disclose a technique for forming irregularities by laser processing on the surface of a ceramic body.

In Patent Document 9 (Japanese Patent No. 5774246) and Patent Document 10 (Japanese Patent No. 5701414), a continuous wave laser is used to continuously irradiate a laser beam at an irradiation speed of 2,000 mm/sec or more to obtain a metal. Although an invention for roughening the surface of a molded body and an invention for a method for producing a composite molded body of a metal molded body and a resin molded body are disclosed, there is no description about ceramics.

JP, 2002-308683, A Japanese Patent No. 6032903 WO2011/121808 A1 JP, 2005-109966, A Japanese Patent No. 6111102 JP, 2003-171190, A JP, 2003-137677, A JP, 2004-66299, A Patent No. 5774246 Japanese Patent No. 5701414

An object of the present invention is to provide, in one aspect thereof, a non-magnetic ceramic compact having a roughened surface structure and a method for producing the same.

The present invention, in one embodiment thereof, is a non-magnetic ceramic compact having a surface-roughened structure,
The roughened structure has irregularities, and the cross-sectional shape in the thickness direction of the irregularities is a curved surface when observed by a scanning electron micrograph (200 times or more), and the curved surface of the convex portion has a length. A wrinkle-shaped projection formed along the direction, or a curved surface of the convex portion has a plurality of independent holes linearly formed along the length direction,
There is provided a non-magnetic ceramic compact having a surface-roughened structure, wherein the non-magnetic ceramic compact is a carbide-based non-magnetic ceramic compact. Further, the present invention provides, in another embodiment, a method for producing such a non-magnetic ceramic compact.

The non-magnetic ceramic compact according to the embodiment of the present invention has a roughened structure on the surface, and can be used as an intermediate for producing a composite compact with another material. Therefore, in another aspect, the present invention is also directed to a method for producing such a composite molded body and a composite molded body.

According to the manufacturing method of the embodiment of the present invention, it is possible to roughen the surface of a carbide-based non-magnetic ceramic compact that is inherently hard and brittle without being separated into two or more by cracking.

The figure which shows the irradiation state of the laser beam of one Embodiment when implementing the 2nd manufacturing method by one example of this invention. It is a figure which shows the irradiation pattern of a laser beam when implementing the 2nd manufacturing method by one example of this invention, (a) is an irradiation pattern of the same direction, (b) is a bidirectional irradiation pattern. (A) is a SEM photograph (200 times) of the roughened structure portion (plan view) of the silicon carbide molded body of Example 1, and (b) is a cross-sectional SEM photograph (200 times) in the thickness direction of (a). is there. 3 is a SEM photograph (200 times) of a roughened structure portion (plan view) of the silicon carbide/aluminum molded body of Example 2. 5 is a SEM photograph (200 times) of a roughened structure portion (plan view) of a silicon carbide/silicon molded body of Example 3. 3 is a SEM photograph (200 times) of a roughened structure portion (plan view) of the silicon carbide molded body of Comparative Example 1. FIG. 3 is a perspective view of a carbide-based ceramics molded body manufactured in Examples and a perspective view for explaining a bonding strength test using a composite molded body of a carbide-based ceramics molded body and a resin molded body.

According to the embodiment of the present invention, the non-magnetic ceramic compact having the roughened structure on its surface contains a carbide-based non-magnetic ceramic. The carbide-based non-magnetic ceramics molded body may be a molded body containing a carbide-based non-magnetic ceramics such as silicon carbide, titanium carbide, tungsten carbide, or boron carbide. Good.

The silicon carbide may be composed of only silicon carbide, or may be composed of a composite of silicon carbide and other non-magnetic ceramics, metal, or semimetal, as long as it is within a predetermined thermal shock temperature. The composite of silicon carbide and metal may be obtained by impregnating the inside of a porous silicon carbide molded body with a metal (for example, aluminum) or a semimetal (for example, silicon). The content ratio of silicon carbide in the composite is 50% by mass or more in a preferable embodiment of the present invention, 60% by mass or more in another preferable embodiment of the present invention, and 70% in another preferable embodiment of the present invention. It is at least mass%.

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

The non-magnetic ceramic compact containing silicon carbide has a thickness of 0.5 mm or more in a preferred embodiment of the present invention in order to prevent cracking during processing. In another preferred embodiment of the present invention, the thickness is 0.5 mm or more. Is 1.0 mm or more. The "crack" in the present invention means that a part of the molded body is cracked and divided into two or more, and "crack" is not included. A "crack" also includes a case where it does not break during processing by laser light irradiation, but its strength is significantly reduced, and it is divided into two or more during subsequent movement and processing.

According to some embodiments of the present invention, a non-magnetic ceramic compact having a surface-roughened structure has a roughened structure, and a scanning electron micrograph (200 times or more) The cross-sectional shape of the unevenness in the thickness direction has a curved surface when observed by.

The cross-sectional shape of the unevenness in the thickness direction may include a partial circular shape or a partial elliptical shape. The partial circular shape is a shape including a part of a circle, such as a semicircular shape and a 1/3 circular shape. The partial elliptical shape is a shape including a part of an ellipse such as a semi-elliptical shape and a 1/3 elliptical shape.

The non-magnetic ceramic molded body having a roughened structure on the surface of the present invention may be such that the irregularities are formed by alternately forming linear convex portions and linear concave portions, and the convex portions have curved surfaces. Wrinkle-shaped protrusions along the lengthwise direction, or a plurality of independent holes in which the curved surface of the convex portion is linearly formed along the lengthwise direction may be formed.

According to one example, the wrinkle-shaped protrusion is a portion that is slightly protruded outward from the surface without the wrinkle-shaped protrusion. The wrinkle-shaped projection may be formed continuously in the length direction, for example, but may have a discontinuous portion. According to one example, the plurality of independent holes formed in a linear shape has a form in which a large number of independent holes are arranged in a linear shape. The wrinkle-shaped projections and/or the plurality of independent holes formed in a linear shape have a width of 1 to 10 μm when the width of each of the linear convex portion and the linear concave portion is 20 to 100 μm. It may be one.

When the wrinkle-shaped protrusions and/or the plurality of independent holes formed in a linear shape are formed along the length direction on the surface (curved surface) of the convex portion and the surface area is increased, for example, a non-magnetic ceramic It is considered that when the molded body is bonded to another member (for example, a resin molded body), the contact area of the bonding surface is increased, so that the bonding strength is increased.

In some examples of the non-magnetic ceramic molded body having a roughened structure on the surface of the present invention, the concave portions of the irregularities of the roughened structure are formed in an island-like dispersed manner, and the portion excluding the concave portions is formed. Is a convex portion, and the convex portion has wrinkle-shaped projections along the length direction and/or a plurality of independent holes in which the curved surface of the convex portion is linearly formed along the length direction. Has been formed.

According to one example, the wrinkle-shaped protrusion is a portion that is slightly protruded outward from the surface without the wrinkle-shaped protrusion. The wrinkle-shaped projection may be formed continuously in the length direction, for example, but may have a discontinuous portion. According to one example, the plurality of independent holes formed in a linear shape has a form in which a large number of independent holes are arranged in a linear shape. The wrinkle-shaped projections and/or the plurality of independent holes formed in a linear shape have a width of 1 to 10 μm when the width of each of the linear convex portion and the linear concave portion is 20 to 100 μm. It may be one.

In this way, wrinkle-shaped projections are formed along the lengthwise direction on the surface (curved surface) of the convex portion and/or a plurality of independent holes in which the curved surface of the convex portion is linearly formed along the lengthwise direction. Is increased, it is considered that, for example, when the non-magnetic ceramic molded body is bonded to another member (for example, a resin molded body), the contact area of the bonding surface is increased and the bonding strength is increased.

According to some examples of the non-magnetic ceramic compact of the present invention, the surface roughness (Ra) of the irregularities is in the range of 2 to 100 μm in a preferred embodiment of the present invention, and another preferred embodiment of the present invention. Is in the range of 5 to 80 μm, and in yet another preferred embodiment of the present invention, it is in the range of 10 to 50 μm.

According to some examples of the non-magnetic ceramic molded body of the present invention, the height difference (Rz) between the convex portion and the concave portion of the unevenness is in the range of 10 to 200 μm in a preferred embodiment of the present invention. In another preferred embodiment of the present invention, the range is 20 to 150 μm, and in another preferred embodiment of the present invention, the range is 20 to 100 μm.

Further, according to some examples of the non-magnetic ceramic compact of the present invention, Sa (arithmetic mean height), Sz (maximum height), and Str (surface texture of the roughened structure portion (uneven portion) are The aspect ratio) may be in the following range.

Sa (arithmetic mean height) is 2 to 100 μm in one preferred embodiment of the present invention, 5 to 80 μm in another preferred embodiment of the present invention, and 10 to 50 μm in yet another preferred embodiment of the present invention. Is.

Sz (maximum height) is 10 to 300 μm in one preferred embodiment of the present invention, 20 to 200 μm in another preferred embodiment of the present invention, and 20 to 150 μm in yet another preferred embodiment of the present invention. is there.

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

Further, the surface roughness (Ra) of the convex portions of the irregularities is in the range of 1 to 10 μm in one preferred embodiment of the present invention, and in the range of 1.5 to 8 μm in another preferred embodiment of the present invention. In yet another preferred embodiment, the range is 2 to 8 μm.

In this case, the height difference (Rz) between the convex portion and the concave portion of the irregularities is in the range of 5 to 50 μm in a preferred embodiment of the present invention, and in the range of 8 to 40 μm in another preferred embodiment of the present invention. In still another preferred aspect of the present invention, the range is 10 to 30 μm.

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

Sa (arithmetic mean height) is 1 to 10 μm in one preferred embodiment of the present invention, 1.5 to 8 μm in another preferred embodiment of the present invention, and 2 in yet another preferred embodiment of the present invention. ~8 μm.

Sz (maximum height) is 8 to 40 μm in one preferred embodiment of the present invention, 10 to 30 μm in another preferred embodiment of the present invention, and 100 to 180 μm in yet another preferred embodiment of the present invention. is there.

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

According to one embodiment of the present invention, the non-magnetic ceramic molded body can be used as a carrier that can hold liquid, powder, etc. in the roughened structure portion, and other materials (carbide-based non-magnetic material). It can also be used as a production intermediate for producing a composite compact with a compact made of a material excluding magnetic ceramics).

<First Method for Producing Carbide-Based Non-Magnetic Ceramics Compact Having Surface Roughened Structure>
Next, a first method for producing a carbide-based nonmagnetic ceramic compact having a roughened structure on the surface according to one embodiment of the present invention will be described. The non-magnetic ceramic compact according to one embodiment of the present invention continuously emits laser light to the surface of a carbide-based non-magnetic ceramic compact using a continuous wave laser at an irradiation speed of 5,000 mm/sec or more. It can be manufactured by irradiation.

The shape, size, thickness, etc. of the carbide-based non-magnetic ceramic molded body used in the manufacturing method according to one embodiment of the present invention are not particularly limited and are selected according to the application and adjusted as necessary. Is done. For example, as a carbide-based non-magnetic ceramic compact, a flat plate, a round rod, a square rod (a rod having a polygonal cross section), a tube, a cup-shaped one, a cube, a rectangular parallelepiped, a sphere or a partial sphere (such as a hemisphere), an ellipsoid Alternatively, existing non-magnetic ceramic products can be used in addition to molded bodies such as partially elliptical spheres (semi-elliptical spheres) and amorphous shapes. The existing carbide-based non-magnetic ceramic products are not only composed of carbide-based non-magnetic ceramics, but also composites of carbide-based non-magnetic ceramics and other materials (metal, resin, rubber, glass, wood, etc.). It may be

According to one embodiment, when continuously irradiating the surface of the carbide-based non-magnetic ceramic molded body with laser light at a irradiation speed of 5,000 mm/sec or more using a continuous wave laser, the same direction or The laser light can be continuously irradiated so that a plurality of lines including straight lines, curved lines, and combinations thereof are formed in different directions.

According to another embodiment, when the surface of the carbide-based nonmagnetic ceramic compact is continuously irradiated with laser light at a irradiation speed of 5,000 mm/sec or more using a continuous wave laser, the same direction is applied. Alternatively, laser light is continuously irradiated so that a plurality of lines including straight lines, curves, and combinations thereof are formed in different directions, and laser light is continuously irradiated a plurality of times to form one straight line or one curve. can do.

According to still another embodiment, when the surface of the carbide-based nonmagnetic ceramic compact is continuously irradiated with laser light at a irradiation speed of 5,000 mm/sec or more using a continuous wave laser, the same direction is applied. Alternatively, the laser light is continuously irradiated so that a plurality of straight lines, curved lines, and a plurality of lines including a combination thereof are formed in different directions, and the plurality of straight lines or the plurality of curved lines have equal intervals or different intervals. Laser light can be continuously irradiated so as to be formed.

The irradiation speed of the laser light may be 5,000 mm/sec or more for roughening the carbide-based non-magnetic ceramic compact, and in a preferred embodiment of the present invention, it is 5,000 to 20,000 mm/sec. Yes, in another preferred aspect of the present invention, it is 5,000 to 10,000 mm/sec. If the irradiation speed of the laser light is less than 5,000 mm/sec, it is difficult to form a roughened structure on the surface of the non-magnetic ceramic compact.

The power of the laser is 50 to 4,000 W in a preferred embodiment of the present invention, 100 to 2,000 W in another preferred embodiment of the present invention, and 100 to 1 in yet another preferred embodiment of the present invention. It is 1,000 W. Adjust the roughening condition by decreasing the laser light output when the laser light irradiation speed is slow within the above range and increasing it when the laser light irradiation speed is high within the above range. You can For example, when the output of the laser light is 100 W, the irradiation speed of the laser light is 5,000 to 7,500 mm/sec in a preferred embodiment of the present invention, and when the output of the laser light is 500 W, the In a preferred aspect of the invention, the irradiation speed of the laser light may be 7,500 to 10,000 mm/sec.

The spot diameter of the laser beam is 10 to 100 μm in a preferred embodiment of the present invention, and 10 to 75 μm in another preferred embodiment of the present invention.

Energy density during the laser beam irradiation, in a preferred embodiment of the present invention are 3~1500MW / cm ^2, in another preferred embodiment of the present invention is a 5~700MW / cm ^2. The energy density at the time of laser light irradiation is calculated by the following formula: laser light output (W) and laser light (spot area (cm ² )(π·[spot diameter/2] ² ): laser light output/spot area) Desired.

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

When repeatedly irradiating one line, bidirectional irradiation or unidirectional irradiation can be selected. When forming one line (groove), bidirectional radiation is from the second end to the first end after irradiating a continuous wave laser from the first end to the second end of the line (groove). This is a method of irradiating with a continuous wave laser, and thereafter repeatedly irradiating with a continuous wave laser from the first end to the second end and from the second end to the first end. Unidirectional irradiation is a method of repeating unidirectional continuous wave laser irradiation from the first end to the second end.

When the laser light is linearly irradiated, the interval (line interval or pitch interval) between the intermediate positions of the widths of the adjacent irradiation lines (grooves formed by the adjacent irradiation) is 0 in a preferred embodiment of the present invention. It is 03 to 1.0 mm, and in another preferred embodiment of the present invention, it is 0.03 to 0.2 mm. The line intervals may be the same or different.

When irradiating with laser light, after bidirectional irradiation or unidirectional irradiation at a line interval described above to form a plurality of grooves, and further from the direction orthogonal or oblique to the plurality of grooves, the above line It is also possible to carry out bi-directional irradiation or cross-irradiation with one direction irradiation at intervals.

The wavelength of the laser light is 300 to 1200 nm in a preferred embodiment of the present invention, and 500 to 1200 nm in another preferred embodiment of the present invention. The defocusing distance when irradiating with laser light is -5 to +5 mm in a preferred embodiment of the present invention, -1 to +1 mm in another preferred embodiment of the present invention, and yet another preferred embodiment of the present invention. In the embodiment, it is -0.5 to +0.1 mm. For the defocusing distance, laser irradiation may be performed with a set value being constant, or laser irradiation may be performed while changing the defocusing distance. For example, at the time of laser irradiation, the defocusing distance may be gradually decreased, or periodically increased or decreased.

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

<Second Method for Producing Carbide-Based Non-Magnetic Ceramics Compact Having Roughened Structure on Surface>
A second method for manufacturing a carbide-based non-magnetic ceramic compact having a surface-roughened structure according to one embodiment of the present invention is different from the above-described first method in a laser light irradiation mode. Others are the same method.

The second manufacturing method uses a continuous wave laser to irradiate a laser beam onto the surface of the carbide-based non-magnetic ceramic molded body at an irradiation speed of 5,000 mm/sec or more in the same manner as the first manufacturing method. In the step of continuously irradiating, a step of irradiating laser light onto the surface of the carbide-based non-magnetic ceramics compact to be roughened so that the laser light irradiation portion and the non-irradiation portion alternate have.

In the second manufacturing method, when the laser light is irradiated so as to form a straight line, a curved line, or a combination of a straight line and a curved line, irradiation is performed so that the laser light irradiation portion and the non-irradiation portion occur alternately. Irradiating the laser light so that the irradiated portion and the non-irradiated portion are alternately generated includes the embodiment in which the irradiation is performed as shown in FIG. FIG. 1 shows that laser light non-irradiated portions 12 of length L2, which are located between laser light irradiated portions 11 of length L1 and laser light irradiation portions 11 of length L1 that are adjacent to each other, are alternately generated. It shows a state in which irradiation is performed so as to form a dotted line. The dotted line includes chain lines such as a one-dot chain line and a two-dot chain line.

When irradiating a plurality of times, the irradiation part of the laser light may be the same, or the irradiation part of the laser light is made different (the irradiation part of the laser light is shifted), so that the entire carbide-based non-magnetic ceramic molded body is formed. May be roughened. When the same portion of the laser light is irradiated and the laser light is irradiated multiple times, the laser light is irradiated in a dotted line, but the laser light irradiation portion is shifted, that is, the portion of the laser light that was originally not irradiated is When the irradiation is repeated by shifting the irradiation parts so that they overlap each other, even if the irradiation is performed in a dotted line, the irradiation is finally performed in a solid line state. The number of repetitions can be 1 to 20 times.

When the carbide-based nonmagnetic ceramic compact is continuously irradiated with laser light, the compact having a small thickness may be deformed such as cracked. However, when the laser irradiation is performed in a dotted line as shown in FIG. 1, the laser light irradiation portion 11 and the laser light non-irradiation portion 12 are alternately generated. Therefore, when the laser light irradiation is continued, Even a small molded body is less likely to be deformed such as cracked. At this time, the same effect can be obtained even when the laser light irradiation portion is different (the laser light irradiation portion is shifted) as described above.

The laser light irradiation method is, for example, a method of irradiating the surface of the metal molded body 20 in one direction as shown in FIG. 2A, or bidirectional irradiation as shown by a dotted line in FIG. 2B. Can be used. Alternatively, a method of irradiating the laser beam so that the dotted line irradiation portions intersect may be used. The distance b1 between the dotted lines after irradiation can be adjusted according to the irradiation target area of the metal molded body, but can be set in the same range as the line distance in the first manufacturing method.

The length (L1) of the laser light irradiation portion 11 and the length (L2) of the laser light non-irradiation portion 12 shown in FIG. 1 are adjusted to be in the range of L1/L2=1/9 to 9/1. can do. The length (L1) of the laser light irradiation portion 11 is 0.05 mm or more in a preferred embodiment of the present invention for roughening a complex porous structure, and is 0 in another preferred embodiment of the present invention. 0.1 to 10 mm, and in yet another preferred embodiment of the present invention, 0.3 to 7 mm.

In one exemplary embodiment of the second manufacturing method of the present invention, the above-mentioned laser light irradiation step includes a fiber laser device in which a direct modulation type modulation device for directly converting a driving current of a laser is connected to a laser power source. Is used to adjust the duty ratio and perform laser irradiation.

There are two types of laser excitation, pulse excitation and continuous excitation, and a pulse wave laser by pulse excitation is generally called a normal pulse. A pulse wave laser can be produced even with continuous excitation, and a pulse width (pulse ON time) is made shorter than a normal pulse to oscillate a laser with high peak power by that amount. External modulation method of generating pulse wave laser by temporally cutting out light by LN light intensity modulator, method of mechanically chopping to make pulse, method of operating galvano mirror to make pulse, laser drive current A pulse wave laser can be produced by a direct modulation method in which is directly modulated to generate a pulse wave laser. The method of pulsing the galvano mirror by operating it is the method of irradiating the laser light oscillated from the laser oscillator through the galvano mirror by the combination of the galvano mirror and the galvano controller. It can be carried out.

The Gate signal is periodically output from the Galvano controller ON/OFF, and the laser light oscillated by the laser oscillator is turned ON/OFF by the ON/OFF signal to pulse the laser light without changing its energy density. be able to. As a result, as shown in FIG. 1, laser light non-irradiated portions 11 and laser light non-irradiated portions 12 between the adjacent laser light irradiated portions 11 are alternately formed so that they are formed in a dotted line shape as a whole. Can be irradiated with laser light. The method of operating the galvanometer mirror to generate pulses is simple in operation because the duty ratio can be adjusted without changing the laser light oscillation state itself.

Among these methods, it is a method that can be easily pulsed (irradiated so that irradiated portions and non-irradiated portions alternate) without changing the energy density of the continuous wave laser. A method of chopping and pulsing, a method of operating a galvano-mirror for pulsing, and a direct modulation method of directly modulating a driving current of a laser to generate a pulse wave laser may be used. In the exemplary embodiment as described above, a fiber laser device in which a direct modulation type modulator for directly converting a laser drive current is connected to a laser power source is used to continuously excite the laser to generate a pulse wave laser. May be created.

The duty ratio is a ratio obtained from the ON time and the OFF time of the output of the laser light by the following formula.
Duty ratio (%)=ON time/(ON time+OFF time)×100
Since the duty ratio corresponds to L1 and L2 (that is, L1/[L1+L2]) shown in FIG. 1, it can be selected from the range of 10 to 90%, for example. By adjusting the duty ratio and irradiating the laser light, it is possible to irradiate in a dotted line as shown in FIG.

Manufacture for producing a composite molded body of a non-magnetic ceramic molded body having a roughened surface structure according to one embodiment of the present invention and a molded body made of another material (a material excluding the non-magnetic ceramics) Some examples of the method for producing a composite molded article when used as an intermediate will be described. The manufacturing method of these composite molded bodies and the manufactured composite molded bodies are also included in the scope of the present invention.

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

In the second step, a portion containing the roughened structure of the carbide-based non-magnetic ceramics molded body having a roughened structure on the surface obtained in the first step is placed in a mold to form the resin molded body. Injecting resin, or, in the second step, disposing at least a portion including the roughened structure of the non-magnetic ceramic molded body irradiated with the laser beam in the first step in a mold to roughen the surface. Compression molding is performed in a state where a portion including a structure and a resin forming the resin molded body are in contact with each other.

The resin used in the second step includes a thermoplastic resin, a thermosetting resin, and a thermoplastic elastomer. The thermoplastic resin can be appropriately selected from known thermoplastic resins depending on the application. For example, polyamide resins (aliphatic polyamides such as PA6 and PA66, aromatic polyamides), polystyrenes, ABS resins, copolymers containing styrene units such as AS resins, 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.

The thermosetting resin can be appropriately selected from known thermosetting resins according to the application. Examples thereof include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane. When the thermosetting resin is used, it is possible to use a prepolymer form and to perform a heat curing treatment in a subsequent step.

The thermoplastic elastomer can be appropriately selected from known thermoplastic elastomers depending on the application. Examples thereof include styrene elastomer, vinyl chloride elastomer, olefin elastomer, urethane elastomer, polyester elastomer, nitrile elastomer, and polyamide elastomer.

A publicly known fibrous filler can be blended with these thermoplastic resins, thermosetting resins, and thermoplastic elastomers. Known fibrous fillers include carbon fibers, inorganic fibers, metal fibers, organic fibers and the like.

Carbon fibers are well known, and PAN type, pitch type, rayon type, lignin type and the like can be used. Examples of the inorganic fiber include glass fiber, basalt fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and the like. Examples of the metal fiber include fibers made of stainless steel, aluminum, copper and the like.
As the organic fibers, polyamide fibers (wholly 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, Polyoxymethylene fiber, polytetrafluoroethylene fiber, polyester fiber (including wholly aromatic polyester fiber), polyphenylene sulfide fiber, polyimide fiber, liquid crystal polyester fiber and other synthetic fibers and natural fibers (cellulosic fibers, etc.) and regenerated cellulose ( Rayon) fiber or the like can be used.

As these fibrous fillers, those having a fiber diameter in the range of 3 to 60 μm can be used, and among them, for example, open holes formed by roughening the joint surface 12 of the metal molded body 10. Fiber diameters smaller than the opening diameter, such as 30, can be used. The fiber diameter is 5 to 30 μm in one preferred embodiment of the present invention, and 7 to 20 μm in another preferred embodiment of the present invention. The blending amount of the fibrous filler with respect to 100 parts by mass of the thermoplastic resin, the thermosetting resin, or the thermoplastic elastomer is 5 to 250 parts by mass in a preferred embodiment of the present invention, and 25 to 200 in another preferred embodiment of the present invention. Parts by mass, and in another preferred embodiment of the present invention, 45 to 150 parts by mass.

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

When applying the press molding method, for example, a portion containing a roughened structure of a carbide-based nonmagnetic ceramics molded body is placed in a mold, and heating and heating are performed on the portion containing the roughened structure. The uncured rubber to be the rubber molded body is pressed in a pressurized state, then cooled and taken out. When applying the transfer molding method, for example, the portion containing the roughened structure of the carbide-based non-magnetic ceramics molded body is placed in the mold, the uncured rubber is injection molded in the mold, then, By heating and pressurizing, the portion containing the roughened structure of the carbide-based non-magnetic ceramic molded body and the rubber molded body are integrated, and taken out after cooling.

In addition, depending on the type of rubber used, mainly to remove residual monomers, a step of further secondary heating (secondary curing) in an oven or the like after removing from the mold can be added.

The rubber of the rubber molded body used in this step is not particularly limited, and a known rubber can be used, but a thermoplastic elastomer is not included. Known rubbers include ethylene-propylene copolymer (EPM), ethylene-propylene-diene terpolymer (EPDM), ethylene-octene copolymer (EOM), ethylene-butene copolymer (EBM), ethylene-octene terpolymer (EODM), Ethylene-α-olefin rubbers such as ethylene-butene terpolymer (EBDM);
Ethylene/acrylic rubber (EAM), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), styrene-butadiene rubber (SBR), alkylated chlorosulfonated polyethylene (ACSM), epichlorohydrin (ECO), polybutadiene rubber (BR), natural rubber (including synthetic polyisoprene) (NR), chlorinated polyethylene (CPE), brominated polymethylstyrene-butene copolymer, styrene-butadiene-styrene and styrene-ethylene-butadiene. -Styrene block copolymers, acrylic rubber (ACM), ethylene-vinyl acetate elastomer (EVM), silicone rubber and the like can be used.

The rubber may optionally contain a curing agent depending on the type of rubber, but various known additives for rubber may be added. Examples of rubber additives include curing accelerators, antioxidants, silane coupling agents, reinforcing agents, flame retardants, antiozonants, fillers, process oils, plasticizers, tackifiers, and processing aids. Can be used.

(2-2) Method for Producing Composite Molded Product (Including Adhesive Layer) of Carbide-based Nonmagnetic Ceramic Molded Product Having Roughened Structure and Rubber Molded Product According to one embodiment, a carbide-based In the method for producing a composite molded body of a magnetic ceramic molded body and a rubber molded body, an adhesive layer can be interposed on the joint surface between the carbide-based nonmagnetic ceramic molded body and the rubber molded body.

In the first step, the continuous wave laser is used in the same manner as in the above method to roughen the carbide-based nonmagnetic ceramic compact. In the second step, an adhesive (adhesive solution) is applied to the roughened structure surface of the carbide-based non-magnetic ceramic compact to form an adhesive layer. At this time, the adhesive may be press-fitted. By applying the adhesive, the adhesive can be present on the roughened structure surface of the non-magnetic ceramic and the internal holes.

The adhesive is not particularly limited, and a known thermoplastic adhesive, thermosetting adhesive, rubber adhesive or the like can be used. Examples of the thermoplastic adhesive include polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic adhesive, 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, polyvinyl ether, polyvinylpyrrolidone, polyamide, nylon, saturated no Mention may be made of regular polyesters and cellulose derivatives.

Examples of thermosetting adhesives include urea resins, melamine resins, phenolic resins, resorcinol resins, epoxy resins, polyurethanes, and vinyl urethanes. Examples of rubber adhesives include natural rubber, synthetic polyisoprene, polychloroprene, nitrile rubber, styrene-butadiene rubber, styrene-butadiene-vinylpyridine terpolymer, polyisobutylene-butyl rubber, polysulfide rubber, silicone RTV, Mention may be made of chlorinated rubber, brominated rubber, kraft rubber, block copolymers, and liquid rubber.

In this example of the manufacturing method, in the third step, a step of adhering a separately molded rubber molded body to the surface of the carbide-based non-magnetic ceramic molded body on which the adhesive layer is formed in the previous step, or the bonding in the previous step The portion including the surface of the carbide-based non-magnetic ceramic molded body on which the agent layer was formed was placed in the mold, and the surface of the carbide-based non-magnetic ceramic molded body was brought into contact with the uncured rubber to be the rubber molded body. The process of heating and pressurizing in the state to integrate is carried out. In the case of this step, in order to mainly remove the residual monomer, it is possible to add a step of further secondary heating (secondary curing) in an oven or the like after taking out from the mold.

(3-1) Method for manufacturing composite molded body of carbide-based ceramic molded body and metal molded body having roughened structure In the first step, the roughened structure is formed by the first manufacturing method or the second manufacturing method. To produce a carbide-based non-magnetic ceramic compact having In the second step, the surface of the roughened carbide-based nonmagnetic ceramic compact is placed in the mold so that the surface including the porous structure portion faces upward. After that, for example, a well-known die casting method is applied to cast the molten metal into the mold, and then cooled.

The metal used is not limited as long as it has a melting point lower than that of the carbide-based nonmagnetic ceramics forming the carbide-based nonmagnetic ceramics molded body. For example, iron, aluminum, aluminum alloy, gold, silver, platinum, copper, magnesium, titanium or their alloys, stainless steel, and other metals can be selected according to the application of the composite molded body.

(3-2) Method for producing a composite molded body (having an adhesive layer) of a carbide-based non-magnetic ceramic molded body having a roughened structure and a metal molded body The first step and the second step are the same as the above-mentioned "( 2-2) Manufacturing method of composite molded body (including adhesive layer) of carbide-based non-magnetic ceramics molded body having roughened structure and rubber molded body" to have an adhesive layer A carbide-based non-magnetic ceramic compact is manufactured.

In the third step, the metal compact is pressed against and adhered to the adhesive layer of the carbide-based non-magnetic ceramic compact having the adhesive layer. When the adhesive layer is made of a thermoplastic resin-based adhesive, it can be bonded to the adhesive surface of the non-metal molded body in a state where the adhesive layer is softened by heating as necessary. When the adhesive layer is composed of a prepolymer of a thermosetting resin adhesive, the prepolymer is heated and cured by leaving it in a heating atmosphere after bonding.

(4) Method for manufacturing composite molded body of carbide-based non-magnetic ceramic molded body having roughened structure and UV curable resin molded body In the first step, the above-mentioned first manufacturing method or second manufacturing method Thus, a carbide-based non-magnetic ceramic compact having a roughened structure on its surface is manufactured.

In the next step, a portion of the carbide-based non-magnetic ceramic compact including a roughened portion is brought into contact with a monomer, an oligomer or a mixture thereof for forming a UV curable resin layer (monomer, oligomer or Contacting the mixtures).
As the step of contacting the monomer, oligomer or mixture thereof, the step of applying the monomer, oligomer or mixture thereof to the portion including the roughened portion of the carbide-based non-magnetic ceramic molded body can be carried out. .. In the step of applying the monomer, oligomer or a mixture thereof, brush application, application using a doctor blade, roller application, casting, potting and the like can be used alone or in combination.

In the step of contacting the monomer, oligomer or mixture thereof, the portion including the roughened portion of the carbide-based non-magnetic ceramic molded body is surrounded by a mold and the monomer, oligomer or mixture thereof is placed in the mold. The step of injecting can be performed.
In addition, the step of contacting the monomer, oligomer or mixture thereof is carried out by placing the non-magnetic ceramic compact of the carbide system in the mold with the roughened portion facing upward, and then, in the mold, the monomer, oligomer or mixture thereof. Can be performed.

By the step of contacting the monomer, oligomer, or mixture thereof, the monomer, oligomer, or mixture thereof enters into the pores of the roughened portion of the carbide-based nonmagnetic ceramic compact. The form in which the monomer, oligomer or mixture thereof enters the pores is, for example, 50% or more of all the pores in one preferred embodiment of the present invention, 70% or more in another preferred embodiment of the present invention, and yet another preferred embodiment of the present invention. In one aspect, 80% or more, and in yet another preferable aspect of the present invention, 90% or more of the pores are filled with the monomer, oligomer, or mixture thereof, and the bottom of the pore is filled with the monomer, oligomer, or mixture thereof. The morphology, a morphology in which a monomer, an oligomer, or a mixture thereof enters to a depth in the middle of the pore depth, and a morphology in which a morphology in which a monomer, an oligomer, or a mixture thereof enters only near the entrance of a pore are mixed is included.

Monomers, oligomers or their mixtures can be applied or injected directly as liquids (including low-viscosity gels) or solution forms dissolved in solvents at room temperature, and solids (powder) can be heated. It can be applied or poured after being melted or dissolved in a solvent.

The monomer, oligomer or mixture thereof used in the step of contacting the monomer, oligomer or mixture thereof is selected from radical polymerizable monomer and oligomer of radical polymerizable monomer, or cationic polymerizable monomer and cation of said monomer. It may be selected from a polymerizable monomer oligomer or a mixture of two or more selected from them.

(Radical polymerizable monomer)
As the radically polymerizable compound, a radically polymerizable group such as a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl ether group, a vinylaryl group, and a vinyloxycarbonyl group is contained in one molecule. Examples thereof include compounds having one or more.

Examples of the compound having one or more (meth)acryloyl groups in one molecule include 1-buten-3-one, 1-penten-3-one, 1-hexen-3-one and 4-phenyl-1-butene-. 3-one, 5-phenyl-1-penten-3-one and the like, and derivatives thereof and the like can be mentioned.

Examples of the compound having one or more (meth)acryloyloxy groups in one molecule include methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth). ) Acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isodecyl(meth)acrylate, n-lauryl(meth)acrylate, n-stearyl(meth)acrylate, n-butoxyethyl(meth)acrylate, Butoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate , Isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, acrylic Acid, methacrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropylphthalate, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-butanediol 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, decandi(meth)acrylate, glycerin Di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, dimethyloltricyclodecanedi(meth)acrylate, trifluoroethyl(meth)acrylate, perfluorooctylethyl(meth)acrylate , Isoamyl (meth)acrylate, isomyristyl (meth)acrylate, γ-( (Meth)acryloyloxypropyltrimethoxysilane, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis(acryloyloxy)ethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 3-( (Meth)acryloyloxypropyltriethoxysilane and the like, and derivatives thereof.

Examples of the compound having one or more (meth)acryloylamino groups in one molecule include 4-(meth)acryloylmorpholine, 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, Nn-butoxymethyl(meth)acrylamide, N- Hexyl (meth)acrylamide, N-octyl (meth)acrylamide and the like, and derivatives thereof and the like can be mentioned.

Examples of the compound having one or more vinyl ether groups in one molecule include 3,3-bis(vinyloxymethyl)oxetane, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, and 2-hydroxy. Isopropyl 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-hydroxy Propyl vinyl ether, 1-hydroxymethyl propyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexane Dimethanol 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 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 derivatives thereof Is mentioned.

Examples of the compound having one or more vinylaryl groups in one molecule include styrene, divinylbenzene, methoxystyrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4-vinylphenyl)dihydroxyborane. , N-(4-vinylphenyl)maleimide and the like, and derivatives thereof and the like.

Examples of the compound having one or more vinyloxycarbonyl groups in one molecule include isopropenyl formate, isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl caproate, isopropenyl valerate and iso Isopropenyl valerate, isopropenyl lactate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, pivalic acid. Examples thereof include vinyl, vinyl octylate, vinyl monochloroacetate, divinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, and the like, and derivatives thereof.

(Cationically polymerizable monomer)
Examples of the cationically polymerizable monomer include compounds having at least one cationically polymerizable group other than oxetanyl group such as epoxy ring (oxiranyl group), vinyl ether group and vinylaryl group in one molecule.

Examples of compounds having one or more epoxy rings in one molecule include glycidyl methyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F diester. Glycidyl 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-epoxycyclohexylmethyl (3,4 -Epoxy)cyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3 ,4-Epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), Dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-epoxyhexahydrophthalate Ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; ethylene glycol, Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol and glycerin; diglycidyl esters of aliphatic long-chain dibasic acids; fats Examples include monoglycidyl ethers of group higher alcohols; phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these; and glycidyl esters of higher fatty acids.

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 radical polymerizable compound.

Examples of the compound having one or more oxetanyl groups in one molecule include trimethylene oxide, 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-Ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3- Ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis{[1-ethyl(3- Oxetanyl)]methyl} ether, 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]cyclohexane, and 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane and the like can be mentioned.

Examples of the oligomer of the radical polymerizable monomer and the cationic polymerizable monomer include monofunctional or polyfunctional (meth)acrylic oligomers. One type or a combination of two or more types can be used. Examples of monofunctional or polyfunctional (meth)acrylic oligomers include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and polyester (meth)acrylate oligomers.

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

The epoxy (meth)acrylate oligomer can be obtained by, for example, an esterification reaction of an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin with acrylic acid. The polyether (meth)acrylate oligomer is obtained by a dehydration condensation reaction of a polyol to obtain a polyether oligomer having hydroxyl groups at both ends, and then esterifying the hydroxyl groups at both ends with acrylic acid. The polyester (meth)acrylate oligomer is obtained by, for example, obtaining a polyester oligomer having hydroxyl groups at both ends by condensation of a polycarboxylic acid and a polyol, and then esterifying the hydroxyl groups at both ends with acrylic acid.

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

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

In the next step, a monomer, an oligomer, or a mixture thereof, which is brought into contact with the portion including the roughened portion of the carbide-based non-magnetic ceramic molded body, is irradiated with UV to be cured and has a curable resin layer. A composite molded body can be obtained.

(5) Composite molded product of carbide-based non-magnetic ceramics molded products having a roughened structure, or composite of carbide-based non-magnetic ceramics molded product having a roughened structure and different types of non-magnetic ceramics molded products Method for manufacturing molded body A composite molded body of carbide-based nonmagnetic ceramics molded bodies having a roughened structure, for example, uses a plurality of carbide-based nonmagnetic ceramics molded bodies having a roughened structure of different shapes. It can be manufactured by joining and integrating them via an adhesive layer formed on their joint surfaces. The adhesive layer can be formed by applying an adhesive to the roughened structure portion of the carbide-based non-magnetic ceramic compact. As the adhesive, the same one as used in the production of the other composite molded body described above can be used.

Further, a composite molded body composed of a nonmagnetic ceramic molded body of a different type from the carbide-based nonmagnetic ceramic molded body can be manufactured in the same manner.

In this embodiment, in addition to a method of forming an adhesive layer on a roughened structure portion of a carbide-based non-magnetic ceramic molded body and joining and integrating with a different type of non-magnetic ceramic molded body, The surface of the ceramic molded body is also roughened to form the adhesive layer, and then the adhesive layer of the non-magnetic ceramic molded body of a different type from the surface having the adhesive layer of the carbide-based nonmagnetic ceramic molded body is formed. The surfaces can be joined and integrated to produce a composite molded body.

Different types of non-magnetic ceramics include oxide-based, nitride-based, boride-based, and silicide-based. As a method for roughening the surface of different types of non-magnetic ceramic molded bodies, the method and conditions differ depending on the type of non-magnetic ceramic, but for example, a method of irradiating laser light, file processing, blasting as in the present invention A method of roughening the surface by processing, etching, etc. can be applied.

The configurations and the combinations thereof in each embodiment are examples, and addition, omission, substitution, and other changes of the configurations can be appropriately made without departing from the spirit of the present invention. The invention is not limited by the embodiments, but only by the claims.

<Thermal shock temperature (JIS R1648:2002)>
The thermal shock temperature is the temperature at which a test piece (4×35×thickness 3 mm) of a heated carbide-based nonmagnetic ceramic compact was destroyed when immersed in water of 30° C. It is destroyed when the internal stress generated by the temperature difference between the inside and the surface when it is rapidly cooled exceeds the strength of the test piece.

Ra (arithmetic mean roughness): 11 lines with a length of 1.5 mm are drawn on the surface of the roughened structural portion of the carbide-based non-magnetic ceramics molded body, and those Ras are measured by a one-shot 3D shape measuring machine (Keyence Manufactured).

Rz (maximum height): 11 lines with a length of 1.5 mm are drawn on the surface of the roughened structure portion of the carbide-based non-magnetic ceramic molded body, and Rz thereof is measured by a one-shot 3D shape measuring machine (manufactured by KEYENCE). ) Was measured.

Sa (arithmetic mean height): Sa within a range of 9×1.8 mm on the surface of the roughened structure portion of the carbide-based non-magnetic ceramic molded body was measured by a one-shot 3D shape measuring machine (manufactured by KEYENCE).

Sz (maximum height): Sz in the range of 9×1.8 mm on the surface of the roughened structure portion of the carbide-based non-magnetic ceramic molded body was measured by a one-shot 3D shape measuring machine (manufactured by KEYENCE).

Str (Aspect ratio of surface texture): Shows isotropic or anisotropic surface texture, and is shown in the range of 0 to 1. Str near 0 indicates striations, and Str near 1 indicates that the surface does not depend on direction. Str was measured with a one-shot 3D shape measuring machine (manufactured by KEYENCE).

Examples 1 to 3, Comparative Example 1
The surface of a non-magnetic ceramics compact (10×50×2 mm thick flat plate) of the type shown in Table 1 is continuously irradiated with laser light under the conditions shown in Table 1 using the following continuous wave laser device. And roughened. As the silicon carbide 70% by mass/aluminum 30% by mass composite of Example 2, trade name SA701 (Japan Fine Ceramics Co., Ltd.) was used. As the silicon carbide 50 mass%/silicon 50 mass% composite of Example 3, trade name SS501 (Japan Fine Ceramics Co., Ltd.) was used.

(Laser device)
Oscillator: IPG-Yb fiber; YLR-300-SM
Galvano Mirror SQUIREEL (made by ARGES)
Focusing system: fc=80mm/fθ=100mm

The bidirectional irradiation was performed as follows.
Bidirectional irradiation: After continuously irradiating continuous-wave laser light linearly so that one groove is formed in one direction, the continuous-wave laser light is also linearly irradiated in the opposite direction at intervals of 0.05 mm. The irradiation was repeated. The spacing of 0.05 mm for bidirectional irradiation is the distance between the middle positions of the widths of adjacent grooves.

3 to 5 and 6 are SEM photographs of portions of the nonmagnetic ceramic compacts of Examples 1 to 3 and Comparative Example 1 having a roughened structure.

Using the non-magnetic ceramic molded body having the roughened structure obtained in Examples 1 to 3 and Comparative Example 1, a composite with a resin molded body (molded body of polyamide 66 containing 30% by mass of glass fiber) was used. A molded body (Fig. 7) was manufactured.

Using the composite molded body obtained in Example 1, the bonding strength between the non-magnetic ceramic molded body and the resin molded body was measured.
[Tensile test]
Using the composite molded body shown in FIG. 7, a tensile test was performed to evaluate the shear bond strength (S1). The tensile test is based on ISO19095, and when the end portion on the nonmagnetic ceramics molded body 30 side is fixed, the nonmagnetic ceramics molded body 30 and the resin molded body 31 are pulled in the X direction shown in FIG. 7 until they break. The maximum load until the joint surface of the sample was broken was measured. The results are shown in Table 1.
<Tensile test conditions>
Testing machine: Shimadzu AUTOGRAPH AG-X plus (50kN)
Tensile speed: 10mm/min
Distance between grips: 50 mm

The unevenness of the roughened structure in the non-magnetic ceramic compacts containing silicon carbide of Examples 1 to 3 had a curved cross-section (partial circle) in the thickness direction of the tip. In Example 1 (FIG. 3), wrinkle-shaped projections were formed continuously along the length direction. In Examples 2 and 3 (FIGS. 4 and 5), a large number of independent holes linearly formed along the length direction were formed. In Comparative Example 1 in which the irradiation speed of the laser light was slow, cracking did not occur, but partial chipping occurred.

INDUSTRIAL APPLICABILITY The carbide-based non-magnetic ceramic molded body having a roughened structure on the surface of the present invention is used as an intermediate for producing a composite molded body of a carbide-based non-magnetic ceramic molded body and a resin, rubber, elastomer, metal or the like. be able to.

Claims (14)

A method for producing a non-magnetic ceramic molded body having a roughened structure on the surface,
The non-magnetic ceramic molded body is a carbide-based non-magnetic ceramic molded body,
The surface of a carbide-based non-magnetic ceramic compact containing silicon carbide is roughened by continuously irradiating it with laser light at an irradiation rate of 5,000 mm/sec or more using a continuous wave laser. A method for producing a non-magnetic ceramic compact having a roughened structure. A method for producing a non-magnetic ceramic molded body having a roughened structure on the surface,
The non-magnetic ceramic molded body is a carbide-based non-magnetic ceramic molded body,
It has a step of continuously irradiating the surface of a carbide-based non-magnetic ceramics compact containing silicon carbide with a continuous wave laser at an irradiation speed of 5,000 mm/sec or more,
The step of irradiating the laser beam, when irradiating the surface of the metal molding to be roughened with the laser beam, is a step of irradiating so that the irradiated portion and the non-irradiated portion of the laser light occur alternately. A method for producing a non-magnetic ceramic compact having a roughened structure on its surface. The roughened structure of the non-magnetic ceramic molded body having a roughened structure on the surface has unevenness, and the thickness of the unevenness when observed by a scanning electron micrograph (taken at a magnification of 200 times or more). The cross-sectional shape in the direction is a curved surface, and the curved surface of the convex portion is a wrinkle-shaped projection formed along the length direction, or a plurality of independent curved surface of the convex portion is formed linearly along the length direction. Which has holes,
The surface roughness (Ra) of the tip portion of the convex portion of the unevenness is in the range of 5 to 40 μm, and the height difference (Rz) between the convex portion and the concave portion of the unevenness is in the range of 50 to 200 μm,
A method for producing a non-magnetic ceramic molded body, wherein the non-magnetic ceramic molded body is a carbide-based non-magnetic ceramic molded body,
The surface of a carbide-based non-magnetic ceramics compact containing silicon carbide is roughened by continuously irradiating it with laser light at an irradiation rate of 5,000 mm/sec or more using a continuous wave laser. A method for producing a non-magnetic ceramic compact having a roughened structure. The roughened structure of the non-magnetic ceramic molded body having a roughened structure on the surface has unevenness, and the thickness of the unevenness when observed by a scanning electron micrograph (taken at a magnification of 200 times or more). The cross-sectional shape in the direction is a curved surface, and the curved surface of the convex portion is a wrinkle-shaped projection formed along the length direction, or a plurality of independent curved surface of the convex portion is formed linearly along the length direction. Which has holes,
The surface roughness (Ra) of the tip portion of the convex portion of the unevenness is in the range of 5 to 40 μm, and the height difference (Rz) between the convex portion and the concave portion of the unevenness is in the range of 50 to 200 μm,
A method for producing a non-magnetic ceramic molded body, wherein the non-magnetic ceramic molded body is a carbide-based non-magnetic ceramic molded body,
It has a step of continuously irradiating the surface of a carbide-based non-magnetic ceramics compact containing silicon carbide with a continuous wave laser at an irradiation speed of 5,000 mm/sec or more,
The step of irradiating the laser beam, when irradiating the surface of the metal molding to be roughened with the laser beam, is a step of irradiating so that the irradiated portion and the non-irradiated portion of the laser light occur alternately. A method for producing a non-magnetic ceramic compact having a roughened structure on its surface. The carbide-based non-magnetic ceramic compact having a roughened structure on the surface has a thickness of 0.5 mm or more and a thermal shock temperature (JIS R1648:2002) in the range of 400 to 500°C. A method for producing a non-magnetic ceramic compact having a surface-roughened structure according to any one of claims 1 to 4. The non-magnetic ceramic having a roughened structure on the surface according to claim 1, wherein the carbide-based non-magnetic ceramic molded body having a roughened structure on the surface is a molded product containing silicon carbide. Method for producing molded body. The carbide-based non-magnetic ceramic molded body having a roughened structure on the surface is a composite body in which pores of porous silicon carbide are impregnated with a metal or a semimetal, and the content ratio of the silicon carbide is 50. The method for producing a non-magnetic ceramic compact having a surface-roughened structure according to any one of claims 1 to 4, which is at least mass%. 5. The cross-sectional shape in the thickness direction of the tip of the convex portion of the unevenness of the carbide-based non-magnetic ceramic molded body having the roughened structure on the surface is a partial circular shape or a partial elliptical shape, or any one of claims 1 to 4. Item 1. A method for producing a non-magnetic ceramic molded body having a roughened structure on the surface according to item 1. The unevenness of the carbide-based non-magnetic ceramics molded body having a roughened structure on the surface is formed by alternately forming linear convex portions and linear concave portions,
When the width of each of the linear convex portion and the linear concave portion is 20 to 100 μm, a wrinkle-shaped protrusion formed in the length direction of the convex portion, or a plurality of linear independent holes The method for producing a non-magnetic ceramic molded body having a roughened structure on the surface according to claim 1, wherein the width is 1 to 10 μm. The concave portion of the unevenness of the carbide-based non-magnetic ceramic molded body having a roughened structure on the surface is formed dispersed in an island shape, the portion excluding the concave portion is a convex portion,
When the width of the convex portion is 20 to 100 μm, the width of the wrinkle-shaped protrusion formed in the length direction of the convex portion or the aggregate of the independent holes formed in the linear shape is 1 to 10 μm. Item 5. A method for producing a non-magnetic ceramic compact having a surface-roughened structure according to any one of Items 1 to 4. The surface roughness (Ra) of the tip of the convex portion of the unevenness of the carbide-based non-magnetic ceramic molded body having a roughened structure on the surface is in the range of 10 to 30 μm, and the height of the convex portion and the concave portion of the unevenness is high. The method for producing a non-magnetic ceramic compact having a surface-roughened structure according to claim 1, wherein the difference (Rz) is in the range of 60 to 180 μm. When continuously irradiating the surface of the non-magnetic ceramic molded body with a laser beam using a continuous wave laser at an irradiation rate of 5,000 mm/sec or more,
The surface is roughened structure according to any one of claims 1 to 11, wherein the laser light is continuously irradiated so that a plurality of lines composed of straight lines, curved lines and combinations thereof are formed in the same direction or different directions. A method for producing a non-magnetic ceramic molded body having: When continuously irradiating the surface of the non-magnetic ceramic molded body with a laser beam using a continuous wave laser at an irradiation rate of 5,000 mm/sec or more,
Continuously irradiating laser light so that a plurality of lines consisting of straight lines, curves and combinations thereof are formed in the same direction or different directions, and continuously irradiating laser light a plurality of times to obtain one straight line or one curved line. A method for producing a non-magnetic ceramic compact having a roughened structure on the surface according to any one of claims 1 to 11, which is formed. When continuously irradiating the surface of the non-magnetic ceramic molded body with a laser beam using a continuous wave laser at an irradiation rate of 5,000 mm/sec or more,
Continuously irradiate laser light so that a plurality of lines composed of straight lines, curved lines and combinations thereof are formed in the same direction or different directions,
The surface is roughened according to any one of claims 1 to 11, wherein the plurality of straight lines or the plurality of curves are continuously irradiated with laser light so as to be formed at equal intervals or different intervals. A method for manufacturing a non-magnetic ceramic compact having a structure.