WO2020067308A1 - Nitride-based nonmagnetic ceramic molding and method for producing same - Google Patents

Abstract

Provided is a nonmagnetic ceramic molding having a roughened structure on the surface thereof, the nonmagnetic ceramic molding being a nitride-based nonmagnetic molding, the roughened structure having recesses and protrusions, and when observed using a scanning electron microscope photograph (50-400x), the cross-sectional shape in the thickness direction of the recesses and protrusions includes a shape in which the tip of the protrusion is curved and the bottom of the recess is V-shaped.

Description

Nitride-based non-magnetic ceramic molded body and method for producing the same

In one aspect, the present invention relates to a nitride-based non-magnetic ceramic molded body having a surface roughened structure and a method for producing the same.

Non-magnetic ceramics are widely used in various molded products as daily necessities such as tableware, cups, vases, and engineering ceramics, and it is known to perform a process of forming irregularities on the surface according to the application to which they are applied.

JP-A-2002-308683 discloses a ceramic member having a concave-convex structure formed with an acidic etching solution. Japanese Patent No. 6032903 describes an invention of a firing setter having a specific uneven structure (claims), and as a material of the firing setter, zirconia, alumina, magnesia, spinel, cordierite, etc. (Paragraph number 0013).

WO2011 / 121808A1 includes a metal or ceramic base material, an impregnated layer provided by forming a concave portion on the sliding side surface of the base material, and an impregnated layer impregnated with the base material. And a resin layer covering the surface on the sliding side of the sliding member, wherein the concave portion is formed by machining (claims). It is described that the concave portion is a plurality of linear grooves, and the maximum depth of the grooves is 200 to 2000 μm (paragraph number 0026).

Examples of the mechanical processing include laser processing and wire cut processing (paragraph number 0014), but there is no description of specific processing conditions, and in the examples, it is described that steel was wire cut. There is no specific description about ceramics.

Japanese Patent Application Laid-Open No. 2015-109966 discloses a method for manufacturing a medical device material in which a specific portion of a medical device material containing tetragonal zirconia is coated with calcium phosphate, and the specific portion is irradiated with an ultrashort pulse laser. A method for manufacturing a medical device material, comprising: a first step of forming irregularities on the surface; and a second step of depositing or depositing calcium phosphate fine particles smaller than the period of the irregularities on the specific portion is disclosed. (Claims).

Japanese Patent No. 6111102 discloses that a laser beam having a wavelength of 300 to 1500 nm is applied to a portion of a planar shape substantially identical to a circuit pattern on at least one surface of a ceramic substrate containing AlN or Al ₂ O ₃ as a main component. An aluminum film is formed on a portion of the ceramic substrate having a planar shape substantially the same as the circuit pattern on at least one surface, and a copper plate is disposed on the aluminum film to have a temperature not lower than the eutectic point of aluminum and copper and not higher than 650 ° C. A method of manufacturing a metal-ceramic bonding substrate, characterized by bonding a copper plate to a ceramic substrate via an aluminum film by heating at a temperature, is disclosed.

Japanese Patent Application Laid-Open No. 2003-171190 discloses that the surface of a substrate made of dense ceramic having a purity of 95% or more is formed with first rounded irregularities having a surface roughness Ra of 3 to 40 μm, and the first There is disclosed a ceramic member in which the surface of the unevenness is formed as a second rounded unevenness having 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.

JP-A-2003-137677 and JP-A-2004-66299 disclose a technique for forming irregularities by laser processing the surface of a ceramic body.

Japanese Patent Nos. 5,774,246 and 5,701,414 disclose a method for roughening the surface of a metal molded body by continuously irradiating a continuous wave laser with a laser beam at an irradiation speed of 2000 mm / sec or more. Although an invention of a method for producing a composite molded article of a molded article and a resin molded article is disclosed, there is no description about ceramics.

One object of the present invention is to provide a nitride-based nonmagnetic ceramic molded body having a roughened structure on the surface and a method for producing the same.

The present invention, in one embodiment thereof, is a non-magnetic ceramic molded body having a surface roughened structure,
The non-magnetic ceramic molded body is a nitride-based non-magnetic ceramic molded body,
The roughened structure has irregularities, and the cross-sectional shape in the thickness direction of the irregularities when observed by a scanning electron microscope photograph (50 to 400 times) is a curved surface at the tip of the convex portion. A non-magnetic ceramic molded body (first embodiment) having a roughened structure on its surface is provided, including one having a concave portion or a concave portion having a V-shaped bottom. In another embodiment, the present invention provides a method of manufacturing the nonmagnetic ceramic molded body according to the first embodiment.

The present invention, in another embodiment, a non-magnetic ceramic molded body having a surface roughened structure,
The non-magnetic ceramic molded body is a nitride-based non-magnetic ceramic molded body,
The roughened structure has irregularities, and the cross-sectional shape in the thickness direction of the irregularities when observed by a scanning electron microscope photograph (50 to 400 times) is a curved surface at the tip of the convex portion. Or the bottom of the recess is V-shaped,
A non-magnetic ceramic molded body (second embodiment) having a roughened structure on the surface, having a projection group composed of projections dispersed at the tip of the projection. In another embodiment, the present invention provides a method of manufacturing the nonmagnetic ceramic molded body according to the second embodiment.

非 The non-magnetic ceramic molded product 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 molded product with another material. Therefore, in another aspect, the present invention is also directed to a method for producing such a composite molded article, and a composite molded article.

According to the production method according to the embodiment of the present invention, the surface of the originally hard and brittle nitride-based nonmagnetic ceramic molded body can be roughened 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 the 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 an SEM photograph (× 200) of a roughened structure portion (plan view) of the aluminum nitride molded product of Example 1, and (b) is an SEM photograph (× 200) of a cross section in the thickness direction of (a). is there. 5 is an SEM photograph (× 400) of a roughened structure portion (plan view) of the aluminum nitride molded body of Example 2. (A) is a SEM photograph (magnification: 400) of the roughened structure portion (plan view) of the silicon nitride molded article of Example 3, and (b) is a SEM photograph (magnification: 200) of a cross section in the thickness direction of (a). is there. 5 is an SEM photograph (× 400) of a roughened structure portion (plan view) of the silicon nitride molded body of Example 4. It is a SEM photograph (200 times) of the roughened structure part (plan view) of titanium carbonitride of Example 5. 4 is an SEM photograph (100 times) of a roughened structure portion (plan view) of the silicon nitride molded body of Comparative Example 1. FIG. 2 is a perspective view of the nitride ceramic molded body manufactured in the example, and a perspective view for describing a test of bonding strength using a composite molded body of the nitride ceramic molded body and the resin molded body. (A) is an SEM photograph of a plan view of a roughened structure portion of the silicon nitride molded body of Example 6, and (b) is an SEM photograph of a cross section in the thickness direction of (a). (A) is an SEM photograph of a plan view of a roughened structure portion of the silicon nitride molded product of Example 7, and (b) is an SEM photograph of a cross section in the thickness direction of (a). (A) is an SEM photograph of a plan view of a roughened structure portion of the silicon nitride molded article of Example 8, and (b) is an SEM photograph of a cross section in the thickness direction of (a).

According to some embodiments, the present invention includes the above-described non-magnetic ceramic molded body of the first embodiment and the method of manufacturing the same, and the non-magnetic ceramic molded body of the second embodiment and the method of manufacturing the same.

According to the embodiment of the present invention, the non-magnetic ceramic molded body having a surface roughened structure includes a nitride-based non-magnetic ceramic. The nitride-based nonmagnetic ceramic molded body may be a molded body containing a nitride-based ceramic such as aluminum nitride, silicon nitride, titanium nitride, sialon (SiAlON), and titanium carbonitride. It may be a molded body containing silicon nitride or titanium carbonitride.

Aluminum nitride, silicon nitride, and titanium carbonitride may be used alone or in addition to aluminum nitride, silicon nitride, titanium carbonitride, and other non-magnetic ceramics, metals, as long as they satisfy a predetermined thermal shock temperature. For example, it may be composed of a composite with aluminum, copper, magnesium, brass) and a metalloid (for example, silicon). When forming the composite, the content ratio of the nitride-based nonmagnetic ceramic is 50% by mass or more in a preferred embodiment of the present invention, and 60% by mass or more in another preferred embodiment of the present invention. In still another preferred embodiment of the present invention, the content is 70% by mass or more.

The predetermined thermal shock temperature (JIS @ R1648: 2002) is in the range of 500 to 750 ° C. in a preferred embodiment of the present invention, and is in the range of 530 to 700 ° C. in another preferred embodiment of the present invention. In another preferred embodiment, the temperature ranges from 530 to 670 ° C.

In a preferred embodiment of the present invention, a nitride-based nonmagnetic ceramic molded body containing aluminum nitride, silicon nitride or titanium carbonitride has a thickness of 0.5 mm or more in order to prevent cracking during processing. According to another preferred embodiment of the present invention, the thickness is 1.0 mm or more. The term “crack” in the present invention means that a part of the molded body is broken and divided into two or more, and does not include “crack”. In addition, “cracking” also includes a case where it does not crack during processing by laser beam irradiation, but has a remarkably reduced strength and is divided into two or more during subsequent movement and processing.

According to some embodiments of the present invention, in the non-magnetic ceramic molded body having a roughened structure on the surface (first and second embodiments), the roughened structure has irregularities. The cross-sectional shape in the thickness direction of the unevenness includes a shape in which the tip of the protrusion is a curved surface, or a shape in which the bottom of the recess is V-shaped. For example, in the non-magnetic ceramic molded bodies having a roughened surface on the surfaces of the first embodiment and the second embodiment, the cross-sectional shape of the tip of the convex is not a curved surface, but the cross-sectional shape of the bottom of the concave is V-shaped. And the cross-sectional shape of the tip of the convex portion may be a curved surface, and the cross-sectional shape of the bottom of the concave portion may not include a V-shape or both.

断面 The cross-sectional shape in the thickness direction of the tip of the convex portion 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 surface on its surface according to the present invention (second embodiment) is obtained by dispersing protrusions dispersed at the tips of the convex portions (the cross-sectional shape is a curved surface and the cross-sectional shape is not a curved surface). May be provided. According to one example, the projection group of the non-magnetic ceramic molded body of the second embodiment may have a form in which a large number of independent projections are dispersed on the surface of the projection. Depending on the form, the following different forms can be taken.

In the embodiment in which the unevenness of the nonmagnetic ceramic molded body of the second embodiment is such that linear convex portions and linear concave portions are alternately formed in one direction, the linear convex portion and the linear concave portion ( When each of the widths of the grooves is 20 to 500 μm, according to a preferred embodiment of the present invention, the diameter of the projections (circular replacement diameter) included in the projection group formed on the projections is 10 to 200 μm. The average formation density is 5 pieces / 250,000 μm ² or more, and in another preferred embodiment of the present invention, the average formation density is 5 to 200 pieces / 250,000 μm ² , and still another preferred embodiment of the present invention. In this case, the average formation density is 8 to 150 pieces / 250,000 μm ² . The diameter of the projection (circular replacement diameter) is the diameter when the planar area of the projection is replaced by a circle having the same area.

Note that the "one direction" is, for example, a direction oblique to the long side direction, the short side direction, or the long side direction or the short side direction when the planar shape of the nonmagnetic ceramic molded body is a rectangle. When the planar shape of the nonmagnetic ceramic molded body is a square, it may be in any side direction or a direction oblique to any of the side directions.

As described above, when the projections are formed on the surface (curved surface) of the projection and the surface area is increased, for example, when joining a non-magnetic ceramic molded body to another member (for example, a resin molded body), The increased contact area increases the bonding strength.

One example of the non-magnetic ceramic molded body of the second embodiment may be a form in which concave portions among the concave and convex portions are formed in an island shape, and portions excluding the concave portions are convex portions. In a preferred embodiment of the present invention, when the width of each of the portion and the concave portion (groove) is 20 to 500 μm, the diameter (circular replacement diameter) of the projection included in the projection group formed on the convex portion is The average formation density of 10 to 200 μm is 5 pieces / 250,000 μm ² or more, and in another preferred embodiment of the present invention, the average formation density is 10 to 30 pieces / 250,000 μm ^2. In another preferred embodiment, the average formation density is 10 to 25 particles / 250,000 μm ² . The diameter of the projection (circular replacement diameter) is a diameter when the plane area of the projection is replaced by a circle having the same area.

As described above, when the projections are formed on the surface (curved surface) of the projection and the surface area is increased, for example, when joining a non-magnetic ceramic molded body to another member (for example, a resin molded body), The increased contact area increases the bonding strength.

According to the examples of the non-magnetic ceramic molded body of the first embodiment and the second embodiment, the surface roughness (Ra) of the unevenness is in the range of 1 to 100 μm in a preferred embodiment of the present invention. In one preferred embodiment of the present invention, the thickness is in the range of 3 to 90 μm, and in still another preferred embodiment of the present invention, the thickness is in the range of 5 to 85 μm.

According to the examples of the non-magnetic ceramic molded body of the first embodiment and the second embodiment, the height difference (Rz) between the convex and concave portions of the unevenness is in the range of 10 to 500 μm in a preferred embodiment of the present invention. In another preferred embodiment of the present invention, it is in the range of 15 to 450 μm, and in still another preferred embodiment of the present invention, it is in the range of 20 to 400 μm.

According to the examples of the non-magnetic ceramic molded body of the first embodiment and the second embodiment, the arithmetic mean height (Sa) of the unevenness is in a range of 3 to 90 μm in a preferred embodiment of the present invention. In another preferred embodiment, it is in the range of 4-85 μm, and in still another preferred embodiment of the present invention, it is in the range of 5-82 μm.

According to the examples of the non-magnetic ceramic molded body of the first embodiment and the second embodiment, the maximum height (Sz) of the convex portion of the unevenness is in the range of 30 to 500 μm in a preferred embodiment of the present invention. In another preferred embodiment of the invention, it is in the range of 35 to 480 μm, and in still another preferred embodiment of the invention, it is in the range of 40 to 450 μm.

According to the examples of the non-magnetic ceramic molded body of the first embodiment and the second embodiment, the developed area ratio (Sdr) of the interface between the irregularities is in the range of 1 to 8 in a preferred embodiment of the present invention. In another preferred embodiment of the present invention, it is in the range of 2 to 7, and in still another preferred embodiment of the present invention, it is in the range of 2.5 to 6.5.

According to the examples of the non-magnetic ceramic molded body of the first embodiment and the second embodiment, the root mean square slope (Sdq) of the unevenness is in the range of 2 to 12 in a preferred embodiment of the present invention, In another preferred embodiment, the range is 2.5 to 11, and in still another preferred embodiment of the present invention, the range is 3 to 10.

<First manufacturing method of nitride-based non-magnetic ceramic molded body having surface roughened structure>
Next, a first method for producing a nitride-based nonmagnetic ceramic molded body having a roughened surface on the surface (first and second embodiments) according to an embodiment of the present invention will be described.

In the method for manufacturing a molded body according to the first embodiment, when the nitride-based nonmagnetic ceramic molded body is aluminum nitride, laser light can be continuously irradiated at an irradiation speed of 5,000 mm / sec or more. In a preferred embodiment of the present invention, the irradiation speed is 5,000 to 20,000 mm / sec. In another preferred embodiment of the present invention, the laser beam can be continuously irradiated at an irradiation speed of 5,000 to 10,000 mm / sec.

In the method for manufacturing a molded body according to the second embodiment, when the nitride-based nonmagnetic ceramic molded body is aluminum nitride, the laser beam may be continuously irradiated at an irradiation speed of 1,000 to 5,000 mm / sec. According to one preferred embodiment of the present invention, continuous irradiation with laser light can be performed at an irradiation speed of 1,000 to 3,000 mm / sec.

In the method for manufacturing a molded body according to the second embodiment, when the nitride-based nonmagnetic ceramic molded body is silicon nitride, laser light can be continuously irradiated at an irradiation speed of 1,000 mm / sec or more. In a preferred embodiment of the present invention, the irradiation speed is 1,000 to 20,000 mm / sec. In another preferred embodiment of the present invention, the laser beam can be continuously irradiated at an irradiation speed of 1,000 to 10,000 mm / sec.

According to the embodiment of the present invention, the shape, size, thickness and the like of the nitride-based non-magnetic ceramic molded body used in the manufacturing method are not particularly limited, are selected according to the application, and may be selected as needed. Is adjusted. For example, nitride-based non-magnetic ceramic molded articles include a flat plate, a round bar, a square bar (a bar having a polygonal cross section), a tube, a cup shape, a cube, a rectangular parallelepiped, a sphere or a partial sphere (such as a hemisphere), and an ellipse. In addition to molded products such as spheres or partially elliptical spheres (such as semi-elliptical spheres) and irregular shapes, existing non-magnetic ceramic products can also be used.

The existing nitride-based non-magnetic ceramic products are made of only nitride-based non-magnetic ceramics, as well as nitride-based non-magnetic ceramics and other materials (metal, resin, rubber, glass, wood, etc.). It may be composed of a composite.

According to one embodiment, in each of the method for manufacturing a molded article according to the first embodiment and the method for manufacturing a molded article according to the second embodiment, when continuously irradiating laser light in the above-described laser light irradiation speed range, The laser beam can be 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.

According to still another embodiment, in each of the method for manufacturing a molded body according to the first embodiment and the method for manufacturing a molded body according to the second embodiment, when the laser beam is continuously irradiated within the above-described laser light irradiation speed range. Irradiating laser light continuously so as to form a plurality of lines composed of straight lines, curves and combinations thereof in the same direction or different directions, and continuously irradiating the laser light a plurality of times to form one straight line or one line Curves can be formed.

According to still another embodiment, in each of the method for manufacturing a molded body according to the first embodiment and the method for manufacturing a molded body according to the second embodiment, when continuously irradiating laser light within the above-described laser light irradiation speed range. In the same direction or different directions, continuously irradiate laser light such that a plurality of lines composed of straight lines, curves and combinations thereof are formed, and the plurality of straight lines or the plurality of curves are at equal intervals or different. Laser light irradiation can be performed continuously so as to be formed at intervals.

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 2,000 W in still another preferred embodiment of the present invention. 5,000W. Adjust the surface roughening state by decreasing the laser light output when the laser light irradiation speed is low within the above range and increasing it when the laser light irradiation speed is high within the above range. Can be.

ス ポ ッ ト The spot diameter of the laser beam is 10 to 100 μm in one 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 is 3 ~ 1,500MW / cm ^2, in another preferred embodiment of the present invention is 5 ~ 700MW / cm ^2. The energy density at the time of laser beam irradiation is calculated by the following formula from the output (W) of the laser beam and the laser beam (spot area (cm ² ) (π · [spot diameter / 2] ² ): laser beam output / spot area. Desired.

The number of repetitions (the number of passes) at the time of laser beam 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 at the time of laser light irradiation is the total number of times of irradiation for forming one line (groove) when laser light is irradiated linearly.

双方 向 When irradiating one line repeatedly, bidirectional irradiation and unidirectional irradiation can be selected. When forming one line (groove), bidirectional radiation irradiates a continuous wave laser from the first end to the second end of the line (groove) and then from the second end to the first end. A method of irradiating a continuous wave laser and thereafter repeatedly irradiating a continuous wave laser from a first end to a second end and from a second end to a first end. One-way irradiation is a method of repeating one-way continuous-wave laser irradiation from a first end to a second end. When bidirectional radiation or unidirectional irradiation is performed, the planar shape of the concave portion of the roughened structure portion may take an elliptical shape or a shape similar to an elliptical shape.

When the shape is similar to an ellipse, for example, the two opposite sides on the long axis side are curved lines (arcs), but the two opposite sides on the short axis side are formed only of straight lines. , And those in which a straight line or a curve on two opposite sides on the short axis side is partially bent.

When irradiating the laser beam linearly, 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 set to 0.1 in a preferred embodiment of the present invention. 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 the laser beam, after forming a plurality of grooves by bidirectional irradiation or unidirectional irradiation at the above-mentioned line interval, further from the direction orthogonal or oblique to the plurality of grooves, the above-mentioned line Cross irradiation in which bidirectional irradiation or unidirectional irradiation is performed at intervals may be performed.

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

A known continuous wave laser can be used, for example, a YVO ₄ laser, a fiber laser (preferably a single mode fiber laser), an excimer laser, a carbon dioxide laser, an ultraviolet laser, a YAG laser, a semiconductor laser, a glass laser, A ruby laser, a He-Ne laser, a nitrogen laser, a chelate laser, and a dye laser can be used. Among them, a fiber laser is preferable, and a single mode fiber laser is particularly preferable, because the energy density is increased.

<Second method for producing nitride-based non-magnetic ceramic molded body having a surface roughened structure>
According to one embodiment of the present invention, a second method for manufacturing a nitride-based nonmagnetic ceramic molded body having a roughened structure on the surface includes the molded body of the first embodiment and the second embodiment. The method is the same as the first method for producing a molded article except that the irradiation form of the laser beam is different.

The second manufacturing method is a step of continuously irradiating the surface of the nitride-based nonmagnetic ceramic molded body with a laser beam at a predetermined irradiation speed using a continuous wave laser in the same manner as in the first manufacturing method. In the method, when irradiating the surface of the nitride-based non-magnetic ceramic molded body to be roughened with a laser beam, there is a step of irradiating the laser beam so that the irradiated portion and the non-irradiated portion alternately occur. ing.

{Circle around (2)} In the second manufacturing method, when irradiating a laser beam so as to form a straight line, a curve, or a combination of a straight line and a curve, the laser beam is irradiated so that a portion irradiated with the laser beam and a non-irradiated portion alternate. Irradiation such that laser light irradiation parts and non-irradiation parts are generated alternately includes the embodiment of irradiation as shown in FIG. FIG. 1 shows that a non-irradiated portion 12 of a laser beam having a length L2 is alternately generated between an irradiated portion 11 of a laser beam having a length L1 and an adjacent irradiated portion 11 of a laser beam having a length L1. An irradiation state is shown so as to form a dotted line. The dotted line also includes a chain line such as a one-dot chain line or a two-dot chain line.

When irradiating a plurality of times, the irradiated portion of the laser beam may be the same, or the irradiated portion of the laser beam may be made different (shifting the irradiated portion of the laser beam) to obtain a non-magnetic ceramic molded body of a nitride system. The whole may be roughened. When the laser beam is irradiated multiple times with the same part irradiated, the laser beam is irradiated in a dotted line, but the laser light irradiated part is shifted, that is, the laser light is first irradiated to the part that was not irradiated with the laser light. If the irradiation is repeated while being shifted so that the irradiation portions overlap, even when 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.

(4) When laser light is continuously irradiated to the nitride-based non-magnetic ceramic molded body, the temperature of the irradiated surface rises, so that a molded article having a small thickness may be deformed such as a crack. However, when laser irradiation is performed in a dotted line as shown in FIG. 1, laser light irradiation portions 11 and laser light non-irradiation portions 12 are alternately generated. Deformation such as cracking hardly occurs even in a small compact. At this time, the same effect can be obtained even when the irradiated portion of the laser beam is changed as described above (the irradiated portion of the laser beam is shifted).

The method of irradiating the laser beam is, for example, a method of irradiating the surface of the metal molded body 20 in one direction as shown in FIG. 2A, or a method of irradiating bidirectionally as shown by a dotted line in FIG. The method can be used. In addition, a method of irradiating the laser beam so that the dotted lines irradiate with each other may be used. The interval b1 between the dotted lines after the irradiation can be adjusted according to the irradiation target area of the metal molded body or the like, but can be in the same range as the line interval 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 in the range of L1 / L2 = 1/9 to 9/1 (that is, L1 / L2). [L1 + L2] is in the range of 10 to 90%). In a preferred embodiment of the present invention, the length (L1) of the irradiated portion 11 of the laser beam is 0.05 mm or more in order to roughen a complex porous structure, and in another preferred embodiment of the present invention, the length (L1) is 0 mm. 0.1 to 10 mm, and in still 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 laser light irradiation step described above is a fiber laser apparatus in which a direct modulation type modulator for directly converting a drive current of a laser is connected to a laser power supply. Is used to adjust the duty ratio (duty ratio) to perform laser irradiation.

There are two types of laser excitation: pulse excitation and continuous excitation. 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, and a Q switch pulse oscillation method for oscillating a laser having a higher peak power is used. An external modulation method in which a pulse wave laser is generated by temporally cutting out light using an LN light intensity modulator, a method of mechanically chopping and pulsing, a method of operating a galvanomirror to form a pulse, and a laser driving current A pulse wave laser can be produced by a direct modulation method in which a pulse wave laser is generated by directly modulating a pulse wave laser. The method of pulsing by operating the galvanomirror is a method of irradiating a laser beam oscillated from a laser oscillator via a galvanomirror by a combination of a galvanomirror and a galvanomirror, specifically, as follows. Can be implemented.

A gate signal is periodically output ON / OFF from a galvano controller, and the laser light oscillated by a laser oscillator is turned ON / OFF by the ON / OFF signal, thereby pulsating the laser light without changing the energy density of the laser light. be able to. As a result, as shown in FIG. 1, the laser light irradiation portions 11 and the non-laser light non-irradiation portions 12 between the adjacent laser light irradiation portions 11 are alternately formed, and are formed in a dotted line as a whole. Can be irradiated with laser light. The method of pulsing by operating the galvanometer mirror is simple in operation because the duty ratio can be adjusted without changing the oscillation state of the laser light itself.

Among these methods, it is easy to pulse (irradiate so that irradiated and non-irradiated portions alternate) without changing the energy density of the continuous wave laser. A method of pulsing by chopping, a method of pulsing by operating a galvanomirror, 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, by using a fiber laser device in which a direct modulation type modulation device that directly converts the driving current of the laser is connected to a laser power supply, the laser is continuously excited to generate a pulsed laser. May be produced.

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 equation.
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, the duty ratio can be selected, for example, from the range of 10 to 90%.

レ ー ザ ー By irradiating the laser beam with the duty ratio adjusted, it is possible to irradiate in a dotted line shape as shown in FIG. When the duty ratio is large, the efficiency of the surface roughening process is improved, but the cooling effect is reduced. When the duty ratio is small, the cooling effect is improved, but the surface roughening efficiency is deteriorated. It is preferable to adjust the duty ratio according to the purpose.

<Third manufacturing method of nitride-based non-magnetic ceramic molded body having surface roughened structure>
According to one embodiment of the present invention, the third manufacturing method is different from the first manufacturing method and the second manufacturing method, and is a method using a pulse wave laser.

(4) When irradiating the pulsed laser light, a roughened structure can be formed on the surface by adjusting the following requirements (i) to (v). The method of irradiating a pulsed laser beam is, for example, a method of irradiating a pulsed laser beam, for example, Japanese Patent No. 5848104, Japanese Patent No. 5788836, Japanese Patent No. 5798534, Japanese Patent No. 5798535, The method can be carried out in the same manner as the pulse wave laser beam irradiation method described in JP-A-2016-203643, Japanese Patent No. 5888975, Japanese Patent No. 5932700, or Japanese Patent No. 6055529.

<Requirement (i) Irradiation direction and irradiation angle when irradiating laser light to nitride-based non-magnetic ceramic molded body>
In a preferred embodiment of the present invention, the surface of the nitride-based nonmagnetic ceramic molded body is irradiated with laser light at an angle of 15 to 90 degrees, and in another preferred embodiment of the present invention, an angle of 45 to 90 degrees. .

<Requirement (ii) Irradiation speed when irradiating laser light to nitride-based non-magnetic ceramic molded body>
The irradiation speed of the laser beam is 10 to 500 mm / sec in a preferred embodiment of the present invention, 10 to 300 mm / sec in another preferred embodiment of the present invention, and 10 to 100 mm / sec in another preferred embodiment of the present invention. / Sec, and in still another preferred embodiment of the present invention, it is 10 to 80 mm / sec.

<(Iii) Energy density when irradiating laser light to nitride-based non-magnetic ceramic molded body>
The energy density at the time of laser light irradiation is obtained from the energy output (W) of one pulse of the laser light and the laser light (spot area (cm ² ) (π · [spot diameter / 2] ² ). energy density during irradiation is 0.1 ~ 50GW / cm ² in a preferred aspect of the present invention, in another preferred embodiment of the present invention is 0.1 ~ 20GW / cm ^2, another preferred of the present invention in one embodiment, it is 0.5 ~ 10GW / cm ^2, in yet another preferred embodiment of the present invention is 0.5 ~ 5GW / cm ^2. energy density increases, the hole becomes deeper and larger.

The energy output (W) of one pulse of laser light is obtained from the following equation.
The energy output (W) of one pulse of laser light = (average output of laser light / frequency) / average output of pulse width laser light is 4 to 400 W in one preferred embodiment of the present invention, and is another preferable embodiment of the present invention. In one embodiment, it is 5 to 100 W, and in still another preferred embodiment of the present invention, it is 10 to 100 W. If the other laser light irradiation conditions are the same, the hole becomes deeper and larger as the output becomes larger, and the hole becomes shallower and smaller as the output becomes smaller. The frequency (KHz) is 0.001 to 1,000 kHz in one preferred embodiment of the present invention, 0.01 to 500 kHz in another preferred embodiment of the present invention, and in still another preferred embodiment of the present invention. It is 0.1 to 100 kHz. The pulse width (nsec) is 1 to 10,000 nsec in a preferred embodiment of the present invention, 1 to 1,000 nsec in another preferred embodiment of the present invention, and 1 in still another preferred embodiment of the present invention. ～ 100 nsec.

The spot diameter (μm) of the laser beam is 1 to 300 μm in one preferred embodiment of the present invention, 10 to 300 μm in another preferred embodiment of the present invention, and 20 to 150 μm in still another preferred embodiment of the present invention. In still another preferred embodiment, the thickness is 20 to 80 μm.

<(Iv) Number of repetitions when irradiating laser light>
The number of repetitions (the total number of laser light irradiations for forming one hole) is 1 to 80 in a preferred embodiment of the present invention, and 3 to 50 in another preferred embodiment of the present invention. In another preferred embodiment of the present invention, the number is 5 to 30 times. Under the same laser irradiation conditions, the hole becomes deeper and larger as the number of repetitions increases, and the hole becomes shallower and smaller as the number of repetitions decreases.

<(V) Line spacing when irradiating laser light to the nitride-based nonmagnetic ceramic molded body>
When irradiating the nitride-based non-magnetic ceramic molded body with a laser beam in a line shape, by increasing or decreasing the interval between adjacent lines, the size of the hole, the shape of the hole, The depth of the holes can be adjusted. Note that the pulsed laser light irradiates a point and connects a plurality of the points to form a line.

The line spacing is in the range of 0.01 to 1 mm in a preferred embodiment of the present invention, in the range of 0.01 to 0.8 mm in another preferred embodiment of the present invention, and 0.1 in another preferred embodiment of the present invention. 03 to 0.5 mm, and in still another preferred embodiment of the present invention 0.05 to 0.5 mm. If the line spacing is small, the thermal effect will also affect adjacent lines, so the hole will be large, the shape of the hole will be complicated, the depth of the hole will tend to be deep, but the thermal effect will be too large In some cases, it is difficult to form a complicated and deep hole. If the line spacing is large, the holes will be small, the shape of the holes will not be complicated and the holes will not be too deep, but the processing speed can be increased.

照射 Other irradiation conditions may include an irradiation mode in which the nitride-based non-magnetic ceramic molded body is irradiated with laser light while radiating heat from the molded body. For example, a method of irradiating laser light in a state where a nitride-based non-magnetic ceramic molded body and a metal molded body having a higher thermal conductivity than the nitride-based non-magnetic ceramic molded body are in contact with each other. A method of irradiating a laser beam while holding it in a hollow state may be used. In addition, the wavelength of the pulsed laser light may be 500 to 11,000 nm in another preferred embodiment of the present invention.

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

(1) A method for producing a composite molded article of a nitride-based non-magnetic ceramic molded article having a roughened structure and a resin molded article In the first step, the above-described first production method, second production method or second production method 3 manufactures a non-magnetic ceramics molded body having a roughened structure on the surface by the manufacturing method.

In the second step, a portion including the roughened structure of the nitride-based nonmagnetic ceramics molded body having a roughened structure on the surface obtained in the first step is arranged in a mold, and the resin molded body is In the second step, the portion including the roughened structure of the non-magnetic ceramics molded body irradiated with the laser beam in the first step is arranged in a mold, and at least the rough surface is formed. Compression molding in a state where the portion including the modified structure and the resin to be the resin molded body are in contact with each other.

樹脂 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 depending on the application. For example, copolymers containing styrene units such as polyamide resins (aliphatic polyamides and aromatic polyamides such as PA6 and PA66), polystyrene, ABS resins, AS resins, etc., polyethylene, copolymers containing ethylene units, polypropylene, propylene Examples 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 depending on the application. For example, urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane can be mentioned. When a thermosetting resin is used, a prepolymer form can be used, and a heat curing treatment can be performed in a later step.

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

公 知 A 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, and organic fibers.

Carbon fibers are well-known, and PAN-based, pitch-based, rayon-based, and lignin-based carbon fibers can be used. Examples of the inorganic fibers include glass fibers, basalt fibers, silica fibers, silica / alumina fibers, zirconia fibers, boron nitride fibers, and silicon nitride fibers. Examples of the metal fibers include fibers made of stainless steel, aluminum, copper, and the like. As 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, Synthetic fiber such as polyoxymethylene fiber, polytetrafluoroethylene fiber, polyester fiber (including wholly aromatic polyester fiber), polyphenylene sulfide fiber, polyimide fiber, liquid crystal polyester fiber, natural fiber (cellulose fiber, 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. Among them, for example, open holes formed by roughening the bonding surface 12 of the metal molded body 10 are described. A fiber having a fiber diameter 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. In one preferred embodiment of the present invention, the compounding amount of the fibrous filler relative to 100 parts by mass of the thermoplastic resin, the thermosetting resin, or the thermoplastic elastomer is 5 to 250 parts by mass. In another preferred embodiment of the present invention, the amount is 25 to 200 parts by mass, and in still another preferred embodiment of the present invention, the amount is 45 to 150 parts by mass.

(2-1) Method for Producing Composite Molded Body of Nitride-Based Non-magnetic Ceramics Molded Body Having Roughened Structure and Rubber Molded Body In the first step, the first production method, the second production method or the second production method A non-magnetic ceramic molded body having a roughened structure on the surface is manufactured by the manufacturing method of 3. In the second step, the nitride-based nonmagnetic ceramic molded body and the rubber molded body obtained in the first step are integrated by applying a known molding method such as press molding or transfer molding.

When the press molding method is applied, for example, a portion including a roughened structure of an oxide-based nonmagnetic ceramic molded body is arranged in a mold, and the portion including the roughened structure is heated. After the uncured rubber to be the rubber molded body is pressed in a pressurized state, it is taken out after cooling. When applying the transfer molding method, for example, a portion including a roughened structure of a nitride-based non-magnetic ceramic molded body is arranged in a mold, and the uncured rubber is injection-molded in the mold, and thereafter, Then, by heating and pressurizing, the portion including the roughened structure of the nitride-based non-magnetic ceramic molded body and the rubber molded body are integrated, and taken out after cooling.

Depending on the type of rubber used, a step of secondary heating (secondary curing) in an oven or the like after removal from the mold can be added in order to mainly remove residual monomers.

ゴ ム The rubber of the rubber molded article used in this step is not particularly limited, and a known rubber can be used, but does not include a thermoplastic elastomer. 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 rubber such as ethylene-butene terpolymer (EBDM); ethylene / acrylate 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 copolymer, acrylic rubber (ACM), ethylene-vinyl acetate elastomer (EVM), and silicone rubber can be used. it can.

(4) The rubber may contain a curing agent according to the type of the rubber, if necessary. In addition, various known rubber additives can be blended. Rubber additives include curing accelerators, anti-aging agents, silane coupling agents, reinforcing agents, flame retardants, ozone deterioration inhibitors, fillers, process oils, plasticizers, tackifiers, and processing aids. Can be used.

(2-2) Method for Producing Composite Molded Body (Including Adhesive Layer) of Nitride-Based Non-Magnetic Ceramics Molded Body Having Roughened Structure and Rubber Molded Body According to one embodiment, a nitride-based molded body is provided. In the method for producing a composite molded article of a non-magnetic ceramic molded article and a rubber molded article described above, an adhesive layer can be interposed on the joint surface between the nitride-based non-magnetic ceramic molded article and the rubber molded article.

In the first step, a nitride-based non-magnetic ceramic molded body is roughened by a first, second or third manufacturing method using a continuous wave laser or a pulse wave laser in the same manner as described above. . In the second step, an adhesive (adhesive solution) is applied to the roughened structure surface of the nitride-based nonmagnetic ceramic molded body 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 surface of the non-magnetic ceramic and on the internal holes.

The adhesive is not particularly limited, and a known thermoplastic adhesive, thermosetting adhesive, rubber-based 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, non-saturated Fixed polyesters and cellulose derivatives can be mentioned.

例 Examples of the thermosetting adhesive include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane. 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, Examples include chlorinated rubber, brominated rubber, kraft rubber, block copolymer, and liquid rubber.

In the example of this manufacturing method, in the third step, a step of bonding a separately molded rubber molded body to the surface of the nitride-based nonmagnetic ceramic molded body on which the adhesive layer was formed in the previous step, or The portion including the surface of the nitride-based non-magnetic ceramic molded body on which the adhesive layer has been formed is placed in a mold, and the surface of the nitride-based non-magnetic ceramic molded body and the uncured rubber to be a rubber molded body are removed. A step of heating and pressurizing in a state of being in contact with each other to perform integration is performed. In the case of this step, a step of secondary heating (secondary curing) in an oven or the like after removal from the mold can be added to remove mainly residual monomers.

(3-1) Method for Producing Composite Molded Body of Nitride-Based Ceramic Molded Body and Metal Molded Body Having Roughened Structure In the first step, the first production method, the second production method or the third production method An oxide-based non-magnetic ceramic molded body having a roughened structure is manufactured by a manufacturing method. In the second step, the surface of the roughened nitride-based non-magnetic ceramic molded body including the porous structure is placed in the mold so that the surface including the porous structure portion faces upward. Thereafter, the metal in a molten state is poured into a mold by, for example, a known die casting method, and then cooled.

The metal to be used is not limited as long as it has a melting point lower than the melting point of the nitride-based non-magnetic ceramic constituting the nitride-based non-magnetic ceramic molded body.
For example, it is possible to select a metal according to the use of the composite molded body such as iron, aluminum, an aluminum alloy, gold, silver, platinum, copper, magnesium, titanium or an alloy thereof, and stainless steel.

(3-2) Manufacturing Method of Composite Molded Body (with Adhesive Layer) of Nitride-Based Non-Magnetic Ceramic Molded Body Having Roughened Structure and Metal Molded Body (2-2) Method for producing composite molded body (including adhesive layer) of nitride-based non-magnetic ceramic molded body and rubber molded body having roughened structure " To produce a nitride-based non-magnetic ceramic molded body having the following.

(4) In the third step, the metal molded body is pressed against the adhesive layer of the nitride-based non-magnetic ceramic molded body having the adhesive layer to be bonded and integrated. When the adhesive layer is made of a thermoplastic resin-based adhesive, the adhesive layer can be adhered 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 made of a thermosetting resin-based adhesive prepolymer, the prepolymer is heated and cured by being left in a heating atmosphere after bonding.

(4) Method for producing composite molded article of nitride-based nonmagnetic ceramic molded article having a roughened structure and UV-curable resin molded article In the first step, the above-mentioned first production method and second production According to the method or the third manufacturing method, a nitride-based nonmagnetic ceramic molded body having a roughened structure on the surface is manufactured.

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

The step of contacting a monomer, an oligomer or a mixture thereof includes enclosing a portion including a roughened portion of a nitride-based non-magnetic ceramic molded body with a mold, and placing the monomer, oligomer or a mixture thereof in the mold. Can be performed. Further, the step of contacting the monomer, the oligomer or a mixture thereof includes, after putting the roughened portion of the nitride-based non-magnetic ceramic molded body into the mold with the roughened portion thereof facing upward, the monomer, the oligomer or a mixture thereof in the mold. A step of injecting the mixture can be performed.

に よ っ て By the contacting step of the monomer, oligomer or mixture thereof, the monomer, oligomer or mixture thereof enters the porosity of the roughened portion of the nitride-based non-magnetic ceramic molded body. The form in which the monomer, oligomer or mixture thereof enters the porosity is, for example, 50% or more of the whole pores in a preferred embodiment of the present invention, 70% or more in another preferred embodiment of the present invention, and still another preferred embodiment of the present invention. In one embodiment, 80% or more, and in still another preferred embodiment of the present invention, 90% or more of the pores contain the monomer, oligomer or mixture thereof, and the monomer, oligomer or mixture thereof enters the bottom of the pore. The form includes a form in which a monomer, an oligomer, or a mixture thereof enters into a partway depth of the pore, and a form in which a form in which a monomer, an oligomer, or a mixture thereof enters only near the entrance of the hole.

Monomers, oligomers or mixtures thereof can be applied or injected as they are in liquid form (including low-viscosity gels) at room temperature or in the form of a solution dissolved in a solvent. Solid (powder) forms 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 a radical polymerizable monomer and an oligomer of a radical polymerizable monomer, or is a cation polymerizable monomer and a cation of the monomer. It may be one selected from polymerizable monomer oligomers or a mixture of two or more selected from them.

(Radical polymerizable monomer)
As the radical polymerizable compound, a radical 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. Compounds having at least one compound are exemplified.

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

Examples of the compound having at least one (meth) acryloyloxy group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth). A) 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) acryl , Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, dimethyl Aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyl Oxyethyl-2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, ethylene glycol di (meth) acrylate, diethyl 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, decane di (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) ) Acrylate, dimethylol tricyclodecane di (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.

Compounds 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 are given.

Compounds having one or more vinyl ether groups in one molecule include, for example, 3,3-bis (vinyloxymethyl) oxetane, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 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-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol Novinyl ether, 1,4-cyclohexane dimethanol monovinyl ether, 1,3-cyclohexane dimethanol 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, tetra Propylene glyco Monovinyl ether, pentapropylene glycol monovinyl ether, oligopropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, and the like, and derivatives thereof.

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

Compounds having one or more vinyloxycarbonyl groups in one molecule include isopropenyl formate, isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl caproate, isopropenyl valerate, 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 Vinyl, vinyl octylate, vinyl monochloroacetate, divinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, and the like Body and the like.

(Cationically polymerizable monomer)
Examples of the cationic polymerizable monomer include compounds having one or more cationic polymerizable groups in one molecule other than an oxetanyl group such as an epoxy ring (oxiranyl group), a vinyl ether group, and a vinyl aryl group.

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 diglycidyl ether. Glycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak 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, (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methyl Cyclohexane carboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxyhexa Dioctyl hydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol Lepropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin. Polyglycidyl ethers of polyether polyols; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; phenol, cresol, butylphenol or polyether alcohols obtained by adding alkylene oxide thereto Monoglycidyl ethers; 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 the compounds exemplified as the radical polymerizable compound.

Compounds 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-ethyloxetan-3-yl) methoxy] methyl} oxetane .

オ リ ゴ マ ー The oligomer of the radical polymerizable monomer and the cationic polymerizable monomer includes a monofunctional or polyfunctional (meth) acrylic oligomer. One type or a combination of two or more types can be used. Monofunctional or polyfunctional (meth) acrylic oligomers include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyether (meth) acrylate oligomers, and polyester (meth) acrylate oligomers.

(4) Examples of the urethane (meth) acrylate oligomer 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 diisocyanate and a (meth) acrylate monomer having a hydroxyl group. Examples of the polyol include a polycarbonate diol, a polyester polyol, a polyether polyol, and a polycaprolactone polyol.

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

重量 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 is 500 to 50,000 in another preferred embodiment of the present invention.

When the above-mentioned monomers, oligomers or mixtures thereof are used, 0.01 to 10 parts by mass of a photopolymerization initiator can be used with respect to 100 parts by mass of the monomers, oligomers or mixture thereof.

In the next step, the monomer, oligomer or mixture thereof in contact with the portion including the roughened portion of the nitride-based non-magnetic ceramic molded body is cured by irradiating UV to cure the curable resin layer. A composite molded article having the same can be obtained.

(5) A composite molded article of a nitride-based nonmagnetic ceramic molded article having a roughened structure, or a nitride-based nonmagnetic ceramic molded article having a roughened structure, and a different type of nonmagnetic ceramic molded article The method of manufacturing a composite molded article of the present invention comprises a composite molded article of a carbide-based nonmagnetic ceramic molded article having a roughened structure, for example, a plurality of nitride-based nonmagnetic ceramic molded articles having a roughened structure having different shapes. And can be manufactured by bonding and integrating via an adhesive layer formed on the bonding surface. The adhesive layer can be formed, for example, by applying an adhesive to the roughened structure portion of the nitride-based non-magnetic ceramic molded body. As the adhesive, the same adhesive as that used in the production of the other composite molded body described above can be used.

Furthermore, a composite molded body composed of a non-magnetic ceramic molded body of a different type from a nitride-based non-magnetic 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 nitride-based non-magnetic ceramic molded body and joining it to a different type of non-magnetic ceramic molded body, a different type of non-magnetic ceramic molded body is used. After forming the adhesive layer with the surface of the magnetic ceramic molded body also having a roughened structure, the adhesive layer of the non-magnetic ceramic molded body of a different type from the surface having the adhesive layer of the nitride non-magnetic ceramic molded body The composite molded body can be manufactured by bonding and integrating the surfaces having the above.

Different types of non-magnetic ceramics include oxides, carbides, borides, and silicides. As methods for roughening the surface of different types of non-magnetic ceramic molded bodies, the methods and conditions differ depending on the type of non-magnetic ceramics. For example, as in the present invention, a method of irradiating a laser beam, filing, blasting A method of roughening by processing, etching, or the like can be applied.

Each configuration in each embodiment and a combination thereof are merely examples, and addition, omission, substitution, and other changes of the configuration can be appropriately made without departing from the gist 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 a temperature at which a heated test piece (4 × 35 × 3 mm in thickness) of a carbide-based nonmagnetic ceramic molded body is broken when immersed in water at 30 ° C. When the internal stress generated by the temperature difference between the inside and the surface when cooled rapidly exceeds the strength of the test piece, it is destroyed.

Ra (arithmetic average roughness): Eleven lines of 1.5 mm length are drawn on the surface of the roughened structure portion of the nitride-based non-magnetic ceramic molded body, and those Ra are measured by a one-shot 3D shape measuring machine ( Keyence).

Rz (maximum height): 11 lines of 1.5 mm length are drawn on the surface of the roughened structure portion of the nitride-based nonmagnetic ceramic molded body, and those Rz are measured by a one-shot 3D shape measuring instrument (Keyence Corporation). Manufactured).

Sa (arithmetic mean height): Sa in a range of 9 × 1.8 mm on the surface of the roughened structure portion of the nitride-based nonmagnetic ceramic molded body was measured with a one-shot 3D shape measuring instrument (manufactured by Keyence).

Sz (maximum height): Sz in a range of 9 × 1.8 mm of the surface of the roughened structure portion of the nitride-based nonmagnetic ceramic molded body was measured by a one-shot 3D shape measuring instrument (manufactured by Keyence).

Sdr (developed area ratio of interface): Indicates how much the developed area (surface area) of the defined area is increased with respect to the area of the defined area, and Sdr of a completely flat surface is 0. Sdr was measured with a one-shot 3D shape measuring instrument (manufactured by Keyence).

Sdq (root-mean-square slope): a parameter calculated by the root-mean-square of the slope at all points in the defined area, and Sdq of a perfectly flat surface is 0. If the surface has a slope, Sdq increases. For example, Sdq becomes 1 on a plane including a 45 ° tilt component. It was measured by a one-shot 3D shape measuring machine (manufactured by Keyence).

<Protrusion diameter and formation density>
SEM imaging was performed on the surface irradiated with the laser light. The magnification may be adjusted to a magnification of 50 to 400 times so that the roughened structure can be easily observed. In Examples 1 to 4, photographing was performed at a magnification of 200 to 400 times. A visual field of 200 μm square was determined, and from the photograph, the width of the projections, the number of projections, and the diameter of the projections were measured, and the average formation density was calculated. The average formation density was similarly measured for a total of three places randomly selected from a range of 50 mm ² , and an average value was obtained. When the average value was less than 1, it was displayed as 0.

Examples 1 to 5, Comparative Example 1
The surface of a nonmagnetic ceramic molded body (10 × 50 × 2 mm thick plate) of the type shown in Table 1 was continuously irradiated with laser light under the conditions shown in Table 1 using the continuous wave laser device described below. And roughened. As the titanium carbonitride of Example 5, "Tial" (trade name of Osaka Koki Co., Ltd.) was used.
(Laser device)
Oscillator: IPG-Yb fiber; YLR-300-SM
Galvano mirror SQUIIREEL (ARGES)
Light collection system: fc = 80 mm / fθ = 100 mm

The bidirectional irradiation was performed as follows.
Bidirectional irradiation: A continuous wave laser beam is radiated linearly so that one groove is formed in one direction, and a continuous wave laser is similarly formed in the opposite direction at a pitch interval (line interval) of 0.05 mm. The irradiation of light in a straight line was repeated. The 0.05 mm spacing for bidirectional irradiation is the distance between the intermediate positions of the width of adjacent grooves.

Ｓ FIGS. 3 to 7 and 8 show SEM photographs of portions having a roughened structure of the nonmagnetic ceramic molded bodies of Examples 1 to 5 and Comparative Example 1.

Using the non-magnetic ceramic molded body having a roughened structure obtained in Example 1 and Example 3, a composite molded body with a resin molded body (a molded body of polyamide 6 containing 30% by mass of glass fiber). (FIG. 9) was produced.

接合 Using each of the obtained composite molded bodies, 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. 9, a tensile test was performed to evaluate the shear bonding strength (S1). Tensile test is based on ISO19095, with the nonmagnetic ceramic molded body 30 fixed at the end, and pulled in the X direction shown in FIG. 9 until the nonmagnetic ceramic molded body 30 and the resin molded body 31 are broken. Was measured under the following conditions until the joint surface was broken. Table 1 shows the results.

<Tensile test conditions>
Testing machine: AUTOGRAPH AG-X plus (50kN) manufactured by Shimadzu Corporation
Tensile speed: 10 mm / min
Distance between grips: 50mm

The unevenness of the roughened structure in the nitride-based non-magnetic ceramic molded bodies of Examples 1 and 3 is such that the cross-sectional shape in the thickness direction of the tip portion is a curved surface (partial circle), and the bottom of the concave portion is V-shaped ones were included. It is considered that the same form is applied to other embodiments.

The unevenness of the roughened structure in the nitride-based non-magnetic ceramic molded bodies of Examples 2 to 5 (FIGS. 4 to 7) is such that the cross-sectional shape in the thickness direction of the tip portion is a curved surface (partial circle). There was a projection group consisting of projections dispersed on the curved surface of the projection.

In Comparative Example 1, since the irradiation speed of the laser beam was too slow, the unevenness of the roughened structure was large. For example, when the composite molded body was manufactured by bonding with another material such as a resin, the unevenness of the bonding state was large. It was thought that the quality was not stable.

The composite molded body of the nitride-based non-magnetic ceramic molded body and the resin molded body of Examples 1 and 3 has a high bonding strength. Since it is recognized that it has, even when a composite molded body with other materials (thermosetting resin, rubber, elastomer, metal, UV-curable resin) is manufactured, a composite with high bonding strength is produced. It is believed that a compact is obtained.

Examples 6 to 8
The surface of a nonmagnetic ceramic molded body (10 mm × 50 mm × 2 mm thick plate) of the type shown in Table 2 was continuously irradiated with pulsed laser light under the conditions shown in Table 2 to roughen the surface. 10 to 12 show SEM photographs after roughening. In Examples 7 and 8, the bonding strength was measured in the same manner as in Examples 1 and 3.
Oscillator: IPG-Yb-Fiber Laser; YLP-1-50-30-30-RA
Galvanometer mirror: XD30 + HurrySCAN10 from SCANLAB
Condensing system: Beam expander double / fθ = 100mm

Cross (cross irradiation): After irradiating continuous wave laser light so that ten grooves (first group of grooves) are formed at intervals of 0.20 mm, in a direction orthogonal to the first group of grooves. The laser beam was applied so that ten grooves (second group of grooves) were formed at intervals of 0.20 mm.

Bidirectional irradiation: After irradiating the laser beam linearly so that one groove is formed in one direction, the laser beam is linearly irradiated in the opposite direction with a pitch interval (line interval) shown in Table 2 Irradiation was repeated. The pitch interval (line interval) is a distance between intermediate positions of adjacent grooves (lines).

凹凸 The irregularities of the roughened structure in the nitride-based nonmagnetic ceramic molded bodies of Examples 6 to 8 included those in which the bottoms of the concave portions were V-shaped. The composite molded body of the nitride-based non-magnetic ceramic molded body and the resin molded body of Examples 7 and 8 has high bonding strength, and also has the same level of bonding strength in Example 6. Therefore, even when a composite molded body with another material (thermosetting resin, rubber, elastomer, metal, UV curable resin) is manufactured, a composite molded body with high bonding strength can be obtained. It is thought that it is possible.

The nitride-based non-magnetic ceramic molded article having a roughened structure on its surface according to the present invention is used as an intermediate for producing a composite molded article of a carbide-based non-magnetic ceramic molded article and a resin, rubber, elastomer, metal, or the like. can do.

Claims (21)

1. A non-magnetic ceramic molded body having a surface roughened structure,
   The non-magnetic ceramic molded body is a nitride-based non-magnetic ceramic molded body,
   The roughened structure has irregularities, and the cross-sectional shape in the thickness direction of the irregularities when observed by a scanning electron microscope photograph (50 to 400 times) is a curved surface at the tip of the convex portion. Or a non-magnetic ceramic molded body including a concave portion having a V-shaped bottom.
2. A non-magnetic ceramic molded body having a surface roughened structure,
   The non-magnetic ceramic molded body is a nitride-based non-magnetic ceramic molded body,
   The roughened structure has irregularities, and the cross-sectional shape in the thickness direction of the irregularities when observed by a scanning electron microscope photograph (50 to 400 times) is a curved surface at the tip of the convex portion. Or the bottom of the recess is V-shaped,
   A nonmagnetic ceramic molded body having a projection group consisting of projections dispersed at the tip of the projection.
3. 3. The non-magnetic ceramic according to claim 1, wherein the nitride-based non-magnetic ceramic molded body has a thermal shock temperature (JIS R1648: 2002) in the range of 500 to 750 ° C. and a thickness of 0.5 mm or more. Molded body.
4. 4. The non-magnetic ceramic molded body according to claim 3, wherein the nitride-based non-magnetic ceramic molded body contains silicon nitride, aluminum nitride, or titanium carbonitride.
5. The unevenness is formed with a linear convex portion and a linear concave portion alternately in one direction,
   When the width of each of the linear projections and the linear recesses is 20 to 500 μm, the diameter of the projections (circular replacement diameter) included in the projection group formed on the projections is 10 to 200 μm. The non-magnetic ceramic molded body according to any one of claims 2 to 4, wherein an average formed density of the non-magnetic ceramic molded body is 5 pieces / 250,000 μm ² or more.
6. The unevenness is formed with a linear convex portion and a linear concave portion alternately in one direction,
   When the width of each of the linear projections and the linear recesses is 20 to 500 μm, the diameter of the projections (circular replacement diameter) included in the projection group formed on the projections is 10 to 200 μm. The non-magnetic ceramic molded article according to any one of claims 2 to 4, wherein an average formation density of the non-magnetic ceramics article is 5 to 200 pieces / 250,000 μm ² .
7. In the planar shape of the roughened structure, the concave portions of the irregularities are formed in an island shape, and the portion excluding the concave portions is a convex portion,
   When the width of the protrusions is 20 to 500 μm, the average formation density of the protrusions included in the protrusion group formed on the protrusions (circular replacement diameter) of 10 to 200 μm is 5/250, The non-magnetic ceramic molded product according to any one of claims 2 to 4, which has a size of 000 µm ² or more.
8. In the planar shape of the roughened structure, the concave portions of the irregularities are formed in an island shape, and the portion excluding the concave portions is a convex portion,
   When the width of the protrusion is 20 to 500 μm, the average formation density of the protrusions (diameter of circular replacement) included in the protrusion group formed in the protrusions of 10 to 200 μm is 5 to 30 / The non-magnetic ceramic molded product according to any one of claims 2 to 4, which has a size of 250,000 μm ² .
9. 9. The method according to claim 1, wherein the surface roughness (Ra) of the unevenness is in a range of 1 to 100 μm, and the height difference (Rz) between the convex portion and the concave portion of the unevenness is in a range of 10 to 500 μm. The non-magnetic ceramic molded article according to the above.
10. The method according to any one of claims 1 to 8, wherein an arithmetic average height (Sa) of the irregularities is in a range of 3 to 90 μm, and a maximum height (Sz) of the convex portions of the irregularities is in a range of 30 to 500 μm. The non-magnetic ceramic molded article according to the above.
11. The method according to any one of claims 1 to 8, wherein a development area ratio (Sdr) of an interface of the unevenness is in a range of 1 to 8, and a root mean square slope (Sdq) of the unevenness is in a range of 2 to 12. Of non-magnetic ceramics.
12. It is a manufacturing method of the non-magnetic ceramic molded body of Claim 1, Comprising:
    It has a step of roughening the surface of the nitride-based non-magnetic ceramic molded body by continuously irradiating a laser beam using a continuous wave laser,
    A method for producing a non-magnetic ceramic molded body, wherein when the nitride-based non-magnetic ceramic molded body is aluminum nitride, a laser beam is continuously irradiated at an irradiation speed of 5,000 mm / sec or more.
13. It is a manufacturing method of the nonmagnetic ceramic molded body of Claim 2, Comprising:
    It has a step of roughening the surface of the nitride-based non-magnetic ceramic molded body by continuously irradiating a laser beam using a continuous wave laser,
    When the nitride-based non-magnetic ceramic molded body is aluminum nitride, a laser beam is continuously irradiated at an irradiation speed of 1,000 to 5,000 mm / sec,
    A method for producing a non-magnetic ceramic molded body, wherein when the nitride-based non-magnetic ceramic molded body is silicon nitride, a laser beam is continuously irradiated at an irradiation speed of 1,000 mm / sec or more.
14. The laser light irradiation step is a step of irradiating the surface of the metal molded body to be roughened, when irradiating the laser light, so that the irradiated part and the non-irradiated part of the laser light alternately occur. The method for producing a non-magnetic ceramic molded body according to claim 12.
15. When continuously irradiating the surface of the non-magnetic ceramic molded body with laser light using a continuous wave laser,
    15. The non-magnetic ceramic molded body according to claim 12, wherein the laser light is continuously irradiated such that a plurality of lines composed of straight lines, curved lines, and combinations thereof are formed in the same direction or different directions. Production method.
16. When continuously irradiating the surface of the non-magnetic ceramic molded body with laser light using a continuous wave laser,
    Laser light is continuously irradiated so that a plurality of lines composed of straight lines, curves and combinations thereof are formed in the same direction or different directions, and laser light is continuously irradiated a plurality of times to form one straight line or one curved line. The method for producing a nonmagnetic ceramic molded article according to any one of claims 12 to 14, wherein
17. When continuously irradiating the surface of the non-magnetic ceramic molded body with laser light using a continuous wave laser,
    Continuously irradiate laser light such that a plurality of lines consisting of straight lines, curves and combinations thereof are formed in the same direction or different directions,
    The nonmagnetic ceramic molded body according to any one of claims 12 to 14, wherein the laser beam is continuously irradiated so that the plurality of straight lines or the plurality of curves are formed at equal or different intervals. Manufacturing method.
18. It is a manufacturing method of the nonmagnetic ceramic molded body of Claim 2, Comprising:
    Manufacture of a non-magnetic ceramic molded body which is roughened by irradiating a pulsed laser beam on the surface of the nitride-based non-magnetic ceramic molded body so as to satisfy the following requirements (i) to (v): Method.
    (I) The irradiation angle when irradiating the surface of the nitride-based non-magnetic ceramic molded body with laser light is 15 to 90 degrees. (Ii) With respect to the surface of the nitride-based non-magnetic ceramic molded body. The irradiation speed when irradiating the laser beam with 10 to 500 mm / sec
    (Iii) The energy density when irradiating the surface of the nitride-based non-magnetic ceramic molded body with laser light is 0.1 to 50 GW / cm ^2.
    (Iv) The number of repetitions of irradiating the surface of the nitride-based non-magnetic ceramic molded body with laser light is 1 to 80 times. (V) With respect to the surface of the nitride-based non-magnetic ceramic molded body. Line spacing when irradiating laser light is 0.01-1mm
19. 19. The method for producing a non-magnetic ceramic molded body according to claim 18, wherein the requirements (i) to (v) are in the following numerical ranges.
    (I) 15 degrees to 90 degrees (ii) 10 to 300 mm / sec
    (Iii) 0.1 to 50 GW / cm ²
    (Iv) 3 to 50 times (v) 0.01 to 0.8 mm
20. 19. The method for producing a non-magnetic ceramic molded body according to claim 18, wherein the requirements (i) to (v) are in the following numerical ranges.
    (I) 15 degrees to 90 degrees (ii) 10 to 100 mm / sec
    (Iii) 0.1 to 20 GW / cm ²
    (Iv) 5 to 30 times (v) 0.03 to 0.5 mm
21. 19. The method for producing a non-magnetic ceramic molded body according to claim 18, wherein the requirements (i) to (v) are in the following numerical ranges.
    (I) 45 degrees to 90 degrees (ii) 10 to 80 mm / sec
    (Iii) 0.5 to 5 GW / cm ²
    (Iv) 5 to 30 times (v) 0.05 to 0.5 mm
    
    

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