JP6754511B1 - Nitride-based non-magnetic ceramic molded product and its manufacturing method - Google Patents

Abstract

A non-magnetic ceramic molded body having a roughened structure on the surface, the non-magnetic ceramic molded body is a nitride-based non-magnetic ceramic molded body, and the roughened structure has irregularities and is scanned. The cross-sectional shape of the unevenness in the thickness direction when observed by a type electron micrograph (50 to 400 times) is that the tip of the convex portion is curved or the bottom of the concave portion is V-shaped. A non-magnetic ceramic molded body having a roughened surface structure.

Description

In one aspect thereof, the present invention relates to a nitride-based non-magnetic ceramic molded product having a roughened surface 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 that they are treated to form irregularities on the surface depending on the application.

Japanese Unexamined Patent Publication No. 2002-308683 discloses a ceramic member having a concavo-convex structure formed by an acidic etching solution. Japanese Patent No. 6032903 describes the invention of a firing setter having a specific uneven structure (claims), and examples of the firing setter material include zirconia, alumina, magnesia, spinel, cordylite, and the like. Is illustrated (paragraph number 0013).

WO2011 / 121808A1 is impregnated with a base material made of metal or ceramics, an impregnated layer provided by forming a recess on the surface portion on the sliding side of the base material, and the impregnated layer, and the base material is impregnated. It is a sliding member including a resin layer covering the surface on the sliding side of the above, and the invention in which the recess is formed by machining is disclosed (claims). It is described that the recess is a plurality of linear grooves, and the maximum depth of the grooves is 200 to 2000 μm (paragraph number 0026).

As the machining, laser machining, wire cutting, etc. are exemplified (paragraph number 0014), but there is no description about specific machining conditions, and in the examples, it is described that steel is wire cut. There is no specific description about ceramics.

Japanese Patent Laying-Open No. 2015-109966 describes a method for producing a medical device material in which a specific site of a medical device material containing square zirconia is coated with calcium phosphate, and the specific site is irradiated with an ultrashort pulse laser. A method for producing a medical device material is disclosed, which comprises a first step of forming irregularities on the surface and a second step of depositing or precipitating calcium phosphate fine particles smaller than the period of the irregularities on the specific portion. (Claims).

Japanese Patent No. 6111102 discloses, by irradiating a laser beam having a wavelength 300~1500nm the circuit pattern and portions of substantially the same planar shape of at least one surface of a ceramic substrate mainly composed of AlN or _Al 2 _{O 3,} An aluminum film is formed on a portion having a planar shape substantially the same as the circuit pattern on at least one surface of the ceramic substrate, and a copper plate is arranged on the aluminum film to be above the symmetry point between aluminum and copper and below 650 ° C. A method for manufacturing a metal-ceramic bonded substrate is disclosed, which comprises joining a copper plate to a ceramic substrate via an aluminum film by heating at a temperature.

According to Japanese Patent Application Laid-Open No. 2003-171190, the surface of a base material made of a dense ceramic having a purity of 95% or more is formed into a rounded first unevenness having a surface roughness Ra3 to 40 μm, and the first unevenness is formed. A ceramic member is disclosed in which the surface of the uneven surface is formed into a second rounded uneven surface 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.

Japanese Unexamined Patent Publication No. 2003-137677 and Japanese Unexamined Patent Publication No. 2004-666299 disclose a technique for forming irregularities on the surface of a ceramic body by laser processing.

Japanese Patent No. 5774246 and Japanese Patent No. 5701414 describe an invention in which a continuous wave laser is used to continuously irradiate a laser beam at an irradiation rate of 2000 mm / sec or more to roughen the surface of a metal molded product. Although the invention of a method for producing a composite molded product of a molded product and a resin molded product is disclosed, there is no description about ceramics.

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

The present invention is, in one embodiment, a non-magnetic ceramic molded body having a roughened surface structure.
The non-magnetic ceramic molded product is a nitride-based non-magnetic ceramic molded product.
The roughened structure has irregularities, and the cross-sectional shape of the irregularities in the thickness direction when observed by a scanning electron micrograph (50 to 400 times) is such that the tip of the convex portion is a curved surface. Provided is a non-magnetic ceramic molded product (first embodiment) having a roughened surface structure, which includes a product or a product having a V-shaped bottom portion of the recess. Further, in another embodiment, the present invention provides a method for producing a non-magnetic ceramic molded product according to the first embodiment.

Further, in another embodiment, the present invention is a non-magnetic ceramic molded product having a roughened surface structure.
The non-magnetic ceramic molded product is a nitride-based non-magnetic ceramic molded product.
The roughened structure has irregularities, and the cross-sectional shape of the irregularities in the thickness direction when observed by a scanning electron micrograph (50 to 400 times) is such that the tip of the convex portion is a curved surface. Includes one or one in which the bottom of the recess is V-shaped.
Provided is a non-magnetic ceramic molded body (second embodiment) having a roughened surface structure, which has a group of protrusions composed of protrusions dispersed at the tip of the convex portion. Further, in another embodiment, the present invention provides a method for producing a non-magnetic ceramic molded product according to a second embodiment.

The non-magnetic ceramic molded product according to the embodiment of the present invention has a roughened surface structure 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 product, and a composite molded product.

According to the manufacturing method according to the embodiment of the present invention, the surface of a nitride-based non-magnetic ceramic molded product that is inherently hard and brittle can be roughened without being separated into two or more by cracking.

The figure which shows the irradiation state of the laser light of one Embodiment when carrying out the 2nd manufacturing method by one example of this invention. It is a figure which shows the irradiation pattern of the laser light when carrying out the 2nd manufacturing method by one example of this invention, (a) is the irradiation pattern in the same direction, (b) is the irradiation pattern in both directions. (A) is an SEM photograph (200 times) of the roughened structure portion (plan view) of the aluminum nitride molded product of Example 1, and (b) is an SEM photograph (200 times) of the cross section in the thickness direction of (a). is there. It is an SEM photograph (400 times) of the roughened structure part (plan view) of the aluminum nitride molded article of Example 2. FIG. (A) is an SEM photograph (400 times) of the roughened structural portion (plan view) of the silicon nitride molded product of Example 3, and (b) is an SEM photograph (200 times) of the cross section in the thickness direction of (a). is there. It is an SEM photograph (400 times) of the roughened structure part (plan view) of the silicon nitride molded article of Example 4. FIG. It is an SEM photograph (200 times) of the roughened structure part (plan view) of titanium carbonitride of Example 5. It is an SEM photograph (100 times) of the roughened structure part (plan view) of the silicon nitride molded article of Comparative Example 1. The perspective view of the nitride ceramic molded body manufactured in the Example, and the perspective view for explaining the test of the bonding strength using the 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 product 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 product of Example 8, and (b) is an SEM photograph of a cross section in the thickness direction of (a).

According to some of the embodiments, the present invention includes the non-magnetic ceramic molded product of the first embodiment and its manufacturing method, and the non-magnetic ceramic molded product of the second embodiment and its manufacturing method.

According to the embodiment of the present invention, the non-magnetic ceramic molded product having a roughened surface structure includes nitride-based non-magnetic ceramics. The nitride-based non-magnetic ceramic molded body may be a molded body containing nitride-based ceramics such as aluminum nitride, silicon nitride, titanium nitride, Sialon, and titanium carbonitride. Among these, aluminum nitride, It may be a molded body containing silicon nitride and titanium carbonitride.

Aluminum nitride, silicon nitride, and titanium nitride are each composed of a single material, and aluminum nitride, silicon nitride, titanium nitride, and other non-magnetic ceramics and 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 semi-metal (for example, silicon). When the composite is formed, the content ratio of the nitride-based non-magnetic ceramics is 50% by mass or more in one preferable aspect of the present invention, and 60% by mass or more in another preferable aspect of the present invention. Yet another preferred embodiment of the present invention is 70% by mass or more.

The predetermined thermal shock temperature (JIS R1648: 2002) is in the range of 500 to 750 ° C. in one preferred embodiment of the present invention and in the range of 530 to 700 ° C. in another preferred embodiment of the present invention. Another preferred embodiment is in the range of 530-670 ° C.

A nitride-based non-magnetic ceramic molded product containing aluminum nitride, silicon nitride, or titanium nitride has a thickness of 0.5 mm or more in a preferred embodiment of the present invention in order to prevent cracking during processing. In another preferred embodiment of the present invention, the thickness is 1.0 mm or more. In addition, "cracking" in the present invention means that a part of the molded product is cracked and divided into two or more, and "cracking" is not included. Further, "cracking" also includes a case where the strength is significantly reduced and the strength is significantly reduced and the material is divided into two or more at the time of subsequent movement and processing, although it does not crack during processing by irradiation with laser light.

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

The cross-sectional shape of the tip portion of the convex portion in the thickness direction may include a partial circular shape or a partial elliptical shape. The partial circular shape is a shape including a part of a circle such as a semicircular shape or a 1/3 circular shape. The partially 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 (second embodiment) having a roughened structure on the surface of the present invention is formed from protrusions dispersed in the tip portions (one having a curved cross-sectional shape and one having a non-curved surface shape) of the convex portion. It may have a group of protrusions. According to one example, the protrusion group of the non-magnetic ceramic molded product of the second embodiment may be in a form in which a large number of independent protrusions are dispersed on the surface of the convex portion, for example, the shape of the convex portion and the protrusion. Depending on the form of, the following different forms can be taken.

In the form in which the unevenness of the non-magnetic ceramic molded body of the second embodiment is formed by alternating linear convex portions and linear concave portions in one direction, the linear convex portions and the linear concave portions ( When the width of each of the grooves) is 20 to 500 μm, in a preferred embodiment of the present invention, the diameter of the protrusion (circular replacement diameter) included in the protrusion group formed in the convex portion is 10 to 200 μm. and the average formation density of 5 / 250,000μm ² or more, further the average formation density in a preferred embodiment is 5 to 200 pieces / 250,000μm ^2, yet another preferred embodiment of the present invention of the present invention The average formation density is 8 to 150 pieces / 250,000 μm ² . The diameter of the protrusion (circular replacement diameter) is the diameter when the plane area of the protrusion is replaced with a circle having the same area.

The above-mentioned "one direction" is, for example, a direction obliquely intersecting in the long side direction, the short side direction, or the long side direction or the short side direction when the plane shape of the non-magnetic ceramic molded body is rectangular. Often, when the planar shape of the non-magnetic ceramic molded body is square, it may be in any side direction or in a direction obliquely intersecting in any of the side directions.

When protrusions are formed on the surface (curved surface) of the convex portion and the surface area is increased in this way, for example, when a non-magnetic ceramic molded product is joined to another member (for example, a resin molded product), the joint surface The joint strength is increased by increasing the contact area.

One example of the non-magnetic ceramic molded body of the second embodiment may be a form in which the concave portions of the unevenness are dispersed and formed in an island shape, and the portion excluding the concave portion is a convex portion. When the width of each of the portion and the concave portion (groove) is 20 to 500 μm, in a preferred embodiment of the present invention, the diameter of the protrusion (circular replacement diameter) included in the protrusion group formed in 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 preferable aspect of the present invention, the average formation density is 10 to 30 pieces / 250,000 μm ² , further of the present invention. In another preferred embodiment, the average formation density is 10 to 25 pieces / 250,000 μm ² . The diameter of the protrusion (circular replacement diameter) is the diameter when the plane area of the protrusion is replaced with a circle having the same area.

When protrusions are formed on the surface (curved surface) of the convex portion and the surface area is increased in this way, for example, when a non-magnetic ceramic molded product is joined to another member (for example, a resin molded product), the joint surface The joint strength is increased by increasing the contact area.

According to the examples of the non-magnetic ceramic molded bodies 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 preferable aspect of the present invention, which is different from that of the present invention. In one preferred embodiment of the invention, the range is 3 to 90 μm, and in yet another preferred embodiment of the present invention, the range is 5 to 85 μm.

According to the example of the non-magnetic ceramic molded product of the first embodiment and the second embodiment, the height difference (Rz) between the convex portion and the concave portion of the unevenness is in the range of 10 to 500 μm in a preferable aspect of the present invention. Another preferred embodiment of the invention is in the range of 15-450 μm and yet another preferred embodiment of the invention is in the range of 20-400 μm.

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

According to the examples of the non-magnetic ceramic molded bodies 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. Another preferred embodiment of the invention is in the range of 35-480 μm, and yet another preferred embodiment of the invention is in the range of 40-450 μm.

According to the examples of the non-magnetic ceramic molded bodies of the first embodiment and the second embodiment, the developed area ratio (Sdr) of the interface of the unevenness is in the range of 1 to 8 in a preferable aspect of the present invention, and the present invention. In another preferred embodiment of the invention, the range is 2 to 7, and in yet another preferred embodiment of the present invention, the range is 2.5 to 6.5.

According to the examples of the non-magnetic ceramic molded bodies of the first embodiment and the second embodiment, the root mean square inclination (Sdq) of the unevenness is in the range of 2 to 12 in a preferable aspect of the present invention, and the present invention Another preferred embodiment is in the range of 2.5-11 and yet another preferred embodiment of the present invention is in the range of 3-10.

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

In the method for producing a molded body of the first embodiment, when the nitride-based non-magnetic ceramic molded body is aluminum nitride, laser light can be continuously irradiated at an irradiation rate of 5,000 mm / sec or more. In one preferred embodiment of the present invention, the laser beam is 5,000 to 20,000 mm / sec, and in another preferred embodiment of the present invention, the laser beam can be continuously irradiated at an irradiation rate of 5,000 to 10,000 mm / sec.

In the method for producing a molded body of the second embodiment, when the nitride-based non-magnetic ceramic molded body is aluminum nitride, laser light can be continuously irradiated at an irradiation rate of 1,000 to 5,000 mm / sec. In a preferred embodiment of the present invention, the laser beam can be continuously irradiated at an irradiation rate of 1,000 to 3,000 mm / sec.

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

According to the embodiment of the present invention, the shape, size, thickness, etc. of the nitride-based non-magnetic ceramic molded product used in the manufacturing method are not particularly limited, and are selected according to the intended use, and if necessary. Is adjusted. For example, as a nitride-based non-magnetic ceramic molded body, a flat plate, a round bar, a square bar (a bar having a polygonal cross section), a tube, a cup-shaped body, a cube, a rectangular parallelepiped, a sphere or a partial sphere (such as a hemisphere), or an ellipsoid. In addition to molded bodies such as spheres or partial ellipsoids (semi-ellipsoids, etc.) and irregular shapes, existing non-magnetic ceramic products can also be used.

The existing nitride-based non-magnetic ceramic products include 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 consist of a complex.

According to one embodiment, in each of the method for producing the molded product of the first embodiment and the method for producing the molded product of the second embodiment, when the laser beam is continuously irradiated within the irradiation rate range of the laser beam described above, The laser beam can be continuously irradiated so that a plurality of lines including straight lines, curves, and combinations thereof are formed in the same direction or different directions.

According to another embodiment, when the laser beam is continuously irradiated in the above-mentioned laser beam irradiation rate range in each of the method for producing the molded product of the first embodiment and the method for producing the molded product of the second embodiment. , Continuously irradiate the laser beam so that a plurality of lines consisting of straight lines, curves and combinations thereof are formed in the same direction or different directions, and continuously irradiate the laser beam multiple times to form one straight line or one. A curve can be formed.

According to still another embodiment, when the laser beam is continuously irradiated in the above-mentioned laser beam irradiation rate range in each of the method for producing the molded product of the first embodiment and the method for producing the molded product of the second embodiment. , The laser beam is continuously irradiated so that a plurality of lines consisting of straight lines, curves and combinations thereof are formed in the same direction or different directions, and the plurality of straight lines or the plurality of curves are equally spaced or different. The laser beam can be continuously irradiated so as to be formed at intervals.

The output of the laser is 50 to 4,000 W in one preferred embodiment of the invention, 100 to 2,000 W in another preferred embodiment of the invention, and 100 to 1 in yet another preferred embodiment of the invention. It is 000W. The roughened state should be adjusted by reducing the laser light output when the laser light irradiation speed is slow within the above range and increasing it when the laser light irradiation speed is high within the above range. Can be done.

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 are 3~1,500MW / cm ^2, in another preferred embodiment of the present invention is a 5~700MW / cm ^2. The energy density at the time of laser light irradiation is based on the laser light output (W) and the laser light (spot area (cm ² ) (π · [spot diameter / 2] ² ) according to the following equation: laser light output / spot area. Desired.

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

When repeatedly irradiating one line, bidirectional irradiation or 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. It is a method of irradiating a continuous wave laser, and then repeatedly irradiating the continuous wave laser from the first end to the second end, from the second end to the first end, and so on. One-way irradiation is a method of repeating one-way continuous wave laser irradiation from the first end to the second end. When radiated in both directions or in one direction, 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 (arc), but the two opposite sides on the short axis side are only straight lines, that is, a straight line and a curved line. It includes those having a shape consisting of, and those in which straight lines or curves on two opposite sides on the short axis side are partially curved.

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

When irradiating the laser beam, bidirectional irradiation or unidirectional irradiation is performed at the above-mentioned line intervals to form a plurality of grooves, and then the above-mentioned lines are formed from a direction orthogonal to or obliquely intersecting the plurality of grooves. Bidirectional irradiation or cross irradiation with unidirectional irradiation can also be performed at intervals.

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

Continuous wave laser may be a known, for example, YVO ₄ laser, a fiber laser (preferably a single mode fiber laser), an excimer laser, a carbon dioxide laser, UV laser, YAG laser, 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 these, a fiber laser is preferable, and a single mode fiber laser is particularly preferable because the energy density is increased.

<Second method for manufacturing a nitride-based non-magnetic ceramic molded product having a roughened structure on the surface>
The second method for producing a nitride-based non-magnetic ceramic molded product having a roughened surface structure according to one embodiment of the present invention is the molded product of the first embodiment and the second embodiment described above. The method is the same as that of the first manufacturing method of the molded product, 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 non-magnetic ceramic molded product with laser light at a predetermined irradiation speed using a continuous wave laser in the same manner as in the first manufacturing method. In the above, when the surface of the nitride-based non-magnetic ceramic molded product to be roughened is irradiated with the laser beam, there is a step of irradiating the surface so that the irradiated portion and the non-irradiated portion of the laser beam are alternately generated. ing.

In the second manufacturing method, when the laser beam is irradiated so as to form a straight line, a curved line, or a combination of a straight line and a curved line, the laser beam is irradiated so that the irradiated portion and the non-irradiated portion are alternately generated. Irradiating the laser beam so that the irradiated portion and the non-irradiated portion alternately occur includes an embodiment of irradiating as shown in FIG. In FIG. 1, the non-irradiated portion 12 of the laser beam of the length L2 alternately generated between the irradiated portion 11 of the laser beam of the length L1 and the irradiated portion 11 of the laser beam of the adjacent length L1 is generated as a whole. It shows the state of irradiation so as to be formed in a dotted line. The dotted line also includes a chain line such as a one-dot chain line and a two-dot chain line.

When irradiating multiple times, the irradiated portion of the laser beam may be the same, or the irradiated portion of the laser beam may be different (the irradiated portion of the laser beam may be shifted) so that the nitride-based non-magnetic ceramic molded body can be irradiated. The whole may be roughened. When the irradiated part of the laser light is the same and irradiated multiple times, it is irradiated in a dotted line, but the irradiated part of the laser light is shifted, that is, the part that was initially the non-irradiated part of the laser light is irradiated with the laser light. When the irradiation is repeated by shifting the irradiation portions so as to overlap each other, 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.

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

The laser light irradiation method is, for example, a method of irradiating the surface of the metal molded body 20 in one direction as shown in FIG. 2A, or a method of irradiating the surface of the metal molded body 20 from both directions as shown by the dotted line in FIG. 2B. You can use the method of In addition, a method of irradiating the laser beam so that the dotted line irradiation portions intersect may be used. The interval b1 of each dotted line after irradiation can be adjusted according to the irradiation target area of the metal molded body and the like, but can be set to the same range as the line interval of the first manufacturing method.

The length (L1) of the laser beam irradiated portion 11 and the length (L2) of the laser light non-irradiated portion 12 shown in FIG. 1 are in the range of L1 / L2 = 1/9 to 9/1 (that is, L1 /). It can be adjusted so that [L1 + L2] is in the range of 10 to 90%). The length (L1) of the irradiated portion 11 of the laser beam is 0.05 mm or more in one preferred embodiment of the present invention in order to roughen a complex porous structure, and 0 in another preferred embodiment of the present invention. It is .1 to 10 mm, and in yet another preferred embodiment of the present invention, it is 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 that directly converts the driving current of the laser is connected to a laser power source. The duty ratio (duty cycle) is adjusted and laser irradiation is performed.

There are two types of laser excitation, pulse excitation and continuous excitation, and a pulse wave laser by pulse excitation is generally called a normal pulse. It is possible to create a pulse wave laser even with continuous excitation, and a Q switch pulse oscillation method that oscillates a laser with a higher peak power by shortening the pulse width (pulse ON time) than a normal pulse, AOM, etc. An external modulation method that generates a pulse wave laser by cutting out light in time with an LN light intensity modulator, a method of mechanically chopping and pulse, a method of operating a galvanometer mirror to pulse, a laser drive current Can be directly modulated to generate a pulse wave laser. A pulse wave laser can be produced by a direct modulation method. The method of manipulating the galvano mirror to pulse it is a method of irradiating the laser light oscillated from the laser oscillator through the galvano mirror by the combination of the galvano mirror and the galvano controller. Can be carried out.

The Gate signal is periodically turned on / off from the galvano controller, and the laser light oscillated by the laser oscillator is turned on / off with the ON / OFF signal to pulse the laser light without changing the energy density. be able to. As a result, as shown in FIG. 1, the non-irradiated portion 12 of the laser light between the irradiated portion 11 of the laser light and the irradiated portion 11 of the adjacent laser light is alternately generated so as to be formed in a dotted line shape as a whole. Can be irradiated with laser light. The method of operating the galvano mirror to pulse it is easy because the duty ratio can be adjusted without changing the oscillation state of the laser beam itself.

Among these methods, since it is a method that can be easily pulsed (irradiating so that the irradiated portion and the non-irradiated portion are alternately generated) without changing the energy density of the continuous wave laser, it is mechanically performed. A method of chopping and pulsing, a method of manipulating a galvanometer mirror to pulsate, and a direct modulation method of directly modulating the driving current of the laser to generate a pulse wave laser may be used. In an exemplary embodiment as described above, a fiber laser device is used in which a direct modulation type modulation device that directly converts the driving current of the laser is connected to a laser power supply to continuously excite the laser to produce a pulse wave laser. You may create it.

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

By adjusting the duty ratio and irradiating the laser beam, it is possible to irradiate in a dotted line as shown in FIG. When the duty ratio is large, the efficiency of the roughening process is improved, but the cooling effect is low, and when the duty ratio is small, the cooling effect is good, but the roughening efficiency is poor. It is preferable to adjust the duty ratio according to the purpose.

<Third manufacturing method of a nitride-based non-magnetic ceramic molded product having a roughened structure on the surface>
The third manufacturing method according to one embodiment of the present invention is a method using a pulse wave laser, unlike the first manufacturing method and the second manufacturing method.

When irradiating the pulse wave laser beam, a roughened structure can be formed on the surface by adjusting the following requirements (i) to (v). The method of irradiating the pulse wave laser light is, in addition to the method of irradiating the usual pulse wave laser light, for example, Japanese Patent No. 5884104, Japanese Patent No. 5788836, Japanese Patent No. 5798534, Japanese Patent No. 5798535, It can be carried out in the same manner as the pulse wave laser light irradiation method described in Japanese Patent No. 2016-203643, Japanese Patent No. 5888775, Japanese Patent No. 5932700, or Japanese Patent No. 6055529.

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

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

<(Iii) Energy density when irradiating a nitride-based non-magnetic ceramic molded product with laser light>
The energy density at the time of irradiation of the laser light 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 with a preferred embodiment of the present invention are 0.1~50GW / cm ^2, in another preferred embodiment of the present invention are 0.1~20GW / cm ^2, another preferred of the present invention In one embodiment it is 0.5-10 GW / cm ² , and in yet another preferred embodiment of the invention it is 0.5-5 GW / cm ^{2. The} higher the energy density, the deeper and larger the pores.

The energy output (W) of one pulse of laser light is obtained from the following equation.
Energy output of one pulse of laser light (W) = (average output of laser light / frequency) / pulse width The average output of laser light is 4 to 400 W in a preferred embodiment of the present invention, which is another preferred aspect of the present invention. In one aspect, it is 5 to 100 W, and in yet another preferred embodiment of the present invention, it is 10 to 100 W. If the irradiation conditions of other laser beams are the same, the larger the output, the deeper and larger the hole, and the smaller the output, the shallower and smaller the hole. The frequency (KHz) is 0.001 to 1,000 kHz in one preferred embodiment of the invention, 0.01 to 500 kHz in another preferred embodiment of the invention, and yet another preferred embodiment of the invention. It is 0.1 to 100 kHz. The pulse width (nsec) is 1 to 10,000 nsec in one preferred embodiment of the invention, 1 to 1,000 nsec in another preferred embodiment of the invention, and 1 in yet another preferred embodiment of the 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 yet another preferred embodiment of the present invention. In yet another preferred embodiment of the above, it is 20-80 μm.

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

<(V) Line spacing when irradiating the nitride-based non-magnetic ceramic molded product with laser light>
When irradiating the nitride-based non-magnetic ceramic molded product with laser light in a line shape, the hole size and hole shape can be determined by widening or narrowing the distance between adjacent lines. The depth of the hole can be adjusted. The pulse wave laser beam irradiates points 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 one preferred embodiment of the invention, in the range of 0.01 to 0.8 mm in another preferred embodiment of the invention, and 0. in another preferred embodiment of the invention. It is 03 to 0.5 mm, and in yet another preferred embodiment of the present invention, it is 0.05 to 0.5 mm. If the line spacing is narrow, the adjacent lines are also thermally affected, resulting in larger holes, more complex hole shapes, and more prone to deeper holes, but the thermal effects are too great. It may be difficult to form holes with a complicated and deep shape. When the line spacing is wide, the holes become smaller, the shape of the holes is not complicated, and the holes tend not to be too deep, but the processing speed can be increased.

As another irradiation condition, when irradiating the nitride-based non-magnetic ceramic molded body with laser light, an irradiation form in which the laser light is irradiated while radiating heat from the molded body can be included. For example, a method of irradiating a laser beam in a state where a nitride-based non-magnetic ceramic molded product and a metal molded product having a higher thermal conductivity than the nitride-based non-magnetic ceramic molded product are in contact with each other. An example is a method of irradiating a laser beam while holding it in a hollow state. In addition, the wavelength of the pulse wave laser light may be 500 to 11,000 nm in another preferred embodiment of the present invention.

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

(1) Method for manufacturing a composite molded body of a nitride-based non-magnetic ceramic molded body having a roughened structure and a resin molded body In the first step, the above-mentioned first manufacturing method, second manufacturing method or first step. No. 3 manufactures a non-magnetic ceramic molded product having a roughened structure on the surface by the manufacturing method of.

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

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

The thermosetting resin can be appropriately selected from known thermosetting resins depending on the intended use. 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, it can be in the form of a prepolymer and can be heat-cured in a subsequent step.

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

Known fibrous fillers can be blended with these thermoplastic resins, thermosetting resins, and thermoplastic elastomers. Examples of 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, lignin-based, and the like can be used. Examples of the inorganic fiber include glass fiber, genbuiwa fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and the like. Examples of the metal fiber include fibers made of stainless steel, aluminum, copper and the like. Examples of organic fibers include polyamide fibers (total 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, and polyolefin fibers. Synthetic fibers such as polyoxymethylene fiber, polytetrafluoroethylene fiber, polyester fiber (including all aromatic polyester fiber), polyphenylene sulfide fiber, polyimide fiber, liquid crystal polyester fiber, natural fiber (cellulose fiber, etc.) and regenerated cellulose (cellulosic fiber, etc.) 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 these, for example, open holes formed by roughening the joint surface 12 of the metal molded body 10. 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. The blending amount of the fibrous filler with respect to 100 parts by mass of the thermoplastic resin, the thermosetting resin, or the thermoplastic elastomer is 5 to 250 parts by mass in a preferable aspect of the present invention. Another preferred embodiment of the present invention is 25 to 200 parts by mass, and yet another preferred embodiment of the present invention is 45 to 150 parts by mass.

(2-1) Method for manufacturing a composite molded body of a nitride-based non-magnetic ceramic molded body having a roughened structure and a rubber molded body In the first step, a first manufacturing method, a second manufacturing method, or a first step. A non-magnetic ceramic molded product having a roughened surface structure is produced by the production method of 3. In the second step, the nitride-based non-magnetic 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 of an oxide-based non-magnetic ceramic molded product containing a roughened structure is arranged in a mold, and the portion including the roughened structure is heated. The uncured rubber to be the rubber molded product is pressed under pressure, cooled, and then taken out. When applying the transfer molding method, for example, a portion of a nitride-based non-magnetic ceramic molded body containing a roughened structure is placed in a mold, and uncured rubber is injection-molded in the mold, and then , Heating and pressurizing to integrate the rubber molded body with the portion containing the roughened structure of the nitride-based non-magnetic ceramic molded body, and take out after cooling.

Depending on the type of rubber used, a step of further secondary heating (secondary curing) in an oven or the like can be added after removing the residual monomer from the mold.

The rubber of the rubber molded product used in this step is not particularly limited, and known rubber can be used, but the thermoplastic elastomer is not included. Known rubbers include ethylene-propylene copolymer (EPM), ethylene-propylene-dienter polymer (EPDM), ethylene-octene copolymer (EOM), ethylene-butene copolymer (EBM), ethylene-octente polymer (EODM), Ethethylene-α-olefin rubbers such as ethylene-butenter polymer (EBDM); ethylene / acrylic acid 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 poly Methylstyrene-butene copolymers, styrene-butadiene-styrene and styrene-ethylene-butadiene-styrene block copolymers, acrylic rubber (ACM), ethylene-vinyl acetate elastomers (EVM), silicone rubber and the like can be used.

The rubber may contain a curing agent according to the type of rubber, if necessary, but other known additives for rubber can be blended. Additives for rubber 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 manufacturing a composite molded body (including an adhesive layer) of a nitride-based non-magnetic ceramic molded body having a roughened structure and a rubber molded body According to one embodiment, the nitride-based In the method for producing a composite molded body of a non-magnetic ceramic molded body and a rubber molded body, an adhesive layer can be interposed at a joint surface between the nitride-based non-magnetic ceramic molded body and the rubber molded body.

In the first step, the nitride-based non-magnetic ceramic molded product is roughened by the 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 structural surface of the nitride-based non-magnetic ceramic molded product 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 structural surface of the non-magnetic ceramic and the holes inside.

The adhesive is not particularly limited, and known thermoplastic adhesives, thermosetting adhesives, rubber-based adhesives and the like can be used. Examples of thermoplastic adhesives include polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic adhesives, polyethylene, chlorinated polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene. -Ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ionomer, chlorinated polypropylene, polystyrene, polyvinyl chloride, plastizol, vinyl chloride-vinyl acetate copolymer, polyvinyl ether, polyvinyl pyrrolidone, polyamide, nylon, no saturation Examples thereof include standard polyester and cellulose derivatives.

Examples of thermosetting adhesives include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane. Examples of rubber-based adhesives include natural rubber, synthetic polyisobutylene, polychloroprene, nitrile rubber, styrene-butadiene rubber, styrene-butadiene-vinylpyridine ternary copolymer, polyisobutylene-butyl rubber, polysulfide rubber, silicone RTV, etc. Examples include chloride rubber, brominated rubber, kraft rubber, block copolymers, and liquid rubber.

In the example of this manufacturing method, in the third step, a step of adhering a separately molded rubber molded body to the surface of the nitride-based non-magnetic ceramic molded body on which the adhesive layer was formed in the previous step, or in the previous step. A portion including the surface of the nitride-based non-magnetic ceramic molded body on which the adhesive layer is formed is arranged in the mold to form the surface of the nitride-based non-magnetic ceramic molded body and the uncured rubber to be the rubber molded body. A step of heating and pressurizing in contact with each other to integrate them is carried out. In the case of this step, in order to mainly remove the residual monomer, a step of taking out from the mold and then further heating (secondary curing) in an oven or the like can be added.

(3-1) Method for manufacturing composite molded body of nitride-based ceramic molded body and metal molded body having a roughened structure In the first step, the first manufacturing method, the second manufacturing method, or the third An oxide-based non-magnetic ceramic molded body having a roughened structure is manufactured by a manufacturing method. In the second step, the surface including the porous structure portion of the roughened nitride-based non-magnetic ceramic molded product is arranged in the mold so as to face up. Then, for example, a well-known die casting method is applied to pour the molten metal into the mold and then cool it.

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

(3-2) Method for manufacturing a composite molded body (with an adhesive layer) of a nitride-based non-magnetic ceramic molded body having a roughened structure and a metal molded body The first step and the second step are described in the above-mentioned " (2-2) A method for manufacturing a composite molded body (including an adhesive layer) of a nitride-based non-magnetic ceramic molded body having a roughened structure and a rubber molded body ”, and the adhesive layer Manufactures a nitride-based non-magnetic ceramic molded product having

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 bond and integrate. When the adhesive layer is made of a thermoplastic resin-based adhesive, it 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 prepolymer of a thermosetting resin adhesive, the prepolymer is heat-cured by leaving it in a heating atmosphere after bonding.

(4) Method for manufacturing a composite molded body of a nitride-based non-magnetic ceramic molded body having a roughened structure and a UV curable resin molded body In the first step, the first manufacturing method and the second manufacturing described above are performed. A nitride-based non-magnetic ceramic molded product having a roughened surface structure is produced by the method or the third production method.

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

In the contact step of the monomer, oligomer or a mixture thereof, a portion including the roughened portion of the nitride-based non-magnetic ceramic molded product is surrounded by a mold, and the monomer, oligomer or a mixture thereof is enclosed in the mold. Can be carried out. Further, in the contact step of the monomer, the oligomer or a mixture thereof, after the roughened portion of the nitride-based non-magnetic ceramic molded product is placed inside the mold, the monomer, the oligomer or a mixture thereof is placed inside the mold. The step of injecting the mixture can be carried out.

By the contacting step of the monomer, the oligomer or the mixture thereof, the monomer, the oligomer or the mixture thereof enters the porous portion of the roughened portion of the nitride-based non-magnetic ceramic molded product. The form in which the monomer, oligomer or mixture thereof is porously inserted is, for example, 50% or more of the entire pores in one preferred embodiment of the present invention, 70% or more in another preferred embodiment of the present invention, and yet another preferred embodiment of the present invention. In one embodiment, 80% or more, and in yet another preferable aspect of the present invention, 90% or more of the pores are filled with monomers, oligomers or a mixture thereof, or the monomers, oligomers or a mixture thereof are penetrated to the bottom of the pores. The morphology includes a form in which a monomer, an oligomer or a mixture thereof has entered to a depth in the middle of the pore depth, and a form in which a monomer, an oligomer or a mixture thereof has entered only near the entrance of the pore.

Monomers, oligomers or mixtures thereof can be applied or injected as they are in the form of liquids (including low-viscosity gels) or solutions dissolved in solvents, and solids (powder) are heated. It can be applied or injected after being melted or dissolved in a solvent.

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

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

Compounds having one or more (meth) acryloyl groups in one molecule include 1-butene-3-one, 1-pentene-3-one, 1-hexene-3-one, 4-phenyl-1-butene-. Examples thereof include 3-one, 5-phenyl-1-pentene-3-one, and derivatives thereof.

Examples of the compound having one or more (meth) acryloyloxy groups in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth). ) Acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, n-butoxyethyl (meth) acrylate, Butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate , Isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylic Acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, glycidyl (meth) acrylate, 2- (Meta) acryloyloxyethyl acid phosphate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl Glycoldi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, decandi (meth) acrylate, glycerin Di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate , Isoamyl (meth) acrylate, isomiristyl (meth) acrylate, γ-( Meta) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxy) ethylisocyanate, 2- (2- (meth) acryloyloxyethyloxy) ethylisocyanate, 3-( Meta) Acryloyloxypropyltriethoxysilane and the like, and derivatives thereof and the like.

Compounds having one or more (meth) acryloylamino groups in one molecule include 4- (meth) acryloylmorpholin, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-methyl. (Meta) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N- Examples thereof include hexyl (meth) acrylamide, N-octyl (meth) acrylamide, and derivatives thereof.

Examples of compounds having one or more vinyl ether groups in one molecule include 3,3-bis (vinyloxymethyl) oxetane, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, and 2-hydroxy. Isopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxy Propyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexylvinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexane Dimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene Glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol monovinyl ether, oligopropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, etc., and derivatives thereof, etc. Can be mentioned.

Compounds 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 the like, and derivatives thereof and the like.

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, iso. Isopropenyl valerate, isopropenyl lactate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, pivalic acid Examples thereof include vinyl, vinyl octylate, vinyl monochloroacetate, divinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamic acid, and derivatives thereof.

(Cation-polymerizable monomer)
Examples of the cationically polymerizable monomer include compounds having one or more cationically polymerizable groups in one molecule other than an oxetanyl group such as an epoxy ring (oxylanyl group), a vinyl ether group, and a vinylaryl group.

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

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

Examples of the compound having one or more oxetane group in one molecule include trimethylene oxide, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl-3-3. (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-ethyl (3-ethyl) Oxetane)] methyl} ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, and Examples thereof include 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane.

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

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 a diisocyanate with a (meth) acrylate monomer having a hydroxyl group. Examples of the polyol include polycarbonate diols, polyester polyols, polyether polyols, and polycaprolactone polyols.

The epoxy (meth) acrylate oligomer can be obtained, for example, by an esterification reaction between an oxylan 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 subjecting a polyol to a dehydration condensation reaction to obtain a polyether oligomer having hydroxyl groups at both ends, and then esterifying the hydroxyl groups at both ends with acrylic acid. The polyester (meth) acrylate oligomer can be obtained, for example, by condensing a polycarboxylic acid and a polyol to obtain a polyester oligomer having hydroxyl groups at both ends, and then esterifying the hydroxyl groups at both ends with acrylic acid.

The weight average molecular weight of the monofunctional or polyfunctional (meth) acrylic oligomer is 100,000 or less in one preferred embodiment of the present invention, and 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 mixtures thereof.

In the next step, the monomer, oligomer, or a mixture thereof in contact with the portion of the nitride-based non-magnetic ceramic molded product containing the roughened portion is irradiated with UV and cured to form a curable resin layer. It is possible to obtain a composite molded product having.

(5) A different type of non-magnetic ceramic molded body from a composite molded body of nitride-based non-magnetic ceramic molded bodies having a roughened structure or a nitride-based non-magnetic ceramic molded body having a roughened structure. Method for manufacturing composite molded body of No. 1 The composite molded body of carbide-based non-magnetic ceramic molded bodies having a roughened structure is, for example, a plurality of nitride-based non-magnetic ceramic molded bodies having roughened structures of different shapes. Can be manufactured by joining and integrating them via an adhesive layer formed on the joining surface. The adhesive layer can be formed by applying an adhesive or the like to the roughened structure portion of the nitride-based non-magnetic ceramic molded product. As the adhesive, the same adhesive used in the production of the other composite molded products described above can be used.

Further, a composite molded body made of a non-magnetic ceramic molded body of a different type from the nitride-based non-magnetic ceramic molded body can also be manufactured in the same manner.

In this embodiment, an adhesive layer is formed on the roughened structure portion of the nitride-based non-magnetic ceramic molded body, and the adhesive layer is joined and integrated with different types of non-magnetic ceramic molded bodies, as well as different types of non-magnetic ceramic molded bodies. The surface of the magnetic ceramic molded body is also roughened to form an adhesive layer, and then an adhesive layer of a non-magnetic ceramic molded body different from the surface having the adhesive layer of the nitride-based non-magnetic ceramic molded body. A composite molded body can be manufactured by joining and integrating the surfaces having the above.

Different types of non-magnetic ceramics include oxide-based, carbide-based, boride-based, and silicified-based. As a method for roughening the surface of a different type of non-magnetic ceramic molded product, the method and conditions differ depending on the type of non-magnetic ceramic, but for example, a method of irradiating a laser beam, sanding, and blasting as in the present invention. A method of roughening by processing, etching, or the like can be applied.

Each configuration and a combination thereof in each embodiment are examples, and the configurations can be added, omitted, replaced, and other changes as appropriate without departing from the gist of the present invention. The present invention is not limited by embodiments, but only by the claims.

<Thermal shock temperature (JIS R1648: 2002)>
The thermal shock temperature is the temperature at which a test piece (4 × 35 × thickness 3 mm) of a heated carbide-based non-magnetic ceramic molded product was destroyed when immersed in water at 30 ° C. It is destroyed 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.

Ra (Arithmetic Mean Roughness): Draw 11 lines with a length of 1.5 mm on the surface of the roughened structure part of the nitride-based non-magnetic ceramic molded body, and draw those Ras on a one-shot 3D shape measuring machine ( Measured by Keyence).

Rz (maximum height): Draw 11 lines with a length of 1.5 mm on the surface of the roughened structure part of the nitride-based non-magnetic ceramic molded body, and draw those Rz on the one-shot 3D shape measuring machine (KEYENCE). Made by).

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 non-magnetic ceramic molded body was measured by a one-shot 3D shape measuring machine (manufactured by KEYENCE).

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

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

Sdq (root mean square slope): A parameter calculated by the root mean square of the slope at all points in the definition region, where Sdq on a perfectly flat surface is zero. If the surface is inclined, Sdq becomes large. For example, on a plane composed of an inclination component of 45 °, Sdq becomes 1. It was measured by a one-shot 3D shape measuring machine (manufactured by KEYENCE).

<Diameter and formation density of protrusions>
SEM photography was performed on the surface irradiated with the laser beam. The magnification may be adjusted to 50 to 400 times so that the roughened structure can be easily observed, and in Examples 1 to 4, the images were taken at 200 to 400 times. A field of view of 200 μm square was determined, and the width of the convex portion, the number of protrusions, and the diameter of the protrusions were measured from the photograph, and the average formation density was calculated. The average formation density was measured in the same manner for a total of three locations randomly selected from the range of 50 mm ² , and the average value was obtained. When the average value was less than 1, it was displayed as 0.

Examples 1-5, Comparative Example 1
The surface of a non-magnetic ceramic molded product (10 × 50 × 2 mm thick flat plate) of the type shown in Table 1 is continuously irradiated with laser light under the conditions shown in Table 1 using the following continuous wave laser device. And roughened. As the titanium nitride of Example 5, the trade name "Tial" of Osaka Koki Co., Ltd. was used.
(Laser device)
Oscillator: IPG-Yb fiber; YLR-300-SM
Galvano Mirror SQUIREEL (manufactured by ARGES)
Condensing system: fc = 80 mm / fθ = 100 mm

The bidirectional irradiation was carried out as follows.
Bidirectional irradiation: After irradiating a continuous wave laser beam linearly so that one groove is formed in one direction, a continuous wave laser is similarly applied in the opposite direction with a pitch interval (line interval) of 0.05 mm. Irradiation of light in a straight line was repeated. The distance of 0.05 mm for bidirectional irradiation is the distance between the intermediate positions of the widths of adjacent grooves.

The SEM photographs of the portion of the non-magnetic ceramic molded product of Examples 1 to 5 and Comparative Example 1 having a roughened structure are shown in FIGS. 3 to 7 and 8.

Using the non-magnetic ceramic molded product having the roughened structure obtained in Examples 1 and 3, a composite molded product with a resin molded product (a molded product of polyamide 6 containing 30% by mass of glass fibers). (Fig. 9) was manufactured.

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 joint strength (S1). The tensile test is based on ISO19095, and the case where the non-magnetic ceramic molded body 30 and the resin molded body 31 are pulled in the X direction shown in FIG. 9 with the end portion on the non-magnetic ceramic molded body 30 side fixed. The maximum load until the joint surface was broken was measured under the following conditions. The results are shown in Table 1.

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

The unevenness of the roughened structure in the nitride-based non-magnetic ceramic molded products of Examples 1 and 3 is such that the cross-sectional shape of the tip portion in the thickness direction is a curved surface (partial circle) shape, and the bottom portion of the recess is further formed. Included were V-shaped. It is considered that the same embodiment is used in other examples.

The unevenness of the roughened structure in the nitride-based non-magnetic ceramic molded product of Examples 2 to 5 (FIGS. 4 to 7) is such that the cross-sectional shape of the tip portion in the thickness direction is a curved surface (partial circle). It had a group of protrusions composed of protrusions dispersed on the curved surface of the convex portion.

In Comparative Example 1, since the irradiation speed of the laser beam was too slow, the roughened structure varied widely. For example, when a composite molded body was manufactured by bonding with another material such as resin, the bonding state also varied greatly. , It was considered 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 high bonding strength, and the bonding strength of Examples 2, 4 and 5 is about the same. 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 It is considered that a molded product can be obtained.

Examples 6-8
The surface of a non-magnetic ceramic molded product (10 mm × 50 mm × 2 mm thick flat plate) of the type shown in Table 2 was continuously irradiated with pulse wave laser light under the conditions shown in Table 2 to roughen the surface. 10 to 12 show SEM photographs after roughening. Further, for Examples 7 and 8, the joint strength was measured in the same manner as in Examples 1 and 3.
Oscillator: IPG-Yb-Fiber Laser; YLP-1-50-30-30-30-RA
Galvano Mirror: XD30 + SCANLAB HurrySCAN10
Condensing system: Beam expander double / fθ = 100mm

Cross (cross irradiation): After irradiating continuous wave laser light so that 10 grooves (grooves of the first group) are formed at intervals of 0.20 mm, in the direction orthogonal to the grooves of the first group. The laser beam was irradiated so that 10 grooves (grooves of the second group) were formed at an interval of 0.20 mm.

Bi-directional 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 the pitch interval (line interval) shown in Table 2. Irradiation was repeated. The pitch interval (line interval) is the distance between the intermediate positions between adjacent grooves (lines).

The unevenness of the roughened structure in the nitride-based non-magnetic ceramic molded product of Examples 6 to 8 included a concave portion having a V-shaped bottom. 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 Example 6 also has the same bonding strength. Therefore, even when a composite molded product with other materials (thermosetting resin, rubber, elastomer, metal, UV curable resin) is manufactured, a composite molded product having high bonding strength can be obtained. It is thought that it will be possible.

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

Claims (10)

A non-magnetic ceramic molded body having a roughened structure on the surface.
The non-magnetic ceramic molded product is a nitride-based non-magnetic ceramic molded product.
The roughened structure has irregularities, and the cross-sectional shape of the irregularities in the thickness direction when observed by a scanning electron micrograph (50 to 400 times) is such that the tip of the convex portion is a curved surface. , or include those bottom of the recess is V-shaped, a manufacturing method of a non-magnetic ceramic body,
It has a step of roughening the surface of a nitride-based non-magnetic ceramic molded product by continuously irradiating the surface with laser light using a continuous wave laser.
A method for producing a non-magnetic ceramic molded product, wherein when the nitride-based non-magnetic ceramic molded product is aluminum nitride, laser light is continuously irradiated at an irradiation rate of 5,000 mm / sec or more. A non-magnetic ceramic molded body having a roughened structure on the surface.
The non-magnetic ceramic molded product is a nitride-based non-magnetic ceramic molded product.
The roughened structure has irregularities, and the cross-sectional shape of the irregularities in the thickness direction when observed by a scanning electron micrograph (50 to 400 times) is such that the tip of the convex portion is a curved surface. , or includes those bottom of the recess is V-shaped,
A method for manufacturing a non-magnetic ceramic molded product, which has a group of protrusions composed of protrusions dispersed at the tip of the convex portion.
It has a step of roughening the surface of a nitride-based non-magnetic ceramic molded product by continuously irradiating the surface with laser light using a continuous wave laser.
When the nitride-based non-magnetic ceramic molded body is aluminum nitride, the laser beam is continuously irradiated at an irradiation speed of 1,000 to 5,000 mm / sec.
When the nitride-based non-magnetic ceramic molded product is silicon nitride, it is continuously irradiated with laser light at an irradiation speed of 1,000 mm / sec or more.
A method for producing a non-magnetic ceramic molded product, wherein when the nitride-based non-magnetic ceramic molded product is titanium carbonitride, laser light is continuously irradiated at an irradiation rate of 7,500 mm / sec or more. The laser light irradiation step is a step of irradiating the surface of the metal molded body to be roughened so that the laser light irradiated portion and the non-irradiated portion are alternately generated. The method for producing a non-magnetic ceramic molded product according to any one of claims 1 or 2 . When the surface of the non-magnetic ceramic molded product is continuously irradiated with laser light using a continuous wave laser,
The non-magnetic ceramic molded product according to any one of claims 1 to 3 , wherein the laser beam is continuously irradiated so as to form a plurality of lines composed of straight lines, curves and combinations thereof in the same direction or different directions. Production method. When the surface of the non-magnetic ceramic molded product is continuously irradiated with laser light using a continuous wave laser,
The laser beam is continuously irradiated so that a straight line, a curved line, and a plurality of lines composed of a combination thereof are formed in the same direction or different directions, and the laser beam is continuously irradiated multiple times to form a straight line or a curved line. The method for producing a non-magnetic ceramic molded product according to any one of claims 1 to 3 , wherein the non-magnetic ceramic molded body is formed. When the surface of the non-magnetic ceramic molded product is continuously irradiated with laser light using a continuous wave laser,
Continuously irradiate the laser beam so that multiple lines consisting of straight lines, curves, and combinations thereof are formed in the same direction or different directions.
The non-magnetic ceramic molded product according to any one of claims 1 to 3 , wherein the laser beam is continuously irradiated so that the plurality of straight lines or the plurality of curves are formed at equal intervals or different intervals. Manufacturing method. A non-magnetic ceramic molded body having a roughened structure on the surface.
The non-magnetic ceramic molded product is a nitride-based non-magnetic ceramic molded product.
The roughened structure has irregularities, and the cross-sectional shape of the irregularities in the thickness direction when observed by a scanning electron micrograph (50 to 400 times) is such that the tip of the convex portion is a curved surface. , or includes those bottom of the recess is V-shaped,
A method for manufacturing a non-magnetic ceramic molded product, which has a group of protrusions composed of protrusions dispersed at the tip of the convex portion.
Manufacture of a non-magnetic ceramic molded product in which the surface of a nitride-based non-magnetic ceramic molded product is roughened by irradiating a pulse wave laser beam 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. Irradiation speed when irradiating laser light is 10 to 500 mm / sec
(Iii) The energy density when irradiating the surface of the nitride-based non-magnetic ceramic molded product with laser light is 0.1 to 50 GW / cm ²
(Iv) The number of repetitions when irradiating the surface of the nitride-based non-magnetic ceramic molded product with laser light is 1 to 80 times. (V) The surface of the nitride-based non-magnetic ceramic molded product Line spacing when irradiating laser light is 0.01 to 1 mm The method for producing a non-magnetic ceramic molded product according to claim 7 , wherein the requirements (i) to (v) are in the following numerical range.
(I) 15 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 The method for producing a non-magnetic ceramic molded product according to claim 7 , wherein the requirements (i) to (v) are in the following numerical range.
(I) 15 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 The method for producing a non-magnetic ceramic molded product according to claim 7 , wherein the requirements (i) to (v) are in the following numerical range.
(I) 45 to 90 degrees (ii) 10 to 80 mm / sec
(Iii) 0.5-5 GW / cm ²
(Iv) 5 to 30 times (v) 0.05 to 0.5 mm