JP2020128336A - Composite molding - Google Patents

Abstract

To provide a composite molding composed of an oxide-based non-magnetic ceramic molding having a roughened structure thereon and a molding of other material.SOLUTION: A composite molding is composed of an oxide-based non-magnetic ceramic molding having a roughened structure thereon and a molding of other material, in which the roughened structure has unevenness, a cross-sectional shape in a thickness direction of the unevenness has a curved surface, surface roughness (Ra) of the unevenness is in a range of 1-30 μm, a difference (Rz) in height between the projection and the recess of the unevenness is 10-200 μm, the molding of the other material is a molding selected from a thermoplastic resin molding, a thermosetting resin molding, a thermoplastic elastomer molding, a rubber molding, a metal molding and a UV curable resin molding, and the composite molding is integrated by bringing the portion having the roughened structure thereon and the molding of the other material into contact with each other.SELECTED DRAWING: Figure 7

Description

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

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

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

Patent Document 3 (WO2011/121808 A1) discloses that a base material made of metal or ceramics, an impregnation layer provided by forming a recess in the surface portion of the base material on the sliding side, and the impregnation layer Disclosed is an invention in which a resin layer that is impregnated and covers the surface of the base material on the sliding side is provided, and the concave portion is formed by machining (Claims). ). It is described that the recess is a plurality of linear grooves, and the maximum depth of the grooves is 200 to 2,000 μm (paragraph number 0026).

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

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

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

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

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

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

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

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

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

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

According to the manufacturing method of one embodiment of the present invention, the surface of the inherently hard and brittle oxide-based nonmagnetic ceramic compact can be roughened without being separated into two or more by cracking.

(A) And (b) is a top view which shows several different embodiment of the recessed part of the unevenness|corrugation of the non-magnetic ceramics compact surface by one example of this invention. (A) And (b) is a top view which shows several different embodiment of the recessed part of the unevenness|corrugation on the surface of the nonmagnetic ceramic molded body by another example of this invention. (A)-(d) is a top view which shows several different embodiment of the recessed part of the unevenness|corrugation of the surface of a nonmagnetic ceramics compact by another example of this invention. (A)-(e) is a top view which shows several different embodiment of the recessed part of the unevenness|corrugation on the surface of the nonmagnetic ceramic molded body by another example of this invention. The figure which shows the irradiation state of the laser beam of one Embodiment when implementing the 2nd manufacturing method by one example of this invention. It is a figure which shows the irradiation pattern of a laser beam when implementing the 2nd manufacturing method by one example of this invention, (a) is an irradiation pattern of the same direction, (b) is a bidirectional irradiation pattern. (A) is a SEM photograph of a plan view of the roughened structure portion of the zirconia molded body of Example 1, and (b) is a SEM photograph of a cross section in the thickness direction of (a). 3 is an SEM photograph of a roughened structure portion (plan view) of an alumina molded body (purity: 92%) of Example 2. 6 is a SEM photograph of a roughened structure portion (plan view) of an alumina molded body (purity: 92%) of Example 3. (A) is a SEM photograph of a plan view of a roughened structure portion of an alumina molded body (purity: 99.5%) of Example 4, and (b) is a SEM photograph of a cross section in the thickness direction of (a). (A) is a SEM photograph of a plan view of a roughened structure portion of an alumina molded body (purity 99.5%) of Example 5, and (b) is a SEM photograph of a cross section in the thickness direction of (a). .. 5 is an SEM photograph of a roughened structure portion (plan view) of an alumina molded body (Comparative Example 9) having a purity of 99.5%. (A) is a SEM photograph of a plan view of the roughened structure portion of the steatite molded body of Example 6, and (b) is a SEM photograph of a cross section in the thickness direction of (a). (A) is a SEM photograph of a plan view of a roughened structure portion of the cordierite molded body of Example 7, and (b) is a SEM photograph of a cross section in the thickness direction of (a). 1 is a perspective view of an alumina molded body manufactured in an example, and a perspective view for explaining a bonding strength test using a composite molded body of an alumina molded body and a resin molded body. (A) is a SEM photograph of a plan view of the roughened structure portion of the steatite molded body of Example 8, and (b) is a SEM photograph of a cross section in the thickness direction of (a).

According to one embodiment of the present invention, the non-magnetic ceramic compact having a roughened surface structure is made of oxide-based non-magnetic ceramics. In a preferred embodiment of the present invention, the oxide-based nonmagnetic ceramic compact is alumina, zirconia, magnesia, silica, titanium oxide, cerium oxide, zinc oxide, tin oxide, uranium oxide, β-alumina, mullite, YAG, A compact containing oxide ceramics such as forsterite (2MgO·SiO2), barium titanate (BaTiO3), steatite (MgO·SiO2), cordierite (2MgO·2Al2O3·5SiO2), or lead zirconate titanate. Of these, another preferred embodiment of the present invention is one containing alumina or zirconia.

Alumina may be made of only alumina, or may be made of a composite of alumina and other non-magnetic ceramics or metal as long as it is within a range satisfying a predetermined thermal shock temperature. The predetermined thermal shock temperature (JIS R1648:2002) is in the range of 150 to 700° C. in a preferred embodiment of the present invention, and in the range of 180 to 680° C. in another preferred embodiment of the present invention. In still another preferred embodiment, the temperature is in the range of 200 to 650°C.

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

The zirconia may be composed of only zirconia, or may be composed of a composite of zirconia and other non-magnetic ceramics or metal as long as it is within the range of satisfying a predetermined thermal shock temperature. The predetermined thermal shock temperature (JIS R1648:2002) is in the range of 1 to 10°C in one preferred embodiment of the present invention, and is 3 to 8°C in another preferred embodiment of the present invention. The non-magnetic ceramic compact containing zirconia has a thickness of 3 mm or more in one preferred embodiment of the present invention in order to prevent cracks from occurring or cracking during irradiation with laser light. In another preferred embodiment, the thickness is 3.5 mm or more.

According to one embodiment of the present invention, in the non-magnetic ceramic molded body having a roughened structure on the surface, the roughened structure has irregularities, and the sectional shape in the thickness direction of the irregularities is a curved surface. It has The cross-sectional shape of the unevenness in the thickness direction may include a partial circular shape or a partial elliptical shape. The partial circular shape is a shape including a part of a circle, such as a semicircular shape and a 1/3 circular shape. The partial elliptical shape is a shape including a part of an ellipse such as a semi-elliptical shape and a 1/3 elliptical shape.

The surface roughness (Ra) of the irregularities is in the range of 1 to 30 μm in one preferred embodiment of the present invention, and in the range of 3 to 25 μm in another preferred embodiment of the present invention, and yet another preferred embodiment of the present invention. In one aspect, it is in the range of 4 to 23 μm. The height difference (Rz) between the convex portion and the concave portion of the unevenness is in the range of 10 to 200 μm in one preferred embodiment of the present invention, and in the range of 15 to 180 μm in another preferred embodiment of the present invention. In yet another preferred embodiment, it is in the range of 20 to 150 μm.

Furthermore, Sa (arithmetic mean height), Sz (maximum height), Sdr (expanded area ratio of the interface) and Sdq (root mean square slope) of the roughened structure portion (uneven portion) are in the following ranges. You may Sa (arithmetic mean height) is 1 to 50 μm in one preferred embodiment of the present invention, 3 to 40 μm in another preferred embodiment of the present invention, and 5 to 30 μm in yet another preferred embodiment of the present invention. Is.

Sz (maximum height) is 30 to 280 μm in one preferred embodiment of the present invention, 40 to 250 μm in another preferred embodiment of the present invention, and 50 to 230 μm in yet another preferred embodiment of the present invention. is there.

Sdr (developed area ratio of the interface) is 0.05 to 2.00 in a preferred embodiment of the present invention, and 0.1 to 1.50 in another preferred embodiment of the present invention. In another preferred embodiment, it is 0.10 to 1.00.

Sdq (root mean square slope) is 0.3 to 3.0 in a preferred embodiment of the present invention, and 0.4 to 2.0 in another preferred embodiment of the present invention. In a preferred embodiment of, it is 0.5 to 2.0.

The cross-sectional shape of the concave-convex concave portion in the depth direction is a wedge shape in which the opening width on the surface side is wide (maximum inner diameter portion) and the width is gradually narrowed in the depth direction (bottom direction), the opening on the surface side. It may include a pot-shaped portion having a narrow width and having a maximum inner diameter portion between the opening and the bottom. The maximum inner diameter portion is 1 to 500 μm in one preferred embodiment of the present invention, 2 to 300 μm in another preferred embodiment of the present invention, and 10 to 100 μm in yet another preferred embodiment of the present invention.

According to one embodiment of the present invention, the non-magnetic ceramic compact having a roughened structure on the surface has a planar shape of the recess when the irregularities are continuously formed linearly at intervals. May include an elliptical shape or a shape similar thereto. The term “the concavities and convexities are continuously formed linearly at intervals” means that the linear convex portions and the linear concave portions are alternately formed in a certain direction.

When the planar shape of the recess is similar to an ellipse, for example, the two opposing sides on the major axis side are curves (arcs) 1a, but the two opposing sides on the minor axis side are only straight lines 2. (FIGS. 1(a) and 1(b)), the two major sides facing each other are curved lines (arcs) 1a, while the two major sides facing each other are straight lines 2 and curved lines 1b. Shaped (FIGS. 2A and 2B), the two opposing sides on the major axis side are curves (arcs) 1a, but the straight lines 2 or the curved line 1b on the two opposing sides on the minor axis side are partially The curved parts (FIGS. 3A to 3D) are included.

According to one embodiment of the present invention, in the non-magnetic ceramic compact having a roughened structure on the surface, when the irregularities are dispersed and formed randomly, the planar shape of the recess is circular or elliptical. Alternatively, it may include a shape similar to them. At this time, the concave portions are formed dispersed in island shapes in the planar shape of the roughened structure, and the portions excluding the concave portions are convex portions. The concavities and convexities may be formed so that the concave portions are dispersed in an island shape at equal intervals, or the concave portions are dispersed in an island shape at different intervals.

When the plane shape of the recess is similar to a circle, for example, a shape having a portion (projection) 5 protruding so that part of the circumference is away from the center of the circle (FIG. 4). (A) and (b)), a shape in which a part of the circumference has a recessed portion (recessed portion) 6 in the circular center direction (FIGS. 4C and 4D), and The shapes are mixed (FIG. 4(e)). There may be a plurality of protrusions 5 and recesses 6, respectively.

When the planar shape of the recess is similar to an ellipse, for example, as shown in FIGS. 1 to 3, the two major sides facing each other are curves (arcs), but the minor axis facing each other. The two sides include a shape formed only of straight lines, a shape formed of straight lines and curves, and a shape in which the straight lines or curves of the two sides facing each other on the minor axis side are partially curved.

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

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

The shape, size, thickness, etc. of the oxide-based non-magnetic ceramic molded body used in the manufacturing method according to one embodiment of the present invention are not particularly limited and are selected according to the application, and if necessary. It is adjusted. For example, oxide-based non-magnetic ceramic compacts such as flat plates, round rods, square rods (polygonal rods in cross section), tubes, cup-shaped ones, cubes, cuboids, spheres or partial spheres (hemispheres), ellipses, etc. In addition to spheres or partially elliptical spheres (semi-ellipsoidal spheres, etc.) and irregular shaped bodies, existing non-magnetic ceramic products can also be used. The existing oxide-based non-magnetic ceramic products are made of only oxide-based non-magnetic ceramics, as well as oxide-based non-magnetic ceramics and other materials (metal, resin, rubber, glass, wood, etc.). It may consist of a complex.

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

According to another embodiment, when the surface of the oxide-based non-magnetic ceramic compact is continuously irradiated with laser light at a irradiation speed of 5,000 mm/sec or more using a continuous wave laser, the same result is obtained. Laser light is continuously irradiated so that a plurality of lines consisting of straight lines, curved lines and combinations thereof are formed in different directions or different directions, and the laser beam is continuously irradiated multiple times to form one straight line or one curved line. Can be formed.

According to another embodiment, when the surface of the oxide-based nonmagnetic ceramic compact is continuously irradiated with laser light at a irradiation speed of 5,000 mm/sec or more using a continuous wave laser, the same result is obtained. Continuously irradiating laser light so that a plurality of lines consisting of straight lines, curved lines and combinations thereof are formed in different directions or different directions, and the plurality of straight lines or the plurality of curved lines have equal intervals or different intervals. Laser light can be continuously irradiated so as to be formed in advance.

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

The laser output is 100 to 4,000 W in a preferred embodiment of the present invention, 200 to 2,000 W in another preferred embodiment of the present invention, and 300 to 1 in yet another preferred embodiment of the present invention. It is 1,000 W. Adjust the roughening condition by decreasing the laser light output when the laser light irradiation speed is slow within the above range and increasing it when the laser light irradiation speed is high within the above range. You can For example, when the output of the laser light is 100 W, the irradiation speed of the laser light is 5,000 to 7,500 mm/sec in a preferred embodiment of the present invention, and when the output of the laser light is 500 W, the In a preferred embodiment of the invention, the irradiation speed of laser light is 7,500 to 10,000 mm/sec.

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

Energy density during the laser beam irradiation, in a preferred embodiment of the present invention are 3~1,500MW / 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 calculated by the following formula: laser light output (W) and laser light (spot area (cm ² )(π·[spot diameter/2] ² ): laser light output/spot area) Desired.

The number of repetitions (passing number) during laser light irradiation is 1 to 50 times in a preferred embodiment of the present invention, 3 to 40 times in another preferred embodiment of the present invention, and 5 in still another preferred embodiment of the present invention. ~ 30 times. The number of repetitions of the laser light irradiation is the total number of times the laser light is irradiated to form one line (groove) when the laser light is linearly irradiated.

When repeatedly irradiating one line, bidirectional irradiation or unidirectional irradiation can be selected. When forming one line (groove), bidirectional radiation is from the second end to the first end after irradiating a continuous wave laser from the first end to the second end of the line (groove). This is a method of irradiating with a continuous wave laser, and thereafter repeatedly irradiating with a continuous wave laser from the first end to the second end and from the second end to the first end. Unidirectional irradiation is a method of repeating unidirectional continuous wave laser irradiation from the first end to the second end. When bidirectional radiation or unidirectional irradiation is performed, the planar shape of the concave portion of the roughened structure portion becomes a shape as shown in FIGS. 1 to 3, for example.

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

When irradiating with laser light, after bidirectional irradiation or unidirectional irradiation at a line interval described above to form a plurality of grooves, and further from the direction orthogonal or oblique to the plurality of grooves, the above line It is also possible to carry out bi-directional irradiation or cross-irradiation with one direction irradiation at intervals. When cross irradiation is performed, the planar shape of the concave portion of the roughened structure portion becomes a shape as shown in FIG. 4, for example.

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

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

<Second Method for Producing Oxide-Based Non-Magnetic Ceramics Compact Having Roughened Structure on Surface>
According to one embodiment of the present invention, a second method for producing an oxide-based non-magnetic ceramic compact having a roughened structure on the surface is different from the above-mentioned first method in that the irradiation form of laser light is different. Except for the difference, it is the same method.

The second manufacturing method is similar to the first manufacturing method in that the surface of the oxide-based non-magnetic ceramic molded body is irradiated with laser light at a irradiation speed of 5,000 mm/sec or more using a continuous wave laser. In the process of continuously irradiating the surface of the oxide-based non-magnetic ceramics compact, the surface of the oxide-based non-magnetic ceramics is irradiated with laser light so that the laser light irradiation part and the non-irradiation part are alternately generated. Has a step of

In the second manufacturing method, when the laser light is irradiated so as to form a straight line, a curved line, or a combination of a straight line and a curved line, irradiation is performed so that the laser light irradiation portion and the non-irradiation portion occur alternately. Irradiating so that the irradiated portion and the non-irradiated portion of the laser light are alternately generated includes an embodiment in which the irradiation is performed as shown in FIG. In FIG. 5, laser light non-irradiated portions 12 of length L2 between the laser light irradiated portions 11 of length L1 and adjacent laser light irradiated portions 11 of length L1 are alternately generated, and as a whole. It shows a state in which irradiation is performed so as to form a dotted line. The dotted line includes chain lines such as a one-dot chain line and a two-dot chain line.

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

When the oxide-based nonmagnetic ceramic compact is continuously irradiated with laser light, the compact having a small thickness may be deformed such as cracked. However, when the laser irradiation is performed in a dotted line as shown in FIG. 5, the laser light irradiation portion 11 and the laser light non-irradiation portion 12 are alternately generated. Therefore, when the laser light irradiation is continued, Even a small molded body is less likely to be deformed such as cracked. At this time, the same effect can be obtained even when the laser light irradiation portion is different (the laser light irradiation portion is shifted) as described above.

The irradiation method of the laser light is, for example, a method of irradiating the surface of the metal molded body 20 in one direction as shown in FIG. 6A or bidirectional irradiation as shown by a dotted line in FIG. 6B. Can be used. Alternatively, a method of irradiating the laser beam so that the dotted line irradiation portions intersect may be used. The distance b1 between the dotted lines after irradiation can be adjusted according to the irradiation target area of the metal molded body, but can be set in the same range as the line distance in the first manufacturing method.

The length (L1) of the laser light irradiation part 11 and the length (L2) of the laser light non-irradiation part 12 shown in FIG. 5 are adjusted to be in the range of L1/L2=1/9 to 9/1. can do. In order to roughen a complicated porous structure, the length (L1) of the laser light irradiation portion 11 is 0.05 mm or more in a preferred embodiment of the present invention, and in another preferred embodiment of the present invention. It is 0.1 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 above-mentioned laser light irradiation step includes a fiber laser device in which a direct modulation type modulation device for directly converting a driving current of a laser is connected to a laser power source. Is used to adjust the duty ratio and perform laser irradiation.

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

The Gate signal is periodically output from the Galvano controller ON/OFF, and the laser light oscillated by the laser oscillator is turned ON/OFF by the ON/OFF signal to pulse the laser light without changing its energy density. be able to. As a result, as shown in FIG. 5, the laser light non-irradiated portions 11 between the laser light irradiated portions 11 and the adjacent laser light irradiated portions 11 are alternately formed so that they are formed in a dotted line shape as a whole. Can be irradiated with laser light. The method of operating the galvanometer mirror to generate pulses is simple in operation because the duty ratio can be adjusted without changing the laser light oscillation state itself.

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

The duty ratio is a ratio obtained from the ON time and the OFF time of the output of the laser light by the following formula.
Duty ratio (%)=ON time/(ON time+OFF time)×100
Since the duty ratio corresponds to L1 and L2 (that is, L1/[L1+L2]) shown in FIG. 5, it can be selected from the range of 10 to 90%, for example. By adjusting the duty ratio and irradiating the laser light, it is possible to irradiate in a dotted line as shown in FIG.

<Third production method of oxide-based non-magnetic ceramic compact having roughened 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.

A roughened structure can be formed on the surface by adjusting the following requirements (i) to (v) when the pulse wave laser light is irradiated. The method of irradiating the pulse wave laser light is not limited to the method of irradiating the ordinary pulse wave laser light, and, for example, Japanese Patent No. 5848104, Japanese Patent No. 578836, Japanese Patent No. 5798534, Japanese Patent No. 5798535, It can be carried out in the same manner as the irradiation method of the pulsed laser light described in 2016-203643, JP 5889775, JP 5932700, or JP 6055529.

<Requirement (i) Irradiation angle when irradiating a laser beam on an oxide-based non-magnetic ceramic compact>
The surface of the oxide-based non-magnetic ceramic compact is irradiated with laser light at an angle of 15 to 90 degrees in a preferred embodiment of the present invention, and at an angle of 45 to 90 degrees in another preferred embodiment of the present invention. ..

<Requirement (ii) Irradiation speed when irradiating a laser beam on an oxide-based nonmagnetic ceramic compact>
The irradiation speed of the laser light is 10 to 1,000 mm/sec in one preferred embodiment of the present invention, 10 to 500 mm/sec in another preferred embodiment of the present invention, and 10 in another preferred embodiment of the present invention. -100 mm/sec, and in yet another preferred embodiment of the present invention, 10-80 mm/sec.

<(iii) Energy Density when Irradiating Laser Light on the Oxide-based Nonmagnetic Ceramic Molding>
The energy density at the time of laser light irradiation is obtained from the energy output (W) of one pulse of laser light and the laser light (spot area (cm ² ) (π·[spot diameter/2] ² ). The energy density during irradiation is 0.1 to 50 GW/cm ² in a preferred embodiment of the present invention, and 0.1 to 20 GW/cm ² in another preferred embodiment of the present invention, and another preferred embodiment of the present invention. In one aspect, 0.5-10 GW/cm ² , and in yet another preferred aspect of the present invention, 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, and another preferred embodiment of the present invention. It is 5 to 100 W in one aspect, and 10 to 100 W in yet another preferable aspect of the present invention. If the other laser light irradiation conditions 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 1000 kHz in a preferred embodiment of the present invention, 0.01 to 500 kHz in another preferred embodiment of the present invention, and is 0.0 in another preferred embodiment of the present invention. 1 to 100 kHz. The pulse width (nsec) is 1 to 10,000 nsec in one 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 a 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 to 80 μm.

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

<(v) Line spacing when irradiating a laser beam on an oxide-based nonmagnetic ceramic compact>
When irradiating the oxide-based non-magnetic ceramic molded body with a laser beam in a line shape, by widening or narrowing the interval between adjacent lines, the size of the hole, the shape of the hole, The depth of the holes can be adjusted. The pulsed laser light irradiates a point and connects the points to form a line.

The line interval 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 0.5 mm in another preferred embodiment of the present invention, and in the preferred embodiment of the present invention is 0. It is 03 to 0.3 mm, and in yet another preferred embodiment of the present invention, it is 0.05 to 0.1 mm. If the line spacing is narrow, the adjacent lines also have a thermal effect, so the holes tend to be large, the shape of the holes becomes complicated, and the depth of the holes tends to be deep, but the thermal effect becomes too large. Therefore, it may be difficult to form a complicated deep hole. If the line spacing is wide, the holes are small, the shape of the holes is not complicated, and the holes do not tend to be too deep, but the processing speed can be increased.

Other irradiation conditions may include an irradiation mode in which the oxide-based non-magnetic ceramic compact is irradiated with laser light while radiating heat from the compact. For example, a method of irradiating a laser beam in a state where an oxide-based nonmagnetic ceramics compact and a metal compact having a higher thermal conductivity than the oxide-based nonmagnetic ceramics compact are in contact with each other, A method of irradiating with laser light in a state of being kept hollow can be mentioned. In addition, the wavelength of the pulse wave laser light may be 500 to 11,000 nm.

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

(1) Method for manufacturing composite molded body of oxide-based non-magnetic ceramic molded body having roughened structure and resin molded body In the first step, the above-mentioned first manufacturing method, second manufacturing method or 3 produces a non-magnetic ceramic compact having a roughened structure on its surface.

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

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

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

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

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

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

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

(2-1) Method for manufacturing composite molded body of oxide-based non-magnetic ceramic molded body having roughened structure and rubber molded body In the first step, the first manufacturing method, the second manufacturing method or the According to the manufacturing method of No. 3, a nonmagnetic ceramic compact having a roughened structure on the surface is manufactured. In the second step, the oxide-based nonmagnetic ceramics molded body obtained in the first step and the rubber molded body are integrated by applying a known molding method such as press molding or transfer molding.

When applying the press molding method, for example, a portion including a roughened structure of an oxide-based non-magnetic ceramics molded body is placed in a mold, and a portion including the roughened structure is heated. After pressing the uncured rubber to be the rubber molded body under pressure, it is taken out after cooling. When the transfer molding method is applied, for example, a portion including a roughened structure of an oxide-based non-magnetic ceramics molded body is placed in a mold, and uncured rubber is injection molded into the mold, and then, Then, by heating and pressurizing, the portion containing the roughened structure of the oxide-based non-magnetic ceramic molded body and the rubber molded body are integrated, and taken out after cooling.

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

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

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

(2-2) Method for producing composite molded body (including adhesive layer) of oxide-based non-magnetic ceramic molded body having roughened structure and rubber molded body According to one embodiment, an oxide-based system In the method for producing a composite molded body of the non-magnetic ceramic molded body and the rubber molded body, the adhesive layer can be interposed on the joint surface between the oxide-based non-magnetic ceramic molded body and the rubber molded body.

In the first step, the oxide-based non-magnetic ceramic compact is roughened by the first, second or third manufacturing method using a continuous wave laser or a pulse wave laser as in the above method. .. In the second step, an adhesive (adhesive solution) is applied to the surface of the roughened structure of the oxide-based non-magnetic ceramic compact to form an adhesive layer. At this time, the adhesive may be press-fitted. By applying the adhesive, the adhesive can be present on the roughened structure surface of the non-magnetic ceramic and the internal holes.

The adhesive is not particularly limited, and a known thermoplastic adhesive, thermosetting adhesive, rubber adhesive or the like can be used. Examples of the thermoplastic adhesive include polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic adhesive, polyethylene, chlorinated polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene. -Ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ionomer, chlorinated polypropylene, polystyrene, polyvinyl chloride, plastisol, vinyl chloride-vinyl acetate copolymer, polyvinyl ether, polyvinylpyrrolidone, polyamide, nylon, saturated no Mention may be made of regular polyesters and cellulose derivatives.

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

In the example of this manufacturing method, in the third step, in the step of adhering the separately molded rubber molded body to the surface of the oxide-based non-magnetic ceramic molded body having the adhesive layer formed in the previous step, or in the previous step The part including the surface of the oxide-based non-magnetic ceramic molded body on which the adhesive layer is formed is placed in the mold, and the surface of the oxide-based non-magnetic ceramic molded body and the uncured rubber to be the rubber molded body are separated. The step of heating and pressurizing in the contacted state to integrate them is carried out. In the case of this step, in order to mainly remove the residual monomer, it is possible to add a step of further secondary heating (secondary curing) in an oven or the like after taking out from the mold.

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

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

(3-2) Method for manufacturing composite molded body (having adhesive layer) of oxide-based non-magnetic ceramic molded body and metal molded body having roughened structure The first step and the second step are the same as those described above. (2-2) Manufacturing method of composite molded body (including adhesive layer) of oxide-based nonmagnetic ceramics molded body having roughened structure and rubber molded body”, and the adhesive layer To produce an oxide-based non-magnetic ceramic compact having

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

(4) Method for manufacturing composite molded body of oxide-based non-magnetic ceramic molded body having surface-roughened structure and UV curable resin molded body In the first step, the above-described first manufacturing method and second manufacturing method are used. By the method or the third manufacturing method, an oxide-based nonmagnetic ceramic compact having a roughened structure on the surface is manufactured.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the next step, the monomer, oligomer, or mixture thereof contacted with the portion including the roughened portion of the oxide-based non-magnetic ceramic molded body is irradiated with UV to be cured to form a curable resin layer. It is possible to obtain a composite molded article having the above.

(5) Oxide-based nonmagnetic ceramics compact having a roughened structure, or a composite non-magnetic ceramics compact having a roughened structure, and a different type of nonmagnetic ceramics compact The method for producing a composite molded body of, for example, the composite molded body of the oxide-based non-magnetic ceramics molded body having a roughened structure, for example, of the oxide-based non-magnetic ceramics molded body having a roughened structure of different shape It can be manufactured by using a plurality of members and integrating them through an adhesive layer formed on their bonding surfaces. The adhesive layer can be formed by applying an adhesive to the roughened structure portion of the oxide-based non-magnetic ceramic compact. As the adhesive, the same one as used in the production of the other composite molded body described above can be used.

Furthermore, a composite molded body composed of a non-magnetic ceramic molded body of a different type from the oxide-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 an oxide-based non-magnetic ceramic molded body to bond and integrate it with a non-magnetic ceramic molded body of a different type, a non-magnetic ceramic molded body of a different type. The surface of the magnetic ceramic compact is also roughened to form the adhesive layer, and then the adhesive layer of the non-magnetic ceramic compact of a different type from the surface having the adhesive layer of the oxide-based nonmagnetic ceramic compact It is possible to manufacture a composite molded body by integrally joining the surfaces having the above.

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

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

<Thermal shock temperature (JIS R1648:2002)>
The thermal shock temperature is the temperature at which a test piece (4×35×thickness 3 mm) of a heated oxide-based nonmagnetic ceramic compact 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 it is rapidly cooled exceeds the strength of the test piece.

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

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

Sa (arithmetic mean height): Sa within a range of 9×1.8 mm on the surface of the roughened structure portion of the oxide-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 oxide-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): This is 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 zero. If the surface has an inclination, Sdq becomes large. For example, Sdq becomes 1 on a plane having an inclination component of 45°. It was measured by a one-shot 3D shape measuring machine (manufactured by KEYENCE).

Examples 1-7, Comparative Examples 1-2
The surface of a non-magnetic ceramics compact (10×50×2 mm thick flat plate) of the type shown in Table 1 is continuously irradiated with laser light under the conditions shown in Table 1 using the following continuous wave laser device. And roughened. In Table 1, alumina 92 has a purity of 92%, and alumina 99 has a purity of 99.5%.
(Laser device)
Oscillator: IPG-Yb fiber; YLR-300-SM
Galvano Mirror SQUIREEL (made by ARGES)
Focusing system: fc=80mm/fθ=100mm

The cross irradiation and the bidirectional irradiation were performed as follows.
Cross (cross irradiation): After irradiating continuous wave laser light so that ten grooves (grooves of the first group) are formed at intervals of 0.05 mm, then in a direction orthogonal to the grooves of the first group. Irradiation with continuous wave laser light was performed so that 10 grooves (grooves of the second group) were formed at intervals of 0.05 mm.

Bi-directional irradiation: Continuous wave laser light is linearly irradiated so that one groove is formed in one direction, and then continuous wave laser light is also linearly irradiated in the opposite direction with an interval of 0.05 mm. The irradiation was repeated.

The interval of 0.05 mm between the cross irradiation and the bidirectional irradiation is the distance between the intermediate positions of the widths of the adjacent grooves (lines).

7 to 14 show SEM photographs of portions of the oxide-based nonmagnetic ceramic compacts of Examples 1 to 7 and Comparative Example 2 having a roughened structure. The SEM photograph was taken at a magnification of 200 times, but is not limited to 200 times, and may be adjusted to a magnification at which the roughened structure can be easily observed. For example, the SEM photograph can be taken at a magnification of 200 to 400 times.

Using the oxide-based non-magnetic ceramic molded bodies having the roughened structure obtained in Examples 1 to 7 and Comparative Examples 1 to 2, resin molded bodies (of polyamide 6 containing 30% by mass of glass fiber) were used. A composite molded body (FIG. 15) with the molded body 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 (test piece conforming to ISO19095-2:2015) shown in FIG. 15, a tensile test was performed under the following conditions to evaluate the shear bond strength (S1). The results are shown in Table 1. The tensile test is based on ISO19095, and the end of the oxide-based nonmagnetic ceramic molded body 30 side is fixed until the oxide-based nonmagnetic ceramic molded body 30 and the resin molded body 31 are broken. The maximum load until the joint surface was broken when pulled in the X direction shown in was measured. The results are shown in Table 1.

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

The unevenness of the roughened structure in the zirconia molded body, the alumina molded body, the steatite molded body, and the cordierite molded body of Examples 1 to 7 was SEM photographs (planar photographs) of FIGS. 7 to 11, FIG. 13, and FIG. It was clear from the cross-sectional photograph) that the cross-sectional shape of the uneven portion in the thickness direction includes a curved surface (partial circle) shape.

The planar shapes of the recesses of Example 1 (FIG. 7), Example 2 (FIG. 8), Example 4 (FIG. 10), and Example 6 (FIG. 13) are as shown in FIGS. 1 to 3. It was The planar shapes of the recesses of Example 3 (FIG. 9) and Example 5 (FIG. 11) are those shown in FIGS. 4A to 4E, and those and FIGS. 1 to 3. It was a combination of such shapes. The planar shape of the recess of Example 7 (FIG. 14) was the shape shown in FIGS. 4(a) to 4(e).

In Comparative Example 1 in which the irradiation speed of the laser light was slow, a crack was generated in a part of the molded body and was divided into two or more. In Comparative Example 2, the hole was not opened and the surface was deformed in a wrinkle shape.

Since the zirconia molded body, the alumina molded body, the steatite molded body, and the composite molded body of the cordierite molded body and the resin molded body of Examples 1 to 7 had high bonding strength, other materials (heat It is considered that even when a composite molded body with a curable resin, rubber, elastomer, metal, or UV curable resin) is manufactured, a composite molded body with high bonding strength can be obtained.

Example 8
The surface of a non-magnetic ceramic compact (10×50×a flat plate having a thickness of 2 mm) of the type shown in Table 2 was irradiated with pulse wave laser light under the conditions shown in Table 2 to roughen the surface. FIG. 16 shows an SEM photograph after roughening.

As is clear from the comparison of the SEM photographs of FIG. 16 (Example 8), FIG. 7 (Example 1), FIG. 10 (Example 4), and FIG. 13 (Example 6), the nonmagnetic ceramic molded body of Example 8 The structure after roughening was similar to that of the other examples.

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

1a: Curve (arc)
1b: curved line 2: straight line 5: protruding part 6: recessed part

Claims (13)

A composite compact comprising an oxide-based non-magnetic ceramic compact having a roughened structure on the surface and a compact of another material,
The surface-roughened structure of the oxide-based non-magnetic ceramics molded body having a surface-roughened structure has unevenness, and the cross-sectional shape in the thickness direction of the unevenness has a curved surface,
The surface roughness (Ra) of the irregularities is in the range of 1 to 30 μm, and the height difference (Rz) between the convex and concave portions of the irregularities is in the range of 10 to 200 μm.
The molded body of the other material is a molded body selected from a thermoplastic resin molded body, a thermosetting resin molded body, a thermoplastic elastomer molded body, a rubber molded body, a metal molded body, and a UV curable resin molded body,
The composite molded body is one in which a portion having a roughened structure of an oxide-based non-magnetic ceramic molded body having a roughened structure on the surface and a molded body of another material are contacted and integrated. Composite molded body. A composite compact comprising an oxide-based non-magnetic ceramic compact having a roughened structure on the surface and a compact of another material,
The surface-roughened structure of the oxide-based non-magnetic ceramics molded body having a surface-roughened structure has unevenness, and the cross-sectional shape in the thickness direction of the unevenness has a curved surface,
The surface roughness (Ra) of the irregularities is in the range of 1 to 30 μm, and the height difference (Rz) between the convex and concave portions of the irregularities is in the range of 10 to 200 μm.
The molded body of the other material is a molded body selected from a rubber molded body, a metal molded body, a carbide-based nonmagnetic ceramics molded body, and a nonmagnetic ceramics molded body of a different type from the carbide-based nonmagnetic ceramics,
In the composite molded body, a portion having a roughened structure of an oxide-based non-magnetic ceramic molded body having a roughened structure on the surface and a molded body of another material are integrated via an adhesive layer. It is a composite molded article. A composite compact comprising an oxide-based non-magnetic ceramic compact having a roughened structure on the surface and a compact of another material,
The surface-roughened structure of the oxide-based non-magnetic ceramics molded body having a surface-roughened structure has unevenness, and the cross-sectional shape in the thickness direction of the unevenness has a curved surface,
The surface roughness (Ra) of the irregularities is in the range of 1 to 30 μm, and the height difference (Rz) between the convex and concave portions of the irregularities is in the range of 10 to 200 μm.
The molded body of the other material is a molded body selected from a thermoplastic resin molded body, a thermosetting resin molded body, a thermoplastic elastomer molded body, a rubber molded body, a metal molded body, and a UV curable resin molded body,
The composite molded body is one in which a portion having a roughened structure of an oxide-based non-magnetic ceramics molded body having a roughened structure on the surface and a molded body of another material are contacted and integrated. Composite molded body. A composite compact comprising an oxide-based non-magnetic ceramic compact having a roughened structure on the surface and a compact of another material,
The surface-roughened structure of the oxide-based non-magnetic ceramics molded body having a surface-roughened structure has unevenness, and the cross-sectional shape in the thickness direction of the unevenness has a curved surface,
The surface roughness (Ra) of the irregularities is in the range of 1 to 30 μm, and the height difference (Rz) between the convex and concave portions of the irregularities is in the range of 10 to 200 μm.
The molded body of the other material is a molded body selected from a rubber molded body, a metal molded body, an oxide-based non-magnetic ceramic molded body, and a non-magnetic ceramic molded body of a type different from the carbide-based non-magnetic ceramic molded body. ,
In the composite molded body, a portion having a roughened structure of an oxide-based non-magnetic ceramic molded body having a roughened structure on the surface and a molded body of another material are integrated via an adhesive layer. It is a composite molded article. The oxide-based non-magnetic ceramic compact having a roughened structure on the surface has a thickness of 0.5 mm or more and a thermal shock temperature (JIS R1648:2002) in the range of 150 to 700° C. The composite molded body according to any one of claims 1 to 4. The composite molded body according to claim 5, wherein the oxide-based nonmagnetic ceramic molded body having a roughened structure on its surface contains alumina. The oxide-based non-magnetic ceramic molded body having a roughened structure on the surface has a thickness of 0.5 mm or more and a thermal shock temperature (JIS R1648:2002) in the range of 1 to 10° C. The composite molded body according to any one of claims 1 to 4. The composite molded body according to claim 7, wherein the oxide-based non-magnetic ceramic having a roughened structure on the surface contains zirconia. 9. The composite according to claim 1, wherein a cross-sectional shape of the unevenness of the oxide-based non-magnetic ceramic having a roughened structure on the surface in the thickness direction is a partial circular shape or a partial elliptical shape. Molded body. The arithmetic mean height (Sa) of the irregularities of the oxide-based non-magnetic ceramic having a roughened structure on the surface is in the range of 1 to 50 μm, and the maximum height (Sz) of the convex portions of the irregularities is 30 to The composite molded body according to any one of claims 1 to 9, which has a range of 280 µm and a developed area ratio (Sdr) of the interface of the irregularities of 0.05 to 2.00. 10. The root mean square slope (Sdq) of the irregularities of the oxide-based non-magnetic ceramic having a roughened structure on the surface is in the range of 0.3 to 3.0. Composite molded body. When the irregularities of the oxide-based non-magnetic ceramics having a roughened structure are continuously formed linearly at intervals, the concave shape may include an elliptical shape or a shape similar thereto. The composite molded body according to any one of claims 1 to 11, wherein When irregularities of oxide-based non-magnetic ceramics having a roughened structure are dispersed and formed randomly on the surface, the planar shape of the concave portion includes a circular shape, an elliptical shape, or a shape similar thereto. The composite molded article according to any one of claims 1 to 11.