WO2020067248A1 - Nitride-based nonmagnetic ceramic molding having roughened structure on the surface thereof, and method for producing same - Google Patents

Abstract

Provided is a nitride-based nonmagnetic ceramic molding having a roughened structure on the surface thereof, wherein the roughened structure has recesses and protrusions, and when viewed using a scanning electron microscope photograph (at a magnification of least 200x), the cross-sectional shape of the recesses and protrusions in the thickness direction is curved, and the curve of the protrusions is a wrinkle-shaped protrusion formed along the length direction, or the curve of the protrusions has a plurality of independent holes formed in a line along the length direction.

Description

Carbide-based non-magnetic ceramics molded body having surface roughened structure and method for producing the same

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

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

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

WO2011 / 121808 @ A1 includes a base made of metal or ceramic, an impregnated layer provided by forming a concave portion on the sliding side surface of the base, and an impregnated layer impregnated with the base. A resin layer covering a surface of the material on the sliding side, wherein the recess is formed by machining (claims). It is described that the concave portion is a plurality of linear grooves, and the maximum depth of the grooves is 200 to 2,000 μm (paragraph number 0026).

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

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

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

Japanese Patent Application Laid-Open No. 2003-171190 discloses that the surface of a substrate made of dense ceramic having a purity of 95% or more is formed with first rounded irregularities having a surface roughness Ra of 3 to 40 μm, and the first There is disclosed a ceramic member in which the surface of the unevenness is formed as a second rounded unevenness having a surface roughness Ra of 0.1 to 2.9 μm. It is shown that the second unevenness covers the entire surface of the first unevenness.

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

Japanese Patent Nos. 5,774,246 and 5,701,414 disclose an invention in which a continuous wave laser is used to continuously irradiate a laser beam at an irradiation speed of 2,000 mm / sec or more to roughen the surface of a metal molded body. Discloses a method of manufacturing a composite molded article of a metal molded article and a resin molded article, but does not disclose ceramics.

One aspect of the present invention is to provide a non-magnetic ceramic molded body having a roughened structure on its surface and a method for producing the same.

The present invention, in one embodiment thereof, is a non-magnetic ceramic molded body having a surface roughened structure,
The roughened structure has irregularities, and the cross-sectional shape in the thickness direction of the irregularities is a curved surface when observed by a scanning electron microscope photograph (200 times or more), and the curved surface of the convex portion has a length. Wrinkle-like projections formed along the direction, or the curved surface of the convex portion has a plurality of independent holes formed linearly along the length direction,
Provided is a non-magnetic ceramic molded body having a roughened structure on its surface, wherein the non-magnetic ceramic molded body is a carbide-based non-magnetic ceramic molded body. In another embodiment, the present invention provides a method for producing such a nonmagnetic ceramic molded body.

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

According to the manufacturing method according to the embodiment of the present invention, the surface of the originally hard and brittle carbide-based nonmagnetic ceramic molded body can be roughened without being separated into two or more by cracking.

The figure which shows the irradiation state of the laser beam of one Embodiment when implementing the 2nd manufacturing method by one example of this invention. It is a figure which shows the irradiation pattern of the laser beam when implementing the 2nd manufacturing method by one example of this invention, (a) is an irradiation pattern of the same direction, (b) is a bidirectional irradiation pattern. (A) is an SEM photograph (magnification: 200) of the roughened structure portion (plan view) of the silicon carbide molded body of Example 1, and (b) is a cross-sectional SEM photograph (magnification: 200) of (a) in the thickness direction. is there. 5 is an SEM photograph (magnification: 200) of a roughened structure portion (plan view) of the silicon carbide / aluminum molded product of Example 2. 4 is an SEM photograph (magnification: 200) of a roughened structure portion (plan view) of the silicon carbide / silicon molded product of Example 3. 5 is an SEM photograph (magnification: 200) of a roughened structure portion (plan view) of the silicon carbide molded body of Comparative Example 1. FIG. 3 is a perspective view of a carbide-based ceramics molded body manufactured in the example, and a perspective view for describing a test of bonding strength using a composite molded body of a carbide-based ceramics molded body and a resin molded body.

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

(4) The silicon carbide may be composed of a composite of silicon carbide and other non-magnetic ceramics, metals, and metalloids, as long as it is within a range satisfying a predetermined thermal shock temperature, in addition to being composed of silicon carbide alone. The composite of silicon carbide and a metal may be a porous silicon carbide molded body in which a metal (for example, aluminum) or a metalloid (for example, silicon) is impregnated in the porous interior. The content ratio of silicon carbide in the composite is 50% by mass or more in a preferred embodiment of the present invention, 60% by mass or more in another preferred embodiment of the present invention, and 70% by mass in another preferred embodiment of the present invention. % By mass or more.

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

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

According to some embodiments of the present invention, the non-magnetic ceramic molded body having a roughened structure on its surface has a roughened structure having irregularities, and a scanning electron micrograph (200 times or more). The cross-sectional shape in the thickness direction of the unevenness has a curved surface when observed by (1).

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

The non-magnetic ceramic molded body having a roughened structure on its surface according to the present invention may be one in which the irregularities are formed by alternately forming linear projections and linear depressions, and the projections have a curved surface. May be formed, or a plurality of independent holes in which a curved surface of the convex portion is linearly formed along the length direction.

に よ According to one example, the wrinkle-shaped protrusion is a portion slightly protruding outward from a surface having no wrinkle-shaped protrusion. The wrinkle-like projection may be formed continuously in the length direction, for example, but may have a discontinuous portion. According to one example, the plurality of independent holes formed linearly has a form in which many independent holes are linearly arranged. The wrinkle-like projections and / or the plurality of linearly formed independent holes have a width of 1 to 10 μm when the width of each of the linear protrusions and the linear recesses is 20 to 100 μm. May be something.

When the surface (curved surface) of the convex portion is formed with a plurality of wrinkled protrusions and / or a plurality of independent holes formed linearly along the length direction and the surface area is increased, for example, non-magnetic ceramics When joining the molded body and another member (for example, a resin molded body), it is considered that the joining area is increased and the joining strength is increased.

In some examples of the non-magnetic ceramic molded body having a roughened structure on the surface according to the present invention, the recesses of the unevenness of the roughened structure are formed in an island shape and are formed by removing the recesses. Is a convex portion, and the convex portion has a plurality of independent holes in which wrinkle-like protrusions along the length direction and / or curved surfaces of the convex portions are linearly formed along the length direction. Is formed.

に よ According to one example, the wrinkle-shaped protrusion is a portion slightly protruding outward from a surface having no wrinkle-shaped protrusion. The wrinkle-like projection may be formed continuously in the length direction, for example, but may have a discontinuous portion. According to one example, the plurality of independent holes formed linearly has a form in which many independent holes are linearly arranged. The wrinkle-like projections and / or the plurality of linearly formed independent holes have a width of 1 to 10 μm when the width of each of the linear protrusions and the linear recesses is 20 to 100 μm. May be something.

In this manner, a plurality of independent holes are formed on the surface (curved surface) of the convex portion along the length direction and / or a plurality of independent holes in which the curved surface of the convex portion is linearly formed along the length direction. If, for example, the non-magnetic ceramic molded body and another member (for example, a resin molded body) are joined together, it is considered that the joining area is increased and the joining strength is increased.

According to some examples of the nonmagnetic ceramic molded body of the present invention, the surface roughness (Ra) of the unevenness is in a range of 2 to 100 μm in a preferred embodiment of the present invention, and another preferred embodiment of the present invention. In another preferred embodiment of the present invention, the thickness is in the range of 5 to 80 μm.

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

Further, according to some examples of the non-magnetic ceramic molded body of the present invention, Sa (arithmetic average height), Sz (maximum height), and Str (surface texture) of the roughened structure portion (irregularities). Aspect ratio) may be in the following range.

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

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

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

The surface roughness (Ra) of the projections of the irregularities is in the range of 1 to 10 μm in a preferred embodiment of the present invention, and is in the range of 1.5 to 8 μm in another preferred embodiment of the present invention. In still another preferred embodiment, the thickness is in the range of 2 to 8 μm.

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

In this case, Sa (arithmetic average height), Sz (maximum height), and Str (surface aspect ratio) of the roughened structure portion (irregularities) may be in the following ranges.

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

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

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

According to one embodiment of the present invention, the non-magnetic ceramic molded body can be used as a carrier capable of holding a liquid, a powder, and the like on the roughened structure portion, and can be made of another material (a carbide-based non-magnetic material). It can also be used as a production intermediate for producing a composite molded body with a molded body made of a material excluding magnetic ceramics).

<First Production Method of Carbide-based Non-magnetic Ceramics Molded Body Having Roughened Structure on Surface>
Next, a first method for producing a carbide-based nonmagnetic ceramic molded body having a roughened structure on the surface according to one embodiment of the present invention will be described. The non-magnetic ceramic molded body according to one embodiment of the present invention is characterized in that the surface of the carbide-based non-magnetic ceramic molded body is continuously irradiated with a laser beam at an irradiation speed of 5,000 mm / sec or more using a continuous wave laser. It can be manufactured by irradiation.

The shape, size, thickness, and the like of the carbide-based nonmagnetic ceramic molded body used in the production method according to one embodiment of the present invention are not particularly limited, and are selected according to the application and adjusted as necessary. Is what is done. For example, carbide-based non-magnetic ceramic molded bodies include flat plates, round bars, square bars (bars with a polygonal cross section), tubes, cups, cubes, cuboids, spheres or partial spheres (such as hemispheres), and elliptical spheres Alternatively, in addition to a molded article having a partially elliptical sphere (such as a semi-elliptical sphere) or an irregular shape, an existing nonmagnetic ceramic product can be used. The existing carbide-based non-magnetic ceramics products include, in addition to those composed of only carbide-based non-magnetic ceramics, composites of carbide-based non-magnetic ceramics and other materials (metal, resin, rubber, glass, wood, etc.). It may be.

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

According to another embodiment, when continuously irradiating the surface of the carbide-based nonmagnetic ceramic molded body with a continuous wave laser at an irradiation speed of 5,000 mm / sec or more, the laser beam is irradiated in the same direction. Alternatively, continuously irradiate laser light so as to form a plurality of lines composed of straight lines, curves and combinations thereof in different directions, and form one straight line or one curved line by continuously irradiating laser light a plurality of times. can do.

According to still another embodiment, when continuously irradiating the surface of the carbide-based nonmagnetic ceramic molded body with a continuous wave laser at an irradiation speed of 5,000 mm / sec or more, the laser beam is irradiated in the same direction. Alternatively, a laser beam is continuously irradiated so that a plurality of lines composed of straight lines, curves and combinations thereof are formed in different directions, and the plurality of straight lines or the plurality of curves are spaced at equal intervals or different intervals. Laser light can be continuously applied so as to be formed.

The irradiation speed of the laser beam may be 5,000 mm / sec or more in order to roughen the carbide-based nonmagnetic ceramic molded body. In a preferred embodiment of the present invention, the irradiation speed is 5,000 to 20,000 mm / sec. Yes, in another preferred embodiment of the present invention, it is 5,000 to 10,000 mm / sec. If the irradiation speed of the laser beam is less than 5,000 mm / sec, it is difficult to form a roughened structure on the surface of the non-magnetic ceramic molded body.

The power of the laser is 50 to 4,000 W in a preferred embodiment of the present invention, 100 to 2,000 W in another preferred embodiment of the present invention, and 100 to 2,000 W in still another preferred embodiment of the present invention. 5,000W. Adjust the surface roughening state by decreasing the laser light output when the laser light irradiation speed is low within the above range and increasing it when the laser light irradiation speed is high within the above range. Can be. For example, when the output of the laser beam is 100 W, in one preferred embodiment of the present invention, the irradiation speed of the laser beam is 5,000 to 7,500 mm / sec. In a preferred embodiment of the present invention, the irradiation speed of the laser beam may be 7,500 to 10,000 mm / sec.

ス ポ ッ ト The spot diameter of the laser beam is 10 to 100 μm in one preferred embodiment of the present invention, and 10 to 75 μm in another preferred embodiment of the present invention.

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

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

双方 向 When irradiating one line repeatedly, bidirectional irradiation and unidirectional irradiation can be selected. When forming one line (groove), bidirectional radiation irradiates a continuous wave laser from the first end to the second end of the line (groove) and then from the second end to the first end. A method of irradiating a continuous wave laser and thereafter repeatedly irradiating a continuous wave laser from a first end to a second end and from a second end to a first end. One-way irradiation is a method of repeating one-way continuous-wave laser irradiation from a first end to a second end.

When irradiating the laser beam linearly, the interval (line interval or pitch interval) between the intermediate positions of the widths of the adjacent irradiation lines (grooves formed by the adjacent irradiation) is set to 0.1 in a preferred embodiment of the present invention. 03 to 1.0 mm, and in another preferred embodiment of the present invention it is 0.03 to 0.2 mm. The line intervals may be the same or different.

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

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

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

<Second method for producing carbide-based non-magnetic ceramic molded body having a roughened surface structure>
According to one embodiment of the present invention, the second method for producing a carbide-based nonmagnetic ceramic molded body having a roughened structure on the surface is different from the above-mentioned first method in the irradiation form of laser light. Others are the same.

In the second manufacturing method, a laser beam is applied to the surface of the carbide-based non-magnetic ceramic molded body at an irradiation speed of 5,000 mm / sec or more using a continuous wave laser in the same manner as in the first manufacturing method. In the step of continuously irradiating, when irradiating the surface of the carbide-based non-magnetic ceramic molded body to be surface-roughened with laser light, the irradiation is performed so that the irradiated part and the non-irradiated part of the laser light alternately occur. have.

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

When irradiating a plurality of times, the laser light irradiation part may be the same, or the laser light irradiation part may be different (the laser light irradiation part is shifted), so that the whole non-magnetic ceramics molded body of the carbide system is formed. May be roughened. When the laser beam is irradiated multiple times with the same part irradiated, the laser beam is irradiated in a dotted line, but the laser light irradiated part is shifted, that is, the laser light is first irradiated to the part that was not irradiated with the laser light. If the irradiation is repeated while being shifted so that the irradiation portions overlap, even when the irradiation is performed in a dotted line, the irradiation is finally performed in a solid line state. The number of repetitions can be 1 to 20 times.

(4) When a laser beam is continuously irradiated on a carbide-based nonmagnetic ceramic molded body, deformation such as cracking may occur in a molded body having a small thickness. However, when laser irradiation is performed in a dotted line as shown in FIG. 1, laser light irradiation portions 11 and laser light non-irradiation portions 12 are alternately generated. Deformation such as cracking hardly occurs even in a small compact. At this time, the same effect can be obtained even when the irradiated portion of the laser beam is changed as described above (the irradiated portion of the laser beam is shifted).

The method of irradiating the laser beam is, for example, a method of irradiating the surface of the metal molded body 20 in one direction as shown in FIG. 2A, or a method of irradiating bidirectionally as shown by a dotted line in FIG. The method can be used. In addition, a method of irradiating the laser beam so that the dotted lines irradiate with each other may be used. The interval b1 between the dotted lines after the irradiation can be adjusted according to the irradiation target area of the metal molded body or the like, but can be in the same range as the line interval in the first manufacturing method.

The length (L1) of the laser light irradiated portion 11 and the length (L2) of the laser light non-irradiated portion 12 shown in FIG. 1 are adjusted so that L1 / L2 = 1/9 to 9/1. can do. The length (L1) of the irradiated portion 11 of the laser beam is 0.05 mm or more in a preferred embodiment of the present invention in order to roughen the surface into a complicated porous structure, and is 0 in another preferred embodiment of the present invention. 0.1 to 10 mm, and in still another preferred embodiment of the present invention 0.3 to 7 mm.

In one exemplary embodiment of the second manufacturing method of the present invention, the laser light irradiation step described above is a fiber laser apparatus in which a direct modulation type modulator for directly converting a drive current of a laser is connected to a laser power supply. Is used to adjust the duty ratio (duty ratio) to perform laser irradiation.

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

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

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

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

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

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

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

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

The thermosetting resin can be appropriately selected from known thermosetting resins depending on the application. For example, urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane can be mentioned. When a thermosetting resin is used, a prepolymer form can be used, and a heat curing treatment can be performed in a later step.

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

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

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

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

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

When the press molding method is applied, for example, a portion including a roughened structure of a carbide-based nonmagnetic ceramics molded body is arranged in a mold, and heating and heating are performed on the portion including the roughened structure. After the uncured rubber to be the rubber molded body is pressed in a pressurized state, it is taken out after cooling. When applying the transfer molding method, for example, a portion including a roughened structure of a carbide-based non-magnetic ceramic molded body is arranged in a mold, and the uncured rubber is injection-molded in the mold, and thereafter, By heating and pressurizing, the part including the roughened structure of the carbide-based nonmagnetic ceramic molded body and the rubber molded body are integrated, and after cooling, they are taken out.

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

The rubber of the rubber molded body used in this step is not particularly limited, and a known rubber can be used, but does not include a thermoplastic elastomer. Known rubbers include ethylene-propylene copolymer (EPM), ethylene-propylene-diene terpolymer (EPDM), ethylene-octene copolymer (EOM), ethylene-butene copolymer (EBM), ethylene-octene terpolymer (EODM), Ethylene-α-olefin rubbers such as ethylene-butene terpolymer (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 polymethylstyrene-butene copolymer, styrene-butadiene-styrene and styrene-ethylene-butadiene -Styrene block copolymers, acrylic rubbers (ACM), ethylene-vinyl acetate elastomers (EVM), silicone rubbers and the like can be used.

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

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

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

The adhesive is not particularly limited, and a known thermoplastic adhesive, thermosetting adhesive, rubber-based adhesive, or the like can be used. Examples of the thermoplastic adhesive include polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic adhesive, polyethylene, chlorinated polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene -Ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ionomer, chlorinated polypropylene, polystyrene, polyvinyl chloride, plastisol, vinyl chloride-vinyl acetate copolymer, polyvinyl ether, polyvinylpyrrolidone, polyamide, nylon, non-saturated Fixed polyesters and cellulose derivatives can be mentioned.

例 Examples of the thermosetting adhesive include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane. Examples of rubber adhesives include natural rubber, synthetic polyisoprene, polychloroprene, nitrile rubber, styrene-butadiene rubber, styrene-butadiene-vinylpyridine terpolymer, polyisobutylene-butyl rubber, polysulfide rubber, silicone RTV, Examples include chlorinated rubber, brominated rubber, kraft rubber, block copolymer, and liquid rubber.

In the example of this manufacturing method, in the third step, a rubber molded body separately molded is bonded to the surface of the carbide-based nonmagnetic ceramic molded body on which the adhesive layer was formed in the previous step, or The part including the surface of the carbide-based non-magnetic ceramic molded body with the agent layer formed was placed in the mold, and the surface of the carbide-based non-magnetic ceramic molded body was brought into contact with the uncured rubber to be the rubber molded body. A step of integrating by heating and pressing in a state is performed. In the case of this step, a step of secondary heating (secondary curing) in an oven or the like after removal from the mold can be added to remove mainly residual monomers.

(3-1) Method for Producing Composite Molded Body of Carbide-Based Ceramics Molded Body and Metal Molded Body Having Roughened Structure In the first step, the roughened structure is formed by the first manufacturing method or the second manufacturing method. To produce a carbide-based non-magnetic ceramic molded article having the following. In the second step, the roughened carbide-based non-magnetic ceramic molded body is placed in the mold such that the surface including the porous structure portion faces upward. Thereafter, the metal in a molten state is poured into a mold by, for example, a known die casting method, and then cooled.

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

(3-2) Manufacturing Method of Composite Molded Body (with Adhesive Layer) of Carbide-Based Non-Magnetic Ceramics Molded Body Having Roughened Structure and Metal Molded Body 2-2) Method for Manufacturing Composite Molded Body (Including Adhesive Layer) of Carbide-Based Non-magnetic Ceramics Molded Body Having Roughened Structure and Rubber Molded Body " Manufactures carbide-based non-magnetic ceramic molded bodies.

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

(4) Method of Manufacturing Composite Molded Body of Carbide-Based Nonmagnetic Ceramic Molded Body Having Roughened Structure and UV-Curable Resin Molded Body In the first step, the above-described first manufacturing method or second manufacturing method is used. To produce a carbide-based non-magnetic ceramic molded body having a roughened structure on the surface.

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

In the contacting step of the monomer, the oligomer or the mixture thereof, the portion including the roughened portion of the carbide-based nonmagnetic ceramic molded body is surrounded by a mold, and the monomer, the oligomer or the mixture thereof is placed in the mold. An injecting step can be performed.
Further, the step of contacting the monomer, the oligomer or the mixture thereof includes the steps of: placing the carbide-based non-magnetic ceramic molded body in a mold with the roughened portion facing upward; Can be performed.

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

Monomers, oligomers or mixtures thereof can be applied or injected as they are in liquid form (including low-viscosity gels) at room temperature or in the form of a solution dissolved in a solvent. Solid (powder) forms can be heated. It can be applied or poured after being melted or dissolved in a solvent.

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

(Radical polymerizable monomer)
As the radical polymerizable compound, a radical polymerizable group such as a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acryloylamino group, a vinyl ether group, a vinylaryl group, and a vinyloxycarbonyl group is contained in one molecule. Compounds having at least one compound are exemplified.

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

Examples of the compound having at least one (meth) acryloyloxy group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth). A) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, n-butoxyethyl (meth) acrylate, Butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acryl , Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, dimethyl Aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyl Oxyethyl-2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, ethylene glycol di (meth) acrylate, diethyl Glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, decane di (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) ) Acrylate, dimethylol tricyclodecane di (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, isoamyl (meth) acrylate, isomyristyl (meth) acrylate, γ- (meth) ) Acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxy) ethyl isocyanate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, 3- (meth) ) Acryloyloxypropyltriethoxysilane and the like, and derivatives thereof.

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

Compounds having one or more vinyl ether groups in one molecule include, for example, 3,3-bis (vinyloxymethyl) oxetane, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy Isopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxy Propyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol Novinyl ether, 1,4-cyclohexane dimethanol monovinyl ether, 1,3-cyclohexane dimethanol monovinyl ether, 1,2-cyclohexane dimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene Glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetra Propylene glyco Monovinyl ether, pentapropylene glycol monovinyl ether, oligopropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, and the like, and derivatives thereof.

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

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

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

Compounds having one or more epoxy rings in one molecule include glycidyl methyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F diglycidyl ether. Glycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl (3,4 -Epoxy) cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methyl Cyclohexane carboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxyhexa Dioctyl hydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol Lepropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin. Polyglycidyl ethers of polyether polyols; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; phenol, cresol, butylphenol or polyether alcohols obtained by adding alkylene oxide thereto Monoglycidyl ethers; and glycidyl esters of higher fatty acids.

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

Compounds having one or more oxetanyl groups in one molecule include trimethylene oxide, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3- Oxetanyl)] methyl} ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Bicyclohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, and 3-ethyl-3 {[(3-ethyloxetan-3-yl) methoxy] methyl} oxetane .

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

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

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

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

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

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

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

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

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

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

Each configuration in each embodiment and a combination thereof are merely examples, and addition, omission, substitution, and other changes of the configuration can be appropriately made without departing from the gist of the present invention. The invention is not limited by the embodiments, but only by the claims.

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

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

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

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

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

Str (Aspect ratio of surface texture): Indicates the isotropic and anisotropy of the surface texture, and is shown in the range of 0 to 1. If Str is close to 0, it indicates that the surface is not direction-dependent, and if Str is close to 1, the surface does not depend on the direction. Str was measured by a one-shot 3D shape measuring machine (manufactured by Keyence).

Examples 1 to 3, Comparative Example 1
The surface of a nonmagnetic ceramic molded body (10 × 50 × 2 mm thick plate) of the type shown in Table 1 was continuously irradiated with laser light under the conditions shown in Table 1 using the continuous wave laser device described below. And roughened. As the composite of 70% by mass of silicon carbide and 30% by mass of aluminum in Example 2, trade name SA701 (Nippon Fine Ceramics Co., Ltd.) was used. As the composite of 50% by mass of silicon carbide and 50% by mass of silicon in Example 3, trade name SS501 (Nippon Fine Ceramics Co., Ltd.) was used.

(Laser device)
Oscillator: IPG-Yb fiber; YLR-300-SM
Galvano mirror SQUIIREEL (ARGES)
Light collection system: fc = 80 mm / fθ = 100 mm

The bidirectional irradiation was performed as follows.
Bidirectional irradiation: After irradiating continuous wave laser light linearly so that one groove is formed in one direction, continuous wave laser light is linearly irradiated in the opposite direction at an interval of 0.05 mm. Irradiation was repeated. The 0.05 mm spacing for bidirectional irradiation is the distance between the intermediate positions of the width of adjacent grooves.

Ｓ FIGS. 3 to 5 and 6 show SEM photographs of portions of the non-magnetic ceramic molded bodies of Examples 1 to 3 and Comparative Example 1 having a roughened structure.

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

Using the composite molded article obtained in Example 1, the bonding strength between the non-magnetic ceramic molded article and the resin molded article was measured.
(Tensile test)
Using the composite molded article shown in FIG. 7, a tensile test was performed to evaluate the shear bonding strength (S1). Tensile test is based on ISO 19095, with the non-magnetic ceramic molded body 30 fixed at the end, and pulled in the X direction shown in FIG. 7 until the non-magnetic ceramic molded body 30 and the resin molded body 31 are broken. The maximum load until the joint surface was destroyed was measured. Table 1 shows the results.
<Tensile test conditions>
Testing machine: AUTOGRAPH AG-X plus (50kN) manufactured by Shimadzu Corporation
Tensile speed: 10 mm / min
Distance between grips: 50mm

凹凸 The irregularities of the roughened structure in the non-magnetic ceramics molded body containing silicon carbide of Examples 1 to 3 were such that the cross-sectional shape in the thickness direction of the tip was a curved surface (partial circle). In Example 1 (FIG. 3), wrinkle-like projections were formed continuously along the length direction. In Examples 2 and 3 (FIGS. 4 and 5), a large number of independent holes formed linearly along the length direction were formed. In Comparative Example 1 in which the irradiation speed of the laser light was low, no cracks occurred, but some chips were missing.

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

Claims (14)

1. A non-magnetic ceramic molded body having a surface roughened structure,
   The roughened structure has irregularities, and the cross-sectional shape in the thickness direction of the irregularities is a curved surface when observed by a scanning electron microscope photograph (200 times or more), and the curved surface of the convex portion has a length. Wrinkle-like projections formed along the direction, or the curved surface of the convex portion has a plurality of independent holes formed linearly along the length direction,
   A non-magnetic ceramic molded body, wherein the non-magnetic ceramic molded body is a carbide-based non-magnetic ceramic molded body.
2. 非 The non-magnetic ceramic molded article according to claim 1, wherein the carbide-based non-magnetic ceramic molded article has a thermal shock temperature (JIS R1648: 2002) in the range of 400 to 500 ° C and a thickness of 0.5 mm or more.
3. 3. The non-magnetic ceramic molded body according to claim 2, wherein the carbide-based non-magnetic ceramic molded body is a molded body containing silicon carbide.
4. The said nonmagnetic ceramics molded body of a carbide type | system | group is a composite body in which the inside of the hole of porous silicon carbide is impregnated with metal or metalloid, and the content rate of the said silicon carbide is 50 mass% or more. 2. The non-magnetic ceramic molded body according to 1.
5. (5) The non-magnetic ceramic molded product according to any one of (1) to (4), wherein a cross-sectional shape in a thickness direction of a tip portion of the projection of the unevenness is a partial circular shape or a partial elliptical shape.
6. The irregularities are formed by alternately forming linear convex portions and linear concave portions,
   When the width of each of the linear protrusions and the linear recesses is 20 to 100 μm, wrinkle protrusions formed in the length direction of the protrusions, or a plurality of independent holes formed in a linear shape. The non-magnetic ceramic molded body according to any one of claims 1 to 5, wherein the width of the non-magnetic ceramic body is 1 to 10 µm.
7. Concave portions of the irregularities are formed in an island-shape, and portions excluding the concave portions are convex portions,
   When the width of the convex portion is 20 to 100 μm, the width of the wrinkle-shaped protrusion formed in the length direction of the convex portion or the aggregate of the independent holes formed in a linear shape is 1 to 10 μm. Item 6. The non-magnetic ceramic molded article according to any one of Items 1 to 5.
8. The surface roughness (Ra) of the tip of the convex part of the irregularities is in the range of 5 to 40 μm, and the height difference (Rz) between the convex part and the concave part of the irregularities is in the range of 50 to 200 μm. 8. The non-magnetic ceramic molded product according to any one of items 7 to 7.
9. The surface roughness (Ra) of the tip of the convex part of the irregularities is in the range of 10 to 30 μm, and the height difference (Rz) between the convex part and the concave part of the irregularity is in the range of 60 to 180 μm. 8. The non-magnetic ceramic molded product according to any one of items 7 to 7.
10. The method for producing a non-magnetic ceramic molded body having a surface roughened structure according to any one of claims 1 to 9,
    The surface of a carbide-based non-magnetic ceramic molded body containing silicon carbide is roughened by continuously irradiating a laser beam at a rate of 5,000 mm / sec or more using a continuous wave laser. Manufacturing method of ceramic molded body.
11. The method for producing a non-magnetic ceramic molded body having a surface roughened structure according to any one of claims 1 to 9,
    A step of continuously irradiating the surface of the carbide-based nonmagnetic ceramic molded body containing silicon carbide with a laser beam at an irradiation speed of 5,000 mm / sec or more using a continuous wave laser,
    The laser light irradiation step is a step of irradiating the surface of the metal molded body to be roughened, when irradiating the laser light, so that the irradiated part and the non-irradiated part of the laser light alternately occur. A method for producing a non-magnetic ceramic molded body.
12. When continuously irradiating the surface of the non-magnetic ceramic molded body with a laser beam at an irradiation speed of 5,000 mm / sec or more using a continuous wave laser,
    The non-magnetic ceramic molded body according to any one of claims 7 to 11, wherein the laser light is continuously irradiated such that a plurality of lines composed of straight lines, curved lines, and combinations thereof are formed in the same direction or different directions. Production method.
13. When continuously irradiating the surface of the non-magnetic ceramic molded body with a laser beam at an irradiation speed of 5,000 mm / sec or more using a continuous wave laser,
    Laser light is continuously irradiated so that a plurality of lines composed of straight lines, curves and combinations thereof are formed in the same direction or different directions, and one straight line or one curved line is continuously irradiated with the laser light plural times. The method for producing a non-magnetic ceramic molded article according to any one of claims 7 to 11, wherein
14. When continuously irradiating the surface of the non-magnetic ceramic molded body with a laser beam at an irradiation speed of 5,000 mm / sec or more using a continuous wave laser,
    Continuously irradiate laser light such that a plurality of lines consisting of straight lines, curves and combinations thereof are formed in the same direction or different directions,
    The non-magnetic ceramic molded body according to any one of claims 7 to 11, wherein the laser beam is continuously irradiated such that the plurality of straight lines or the plurality of curves are formed at equal intervals or at different intervals. Manufacturing method.
    
    

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