WO2020067249A1 - Corps moulé en céramique non magnétique doté, sur sa surface, d'une structure rugueuse et procédé de fabrication associé - Google Patents

Corps moulé en céramique non magnétique doté, sur sa surface, d'une structure rugueuse et procédé de fabrication associé Download PDF

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WO2020067249A1
WO2020067249A1 PCT/JP2019/037772 JP2019037772W WO2020067249A1 WO 2020067249 A1 WO2020067249 A1 WO 2020067249A1 JP 2019037772 W JP2019037772 W JP 2019037772W WO 2020067249 A1 WO2020067249 A1 WO 2020067249A1
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molded body
ceramic molded
magnetic ceramic
oxide
laser
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PCT/JP2019/037772
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English (en)
Japanese (ja)
Inventor
清水　潔
雅彦 板倉
法寿 和田
孝之 宇野
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ダイセルポリマー株式会社
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Priority to JP2020501409A priority Critical patent/JP6804689B2/ja
Publication of WO2020067249A1 publication Critical patent/WO2020067249A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/91—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching

Definitions

  • the present invention relates to a non-magnetic ceramic molded article having a roughened structure on its surface and a method for producing the same.
  • Non-magnetic ceramics are widely used in various molded products as daily necessities such as tableware, cups, vases, and engineering ceramics, and it is known to perform a process of forming irregularities on the surface according to the application to which they are applied.
  • JP-A-2002-308683 discloses a ceramic member having a concave-convex structure formed with an acidic etching solution.
  • Japanese Patent No. 6032903 describes an invention of a firing setter having a specific uneven structure (claims), and as a material of the firing setter, zirconia, alumina, magnesia, spinel, cordierite, etc. (Paragraph number 0013).
  • WO2011 / 121808A1 includes a metal or ceramic base material, an impregnated layer provided by forming a concave portion on the sliding side surface of the base material, and an impregnated layer impregnated with the base material. And a resin layer covering the surface on the sliding side of the sliding member, wherein the concave portion is formed by machining (claims). It is described that the concave portion is a plurality of linear grooves, and the maximum depth of the grooves is 200 to 2000 ⁇ m (paragraph number 0026).
  • Examples of the mechanical processing include laser processing and wire cut processing (paragraph number 0014), but there is no description of specific processing conditions, and in the examples, it is described that steel was wire cut. There is no specific description about ceramics.
  • Japanese Patent Application Laid-Open No. 2015-109966 discloses a method for manufacturing a medical device material in which a specific portion of a medical device material containing tetragonal zirconia is coated with calcium phosphate, and the specific portion is irradiated with an ultrashort pulse laser.
  • a method for manufacturing a medical device material comprising: a first step of forming irregularities on the surface; and a second step of depositing or depositing calcium phosphate fine particles smaller than the period of the irregularities on the specific portion is disclosed. (Claims).
  • Japanese Patent No. 6111102 discloses that a laser beam having a wavelength of 300 to 1500 nm is applied to a portion of a planar shape substantially identical to a circuit pattern on at least one surface of a ceramic substrate containing AlN or Al 2 O 3 as a main component.
  • An aluminum film is formed on a portion of the ceramic substrate having a planar shape substantially the same as the circuit pattern on at least one surface, and a copper plate is disposed on the aluminum film to have a temperature not lower than the eutectic point of aluminum and copper and not higher than 650 ° C.
  • a method of manufacturing a metal-ceramic bonding substrate, characterized by bonding a copper plate to a ceramic substrate via an aluminum film by heating at a temperature, is disclosed.
  • Japanese Patent Application Laid-Open No. 2003-171190 discloses that the surface of a substrate made of dense ceramic having a purity of 95% or more is formed with first rounded irregularities having a surface roughness Ra of 3 to 40 ⁇ m, 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 ⁇ m. It is shown that the second unevenness covers the entire surface of the first unevenness.
  • JP-A-2003-137677 and JP-A-2004-66299 disclose a technique for forming irregularities by laser processing the surface of a ceramic body.
  • Japanese Patent Nos. 5,774,246 and 5,701,414 disclose a method for roughening the surface of a metal molded body by continuously irradiating a continuous wave laser with a laser beam at an irradiation speed of 2000 mm / sec or more. Although an invention of a method for producing a composite molded article of a molded article and a resin molded article is disclosed, there is no description about ceramics.
  • One 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 roughening structure has irregularities, and the cross-sectional shape in the thickness direction of the irregularities has a curved surface
  • a non-magnetic ceramic molded body having a roughened surface on the surface wherein the non-magnetic ceramic is an oxide-based non-magnetic ceramic.
  • the present invention provides a method for producing a non-magnetic ceramic molded body having a surface roughened structure.
  • the non-magnetic ceramic molded article having a roughened structure on the surface according to one embodiment of the present invention can be used as an intermediate for producing a composite molded article 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.
  • the surface of an inherently hard and brittle oxide-based nonmagnetic ceramic molded body can be roughened without being separated into two or more by cracking.
  • (A) And (b) is a top view which shows some different embodiment of the recessed part of the unevenness
  • (A) And (b) is a top view which shows some different embodiment of the recessed part of the unevenness
  • (A)-(d) is a top view which shows several different embodiment of the recessed part of the unevenness
  • FIG. 1 is a top view which shows several different embodiment of the recessed part of the unevenness
  • (A) is an SEM photograph of a plan view of a roughened structure portion of the zirconia molded body of Example 1, and (b) is an SEM photograph of a cross section in a thickness direction of (a).
  • 5 is an SEM photograph of a roughened structure portion (plan view) of an alumina molded body (purity: 92%) of Example 2.
  • 6 is an SEM photograph of a roughened structure portion (plan view) of the alumina molded body (purity: 92%) of Example 3.
  • (A) is an SEM photograph of a plan view of a roughened structure portion of the alumina molded body (purity 99.5%) of Example 4
  • (b) is an SEM photograph of a cross section in the thickness direction of (a).
  • (A) is an SEM photograph of a plan view of a roughened structure portion of the alumina molded body (purity 99.5%) of Example 5, and (b) is an SEM photograph of a cross section in the thickness direction of (a).
  • . 9 is an SEM photograph of a roughened structure portion (plan view) of the alumina molded body (purity: 99.5%) of Comparative Example 2.
  • (A) is an SEM photograph of a plan view of a roughened structure portion of the steatite molded body of Example 6, and (b) is an SEM photograph of a cross section in the thickness direction of (a).
  • FIG. 2 is a perspective view of an alumina molded body manufactured in an example, and a perspective view for describing a test of bonding strength using a composite molded body of an alumina molded body and a resin molded body.
  • (A) is an SEM photograph of a plan view of a roughened structure portion of the steatite molded article of Example 8, and (b) is an SEM photograph of a cross section in the thickness direction of (a).
  • the non-magnetic ceramic molded body having a surface roughened structure is made of an oxide-based non-magnetic ceramic.
  • the oxide-based non-magnetic ceramic molded body includes alumina, zirconia, magnesia, silica, titanium oxide, cerium oxide, zinc oxide, tin oxide, uranium oxide, ⁇ -alumina, mullite, YAG, forsterite (2MgO ⁇ SiO 2), barium titanate (BaTiO 3), steatite (MgO ⁇ SiO 2), cordierite (2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2), or an oxide such as lead zirconate titanate It is a molded body containing a base ceramic, and among these, another preferred embodiment of the present invention contains alumina or zirconia.
  • Alumina may be composed of a composite of alumina, other non-magnetic ceramics, and metal as long as it is within a range satisfying a predetermined thermal shock temperature, in addition to alumina.
  • the predetermined thermal shock temperature JIS @ R1648: 2002
  • JIS @ R1648: 2002 is in a range of 150 to 700 ° C. in a preferred embodiment of the present invention, and in a range of 180 to 680 ° C. in another preferred embodiment of the present invention.
  • the temperature is in the range of 200 to 650 ° C.
  • the non-magnetic ceramics molded body containing alumina has a thickness of 0.5 mm or more in a preferred embodiment of the present invention in order to prevent cracking at the time of processing by laser light irradiation.
  • the thickness is 1.0 mm or more.
  • the term “crack” in the present invention means that a part of the molded body is broken and divided into two or more, and does not include “crack”.
  • “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.
  • Zirconia may be composed of a composite of zirconia, other non-magnetic ceramics, and a metal as long as the zirconia is within a range satisfying a predetermined thermal shock temperature.
  • the predetermined thermal shock temperature JIS @ R1648: 2002
  • JIS @ R1648: 2002 is in the range of 1 to 10 ° C. in a preferred embodiment of the present invention, and is 3 to 8 ° C. in another preferred embodiment of the present invention.
  • the nonmagnetic ceramic molded body containing zirconia has a thickness of 3 mm or more in order to prevent cracks or cracks from being generated during laser irradiation. In another preferable embodiment, the thickness is 3.5 mm or more.
  • the roughened structure has irregularities
  • the cross-sectional shape of the irregularities in the thickness direction is a curved surface. It has.
  • the cross-sectional shape in the thickness direction of the unevenness 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 ⁇ m in a preferred embodiment of the present invention, and in the range of 3 to 25 ⁇ m in another preferred embodiment of the present invention. In one embodiment, it is in the range of 4 to 23 ⁇ m.
  • the height difference (Rz) between the convex portion and the concave portion of the unevenness is in the range of 10 to 200 ⁇ m in a preferred embodiment of the present invention, and is in the range of 15 to 180 ⁇ m in another preferred embodiment of the present invention. In still another preferred embodiment, the thickness is in the range of 20 to 150 ⁇ m.
  • Sa (arithmetic mean height), Sz (maximum height), Sdr (interface development area ratio), and Sdq (root mean square slope) of the roughened structure portion (irregularity portion) are in the following ranges. May be.
  • Sa (arithmetic mean height) is 1 to 50 ⁇ m in a preferred embodiment of the present invention, 3 to 40 ⁇ m in another preferred embodiment of the present invention, and 5 to 30 ⁇ m in still another preferred embodiment of the present invention. It is.
  • Sz (maximum height) is 30 to 280 ⁇ m in one preferred embodiment of the present invention, 40 to 250 ⁇ m in another preferred embodiment of the present invention, and 50 to 230 ⁇ m in still another preferred embodiment of the present invention. is there.
  • the Sdr (developed area ratio of the interface) is 0.05 to 2.00 in one 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
  • Sdq root mean square slope
  • the cross-sectional shape of the concave and convex portions in the depth direction is a wedge shape in which the opening width on the front side is wide (maximum inner diameter portion) and the width is gradually narrowed in the depth direction (bottom direction). It may include a pot-shaped one in which the width of the portion is narrow and a maximum inner diameter portion exists from the opening to the bottom.
  • the maximum inner diameter portion is 1 to 500 ⁇ m in a preferred embodiment of the present invention, 2 to 300 ⁇ m in another preferred embodiment of the present invention, and 10 to 100 ⁇ m in still another preferred embodiment of the present invention.
  • the non-magnetic ceramic molded body having a surface roughened structure has a planar shape of the concave portion when the irregularities are continuously formed linearly at intervals. May include an elliptical shape or a similar shape.
  • the expression that the irregularities are continuously formed linearly at intervals means a form in which linear convex portions and linear concave portions are alternately formed in a certain direction.
  • planar shape of the concave portion is similar to an elliptical shape, for example, two opposing sides on the long axis side are curves (arcs) 1a, but two opposing sides on the short axis side are only the straight line 2.
  • two opposite sides on the long axis side are curves (arcs) 1a, but two opposite sides on the short axis side are a straight line 2 and a curve 1b.
  • two opposite sides on the long axis side are curves (arcs) 1a, but a straight line 2 or a curve 1b on the two opposite sides on the short axis side is partially formed.
  • FIGGS. 3A to 3D are two opposite sides on the long axis side.
  • the planar shape of the concave portion is circular or elliptical. Or, it may include a shape similar to them.
  • the concave portions at this time are formed in an island shape in the planar shape of the roughened structure, and the portions excluding the concave portions are convex portions.
  • the irregularities may be formed such that concave portions are dispersed in an island shape at equal intervals, or concave portions may be formed in an island shape at different intervals.
  • planar shape of the concave portion is similar to a circular shape, for example, a shape having a portion (protruding portion) 5 in which a part of the circumference protrudes away from the center of the circular shape (FIG. 4) (A) and (b)), shapes (FIGS. 4 (c) and (d)) in which a part of the circumference has a part (recess part) 6 that is concave toward the center of the circle, and These are mixed shapes (FIG. 4E). There may be a plurality of projections 5 and depressions 6, respectively.
  • two opposite sides on the long axis side are curved lines (arcs), but two opposite sides on the short axis side.
  • the two sides include a shape consisting of only a straight line, a shape consisting of a straight line and a curve, and a shape in which a straight line or a curve of two opposite sides on the short axis side is partially bent.
  • the non-magnetic ceramic molded body can be used as a carrier or the like capable of holding a liquid, a powder, or the like on the roughened structure portion, and can be made of another material (non-magnetic ceramics). (Excluding materials) can also be used as a production intermediate for producing a composite molded article with a molded article comprising the same.
  • the non-magnetic ceramic molded body according to one embodiment of the present invention emits a laser beam to the surface of the oxide-based non-magnetic ceramic molded body at a radiation speed of 5,000 mm / sec or more using a continuous wave laser. It can be manufactured by continuous irradiation.
  • oxide-based non-magnetic 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 may be selected as needed. It will be adjusted.
  • oxide-based non-magnetic ceramic moldings include flat plates, round bars, square bars (bars having a polygonal cross section), tubes, cups, cubes, cuboids, spheres or partial spheres (hemispheres, etc.), ellipses
  • molded products such as spheres or partially elliptical spheres (such as semi-elliptical spheres) and irregular shapes
  • existing non-magnetic ceramic products can also be used.
  • the existing 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 be composed of a composite.
  • laser light can be continuously irradiated so that a plurality of lines formed of straight lines, curves, and combinations thereof are formed in different directions.
  • the irradiation speed of the laser beam may be 5,000 mm / sec or more in order to roughen the oxide-based nonmagnetic ceramic molded body.
  • the irradiation speed is 5,000 to 20,000 mm / sec.
  • the pressure 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 100 to 4,000 W in one preferred embodiment of the present invention, 200 to 2,000 W in another preferred embodiment of the present invention, and 300 to 1 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.
  • the output of the laser beam is 100 W
  • the irradiation speed of the laser beam is 5,000 to 7,500 mm / sec.
  • the irradiation speed of the laser beam is 7,500 to 10,000 mm / sec.
  • the spot diameter of the laser beam is 10 to 100 ⁇ m in one preferred embodiment of the present invention, and 10 to 75 ⁇ m in another preferred embodiment of the present invention.
  • Energy density during the laser beam irradiation in a preferred embodiment of the present invention is 3 ⁇ 1,500MW / cm 2, in another preferred embodiment of the present invention is 5 ⁇ 700MW / cm 2.
  • the energy density at the time of laser beam irradiation is calculated by the following formula from the output (W) of the laser beam and the laser beam (spot area (cm 2 ) ( ⁇ ⁇ [spot diameter / 2] 2 ): laser beam output / spot area. Desired.
  • the number of repetitions (the number of passes) upon laser beam 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. Up to 30 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.
  • bidirectional irradiation and unidirectional irradiation can be selected.
  • 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.
  • One-way irradiation is a method of repeating one-way continuous-wave laser irradiation from a first end to a second end.
  • 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.
  • the line intervals may be the same or different.
  • the above-mentioned line Cross irradiation in which bidirectional irradiation or unidirectional irradiation is performed at intervals may be performed.
  • the planar shape of the concave portion of the roughened structure portion has a shape as shown in FIG. 4, for example.
  • 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.
  • laser irradiation may be performed with the set value kept constant, or laser irradiation may be performed while changing the defocusing distance. For example, at the time of laser irradiation, the defocus distance may be gradually reduced, or may be periodically increased or decreased.
  • a known continuous wave laser can be used, for example, a YVO 4 laser, a fiber laser (preferably a single mode fiber laser), an excimer laser, a carbon dioxide laser, an ultraviolet laser, a YAG laser, a semiconductor laser, a glass laser, A ruby laser, a He-Ne laser, a nitrogen laser, a chelate laser, and a dye laser can be used.
  • a fiber laser is preferable, and a single mode fiber laser is particularly preferable, because the energy density is increased.
  • the second method for producing an oxide-based non-magnetic ceramic molded body having a surface roughened structure is different from the first method described above in that the laser light irradiation mode is different from that of the first method. The difference is the same method.
  • the second manufacturing method uses a continuous wave laser to irradiate the surface of the oxide-based non-magnetic ceramic molded body with a laser beam at an irradiation speed of 5,000 mm / sec or more in the same manner as the first manufacturing method.
  • the irradiation is performed so that the irradiated portion and the non-irradiated portion alternately occur.
  • the laser beam 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. 5 shows that the non-irradiated portion 12 of the laser beam having the length L2 between the irradiated portion 11 of the laser beam having the length L1 and the adjacent irradiated portion 11 of the laser beam having the length L1 is alternately formed.
  • 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.
  • the irradiated portion of the laser beam may be the same, or the irradiated portion of the laser beam may be different (by shifting the irradiated portion of the laser beam) to form the oxide-based non-magnetic ceramic molded body. The whole may be roughened.
  • 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.
  • the number of repetitions can be 1 to 20 times.
  • the oxide-based non-magnetic ceramic molded body is continuously irradiated with a laser beam, deformation such as cracking may occur in a molded body having a small thickness.
  • deformation such as cracking may occur in a molded body having a small thickness.
  • laser irradiation is performed in a dotted line as shown in FIG. 5, laser light irradiation portions 11 and laser light non-irradiation portions 12 occur alternately. 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. 6A, or a method of irradiating the surface from both directions as shown by a dotted line in FIG.
  • the method can be used.
  • 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 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 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.
  • 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.
  • 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.
  • 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.
  • laser light irradiation portions 11 and laser light non-irradiation portions 12 between adjacent laser light irradiation portions 11 are alternately formed, and are formed as a whole as a dotted line. 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.
  • 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.
  • 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. 5, it can be selected from a range of, for example, 10 to 90%.
  • the duty ratio corresponds to L1 and L2 (that is, L1 / [L1 + L2]) shown in FIG. 5, it can be selected from a range of, for example, 10 to 90%.
  • the third manufacturing method is different from the first manufacturing method and the second manufacturing method, and is a method using a pulse wave laser.
  • the method of irradiating a pulsed laser beam is, for example, a method of irradiating a pulsed laser beam, for example, Japanese Patent No. 5848104, Japanese Patent No. 5788836, Japanese Patent No. 5798534, Japanese Patent No. 5798535, The method can be carried out in the same manner as the pulse wave laser beam irradiation method described in JP-A-2016-203643, Japanese Patent No. 5888975, Japanese Patent No. 5932700, or Japanese Patent No. 6055529.
  • the surface of the oxide-based non-magnetic ceramic molded body is irradiated with a laser beam at an angle of 15 ° to 90 °, and in another preferred embodiment of the present invention, at an angle of 45 ° to 90 °. .
  • Irradiation rate when irradiating laser light to oxide-based non-magnetic ceramic molded body The irradiation speed of the laser beam is 10 to 1,000 mm / sec in a preferred embodiment of the present invention, 10 to 500 mm / sec in another preferred embodiment of the present invention, and 10 to 500 mm / sec in another preferred embodiment of the present invention. ⁇ 100 mm / sec, and in still another preferred embodiment of the present invention, it is 10-80 mm / sec.
  • Energy density when irradiating the oxide-based non-magnetic ceramic molded body with laser light is obtained from the energy output (W) of one pulse of the laser light and the laser light (spot area (cm 2 ) ( ⁇ ⁇ [spot diameter / 2] 2 ).
  • energy density during irradiation is 0.1 ⁇ 50GW / cm 2 in a preferred aspect of the present invention, in another preferred embodiment of the present invention is 0.1 ⁇ 20GW / cm 2, another preferred of the present invention in one embodiment, it is 0.5 ⁇ 10GW / cm 2, in yet another preferred embodiment of the present invention is 0.5 ⁇ 5GW / cm 2. energy density increases, the hole becomes deeper and larger.
  • the energy output (W) of one pulse of laser light is obtained from the following equation.
  • the energy output (W) of one pulse of laser light (average output of laser light / frequency) / average output of pulse width laser light is 4 to 400 W in one preferred embodiment of the present invention, and is another preferable embodiment of the present invention. In one embodiment, it is 5 to 100 W, and in still another preferred embodiment of the present invention, it is 10 to 100 W. If the other laser light irradiation conditions are the same, the hole becomes deeper and larger as the output becomes larger, and the hole becomes shallower and smaller as the output becomes smaller.
  • the frequency (KHz) is 0.001 to 1000 kHz in a preferred embodiment of the present invention, 0.01 to 500 kHz in another preferred embodiment of the present invention, and 0.1 in still another preferred embodiment of the present invention. It is 1 to 100 kHz.
  • the pulse width (nsec) is 1 to 10,000 nsec in a preferred embodiment of the present invention, 1 to 1,000 nsec in another preferred embodiment of the present invention, and 1 in still another preferred embodiment of the present invention. ⁇ 100 nsec.
  • the spot diameter ( ⁇ m) of the laser beam is 1 to 300 ⁇ m in one preferred embodiment of the present invention, 10 to 300 ⁇ m in another preferred embodiment of the present invention, and 20 to 150 ⁇ m in still another preferred embodiment of the present invention. In still another preferred embodiment, the thickness is 20 to 80 ⁇ m.
  • the number of repetitions (the total number of laser light irradiations for forming one hole) is 1 to 80 in a preferred embodiment of the present invention, and 3 to 50 in another preferred embodiment of the present invention. In another preferred embodiment of the present invention, the number is 5 to 30 times. Under the same laser irradiation conditions, the hole becomes deeper and larger as the number of repetitions increases, and the hole becomes shallower and smaller as the number of repetitions decreases.
  • the line spacing is in a preferred embodiment of the present invention in the range of 0.01 to 1 mm, in another preferred embodiment of the present invention in the range of 0.01 to 0.5 mm, and in another preferred embodiment of the present invention, 0.1. 03 to 0.3 mm, and in still another preferred embodiment of the present invention it is 0.05 to 0.1 mm. If the line spacing is small, the thermal effect will also affect adjacent lines, so the hole will be large, the shape of the hole will be complicated, the depth of the hole will tend to be deep, but the thermal effect will be too large In some cases, it is difficult to form a complicated and deep hole. If the line spacing is large, the holes will be small, the shape of the holes will not be complicated and the holes will not be too deep, but the processing speed can be increased.
  • Other irradiation conditions may include an irradiation mode of irradiating a laser beam on the oxide-based non-magnetic ceramic molded body while radiating heat from the molded body.
  • an irradiation mode of irradiating a laser beam on the oxide-based non-magnetic ceramic molded body while radiating heat from the molded body For example, a method of irradiating a laser beam in a state where an oxide-based non-magnetic ceramic molded body and a metal molded body having a higher thermal conductivity than the oxide-based non-magnetic ceramic molded body are in contact with each other. A method of irradiating a laser beam while holding it in a hollow state may be used.
  • the wavelength of the pulsed laser light may be 500 to 11,000 nm.
  • a method for producing a composite molded article of an oxide-based nonmagnetic ceramic molded article having a roughened structure and a resin molded article In the first step, the first production method, the second production method, or the second 3 manufactures a non-magnetic ceramics molded body having a roughened structure on the surface by the manufacturing method.
  • a portion including the roughened structure of the oxide-based nonmagnetic ceramics molded body having a roughened surface on the surface obtained in the first step is arranged in a mold, and the resin molded body is
  • the portion including the roughened structure of the non-magnetic ceramics molded body irradiated with the laser beam in the first step is arranged in a mold, and at least the rough surface is formed. Compression molding in a state where the portion including the modified structure and the resin to be the resin molded body are in contact with each other.
  • 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.
  • 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.
  • 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.
  • a thermosetting resin a prepolymer form can be used, and a heat curing treatment can be performed in a later step.
  • 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.
  • a known fibrous filler can be blended with these thermoplastic resins, thermosetting resins, and thermoplastic elastomers.
  • Known fibrous fillers include carbon fibers, inorganic fibers, metal fibers, and organic fibers.
  • Carbon fibers are well-known, and PAN-based, pitch-based, rayon-based, and lignin-based carbon fibers can be used.
  • the inorganic fibers include glass fibers, basalt fibers, silica fibers, silica / alumina fibers, zirconia fibers, boron nitride fibers, and silicon nitride fibers.
  • the metal fibers include fibers made of stainless steel, aluminum, copper, and the like.
  • polyamide fibers whole 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.
  • 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.
  • these fibrous fillers those having a fiber diameter in the range of 3 to 60 ⁇ m 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 ⁇ m in one preferred embodiment of the present invention, and 7 to 20 ⁇ m in another preferred embodiment of the present invention.
  • the compounding amount of the fibrous filler relative to 100 parts by mass of the thermoplastic resin, the thermosetting resin, or the thermoplastic elastomer is 5 to 250 parts by mass. In another preferred embodiment of the present invention, the amount is 25 to 200 parts by mass, and in still another preferred embodiment of the present invention, the amount is 45 to 150 parts by mass.
  • the first manufacturing method, the second manufacturing method, or the second manufacturing method is performed.
  • a non-magnetic ceramic molded body having a roughened structure on the surface is manufactured by the manufacturing method of 3.
  • the oxide-based nonmagnetic ceramic molded article and the rubber molded article obtained in the first step are integrated by applying a known molding method such as press molding or transfer molding.
  • a portion including a roughened structure of an oxide-based nonmagnetic ceramic molded body is arranged in a mold, and the portion including the roughened structure is heated. After the uncured rubber to be the rubber molded body is pressed in a pressurized state, it is taken out after cooling.
  • the transfer molding method for example, a portion including a roughened structure of an oxide-based non-magnetic ceramic molded body is placed in a mold, and the uncured rubber is injection-molded in the mold, and then Then, by heating and pressurizing, the portion including the roughened structure of the oxide-based non-magnetic ceramics molded body and the rubber molded body are integrated, and taken out after cooling.
  • 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 article used in this step is not particularly limited, and a known rubber can be used, but does not include a thermoplastic elastomer.
  • Known rubbers include ethylene-propylene copolymer (EPM), ethylene-propylene-diene terpolymer (EPDM), ethylene-octene copolymer (EOM), ethylene-butene copolymer (EBM), ethylene-octene terpolymer (EODM), Ethylene- ⁇ -olefin rubber such as ethylene-butene terpolymer (EBDM); ethylene / acrylate rubber (EAM), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), styrene- Butadiene rubber (SBR), alkylated chlorosulfonated polyethylene (ACSM), epichlorohydrin (ECO), polybutadiene rubber (BR), natural rubber (
  • the rubber may contain a curing agent according to the type of the rubber, if necessary.
  • 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.
  • an adhesive layer can be interposed on the joint surface between the oxide-based non-magnetic ceramic molded article and the rubber molded article.
  • the oxide-based non-magnetic ceramic molded body is roughened by the first, second, or third manufacturing method using a continuous wave laser or a pulse wave laser in the same manner as described above.
  • an adhesive adheresive solution
  • the adhesive may be press-fitted.
  • the adhesive is not particularly limited, and a known thermoplastic adhesive, thermosetting adhesive, rubber-based adhesive, or the like can be used.
  • 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.
  • thermosetting adhesive examples include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane, and vinyl urethane.
  • 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.
  • the part including the surface of the oxide-based non-magnetic ceramic molded body on which the adhesive layer is formed is placed in a mold, and the surface of the oxide-based non-magnetic ceramic molded body and the uncured rubber to be a rubber molded body are removed.
  • a step of heating and pressurizing in a state of being in contact with each other to perform integration is performed.
  • 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.
  • the metal used is not limited as long as it has a melting point lower than the melting point of the oxide-based non-magnetic ceramic constituting the oxide-based non-magnetic ceramic molded body.
  • 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.
  • the metal molded body is pressed against the adhesive layer of the oxide-based non-magnetic ceramic molded body having the adhesive layer to be bonded and integrated.
  • 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.
  • 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.
  • the monomer, oligomer or mixture thereof forming the UV-curable resin layer is brought into contact with the portion including the roughened portion of the oxide-based non-magnetic ceramic molded body (monomer, oligomer Or contacting a mixture thereof).
  • a step of applying the monomer, the oligomer, or a mixture thereof to a portion including a roughened portion of the oxide-based nonmagnetic ceramic molded body may be performed. it can.
  • brush coating, application using a doctor blade, roller application, casting, potting, or the like can be used alone or in combination.
  • the step of contacting the monomer, the oligomer or a mixture thereof includes enclosing a portion including a roughened portion of the oxide-based non-magnetic ceramic molded body with a mold, and placing the monomer, oligomer or a mixture thereof in the mold. Can be performed.
  • the oxide-based nonmagnetic ceramic molded body is placed in a mold with the roughened portion facing upward, and then the monomer, oligomer or a mixture thereof is placed in the mold.
  • a step of injecting the mixture can be performed.
  • the contacting step of the monomer, the oligomer or the mixture thereof, the monomer, the oligomer or the mixture thereof enters the pores of the roughened portion of the oxide-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).
  • 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 mono
  • 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.
  • cationic polymerizable monomer examples 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.
  • 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 [
  • the oligomer of the radical polymerizable monomer and the cationic polymerizable monomer includes a monofunctional or polyfunctional (meth) acrylic oligomer.
  • 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.
  • 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.
  • 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.
  • a photopolymerization initiator can be used with respect to 100 parts by mass of the monomers, oligomers or mixture thereof.
  • the monomer, oligomer or mixture thereof in contact with the portion including the roughened portion of the oxide-based non-magnetic ceramic molded body is cured by irradiating UV to cure the curable resin layer.
  • a composite molded article having the same can be obtained.
  • the method for producing a composite molded article of the present invention is a composite molded article of an oxide non-magnetic ceramic molded article having a roughened structure, for example, an oxide non-magnetic ceramic molded article having a roughened structure having a different shape. It can be manufactured by using a plurality of pieces and joining and integrating them via an adhesive layer formed on the joining surface.
  • the adhesive layer can be formed, for example, by applying an adhesive to the roughened structure portion of the oxide-based nonmagnetic ceramic molded body.
  • the adhesive the same adhesive as that used in the production of the other composite molded body described above can be used.
  • a composite molded article composed of a non-magnetic ceramic molded article of a different type from an oxide-based non-magnetic ceramic molded article can be manufactured in the same manner.
  • a different type of non-magnetic ceramic molded body is used. After forming the adhesive layer with the surface of the magnetic ceramic molded body also having a roughened structure, the adhesive layer of the non-magnetic ceramic molded body of a different type from the surface having the adhesive layer of the oxide non-magnetic ceramic molded body
  • the composite molded body can be manufactured by bonding and integrating the surfaces having the above.
  • non-magnetic ceramics include carbides, nitrides, borides, and silicides.
  • 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.
  • the thermal shock temperature is a temperature at which a test piece (4 ⁇ 35 ⁇ 3 mm thick) of a heated oxide-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 oxide-based non-magnetic ceramic molded body, and those Ra are measured by a one-shot 3D shape measuring machine ( Keyence).
  • Rz maximum height: 11 lines of 1.5 mm length are drawn on the surface of the roughened structure portion of the oxide-based non-magnetic ceramic molded body, and those Rz are measured with a one-shot 3D shape measuring instrument (Keyence Corporation). Manufactured).
  • Sa (arithmetic mean height): Sa in a range of 9 ⁇ 1.8 mm on the surface of the roughened structure portion of the oxide-based non-magnetic ceramic molded body was measured by a one-shot 3D shape measuring instrument (manufactured by Keyence).
  • Sz (maximum height) Sz in 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 instrument (manufactured by Keyence).
  • Sdr developed area ratio of interface: Indicates how much the developed area (surface area) of the defined area is increased with respect to the area of the defined area, and Sdr of a completely flat surface is 0. Sdr was measured with a one-shot 3D shape measuring instrument (manufactured by Keyence).
  • Sdq root-mean-square slope: a parameter calculated by the root-mean-square of the slope at all points in the defined area, and Sdq of a perfectly flat surface is 0. If the surface has a slope, Sdq increases. For example, Sdq becomes 1 on a plane including a 45 ° tilt component. It was measured by a one-shot 3D shape measuring machine (manufactured by Keyence).
  • cross irradiation After irradiating continuous wave laser light so that ten grooves (first group of grooves) are formed at an interval of 0.05 mm, in a direction orthogonal to the first group of grooves.
  • the continuous wave laser beam was applied so that ten grooves (second group of grooves) were formed at intervals of 0.05 mm.
  • 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 interval between the cross irradiation and the bidirectional irradiation is the distance between the intermediate positions of the widths of adjacent grooves (lines).
  • FIGS. 7 to 14 show SEM photographs of portions of the oxide-based non-magnetic ceramic molded bodies of Examples 1 to 7 and Comparative Example 2 having a roughened structure.
  • the magnification of the SEM photograph was taken at 200 ⁇ , but is not limited to 200 ⁇ , and may be adjusted to a magnification at which the roughened structure can be easily observed.
  • the photograph can be taken at 200 to 400 ⁇ .
  • Example 1 The planar shapes of the concave portions in Example 1 (FIG. 7), Example 2 (FIG. 8), Example 4 (FIG. 10), and Example 6 (FIG. 13) are as shown in FIGS. Was.
  • the planar shapes of the concave portions of the third embodiment (FIG. 9) and the fifth embodiment (FIG. 11) are shown in FIGS. 4 (a) to 4 (e) and those shown in FIGS. Such a shape was combined.
  • the planar shape of the recess in Example 7 (FIG. 14) was as shown in FIGS. 4 (a) to 4 (e).
  • Comparative Example 1 in which the irradiation speed of the laser beam was slow was broken into a part of the molded body and divided into two or more parts. In Comparative Example 2, no hole was formed and the surface was deformed in a wrinkled shape.
  • the zirconia molded articles, alumina molded articles, steatite molded articles, and composite molded articles of the cordierite molded articles and the resin molded articles of Examples 1 to 7 had high bonding strength, so that other materials (heat It is considered that a composite molded article having high bonding strength can be obtained even when a composite molded article with a curable resin, rubber, elastomer, metal, or UV curable resin) is manufactured.
  • Example 8 The surface of a nonmagnetic ceramic molded body (10 ⁇ 50 ⁇ 2 mm thick plate) of the type shown in Table 2 was irradiated with pulsed laser light under the conditions shown in Table 2 to roughen the surface.
  • FIG. 16 shows an SEM photograph after roughening.
  • Example 8 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 non-magnetic ceramic molded body of Example 8 The structure after roughening was the same as that of the other examples.
  • the oxide-based non-magnetic ceramic molded article having a roughened structure on its surface according to the present invention is used as an intermediate of a composite molded article of the oxide-based non-magnetic ceramic molded article and a resin, rubber, elastomer, or metal. be able to.

Abstract

L'invention concerne un corps moulé en céramique non magnétique doté, sur sa surface, d'une structure rugueuse, la structure rugueuse présentant des irrégularités, la forme de la section transversale des irrégularités, dans la direction de l'épaisseur, ayant une surface courbe, et la céramique non magnétique étant une céramique non magnétique à base d'oxyde.
PCT/JP2019/037772 2018-09-27 2019-09-26 Corps moulé en céramique non magnétique doté, sur sa surface, d'une structure rugueuse et procédé de fabrication associé WO2020067249A1 (fr)

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