WO2015199244A1 - 構造体の形成に用いる形成用材料と形成方法 - Google Patents
構造体の形成に用いる形成用材料と形成方法 Download PDFInfo
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- WO2015199244A1 WO2015199244A1 PCT/JP2015/068725 JP2015068725W WO2015199244A1 WO 2015199244 A1 WO2015199244 A1 WO 2015199244A1 JP 2015068725 W JP2015068725 W JP 2015068725W WO 2015199244 A1 WO2015199244 A1 WO 2015199244A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/148—Agglomerating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
- B22F10/16—Formation of a green body by embedding the binder within the powder bed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
- B22F10/18—Formation of a green body by mixing binder with metal in filament form, e.g. fused filament fabrication [FFF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Definitions
- the present invention relates to a forming material and a forming method used for forming a structure.
- This application claims priority based on Japanese Patent Application No. 2014-133021 filed on June 27, 2014, the entire contents of which are incorporated herein by reference.
- a metal material and a ceramic material have been widely used in general since characteristics such as high strength can be realized.
- resin materials having various functions have been combined and used for the purpose of adding further functions to the metal material or ceramic material.
- a method for forming a structure including a resin material for example, a casting molding method or an injection molding method is known.
- a thermoplastic resin as a main component and, if necessary, a forming material containing a material other than a thermoplastic resin such as metal or ceramic is heated to a temperature at which a predetermined fluid state can be obtained.
- a structure having the target shape is formed by casting or injecting into a mold having a cavity having a shape.
- these forming materials contain carbon fiber or metal oxide powders for the purpose of improving the mechanical strength of the structure.
- examples of a method for forming a structure without using a mold include a thermal spraying method and a three-dimensional molding method (also referred to as an additive manufacturing method).
- a thermal spraying method a powdered thermal spraying material including a resin material and a material other than a resin such as a metal or ceramic is heated, and the thermal spraying material in a softened or molten state is sprayed on the base material and deposited.
- a structure made of this thermal spray material is formed.
- a powder spray composition composed of two or more kinds of thermoplastic resins, a simple metal, a metal oxide powder, and wear-resistant particles are added. Etc. are disclosed.
- the above-described injection molding method has a demerit that a molding die must be prepared for each structure. Further, this mold has a problem that it is easily deformed when an injection molding material including a relatively hard non-resin material is used. Further, in the above-described thermal spraying method, since the thermal spray material is heated to an extremely high temperature, the resin material is altered during the thermal spraying process, and the resin material can function as a binder, but the characteristics inherent to the resin material are lost. Inevitable or reduced.
- the formed structure has a large variation in characteristics between a portion made of a resin material and a portion made of a non-resin material, and it is difficult to obtain a homogeneous structure. It was. In general, since the difference in density between a resin material and a non-resin material such as metal or ceramic is large, this problem tends to become more prominent as the size of the non-resin material compounded in the resin material becomes smaller.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a highly homogenous structure including a resin material and a non-resin material such as metal or ceramic without using a mold. It is providing the forming material which can form. Moreover, this invention provides the formation method using this formation material as another side surface.
- This forming material is a powder containing a resin material and at least one non-resin material selected from the group consisting of metals and ceramics.
- the lowest heater temperature at which the resin material can be molded with an indentation pressure of 3500 psi using an indentation molding machine is set as the minimum molding temperature, and the resin material with an indentation pressure of 3500 psi using an indentation molder.
- the powder was deposited in a softened or molten state within a temperature range of the resin material molding upper limit temperature + 100 ° C.
- the homogeneity index N obtained by dividing the variation of the porosity Rn by the average value of the porosity Rn Is less than 0.2.
- the ratio of the resin material to the total of the resin material and the non-resin material is 20% by volume to 80% by volume. .
- the upper average particle diameter is 5 ⁇ m or more and 200 ⁇ m or less.
- the resin material and the non-resin material are blended more uniformly, and the unevenness and variation in the characteristics of the structure can be suppressed.
- the “average particle diameter” means, unless otherwise specified, the particle diameter (50%) in the volume-based particle size distribution measured by the particle size distribution measuring apparatus based on the laser scattering / diffraction method. volume-average particle size, hereinafter, shall mean also) be abbreviated as D 50..
- the forming material may be a mixed powder in which particles made of the resin material and particles made of the non-resin material are mixed.
- it may be a granulated powder obtained by granulating particles made of the resin material and particles made of the non-resin material.
- both the particles made of the resin material and the particles made of the non-resin material have an average particle diameter of 5 ⁇ m or more and 200 ⁇ m or less.
- the forming material may be a composite powder in which the resin material is provided on at least a part of the surface of the particles made of the non-resin material. With such various configurations, for example, even when there is a difference in density between the resin material and the non-resin material, it is preferable that both can be blended more uniformly in the structure.
- the resin material is selected from the group consisting of polyolefin, polyvinyl carbonate, polyvinyl phenol, polyurethane, polystyrene, acrylonitrile / butadiene / styrene copolymer, polyethylene terephthalate, and polyamide. It is characterized by being 1 type or 2 types or more. A structure having the characteristics of the specific resin material can be realized while utilizing the characteristics of these resin materials.
- the resin material has an antibacterial property having an antibacterial activity value of 2.0 or more. With such a configuration, a structure having such antibacterial activity can be obtained even after formation.
- the technology disclosed herein provides a method for forming a structure.
- a forming method includes preparing a powdery forming material including a resin material and at least one non-resin material selected from the group consisting of metals and ceramics, and forming the forming material into the resin material.
- Forming a structure having a predetermined shape without using a mold by depositing in a softened or molten state in a temperature range of not less than the molding lower limit temperature of the resin material and not exceeding the molding upper limit temperature of the resin material + 100 ° C. It is characterized by.
- the molding lower limit temperature is the lowest heater temperature at which the resin material can be molded with an indentation pressure of 3500 psi using an indentation mold molding machine (also referred to as a heating and pressure embedding machine). Is the highest heater temperature at which the resin material can be molded at an indentation pressure of 3500 psi using an indentation molding machine. As a result, it is possible to form a highly homogenous structure having both the original properties of the resin and the characteristics of the non-resin material without using a mold while suppressing the deterioration of the resin material.
- the forming material is heated in a state of being dispersed in a dispersion medium.
- the forming material can be efficiently used for forming according to the forming method.
- the forming material is deposited using a thermal spraying method to form the structure.
- a structure having a more precise structure can be formed.
- the forming material is deposited using a three-dimensional molding machine to form the structure. Thereby, the structure of a more complicated form can be formed.
- the method of forming a structure disclosed herein is characterized by essentially including the following steps. (1) Preparing a powdery forming material containing a resin material and at least one non-resin material selected from the group consisting of metals and ceramics. (2) A molding die is used by depositing the forming material in a softened or molten state in a temperature range of not less than the lower limit molding temperature of the resin material and not higher than the upper limit molding temperature of the resin material + 100 ° C. Without forming a structure of a predetermined shape.
- the resin material used in the technology disclosed herein plays a role as a binder that binds the non-resin material in the structure after formation, and a role as a functional material that imparts desired characteristics to the structure. Can also be included.
- a resin material is not particularly limited, and various resin materials can be appropriately selected and used according to desired characteristics and the like. For example, specifically, it is preferable to use a thermoplastic resin, a thermosetting resin, or the like that can be suitably formed by heating.
- thermoplastic resin synthetic resins that can be molded by heating can be broadly included without limitation.
- thermoplastic means a property that reversibly softens when heated and can be plastically deformed, and reversibly cures when cooled.
- a resin having a chemical structure composed of a linear or branched polymer can be considered.
- polyvinyl chloride PVC
- PE polyethylene
- PP polypropylene
- PS polystyrene
- thermoplastic polyester acrylonitrile butadiene styrene
- ABS acrylonitrile styrene
- AS polyacrylonitrile styrene
- PMMA methyl methacrylate
- PVA polyvinyl alcohol
- PVDC polyvinylidene chloride
- PET polyethylene terephthalate
- PET vinyl acetate
- PA polyamide
- POM polyacetal
- PC polycarbonate
- PPE polyphenylene ether
- m-PPE modified polyphenylene ether
- PBT ultrahigh molecular weight polyethylene
- UHPE polyvinylidene fluoride
- PVdF polyvinylidene fluoride
- Zineering plastic polysulfone (PSF), polyethersulfone (PES), polyphenylene sulfide (PPS), polyarylate (PAR), polyamideimide (PAI), polyetherimide (PEI), polyetheretherketone (PEEK) And super engineering plastics such as polyimide (PI), liquid crystal polymer (LCP), and polytetrafluoroethylene (PTFE).
- PSF polysulfone
- PES polyethersulfone
- PPS polyphenylene sulfide
- PAR polyarylate
- PAI polyamideimide
- PEI polyetherimide
- PEEK polyetheretherketone
- super engineering plastics such as polyimide (PI), liquid crystal polymer (LCP), and polytetrafluoroethylene (PTFE).
- polyalkylene terephthalate represented by polyvinyl chlorides, polycarbonates, PET, PBT and the like, PMMA, and the like are preferable. Any one of these may be used alone,
- thermosetting resin a synthetic resin that undergoes polymerization to form a polymer network structure upon heating and cannot be restored by curing can be widely included without limitation.
- thermosetting is a property in which a reaction proceeds in a polymer by heating and crosslinking occurs to form a network structure and cure.
- phenol resin PF
- epoxy resin EP
- melamine resin MF
- urea resin urea resin, UF
- unsaturated polyester resin UP
- alkyd resin polyurethane
- PUR polyurethane
- thermosetting resin such as polyvinylphenol (PVP) and novolac type phenol resins, epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins and biphenyl type epoxy resins, polyurethane resins such as polyurethane foams and polyurethane elastomers, etc.
- the thermosetting resin may be, for example, a mixture of low molecular weight monomers or a polymer that has been polymerized to some extent. Any one of these may be used alone, or two or more of them may be used in combination (including a blend).
- Non-resin material used in the technology disclosed herein can have a role as a functional material that imparts desired characteristics to the structure together with the non-resin material in the structure after formation.
- a non-resin material is not particularly limited, but various materials can be appropriately selected from various metal materials and ceramic materials according to desired characteristics.
- the metal material may be a simple substance of various metal elements or an alloy thereof.
- an alloy here is the meaning which includes the substance which consists of one metallic element and other one or more elements, and shows a metallic property, Comprising:
- the mixing method is a solid solution, an intermetallic compound. And a mixture thereof.
- this metal material is an alloy, the number of constituent elements is not particularly limited. For example, it may be two types (binary alloys) or three or more types (ternary or higher alloys). May be.
- Specific examples of metal elements constituting such a metal material include metalloid elements such as B, Si, Ge, Sb, and Bi, Mg, Ca, Sr, Ba, Zn, Al, Ga, In, and Sn.
- Pb and other typical elements Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Au and other transition metal elements, La
- Examples include lanthanoid elements such as Ce, Pr, Nd, Er, and Lu.
- the ceramic material is not particularly limited.
- an oxide ceramic made of a metal oxide a nitride ceramic made of a metal nitride, a carbide ceramic made of a metal carbide, other metal borides, and fluoride.
- examples thereof include ceramics composed of fluoride, hydroxide, carbonate, phosphate and the like.
- the metal constituting the ceramic for example, the metal elements listed above can be considered.
- Ceramic materials include silica (SiO 2 ), magnesia (MgO), calcia (CaO), strontium oxide (SrO), scandium oxide (Sc 2 O 3 ), and yttria (Y 2 ).
- CoO X cobalt oxide
- NiO nickel oxide
- CuO silver oxide
- AuO silver oxide
- ZnO zinc oxide
- alumina Al 2 O 3
- gallium oxide Ga 2 O 3
- indium oxide In 2 O 3
- tin oxide SnO 2
- bismuth oxide BiO X ; for example, Bi 2 O 3
- ceria CeO 2
- PrO X praseodymium oxide
- Nd 2 O 3 oxidation Oxide ceramics such as erbium (Er 2 O 3 ), lutetium oxide (Lu 2 O 3 ), germanium oxide (GeO 2 ), antimony oxide (Sb 2 O 5 ); silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), boron nitride (BN), sialon (sial
- the ceramic material disclosed here is not necessarily limited to the above composition.
- it may be a material to which various other elements are added or a compounded material for the purpose of obtaining desired characteristics. These ceramics may be used alone or in combination of two or more.
- any one or more of the above resin materials, metal materials, and ceramic materials preferably have any functionality. Since the structure formation method disclosed herein performs the formation process of the next step at a low temperature, these functionalities can be maintained even in the structure. Such functionality is not particularly limited. For example, as an example, high strength, high hardness, high toughness, high elasticity, high ductility, heat resistance, wear resistance, biodegradability, conductivity, piezoelectricity, antibacterial properties, Examples thereof include light transmissivity, hydrophilicity, polarization, releasability, photochromic property, photocatalytic activity, biofunctionality, design properties (for example, color tone, glossiness), discoloration resistance, weather resistance (light) property, and the like.
- the antibacterial property may be an antibacterial property inherently possessed by polyvinylphenol resin or the like based on its phenol skeleton, or an antibacterial property inherently possessed by silver, copper, zinc, etc. It may be antibacterial that the material comes to be provided with.
- the resin material that is particularly easily altered by heat has an antibacterial property having an antibacterial activity value of 2.0 or more.
- antibacterial activity value is more preferably 3.0 or more, and further preferably 5.0 or more.
- antibacterial activity value refers to a test product (for example, antibacterial processed product) and a reference product (for example, unprocessed product) based on the provisions of JIS Z2801: 2012 (for ceramic materials, JIS R1702: 2012).
- this antibacterial activity value is 2.0 or higher, that is, a death rate of 99% or higher, it can be determined that there is an antibacterial effect (has antibacterial properties).
- a ceramic material that selectively absorbs visible light of a specific wavelength and exhibits vivid color.
- a ceramic material is not particularly limited, but may be colored by a color tone based on its own composition and crystal structure, or may be titanium (Ti), vanadium (V), chromium (Cr), manganese ( Transition elements (which may be in the form of ions) such as Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu) may be included as a cause of coloring.
- Such a ceramic material tends to change its color tone unintentionally due to a change in crystal structure or the like due to heating.
- the color tone of the material is suitably maintained, and the color tone change is suppressed.
- a material having any one color tone may be used, or materials having two or more different color tones may be used separately or mixed.
- color tone represents the color tone (color) of the resin material, metal material, and ceramic material based on attributes such as hue, brightness, and saturation.
- This color can be expressed and evaluated based on, for example, a human sensitive evaluation or a color display method defined in JIS Z 8730: 2009. Sensitive evaluation by humans enables more practical evaluation with weighting that takes into account the characteristics and application of the evaluation object.
- the evaluation by color display is, for example, by converting the color into a tristimulus value such as hue, brightness, and saturation and converting it into a uniform color space (UCS), for example, L * a * b * color system, etc. Can be displayed, and more objective evaluation is possible.
- the L * a * b * color system (CIE1976 (L * a * b * ); also referred to as CIELAB) can adopt a value measured by measurement using a color difference meter. .
- the above forming materials can be used in the form of powder.
- Such powders can be of various configurations.
- a mixed powder in which particles made of a resin material and particles made of a non-resin material are mixed or (b) particles made of a resin material, and a non-resin Examples thereof include a granulated powder obtained by granulating particles made of a material, and (c) a composite powder in which a resin material is provided on at least a part of the surface of a particle made of a non-resin material.
- the mixed powder is a mixture of particles made of a resin material and particles made of a non-resin material.
- the shape of these particles is not particularly limited, and if the size is sufficiently fine with respect to the maximum size of the structure (for example, 1/1000 or less of the maximum size of the structure), the particle referred to in the present invention. Can be included.
- the shape of such particles may be spherical, polygonal with corners, granular without corners, or indefinite shape. Further, for example, a prismatic shape, a plate shape, a needle shape, a fiber shape, or the like may be used.
- the size of these particles is not strictly limited. For example, it can be adjusted according to desired characteristics required for the structure, the configuration of an apparatus used for formation, and the like. For example, from the viewpoint that both are more uniformly dispersed in the structure, it is preferable that the particles made of the resin material and the particles made of the non-resin material have substantially the same size. Therefore, as an approximate guide, the upper limit of the average particle diameter of these particles can be, for example, about 50 ⁇ m or less, preferably 40 ⁇ m or less, more preferably about 35 ⁇ m or less.
- the lower limit of the average particle diameter is not particularly limited, and can be set to, for example, 0.5 ⁇ m or more, preferably 1 ⁇ m or more, more preferably 5 ⁇ m, in consideration of the handleability of the forming material as a powder.
- the thickness can be 10 ⁇ m or more.
- the forming material in the form of powder can be used for forming in the form of slurry (also referred to as suspension or ink) dispersed in an appropriate liquid medium.
- finer particles can be used, and a portion derived from the resin material and a portion derived from the non-resin material can be present in a more uniformly dispersed manner in the formed structure.
- the average particle diameter of each particle in preparing such a slurry is not strictly limited, but can be, for example, about 10 ⁇ m or less, preferably 8 ⁇ m or less, more preferably about 5 ⁇ m or less. can do.
- the granulated powder is a powder composed of particles having a larger particle diameter (granulated particles) formed by bonding particles made of a resin material and particles made of a non-resin material.
- the shape of the particles made of the resin material and the non-resin material, and the shape of the granulated particles are not particularly limited, and can be considered in the same manner as in the above-described mixed powder.
- particles made of a resin material having a finer particle diameter and particles made of a non-resin material are mixed together with a predetermined ratio of binder in a dry or wet manner, and classified as necessary. Can be prepared.
- particles made of a resin material adhere to particles made of a plurality of non-resin materials, and particles made of a plurality of non-resin materials are bonded together to form a granulated particle (agglomerated as a whole).
- Granular powder may be formed.
- the average particle diameter of the particles made of the resin material and the particles made of the non-resin material constituting the granulated powder may be substantially the same, or one of them may be intentionally made larger (or smaller). . From the viewpoint of forming a more homogeneous structure, the average particle size of these particles is substantially the same, and both are compared with the average particle size of the granulated powder (ie, the average particle size of the forming material). And sufficiently small.
- the average particle diameter (also referred to as the average primary particle diameter) of each of the particles made of the resin material and the non-resin material is, for example, 1/1000 of the average particle diameter (also referred to as the average secondary particle diameter) of the granulated powder.
- It can be set to about 1/10 (preferably 1/800 to 1/50, for example 1/500 to 1/100). Although not necessarily limited to this, more specifically, it is preferably 0.5 nm or more and 20 ⁇ m or less, more preferably 50 nm or more and 10 ⁇ m or less, and 0.5 ⁇ m or more and 5 ⁇ m or less. Particularly preferred.
- the binder is not particularly limited.
- an aqueous polymer binder such as polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), and styrene butadiene rubber (SBR), polyvinylidene fluoride (PVDF), polyvinylidene chloride ( Non-aqueous polymer binders such as vinyl halide resins such as PVDC), polyalkylene oxides such as polyethylene oxide (PEO), and acrylic resins can be preferably used.
- the binder is not particularly limited, and a polymer binder that can be bonded to the particles by being present in the form of particles or fibers in the granulated powder can be suitably used.
- the granulation method is not particularly limited, and various known granulation methods can be employed. For example, specifically, one or more methods such as rolling granulation method, fluidized bed granulation method, stirring granulation method, compression granulation method, extrusion granulation method, crushing granulation method, spray drying method, etc. Can be adopted. A spray drying method is preferable. Thereby, the particle
- the average particle size of the granulated powder is not particularly limited, but can be, for example, about 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably about 30 ⁇ m or less.
- the lower limit of the average particle diameter there is no particular limitation on the lower limit of the average particle diameter, and when considering the handleability of the forming material as a powder, for example, it can be 5 ⁇ m or more, preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, For example, it can be 20 ⁇ m or more.
- the composite powder is in a form in which a resin material is provided on at least a part of the surface of particles made of a non-resin material.
- the shape of the particles made of the non-resin material is not particularly limited, and can be considered in the same manner as in the above mixed powder.
- grains which consist of non-resin material should just be coat
- the form of the coating is not particularly limited, and the resin material may be provided in a substantially uniform layer shape on the surface of the particles made of the non-resin material. For example, a structure in which a non-resin material and a resin material are laminated may be used.
- a granular or small lump resin material may be integrally provided on the surface of particles made of a non-resin material.
- one or more granular or small block resin materials may be provided, or two or more resin materials may be provided.
- the method for producing this composite powder is not particularly limited.
- Particles made of a non-resin material may be prepared, and a resin material having a predetermined shape may be attached to at least a part of the surface of the particle or may be coated with an indefinite shape resin material.
- a composite material having a laminated structure is prepared by, for example, applying or bonding a resin material to a sheet-like non-resin material, and then pulverizing the composite to obtain a composite powder having an appropriate particle size. May be.
- the average particle size of the composite powder is not particularly limited, and for example, it is preferable to have the same size as that of the granulated powder.
- the content ratio of the resin material and the non-resin material is not particularly limited, and can be appropriately adjusted so that desired characteristics can be expressed in the structure.
- the ratio of the resin material to the total of the resin material and the non-resin material can be adjusted, for example, in the range of 20% by volume to 80% by volume.
- the ratio of the resin material is 20% by volume to 50% by volume (preferably 20% by volume to 40% by volume).
- the ratio of the resin material is 50% by volume to 80% by volume (preferably 60% by volume to 80% by volume). It can be.
- the forming material prepared above is used in an appropriate molding temperature range that is equal to or higher than the lower limit molding temperature of the resin material (the upper molding temperature limit of the resin material + 100 ° C.). It is deposited in a softened state or a molten state. As a result, the forming material in a softened or molten state is cooled, and a structure as a cured body formed by bonding the powders of the forming material to each other can be formed.
- the “minimum molding temperature” for the resin material is defined as the lowest heater temperature at which the resin material can be molded at 3500 psi using an indentation molding machine.
- the “maximum molding temperature” is defined as the highest heater temperature at which the resin material can be molded at 3500 psi using a cylinder molding machine. Further, the “heater temperature” is a temperature measured by using a thermocouple for the temperature of the housing portion of the molding material in this indentation molding machine.
- a pressure-type sample preparation machine equipped with a hydraulic pressure mechanism and a heating mechanism, which is widely used for the production of observation or test pellets, etc.
- a sample embedding machine that can embed an observation sample in a resin material can be particularly preferably used.
- the size of the molded body to be formed is, for example, about 20 mm to 50 mm in diameter (the thickness can be adjusted to about 10 mm to 100 mm depending on the sample amount), for example. It can be.
- the above-described molding lower limit temperature and molding upper limit temperature are measured using Simplimet 3000 manufactured by BUEHLER as an indentation molding machine.
- Simplimet 3000 for example, the temperature of the molding material container (mold) can be adjusted in units of 10 ° C. within a range of about 50 ° C. to 180 ° C.
- Whether molding is possible or not can be determined by determining whether the molding material used is a pellet-like solid (molded body) (that is, molding is possible). Specifically, if the molding material is not softened or melted properly below the lower molding temperature limit, the molding material is only pressed (consolidated) in the form of a powder, and compacted after molding. Collapses without maintaining its shape.
- whether or not the resin material can be molded is determined by placing the 100 g cylindrical weight in the center of the upper surface of the molded body without causing deformation such as depression or collapse. It can be implemented depending on whether it is maintained or not.
- an OIML standard weight (cylindrical type, F1 class, bottom surface) manufactured by Murakami Henki Seisakusho Co., Ltd. conforming to JIS B 7609: 2008 is used for a molded body formed of a resin material of 14 g using a mold having a diameter of 25 mm. It was evaluated whether or not formation was possible by placing a 22.0 mm diameter).
- the molding upper limit temperature if the molding upper limit temperature is exceeded, the forming material may be altered or decomposed, or the curing may be started (for example, when a thermosetting resin is included as a resin material), or softening or Since it is not melted, the molding material after molding becomes malfunctioning (deterioration or decomposition of the resin material), or the pressing itself becomes difficult due to curing, so it can be determined that molding is impossible.
- the presence or absence of alteration of the resin material is determined by appropriate analysis methods (for example, X-ray diffraction (XRD) method, Auger electron spectroscopy (AES) method, X-ray photoelectron spectroscopy (XPS) method).
- FT-IR Fourier transform infrared spectroscopy
- EDX energy dispersive X-ray spectroscopy
- WDX wavelength dispersive X-ray spectroscopy
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- the molding upper limit temperature of the resin material will be briefly described.
- the spraying temperature is equal to or lower than the molding upper limit temperature of the resin material (PPS) included in the amount of the forming agent (a) 200 ° C., and (b) 300 ° C.
- FIG. 1 shows the result of XRD analysis of the thermal spray coating (a) and (b) as a structure obtained by thermal spraying by the cold spray method. As shown in FIG. 1, when the molding material is molded at an appropriate temperature, the diffraction peak attributed to the resin material (PPS) is maintained even in the sprayed coating, and the resin material changes in quality before or after heating and molding. It turns out that it is not disassembled.
- the peak of the resin material in the XRD pattern is lowered or disappears, and in some cases, the peak of the decomposition product is confirmed. In this way, it is possible to confirm the presence or absence of alteration and decomposition of the resin material. Further, such an analysis result can be used in determining the above-described molding upper limit temperature.
- This forming material is made of non-resin material alumina (Al 2 O 3 , average particle size: 2 ⁇ m) and resin material polyphenylene sulfide (PPS, average particle size: 3 ⁇ m) in a volume of 1: 1. It is a granulated powder mixed and granulated at a ratio.
- a suitable molding temperature range for this forming material is 150 ° C. to 320 ° C., and the homogeneity index N is 0.15.
- the average particle size is 30 ⁇ m, and the particle size is 15 to 45 ⁇ m.
- the composite material of Al 2 O 3 and PPS is obtained by spraying this forming material by the cold spray method at (a) 200 ° C. and (b) 300 ° C. within the appropriate molding temperature range. It can be confirmed that a sprayed coating consisting of In addition, the hardness in the cross section of these sprayed coatings is 30 as Hv 0.05 , and it is confirmed that it is a favorable hardness.
- the molding lower limit temperature and the molding upper limit temperature as described above vary depending on conditions such as the chemical composition of the target resin material. Moreover, even if it is the resin material represented by the same chemical composition, it may differ also by the average number molecular weight etc.
- the temperature for a typical resin material is exemplified below as “molding lower limit temperature to molding upper limit temperature”.
- Polypropylene 180 ° C to 300 ° C
- Polyvinylphenol 160 ° C to 230 ° C
- ABS resin 200 ° C to 260 ° C
- Polyamide 240 ° C to 290 ° C
- Silicone resin 140 ° C-180 ° C
- Melamine resin 150-560 ° C
- PPS 150 ° C-320 ° C
- the method for depositing the forming material in a softened or molten state is not particularly limited.
- the forming material in the fluidized state or the softened and melted state is supplied onto the substrate, thereby being deposited. can do.
- heating this forming material to the moldable temperature range is illustrated.
- the deposition is not limited to depositing the forming material in a desired structure shape at a time, but the formation of the desired structure shape by repeatedly depositing the forming material in layers. It's okay.
- the means for supplying the forming material in a powder state or the forming material in a fluidized state or a softened and melted state is not particularly limited.
- any of a supply method in which a forming material and a supply device are supplied to a base material in a contact state a supply method in which a formation material is supplied from a supply device through a non-contact state, etc. Available. Examples of such a supply method include various contact or non-contact coating methods, printing methods, spraying methods, thermal spraying methods, and the like.
- the method for heating the forming material to the above state is not particularly limited.
- heating by heat conduction from a heat source, convection (conduction through a medium), radiation (radiation) or the like, or heating by a combination of two or more of these can be used.
- Examples of such a heating method include direct heating with a flame, plasma flame, high-temperature gas, etc., heating by heat transfer using heating means such as an electric furnace, heating by radiation of infrared rays, ultraviolet rays, lasers, etc.
- the heating temperature is set to a temperature equal to or higher than the molding lower limit temperature of the resin material included in the forming material. Heating to a temperature equal to or higher than the molding lower limit temperature is preferable because the forming material is provided with appropriate fluidity and can be densely deposited when supplied onto the substrate.
- the temperature of such heating depends on the supply method employed, it can be determined with reference to a temperature range in which a state in which molding is possible in the conventional injection molding method can be realized, as described above.
- the heating of the forming material is preferably not less than the above molding lower limit temperature, more preferably (molding lower limit temperature + 20) ° C. or more.
- the upper limit of heating can be set to a temperature of (molding upper limit temperature + 100) ° C.
- Such a temperature can be considered to be in a temperature range of approximately 500 ° C. or less although it depends on the resin material contained in the forming material. By depositing such a resin material at a relatively low temperature that does not cause alteration, characteristics inherent to the resin material can be exhibited in the structure.
- the heating temperature is preferably (forming upper limit temperature + 80) ° C. or less, more preferably (forming upper limit temperature + 50) ° C. or less, although it depends on the supply method employed.
- the thermal spraying method is a method of forming a deposit made of this material by spraying a powdered thermal spray material (formation material here) in a softened or molten state.
- a thermal spraying method having a lower operating temperature can be preferably employed.
- Typical examples of the thermal spraying method include a cold spray method, a low-temperature atmospheric pressure plasma spraying method, and a cold plasma method.
- the cold spray method is a method in which a working gas heated to a temperature lower than the melting point or softening point is accelerated to supersonic speed, and the accelerated working gas is in a solid phase state without melting the sprayed material.
- the substrate is deposited by colliding with the substrate at high speed.
- the resin material contained in this forming material can be softened by heat and deposited on the base material together with the non-resin material.
- the softened forming material is sprayed onto the substrate at a high speed, which is preferable in that an extremely dense structure can be obtained.
- a structure having a porosity of 10% or less, more preferably 7% or less, still more preferably 5% or less, particularly preferably 3% or less, for example, 1% or less can be formed.
- the “porosity” in the present specification refers to a value calculated by an image analysis method for the ratio of the pores in the structure in the cross-sectional image of the structure.
- the porosity is determined by cutting the structure at a plane orthogonal to the surface of the substrate, filling the resulting cross section with resin, and polishing with a digital microscope (for example, VC-7700, manufactured by OMRON Corporation).
- the cross-sectional image (for example, magnification 490 times) is acquired.
- the thermal spraying conditions by the cold spray method can be determined according to a conventional method.
- the cold spray method can be distinguished as a low pressure cold spray when the upper limit of the working gas pressure is 1 MPa, and as a high pressure cold spray when the upper limit of the working gas pressure is 5 MPa.
- an inert gas such as helium gas, nitrogen gas or a mixed gas thereof is mainly used as a working gas.
- the low pressure type cold spray the same kind of gas as that used in the high pressure type cold spray or compressed air is used as the working gas.
- it is more preferable to employ a low-pressure type cold spray because a forming material containing different materials is used as the thermal spray material.
- the working gas When forming a structure by high-pressure cold spray, the working gas is preferably cold at a pressure of 0.5 to 5 MPa, more preferably 0.7 to 5 MPa, even more preferably 1 to 5 MPa, and particularly preferably 1 to 4 MPa. It supplies to a spray apparatus and heats to the said predetermined temperature.
- a forming material is supplied to the working gas.
- the feed rate of the forming material is not particularly limited, but is preferably 1 to 200 g / min, more preferably 10 to 100 g / min.
- the forming material is preferably supplied to the working gas from the same direction as the working gas (coaxially rearward).
- the distance (spraying distance) from the nozzle tip of the cold spray device to the base material during spraying is preferably 5 to 200 mm, more preferably 10 to 100 mm, and the traverse speed of the nozzle of the cold spray device is preferably Is 1 to 300 mm / sec, more preferably 10 to 150 mm / sec.
- the dimension in the thickness direction of the structure formed at one time is, for example, preferably 50 to 1000 ⁇ m, and more preferably 100 to 500 ⁇ m.
- the structure body may be formed in a plurality of stages by once forming the structure body and stabilizing the structure body and further depositing a forming material on the surface of the structure body.
- the working gas is supplied to the cold spray device at a pressure of preferably 0.3 to 0.9 MPa, more preferably 0.4 to 0.6 MPa, and the above temperature is reached. Until heated.
- a forming material is supplied to the working gas.
- the supply speed of the forming material is not particularly limited, but it is preferable to supply the working gas from the direction coaxial with the working gas at a feeding speed of preferably 1 to 100 g / min, more preferably 10 to 100 g / min.
- the distance from the nozzle tip of the cold spray device to the substrate during spraying is preferably 5 to 100 mm, more preferably 10 to 40 mm, and the traverse speed of the nozzle of the cold spray device is preferably 1 to 300 mm.
- the dimension in the thickness direction of the structure formed at one time is, for example, preferably 50 to 1000 ⁇ m, more preferably 100 to 500 ⁇ m, and still more preferably 100 to 300 ⁇ m.
- the structure body may be formed in a plurality of stages by once forming the structure body and stabilizing the structure body and further depositing a forming material on the surface of the structure body.
- the working gas is preferably 0.3 to 1 MPa, more preferably 0.5 to 1 MPa, and most preferably 0.7. Supply to a cold spray device at a pressure of ⁇ 1 MPa and heat to the above temperature. Other conditions can be implemented similarly to the case where the above-described inert gas is used as the working gas.
- the forming material as the thermal spray material may be supplied to the thermal sprayer in the form of a slurry dispersed in an appropriate dispersion medium instead of in the form of powder.
- a dispersion medium containing an organic solvent examples include alcohols such as methanol, ethanol and isopropyl alcohol, toluene, hexane, and kerosene.
- Such a dispersion medium may be a mixture of water and an organic solvent as long as it contains an organic solvent.
- the content of the forming material in the slurry is not particularly limited.
- the solid concentration is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more. Especially preferred. In this case, it becomes easy to improve the size (thickness) of the structure manufactured per unit time from the forming material supplied as the slurry, that is, the thermal spraying efficiency.
- the content of the forming material in the slurry is preferably 85% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less. In this case, a slurry having required fluidity suitable for supply to the thermal spraying apparatus can be prepared.
- the three-dimensional molding method is a method of forming a structure made of this material by depositing the forming material in a layered form in a softened or molten state and laminating it corresponding to a desired three-dimensional shape. is there.
- the forming material may be deposited after being softened or melted, may be deposited after the forming material is deposited, or may be softened or melted, or the forming material may be deposited. It may be softened or melted.
- a linear material (for example, a material in the form of a wire, a rod, or the like) may be made based on the forming material disclosed herein, and the linear material may be melted and deposited.
- the following procedure can be used. That is, the above powdery forming material is prepared in a softened or molten state and supplied to the discharge means (modeling head) of the layered modeling apparatus. And while moving this discharge means at a high speed in the X-axis and Y-axis directions, the molding material in the softened / molten state is little by little from the discharge means while raising and lowering the modeling table appropriately in the Z-axis direction. Discharge in layers corresponding to the cross-sectional shape of the structure. Since the molding material is cooled and cured after being discharged, the molding material in a softened and molten state can be further deposited on the cured molding material. By repeating such a deposition operation, a three-dimensional laminated structure can be precisely formed.
- the forming material when the forming material is deposited and then softened or melted, the following procedure can be used. That is, the forming material is prepared as a powder or in the form of a slurry dispersed in an appropriate dispersion medium and supplied to the supply means. The supply means is moved at high speed in the X-axis and Y-axis directions, and the molding material is deposited in layers on the modeling table little by little from the supply means while appropriately moving the modeling table up and down in the Z-axis direction.
- the molding material is heated only in a portion corresponding to the cross-sectional shape of the target structure using a non-contact (for example, radiation) heating means such as infrared rays, ultraviolet rays, and lasers, and is softened or melted.
- a non-contact (for example, radiation) heating means such as infrared rays, ultraviolet rays, and lasers.
- the dispersion medium may be removed by drying such as natural drying or by such heating. Since the softened or melted molding material is cooled and hardened after a certain time, a powdery molding material can be further deposited on the cured molding material. By repeating such deposition and heating operations, a three-dimensional laminated structure can be precisely formed.
- the fluidity of a powdery forming material can be determined from the angle of repose.
- the angle of repose is an index that can indicate the fluidity of the powder, and since it depends on the particle size (average particle diameter) of the powder, etc.
- the angle of repose can be increased in the case of a powder having a small particle size and poor fluidity.
- the angle of repose is preferably 45 degrees or less, more preferably 35 degrees or less, and most preferably 30 degrees or less.
- the lower limit of the angle of repose is not particularly limited. For example, from the viewpoint of being hardly scattered, the angle of repose is set to 10 degrees or more, for example, 20 degrees or more.
- the forming material is a fine powder, it can be easily softened and melted by non-contact heating, or a more precise three-dimensional structure can be formed. From this viewpoint, it is preferable that the average particle diameter is 40 ⁇ m or less. More preferably, it is 30 micrometers or less, More preferably, it is 20 micrometers or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 5 ⁇ m or more because good fluidity is easily secured.
- the angle of repose is a base angle calculated from the diameter and height of a conical deposit generated when a forming material is dropped from a fixed height funnel onto a horizontal substrate. Is defined as Such angle of repose can be measured, for example, according to the provisions of JIS R 9301-2-2: 1999 “Alumina powder physical property measurement method-2: angle of repose”.
- the deposition of the forming material and heating without contact are performed. It should be done at the same time.
- the structure which consists of the said forming material can be formed at low temperature, without using a shaping
- a difference in density tends to occur between a resin material and a non-resin material such as a ceramic material or a metal material.
- the particles made of the resin material and the non-resin material such as the ceramic material or the metal material have an action in which the higher density moves downward and the lower density moves upward. Therefore, for example, if a forming material that is in a fluid state is put into a mold at once, the homogeneity between the resin material and the non-resin material is easily lost through such a molding process, and the structure also has uneven characteristics. Inclination is likely to occur.
- the forming material is deposited while being heated. Therefore, it is possible to suppress the loss of homogeneity between the resin material and the non-resin material in the structure and the occurrence of unevenness or inclination in the characteristics.
- the resin material and the non-resin material are integrated in the state of the forming material, and this state can be substantially maintained throughout the forming process. Thereby, a structure with higher homogeneity can be obtained.
- the structure can be determined based on the homogeneity index N calculated as follows.
- the uniformity index N can be obtained by dividing the variation in the porosity Rn obtained at this time by the average value of the porosity Rn.
- the “porosity” may be a porosity based on the image analysis method described above. Further, the “variation” is calculated by a value [1/2 of the difference between the maximum value (Rn max ) and the minimum value (Rn min ) of the obtained porosity Rn [(Rn max ⁇ Rn min ) / 2]. Can do. In the technique disclosed herein, the degree of variation regarding the porosity Rn is evaluated in a non-dimensional manner.
- the homogeneity index N when the homogeneity index N is less than 0.2, it is determined that the structure is homogeneous.
- a material having high homogeneity can be in a state where a non-resin material that is relatively difficult to mold and a resin material that is easy to mold are sufficiently mixed. For this reason, even if a non-resin material that is difficult to mold is included, a structure having suitable characteristics can be easily formed by managing the molding process within the temperature range in which molding is possible.
- the homogeneity index N is more preferably 0.18 or less, further preferably 0.14 or less, and particularly preferably 0.1 or less. Further, when the homogeneity index N is 0.2 or more, it can be determined that the structure is not homogeneous.
- the boundary value (here 0.2) of evaluation of homogeneity / heterogeneity based on the above-mentioned homogeneity index N can be changed depending on, for example, the density required for the structure and the shape precision.
- the structure formed in this way can suitably maintain the characteristics of the resin material and the non-resin material (metal material and / or ceramic material) included in the forming material. Therefore, for example, the functionality possessed by these resin materials and non-resin materials (metal materials and / or ceramic materials) is the same or well improved in structural materials, or the functionality is reduced. Small is preferable.
- the antibacterial activity value of the structure is preferably 2.0 or more.
- the antibacterial activity value is more preferably 3.0 or more, and further preferably 5.0 or more.
- it may be desirable that the difference between the antibacterial activity value in the resin material or non-resin material and the antibacterial activity value in the structure is small. More specifically, the difference in antibacterial activity value is preferably 1.5 or less, more preferably 1.0 or less, and particularly preferably 0.5 or less.
- the color tone for example, when it is desired to reflect the color tone of the material as it is or equivalently to the structure, it is desirable that the change in the color tone between the material and the structure is small.
- the change in the color tone between the material having the color tone and the structure can be grasped by, for example, the color difference.
- the index relating to the color difference There is no particular limitation on the index relating to the color difference.
- a lightness difference that is a difference between CIE lightness L * defined by JIS Z 8730: 2009 as described above: ⁇ L (may be expressed as ⁇ L * ) or , Ab hue difference: ⁇ ab (may be expressed as ⁇ H * ab ).
- the lightness difference ⁇ L is, for example, preferably 22 or less, more preferably 20 or less, from the viewpoint that the color of the desired material (particularly lightness) is suitably reflected in the structure.
- the following for example, 15 or less
- the hue difference ⁇ ab is preferably 10 or less, more preferably 8 or less, for example, from the viewpoint that the color of the desired material (particularly the hue) is suitably reflected in the structure. Particularly preferred is 5 or less.
- the hardness index when it is desired to reflect the hardness of the material as it is or equivalently in the structure, it is desirable that the hardness is maintained in the structure.
- the hardness index there are no particular limitations on the hardness index because various factors can be considered. For example, typically, Vickers hardness is adopted, and the ratio (hardness ratio) of the Vickers hardness of the structure to the material is 1 or more, that is, it is desirable that the hardness is maintained or improved. possible. Such hardness ratio can be measured based on the Vickers hardness test method defined in JISJZ 2244: 2009 and JIS R1610: 2003.
- a value calculated from the diagonal line of the indentation when a test load is applied to the surface of the test piece with an appropriate indenter using a commercially available hardness tester can be suitably employed.
- This hardness ratio is preferably 2 or more, and more preferably 3 or more.
- the upper limit of the hardness ratio is not particularly limited.
- glossiness when it is desired to reflect the glossiness of the material as it is or equivalently to the structure, it may be desirable that the glossiness is maintained in the structure.
- glossiness (measurement angle 20 °) can be adopted as an index that can be used to evaluate a high-quality and suitable glossiness, and the glossiness (also referred to as gloss value) is 50 or more. Is desirable.
- glossiness the glossiness of the direction of the structure measured using a commercially available glossometer at a measurement angle of 20 ° can be employed based on the method of measuring the specular glossiness described in JIS Z8741: 1997. .
- the glossiness is, for example, more preferably 70 or more, further preferably 80 or more, and 90 or more (for example, 100 or more) from the viewpoint that the structure has a high-quality gloss. It is particularly preferred.
- the upper limit of the glossiness is not particularly limited.
- Example 1 As a resin material, powdery polyvinylphenol (PVP, D 50 : 2 ⁇ m, average molecular weight: about 10,000, true density: 1.2 g / ml, moldable temperature range: 160 to 230 ° C.) was prepared.
- PVP powdery polyvinylphenol
- alumina powder Al 2 O 3 , D 50 : 5 ⁇ m
- cobalt powder Co, D 50 : 3 ⁇ m
- Iron powder AISI 4140 steel, D 50 : 8 ⁇ m
- forming materials 1 to 11 were prepared.
- the resin material and the non-resin material were mixed or blended so that the volume ratio was 1: 1.
- Liquid indicates a resin dispersion obtained by dissolving a resin material in an organic solvent (ethyl cellosolve).
- granulated indicates a granulated powder obtained by granulating a resin material and a non-resin material using a binder and integrating them.
- cladding indicates a composite powder made of coated particles in which the surface of particles made of a non-resin material is coated with a resin material.
- slurry indicates a form of slurry in which a powder made of a resin material and a powder made of a non-resin material are dispersed in ethanol as a dispersion medium at a ratio of 5% by volume.
- mixed powder indicates a mixed powder obtained by mixing a powder made of a resin material and a powder made of a non-resin material.
- the prepared forming materials 1 to 11 were supplied to the surface of the substrate by the forming method shown in Table 1 below to form a film-like structure.
- a base material an SS400 steel plate (70 mm ⁇ 50 mm ⁇ 2.3 mm) subjected to blasting with an alumina # 40 abrasive was used.
- “coating” is a method of preparing a PVP composition by dissolving the above PVP in toluene as a solvent, and spraying this PVP composition onto the surface of the substrate at room temperature (25 ° C.). After the coating, the PVP composition was heated to 100 ° C. together with the substrate, and then heated to 210 ° C. and thermally cured to form a layered structure having a thickness of 50 ⁇ m.
- “spraying A” uses the prepared forming material as a spraying material, and performs a CS spraying using a commercially available cold spray (CS) apparatus (made by Russia OCPS, Dymet), and has a thickness of 40 ⁇ m. It shows that a layered structure was formed.
- the spraying conditions were such that air was used as the working gas, the working gas pressure was 0.7 MPa, the working gas heater temperature was 500 ° C., the spraying distance was 20 mm, the spraying gun moving speed was 5 mm / sec, and the spraying powder supply rate was 15 g / min.
- the forming material is heated to about 150 ° C. or more and about 500 ° C. or less. Note that the temperature at which the forming material was heated in the CS apparatus was estimated from a value obtained by measuring the temperature of the forming material immediately after being deposited on the substrate using an infrared temperature measuring device.
- “Spraying B” uses the prepared forming material as the spraying material, and performs AP spraying using a commercially available atmospheric pressure plasma spraying (AP) apparatus (Praxair® Surface® Technologies, SG-100). This shows that a layered structure having a thickness of 40 ⁇ m was formed.
- the plasma generation conditions were as follows: argon gas 50 psi (0.34 MPa) and helium gas 50 psi (0.34 MPa) were used as the plasma working gas, the plasma generation voltage was 37.0 V, and the plasma generation current was 900 A.
- the spraying conditions were a spraying distance of 120 mm, a spraying gun moving speed of 5 mm / s, and a spraying powder supply amount of 20 g / min.
- the forming material is heated to about 1000 ° C. or higher.
- the temperature at which the forming material was heated in the AP apparatus was estimated from the value obtained by measuring the temperature of the forming material immediately after being deposited on the base material using an infrared temperature measuring device.
- the antibacterial activity value was calculated from the logarithmic value of the number obtained by dividing the number of bacteria after 24-hour culture of the reference product by the number of bacteria after 24-hour culture of the test product. The results are shown in the column of “Antimicrobial activity value” in Table 1.
- the antibacterial property can be determined to be effective (antibacterial property) when the antibacterial activity value is 2.0 or more, that is, the death rate is 99% or more.
- the porosity of each structure obtained above was measured as follows, and the homogeneity index N was calculated. That is, twelve cross-sectional images of each structure are taken with a microscope (490 times), and the ratio of the pore portion to the entire cross section is calculated from the area of the pore portion and the entire cross section based on each image. The porosity was determined. For this analysis, image analysis software (for example, Image Pro manufactured by Nippon Roper Co., Ltd.) was used. It was confirmed that the porosity of 12 for each structure thus obtained showed normality and equidispersity. And about these porosity, the homogeneity index
- the structure 3 was formed by thermal spraying B (atmospheric pressure plasma spraying method) at a high temperature, PVP was altered during the formation process, and the structure did not exhibit antibacterial properties. Further, since the structure is composed only of modified PVP, the hardness is No. It was about the same as 1, and it was confirmed that the uniformity was excellent.
- the structure 4 is formed by thermal spraying A at a low temperature using a granulated powder of PVP and alumina powder.
- the antibacterial property was lowered by the amount of the alumina powder blended, it was confirmed that the sufficiently high antibacterial activity value was maintained.
- the homogeneity index was 0. It was confirmed that a structure excellent in homogeneity with 1 was obtained. Also, the hardness ratio was 3, indicating that the hardness of the structure was greatly increased (that is, 3 times that of the PVP bulk body).
- the structure 5 is formed by thermal spraying B at a high temperature, although a granulated powder of PVP and alumina powder is used.
- PVP is altered and no. Similar to 3, the structure did not exhibit antibacterial properties.
- the homogeneity in the thermal spraying process is greatly deteriorated due to the alteration of PVP.
- hard alumina powder is blended, the hardness of the structure is No. Similar to 4, a high value was obtained.
- the structure 6 is formed by thermal spraying A at a low temperature using clad powder in which the surface of powdery alumina is coated with PVP.
- the antibacterial property was reduced by the amount of alumina, but no. It was confirmed that a sufficiently high antibacterial activity value almost equal to 4 was maintained. It was confirmed that the homogeneity index was less than 0.2, and in the clad powder, the homogeneity of PVP and alumina was maintained even in the thermal spraying process, and a structure having excellent homogeneity was obtained. Further, in the structure, No. is obtained by blending hard alumina. High hardness similar to 4 was obtained.
- the forming material is prepared in a slurry state and formed by thermal spraying A at a low temperature.
- the structure 8 is formed by thermal spraying A at a low temperature using a mixed powder of PVP and alumina powder.
- the hardness ratio is 2, and the hardness of the structure is No. 1. It was slightly lower than 4. However, no. The hardness was higher than 1. From the results of homogeneity, No. 1 formed from a slurry of PVP and alumina powder.
- a structure excellent in homogeneity was obtained.
- No. 9 The structure of No. 9 is No. 9.
- the forming material was prepared using titania powder instead of the alumina powder in Example 4. It was confirmed that the antibacterial property can be improved by changing the ceramic material to titania. In addition, regarding the homogeneity and hardness of the structure, no. It was confirmed that good results similar to those of No. 4 were obtained.
- No. The structure of No. 10 is No. 10.
- the forming material was prepared using cobalt powder instead of the alumina powder in Example 4. It was confirmed that the antibacterial property was further improved by changing alumina as a ceramic material to metallic cobalt. Since the bond strength at the interface between the cobalt powder and PVP is slightly inferior, the hardness ratio is 2, and the hardness of the structure is No. 1. It was lower than 4. However, no. The hardness was higher than 1. Regarding the homogeneity of the structure, no. It was confirmed that good results similar to those of No. 4 were obtained.
- No. The structure of No. 11 is No. 11.
- the forming material was prepared using iron powder instead of the alumina powder in Example 4.
- Iron (Fe) is a component that can be a nutrient for bacteria and bacteria. No. 2 and no. From the comparison with 4, it was confirmed that the antibacterial property of PVP could be completely eliminated by changing alumina as a ceramic material to metallic iron. In other words, it can be said that a structure suitable for bacteria retention was obtained. Since the bond strength at the interface between the iron powder and PVP is slightly inferior, the hardness ratio is 2, and the hardness of the structure is No. 1. It was lower than 4. However, no. The hardness was higher than 1. Regarding the homogeneity of the structure, no. It was confirmed that good results similar to those of No. 4 were obtained.
- a homogeneous structure can be formed by using the forming material disclosed herein and forming the structure by the molding method disclosed herein. Moreover, it has confirmed that this structure can be maintained after formation about the antibacterial property with which the material which comprises the forming material is provided, for example. Note that the forming material disclosed herein is in a state where the non-resin material and the resin material are sufficiently mixed. Therefore, it was confirmed that a structure having suitable characteristics as compared with conventional materials can be formed only by controlling the molding temperature within the temperature range in which the forming material can be molded.
- Example 2 (Forming material) Next, whether or not the structure formed using the forming material disclosed herein can appropriately maintain the color tone of the material constituting the forming material was confirmed below. That is, powdery polypropylene (PP, D 50 : 3 ⁇ m, melting point: 130 ° C., true density: about 0.9 g / cm 3 ) is used as the resin material, and iron-based ceramic powder ((Fe, Al, Mg) Cr 2 O, D 50 : 5 ⁇ m), and the forming materials 1 to 6 having the combinations and forms shown in Table 2 below were prepared. In the forming materials 2 to 5, the resin material and the ceramic material were mixed or blended so that the volume ratio was 1: 1.
- No. 2 formed by thermal spraying B of iron-based ceramic powder at high temperature. Although the structure No. 1 had high glossiness and full of glossiness, the maroon color, which is the color tone of the original Fe-based ceramic material, was changed to black, and the hue was lost in the formation process.
- the structure 6 is formed by thermal spraying A at low temperature using only PP powder. No. Although the structure 6 has a relatively small color difference due to thermal spraying, it is composed of only a resin material, so that the gloss value is the lowest value in all examples. That is, it can be said that this structure is not suitable for applications that require a certain aesthetic appearance such as gloss and gloss.
- the structure 2 is formed by thermal spraying A at a low temperature using a granulated powder of iron-based ceramic powder and PP powder. Glossiness is No. because PP is blended. Although it was lower than 1. Compared with 6, the value was sufficiently high. Since it was formed by thermal spraying A at a low temperature, the color difference was small, and it was confirmed that the color tone of the iron-based ceramic was generally maintained in the structure.
- No. 3 The structure of No. 3 is No. 3. 2 is formed by thermal spraying B at a high temperature using the same forming material as in FIG. Therefore, both the iron-based ceramic and PP in the granulated powder are altered. As compared with 2, the glossiness was further lowered and the color difference was increased.
- the structure 4 is formed by thermal spraying A at a low temperature using a clad powder of iron-based ceramic powder and PP.
- the clad powder is slightly inferior in homogeneity between the iron-based ceramic powder and PP as compared with the granulated powder. Although the glossiness was lower than that of No. 2, no. Compared with 6, the value was sufficiently high. The color difference was small, and it was confirmed that the color tone of the iron-based ceramic was well maintained in the structure.
- the structure 5 is formed by thermal spraying A at a low temperature using a mixed powder of iron-based ceramic powder and PP powder.
- the mixed powder was slightly inferior in homogeneity during movement due to the difference in density between the iron-based ceramic powder and PP, and the gloss value in the structure further decreased.
- no discoloration or the like due to heating of the PP powder was observed, the color difference was relatively small, and it was confirmed that the color tone of the iron-based ceramic was suitably maintained even in the structure.
Abstract
Description
また、上記の溶射法においては、溶射用材料を極めて高温にまで加熱するため、溶射過程において樹脂材料が変質してしまい、樹脂材料はバインダとして機能し得るものの、樹脂材料が本来有する特性が失われるか低減されることが避けられなかった。
これにより、樹脂材料の変質を抑えて、樹脂本来の性質と非樹脂材料の特性とを併せ持った均質性の高い構造体を、成形型を使用することなく形成可能な形成用材料が提供される。
なお、本明細書中における「平均粒子径」とは、特記しない限り、レーザ散乱・回折法に基づく粒度分布測定装置により測定された体積基準の粒度分布における積算50%での粒径(50%体積平均粒子径;以下、D50と略記する場合もある。)を意味するものとする。
このような多様な構成により、例えば、樹脂材料と非樹脂材料とに密度差がある場合であっても、構造体において両者をより均一に配合することができて好ましい。
これにより、樹脂材料の変質を抑えて、樹脂本来の性質と非樹脂材料の特性とを併せ持った均質性の高い構造体を、成形型を使用することなく形成することができる。
(1)樹脂材料と、金属およびセラミックからなる群から選択される少なくとも1種の非樹脂材料と、を含む粉末状の形成用材料を用意すること。
(2)上記形成用材料を、上記樹脂材料の成形下限温度以上で、(上記樹脂材料の成形上限温度+100℃)以下の温度範囲の軟化または溶融状態で堆積させることにより、成形型を用いることなく所定形状の構造体を形成すること。
(樹脂材料)
ここで開示される技術で用いる樹脂材料は、形成後の構造体において、上記の非樹脂材料を結合するバインダとしての役割を担うと共に、構造体に所望の特性を付与する機能性材料としての役割をも有することができる。このような樹脂材料としては特に制限されず、所望の特性等に応じて各種の樹脂材料を適宜選択して用いることができる。例えば、具体的には、加熱による形成を好適に行える、熱可塑性樹脂や熱硬化性樹脂等を用いることが好ましい。
熱硬化性樹脂としては、加熱すると重合を起こして高分子の網目構造を形成し、硬化して元に戻らなくなる合成樹脂を広く制限なく包含し得る。本明細書において、「熱硬化性」とは、加熱によって重合体中で反応が進行し、橋かけがおこって網状構造が形成され、硬化する性質である。具体的には、例えば、フェノール樹脂(PF),エポキシ樹脂(EP),メラミン樹脂(MF),尿素樹脂(ユリア樹脂、UF),不飽和ポリエステル樹脂(UP),アルキド樹脂,ポリウレタン(PUR),熱硬化性ポリイミド(PI)等が例示される。なかでも、ポリビニルフェノール(PVP),ノボラック型フェノール樹脂等のフェノール樹脂、ビスフェノールA型エポキシ樹脂,ビスフェノールF型エポキシ樹脂,ビフェニル型エポキシ樹脂等のエポキシ樹脂、ポリウレタンフォーム,ポリウレタンエラストマー等のポリウレタン等の樹脂であるのが好ましい。この熱硬化性樹脂としては、例えば、低分子単量体の混合物の状態であっても良いし、ある程度まで重合が進行した高分子であってもよい。これらは、いずれか1種を単独で用いても良いし、2種以上を組み合わせて(ブレンドを含む)用いるようにしても良い。
ここで開示される技術で用いる非樹脂材料は、形成後の構造体において、上記の非樹脂材料と共に、構造体に所望の特性を付与する機能性材料としての役割を有することができる。このような非樹脂材料としては、特に制限されないものの、各種の金属材料およびセラミック材料等の中から所望の特性等に応じて各種の材料を適宜選択して用いることができる。
金属材料としては、各種の金属元素の単体もしくはその合金であってよい。なお、ここでいう合金とは、一の金属元素と、他の一以上の元素とからなり、金属的な性質を示す物質を包含する意味であって、その混ざり方は、固溶体、金属間化合物およびそれらの混合のいずれであっても良い。この金属材料が合金である場合、その構成元素の数は特に制限されず、例えば、2種類(2元系合金)であっても良いし、3種類以上(3元系以上の合金)であっても良い。かかる金属材料を構成する金属元素としては、例えば、具体的には、B,Si,Ge,Sb,Bi等の半金属元素、Mg,Ca,Sr,Ba,Zn,Al,Ga,In,Sn,Pb等の典型元素、Sc,Y,Ti,Zr,Hf,V,Nb,Ta,Cr,Mo,W,Mn,Fe,Co,Ni,Cu,Ag,Au等の遷移金属元素、La,Ce,Pr,Nd,Er,Lu等のランタノイド元素が挙げられる。
セラミック材料としては特に制限されず、例えば、金属の酸化物からなる酸化物系セラミック,金属の窒化物からなる窒化物系セラミック,金属の炭化物からなる炭化物系セラミック,その他、金属のホウ化物,フッ化物,水酸化物,炭酸塩,リン酸塩等からなるセラミックが挙げられる。ここでセラミックを構成する金属としては、例えば、上記で挙げた金属元素を考慮することができる。
以上の樹脂材料、金属材料およびセラミック材料のいずれか1つ以上は、任意の機能性を備えているのが好ましい。ここに開示される構造体の形成方法は、次工程の形成プロセスを低温で行うため、これらの機能性が構造体においても維持され得る。かかる機能性とは特に制限されず、例えば、一例として、高強度、高硬度、高靱性、高弾性、高延性、耐熱性、耐摩耗性、生分解性、導電性、圧電性、抗菌性、光透過性、親水性、偏光性、剥離性、ホトクロミック性、光触媒活性、生体機能性、意匠性(例えば、色調、艶性等)、耐変色性、耐候(光)性等が挙げられる。
例えば、抗菌性については、ポリビニルフェノール樹脂等がそのフェノール骨格に基づき本質的に備えている抗菌性や、銀、銅、亜鉛等が本質的に備えている抗菌性であっても良いし、各種の抗菌剤が付与されることで当該材料が備えるようになった抗菌性であっても良い。
また、例えば、色調等の美観性については、アルミナやジルコニア等のセラミック材料等がその組成および結晶構造等に基づき本質的に備えている色調や、樹脂材料がその組成および構造に基づき本質的に備えている色調であっても良い。あるいはこれらの材料が、各種の着色料や顔料が添加されることで当該材料が備えるようになった色調であっても良い。
ここに開示される技術においては、特に熱により変質されやすい樹脂材料が、抗菌活性値2.0以上の抗菌性を有していることを好ましい態様としている。かかる抗菌性は、次工程の形成により得られる構造体において好適に維持される。この抗菌性は、抗菌活性値が3.0以上であるのがより好ましく、5.0以上であるのがさらに好ましい。
なお、本明細書において「抗菌活性値」とは、JIS Z2801:2012(セラミック材料についてはJIS R1702:2012)の規定に基づいて、試験品(例えば抗菌加工品)と参照品(例えば無加工製品)とにおける細菌を接種培養後の生菌数の対数値の差を示す値である。この抗菌活性値が2.0以上、すなわち99%以上の死滅率の場合に、抗菌効果がある(抗菌性がある)と判断することができる。
また、ここに開示される技術においては、上記の樹脂材料、金属材料およびセラミック材料の少なくとも1種が所望の色調(色、色彩)を備えたものであることを好ましい態様としている。特に、特定の波長の可視光を選択的に吸収して鮮やかな発色を呈するセラミック材料を備えていることが好ましい。かかるセラミック材料としては、特に限定されないが、自身の組成および結晶構造に基づく色調により着色しているものであっても良いし、チタン(Ti)、バナジウム(V)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)等の遷移元素(イオンの形態であり得る)が着色原因として含まれるものであっても良い。このようなセラミック材料は、加熱により結晶構造等が変化する等して、色調が意図せず変化されやすいが、ここに開示される技術によると、次工程の形成により得られる構造体において当該セラミック材料の色調が好適に維持され、色調変化が抑制される。このような色調を備える材料は、いずれか1色の色調を備える材料を用いても良いし、異なる2色以上の色調を備える材料を別々にまたは混合して用いるようにしても良い。
ここで混合粉末は、樹脂材料からなる粒子と、非樹脂材料からなる粒子とが混合された状態のものである。これらの粒子の形状は特に制限されず、その寸法が構造体の最大寸法に対して十分に微細であれば(例えば、構造体の最大寸法の1/1000以下)、本発明でいうところの粒子に包含することができる。このような粒子の形状は、球形であってもよいし、角のある多角形や、角のない粒状、不定形状などであってよい。また例えば、角柱状、板状、針状、繊維状等の形状であってもよい。
ここで造粒粉末は、樹脂材料からなる粒子と、非樹脂材料からなる粒子とを互いに結合させてなる、より粒径の大きな粒子(造粒粒子)からなる粉末である。これら樹脂材料からなる粒子および非樹脂材料からなる粒子の形状、さらに造粒粒子の形状は、特に制限されず、上述の混合粉末における場合と同様に考慮することができる。このような造粒粉末は、例えば、粒径のより微細な樹脂材料からなる粒子および非樹脂材料からなる粒子を所定の割合のバインダとともに乾式または湿式で混合し、必要に応じて分級等することで用意することができる。なお、バインダを使用することなく、樹脂材料からなる粒子が、複数の非樹脂材料からなる粒子に付着し、複数の非樹脂材料からなる粒子を互いを結合して、全体として造粒粒子(造粒粉末)を形成していてもよい。
複合粉末は、非樹脂材料からなる粒子の表面の少なくとも一部に、樹脂材料が備えられた形態のものである。非樹脂材料からなる粒子の形状は特に制限されず、上述の混合粉末におけるのと同様に考慮することができる。非樹脂材料からなる粒子は、表面の少なくとも一部が非樹脂材料によって被覆されていれば良く、表面の全部が被覆されていても良い。被覆の形態も特に制限されず、非樹脂材料からなる粒子の表面に、略均一な層状に樹脂材料が備えられていても良い。例えば、非樹脂材料と樹脂材料とが積層された構造であっても良い。或いは、非樹脂材料からなる粒子の表面に、例えば粒状ないしは小塊状の樹脂材料が一体的に備えられていても良い。このとき、粒状ないしは小塊状の樹脂材料が、一つ備えられていても良いし、二つ以上備えられていても良い。
ここで開示される技術では、上記で用意した形成用材料を、上記樹脂材料の成形下限温度以上(上記樹脂材料の成形上限温度+100℃)以下の適切な成形温度範囲における軟化状態または溶融状態で堆積させる。これにより、軟化または溶融状態にあった形成用材料が冷却されて、形成用材料の粉末が互いに結合してなる硬化体としての構造体を形成することができる。
なお、上記樹脂材料についての「成形下限温度」とは、押し込み型成型機を用い、3500psiでこの樹脂材料の成型が可能となる最も低いヒーター温度として規定される。「成形上限温度」は、シリンダ型成型機を用い、3500psiでこの樹脂材料の成型が可能となる最も高いヒーター温度として規定される。また、「ヒーター温度」は、この押し込み型成型機における成形用材料の収容部の温度を、熱電対を用いて測定された温度である。
ポリプロピレン:180℃~300℃
ポリビニルフェノール:160℃~230℃
ABS樹脂:200℃~260℃
ポリアミド:240℃~290℃
シリコン樹脂:140℃~180℃
メラミン樹脂:150℃~560℃
PPS:150℃~320℃
なお、以下、本明細書において、上記の「成形下限温度~成形上限温度+100℃」の温度範囲を、単に、「成形可能温度範囲」と表現する場合がある。
(溶射法)
溶射法とは、粉末状の溶射材料(ここでいう形成用材料)を軟化または溶融状態として吹き付けることで、この材料からなる堆積物を形成する方法である。この溶射法としては、上記のとおり、形成用材料を500℃以下の温度範囲で堆積させることから、作動温度がより低温の溶射法を好ましく採用することができる。かかる溶射法としては、代表的には、コールドスプレー法,低温大気圧プラズマ溶射法,コールドプラズマ法が挙げられる。
スラリー中の形成用材料の含有量は、85質量%以下であることが好ましく、70質量%以下であるのがより好ましくは、50質量%以下であるのがさらに好ましい。この場合、溶射装置への供給に適した所要の流動性を有するスラリーを調製できる。
他の好適な一形態として、供給法として三次元造型法を採用した場合を例にして詳細に説明する。
三次元造型法とは、形成用材料を軟化または溶融状態で層状に堆積させ、これを所望の三次元形状に対応させて積層してゆくことで、この材料からなる構造体を形成する方法である。ここに開示される技術においては、形成用材料を軟化または溶融状態としてから堆積させてもよいし、形成用材料を堆積させてから軟化または溶融状態としてもよいし、あるいは形成用材料を堆積過程において軟化または溶融状態としてもよい。さらには、ここに開示される形成用材料をもとに線形材料(例えば、ワイヤー状、棒状等の形態の材料)を作り、その線形材料を溶融して堆積させてもよい。
例えば、粉末状の形成用材料の流動性については安息角により把握することができる。安息角は、粉体の流動性を示し得る指標であり、粉体の粒度(平均粒子径)等にもよるため一概には言えないものの、一般的に、流動性の良い粉体ほど安息角が小さく、流動性の良くない粉体の場合には安息角が大きくなり得る。ここに開示される技術においては、例えば、安息角が45度以下、より好ましくは35度以下、最も好ましくは30度以下であることが好ましい。安息角の下限については特に制限されない。例えば、飛散され難い等の観点から、安息角を10度以上、例えば20度以上とすることが例示される。
これにより、成形型を使用することなく、低温で、上記形成用材料からなる構造体を形成することができる。なお、一般的に、樹脂材料と、セラミック材料や金属材料などの非樹脂材料とは、密度に差が生じ易い。すると、通常、樹脂材料からなる粒子と、セラミック材料や金属材料などの非樹脂材料とは、より密度が高いものが下方に移動し、より密度の低いものが上方に移動する作用が働く。したがって、例えば、流動状態にある形成用材料を成形型に一度に投入したとすると、かかる成形プロセスを通じて、樹脂材料と非樹脂材料との均質性が失われやすく、構造体においても特性にムラや傾斜が生じ易い。
ここに開示される技術においては、このように、気孔率Rnに関するばらつきの度合いを無次元化して評価するようにしている。
なお、上記の均質性指数Nに基づく均質/不均質の評価の境界値(ここでは0.2)は、例えば、構造体に要求される緻密さや形状精密度等により変化させることもできる。
また、これら樹脂材料や非樹脂材料における抗菌活性値と、構造体における抗菌活性値との差が小さいことが望ましい態様であり得る。より具体的には、抗菌活性値の差は1.5以下であることが好ましく、1.0以下であることがより好ましく、0.5以下であることが特に好ましい。
また色相差Δabは、所望の材料の色(特に色相)が構造体に好適に反映されているとの観点から、例えば、10以下であることが好ましく、8以下であることがより好ましく、例えば5以下であることが特に好ましい。
(形成用材料)
樹脂材料として粉末状ポリビニルフェノール(PVP,D50:2μm,平均分子量:約10,000,真密度:1.2g/ml,成型可能温度範囲:160~230℃)を用意した。非樹脂材料については、セラミック材料としてチタニア粉末(TiO2,D50:5μm)またはアルミナ粉末(Al2O3,D50:5μm)を、金属材料としてコバルト粉末(Co,D50:3μm)または鉄粉末(AISI4140鋼,D50:8μm)を用意した。そしてこれらの材料を下記の表1に示す組み合わせおよび形態に調製することで、形成用材料1~11を用意した。
表1中、「液体」は、樹脂材料を有機溶剤(エチルセロソルブ)に溶解させた樹脂分散液であることを示す。
表1中、「造粒」は、樹脂材料と非樹脂材料とをバインダを用いて造粒し、一体化させた造粒粉末であることを示す。
表1中、「クラッド」は、非樹脂材料からなる粒子の表面を樹脂材料で被覆した被覆粒子からなる複合粉末であることを示す。
表1中、「スラリー」は、樹脂材料からなる粉末と非樹脂材料からなる粉末とを、分散媒としてのエタノールに5体積%の割合で分散させたスラリーの形態であることを示す。
表1中、「混合粉」は、樹脂材料からなる粉末と非樹脂材料からなる粉末とを混合した混合粉末であることを示す。
そして、用意した形成用材料1~11を、下記の表1に示す形成法で基材の表面に供給し、膜状の構造体を形成した。基材には、アルミナ#40研磨剤によるブラスト処理を施したSS400鋼板(70mm×50mm×2.3mm)を用いた。
表1中、「塗布」は、上記のPVPを溶剤としてのトルエンに溶解させてPVP組成物を調製し、このPVP組成物を、室温(25℃)にて基材の表面に噴霧手法を用いて塗布したのち、かかるPVP組成物を基材ごと100℃に加熱した後に210℃に加熱し熱硬化させることにより、厚さ50μmの層状の構造体を形成したことを示す。
[抗菌活性]
上記で得られた各構造体の抗菌性を、JIS Z2801:2010で規定される抗菌性試験方法に基づき評価した。具体的には、試験菌として黄色ぶどう球菌(NBRC 12732)を用い、試験片としては、上記の構造体を基板ごと5cm×5cmに切り出したもの(試験品)と、未表面処理の基材(基準品)のそれぞれについて試験菌液を滴下し、フィルムを被せてシャーレ内、35℃で24時間培養した後の生菌数を測定した。そして、基準品の24時間培養後菌数を試験品の24時間培養後菌数で除した数の対数値から、抗菌活性値を算出した。その結果を、表1の「抗菌活性値」の欄に示した。なお、抗菌性は、抗菌活性値2.0以上、すなわち99%以上の死滅率の場合に、効果がある(抗菌性がある)と判断することができる。
上記で得られた各構造体の硬度を、JIS Z 2244:2009およびJIS R1610:2003に規定されるビッカース硬さ試験方法に基づき測定した。具体的には、硬微小硬度測定器(株式会社島津製作所製、HMV-1)を用い、構造体の表面に対面角136°のダイヤモンド圧子を試験力1.96Nで押圧したときに得られる圧痕から、ビッカース硬さ(Hv0.2)を算出した。また、上記で用いたのと同じPVPのバルク体の表面について同様にビッカース硬さ(Hv0.2)を算出した。そして、次式に基づき硬度比を算出した結果を、表1の「硬度比」の欄に示した。
硬度比=(構造体のビッカース硬さ)/(PVPバルク体のビッカース硬さ)
上記で得られた各構造体の気孔率を以下のように測定し、均質性指数Nを算出した。すなわち、各構造体の断面画像を、マイクロスコープにて12枚ずつ撮影(490倍)し、各画像に基づき気孔部分と断面全体との面積から、気孔部分が断面全体に占める割合を算出すること気孔率を求めた。かかる解析には、画像解析ソフト(例えば、株式会社日本ローパー製、Image Pro)を用いた。このようにして得られた各構造体につき12の気孔率が、正規性および等分散性を示すことを確認した。そしてこれらの気孔率について、ばらつきを平均値で割ることにより均質性指数Nを算出した。得られた均質性指数Nを、表1の「均質性」の欄に示した。
(形成用材料)
次いで、ここに開示される形成用材料を用いて成形された構造体が、形成用材料を構成する材料の色調を好適に維持しうるかどうかについて、以下で確認を行った。すなわち、樹脂材料として粉末状ポリプロピレン(PP,D50:3μm,融点:130℃,真密度:約0.9g/cm3)を、非樹脂材料としてのセラミック材料として鉄系セラミック粉末((Fe,Al,Mg)Cr2O,D50:5μm)を用い、下記の表2に示す組み合わせおよび形態の形成用材料1~6を用意した。
なお、形成用材料2~5において、樹脂材料と、セラミック材料とは体積比で1:1となるように混合又は配合した。
そして、用意した形成用材料1~6を、下記の表2に示す形成法で基材の表面に供給し、膜状の構造体を形成した。基材には、アルミナ#40研磨剤によるブラスト処理を施したSS400鋼板(70mm×50mm×2.3mm)を用いた。
なお、表2中の「形態」の欄の表記は表1と共通である。
また、表2中の「形成法」の欄の表記は表1と共通である。
[色差]
上記で得られた各構造体の表面の色彩;明度(L),色相(a),彩度(b)を、ハンター式測色色差計(日本電色工業、SE-2000)を用いて測定した。そして使用した形成用材料を、押し込み型成型機を用いて成型温度200℃で成型した成型体との色相差Δabおよび明度差ΔLを算出した。これらの結果を、表2の「Δab」および「ΔL」の欄に示した。なお、上記の押し込み型成型機における成形温度「200℃」は、使用したPPの推奨成型温度である。すなわち、具体的なデータは示さないが、このPPを200℃で堆積させたときに形成される構造体について、均質性指数Nが0.2未満となることが確認されている。
上記で得られた各構造体の光沢度を、光沢計(コニカミノルタオプティクス社製,GM-268Plus)を用い、測定角度を20°として測定した。その結果を、表2の「グロス値」の欄に示した。
Claims (13)
- 樹脂材料と、金属およびセラミックからなる群から選択される少なくとも1種の非樹脂材料とを含む粉末からなる形成用材料であって、
前記樹脂材料について、
押し込み型成型機を用い3500psiの押し込み圧で当該樹脂材料の成型が可能となる最も低いヒーター温度を成形下限温度とし、
押し込み型成型機を用い3500psiの押し込み圧で当該樹脂材料の成型が可能となる最も高いヒーター温度を成形上限温度として、
前記粉末を、前記樹脂材料の成形下限温度以上で前記樹脂材料の成形上限温度+100℃以下の温度範囲の軟化または溶融状態で堆積させたときに形成される構造体について、画像解析法に基づき気孔率Rnを12カ所で測定したとき、
前記気孔率Rnのばらつきを前記気孔率Rnの平均値で除することにより得られる均質性指数Nが0.2未満である、形成用材料。 - 前記樹脂材料と前記非樹脂材料との合計に占める前記樹脂材料の割合が、20体積%以上80体積%以下である、請求項1に記載の形成用材料。
- 平均粒子径が5μm以上200μm以下である、請求項1または2に記載の形成用材料。
- 前記粉末は、前記樹脂材料からなる粒子と、前記非樹脂材料からなる粒子とが混合されている混合粉末である、請求項1~3のいずれか1項に記載の形成用材料。
- 前記粉末は、前記樹脂材料からなる粒子と、前記非樹脂材料からなる粒子とが造粒されてなる造粒粉末である、請求項1~3のいずれか1項に記載の形成用材料。
- 前記樹脂材料からなる粒子および前記非樹脂材料からなる粒子は、いずれも平均粒子径が0.5nm以上20μm以下である、請求項5に記載の形成用材料。
- 前記粉末は、前記非樹脂材料からなる粒子の表面の少なくとも一部に、前記樹脂材料が備えられている複合粉末である、請求項1~3のいずれか1項に記載の形成用材料。
- 前記樹脂材料は、ポリオレフィン,ポリビニルカーボネート,ポリビニルフェノール,ポリウレタン,ポリスチレン,アクリロニトリル・ブタジエン・スチレン共重合体,ポリエチレンテレフタラートおよびポリアミドからなる群から選択される1種または2種以上である、請求項1~7のいずれか1項に記載の形成用材料。
- 前記樹脂材料は、抗菌活性値2.0以上の抗菌性を有する、請求項1~8のいずれか1項に記載の形成用材料。
- 樹脂材料と、金属およびセラミックからなる群から選択される少なくとも1種の非樹脂材料と、を含む粉末状の形成用材料を用意すること、
前記形成用材料を、前記樹脂材料の成形下限温度以上で前記樹脂材料の成形上限温度+100℃以下の温度範囲の軟化または溶融状態で堆積させることにより、成形型を用いることなく所定形状の構造体を形成すること、
ここで、前記成形下限温度は、押し込み型成型機を用い、3500psiの押し込み圧で当該樹脂材料の成型が可能となる最も低いヒーター温度であり、前記成形上限温度は、押し込み型成型機を用い3500psiの押し込み圧で当該樹脂材料の成型が可能となる最も高いヒーター温度である、
を包含する、構造体の形成方法。 - 前記形成用材料を分散媒に分散した状態で加熱する、請求項10に記載の構造体の形成方法。
- 前記形成用材料を、溶射法を利用して堆積し、前記構造体を形成する、請求項10または11に記載の構造体の形成方法。
- 前記形成用材料を、三次元造型機を用いて堆積し、前記構造体を形成する、請求項10または11に記載の構造体の形成方法。
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JP2019510094A (ja) * | 2016-01-21 | 2019-04-11 | スリーエム イノベイティブ プロパティズ カンパニー | フルオロポリマーの積層プロセス |
JP2017155276A (ja) * | 2016-03-01 | 2017-09-07 | 株式会社ノリタケカンパニーリミテド | 三次元立体造形用粉体および三次元立体造形物 |
JP2017202046A (ja) * | 2016-05-10 | 2017-11-16 | 株式会社リコー | 立体造形材料セット、立体造形物の製造方法、及び立体造形物の製造装置 |
JP2018012852A (ja) * | 2016-07-19 | 2018-01-25 | 株式会社東芝 | 凝集体およびその製造方法、ならびにこの凝集体を用いた被膜の形成方法 |
CN107686577A (zh) * | 2016-08-04 | 2018-02-13 | 中国石油化工股份有限公司 | 一种聚乙烯组合物和应用以及激光烧结方法和三维制品 |
CN107686577B (zh) * | 2016-08-04 | 2020-01-17 | 中国石油化工股份有限公司 | 一种聚乙烯组合物和应用以及激光烧结方法和三维制品 |
JP2018154116A (ja) * | 2017-03-17 | 2018-10-04 | 株式会社リコー | 立体造形用樹脂粉末、及び立体造形物の製造装置 |
JP7123288B1 (ja) * | 2021-12-17 | 2022-08-22 | 三菱電機株式会社 | 樹脂複合材料皮膜及び樹脂複合材料皮膜の製造方法 |
WO2023112310A1 (ja) * | 2021-12-17 | 2023-06-22 | 三菱電機株式会社 | 樹脂複合材料皮膜及び樹脂複合材料皮膜の製造方法 |
Also Published As
Publication number | Publication date |
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US10661550B2 (en) | 2020-05-26 |
CN106470823A (zh) | 2017-03-01 |
CN106470823B (zh) | 2020-05-26 |
EP3162541A4 (en) | 2018-03-07 |
EP3162541A1 (en) | 2017-05-03 |
US20170157842A1 (en) | 2017-06-08 |
JPWO2015199244A1 (ja) | 2017-04-27 |
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