Components including laminates and methods for manufacturing components including laminates

Abstract

This invention relates to components comprising laminates and methods for manufacturing components comprising laminates. A component is provided in which the strength of a second layer located on the outermost surface is improved to adequately perform and maintain function, thereby improving impact resistance and scratch resistance. The component comprises, in sequence, a substrate, a first layer, a second layer, and a third layer, wherein the first layer is an inorganic porous layer in which a plurality of inorganic particles are bonded to each other, and the first and second layers have a total thickness of 0.3 μm or more and 2 μm or less, wherein the third layer contains resin and has a thickness of 0.4 μm or more and 2000 μm or less, and wherein the second layer contains inorganic particles and resin.

Description

Technical Field

[0001] This invention relates to a component with excellent impact and scratch resistance, and a method for manufacturing the component. Background Technology

[0002] In components of products intended for outdoor and indoor use, as well as components intended for use in printing paper, belts, or handbags, decorative layers, hard coatings, etc., are formed on a substrate to improve aesthetics and strength. Outdoor products include, for example, automotive parts, smartphones, and drones; indoor products include, for example, laptops and home appliances. In Japanese Patent Application Publication No. 2015-66796, a suitable primer layer is used between the substrate and the decorative layer to improve adhesion and prevent the decorative layer from peeling off the substrate.

[0003] Depending on the usage environment, external components may possess functions such as antifouling properties, hydrophilicity, antibacterial properties, antiviral properties, or decorative features. To fully realize and maintain these functions, it is important to improve the impact and scratch resistance of the layer on the outermost surface of the exterior (the surface layer). The primer layer in Japanese Patent Application Publication No. 2015-66796 contains resin, resulting in insufficient film hardness. Consequently, the force applied to the surface layer causes deformation of the primer layer. Therefore, the impact and scratch resistance of the surface layer cannot be improved. Summary of the Invention

[0004] The present invention was made in view of the above background technology, and the present invention provides a component with excellent impact resistance and scratch resistance by means of an inorganic porous layer that connects the layer and the substrate located on the outermost surface to each other, as well as a method for manufacturing the component, the inorganic porous layer containing a plurality of inorganic particles bonded to each other.

[0005] The component according to the present invention comprises a substrate, a first layer, a second layer and a third layer in sequence, wherein the first layer is an inorganic porous layer in which a plurality of inorganic particles are bonded to each other, wherein the third layer is a resin-containing layer, wherein the second layer is a layer containing a plurality of inorganic particles and resin, wherein the first layer and the second layer have a total thickness of 0.3 μm or more and 2 μm or less, and wherein the third layer has a thickness of 0.4 μm or more and 2000 μm or less.

[0006] Other features of the invention will become clear from the following description of exemplary embodiments with reference to the accompanying drawings. Attached Figure Description

[0007] Figure 1A This is a perspective view illustrating an example of component 1.

[0008] Figure 1B Yes, along Figure 1A The cross-sectional view of component 1 obtained by line AB shown is shown. Detailed Implementation

[0009] Embodiments of the present invention are described below with reference to the accompanying drawings. In the following description and drawings, common elements in the plurality of drawings are denoted by common symbols. Furthermore, common elements may be described by referring to the plurality of drawings mutually without further statement. Additionally, descriptions of elements denoted by common symbols may be omitted.

[0010] <Component 1>

[0011] Figure 1A This is a perspective view of an example of component 1 according to an embodiment of the present invention. Component 1 has a shape depending on its application, such as a membrane shape, sheet shape, plate shape, dome shape, or spherical shape. When component 1 has a membrane shape, component 1 may be referred to as a "membrane". When component 1 has a sheet shape, component 1 may be referred to as a "sheet". When component 1 has a plate shape, component 1 may be referred to as a "plate". Component 1 has a front surface 110 and a rear surface 120, and the front surface 110 and the rear surface 120 have substantially the same shape. The distance between the front surface 110 and the rear surface 120 (i.e., the thickness T of component 1) is less than the maximum width L of the front surface 110 and the rear surface 120, and may be, for example, less than 1 / 100 of the maximum width L. In this example, the front surface 110 and the rear surface 120 of component 1 are each quadrilateral, but are not limited thereto.

[0012] Additionally, when component 1 has a dome shape or a spherical shape, component 1 may have a hemispherical shape or a near-spherical shape. The specific shape depends on the application, but the thickness T of the substrate needs to be set to maintain the dome shape or spherical shape.

[0013] Figure 1B It is along Figure 1A The cross-sectional view of component 1 obtained by line AB shown is shown.

[0014] Component 1 is a laminate formed of at least three layers and includes: a substrate 2, a first layer 3 containing particles disposed on the substrate 2, a third layer 4 disposed above the first layer 3, and a second layer 5 formed between the first layer 3 and the third layer 4. The second layer 5 can bond the third layer 4 to the first layer 3. In addition, the first layer 3 is an inorganic porous layer. Therefore, impacts applied to the third layer 4 are absorbed, and the degree of deformation caused by impact is small, resulting in improved impact resistance and scratch resistance of the third layer 4.

[0015] <Substrate 2>

[0016] The substrate 2 is not particularly limited, as long as it has excellent processability and can form a layer on its surface. The substrate 2 has two main surfaces 101 and 102 that are opposite to each other. The distance between the main surfaces 101 and 102 is the thickness Tb of the substrate 2. The thickness Tb of the substrate 2 can be greater than 1 μm and less than 100 mm. When the thickness Tb of the substrate 2 is less than 250 μm and the component 1 is flexible, the component 1 can be said to have a film shape. When the thickness Tb of the substrate 2 is greater than 250 μm and the component 1 is flexible, the component 1 can be said to have a sheet shape. When the component 1 is not flexible, the component 1 can be said to have a plate shape.

[0017] A first layer 3 is formed on the main surface 101 of the substrate 2, and a second layer 5 and a third layer 4 are formed sequentially on the first layer 3. If necessary, the first layer 3, the second layer 5 and the third layer 4 can be formed on the main surface 102 of the substrate 2, and the first layer 3, the second layer 5 and the third layer 4 formed on the main surface 101 can be different from those layers formed on the main surface 102.

[0018] The substrate 2 is not particularly limited, as long as it is made of a material that can maintain the shape of the component 1, such as resin, glass, metal or ceramic.

[0019] Specific examples of resins to be used in substrate 2 include: polyester resins such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polycarbonate (PC) resin, cellulose triacetate (TAC) resin, cyclic olefin (COP) resin, polymethyl methacrylate (PMMA) resin, acrylic polyvinyl alcohol (PVA) resin, polyacetal (POM) resin, polyamide resin, polyphenylene sulfide (PPS) resin, polyether ether ketone (PEEK) resin, glass fiber reinforced polyamide MXD6 (RENY) resin, polyvinyl chloride (PVC) resin, polypropylene (PP) resin, ABS resin, polyimide (PI) resin, tetrafluoroethylene (PTFE) resin, perfluoroalkoxyalkane (PFA) resin, and vinylidene fluoride (PVDF) resin.

[0020] In addition, the resin can contain organic fillers, inorganic fillers, etc. in the raw materials, and different resins can be mixed as needed.

[0021] Alternatively, inorganic glasses containing, for example, zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, lanthanum oxide, gadolinium oxide, silicon oxide, calcium oxide, barium oxide, sodium oxide, potassium oxide, boron oxide, or aluminum oxide can be used as the glass substrate. A glass substrate formed by grinding, polishing, molding, float glass forming, or the like can be used as the glass substrate.

[0022] A metal containing one metal element or an alloy containing two or more elements can be used as the metal. Examples thereof include carbon steel, alloy steel, cast iron, non-ferrous metals such as copper, aluminum and nickel and their alloys, gold, silver, platinum, tin, lead, bismuth, magnesium, titanium and zinc.

[0023] In order to improve the adhesion between, for example, the base material 2 and the first layer 3 or the strength and flatness of the first layer, the surface of the base material can be cleaned or polished. In addition, a fifth layer can be formed between the first layer 3 and the base material 2 to improve the adhesion. As a preferred example of the fifth layer, a layer containing at least one selected from the following is given: zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, silicon oxide, aluminum oxide and resin.

[0024] The intermediate layer can be a single layer made of the above materials or a laminate of multiple layers.

[0025] <The first layer 3>

[0026] The thickness of the region containing inorganic particles on the main surface 101, that is, the total thickness of the first layer 3 and the second layer 5, is the physical thickness Ta, and the third layer 4 has a physical thickness Tc. The physical thicknesses Ta and Tc are each less than the thickness Tb of the base material 2, and Ta is less than Tc (Ta < Tc < Tb). Therefore, the shape and mechanical properties of the component 1 are mainly determined by the base material 2.

[0027] The physical thickness Ta is 0.3 μm or more and 2 μm or less, preferably 0.5 μm or more and 1.5 μm or less. When the physical thickness Ta is less than 0.3 μm, the hardness of the region containing inorganic particles is insufficient and the scratch resistance is not high enough. When the physical thickness Ta is greater than 2 μm, cracks may occur due to the curing shrinkage during the formation of the porous layer before the second layer 5 is formed. The hardness of the first layer is preferably 1.5 GPa or more. When the hardness of the first layer is less than 1.5 GPa, the impact resistance and scratch resistance of the third layer tend to be low.

[0028] The first layer 3 is a porous layer containing a plurality of inorganic particles 7 joined to each other. The inorganic particles 7 (sometimes simply referred to as "particles 7" hereinafter) can be joined to each other by the interaction between the particles 7 or can be joined via an inorganic binder. The inorganic binder is preferably a silica binder, which is a cured product of a silica compound such as a silica oligomer obtained by hydrolysis and condensation of a silicate ester.

[0029] The first layer 3 contains 50% by volume or more of particles 7. Therefore, the membrane has high strength and is unaffected by swelling when absorbing water or moisture. A second layer 5 is present, formed between the first layer 3 and the third layer 4 when a portion of the resin contained in the third layer 4 penetrates into a portion of the pores 6 of the inorganic porous layer formed by the multiple particles 7 bonded together. When the resin contained in the third layer 4 penetrates from the surface of the inorganic porous layer to a depth of 0.1 μm or more, the shedding of the third layer 4 can be suppressed. The thickness of the second layer is preferably 0.1 μm or more and 1 μm or less, more preferably 0.1 μm or more and 0.5 μm or less.

[0030] In many cases, the first layer 3 remains in a state close to the porous layer before the third layer 4 is formed, and preferably, the pores 6 are connected to each other. It is required that the resin contained in the third layer 4 penetrates into the pores; therefore, it is preferable that the pores 6 are in communication with the membrane surface before the formation of the third layer 4. Whether the pores 6 of the porous layer are in communication with the membrane surface before the formation of the third layer 4 can be confirmed by observing the resin penetration state in the cross-section of the second layer 5.

[0031] The amount of pores 6 contained in the first layer 3 can be determined by nitrogen adsorption and used as the pore volume. The preferred pore volume is 0.1 cm³. 3 / g or more and 0.51cm 3 / g or less.

[0032] When the pore volume is less than 0.1 cm³ 3 At a certain temperature (g), most of the porosity is lost, and the hardness becomes excessively high. As a result, the component loses its impact resistance and cracks propagate.

[0033] When the pore volume is 0.1 cm³ 3 When the volume is above 0.51 cm³, a second layer 5 with sufficient thickness can be formed, thus improving the adhesion between the first layer 3 and the third layer 4. Furthermore, when the component is subjected to impact, the pores absorb the impact, thereby improving impact resistance. Additionally, even when a crack occurs in a portion of the component, crack propagation can be suppressed. When the pore volume is 0.51 cm³... 3 At a density of / g or less, sufficient strength can be obtained without any reduction in skeleton stiffness. A more preferred pore volume is 0.34 cm³. 3 / g or more and 0.50cm 3 / g or less.

[0034] Additionally, when the pore volume is greater than 0.50 cm³ 3 At / g, the components become brittle due to the large number of air gaps, resulting in reduced durability.

[0035] <Particle 7>

[0036] Particle 7 can have any shape, such as a true circle, an oval, a disc, a rod, a needle, a chain, or a square, and two or more particles can be used as a mixture thereof.

[0037] Particle 7 can be a solid particle. As a solid particle, particle 7 can be formed from a uniform solid material, or particle 7 can be formed to have a core-shell structure in which a solid core is surrounded by a solid shell.

[0038] Alternatively, particle 7 can be a hollow particle. Each hollow particle has a shape in which the hollow portion is enclosed by a solid shell. The shell may contain an inorganic material such as silicon oxide, as described above.

[0039] Particle 7 can be chain-shaped particles. That is, each chain-shaped particle 7 has a shape in which multiple particles are connected to each other. A hole 6 is formed between two chain-shaped particles. Even when the chain-shaped particles form a film, they maintain their chain-shaped or bead-shaped connection, thus increasing porosity compared to using a single particle. The number of particles connected in a chain-shaped particle is 2 or more and 10 or less, preferably 3 or more and 6 or less. When the number of connected particles is greater than 10, large pores are easily formed, resulting in reduced wear resistance. For particles with short and long diameters (such as chain-shaped particles), the short diameter is taken as the average particle diameter.

[0040] The average particle diameter of particle 7 is preferably 10 nm or more and 80 nm or less, more preferably 12 nm or more and 60 nm or less. When the average particle diameter of solid particles is less than 10 nm, the pores between particles and within particles become too small, and the resin contained in the third layer cannot penetrate the first layer. As a result, the adhesion between the first and third layers decreases. In addition, when the average particle diameter is greater than 80 nm, the size of each pore between particles becomes larger, thus easily generating large voids, resulting in reduced film strength and a higher likelihood of film cracking. The average particle diameter is the average Ferrette diameter. The average Ferrette diameter can be measured by image processing of an image observed using a transmission electron microscope. Commercially available image processing software such as Image-Pro Plus (manufactured by Media Cybernetics, Inc.) can be used as the image processing method. In a predetermined image area, the contrast is appropriately adjusted as needed, and the average Ferrette diameter of each particle is measured by particle measurement, thereby allowing the average value to be calculated and determined.

[0041] Particle 7 is a particle containing SiO2 as its main component, and Si accounts for more than 80 atomic percent and more than 90 atomic percent of the elements other than oxygen. When Si accounts for less than 80 atomic percent, the number of silanol (Si-OH) groups on the particle surface that react with the binder decreases, thereby reducing wear resistance.

[0042] Besides SiO2, metal oxides such as Al2O3, TiO2, ZnO2, and ZrO2 can be used for particles 7, and organic components such as alkyl groups and fluoroalkyl groups can be introduced into the silica particles or particle surface via Si atoms. Considering the reactivity between particles or between particles and the binder, hydrophilic particles in which silanol (Si-OH) groups are retained on the particle surface are more preferred. Particles whose particle surface is modified with organic groups, etc., and whose remaining silanol groups become less than 70%, lose their hydrophilicity. In components using such particles, the film strength decreases due to reduced interactions and reactivity between particles and between particles and the binder. In this invention, the interactions and reactivity between particles 7 or between particles 7 and the binder contained in the first layer 3 are maintained, therefore the film strength is not reduced.

[0043] <Method for manufacturing component 1>

[0044] Component 1 has the following structure: a first layer 3, a third layer 4, and a second layer 5 formed between the first layer 3 and the third layer 4 are included on a substrate 2. Component 1 is not limited to... Figure 1B The structure shown can be combined or joined with another substrate. Figure 1B The substrate 2 is formed. For example, the component 1 can be manufactured by forming a laminate using the substrate 2 as a resin film or by forming a laminate on another substrate through general insert molding or the like.

[0045] The laminate is manufactured by applying a coating liquid to a substrate 2 to form a coating film, drying and / or calcining the substrate 2 on which the coating film is formed to form the first layer 3, and then forming the third layer 4.

[0046] <Methods for forming the first layer 3>

[0047] The coating liquid used to form the first layer 3 only needs to contain at least inorganic particles and solvent, and the coating liquid preferably also contains components that act as a binder.

[0048] Examples of methods for applying a coating liquid include: bar coating, gravure coating, die coating, spin coating, doctor blade coating, roll coating, slot coating, printing, and dip coating. In particular, spraying and spin coating can be used when manufacturing parts with complex three-dimensional shapes (e.g., dome or spherical shapes) and including thin films, having convex or concave surfaces. Furthermore, in cases where the coating liquid is applied to a large area of ​​thin substrate, such as a film or sheet, gravure coating is preferred from the viewpoint of thickness uniformity. In particular, in cases where the coating liquid is applied to a roll of long film, roll-to-roll gravure coating is preferred.

[0049] To form the first layer 3, a coating liquid is applied to the substrate 2 and dried and / or cured. Drying and / or curing is a process used to remove solvent and deposited particles 7 while simultaneously bonding the particles 7 together without disturbing their arrangement, thereby forming a porous layer. The temperature used for drying and / or curing depends on the heat resistance temperature of the substrate 2, but is preferably above 20°C and below 200°C. The time used for drying and / or curing can be a period of time that does not affect the substrate 2 and allows the organic solvent in the layer to evaporate, preferably 10 minutes or more and 200 hours or less, more preferably 30 minutes or more and 24 hours or less.

[0050] To obtain a porous layer in which the particles 7 are highly arranged, a satisfactory arrangement of the particles 7 is preferred. The variation in the arrangement of the particles 7 depends primarily on the dispersion state of the particles 7 in the coating solution used to form the second layer and the dispersion state of the particles 7 during the formation of the coating film.

[0051] When the particles 7 in the coating liquid are fully dispersed and unaffected by the dispersion medium or binder, the particles 7 are easy to align. However, when the particles 7 are dispersed in a slightly aggregated state due to the influence of the dispersion medium and binder, the alignment deteriorates.

[0052] Furthermore, the particle flow caused by evaporation, drying, and solvent concentration significantly affects the alignment of particles 7 when the coating liquid is applied to the substrate 2 to form a coating film. Even when the dispersion of particles 7 in the coating liquid is satisfactory, particle aggregation during drying to form the coating film disrupts the alignment of particles 7. As a result, the gaps between particles 7 increase during coating film formation, and the voids in the surface direction of the substrate 2 also increase. When the coating film is formed with particles 7 displaced without alignment and deposition, the stress distribution of the coating film becomes uneven, and the film strength cannot be adequately maintained.

[0053] By using particles 7 with added surface treatment agent as described above in the porous layer, a coating film can be formed in the state of particle arrangement and deposition without disturbing the particle arrangement.

[0054] The surface treatment agent contained in the porous layer can be determined, for example, by elemental analysis of particles 7 and the porous layer or by separation and quantitative analysis using methods such as ion exclusion chromatography.

[0055] <Third Floor 4>

[0056] The third layer 4 may include one or more layers. Alternatively, another film or component may be formed by an adhesive layer containing resin, or printing may be performed using a resin-containing paint or ink.

[0057] The physical thickness Tc of the third layer 4 is 0.4 μm or more and 2000 μm or less. When the physical thickness Tc is less than 0.4 μm, Tc is often less than the indentation depth during the scratch resistance test, and the surface of the third layer 4 may be scratched off. Furthermore, when the thickness of the third layer is greater, scratch resistance and impact resistance become higher. However, when the physical thickness Tc is greater than 2000 μm, peeling may occur at the interface between the substrate 2 and the first layer 3 due to the film stress of the third layer 4. A physical thickness Tc is more preferably 0.5 μm or more and 50 μm or less.

[0058] When a resin-containing coating liquid is applied to the surface of a porous layer formed on a substrate, the resin penetrates from the surface of the porous layer to form a second layer 5. The second layer 5 improves the adhesion between the first layer 3 and the third layer 4.

[0059] Examples of resins to be used in the third layer 4 include: polyester resins such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polycarbonate (PC) resins, cellulose triacetate (TAC) resins, cycloolefin (COP) resins, polymethyl methacrylate (PMMA) resins, acrylic polyvinyl alcohol (PVA) resins, polyacetal (POM) resins, polyamide resins, polyphenylene sulfide (PPS) resins, polyether ether ketone (PEEK) resins, glass fiber reinforced polyamide MXD6 (RENY) resins, polyvinyl chloride (PVC) resins, polypropylene (PP) resins, ABS resins, polyimide (PI) resins, tetrafluoroethylene (PTFE) resins, perfluoroalkoxyalkane (PFA) resins, and vinylidene fluoride (PVDF) resins.

[0060] Additionally, the resin used for the hard coating is suitable for the third layer 4. For example, an ionizing radiation-curable resin is used, and preferably an acrylate oligomer or prepolymer, including polyfunctional compounds such as polyol acrylate resins, acrylic resins, alkyd resins, polyester resins, polyether resins, epoxy resins, urethane resins, spiroacetal resins, polybutadiene resins, or polyol polyene resins. These resins can be used alone or as mixtures thereof as needed.

[0061] In addition, the resin can contain organic fillers, inorganic fillers, etc. in the raw materials, and different resins can be mixed as needed.

[0062] Resins that can be cured by ionizing radiation can be easily cured by combining them with photoinitiators. Examples of photoinitiators include: thioxanthone-based photoinitiators such as 2,4-diethylthioxanthone or 2-chlorothioxanthone; phosphorus-based photoinitiators such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; michalcone-based photoinitiators such as 4,4-bisdiethylaminobenzophenone; and benzoyl.

[0063] Depending on the requirements, other additives such as ultraviolet absorbers, coloring pigments, antioxidants, silane coupling agents, and antistatic agents may also be used.

[0064] In addition, to impart functions such as antifouling, hydrophilicity, antibacterial and antiviral properties, materials with their respective functions can be mixed into the resin, or a third layer 4 including a functional layer can be formed.

[0065] For example, given materials, such as copper compounds and silver compounds, each possess antibacterial properties. Alternatively, a third layer 4 can be formed by coating a resin-containing layer and then further forming a functional material thereon. For example, a functional layer 30, such as an antifouling layer or a hydrophilic layer, can be formed on the surface of the hard coating material to impart antifouling and water-repellent properties. Examples of antifouling layers include layers containing fluoropolymers, fluorosilane monolayers, and layers containing titanium dioxide particles. For hydrophilic layers, hydrophilic polymer layers are preferred, and layers containing polymers having amphoteric hydrophilic groups such as sulfobetaine, carbobetaine, or phosphorcholine groups are particularly preferred. Films with low refractive indices can be formed to impart antireflective properties.

[0066] The method for forming the third layer 4 is appropriately selected based on the composition of the materials. For example, the third layer 4 can be formed by wet coating or dry coating, or by bonding a film or another component.

[0067] Examples of wet coating methods include rod coating, gravure coating, die coating, spin coating, doctor blade coating, roll coating, slot coating, printing, inkjet coating, and dip coating. In particular, spray coating, spin coating, and inkjet coating can be used when manufacturing parts with complex three-dimensional shapes (e.g., dome or spherical shapes) and including thin films, having convex or concave surfaces. Furthermore, gravure coating is preferred from the viewpoint of thickness uniformity when applying a coating solution to a large area of ​​thin substrate, such as a film or sheet. In particular, roll-to-roll gravure coating is preferred when applying a coating solution to a roll of long film. Alternatively, electroplating, electroless plating, or electroforming coating can be used.

[0068] Examples of dry coating methods include: resistance heating, high-frequency induction heating, electron beam heating, arc discharge, and vacuum deposition methods such as laser ablation, magnetron sputtering, ion beam sputtering, ion beam deposition, ion beam-assisted deposition, and ion beam sputtering.

[0069] Example

[0070] [Example 1]

[0071] Manufacture the parts as described below.

[0072] <Preparation of the coating liquid for forming the first layer 3 1>

[0073] A coating solution for forming the first layer 3 was prepared by blending components having the following composition. 6.00 g of an IPA dispersion of chain-shaped silica particles (IPA-ST-UP, manufactured by Nissan Chemical Industries, Ltd., average particle diameter: 12 nm, solids concentration: 15% by mass) was diluted with 22.13 g of 1-ethoxy-2-propanol to prepare a chain-shaped silica particle coating solution (solids concentration: 3.20% by mass).

[0074] In another container, 1.7 g of pre-diluted aqueous nitric acid (concentration: 3.7 wt%) and 2.30 g of ethanol were slowly added to a solution of 4.17 g of tetraethyl orthosilicate and 2.30 g of ethanol. The mixture was stirred at room temperature for 15 hours, and then 2.00 g of the weighed reaction solution was diluted with 36.33 g of 2-ethyl-1-butanol to prepare silica sol (solids content concentration: 0.6 wt%).

[0075] After diluting the dispersion with ethyl lactate to achieve a solids content concentration of 3.9% by mass, silica sol was added to the resulting mixture to achieve a chain silica particle to silica sol ratio of 100 / 12. The mixture was then stirred at room temperature for 2 hours to provide a coating solution containing chain silica particles.

[0076] <Methods for measuring orifice volume>

[0077] To measure the pore volume, the nitrogen adsorption isotherm was measured using an automatic vapor adsorption capacity measuring device (BELSORP-MAX, manufactured by BelJapan, Inc.), and the pore volume was determined using the BJH method.

[0078] <Methods for measuring thickness>

[0079] The thickness of each layer can be measured by image processing of a cross-section of component 1 observed with an electron microscope. Commercially available image processing software such as Image-Pro Plus (manufactured by Media Cybernetics, Inc.) can be used as the image processing method. Within a predetermined image area, contrast can be adjusted appropriately as needed, and the average thickness can be calculated and determined.

[0080] <Manufacturing method of test specimens for evaluation>

[0081] As a test specimen for evaluation, a coating droplet was applied to a polycarbonate substrate (φ30mm, thickness: 2mm, mirror finish on both sides), and a porous layer with a thickness of approximately 1.1μm was formed using a spin coater. An AronixUV-6524 coating film (manufactured by Toagosei Co., Ltd.) was then formed on the porous layer using a rod coating method, followed by exposure to a metal halide lamp at 1000mJ / cm². 2 Cured under irradiation conditions. Observation of the cross-section of samples manufactured in the same manner revealed that the thickness of the first layer was 1 μm, the thickness of the second layer was 0.1 μm, and the thickness of the third layer was approximately 5 μm.

[0082] The test specimens were evaluated as described below. Table 1 shows the conditions for the test specimens of Example 1, and Table 2 shows the evaluation results.

[0083] <Evaluation of the impact resistance of components>

[0084] The drop resistance test (JIS K 5600-5-3) was used as the test method. A 300g weight was dropped from 100mm above the test specimen, and a visual evaluation was performed. The evaluation was based on the following criteria.

[0085] A: There were no cracks or peeling caused by heavy impact.

[0086] B: Slight changes were observed and tiny cracks appeared due to impact from heavy objects.

[0087] C: Cracks and peeling occur due to impact from heavy objects.

[0088] In this invention, an evaluation of A indicates excellent impact resistance. An evaluation of B indicates satisfactory impact resistance. An evaluation of C indicates unsatisfactory impact resistance.

[0089] <Evaluation of the scratch resistance of components>

[0090] After undergoing 100 reciprocating cycles under a load of 700g and steel wool #0000, the appearance was visually evaluated. The evaluation criteria are described below.

[0091] A: The appearance showed almost no change.

[0092] B: Slight changes in appearance were observed, and minor scratches or lines appeared.

[0093] C: Obvious changes in appearance were observed, including scratches and film peeling.

[0094] In this invention, an evaluation of A indicates excellent scratch resistance. An evaluation of B indicates satisfactory scratch resistance. An evaluation of C indicates unsatisfactory scratch resistance.

[0095] The evaluation of component 1 is performed as follows. Table 1 shows the conditions of the component of Example 1, and Table 2 shows the evaluation results.

[0096] [Example 2]

[0097] Part 1 was manufactured using the same substrate as in Example 1. A porous layer was formed in the same manner as in Example 1, and the number of spin coats was appropriately adjusted to achieve a thickness of 0.5 μm. Subsequently, a resin-containing coating solution was applied and cured in the same manner as in Example 1.

[0098] Table 1 shows the conditions of component 1 in Example 2, and Table 2 shows its evaluation results.

[0099] [Example 3]

[0100] Part 1 was manufactured using the same substrate as in Example 1. A porous layer was formed in the same manner as in Example 1, and the number of spin coats was appropriately adjusted to achieve a thickness of 2.1 μm. Subsequently, a resin-containing coating solution was applied and cured in the same manner as in Example 1.

[0101] Table 1 shows the conditions of component 1 in Example 3, and Table 2 shows its evaluation results.

[0102] [Example 4]

[0103] Component 1 was manufactured using the same substrate as in Example 1. A porous layer was formed in the same manner as in Example 2. Subsequently, a resin-containing coating liquid, the same as in Example 1, was applied under different spin-coating conditions to make the thickness of the third layer 0.5 μm, and then cured to form a resin-containing layer.

[0104] Table 1 shows the conditions of component 1 in Example 4, and Table 2 shows its evaluation results.

[0105] [Example 5]

[0106] Component 1 was manufactured in the same manner as in Example 1, except that the spin coating conditions when applying the coating liquid containing resin were changed so that the thickness of the third layer was 100 μm.

[0107] Table 1 shows the conditions of component 1 in Example 5, and Table 2 shows its evaluation results.

[0108] [Example 6]

[0109] Part 1 was manufactured using the same substrate as in Example 1. A porous layer was formed by appropriately adjusting the number of spin coats, resulting in a thickness of 1.1 μm using the same coating solution and method as in Example 1. Subsequently, Durazane 2600 (manufactured by Merck Ltd.) (which is a polysilazane solution) was adjusted to 1.2% by weight. The porous layer was then coated with the polysilazane solution by spin coat, allowing the solution to permeate the particles, thereby adjusting the pore volume of the porous layer to 0.1 cm³. 3 / g. Subsequently, the same resin-containing coating solution as in Example 1 was applied under different spin-coating conditions and cured to form a resin-containing layer. Observation of the cross-section of the sample manufactured in the same manner revealed that the thickness of the first layer was 1 μm, the thickness of the second layer was 0.2 μm, and the thickness of the third layer was approximately 5 μm.

[0110] Table 1 shows the conditions of component 1 in Example 6, and Table 2 shows its evaluation results.

[0111] [Example 7]

[0112] Component 1 is manufactured using the same substrate as in Example 1.

[0113] A coating solution for forming the first layer 3 was prepared by blending components having the following composition. 6.00 g of an IPA dispersion of chain-shaped silica particles (IPA-ST-UP, manufactured by Nissan Chemical Industries, Ltd., average particle diameter: 12 nm, solids concentration: 15% by mass) was diluted with 22.13 g of 1-ethoxy-2-propanol to prepare a chain-shaped silica particle coating solution (solids concentration: 3.20% by mass).

[0114] In another container, a solution of 1.7 g of pre-diluted nitric acid (concentration: 3.7 wt%) and 2.30 g of ethanol was slowly added to a solution of 4.17 g of tetraethyl orthosilicate and 2.30 g of ethanol. The mixture was stirred at room temperature for 15 hours, and then 2.00 g of the weighed reaction solution was diluted with 36.33 g of 2-ethyl-1-butanol to prepare silica sol (solids content concentration: 0.6 wt%).

[0115] After diluting the dispersion with ethyl lactate to achieve a solids content concentration of 3.9% by mass, silica sol was added to the resulting mixture to achieve a chain silica particle to silica sol ratio of 100 / 6. The mixture was then stirred at room temperature for 2 hours to provide a coating solution containing chain silica particles. This coating solution was then spin-coated onto a substrate to form a porous layer with a thickness of 1.1 μm.

[0116] In this case, the pore volume is 0.51 cm³.3 / g. Subsequently, the same resin-containing coating solution as in Example 1 was applied under different spin-coating conditions and cured to form a resin-containing layer.

[0117] Table 1 shows the conditions of component 1 in Example 7, and Table 2 shows its evaluation results.

[0118] [Example 8]

[0119] Component 1 is manufactured using the same substrate as in Example 1.

[0120] A coating solution for forming the first layer 3 is prepared by blending components having the following composition. When 1-ethoxy-2-propanol (hereinafter abbreviated as "1E2P") is added to an isopropanol dispersion of 580 g of hollow silica particles (THRULYA 1110, manufactured by JGCCatalysts and Chemicals Ltd., average particle diameter: approximately 50 nm, shell thickness: approximately 10 nm, solids concentration: 20.5% by mass), the isopropanol is distilled off by heating. The isopropanol is distilled off until the solids concentration becomes 19.5% by mass, thereby preparing a 1E2P solvent substitute solution (hereinafter referred to as "solvent substitute solution 1001") of 610 g of hollow silica particles. A surface treatment agent is added to the obtained solvent substitute solution 1001 such that the ratio of hollow silica particles to the surface treatment agent (heptafluorobutyric acid, manufactured by Tokyo Chemical Industry Co., Ltd.) becomes 100 / 1, thereby providing dispersion 1002.

[0121] The dispersion 1002 was diluted with ethyl lactate to a solid content concentration of 3.9% by mass. Then, silica sol was added to the result to achieve a hollow silica particle to silica sol ratio of 100 / 12. Further, the result was mixed and stirred at room temperature for 2 hours, thereby providing a coating solution 1007 containing hollow silica particles. The coating solution containing chain-like silica particles was applied to a substrate by spin coating to form a porous layer with a thickness of 1.1 μm. In this case, the pore volume was 0.22 cm³. 3 / g. Subsequently, the same resin-containing coating solution as in Example 1 was applied under different spin-coating conditions and cured to form a resin-containing layer.

[0122] Table 1 shows the conditions of component 1 in Example 8, and Table 2 shows its evaluation results.

[0123] [Example 9]

[0124] Part 1 was manufactured using the same coating solution as in Example 1. Film formation on the PET film was performed under the following conditions. A roll of polyester film (Lumirror #188-U34, manufactured by Toray Industries, Inc.) with a width of 300 mm and a length of 200 mm was used as the substrate. Film formation was performed using a roll-to-roll coater (UVS-700, manufactured by Labo Co., Ltd.) as the film-forming apparatus. A gravure system was used as the coating system at a film-forming speed of 2.5 m / min.

[0125] First, a coating solution 1005 is prepared in the apparatus tray, and the ratio between the film-forming speed and the rotational speed of the micro-gravure roller is adjusted so that the thickness of the porous layer to be obtained is 1 μm. The coating solution is applied to the substrate, and the drying temperature is set to 80°C. Subsequently, a resin-containing coating solution, the same as that in Example 1, is formed using a gravure system.

[0126] Table 1 shows the conditions of component 1 in Example 9, and Table 2 shows its evaluation results.

[0127] [Example 10]

[0128] Part 1 was manufactured using the same coating liquid as in Example 1. The part was formed on the polished surface of a fused silica substrate (φ30mm, thickness: 1mm, polished on one side) that served as the substrate, in the same manner as in Example 1.

[0129] Table 1 shows the conditions of component 1 in Example 10, and Table 2 shows its evaluation results.

[0130] [Example 11]

[0131] Part 1 was manufactured using the same coating liquid as in Example 1. The coating was applied to a 30mm thick SUS304 substrate, which served as the base material, in the same manner as in Example 1. 2 Components are manufactured on (thickness: 1mm).

[0132] Table 1 shows the conditions of component 1 in Example 11, and Table 2 shows its evaluation results.

[0133] [Comparative Example 1]

[0134] Part 1 was manufactured using the same substrate as in Example 1. Thereafter, the part was manufactured in the same manner as in Example 1.

[0135] Table 1 shows the conditions of component 1 of Comparative Example 1, and Table 2 shows its evaluation results.

[0136] [Comparative Example 2]

[0137] Part 1 was manufactured using the same substrate as in Example 1. The first layer 3 was formed in the same manner as in Example 1, and the number of spin coats was appropriately adjusted so that the thickness of the porous layer became 0.3 μm. Subsequently, a resin-containing coating solution was applied in the same manner as in Example 1 and then cured to form the part.

[0138] Table 1 shows the conditions of component 1 of Comparative Example 2, and Table 2 shows its evaluation results.

[0139] [Comparative Example 3]

[0140] Part 1 was manufactured using the same substrate as in Example 1. A film was formed on the substrate using bar coating, and the bar coating conditions were adjusted so that the thickness of the porous layer to be obtained was 2.6 μm. Subsequently, a resin-containing coating solution was applied in the same manner as in Example 1 and then cured to form the part. As a result, cracks appeared on the surface of the part.

[0141] Table 1 shows the conditions of component 1 of Comparative Example 3, and Table 2 shows its evaluation results.

[0142] [Comparative Example 4]

[0143] Part 1 was manufactured using the same substrate as in Example 1. A porous layer was formed in the same manner as in Example 1. Subsequently, a resin-containing coating liquid was applied in the same manner as in Example 1, except that the spin coating conditions were adjusted so that the thickness of the third layer was 0.1 μm, and then cured to form the part.

[0144] Table 1 shows the conditions of component 1 of Comparative Example 4, and Table 2 shows its evaluation results.

[0145] [Comparative Example 5]

[0146] Part 1 was manufactured using the same substrate as in Example 1. A porous layer was formed in the same manner as in Example 1. Subsequently, a resin-containing coating liquid was applied in the same manner as in Comparative Example 3, except that the application of the third layer by bar coating was repeated until the thickness of the third layer was 3000 μm, and then cured to form the part. The resulting part has a film peel-off between the substrate and the first layer.

[0147] Table 1 shows the conditions of component 1 of Comparative Example 5, and Table 2 shows its evaluation results.

[0148] [Comparative Example 6]

[0149] Component 1 was manufactured using the same substrate as in Example 1. The first layer 3 was formed in the same manner as in Example 1, and the number of spin coats was appropriately adjusted so that the thickness of the porous layer to be obtained was 0.3 μm. Subsequently, a resin-containing coating solution was applied in the same manner as in Example 1, except that the spin coat conditions were changed, and then cured to form the component.

[0150] Table 1 shows the conditions of component 1 of Comparative Example 6, and Table 2 shows its evaluation results.

[0151] [Comparative Example 7]

[0152] Part 1 was manufactured using the same substrate as in Example 1. A film was formed on the substrate using bar coating, and the bar coating conditions were adjusted so that the thickness of the porous layer to be obtained was 2.6 μm. Subsequently, a resin-containing coating solution was applied in the same manner as in Comparative Example 4, and then cured to form a part. The resulting part exhibited film peeling between the substrate and the first layer. Table 1 shows the conditions of Part 1 of Comparative Example 7, and Table 2 shows its evaluation results.

[0153] Table 1

[0154]

[0155] Table 2

[0156]

[0157] The results in Table 2 demonstrate that satisfactory impact and scratch resistance can be achieved in the embodiments as components for a variety of applications.

[0158] According to the present invention, a technology that is beneficial to improving the impact resistance and scratch resistance of components can be provided.

[0159] While the invention has been described with reference to exemplary embodiments, it should be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is accorded the broadest interpretation, thereby covering all such modifications and equivalent structures and functions.

Claims

1. A member comprising, in order, a substrate, a first layer, a second layer, and a third layer, wherein the first layer is an inorganic porous layer in which a plurality of inorganic particles are joined to each other, wherein the third layer is a layer containing a resin, wherein the second layer is a layer containing a plurality of inorganic particles and a resin, wherein the first layer and the second layer have a total thickness of 0.3 μm or more and 2 μm or less, and wherein the third layer has a thickness of 0.4 pm or more and 2000 pm or less, wherein the first layer has a pore volume of 0.1 cm 3 / g or more and 0.51 cm 3 / g or less.

2. The member according to claim 1, wherein the first layer contains the plurality of inorganic particles in an amount of 50% by volume or more.

3. The member according to claim 1, wherein each of the plurality of inorganic particles contains a metal oxide.

4. The member according to claim 3, wherein each of the plurality of inorganic particles contains any one selected from the group consisting of Si02; AI2O3; Ti02; Zn02; and Zr02.

5. The member according to claim 1, wherein at least one of the plurality of inorganic particles is one of a solid particle, a chain-shaped particle, or a hollow particle.

6. The member according to claim 1, wherein the plurality of inorganic particles are joined to each other via an inorganic binder.

7. The member according to claim 6, wherein the inorganic binder is a silicon oxide binder.

8. The member according to claim 1, wherein the thickness of the second layer is 0.1 μm or more and 1 μm or less.

9. The member according to claim 1, further comprising a fifth layer between the substrate and the first layer.

10. The member according to claim 9, wherein the fifth layer contains at least one selected from the group consisting of zirconium oxide; titanium oxide; tantalum oxide; niobium oxide; hafnium oxide; silicon oxide; aluminum oxide; and a resin.

11. The member according to claim 1, wherein the third layer has a function selected from the group consisting of antifouling properties; hydrophilicity; antibacterial properties; antiviral properties; and decoration.

12. A method of manufacturing a member, the method comprising: applying a coating liquid containing a plurality of inorganic particles and a solvent to a substrate to form a coated film; drying and / or calcining the substrate on which the coated film is formed to form a porous layer in which the plurality of inorganic particles are joined to each other; and applying a coating liquid containing a resin to the porous layer to cause partial resin to intrude into a portion of the porous layer, and then curing, wherein the member has: a porous layer region into which the resin is prevented from intruding and which has a thickness of 0.3 μm or more and 2 μm or less; and a region in which the resin is cured without intruding into the porous layer, which has a thickness of 0.4 μm or more and 2000 μm or less, wherein the porous layer has a pore volume of 0.1 cm 3 / g or more and 0.51 cm 3 / g or less.

13. The method of manufacturing a member according to claim 12, wherein each of the plurality of inorganic particles contains a metal oxide.

14. The method of manufacturing a member according to claim 12, wherein each of the plurality of inorganic particles contains any one selected from the group consisting of Si02; AI2O3; Ti02; Zn02; and Zr02.

15. The method of manufacturing a member according to claim 12, wherein the thickness of the region in which the resin intrudes into the porous layer is set to 0.1 μm or more and 1 μm or less.

16. The method of manufacturing a component according to claim 12, wherein the coating liquid containing the plurality of inorganic particles and the solvent includes a component that functions as a binder to bond the plurality of inorganic particles to each other.

17. The method of manufacturing a component according to claim 16, wherein the component that functions as a binder is a silicon oxide compound.

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