A component having a laminate, and a method for forming a component having a laminate.

Abstract

The materials used for exteriors possess functions such as stain resistance, hydrophilicity, antibacterial properties, antiviral properties, and decorative properties, depending on the usage environment. To fully demonstrate and maintain these functions, the strength of the second layer on the outermost surface of the exterior is improved, providing materials with enhanced impact resistance and scratch resistance. [Solution] A component having a base material, a first layer, a second layer, and a third layer in this order, The first layer is an inorganic porous layer in which a plurality of inorganic particles are bonded together, and the combined thickness of the first layer and the second layer is 0.3 μm or more and 2 μm or less. The third layer contains resin and has a thickness of 0.4 μm or more and 2000 μm or less. The second layer is characterized by containing the inorganic particles and the resin.

Description

[Technical Field]

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

[0002] Components used in automotive parts, smartphones, drones and other outdoor products, laptops and home appliances used indoors, printing paper, leather belts, and bags often have decorative layers or hard coats formed on the base material to improve their appearance and strength. For example, by using an appropriate primer layer between the base material and the decorative layer, adhesion is improved and the detachment of the decorative layer from the base material is suppressed. (Patent Document 1) [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2015-66796 [Overview of the project] [Problems that the invention aims to solve]

[0004] Exterior components have functions such as stain resistance, hydrophilicity, antibacterial properties, antiviral properties, or decorative properties, depending on the environment in which they are used. In order to fully exhibit and maintain these functions, it is important to improve the impact resistance and scratch resistance of the outermost layer (surface layer) of the exterior. The primer layer in Patent Document 1 contains resin, so the film is not hard enough and deforms when force is applied to the surface layer, and therefore cannot improve the impact resistance and scratch resistance of the surface layer.

[0005] This invention has been made in view of the above background art, and provides a component with excellent impact resistance and scratch resistance, and a method for manufacturing the same, by connecting the outermost layer and the substrate via an inorganic porous layer containing a plurality of inorganic particles bonded together. [Means for solving the problem]

[0006] The component according to the present invention is a component having a base material, a first layer, a second layer, and a third layer in this order, The first layer is an inorganic porous layer in which a plurality of inorganic particles are bonded together, and the combined thickness of the first layer and the second layer is 0.3 μm or more and 2 μm or less. The third layer contains resin and has a thickness of 0.4 μm or more and 2000 μm or less. The second layer is characterized by containing the inorganic particles and the resin. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a technology that is advantageous in improving the impact resistance and scratch resistance of components. [Brief explanation of the drawing]

[0008] [Figure 1] A schematic diagram illustrating an example of a component. [Modes for carrying out the invention]

[0009] Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. In the following description and drawings, components common to multiple drawings are denoted by the same reference numerals. In some cases, common components may be described by referring to multiple drawings without further explanation. Also, the description of components denoted by the same reference numerals may be omitted.

[0010] <Component 1> Figure 1(a) is a perspective view of an example of member 1 according to this embodiment. Member 1 has a shape according to its respective application, such as film-like, sheet-like, plate-like, dome-like, or spherical. If member 1 is film-like, it can be called a film; if member 1 is sheet-like, it can be called a sheet; and if member 1 is plate-like, it can be called a plate. Member 1 has a surface 110 and a back surface 120, the surface 110 and the back surface 120 are substantially the same shape, and the distance between the surface 110 and the back surface 120, i.e., the thickness T of member 1, is smaller than the maximum width L of the surface 110 and the back surface 120, for example, it may be less than 1 / 100 of the maximum width L. In this example, the surface 110 and the back surface 120 of member 1 are quadrilaterals, but are not limited to this.

[0011] Furthermore, if component 1 is dome-shaped or spherical, it should be hemispherical or nearly spherical, and the detailed shape will depend on the intended use, but the thickness T of the base material must be sufficient to maintain the dome-shaped or spherical shape.

[0012] Figure 1(b) is a cross-sectional view of member 1 along the line AB shown in Figure 1(a). The component 1 is a laminate consisting of at least three layers, comprising a base material 2, a first layer 3 containing particles placed on the base material 2, a third layer 4 placed on the first layer 3, and a second layer 5 provided between the first layer 3 and the third layer 4. The second layer 5 allows the third layer 4 to be bonded to the first layer 3. In addition, because the first layer 3 is an inorganic porous layer, it absorbs impacts applied to the third layer 4 and reduces deformation caused by such impacts, thereby improving the impact resistance and scratch resistance of the third layer 4.

[0013] <Base material 2> The base material 2 is not particularly limited as long as it has excellent processability and can form a layer on its surface. The base material 2 has two main surfaces 101 and 102 facing each other. The distance between the main surface 101 and the main surface 102 is the thickness Tb of the base material 2. The thickness Tb of the base material 2 can be 1 μm or more and less than 100 mm. When the thickness Tb of the base material 2 is less than 250 μm and the member 1 has flexibility, it can be said that the member 1 is in the form of a film. When the thickness Tb of the base material 2 is 250 μm or more and the member 1 has flexibility, it can be said that the member 1 is in the form of a sheet. When the member 1 does not have flexibility, it can be said that the member 1 is in the form of a plate.

[0014] The first layer 3 is provided on the main surface 101 of the base material 2, and the second layer 5 and the third layer 4 are provided in this order on the first layer 3. If necessary, the first layer 3, the second layer 5, and the third layer 4 may be provided on the main surface 102 of the base material 2, or the first layer 3, the second layer 5, and the third layer 4 provided on the main surface 101 and the main surface 102 may be different from each other.

[0015] The base material 2 is not particularly limited as long as it is a material such as resin, glass, metal, or ceramics that can hold the form of the member 1.

[0016] Specific resins used for the base material 2 include, for example, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polycarbonate (PC) resin, triacetate cellulose (TAC) resin, cycloolefin (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, polytetrafluoroethylene (PTFE) resin, perfluoroalkoxy alkane (PFA) resin, vinylidene fluoride (PVDF) resin, and the like.

[0017] In addition, the resin may contain organic fillers, inorganic fillers, etc. in the raw materials, or different resins may be mixed as required.

[0018] As the glass, inorganic glass containing 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, aluminum oxide, etc. can be used. As the glass substrate, a glass substrate formed by grinding and polishing, mold forming, float forming, etc. can be used.

[0019] As the metal, those composed of one type of metal element or alloys containing two or more types of elements can be used. For example, carbon steel, alloy steel, cast iron, etc., and non-ferrous metals such as copper, aluminum, nickel and its alloys, gold, silver, platinum, tin, lead, bismuth, magnesium, titanium, zinc, etc. can be mentioned.

[0020] In order to improve the adhesion between the substrate 2 and the first layer 3, or the strength and flatness of the first layer, etc., the surface of the substrate may be cleaned or polished. Further, a fifth layer for improving the adhesion between the first layer 3 and the substrate 2 may be provided. Preferred examples of the fifth layer include a layer containing at least one selected from the group consisting of zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, silicon oxide, aluminum oxide, and resin.

[0021] The intermediate layer may be a single layer made of the materials described above, or may be composed of a plurality of types of layers laminated.

[0022] <The first layer 3> The thickness of the region containing inorganic particles on the main surface 101, that is, the combined film thickness of the first layer 3 and the second layer 5 is the physical film thickness Ta, and the third layer 4 has a physical film thickness Tc. The physical film thicknesses Ta and Tc are smaller than the thickness Tb of the substrate 2, and Ta is smaller than Tc (Ta < Tc < Tb). Therefore, the shape and mechanical properties of the member 1 are mainly borne by the substrate 2.

[0023] The physical film thickness Ta is between 0.3 μm and 2 μm, preferably between 0.5 μm and 1.5 μm. If it is less than 0.3 μm, the hardness of the region containing inorganic particles is insufficient, and the scratch resistance is not sufficiently high. If it is greater than 2 μm, cracking due to hardening shrinkage may occur during the formation of the porous layer before the formation of the second layer 5. The hardness of the first layer is preferably 1.5 GPa or higher. If the hardness of the first layer is lower than 1.5 GPa, the impact resistance and scratch resistance of the third layer tend to be lower.

[0024] The first layer 3 is a porous layer containing a plurality of inorganic particles 7 bonded together. The inorganic particles 7 (hereinafter sometimes simply referred to as particles 7) may be bonded together by interactions between particles 7, or by an inorganic binder. The inorganic binder is preferably a silicon oxide binder, which is a cured product of a silicon oxide compound, such as a silicon oxide oligomer obtained by hydrolysis and condensation of a silicate ester. Since the first layer 3 contains 50% or more of particles 7, the film has high strength and is unaffected by swelling due to water absorption or moisture absorption. Between the first layer 3 and the third and fourth layers, there is a second layer 5 formed by a portion of the resin contained in the third layer 4 penetrating into some of the pores 6 of an inorganic porous layer made up of multiple particles 7 bonded together. If the resin contained in the third layer 4 penetrates to a depth of 0.1 μm or more from the surface of the inorganic porous layer, 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, and more preferably 0.1 μm or more and 0.5 μm or less. The first layer 3 often remains in a state similar to the porous layer before the formation of the third layer 4, and it is preferable that the pores 6 are connected to each other. Since it is necessary for the resin contained in the third layer 4 to penetrate into the pores, it is preferable that the pores 6 communicate with the film surface before the formation of the third layer 4. Whether the pores 6 of the porous layer before the formation of the third layer 4 communicated with the film surface can be confirmed by observing the state of resin penetration in a cross-section of the second layer 5.

[0025] The amount of pores 6 contained in the first layer 3 can be determined as pore volume by nitrogen gas adsorption. The pore volume is 0.1 cm³. 3 / g or more 0.51cm 3 It is preferable that the value be less than or equal to / g.

[0026] The pore volume is 0.1 cm³. 3 Below 1g, most of the voids are lost, the hardness becomes too high, the impact resistance of the material is lost, and cracks spread.

[0027] Pore ​​volume is 0.1 cm 3 If the pore volume is 0.51 cm³ or more, a second layer 5 of sufficient thickness can be formed, 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, improving impact resistance. Also, if a crack occurs in a part of the component, the spread of the crack can be suppressed. 3 If the density is less than / g, sufficient strength can be obtained without a decrease in the rigidity of the skeleton. A more preferable pore volume is 0.34 cm³. 3 / g or more 0.50cm 3 It is less than / g. Also, 0.50cm 3 When the value exceeds / g, the material becomes brittle due to the large number of voids, resulting in reduced durability.

[0028] <Particle 7> Particle 7 may be circular, elliptical, disc-shaped, rod-shaped, needle-shaped, chain-shaped, or angular in shape, and two or more particles may be mixed and used.

[0029] Particle 7 can be a solid particle. As a solid particle, particle 7 may be composed of a uniform solid material, or particle 7 may be configured to have a core-shell structure in which a solid core is encased in a solid shell.

[0030] Alternatively, particle 7 may be a hollow particle. A hollow particle has a shape in which the hollow part is encased in a solid shell. The shell may contain an inorganic material such as silica, which is silicon oxide as described above.

[0031] Particle 7 can be a chain-like particle. That is, as a chain-like particle, particle 7 has a shape in which multiple particles are linked together. A void 6 is provided between two chain-like particles. Since the chain-like or bead-like arrangement of the chain-like particles is maintained even when a film is formed, the porosity can be increased compared to when a single particle is used. The number of particles linked in one chain-like particle is between 2 and 10, preferably between 3 and 6. If the number of linked particles exceeds 10, large voids are likely to occur, and the abrasion resistance decreases. For particles with a short axis and a long axis, such as chain-like particles, the particle size is defined so that the short axis is the average particle diameter.

[0032] Particle 7 preferably has an average particle diameter of 10 nm to 80 nm, and more preferably 12 nm to 60 nm. If the average particle diameter of the solid particles is less than 10 nm, the pores between and within the particles become too small, preventing the resin contained in the third layer from entering, thus reducing the adhesion between the first and third layers. If the average particle diameter exceeds 80 nm, the size of the pores between the particles becomes large, making it easy for large voids to occur, reducing the strength of the film and making it prone to cracking. The average particle diameter of the particles is the average Ferret diameter. This average Ferret diameter can be measured by image processing of images observed using a transmission electron microscope. Commercially available image processing software such as image Pro PLUS (manufactured by Media Cybernetics, Inc.) can be used for image processing. In a predetermined image area, the contrast can be adjusted as needed, the average Ferret diameter of each particle can be measured by particle measurement, and the average value can be calculated.

[0033] Particle 7 is a particle mainly composed of SiO2, and preferably contains 80 atomic percent or more Si among the elements excluding oxygen, and more preferably 90 atomic percent or more. If the Si content is less than 80 atomic percent, the number of silanol (Si-OH) groups on the particle surface that react with the binder decreases, resulting in reduced wear resistance.

[0034] In addition to SiO2, metal oxides such as Al2O3, TiO2, ZnO2, and ZrO2 can be used for particle 7, and organic components such as alkyl groups and alkyl fluorides can be introduced into or on the silicon oxide particles via Si atoms. Considering the reactivity between particles or between particles and the binder, it is more preferable to use hydrophilic particles in which silanol (Si-OH) groups remain on the particle surface. Particles whose surface is modified with organic groups and in which the remaining silanol group content is less than 70% lose their hydrophilicity, and the film strength of components using such particles decreases due to reduced interaction and reactivity between particles and with the binder. In the present invention, since the interaction and reactivity between particles 7 contained in the first layer 3 or between particles 7 and the binder are maintained, the film strength does not decrease.

[0035] <Method for manufacturing component 1> Component 1 consists of a base material 2, a first layer 3, a third layer 4, and a second layer 5 provided between the first layer 3 and the third layer 4. Component 1 is not limited to the configuration shown in Figure 1; it may be formed by bonding or joining the base material 2 shown in Figure 1 to another substrate. For example, the base material 2 may be a resin film, a laminate may be formed, and the laminate may be formed on another substrate by general insert molding or the like to produce component 1.

[0036] The laminate is manufactured by applying a coating liquid to a substrate 2 to form a coating film, drying and / or firing the substrate 2 on which the coating film has been formed to form the first layer 3, and then forming a third layer 4.

[0037] <Method for forming the first layer 3> The coating solution for forming the first layer 3 may contain at least inorganic particles and a solvent, but it is preferable that it also contains a binder component. Methods for applying coating liquids include bar coating, gravure coating, die coating, spin coating, blade coating, roll coating, slit coating, printing, and dip coating. In particular, when manufacturing components with complex three-dimensional shapes such as dome shapes or spheres, or with convex or concave surfaces, and thin films, spray coating and spin coating methods are recommended. Furthermore, for coating large areas on thin substrates such as films and sheets, gravure coating is preferred from the viewpoint of uniformity of film thickness. In particular, roll-to-roll gravure coating is preferred for coating long roll films.

[0038] To form the first layer 3, the coating liquid is applied to the substrate 2 and dried and / or cured. Drying and / or curing is a process to remove the solvent and deposit the particles 7 without disrupting their arrangement while binding them together, thereby forming a porous layer. The drying and / or curing temperature depends on the heat resistance temperature of the substrate 2, but is preferably between 20°C and 200°C. The drying and / or curing time should be long enough not to affect the substrate 2 and to allow the organic solvent in the layer to evaporate, but is preferably between 10 minutes and 200 hours, and more preferably between 30 minutes and 24 hours.

[0039] To obtain a porous layer with highly aligned particles 7, it is preferable that the particles 7 are in a well-ordered state. Differences in the arrangement of particles 7 are mainly due to the dispersion state of particles 7 in the coating liquid forming the second layer and the dispersion state of particles 7 during film formation.

[0040] If the particles 7 in the coating solution are sufficiently dispersed and unaffected by the dispersion medium or binder, the particles 7 will easily align. However, if the particles 7 are dispersed in a slightly aggregated state due to the influence of the dispersion medium or binder, the alignment will deteriorate.

[0041] Furthermore, the evaporation and drying of the solvent and the flow of particles 7 due to concentration during the application of the coating liquid onto the substrate 2 to form a coating film also greatly affect the arrangement. Even if the dispersion state of particles 7 in the coating liquid is good, if the particles 7 aggregate during the drying process to form the coating film, the arrangement of particles 7 will be disrupted, resulting in larger gaps between particles 7 in the coating film and larger voids in the direction of the substrate 2 plane. When particles 7 are formed in a shifted state rather than in an aligned and deposited state, the stress distribution of the coating film becomes uneven, and the strength of the film is not sufficiently maintained.

[0042] As described above, by using particles 7 to which a surface treatment agent has been added, the porous layer can be formed into a coating film in which the particles 7 are aligned and deposited without disrupting their arrangement.

[0043] The surface treatment agent contained in the porous layer can be determined by elemental analysis of particles 7 and the porous layer, or by separation and quantitative analysis using ion exclusion chromatography, etc.

[0044] <Third Layer 4> The third layer 4 may be a single layer or multiple layers. Alternatively, other films or components may be formed via an adhesive layer containing resin, or printing or markings may be performed using ink or paint containing resin.

[0045] The physical film thickness Tc of the third layer 4 is between 0.4 μm and 2000 μm. If it is less than 0.4 μm, Tc tends to be shallower than the indentation depth during the scratch resistance test, and the surface of the third layer 4 may be scraped off. Also, while a thicker third layer improves scratch resistance and impact resistance, if it is thicker than 2000 μm, delamination may occur at the interface between the substrate 2 and the first layer 3 due to film stress in the third layer 4. More preferably, it is between 0.5 μm and 50 μm.

[0046] 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, forming a second layer 5. This second layer 5 improves the adhesion between the first layer 3 and the third layer 4.

[0047] Examples of resins used in the third layer 4 include polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polycarbonate (PC) resin, triacetate cellulose (TAC) resin, cycloolefin (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.

[0048] Furthermore, a resin used for the hard coat is preferred as the third layer 4. For example, an ionizing radiation-curable resin can be used, preferably an acrylate-based resin. Oligomers and prepolymers such as acrylate resins of polyfunctional compounds like polyhydric alcohols, acrylic resins, alkyd resins, polyester resins, polyether resins, epoxy resins, urethane resins, spiroacetal resins, polybutadiene resins, and polyol-polyene resins can be used. These resins may be used individually, or two or more may be mixed and used as needed.

[0049] Furthermore, the resin may contain organic fillers, inorganic fillers, etc., in its raw materials, and different resins may be mixed in as needed.

[0050] Ionizing radiation-curable resins can be easily cured by using a photoinitiator in combination. Examples of photoinitiators include thioxanthones such as 2,4-diethylthioxanthone and 2-chlorothioxanthone, phosphorus-based compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, Michler ketones such as 4,4-bisdiethylaminobenzophenone, and benzyl.

[0051] If necessary, other additives such as UV absorbers, coloring pigments, antioxidants, silane coupling agents, and antistatic agents can also be used.

[0052] Furthermore, in order to provide functions such as stain resistance, hydrophilicity, antibacterial properties, and antiviral properties, functional materials may be mixed into the resin, or a third layer 4 including a functional layer may be formed.

[0053] For example, materials with antibacterial properties such as copper compounds and silver compounds can be used. Alternatively, a third layer 4 may be formed by coating a resin-containing layer and then forming a functional material on top of it. For example, a functional layer 30 such as an antifouling layer or a hydrophilic layer may be provided on the surface of the hard coat material to provide antifouling and water repellency. Examples of antifouling layers include a layer containing a fluoropolymer, a fluorosilane monolayer, and a layer containing titanium dioxide particles. A hydrophilic polymer layer is preferred for the hydrophilic layer, and a layer containing a polymer having amphoteric hydrophilic groups such as sulfobetaine groups, carbobetine groups, and phosphoroline groups is particularly preferred. A film with a low refractive index may be formed to provide anti-reflective properties.

[0054] The method for forming the third layer 4 is appropriately selected depending on the constituent materials. For example, it may be formed by wet coating, dry coating, or by laminating a film or another component.

[0055] Wet coating methods include bar coating, gravure coating, die coating, spin coating, blade coating, roll coating, slit coating, printing, inkjet, and dip coating. In particular, when manufacturing components with complex three-dimensional shapes such as dome shapes or spheres, convex and concave surfaces, and thin films, spray coating, spin coating, and inkjet are recommended. Furthermore, for coating large areas on thin substrates such as films and sheets, gravure coating is preferred from the viewpoint of uniformity of film thickness. Roll-to-roll gravure coating is especially preferred for coating long roll films. Electrolytic plating, electroless plating, or electroforming coating may also be used.

[0056] Dry coating methods include vacuum deposition methods such as resistance heating, high-frequency induction heating, electron beam heating, arc discharge, and laser ablation, as well as magnetron sputtering, ion beam sputtering, ion beam deposition, ion beam assisted deposition, and ion beam sputtering. [Examples]

[0057] [Example 1] The components were fabricated as follows: <Preparation of coating solution for forming the first layer 3 1> A coating solution for forming the first layer 3 was prepared by blending the following components: 6.00 g of a chain-like silicon dioxide particle IPA dispersion (IPA-ST-UP, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm, solid content concentration 15% by mass) was diluted with 22.13 g of 1-ethoxy-2-propanol to prepare a chain-like silicon dioxide particle coating solution (solid content concentration 3.20% by mass).

[0058] To another container, a solution of 4.17 g of ethyl silicate and 2.30 g of ethanol was slowly added with a solution of 1.7 g of diluted nitric acid water (concentration 3.7 mass%) and 2.30 g of ethanol that had been diluted in advance. After stirring at room temperature for 15 hours, 2.00 g of the weighed reaction solution was diluted with 36.33 g of 2-ethyl-1-butanol to prepare a silica sol (solid content concentration 0.6 mass%).

[0059] The dispersion was diluted with ethyl lactate so that the solid content concentration became 3.9 mass%, and then silica sol was added so that the ratio of chain-like silicon oxide particles to the silica sol component was 100 / 12. Further, by mixing and stirring at room temperature for 2 hours, a coating liquid containing chain-like silicon oxide particles was obtained.

[0060] <Method for measuring pore volume> The pore volume was measured by measuring the nitrogen adsorption isotherm using an automatic vapor adsorption measurement device (BELSORP-MAX manufactured by BEL Japan, Inc.) and obtaining the pore volume by the BJH method. <Method for measuring film thickness> For the cross-section of member 1 observed by an electron microscope image, the film thickness of each layer can be measured by image processing. As the image processing method, commercially available image processing such as image Pro PLUS (manufactured by Media Cybernetics) can be used. In a predetermined image region, contrast adjustment can be appropriately performed as necessary, and the average value of the film thickness can be calculated and obtained.

[0061] <Method for producing test piece for evaluation> As a test piece for evaluation, the coating liquid was dropped onto a polycarbonate substrate (φ30 mm, both sides with a thickness of 2 mm and a mirror finish), and a porous layer with a thickness of about 1.1 μm was formed using a spin coater. On top of the porous layer, Aronix UV-6524 (manufactured by Toagosei Co., Ltd.) was coated by the bar coating method to form a coating film, and then cured under irradiation conditions of 1000 mJ / cm 2 When the cross-section of a sample prepared in the same manner was observed, the thickness of the first layer was 1 μm, the second layer was 0.1 μm, and the thickness of the third layer was about 5 μm.

[0062] The test specimens were evaluated as follows. The conditions for the test specimens in Example 1 are shown in Table 1, and the evaluation results are shown in Table 2.

[0063] <Evaluation of impact resistance of components> The test method used was a weight drop resistance test (JIS K 5600-5-3). A 300g weight was dropped from 100mm above the test specimen, and a visual evaluation was performed. The evaluation was conducted according to the following criteria. A: It will not crack or peel due to the impact of the weight. B: Slight changes are visible due to the impact of the weight, and tiny cracks have formed. C: Cracks and peeling occurred due to the impact of the weight. In this invention, an A rating indicates excellent impact resistance, a B rating indicates good impact resistance, and a C rating indicates poor impact resistance.

[0064] <Evaluation of scratch resistance of components> The test was conducted using steel wool #0000 with a load of 700g x 100 back-and-forth cycles, after which the appearance was visually evaluated. The evaluation criteria are as follows: A: There are almost no visible changes in appearance. B: There are slight changes in the appearance, including minor scratches. C: The appearance has changed significantly, with scratches, peeling of the film, etc. In this invention, an evaluation of A indicates excellent scratch resistance, an evaluation of B indicates good scratch resistance, and an evaluation of poor scratch resistance. The evaluation of component 1 was performed as follows. The conditions for component 1 in Example 1 are shown in Table 1, and the evaluation results are shown in Table 2.

[0065] [Example 2] Component 1 was fabricated using the same substrate as in Example 1. The porous layer was formed in the same manner as in Example 1, and the spin-coating rotation speed was adjusted as appropriate so that the film thickness was 0.5 μm. Then, a coating solution containing resin was applied and cured in the same manner as in Example 1. Table 1 shows the conditions for component 1 in Example 2, and Table 2 shows the evaluation results.

[0066] [Example 3] Component 1 was fabricated using the same substrate as in Example 1. The porous layer was formed in the same manner as in Example 1, and the spin-coating rotation speed was adjusted as appropriate to achieve a film thickness of 2.1 μm. Subsequently, a coating solution containing resin was applied and cured in the same manner as in Example 1. The conditions for component 1 in Example 3 are shown in Table 1, and the evaluation results are shown in Table 2.

[0067] [Example 4] Component 1 was fabricated using the same substrate as in Example 1. The porous layer was formed in the same manner as in Example 2. Subsequently, the coating solution containing the same resin as in Example 1 was applied under modified spin-coating conditions so that the thickness of the third layer was 0.5 μm, and then cured to form a resin-containing layer. The conditions for component 1 in Example 4 are shown in Table 1, and the evaluation results are shown in Table 2.

[0068] [Example 5] The component was fabricated in the same manner as in Example 1, except that the spin-coating conditions for applying the resin-containing coating solution were changed so that the film thickness of the third layer was 100 μm. The conditions for component 1 in Example 5 are shown in Table 1, and the evaluation results are shown in Table 2.

[0069] [Example 6] Component 1 was fabricated using the same substrate as in Example 1. A porous layer was formed using the same coating solution and method as in Example 1, by adjusting the spin-coating rotation speed as appropriate to achieve a film thickness of 1.1 μm. Subsequently, Durazne 2600 (Merck), a polysilazane solution, was adjusted to 1.2 wt% and overcoated by spin-coating, allowing the polysilazane solution to penetrate the particles, resulting in a pore volume of 0.1 cm³ in the porous layer. 3 The concentration was adjusted to be / g. Then, a coating solution containing the same resin as in Example 1 was applied and cured under modified spin-coating conditions to form a resin-containing layer. When the cross-section of the similarly prepared sample was observed, the thickness of the first layer was 1 μm, the second layer was 0.2 μm, and the thickness of the third layer was approximately 5 μm. Table 1 shows the conditions for component 1 in Example 6, and Table 2 shows the evaluation results.

[0070] [Example 7] Component 1 was fabricated using the same substrate as in Example 1. A coating solution for forming the first layer 3 was prepared by blending the following components: 6.00 g of a chain-like silicon dioxide particle IPA dispersion (IPA-ST-UP, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm, solid content concentration 15% by mass) was diluted with 22.13 g of 1-ethoxy-2-propanol to prepare a chain-like silicon dioxide particle coating solution (solid content concentration 3.20% by mass).

[0071] In a separate container, a solution of 4.17 g of ethyl silicate and 2.30 g of ethanol was slowly added to a solution of 1.7 g of pre-diluted nitric acid water (concentration 3.7% by mass) and 2.30 g of ethanol. After stirring at room temperature for 15 hours, 2.00 g of the measured reaction solution was diluted with 36.33 g of 2-ethyl-1-butanol to prepare silica sol (solid content concentration 0.6% by mass).

[0072] The dispersion was diluted with ethyl lactate to a solid content concentration of 3.9% by mass, and then silica sol was added so that the ratio of linear silicon oxide particles to silica sol component was 100 / 6. Furthermore, the mixture was mixed and stirred at room temperature for 2 hours to obtain a coating solution containing linear silicon oxide particles. The coating solution containing linear silicon oxide particles was applied to the substrate by spin coating to form a porous layer with a film thickness of 1.1 μm. At this time, the pore volume was 0.51 cm³. 3 The result was / g. Subsequently, a coating solution containing the same resin as in Example 1 was applied and cured under modified spin-coating conditions to form a resin-containing layer. Table 1 shows the conditions for component 1 in Example 7, and Table 2 shows the evaluation results.

[0073] [Example 8] Component 1 was fabricated using the same substrate as in Example 1. A coating solution for forming the first layer 3 was prepared by blending components with the following composition. 580 g of an isopropyl alcohol dispersion of hollow silicon oxide particles (JGC Catalysts & Chemicals, Ltd., Thru-Ria 1110, average particle size approximately 50 nm, shell thickness approximately 10 nm, solid content concentration 20.5% by mass) was heated and distilled off while adding 1-ethoxy-2-propanol (hereinafter abbreviated as 1E2P). The isopropyl alcohol was distilled off until the solid content concentration was 19.5% by mass to prepare 610 g of a 1E2P solvent-substituted solution for hollow silicon oxide particles (hereinafter referred to as solvent-substituted solution 1001). A surface treatment agent (Heptafluorobutyric acid, Tokyo Chemical Industry Co., Ltd.) was added to the obtained solvent-substituted solution 1001 so that the ratio of hollow silicon oxide particles to surface treatment agent components was 100 / 1 to obtain dispersion 1002.

[0074] Dispersion 1002 was diluted with ethyl lactate to a solid content concentration of 3.9% by mass, and then silica sol was added so that the ratio of hollow silicon oxide particles to silica sol component was 100 / 12. Furthermore, the mixture was mixed and stirred at room temperature for 2 hours to obtain coating solution 1007 containing hollow silicon oxide particles. The coating solution containing chain-like silicon oxide particles was applied to the substrate by spin coating to form a porous layer with a film thickness of 1.1 μm. At this time, the pore volume was 0.22 cm³. 3 The result was / g. Subsequently, a coating solution containing the same resin as in Example 1 was applied and cured under modified spin-coating conditions to form a resin-containing layer. Table 1 shows the conditions for component 1 in Example 8, and Table 2 shows the evaluation results.

[0075] [Example 9] Component 1 was prepared using the same coating solution as in Example 1. Film deposition on the PET film was performed under the following conditions. The substrate used was a roll of polyester film (Toray Industries: Lumirror #188-U34) with a width of 300 mm and a length of 200 m. A roll-to-roll coater (Labo Co., Ltd.: UVS-700) was used as the film deposition apparatus. The coating method was gravure, and the deposition speed was set to 2.5 m / min.

[0076] First, coating solution 1005 was prepared in the apparatus pan, and the film deposition rate was adjusted in the ratio of the film deposition rate to the rotation speed of the microgravure roll so that the resulting porous layer thickness would be 1 μm. The coating solution was then applied to the substrate at a drying temperature of 80°C. Subsequently, a coating solution containing the same resin as in Example 1 was formed using the gravure method. The conditions for component 1 in Example 9 are shown in Table 1, and the evaluation results are shown in Table 2.

[0077] [Example 10] Component 1 was fabricated using the same coating solution as in Example 1. The substrate was a fused silica substrate (φ30 mm, 1 mm thick, polished on one side), and the component was formed on the polished surface in the same manner as in Example 1. The conditions for component 1 in Example 10 are shown in Table 1, and the evaluation results are shown in Table 2.

[0078] [Example 11] Component 1 was fabricated using the same coating solution as in Example 1. The base material was a SUS304 substrate (30 mm square, 1 mm thick), and the component was fabricated using the same method as in Example 1. The conditions for component 1 in Example 11 are shown in Table 1, and the evaluation results are shown in Table 2.

[0079] [Comparative Example 1] Component 1 was fabricated using the same substrate as in Example 1. Subsequently, components were fabricated in the same manner as in Example 1. Table 1 shows the conditions for component 1 of Comparative Example 1, and Table 2 shows the evaluation results.

[0080] [Comparative Example 2] Component 1 was fabricated using the same substrate as in Example 1. The first layer 3 was formed in the same manner as in Example 1, and the spin-coating rotation speed was adjusted as appropriate so that the thickness of the porous layer was 0.3 μm. After that, a coating liquid containing resin was applied and cured in the same manner as in Example 1 to form the component. Table 1 shows the conditions for component 1 of Comparative Example 2, and Table 2 shows the evaluation results.

[0081] [Comparative Example 3] Component 1 was fabricated using the same substrate as in Example 1. Film deposition on the substrate was performed by bar coating, and the bar coating conditions were adjusted so that the thickness of the resulting porous layer was 2.6 μm. Subsequently, a coating liquid containing resin was applied and cured in the same manner as in Example 1 to form the component, but cracks appeared on the surface of the component. The conditions for component 1 of Comparative Example 3 are shown in Table 1, and the evaluation results are shown in Table 2.

[0082] [Comparative Example 4] Component 1 was fabricated using the same substrate as in Example 1. A porous layer was formed in the same manner as in Example 1. Then, except that the spin-coating conditions were adjusted so that the film thickness of the third layer was 0.1 μm, a coating solution containing resin was applied and cured in the same manner as in Example 1 to form the component. Table 1 shows the conditions for component 1 of Comparative Example 4, and Table 2 shows the evaluation results.

[0083] [Comparative Example 5] Component 1 was prepared using the same substrate as in Example 1. A porous layer was formed in the same manner as in Example 1. Then, a coating liquid containing resin was applied and cured in the same manner as in Comparative Example 3, except that the coating was repeatedly applied by bar coating so that the film thickness of the third layer was 3000 μm. The resulting component showed delamination between the substrate and the first layer. The conditions for component 1 of Comparative Example 5 are shown in Table 1, and the evaluation results are shown in Table 2.

[0084] [Comparative Example 6] Component 1 was fabricated using the same substrate as in Example 1. The first layer 3 was formed in the same manner as in Example 1, and the spin-coating rotation speed was adjusted as appropriate so that the thickness of the resulting porous layer was 0.3 μm. Then, except for the change in spin-coating conditions, a coating solution containing resin was applied and cured in the same manner as in Example 1 to form the component. The conditions for component 1 of Comparative Example 6 are shown in Table 1, and the evaluation results are shown in Table 2.

[0085] [Comparative Example 7] Component 1 was fabricated using the same substrate as in Example 1. Film deposition on the substrate was performed by bar coating, and the bar coating conditions were adjusted so that the thickness of the resulting porous layer was 2.6 μm. Subsequently, a coating liquid containing resin was applied and cured, similar to Comparative Example 4, to form the component. Film delamination occurred between the substrate and the first layer in the obtained component. The conditions for component 1 in Comparative Example 7 are shown in Table 1, and the evaluation results are shown in Table 2.

[0086] [Table 1]

[0087] [Table 2]

[0088] The results in Table 2 confirm that the examples can achieve good impact resistance and scratch resistance as components for various applications. [Explanation of Symbols]

[0089] 1 component 2 Base material 3. The first layer 4. The third layer 5. The second layer 6. Holes 7 particles 101 Main surface of the substrate 102 Main surface of the substrate 110 Surface 120 Back side

Claims

1. A component having a base material, a first layer, a second layer, and a third layer in this order, The first layer is an inorganic porous layer in which a plurality of inorganic particles are bonded to each other, and the combined thickness of the first layer and the second layer is 0.3 μm or more and 2 μm or less. The third layer contains resin and has a thickness of 0.4 μm or more and 2000 μm or less. The second layer is characterized by containing the inorganic particles and the resin.

2. The pore volume of the first layer is 0.1 cm³. 3 / g or more 0.51cm 3 The component according to claim 1, characterized in that it is less than or equal to / g.

3. The member according to claim 1 or 2, characterized in that the first layer contains 50% or more by volume of inorganic particles.

4. The member according to any one of claims 1 to 3, characterized in that the inorganic particles include a metal oxide.

5. The inorganic particles are SiO 2 Al 2 O 3 , TiO 2 , ZnO 2 , ZrO 2 The member according to claim 4, characterized in that it includes any one selected from the group consisting of the following.

6. The member according to any one of claims 1 to 5, characterized in that at least one of the inorganic particles is a solid particle, a chain particle, or a hollow particle.

7. The member according to any one of claims 1 to 6, characterized in that the plurality of inorganic particles are bonded together by an inorganic binder.

8. The member according to claim 7, characterized in that the inorganic binder is a silicon oxide binder.

9. The member according to any one of claims 1 to 8, characterized in that the thickness of the second layer is 0.1 μm or more and 1 μm or less.

10. The member according to any one of claims 1 to 9, characterized in that it has a fifth layer between the substrate and the first layer.

11. The member according to claim 10, characterized in that the fifth layer includes at least one selected from the group consisting of zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, silicon oxide, aluminum oxide, and resin.

12. The member according to any one of claims 1 to 9, characterized in that the third layer has one function selected from the group consisting of stain resistance, hydrophilicity, antibacterial properties, antiviral properties, and decorative properties.

13. A method for manufacturing a component, A process of applying a coating liquid containing multiple inorganic particles and a solvent onto a substrate to form a coating film, A step of drying and / or firing the substrate on which the coating film has been formed to form a porous layer in which the plurality of inorganic particles are bonded to each other, The process involves applying a coating liquid containing a resin onto the porous layer, allowing a portion of the resin to penetrate a portion of the porous layer, and then curing it. It has, A method for manufacturing a member, characterized in that the thickness of the region in the porous layer where the resin has not penetrated is 0.3 μm or more and 2 μm or less, and the thickness of the region where the resin has hardened without penetrating the porous layer is 0.4 μm or more and 2000 μm or less.

14. The pore volume of the porous layer is 0.1 cm 3 / g or more and 0.51 cm 3 / g or less, and the manufacturing method of the member according to claim 13, characterized in that.

15. The method for manufacturing a member according to claim 13 or 14, characterized in that the plurality of inorganic particles include a metal oxide.

16. The plurality of inorganic particles are SiO 2 Al 2 O 3 , TiO 2 , ZnO 2 , ZrO 2 A method for manufacturing a member according to any one of claims 13 to 15, characterized by including one selected from the group consisting of the following.

17. A method for manufacturing a member according to any one of claims 13 to 16, characterized in that the thickness of the region in which the resin is impregnated in the porous layer is 0.1 μm or more and 1 μm or less.

18. A method for manufacturing a member according to any one of claims 13 to 17, characterized in that the coating solution containing the plurality of inorganic particles and a solvent contains a component that serves as a binder for joining the plurality of inorganic particles.

19. The method for producing the member according to claim 18, characterized in that the binder component is a silicon dioxide compound.

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