Materials

Abstract

To enhance anti-fouling property in a member having a low glossy surface.SOLUTION: A member 1 has a substrate 3 and a surface layer 5 above the substrate 3. On the surface of the surface layer 5, the specular glossiness is equal to or less than 30 at 60 degrees of JIS Z8741:1997 and an arithmetic average roughness Ra' is equal to or less than 9.3×10-2 μm when a cut-off value λc is 0.008 mm.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a member. [Background technology]

[0002] Low-gloss components are generally designed with unevenness on the material surface to diffuse light. The unevenness of these components makes it easier for dirt to get into them, reducing their stain resistance. Therefore, for example, in Patent Document 1, the roughness index value is set within a specific range to ensure stain resistance in the low-gloss region. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-104272 Summary of the Invention [Problem to be solved by the invention]

[0004] In the technology of Patent Document 1, the value of the maximum height among the roughness indices is set to a value smaller than a predetermined value. Patent Document 1 describes that this makes it possible to achieve a uniform and moist surface condition.

[0005] To achieve a low gloss surface with a wavy texture, such as a ceramic finish, using this technique requires a large maximum height value, but this also makes it easier for dirt to get into the unevenness.

[0006] In view of the above circumstances, the present disclosure aims to improve the antifouling properties of a member having a low-gloss surface. [Means for solving the problem]

[0007] A member having a substrate and a surface layer located above the substrate, wherein the surface of the surface layer has a specular gloss of 30 or less at 60 degrees according to JIS Z8741:1997, and an arithmetic mean roughness Ra' of 9.3 x 10 when the cutoff value λc is 0.008 mm. -2 A component that is less than μm in size. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a conceptual diagram showing a cross section of a member according to one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] 1. Component 1 The member 1 has a substrate 3 and a surface layer 5 located above the substrate 3. The surface 5A of the surface layer 5 has a specular gloss at 60 degrees according to JIS Z8741:1997 of 30 or less. The member 1 has an arithmetic mean roughness Ra' of 9.3 x 10 when the cutoff value λc is 0.008 mm. -2 μm or less.

[0010] (1) Specular gloss From the viewpoint of imparting a matte finish to the surface 5A of the surface layer 5, i.e., from the viewpoint of making the surface 5A matte, the specular gloss at 60 degrees according to JIS Z8741:1997 is 30 or less, preferably 28 or less, and more preferably 25 or less. The lower limit of the specular gloss is not particularly limited. From the viewpoint of antifouling properties, the specular gloss is preferably greater than 5, more preferably 7 or more, and even more preferably 10 or more. From these viewpoints, the specular gloss at 60 degrees is preferably from 5 to 30, more preferably from 7 to 28, and even more preferably from 10 to 25.

[0011] Specular gloss can be measured using a glossmeter, the Gloss Checker IG-320, manufactured by Horiba Ltd. Gloss is measured by shining light from a light source onto the sample surface at a specified angle of incidence θ, and measuring the light reflected at a reflection angle θ' in the direction of specular reflection with a photodetector. The JIS standard (Z8741) uses a black mirrored glass plate with a refractive index of 1.567 as the standard, and defines the specular reflectance at a specified angle of incidence θ as a specular gloss of 100. The optical system conditions used for measurement can be set as follows: <Optical system> Incident angle 60° - acceptance angle 60° Measurement area: 12mm x 6mm oval Light source: LED (wavelength 880nm) Operating temperature range: 0°C to 40°C

[0012] (2) Arithmetic mean roughness Ra' The arithmetic mean roughness Ra′ of the surface 5A of the surface layer 5 is set to 9.3×10 -2 μm or less is preferable, and 8.0 × 10 -2 μm or less is more preferable, and 7.0 × 10 -2 On the other hand, from the viewpoint of low gloss, the arithmetic mean roughness Ra' is 1.0 × 10 -2 Preferably, it is greater than 2.2 × 10 -2 μm or more is more preferable, and 2.5×10 -2 From these viewpoints, the arithmetic mean roughness Ra' is 1.0 × 10 -2 μm or more 9.3×10 -2 μm or less is preferable, and 2.2 × 10 -2 μm or more 8×10 -2 μm or less is more preferable, and 2.5 × 10 -2 μm or more 7×10 -2 It is more preferably 1 μm or less.

[0013] The arithmetic mean roughness Ra' can be measured using a laser microscope conforming to JIS B 0601:2001 (for example, a KEYENCE VK-X150 laser microscope). The arithmetic mean roughness measured under the conditions specified in JIS B 0633:2001 is defined as Ra. In contrast, the arithmetic mean roughness measured under the following conditions is defined as Ra'. A 50x objective lens is used, and images of 200 μm x 275 μm are taken per field of view. Three images are taken per sample. The cutoff value λc is set to 0.008 mm, and the evaluation length is 264 μm (40 μm or more recommended), and the line roughness is measured at 10 points per image. The average value of the 10 points on each image is calculated. The average values ​​calculated for each of the three images are then further averaged to determine Ra'.

[0014] (3) Surface roughness Sz The surface roughness Sz (maximum height) of the surface 5A of the surface layer 5 is not particularly limited. From the viewpoint of a matte finish, the surface roughness Sz is preferably 4.0 μm or more, more preferably 5.0 μm or more, and even more preferably 6.0 μm or more. On the other hand, from the viewpoint of antifouling properties, the surface roughness Sz is preferably 20.0 μm or less, more preferably 18.0 μm or less, and even more preferably 16.0 μm or less. From these viewpoints, the surface roughness Sz is preferably 4.0 μm or more and 20.0 μm or less, more preferably 5 μm or more and 18 μm or less, and even more preferably 6 μm or more and 16 μm or less.

[0015] Surface roughness Sz can be measured using a laser microscope conforming to JIS B 0601:2001 (for example, a KEYENCE VK-X150 laser microscope). The maximum height Sz specified in ISO 25178 is calculated under the following conditions: A 50x objective lens is used, and images of 200 μm x 275 μm per field of view are taken. Plane tilt correction is selected for F-operation (shape correction), and no L-filter or S-filter is set. Three images are taken per sample, and the average value is used.

[0016] (4) Base material 3 The substrate 3 is not particularly limited. For example, inorganic substrates and organic substrates can be used as the substrate 3. The inorganic substrate is not particularly limited, but examples thereof include glass substrates such as soda glass, quartz glass, and borosilicate glass; metal substrates; and ceramic substrates such as pottery and porcelain. The organic substrate is not particularly limited, but examples thereof include resin substrates, wood substrates (wood, etc.), and paper substrates. The resin substrate is not particularly limited, but examples thereof include polyesters such as PET (polyethylene terephthalate); PVC (polyvinyl chloride); polyolefin resins such as PP (polypropylene) and PE (polyethylene); PA (polyamide); ABS resin; fluororesins such as PFA (perfluoroalkoxyalkane) and PTFE (polytetrafluoroethylene); and silicone resins.

[0017] (5) Surface layer 5 The material of the surface layer 5 is not particularly limited. The surface layer 5 may be, for example, a glaze layer or a resin layer. The material of the base material 3 and the material of the surface layer 5 may be the same or different. When the base material 3 and the surface layer 5 are made of the same material, there may or may not be an interface between them. Another layer (intermediate layer) may be present between the base material 3 and the surface layer 5. When the surface layer 5 is a glaze layer, it has, for example, the following composition after firing. The composition of the glaze layer can be measured by EDS (energy dispersive X-ray spectrometry). (Example of glaze layer composition) SiO2: 50% by mass or more and 75% by mass or less Al2O3: 3% by mass or more and 20% by mass or less CaO: 5% by mass or more and 22% by mass or less MgO: 1% by mass or more and 20% by mass or less K2O: 0.1% by mass or more and 10% by mass or less Na2O: 0.1% by mass or more and 5% by mass or less ZnO: 0 mass% or more and 15 mass% or less ZrO2: 0 mass% or more and 20 mass% or less

[0018] There are no particular limitations on the thickness of the surface layer 5. From the viewpoint of imparting water resistance and penetration resistance to the surface layer 5, the thickness is preferably 0.2 mm to 1 mm, more preferably 0.3 mm to 0.8 mm, and even more preferably 0.4 mm to 0.8 mm.

[0019] 2. Manufacturing method of member 1 The manufacturing method of the member 1 is not particularly limited as long as it is possible to adjust the arithmetic mean roughness Ra' to fall within a specific range.

[0020] In the case of a member 1 in which the substrate 3 is a ceramic substrate and the surface layer 5 is a glaze layer, the member 1 can be manufactured, for example, as follows.

[0021] Water is added to the ceramic raw materials and they are pulverized to prepare a base slurry. The base slurry is formed into a desired shape to produce a molded body. The molded body is dried to produce a dried body. The dried body is then glazed with a glaze slurry. The glazed body is then fired.

[0022] Examples of ceramic raw materials include feldspar, pottery stone, kaolin, and clay. For pulverization, a ball mill or the like is used. For forming a molded body, a plaster mold or the like is used. The drying temperature of the molded body is, for example, 20°C or higher and 80°C or lower. The firing temperature is, for example, 1200°C or higher and 1300°C or lower.

[0023] The method for adjusting the arithmetic mean roughness Ra' is not particularly limited. For example, the arithmetic mean roughness Ra' can be adjusted by devising a method for preparing the glaze slurry. For example, the arithmetic mean roughness Ra' can be adjusted by adjusting the median diameter (d50) of the glaze raw materials involved in the formation of diopside to 15 μm or more and 50 μm or less, and controlling the median diameter (d50) of the other raw materials to 3 μm or more and 15 μm or less. Examples of raw materials involved in the formation of diopside include dolomite and calcium carbonate. Examples of other raw materials include feldspar, zircon, zinc oxide, clay, alumina, glass frit, and silica sand. To adjust the median diameter of the glaze raw materials in this way, for example, the raw materials involved in the formation of diopside and the other raw materials can be milled separately to control the median diameter of both. For example, the median diameter can be controlled by adjusting the milling time in a ball mill. In order to adjust the median diameter of the glaze raw materials in this way, raw materials that have been adjusted to a desired median diameter in advance (raw materials with adjusted initial particle size) may be used. When the median diameter (d50) of the raw materials involved in the formation of diopside is adjusted to 15 μm or more and 50 μm or less, and the median diameter (d50) of the other raw materials is controlled to 3 μm or more and 15 μm or less, the arithmetic mean roughness Ra' can be calculated as follows: -2 It is estimated that the roughness is adjusted to less than 9.3 × 10 μm. The raw materials involved in the formation of diopside (the glaze raw materials that are the source of crystals) are relatively large, so they act as seeds (sources of crystals), and as diopside crystals grow from these seeds, the arithmetic mean roughness Ra' is 9.3 × 10 -2 The median particle size can be measured by laser diffraction scattering.

[0024] As a method for adjusting the arithmetic mean roughness Ra', post-processing of the surface layer 5 is also suitably adopted. For example, the post-processing may be a blasting treatment such as a wet blasting treatment.

[0025] When the surface layer 5 is a resin layer, the arithmetic mean roughness Ra' can be adjusted by subjecting the surface of a mold (e.g., a metal die) used to form the surface of the resin layer to a desired surface shape through etching, sandblasting, glass bead blasting, plating, or other treatments. When the surface layer 5 is a resin layer, the substrate 3 is also preferably a resin substrate. In this case, the substrate 3 and the surface layer 5 are preferably made of the same resin material.

[0026] 3. Use of Component 1 The use of the member of the present disclosure is not particularly limited. The member 1 of the present disclosure has stain resistance and low gloss, and is therefore suitable for use in applications that take advantage of these properties, such as toilet bowls, washbasins, toilet tanks, toilet covers, and toilet seat covers.

[0027] 4. Effect of Component 1 The member 1 of the present disclosure has high antifouling properties even though it has a low gloss surface. [Example]

[0028] 1. Preparation of evaluation samples for experimental examples (1) Experimental Example 1-21 Experimental Examples 1-21 shown in Table 1 were prepared as follows. Water was added to the ceramic raw materials and the materials were pulverized to prepare a base slurry. Feldspar, pottery stone, kaolin, and clay were used as the ceramic raw materials. The base slurry was formed into a predetermined shape to produce a molded body. The molded body was dried at 40°C to produce a dried body. The dried body was then glazed with a glaze slurry. The glazed body was then fired at a temperature of 1200°C to 1300°C to produce a sample (fired body).

[0029] The glaze slurries used in each experiment were prepared by appropriately adjusting the blending ratios of the glaze ingredients: dolomite, calcium carbonate, feldspar, zircon, zinc oxide, clay, alumina, glass frit, and silica sand. The composition of the glaze layer for each experiment is shown in Table 3. The glaze ingredients were blended so that the glaze layer after firing would have the respective composition. The composition of the glaze layer was measured using EDS.

[0030] In preparing the glaze slurry, in Experimental Examples 1, 4, 6, and 9, the dolomite and calcium carbonate glaze raw materials that serve as crystal sources were ground separately from the other glaze raw materials. As a result, the median diameter of the glaze raw material that serves as the crystal source (a mixture of dolomite and calcium carbonate) differs from the median diameter of the other glaze raw materials (a mixture of feldspar, zircon, zinc oxide, clay, alumina, glass frit, and silica sand). In Table 1, the median diameter of the glaze raw material that serves as the crystal source is shown as the "particle size of the crystal source raw material," and the median diameter of the other glaze raw materials is shown as the "particle size of the glaze raw material."

[0031] In preparing the glaze slurry, dolomite, calcium carbonate, feldspar, zircon, zinc oxide, clay, alumina, glass frit, and silica sand were ground together in Examples 2, 3, 5, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and 21. In these examples, the median diameter of the mixture of feldspar, zircon, zinc oxide, clay, alumina, glass frit, and silica sand is shown as the "particle size of the glaze raw materials."

[0032] In Experimental Example 17, the surface roughness of the surface of the glaze layer (surface layer) of the fired sample (fired body) was further adjusted by wet blasting.

[0033] (2) Experimental Examples 22-27 The evaluation samples of Experimental Examples 22-27 shown in Table 2 were produced by injection molding. ABS or PP resin was used. The surface of the mold used to form the surface of the resin layer was shaped to the desired surface shape by etching, sandblasting, glass bead blasting, or plating, thereby adjusting the arithmetic mean roughness Ra, Ra', and Sz of the surface layer of the evaluation samples.

[0034] [Table 1]

[0035] [Table 2]

[0036] [Table 3]

[0037] 2. Evaluation Method The specular gloss, Ra, Ra', Sz and matt finish of the surface layer of the evaluation sample were measured. (1) Specular gloss The specular gloss was measured using a gloss meter "Gloss Checker IG-320" manufactured by Horiba, Ltd. Details are as described in the above section "(1) Specular gloss." The matte finish was evaluated according to the following criteria. Good: Specular gloss at 60 degrees is 30 or less. Poor: Specular gloss at 60 degrees is greater than 30. (2) Measurement of Ra Measurement was carried out using a laser microscope conforming to JIS B 0601:2001. (3) Measurement of Ra' Measurement was performed using a laser microscope in accordance with JIS B 0601: 2001. Details are as described in the above section "(2) Arithmetic mean roughness Ra'." (4) Measurement of Sz Measurement was performed using a laser microscope in accordance with JIS B 0601: 2001. Details are as described in the above section "(3) Surface roughness Sz." (5) Method for measuring the contamination recovery rate First, the diffuse reflectance of the uncontaminated sample surface was measured using a Konica Minolta CR-400 color difference meter. Next, a contaminant made by kneading petrolatum and carbon black in a 10:1 ratio (by mass) was rubbed onto the sample surface and left for 30 minutes, after which the contaminant was wiped off with dry absorbent cotton. The diffuse reflectance of the sample surface from which the contaminant had been wiped off was measured again. The contamination recovery rate Y (%) was calculated using the following formula: Y(%)=(Y1 / Y0)×100 Here, Y1 is the diffuse reflectance after the soiling test, and Y0 is the diffuse reflectance before the soiling test. In this test, the resistance to soiling (soil resistance) was evaluated according to the following criteria. Good: Y is 85% or more. Poor: Y is less than 85%.

[0038] 3.Results The evaluation results of the evaluation samples of the experimental examples are shown in Tables 1 and 2. The specular gloss at 60 degrees is 30 or less, and the arithmetic mean roughness Ra' is 9.3 × 10 -2 Experimental Examples 1, 2, 4, 6, 8, 9, 15, 17, 18, 22, 23, 24, and 25, which had a particle size of 1 μm or less, had a low gloss surface (a matte finish) and were highly resistant to dirt. [Explanation of symbols]

[0039] 1...member, 3...base material, 5...surface layer

Claims

1. A member having a substrate and a surface layer located above the substrate, The surface layer is a glaze layer having the following composition: The surface of the surface layer has a specular gloss at 60 degrees according to JIS Z8741:1997 of 30 or less, When the cutoff value λc is set to 0.008 mm, the arithmetic mean roughness Ra′ defined below is greater than 2.7×10 −2 μm and is less than 9.3×10 －２ A member having a diameter of 1 μm or less. <Composition of the Glaze Layer> SiO2: 50% by mass or more and 75% by mass or less Al2O3: 3% by mass or more and 20% by mass or less CaO: 5% by mass or more and 22% by mass or less MgO: 1% by mass or more and 20% by mass or less K 2 O: 0.1% by mass or more and 10% by mass or less Na 2 O: 0.1% by mass or more and 5% by mass or less ZnO: 0% by mass or more and 15% by mass or less ZrO2: 0 mass% or more and 20 mass% or less <Definition of arithmetic mean roughness Ra'> The arithmetic mean roughness Ra' is measured under the following conditions using a laser microscope conforming to JIS B 0601:2001. A 50x objective lens is used, and an image of 200 μm × 275 μm is taken per field of view. Three images are taken per sample. The cutoff value λc is set to 0.008 mm, the evaluation length is set to 264 μm, and the line roughness is measured at 10 locations per image. The average value of the 10 points in each image is calculated, and the average values ​​calculated for the three images are further averaged to obtain Ra'.

2. A member having a substrate and a surface layer located above the substrate, the material of the surface layer is selected from the group consisting of polyester, PVC (polyvinyl chloride), polyolefin resin, PA (polyamide), ABS resin, fluororesin, and silicone resin; The surface of the surface layer has a specular gloss at 60 degrees according to JIS Z8741:1997 of 30 or less, When the cutoff value λc is set to 0.008 mm, the arithmetic mean roughness Ra′ defined below is greater than 2.7×10 −2 μm and is less than 9.3×10 －２ A member having a diameter of 1 μm or less. <Definition of arithmetic mean roughness Ra'> The arithmetic mean roughness Ra' is measured under the following conditions using a laser microscope conforming to JIS B 0601:2001. A 50x objective lens is used, and an image of 200 μm × 275 μm is taken per field of view. Three images are taken per sample. The cutoff value λc is set to 0.008 mm, the evaluation length is set to 264 μm, and the line roughness is measured at 10 locations per image. The average value of the 10 points in each image is calculated, and the average values ​​calculated for the three images are further averaged to obtain Ra'.

3. The member according to claim 1 or 2, wherein the substrate and the surface layer are made of the same material.

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