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WO2017073726A1 - Article résistant aux taches et procédé de production d'article résistant aux taches - Google Patents

Article résistant aux taches et procédé de production d'article résistant aux taches Download PDF

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Publication number
WO2017073726A1
WO2017073726A1 PCT/JP2016/082054 JP2016082054W WO2017073726A1 WO 2017073726 A1 WO2017073726 A1 WO 2017073726A1 JP 2016082054 W JP2016082054 W JP 2016082054W WO 2017073726 A1 WO2017073726 A1 WO 2017073726A1
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WIPO (PCT)
Prior art keywords
antifouling
layer
water
antifouling article
article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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PCT/JP2016/082054
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English (en)
Japanese (ja)
Inventor
万江美 増田
久美子 諏訪
雄一 ▲桑▼原
広和 小平
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AGC Inc
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Asahi Glass Co Ltd
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Filing date
Publication date
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Publication of WO2017073726A1 publication Critical patent/WO2017073726A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions

Definitions

  • the present invention relates to an antifouling article and a method for producing the antifouling article.
  • Patent Document 1 discloses a hydrophilic surface in which silica fine particles are bonded with a siliceous binder, the surface of which is a fine rough surface with protruding silica fine particles, and a large number of bent fine pores communicating from the surface to the inside.
  • a structure having a fine porous antifouling layer on the outer surface of a substrate has been proposed.
  • the fine porous antifouling layer protruding from the silica fine particles described in Patent Document 1 is not sufficiently antifouling, and if the surface is wiped with a cloth or the like, the uneven structure is worn and the antifouling property is further lowered. . *
  • the present invention provides an antifouling article excellent in antifouling properties and wear resistance and a method for producing the antifouling article, which solves the conventional problems as described above.
  • the present invention comprises the following.
  • An antifouling article having a substrate and an antifouling layer disposed on the substrate, wherein the antifouling layer has a plurality of protrusions including aggregates of particles and a binder on the surface.
  • the antifouling article After sprinkling the following mixed powder for evaluation on the antifouling layer on the antifouling article and allowing it to stand for 10 seconds, the antifouling article is tilted 135 ° and from a height of 3 cm from the ground to 10 cm / second After the test, when the antifouling article was brought into contact with the ground twice at a speed of 5 times, the evaluation mixed powder was dropped and the haze value of the antifouling article was measured five times.
  • the haze value change obtained by subtracting the haze value of the antifouling article before the test from the average haze value of the antifouling article was 1.0% or less, and 1 ⁇ l of water droplets were applied to the antifouling layer.
  • a step of preparing a concavo-convex layer-forming composition containing a pearl necklace-like or chain-like particle aggregate and a binder precursor, a water-repellent layer-forming composition, and a base, and the concavo-convex layer on the base A method for producing an antifouling article, comprising: a step of applying a forming composition to form an uneven layer; and a step of applying a water repellent layer forming composition on the uneven layer to form a water repellent layer.
  • a step of preparing a water-repellent uneven layer including a pearl necklace-like or chain-like particle aggregate and a fluorine-containing binder precursor, and a base; and the water-repellent uneven layer on the base Applying the forming composition to form a water-repellent concavo-convex layer, and a method for producing an antifouling article.
  • the particle aggregate has an average primary particle diameter of 5 to 300 nm, and the volume ratio of the particle aggregate and the binder precursor in terms of metal oxide is 7/93 to 95/5.
  • an antifouling article excellent in antifouling properties and abrasion resistance and a method for producing the antifouling article.
  • the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • the primary particle diameter of the particle is a particle diameter determined by observation with a scanning electron microscope.
  • the secondary particle diameter is a particle diameter measured by a dynamic light scattering method.
  • pearl necklace refers to a pearl necklace in which a plurality of spherical particles are joined together and secondarily aggregated, that is, a plurality of pearls, which are decorative items, are connected in a rosary shape. As described above, it refers to a shape in which a plurality of particles are connected, and the connection method may be linear or branched.
  • a circular figure caused by a spherical portion has a roundness of 70% or more, and the total area of the inscribed circles of each circular figure is a secondary particle.
  • Aggregates that occupy 70% or more of the total projected area and in which the inscribed circles of the circular figures do not overlap each other are called “pearl necklaces”, and those with few spherical parts are called “chains”.
  • the roundness is represented by the ratio of the radius of the inscribed circle to the radius of the circumscribed circle of the target figure outline, and is 100% for a perfect circle.
  • FIG. 1 and 2 are diagrams showing an example of an antifouling article according to the present invention.
  • the antifouling article 1 shown in FIG. 1 has a base 2 and an antifouling layer 8 disposed on the base 2.
  • the antifouling layer 8 has a plurality of protrusions 5 including aggregates of particles 3 and a binder 4.
  • the antifouling article 10 shown in FIG. 2 has a base 12 and an antifouling layer 16 disposed on the base 12.
  • the antifouling layer 16 has a plurality of protrusions 15 including aggregates of particles 13 and a binder 14 having water repellency.
  • the material of the substrate is not particularly limited, and examples thereof include glass, plastic, metal, ceramics, and combinations thereof (for example, composite materials and laminated materials).
  • the substrate is preferably a light transmissive substrate made of glass or plastic.
  • the glass may be a tempered glass subjected to a physical tempering treatment or a chemical tempering treatment, or may be a laminated glass in which a plurality of glass plates are laminated via an adhesive layer.
  • the shape of the substrate is not particularly limited, and examples thereof include a flat plate shape and a shape having a curvature on the entire surface or a part thereof.
  • the thickness of the substrate is not particularly limited and can be appropriately selected depending on the use of the antifouling article.
  • the thickness of the substrate is preferably 1 to 10 mm from the viewpoint of ease of handling.
  • the antifouling layer is disposed on the substrate and has a plurality of protrusions including particle aggregates and a binder on the surface. Since the antifouling layer has fine protrusions on the surface, dirt adhering to the antifouling article first comes into contact with the tips of the protrusions. Therefore, this antifouling layer has a small contact area with dirt, and dirt is difficult to adhere.
  • the arithmetic average roughness (hereinafter also referred to as “surface Ra”) of the antifouling layer is preferably 5 to 30 nm, more preferably 6 to 25 nm, and particularly preferably 7 to 20 nm. If the surface Ra is 5 nm or more, the contact between the part having a smaller film thickness than the apex of the convex part including the single particles and the binder and the dirt is suppressed, and more excellent antifouling property is obtained. If the surface Ra is 30 nm or less, the wear resistance is excellent.
  • the surface Ra can be measured with a scanning probe microscope.
  • the film thickness of the antifouling layer is not particularly limited, but is preferably 20 to 350 nm, more preferably 30 to 300 nm, and particularly preferably 50 to 300 nm. If the film thickness of the antifouling layer is 20 nm or more, the antifouling property tends to be high, and if it is 350 nm or less, the mechanical strength is excellent.
  • the film thickness is 10 in descending order from the protrusion having the maximum height in the range of 1.5 ⁇ m in the direction parallel to the surface having the antifouling layer of the substrate from the film cross-sectional image obtained by an electron microscope or the like. This is a value obtained by extracting 10 points up to the first protrusion and averaging the heights of the protrusions at the 10 points.
  • the antifouling layer includes a plurality of protrusions including aggregates of the particles and a binder protruding on the surface, and other regions (for example, convex portions and / or binders including non-aggregated particles and a binder). Thus, irregularities are formed on the surface. Since the protrusions are aggregates of particle aggregates and binders that are non-uniformly present on the surface of the substrate, more appropriate unevenness is formed compared to the unevenness formed by the particles alone. Dirty.
  • the surface of the protrusion preferably has water repellency.
  • the protrusion may have a structure having a water-repellent layer on the surface or a structure containing a water-repellent binder.
  • the protrusion 5 shown in FIG. 1 has a water-repellent layer 7 on the surface.
  • the binder 14 that binds the particles 13 has water repellency. Since the surface of the protrusion has water repellency, the surface energy of the outermost surface is small, and thus the surface frictional force is small. Therefore, the surface of the protrusion is not easily worn, and even when the dirt attached to the surface of the antifouling layer is wiped off with a cloth or the like, the antifouling performance is not easily lowered.
  • the protrusion preferably has a water repellent layer on the surface. This is because the protrusion has the water-repellent layer on the surface, so that the water repellency of the surface of the antifouling film becomes higher. Moreover, the intensity
  • the water repellent layer will be described later.
  • the shape of the protrusion is not particularly limited, and examples thereof include a substantially quadrangular pyramid, a substantially triangular pyramid, and a substantially cone.
  • the radius of curvature of the partial spherical surface is preferably 5 nm or more, and more preferably 5 nm to 15 nm.
  • the height of the protrusion is preferably 10 nm or more, more preferably 30 to 200 nm.
  • the height of the protrusion is the height from the substrate surface to the apex of the protrusion, and can be measured using a scanning electron microscope.
  • the number of protrusions in the antifouling layer is preferably 30 to 100 / ⁇ m 2, and more preferably 50 to 100 / ⁇ m 2 .
  • the number of protrusions can be measured, for example, by observing the film cross section with a scanning electron microscope.
  • the size of the bottom surface of the protrusion is preferably 10 to 700 nm, more preferably 30 to 200 nm.
  • the average value of the angle between the bottom surface of the protrusion (ie, the surface parallel to the substrate) and the side surface is not particularly limited, but is preferably 10 to 90 °, more preferably 20 to 70 °. If the angle between the bottom surface and the side surface of the protrusion is 10 ° or more, a steeper protrusion can be obtained.
  • the size of the bottom surface of the protrusion is defined as the diameter of a circle in which the bottom shape of the protrusion is inscribed. The size of the bottom surface of the protrusion can be measured using a scanning electron microscope.
  • the antifouling layer is an average value of distances between apexes of adjacent protrusions T (hereinafter, simply referred to as “protrusions T” having a height of 90% or more with reference to the protrusions having the maximum height from the substrate surface).
  • the “distance between vertices” is preferably 100 to 1,000 nm, more preferably 100 to 800 nm, and particularly preferably 100 to 500 nm. That the distance between vertices is 100 nm or more means that the interval between the irregularities formed by the protrusions T on the surface of the antifouling layer is large.
  • the distance between the vertices is 100 nm or more, the adsorption of dirt due to capillary action can be suppressed. As a result, oil stains and the like are hardly attached, and even if attached, they can be easily removed.
  • the distance between vertices can be measured with a scanning electron microscope.
  • the distance between the vertices is a protrusion having the maximum height among protrusions existing in a predetermined region in a direction parallel to the surface of the substrate having the antifouling layer, from a cross-sectional photograph of the antifouling article.
  • Select a body select a protrusion T having a height of 90% or more, measure the distance between vertices of adjacent protrusions T (that is, the distance between the vertices), and calculate the average value. To do.
  • the ratio of the total covered area of the aggregate of particles to the area of the substrate on which the antifouling layer is disposed is preferably 12 to 100%.
  • the convex portion coverage is preferably 15 to 100%, more preferably 20 to 100%, and particularly preferably 50 to 100%.
  • the convex portion coverage can be measured with a scanning electron microscope.
  • the volume ratio (particle / binder) of the aggregate of particles forming the protrusions to the binder is preferably 7/93 to 95/5. If the volume ratio of the particles to the binder is 7/93 or more, an antifouling layer having an appropriate distance between the apexes of the protrusions can be formed on the surface of the substrate, so that the antifouling property tends to increase. If it is 5 or less, the adhesion between the substrate and the antifouling layer tends to be high.
  • the aggregate of the particles constituting the protrusion is not particularly limited as long as it forms an aggregate together with a binder described later and can form the protrusion on the surface of the antifouling layer.
  • inorganic particles are preferred.
  • the inorganic particles include metal oxide particles such as silica, titania, alumina, and zirconia.
  • silica particles are preferable. If the particles are silica particles, light scattering is suppressed and the color of the substrate is not impaired. In particular, when the substrate is glass, the particles are preferably silica particles.
  • the particles may be one type or a combination of two or more types.
  • the particles preferably have a silica content of 50% by mass or more, and more preferably 75% by mass or more.
  • the shape of the aggregate is not particularly limited, but a chain shape or a pearl necklace shape is preferable, and a pearl necklace shape is particularly preferable. If the shape of the aggregate is a pearl necklace shape, more appropriate uneven projections are easily formed, and the antifouling property tends to be improved.
  • the average primary particle size of the particles constituting the aggregate is preferably 5 to 300 nm, more preferably 10 to 100 nm, still more preferably 10 to 50 nm, and particularly preferably 10 to 30 nm.
  • the average primary particle diameter of the particles is 5 nm or more, it becomes easy to form protrusions and the antifouling property tends to be improved.
  • grains is 300 nm or less, a haze value can be made small.
  • the secondary particle diameter of the aggregate is preferably 40 to 200 nm, more preferably 50 to 100 nm, and particularly preferably 60 to 90 nm.
  • the particle aggregates may include both pearl necklace aggregates and chain aggregates. Further, the protrusion may contain spherical particles within a range not impairing the effects of the present invention.
  • the chain aggregate has, for example, an average primary particle diameter d of 10 to 100 nm, an average length (L) of 60 to 500 nm, and a ratio of the average length to the average primary particle diameter of 3 to 20 nm (L / D).
  • spherical particles examples include spherical particles having an average primary particle diameter d of 1 to 1000 nm.
  • the binder is preferably an inorganic binder in terms of excellent durability. It is preferable that the binder is a hydrolyzate of a hydrolyzable silane compound containing a fluorinated alkyl group or a fluorinated alkylene group because an uneven layer with high water repellency can be obtained.
  • the binder is a hydrophilic inorganic binder because the antifouling property is increased. Moreover, since the uneven
  • the hydrophilic inorganic binder include metal oxides such as silica, alumina, titania, zirconia, tantalum oxide, and tin oxide.
  • the binder is more preferably a silica binder in terms of ease of handling.
  • the silica binder preferably has a small alkali component content.
  • silica binder having a low alkali component content examples include a hydrolyzate of an alkoxysilane compound or a hydrolyzate of demineralized silicic acid obtained by removing a part of an alkali metal from an alkali metal salt of silicic acid. Note that these hydrolysates may have an unreacted silanol group (Si—OH) group.
  • the binder may be a mixture of two or more binders. 50 mass% or more is preferable and, as for the silica content rate in a binder, 75 mass% or more is more preferable.
  • the concavo-convex layer can contain further components as long as the effects of the present invention are not impaired.
  • Further components include surfactants, antifoaming agents, leveling agents, ultraviolet absorbers, viscosity modifiers, antioxidants, fungicides, pigments and the like.
  • the total content of the further components is preferably 5% by mass or less, more preferably 1% by mass or less in the antifouling layer.
  • the water repellent layer is not essential when the above-mentioned binder has water repellency, but may be provided to further increase the water repellency of the antifouling layer.
  • the thickness of the water repellent layer is substantially uniform. If the thickness of the water repellent layer is reduced at the tip of the protrusion, the water repellency of the antifouling layer may be reduced, or the stain removability may be reduced.
  • the water repellent layer is made of a silane compound containing fluorine, since the water repellency becomes high.
  • the water repellent layer is more preferably made of a hydrolyzed condensate of fluorine-containing alkoxysilane.
  • This antifouling article has excellent antifouling properties against various stains.
  • dirt inorganic dirt such as dust remaining in the atmosphere, alkali wall residue from the concrete wall (water dry spots), water stains, burns on the glass itself, smoke in the atmosphere, automobile exhaust gas, tobacco Organic stains such as smoke and oil.
  • the antifouling article has a better antifouling effect against dust and oil stains.
  • the mixed powder for evaluation is a mixed powder used in an antifouling evaluation test conducted by the Public Works Research Center, 2.3% by mass of carbon black 1 (particle size: 0.002 to 0.028 ⁇ m) 9.3 mass% carbon black 2 (12 types of JIS test powder 1), 62.8 mass% yellow ocher (natural ocher for pigments), and 20.9 mass% calcined Kanto loam (JIS test powder) 8) and 4.7% by mass of silica powder (3 types of JIS test powder 1).
  • the fact that such a mixed powder for evaluation is difficult to adhere means that it is difficult to get dirty even when used outdoors for a long time.
  • the water contact angle is an index representing the water repellency of the antifouling layer.
  • This antifouling layer applies a sessile drop method specified in JIS R3257: 1999 to drop 1 ⁇ l of water droplets on the antifouling layer, and the water contact angle measured after 3 seconds is 80 ° or more. That is, the surface of the antifouling layer has water repellency. Accordingly, the adhesion force acting between the dirt and the antifouling layer is small. Therefore, not only dirt containing moisture such as mud dirt is hard to adhere, but even if dirt adheres, the attached dirt is easily removed by wind or gravity. When the water contact angle is 80 ° or more, the water repellency is excellent.
  • this antifouling layer has water repellency, it has a small surface friction coefficient and is less likely to be worn by rubbing. Therefore, even when the attached dirt is wiped off with a cloth or the like, the antifouling performance is not easily lowered.
  • the water contact angle is 150 ° or less because productivity is increased.
  • the antifouling layer preferably has a dry sand falling angle determined by the following measurement method of less than 50 ° because it can easily be removed by gravity even if dirt such as sand adheres and can be easily removed.
  • the antifouling layer has a wet sand falling angle of less than 50 ° obtained by the following method, because dirt containing moisture is easily dropped by gravity and can be easily removed.
  • the antifouling layer preferably has a haze value change value within 1.0% according to the wind removability test of dry sand obtained by the following method, because it is easily removed by wind even if dirt such as sand adheres. .
  • the initial haze value is measured for a 5 cm ⁇ 5 cm antifouling article. Thereafter, 0.5 g of three types of JIS test powder 1 is sprinkled on the surface of the antifouling layer on the antifouling article, left to stand for 10 seconds, left in a 10 ° C. environment for 30 minutes, and then at 35 ° C. and 95% RH for 1 hour. After standing, the sand is blown away with a wind speed of 1 to 2 m / s to measure the haze value, and a value obtained by subtracting the haze value before the test from the value is evaluated as a value of change in haze value ( ⁇ Hdw).
  • the antifouling layer preferably has a haze value change value of 1.0% or less by a wind removability test of wet sand obtained by the following method, since it is easily removed by wind even if dirt containing moisture adheres. .
  • the initial haze value is measured for a 5 cm ⁇ 5 cm antifouling article. Thereafter, 0.5 g of three types of JIS test powder 1 is sprinkled evenly on the surface of the antifouling layer on the antifouling article using a sieve. The antifouling article sprinkled with powder is allowed to stand at 10 ° C. for 30 minutes, and then held for 1 hour in a 35 ° C. and 95% RH thermostatic bath environment. Thereafter, the antifouling article is taken out of the thermostatic bath, and the sand is blown away with a wind speed of 1 to 2 m / s. A value obtained by subtracting the initial haze value from a value obtained by averaging the haze values after blowing sand is evaluated as a value ( ⁇ Hww) of change in haze value.
  • This antifouling layer has a cotton cloth specified in JIS L0803 placed on the surface of the antifouling layer, and a pressure of 2.95 ⁇ 10 4 N / m 2 is applied to the cotton cloth to reciprocate the cotton cloth and the antifouling layer 1500 times. Rubbed. Then, as a test, the mixed powder for evaluation was sprinkled and allowed to stand for 10 seconds, and then the antifouling article was tilted 135 ° and brought into contact with the ground twice at a speed of 10 cm / second from a height of 3 cm from the ground.
  • the average value of the haze values after the test (when the sample was divided into three regions, the upper region, the central region, and the lower region)
  • the value obtained by subtracting the haze value before the test from the arithmetic mean value of the three haze values near the center of the upper region, the center of the central region, and the center of the lower region) is evaluated as the value of change in the haze value ( ⁇ Hr).
  • a haze value change value ( ⁇ Hr) within 5.0% is preferable because it indicates that the antifouling layer has high wear resistance.
  • the manufacturing method of this antifouling article is manufacturing method 1 or manufacturing method 2 described below.
  • Production method 1 is a step of preparing a concavo-convex layer-forming composition containing a pearl necklace-like or chain-like particle aggregate and a binder precursor, a water-repellent layer-forming composition, and a substrate (referred to as “preparation step 1”). ), A step of applying the concavo-convex layer forming composition 1 on the substrate to form a concavo-convex layer (referred to as “concave layer forming step 1”), and a water repellent layer forming composition on the formed concavo-convex layer. And a step of forming a water-repellent layer by applying (referred to as “water-repellent layer forming step 1”).
  • the preparation step 1 is a step of preparing a concavo-convex layer forming composition 1 containing a pearl necklace-like or chain-like particle aggregate and a binder precursor, a water repellent layer forming composition, and a substrate.
  • the uneven layer forming composition 1 includes a pearl necklace-like or chain-like particle aggregate and a binder precursor.
  • the uneven layer forming composition 1 contains a pearl necklace-like or chain-like particle aggregate, it is easy to locally laminate the particles when the uneven layer forming composition 1 is applied to the substrate surface. Unevenness is easily formed on the surface. Moreover, the uneven
  • the binder precursor is a component that forms the above-described binder by heat treatment, solvent removal treatment, photocuring treatment, or the like.
  • the binder precursor include an inorganic binder precursor and an organic-inorganic hybrid binder precursor.
  • a silica precursor is preferable.
  • the uneven layer forming composition 1 contains the silica precursor, the adhesion between the antifouling layer to be formed and the substrate can be further improved.
  • the silica precursor include a silane compound having a hydrolyzable group and silicic acid.
  • the binder precursor other than the silica precursor include a metal oxide precursor having a hydrolyzable group.
  • the metal oxide precursor is a component that forms a metal oxide by a hydrolysis reaction.
  • One type of binder precursor may be used alone, or two or more types may be used in combination.
  • the silica precursor examples include silicic acid and a silane compound having a hydrolyzable group.
  • the silica precursor one having a low alkali metal content is preferable because it further improves the adhesion between the antifouling layer to be formed and the substrate.
  • the silica precursor is obtained by removing a part of the alkali metal from the alkali metal salt of silicic acid.
  • a chlorosilicic acid or an alkoxysilane compound or a partial hydrolysis condensate thereof is preferred.
  • the alkali metal salt of silicic acid include sodium silicate, lithium silicate and potassium silicate, and sodium silicate is particularly preferable.
  • An aqueous solution of sodium silicate having a large SiO 2 / Na 2 O molar ratio is preferable because alkali metal ions can be easily removed, and an SiO 2 / Na 2 O molar ratio of 3 or more is particularly preferable.
  • a silane compound having a hydrolyzable group is a compound having 1 to 4 hydrolyzable groups bonded to a silicon atom in one molecule.
  • the hydrolyzable group include an alkoxy group, an isocyanato group, an acyloxy group, an aminoxy group, a halogen and the like, and an alkoxy group is preferable. Therefore, an alkoxysilane compound is preferable as the silane compound having a hydrolyzable group.
  • the alkoxysilane compound may be a condensate in which at least some of the molecules are hydrolyzed and condensed (hereinafter also referred to as “partially hydrolyzed condensate of alkoxysilane compound”).
  • the alkoxysilane compound is a compound having 1 to 4 alkoxy groups bonded to a silicon atom in one molecule, and examples thereof include compounds represented by the following general formula (I).
  • each R 1 independently represents an alkyl group having 1 to 4 carbon atoms
  • each R 2 independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • P represents a number from 1 to 4.
  • R 1 is an alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl, and methyl and ethyl are preferable.
  • the alkyl group having 1 to 10 carbon atoms in R 2 is linear or branched, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, decyl and the like.
  • R 2 is preferably an alkyl group having 1 to 6 carbon atoms.
  • the substituent in R 2 is not particularly limited, but epoxy group, glycidoxy group, methacryloyloxy group, acryloyloxy group, isocyanato group, hydroxy group, amino group, phenylamino group, alkylamino group, aminoalkylamino group, ureido Group, mercapto group and the like.
  • the “alkyl group having 1 to 10 carbon atoms” in R 2 means that the alkyl group portion excluding the substituent has 1 to 10 carbon atoms.
  • alkoxysilane compound examples include tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl
  • the binder precursor is preferably a fluorine-containing hydrolyzable silane compound because of high water repellency.
  • the volume ratio in terms of metal oxide between the particles and the binder precursor is preferably 7/93 or more because the antifouling property is obtained by the concavo-convex shape, and the adhesion to the substrate is high. In order to obtain it, 95/5 or less is preferable.
  • the concavo-convex layer-forming composition contains a pearl necklace-like silica having an average primary particle diameter of 5 to 300 nm and a silica precursor, the pearl necklace-like silica and the silica precursor are converted into silica.
  • the volume ratio (pearl necklace-like silica / silica precursor) is 7/93 to 95/5.
  • the silica precursor is preferably desalted silicic acid or a hydrolyzate of alkoxysilane.
  • content of the partial hydrolysis-condensation product of an alkoxysilane compound is the conversion amount of a silica.
  • the uneven layer forming composition 1 may contain water and an acid under the condition that a hydrolysis condensate of the binder precursor is obtained.
  • corrugated layer forming composition 1 advances a hydrolysis-condensation reaction by containing water.
  • the amount of water contained in the uneven layer forming composition 1 is preferably 10 to 500 parts by mass, more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the binder precursor.
  • the amount of the binder precursor is an amount in terms of metal oxide.
  • corrugated layer forming composition 1 can adjust the reaction rate of the hydrolysis condensation of a binder precursor by containing an acid.
  • the acid include hydrochloric acid, nitric acid, sulfuric acid and the like.
  • the amount of the acid contained in the uneven layer forming composition 1 is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.5 parts by mass with respect to 100 parts by mass of the binder precursor.
  • the amount of the binder precursor is an amount in terms of metal oxide.
  • the uneven layer forming composition 1 may contain a solvent for the purpose of improving workability.
  • the solvent is preferably a solvent that has good dispersibility of the particles capable of forming the protrusions and the binder precursor and has low reactivity with the components of the particles and the binder precursor.
  • the solvent include alcohol (methanol, ethanol, 2-propanol, etc.), ester (acetic ester, butyl acetate, etc.), ether (diethylene glycol dimethyl ether, etc.), ketone (methyl ethyl ketone, etc.), water and the like.
  • the solvent is preferably an ester or an alcohol, more preferably an alcohol, in that the appearance is good.
  • the solvent may be a single type or a combination of two or more types.
  • the content of the solvent is not particularly limited, but is preferably 1,000 to 100,000 parts by mass, more preferably 2,000 to 50,000 parts by mass with respect to 100 parts by mass in total of the particles and the binder precursor. If the content of the solvent is 1,000 parts by mass or more with respect to a total of 100 parts by mass of the particles and the binder precursor, rapid progress of hydrolysis and condensation reaction can be prevented, and 100,000 parts by mass If it is below, a hydrolysis and a condensation reaction will advance.
  • the amount of the particles and the binder precursor is an amount in terms of metal oxide.
  • the uneven layer forming composition 1 can contain further components within a range not impairing the effects of the present invention.
  • Such components include surfactants, antifoaming agents, leveling agents, ultraviolet absorbers, viscosity modifiers, antioxidants, fungicides, and pigments.
  • the content of the further component in the concavo-convex layer forming composition 1 is not particularly limited, but is preferably 0.02 to 1 part by mass with respect to 100 parts by mass in total of the particles capable of forming the protrusions and the binder precursor,
  • the amount is more preferably 0.02 to 0.5 parts by mass, and particularly preferably 0.02 to 0.3 parts by mass.
  • the amount of the binder precursor is an amount in terms of metal oxide.
  • the water repellent layer-forming composition preferably contains a fluorine-containing hydrolyzable silane compound.
  • the water repellent layer forming composition may contain a solvent for the purpose of improving workability.
  • the solvent is preferably a solvent having good solubility of the fluorine-containing hydrolyzable silane compound and low reactivity to these components.
  • examples of the solvent include alcohol (methanol, ethanol, 2-propanol, etc.), hydrofluorocarbon and the like.
  • the solvent may be a single type or a combination of two or more types.
  • the content of the solvent is not particularly limited, but is preferably 1,000 to 100,000 parts by weight, more preferably 2,000 to 50,000 parts by weight, based on 100 parts by weight of the total of the fluorine-containing hydrolyzable silane compound. preferable.
  • the content of the solvent is in the above range, sufficient antifouling property can be imparted and the appearance of the resulting film is improved.
  • fluorine-containing hydrolyzable silane compound examples include compounds represented by the following formula (1) as hydrolyzable silane compounds having a fluorine-containing alkyl group or a fluorine-containing alkylene group.
  • Rf is a divalent organic group having 1 to 20 carbon atoms including at least one fluoroalkyl group
  • A is a fluorine atom or —Si (R3) vX3 (3-v)
  • R3 is A substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which does not have a fluorine atom
  • X3 represents a hydrolyzable group.
  • r is 1 or 2
  • v is 0, 1 or 2.
  • R3 is preferably a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably a methyl group.
  • r is 1 and v is 0 or 1.
  • X3 includes an alkoxy group, a halogen atom, an acyl group, and the like.
  • X3 is an alkoxy group having 1 to 4 carbon atoms from the viewpoint that a hydroxyl group (silanol group) is formed by a hydrolysis reaction, and a reaction in which an Si—O—Si bond is formed by condensation reaction between atoms is easy to proceed smoothly.
  • a halogen atom are preferable, a methoxy group, an ethoxy group, and a chlorine atom are more preferable, and a methoxy group and an ethoxy group are particularly preferable.
  • fluorine-containing hydrolyzable silane compound (1) examples include the following compounds.
  • those having no ether group are preferable because they are excellent in light resistance.
  • F (CF 2 ) 4 CH 2 CH 2 Si (OC 2 H 5 ) 3 is particularly preferable in that the deterioration of the water repellent layer forming composition itself is small.
  • the content of the fluorine-containing hydrolyzable silane compound in the water-repellent layer-forming composition is appropriately adjusted according to the type and combination of the fluorine-containing hydrolyzable silane compound used.
  • the content of the fluorine-containing hydrolyzable silane compound is preferably 0.01 to 10% by mass with respect to the total solid content in the water repellent layer forming composition.
  • the content of the fluorine-containing hydrolyzable silane compound in the water-repellent layer forming composition is in the above range, sufficient antifouling property can be imparted to the upper surface of the resulting silicon oxide matrix film, and unevenness can be imparted to the resulting film. The appearance such as the occurrence of is not impaired.
  • a concavo-convex layer forming composition 1 is applied on a substrate to form a concavo-convex layer forming composition layer, and the concavo-convex layer forming composition layer is heat-treated to form a concavo-convex layer. Including the step of.
  • the uneven layer forming composition can be applied by various wet coating methods.
  • the wet coating method include spin coating, dip coating, spray coating, flow coating, curtain flow coating, die coating, and squeegee coating, and spin coating is preferable.
  • the uneven layer forming composition 1 is preferably applied to at least a part of the surface of the substrate and applied to the entire surface of at least one main surface of the substrate.
  • the thickness of the uneven layer forming composition layer is not particularly limited as long as a desired antifouling layer is obtained.
  • the amount of the uneven layer forming composition 1 applied on the substrate is not particularly limited as long as a desired antifouling layer can be obtained, and the solid content is 1.6 to 1,600 g / m 2 . It is preferably 8.0 to 800 g / m 2 .
  • the content of the component in terms of solid content refers to the mass of the residue excluding volatile components such as water.
  • the formed uneven layer forming composition layer becomes an uneven layer by curing. Curing is accelerated by heating.
  • the binder precursor may react with the particles by heating.
  • the uneven layer forming composition contains pearl necklace-like silica and silicic acid and an alkoxysilane compound
  • the silicic acid and the alkoxysilane compound are hydrolyzed and condensed to obtain a silica binder.
  • at least a part of the silicic acid and the alkoxysilane compound may undergo hydrolytic condensation with silanol groups present on the surface of the pearl necklace-like silica particles.
  • the heating can be performed by any heating means such as an electric furnace, a gas furnace, or an infrared heating furnace.
  • the heat treatment temperature is preferably 20 to 700 ° C, more preferably 80 to 500 ° C, and particularly preferably 100 to 400 ° C.
  • the heat treatment temperature is 20 ° C. or higher, the adhesion between the substrate and the antifouling layer is further improved.
  • the heat treatment temperature is 700 ° C. or less, deterioration of the substrate due to heat is suppressed, and productivity is excellent.
  • the heat treatment time varies depending on the heat treatment temperature, but is preferably 1 to 180 minutes, more preferably 5 to 120 minutes, and particularly preferably 10 to 60 minutes. When the heat treatment time is 1 minute or more, the adhesion between the substrate and the antifouling layer is further improved, and when it is 180 minutes or less, deterioration of the substrate due to heat is suppressed and the productivity is excellent.
  • Water repellent layer forming step 1 The water-repellent layer is formed by applying a water-repellent layer-forming composition on the uneven layer obtained in the above-described step and curing it. As needed, you may remove the excess liquid contained in the water repellent layer forming composition apply
  • the anti-staining layer is obtained by curing the water-repellent layer forming composition applied on the uneven layer. Curing of the water repellent layer forming composition is accelerated by heating or humidification.
  • Heating can be performed by any heating means such as an electric furnace, a gas furnace or an infrared heating furnace.
  • the heat treatment temperature is preferably 20 to 200 ° C, more preferably 50 to 180 ° C, and more preferably 80 to 150 ° C.
  • the heating treatment temperature is preferably 50 ° C. or higher, and more preferably 80 ° C. or higher.
  • Humidification can be performed by any humidifying means such as a constant temperature and high humidity tank.
  • the humidity is preferably 50 to 95% RH.
  • the curing treatment time is preferably 1 to 60 minutes, and more preferably 10 to 20 minutes.
  • the curing treatment time is 10 minutes or more, the adhesion between the uneven layer and the water repellent layer is further improved, and when it is 60 minutes or less, the productivity is excellent.
  • the production method 2 includes a step of preparing a water-repellent uneven layer forming composition 2 containing a pearl necklace-like or chain-like particle aggregate and a fluorine-containing binder precursor and a substrate (referred to as “preparation step 2”), Applying a water-repellent uneven layer forming composition 2 on a substrate to form a water-repellent uneven layer (referred to as “uneven layer forming step 2”).
  • Preparation process 2 In the preparation process 2, the water-repellent uneven layer forming composition 2 and the substrate are prepared. Since the substrate is the same as the substrate in the preparation step 1, description thereof is omitted.
  • the water-repellent uneven layer forming composition 2 is the same as the uneven layer forming composition 1 described above except that the binder precursor contains fluorine.
  • the water repellent concavo-convex layer forming composition 2 the water repellent property of the concavo-convex layer is increased when the binder precursor contains fluorine.
  • a fluorine-containing silane compound is preferable. Description of other components is omitted.
  • the concavo-convex layer forming step 2 is the same as the concavo-convex layer forming step 1 except that the water-repellent concavo-convex layer forming composition 2 is used instead of the concavo-convex layer forming composition 1, and thus the description thereof is omitted.
  • the antifouling article includes window glass (for example, window glass for transportation equipment such as automobiles, railroads, ships, airplanes), walls (for example, partitions, road walls, etc.), refrigerated showcases, mirrors (for example, vanity tables) Mirrors, bathroom mirrors, etc.), optical instruments, tiles, toilets, bathtubs, bathroom walls, vanity tables, curtain walls, aluminum sashes, faucet fittings, building boards, lenses, cover glasses, condensing mirrors It is done.
  • window glass for example, window glass for transportation equipment such as automobiles, railroads, ships, airplanes
  • walls for example, partitions, road walls, etc.
  • refrigerated showcases for example, mirrors (for example, vanity tables) Mirrors, bathroom mirrors, etc.)
  • optical instruments tiles, toilets, bathtubs, bathroom walls, vanity tables, curtain walls, aluminum sashes, faucet fittings, building boards, lenses, cover glasses, condensing mirrors It is done.
  • cover glass examples include a solar cell, a condensing lens, and a condensing mirror cover glass.
  • a condensing lens or a condensing mirror is used for a concentrating solar power generation device or a concentrating solar power generation device, for example.
  • This antifouling article is particularly suitable for outdoor use in areas with little rain, such as deserts. Since this antifouling article is excellent in wear resistance, it is also suitable as a window glass for automobiles and the like.
  • Examples 1 to 3, 5 to 9, 11, 12, and 14 described below are examples, and examples 4, 10, 13, 15, and 16 are comparative examples.
  • Example 1 While stirring 237.5 g of distilled water, sodium silicate 4 (manufactured by Nippon Chemical Industry Co., Ltd., (SiO 2 : 24.0% by mass, Na 2 O: 7.0% by mass, SiO 2 / Na 2 O 62.5 g of a molar ratio of 3.5 / 1) and 180 g of a cation exchange resin (Diaion SK1BH, manufactured by Mitsubishi Chemical Corporation) were added and stirred for 10 minutes or more, and then the cation exchange resin was separated by suction filtration. Then, a desalted sodium silicate solution having a solid content concentration in terms of silicon oxide of 5% by mass was obtained.
  • sodium silicate 4 manufactured by Nippon Chemical Industry Co., Ltd., (SiO 2 : 24.0% by mass, Na 2 O: 7.0% by mass, SiO 2 / Na 2 O 62.5 g of a molar ratio of 3.5 / 1
  • a cation exchange resin Diaion SK1BH, manufactured by Mitsubishi Chemical
  • a glass plate (sodium lime glass manufactured by Asahi Glass) with a length of 100 mm, width of 100 mm, and thickness of 3.5 mm on a spin coater, and drop coat 2.0 g of the uneven layer forming composition (A1) onto the surface of the glass plate. Then, heat treatment was performed at 200 ° C. for 30 minutes.
  • the glass plate on which the concavo-convex layer was formed was set on a spin coater, 4.0 g of the water repellent layer forming composition (B1) was dropped on the surface and spin-coated, and then a high temperature set to 20 ° C. and 50 RH%. After holding for 15 minutes in a high-humidity tank, denatured alcohol is dropped on the surface, and excess components are removed using a spin coater, thereby providing an antifouling article having a water-repellent layer (film thickness: 1 nm) on the outermost layer.
  • Example 2 While stirring 17.2 g of 2-propanol, 0.37 g of tetraethoxysilane (silica conversion solid content 28%: manufactured by Kanto Chemical Co., Ltd.), trifluoropropyltrimethoxysilane (water repellent binder, Shin-Etsu Chemical Co., Ltd.) KBM7103) 0.04 g, distilled water 2.26 g, 10 mass% aqueous nitric acid solution 0.1 g in this order, and then stirred at 25 ° C. for 60 minutes to obtain a silica-converted solid content concentration of 3 mass% alkoxysilane.
  • a binder precursor (2) was obtained as a solution of the partial hydrolysis-condensation product of the compound.
  • binder precursor (2) To this binder precursor (2) was added 2.79 g of a pearl necklace-like silica aggregate dispersion (Snowtex PS-SO, manufactured by Nissan Chemical Co., Ltd.), and the mixture was stirred at 25 ° C. for 30 minutes to form an uneven layer. It was set as the composition (A2). Antifouling treatment was conducted in the same manner as in Example 1 except that the uneven layer forming composition (A2) was used instead of the uneven layer forming composition (A1), and the uneven layer and the water repellent layer were integrated using a water repellent binder. A product was manufactured.
  • a pearl necklace-like silica aggregate dispersion Snowtex PS-SO, manufactured by Nissan Chemical Co., Ltd.
  • Example 3 While stirring 16.27 g of denatured alcohol (manufactured by Nippon Alcohol Sales Co., Ltd., AP-1), 0.88 g of tetraethoxysilane (TEOS; Tetraethyl orthosilicate) (manufactured by Kanto Chemical Co., Inc .: silica equivalent solid content 28%) Then, 2.24 g of a dispersion of pearl necklace-like silica aggregate (manufactured by Nissan Chemical Co., Ltd., Snowtex PS-SO) and 0.61 g of 0.01 N nitric acid aqueous solution were added in this order, and then 60 ° C. at 25 ° C.
  • TEOS Tetraethoxysilane
  • A3 a concavo-convex layer-forming composition having a silica-converted solid content concentration of 3% by mass and a silica-converted solid content mass ratio between the particles and the binder precursor of 57/43.
  • a 150 mm long, 150 mm wide, 3.5 mm thick glass plate (Asahi Glass soda lime glass) is set on a spin coater, and 4.0 g of the uneven layer forming composition (A3) is dropped on the surface of the glass plate, followed by spin coating. Then, heat treatment was performed at 200 ° C. for 30 minutes. Next, a water-repellent layer was formed under the same conditions as in Example 1 to obtain an antifouling article.
  • Example 4 An antifouling article was produced in the same manner as in Example 3 except that the water repellent layer was not formed.
  • Example 5 An antifouling article was produced in the same manner as in Example 1 except that the silica-converted solid mass ratio between the particles and the binder precursor was 57/43.
  • Example 6 to 10 The uneven layer forming compositions (A4) to (A8) are the same as in Example 3, except that the silica-converted solid mass ratio of particles and binder precursor (particle / binder precursor) is as shown in Table 1. ) was prepared. Subsequently, an antifouling article was produced in the same manner as in Example 3 using the uneven layer forming compositions (A4) to (A8). In addition, as shown also in Table 1, the uneven
  • Example 11 The water-repellent layer forming composition was changed to a mixture of 9.98 g of butyl acetate and 7.98 g of tridecafluorooctyltrimethoxysilane (Trideca Fluoro-octyl Trimethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd.) In the same manner as in Example 8, an antifouling article was produced.
  • Trideca Fluoro-octyl Trimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 12 A water repellent layer-forming composition was prepared by adding 7.98 g of hydrofluoroether (Asahi Glass Co., Ltd., AE3000), 2.0 g of 2-propanol, and perfluoroether (CF 3- (OCF 2 CF 2 ) n having a molecular weight of about 1000.
  • a mixture of 0.03 g of —OCF 2 —CONH—C 3 H 6 —Si (OCH 3 ) 3 , (n 7-8): Asahi Glass Co., Ltd., 1000 MAS) and 0.001 g of a 10 wt% nitric acid aqueous solution
  • An antifouling article was produced in the same manner as in Example 8 except that
  • Example 13 The water-repellent layer forming composition was changed to a mixture of 9.98 g of butyl acetate and 0.03 g of OH— (Si (CH 3 ) 2 O) 20 —OH (manufactured by Shin-Etsu Chemical Co., Rf-PDMS20). Produced an antifouling article in the same manner as in Example 8.
  • Example 14 An antifouling article was produced in the same manner as in Example 8, except that methyltrimethoxysilane (MTMS) (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the binder precursor instead of tetraethoxysilane.
  • MTMS methyltrimethoxysilane
  • Example 15 An antifouling article was produced in the same manner as in Example 8 except that 3-glycidoxypropyltrimethoxysilane (GPTMS) (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the binder precursor instead of tetraethoxysilane.
  • GTMS 3-glycidoxypropyltrimethoxysilane
  • Example 16 The glass plate on which the uneven layer forming composition and the water repellent layer forming composition were not applied was evaluated as it was.
  • the cross section of the antifouling article is observed with a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.), and is randomly extracted from the obtained image in a direction parallel to the surface of the glass plate having the antifouling layer.
  • S-4800 scanning electron microscope
  • the distance between the vertices of adjacent protrusions with respect to a protrusion having a height of 90% or more of the height from the glass plate surface in the 1.5 ⁇ m range as a reference. Were measured and the average value was calculated.
  • Water contact angle CA A 1 ⁇ l water droplet was dropped on the surface of the antifouling layer, and the water contact angle measured 3 seconds later was measured with a contact angle measuring device (DM-701, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at three different points, and the average value was calculated.
  • Wind removability of dry sand A 5 cm ⁇ 5 cm test piece was cut out from the antifouling article, and the initial haze value was measured. Thereafter, 0.5 g of three types of JIS test powder 1 as sand was sprinkled evenly on the surface of the antifouling layer using a tea strainer. The mixture was allowed to stand for 10 seconds, left in a 10 ° C. environment for 30 minutes, then left at 35 ° C. and 95% RH for 1 hour, and then the sand was blown off with a wind speed of 1 to 2 m / s. A value ( ⁇ Hdw) obtained by subtracting the initial haze value from the haze value after blowing sand was obtained.
  • the antifouling article of Example 1 (Example) has a dry sand falling angle of 39.4 ° and a wet sand falling angle of 40 °
  • the antifouling article of Example 2 (Example) has a dry sand falling angle of 39.6. It was easy to remove even if dirt was attached.
  • the antifouling article of Example 4 (Comparative Example) had a dry sand falling angle of 57.9 °
  • the antifouling article of Example 16 (Comparative Example) had both a dry sand falling angle and a wet sand falling angle of 85 °. It was difficult to remove when it was over and dirty.
  • the antifouling article of Example 1 has a wind removal property ⁇ Hdw of dry sand of 0.8% and a wind removal property ⁇ Hww of wet sand of 0.95%, and is easily removed by wind even if dirt is attached.
  • the antifouling article of Example 16 had a wind removal property ⁇ Hdw of dry sand of 23.5% and a wind removal property ⁇ Hww of wet sand of 51.8%, and was removed by wind when dirt adhered. It was difficult.
  • the friction force of the antifouling article of Example 1 was 0.59N.
  • a reciprocating traverse tester (manufactured by KT Corporation) is attached with a cotton cloth conforming to JIS L0803, and a weight of 2.95 ⁇ 10 4 N / m 2 is applied using a weight of 1.2 kg. Was rubbed back and forth 1500 times, and then the antifouling article was washed with water.
  • the appearance of the antifouling article after rubbing and washing with water is visually observed, and when there are no scratches, “A”, when there are few scratches, “B”, and when many scratches are noticeable, “C”. It was. Moreover, the haze value of the antifouling article after being rubbed and washed with water was measured. Further, the above-mentioned dirt adhesion test was performed on the surface after friction, and the change in haze value ( ⁇ Hr) after friction was obtained. Moreover, the water contact angle was measured.
  • the antifouling article of this example has a small change in haze value according to the dirt adhesion test and is excellent in antifouling property. Examples 10, 15, and 16 having no predetermined uneven layer were not sufficiently antifouling.
  • Examples 3, 5 to 9, 11, 12, and 14 have excellent antifouling properties and excellent wear resistance even after the friction test.
  • Example 4 having no water repellent layer, scratches were caused by friction, and the wear resistance was not sufficient.
  • Example 13 in which the water repellent layer is silicone containing no fluorine did not have sufficient wear resistance.
  • window glass for example, window glass for transportation equipment such as automobiles, railways, ships, airplanes, etc.
  • cover glass for solar cells
  • walls for example, , Partitions, road walls, etc.
  • refrigerated showcases for example, mirrors (for example, vanity mirrors, bathroom mirrors, etc.), optical equipment, tiles, toilet bowls, bathtubs, bathroom walls, vanity tables, curtain walls, aluminum sashes Can be used for faucets, construction boards, lenses, etc.

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Abstract

L'invention concerne un article résistant aux taches comprenant un substrat et une couche résistant aux taches disposée sur le substrat. La couche résistant aux taches comprend une pluralité de saillies sur sa surface et lesdites saillies contiennent des agrégats de particules et un liant. Les étapes suivantes sont répétées cinq fois en tant que test : une poudre mélangée pour évaluation est pulvérisée sur la couche résistant aux taches de l'article résistant aux taches et laissée pendant dix secondes ; l'article résistant aux taches est ultérieurement incliné de 135 ° et amené en contact avec le sol deux fois à une vitesse de 10 cm/seconde depuis une hauteur à 3 cm du sol, de sorte que la poudre mélangée pour l'évaluation tombe ; et l'indice de trouble de l'article résistant aux taches est mesuré. À cette occasion, la valeur d'un changement de l'indice de trouble obtenue en soustrayant l'indice de trouble de l'article résistant aux taches avant le test de la valeur moyenne de l'indice de trouble de l'article résistant aux taches après le test est de 1,0 % environ. L'angle de contact avec l'eau mesuré trois secondes après avoir fait goutter une gouttelette d'eau d'1 µl sur la couche résistant aux taches est supérieur ou égal à 80°.
PCT/JP2016/082054 2015-10-28 2016-10-28 Article résistant aux taches et procédé de production d'article résistant aux taches Ceased WO2017073726A1 (fr)

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JP2005343016A (ja) * 2004-06-03 2005-12-15 Nippon Sheet Glass Co Ltd 超撥水性被膜被覆物品
WO2011090035A1 (fr) * 2010-01-19 2011-07-28 旭硝子株式会社 Base hydrofuge et son procédé de fabrication
JP2013081941A (ja) * 2011-09-30 2013-05-09 Dainippon Toryo Co Ltd 防汚塗膜の形成方法及び防汚塗装物
WO2016010080A1 (fr) * 2014-07-18 2016-01-21 旭硝子株式会社 Article antisalissure, son procédé de production, composition formant couche antisalissure et verre de couverture pour cellules solaires

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WO2018051958A1 (fr) * 2016-09-16 2018-03-22 旭硝子株式会社 Article antisalissure
JP2019116097A (ja) * 2017-06-21 2019-07-18 Ａｇｃ株式会社 撥水撥油層付き物品およびその製造方法
JP7063288B2 (ja) 2017-06-21 2022-05-09 Ａｇｃ株式会社 撥水撥油層付き物品およびその製造方法
CN109733592A (zh) * 2018-11-23 2019-05-10 中国航空工业集团公司沈阳飞机设计研究所 飞机自动配平控制方法及系统
CN109733592B (zh) * 2018-11-23 2022-05-06 中国航空工业集团公司沈阳飞机设计研究所 飞机自动配平控制方法及系统
JP2021147556A (ja) * 2020-03-23 2021-09-27 三菱マテリアル電子化成株式会社 撥水撥油性膜形成用液組成物及びその製造方法
JP7596074B2 (ja) 2020-03-23 2024-12-09 三菱マテリアル電子化成株式会社 撥水撥油性膜形成用液組成物の製造方法

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