WO2014061605A1 - シリカ系多孔質膜、シリカ系多孔質膜付き物品およびその製造方法 - Google Patents

シリカ系多孔質膜、シリカ系多孔質膜付き物品およびその製造方法 Download PDF

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WO2014061605A1
WO2014061605A1 PCT/JP2013/077814 JP2013077814W WO2014061605A1 WO 2014061605 A1 WO2014061605 A1 WO 2014061605A1 JP 2013077814 W JP2013077814 W JP 2013077814W WO 2014061605 A1 WO2014061605 A1 WO 2014061605A1
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Prior art keywords
silica
based porous
porous film
compound
particles
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PCT/JP2013/077814
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English (en)
French (fr)
Japanese (ja)
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洋平 河合
米田　貴重
阿部　啓介
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旭硝子株式会社
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • 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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/107—Porous materials, e.g. for reducing the refractive index
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/109—Sols, gels, sol-gel materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0247—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of voids or pores

Definitions

  • the present invention relates to a silica-based porous film, an article with a silica-based porous film, and a method for producing the same.
  • a glass plate with an antireflection film having an antireflection film on the surface of the glass plate is used as a cover glass for solar cells, various displays and their front plates, various window glasses, a cover glass for touch panels, and the like.
  • One of antireflection films used for glass plates and the like is a silica-based porous film. Since the silica-based porous film has pores in a matrix containing silica as a main component, the refractive index is lower than that in the case where there are no pores.
  • a silica-based porous membrane there is a method of applying and heat-treating a coating liquid containing a silica precursor such as alkoxysilane and pore forming particles (see, for example, Patent Document 1).
  • a coating liquid containing a silica precursor such as alkoxysilane and pore forming particles
  • the pore-forming particles are removed simultaneously with the formation of the matrix by the heat treatment or after the formation of the matrix, thereby forming the pores.
  • This method has an advantage that the process is simple and the size and porosity of the pores can be controlled by the size and blending amount of the pore-forming particles used as a template.
  • an alkali barrier layer such as a non-porous silica film is provided as an undercoat layer on the glass plate surface (for example, patents). Reference 2).
  • a technique is disclosed in which durability is ensured by using core-shell type particles or hollow particles to form closed holes in which each hole exists independently (see, for example, Patent Documents 3 and 4). .
  • the present invention has been made in view of the above circumstances, and is a silica-based porous film that can maintain a porous structure for a long period of time even when directly formed on a glass plate, and has excellent antireflection performance and durability.
  • An object of the present invention is to provide an article with a silica-based porous film comprising the silica-based porous film, and a production method capable of easily producing the article with a silica-based porous film.
  • the refractive index of the silica-based porous film is in the range of 1.10 to 1.38
  • the outermost surface side of the silica-based porous membrane has an outermost surface dense layer,
  • the number of pores having a diameter of 20 nm or more opened in the outermost surface of the outermost surface dense layer is 13/10 6 nm 2 or less.
  • [3] The silica-based porous membrane according to [1] or [2], wherein the average diameter of the pores is 15 to 100 nm.
  • [4] The silica-based porous membrane according to any one of [1] to [3], wherein the pores having a diameter of 20 nm or more existing inside the silica-based porous membrane are independent pores.
  • [5] The silica-based porous membrane according to any one of [1] to [4], wherein the arithmetic average roughness (Sa) of the outermost surface is 3.0 nm or less.
  • a method for producing an article with a silica-based porous film having a plurality of pores in a matrix mainly composed of silica Applying a coating liquid containing a matrix precursor (A), particles (B) removable from the matrix, and a liquid medium (C) to the surface of the article and heat-treating the coating liquid;
  • the matrix precursor (A) comprises at least one compound (A1) selected from the group consisting of the compound (a1) represented by the following general formula (a1), a hydrolyzate and a partial condensate thereof, and the following general formula Containing at least one compound (A2) selected from the group consisting of the compound (a2) represented by the formula (a2), its hydrolyzate and partial condensate,
  • the ratio of the content of the compound (A1) and the compound (A2) in the matrix precursor (A) is the molar ratio of the compound (a1) and the compound (a2) ((a1) / ( a2)) in the range of 0.1 to 3.0,
  • X represents a hydrolyzable group
  • Y represents a non-hydrolyzable group whose dielectric constant of Y—OH is 35 F / m or less
  • n represents an integer of 1 to 3.
  • the mass ratio ((A) / (B)) of the content of the matrix precursor (A) in terms of SiO 2 and the content of the particles (B) is in the range of 0.3 to 4.0.
  • the porous structure can be maintained for a long period of time, and the silica-based porous film having excellent antireflection performance and durability, the silica-based porous film It is possible to provide an article with a silica-based porous film and a production method capable of easily producing the article with a silica-based porous film.
  • FIG. 1 It is sectional drawing which shows one Embodiment of the articles
  • FIG. 6 is a scanning electron micrograph ((a) upper surface, (b) cross section) of a glass plate with a silica-based porous film obtained in Example 5.
  • FIG. It is a scanning electron micrograph ((a) upper surface, (b) cross section) of the glass plate with a silica type porous membrane obtained in Example 7.
  • FIG. It is a scanning electron micrograph ((a) upper surface, (b) cross section) of the glass plate with a silica type porous membrane obtained in Example 9.
  • FIG. 2 is a scanning electron micrograph ((a) upper surface, (b) cross section) of a glass plate with a silica-based porous film obtained in Example 11.
  • FIG. It is a scanning electron micrograph ((a) upper surface, (b) cross section) of the glass plate with a silica type porous membrane obtained in Example 12.
  • FIG. It is a scanning electron micrograph ((a) upper surface, (b) cross section) of the glass plate with a silica type porous membrane obtained in Example 13.
  • FIG. It is a scanning electron micrograph ((a) upper surface, (b) cross section) of the glass plate with a silica type porous membrane obtained in Example 14.
  • FIG. 1 is a cross-sectional view showing a first embodiment of an article with a silica-based porous film having the silica-based porous film of the present invention on the surface of the article.
  • the article 10 with a silica-based porous film of the present embodiment has a glass plate 12 and a silica-based porous film 14 formed on the surface of the glass plate 12.
  • the glass plate 12 is a kind of article that forms a silica-based porous film, and is a base material that forms a so-called silica-based porous film.
  • Glass plate 12 examples of the glass plate 12 include a glass plate made of soda lime glass, borosilicate glass, aluminosilicate glass, alkali-free glass, and the like.
  • the glass plate 12 may be a smooth glass plate formed by a float method or the like, or may be a template glass having irregularities on the surface. Further, not only flat glass but also glass having a curved surface shape may be used.
  • the thickness of the glass plate 12 is not particularly limited, and glass having a thickness of 0.2 to 10 mm can be used. The thinner the thickness, the lower the light absorption, which is preferable for the purpose of improving the transmittance.
  • soda lime glass having the following composition is preferred.
  • Oxide-based mass percentage display (hereinafter, “mass percentage display” is also simply referred to as “%”, hereinafter the same).
  • SiO 2 65 to 75%
  • Al 2 O 3 0 to 10%
  • CaO 5 to 15%
  • MgO 0 to 15%
  • K 2 O 0 to 3%
  • Fe 2 O 3 0 to 3%
  • TiO 2 0 to 5%
  • SrO: 0-5% B 2 O 3 : 0 to 15%
  • ZrO 2 0 to 5%
  • SnO 2 : 0 to 3% SO 3 : 0 to 0.5%.
  • the glass plate 12 is an alkali free glass, what has the following composition is preferable.
  • SiO 2 39 to 70%
  • Al 2 O 3 3 to 25%
  • B 2 O 3 1-30%
  • MgO 0 to 10%
  • CaO 0 to 17%
  • SrO 0 to 20%
  • BaO 0 to 30%.
  • the glass plate 12 is a mixed alkali glass, those having the following composition are preferred.
  • SiO 2 50 to 75%
  • Al 2 O 3 0 to 15%
  • MgO + CaO + SrO + BaO + ZnO 6 to 24%
  • Na 2 O + K 2 O 6-24%.
  • the glass plate 12 is a solar cell cover glass
  • a satin-patterned template glass with an uneven surface is preferable.
  • iron component ratio is smaller than soda lime glass (so-called soda lime glass: common name of soda lime glass with a slight bluish tint) used for ordinary window glass, etc.
  • Soda lime glass is preferable.
  • FIG. 2 is a schematic cross-sectional view schematically illustrating the configuration of the silica-based porous film 14.
  • the silica-based porous film 14 has a plurality of pores 22 having a diameter of 20 nm or more in a matrix 21 mainly composed of silica.
  • the silica-based porous film 14 has a relatively low refractive index and a low reflectance because the matrix 21 is mainly composed of silica.
  • the silica-based porous film 14 is excellent in chemical stability, adhesion to the glass plate 12, wear resistance, and the like. Furthermore, by having the holes 22 in the matrix 21, the refractive index is lower than when the holes 22 are not provided.
  • the silica-based porous film 14 may have pores with a diameter of less than 20 nm (not shown) in the matrix 21.
  • That the matrix 21 has silica as a main component means that the proportion of silica is 90% by mass or more in the matrix (100% by mass).
  • the matrix 21 is preferably made of silica substantially.
  • the phrase “substantially composed of silica” means that it is composed only of silica excluding inevitable impurities (for example, a structure derived from the compound (a2) described later).
  • the matrix 21 may contain a small amount of components other than silica.
  • the components include Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Sr.
  • the matrix 21 may include not only two-dimensionally polymerized matrix components but also three-dimensionally polymerized nanoparticles.
  • the composition of the nanoparticles include Al 2 O 3 , SiO 2 , SnO 2 , TiO 2 , ZnO, and ZrO 2 .
  • the size of the nanoparticles is preferably 1 to 100 nm.
  • the shape of the nanoparticles is not particularly limited, and examples thereof include a spherical shape, a needle shape, a hollow shape, a sheet shape, and a square shape.
  • the proportion of the nanoparticles is preferably 20% by mass or less based on the matrix solid content. Within this range, sufficient film strength is maintained.
  • the silica-based porous film 14 includes pores 22 having a diameter of 20 nm or more. Thereby, the excellent antireflection performance is obtained.
  • conventional porous silica membranes contain pores with a diameter of 20 nm or more, the pores communicate with each other and many open pores are formed on the membrane surface. When performed, the porous structure is broken and the antireflection performance is likely to be lowered. Excellent durability.
  • the diameter of the pores is measured from an image obtained by observing a cross section of the silica-based porous film 14 using a scanning electron microscope (hereinafter also referred to as SEM). When the shape of the hole in the image is not a perfect circle, the average value of the minor axis and the major axis is taken as the diameter.
  • the average diameter of all the pores contained in the matrix 21 is preferably 15 to 100 nm, and more preferably 20 to 80 nm.
  • the average pore diameter can be obtained by measuring the diameter of 100 pores from an image obtained by observing the cross section of the silica-based porous film 14 using SEM and calculating the average value thereof.
  • the silica-based porous film 14 has an outermost surface dense layer 14b on the outermost surface 14a side opposite to the glass plate 12 side.
  • the outermost surface dense layer 14b is a region that does not substantially include the holes 22 having a diameter of 20 nm or more.
  • “Substantially free” means the number of open pores 22 (open holes) that may be present on the outermost surface 14a of the silica-based porous membrane 14 (hereinafter also referred to as “the number of outermost open holes”). It shows that it is 13 pieces / 10 6 nm 2 or less.
  • the number of holes on the outermost surface is preferably 10/10 6 nm 2 or less, particularly preferably 0. That is, it is particularly preferable that the outermost surface dense layer 14b is a region where there is no hole 22 having a diameter of 20 nm or more.
  • the number of open pores on the outermost surface is in the region of 1000 nm ⁇ 1000 nm from an image obtained by observing the outermost surface of the silica-based porous film 14 (that is, the surface opposite to the glass plate 12 side) with an SEM
  • the number of openings having a diameter of 20 nm or more is measured.
  • the shape of the opening in the image is not a perfect circle, the average value of the minor axis and the major axis is taken as the diameter.
  • the silica-based porous membrane 14 has excellent durability because the outermost surface open layer number of the outermost surface dense layer 14b is 13/10 6 nm 2 or less.
  • the porous structure at the portion in contact with the glass plate 12 under wet heat conditions is broken by the influence of alkali, and the antireflection performance is lowered.
  • the silica-based porous film 14 of the present invention is directly formed on the surface of the glass plate 12 and kept under wet heat conditions, the porous structure is maintained for a long period of time and the antireflection performance is lowered. Hateful.
  • the outermost surface dense layer 14b can prevent moisture in the outside air from passing through the silica-based porous film 14 and reaching the glass plate 12 to generate alkali.
  • the said silica type porous membrane 14 does not have a large diameter void
  • the antifouling property is improved such that the dirt does not easily penetrate into the pores in the film and the attached dirt is easily removed, and the usefulness as an antireflection film is improved.
  • hole less than 20 nm in diameter has on durability is small. Therefore, the silica-based porous film 14 may have pores having a diameter of less than 20 nm (not shown) in the outermost surface dense layer 14b and the matrix 21 in other regions.
  • the holes 22 having a diameter of 20 nm or more present in the silica-based porous film 14 are preferably independent holes, not connecting holes.
  • the term “independent pores” refers to granular pores that exist independently in the matrix. It is preferable that the pores 22 existing inside the silica-based porous membrane 14 are independent pores, so that water vapor or the like hardly penetrates the interface between the glass and the membrane and is excellent in heat and moisture resistance.
  • organic polymer nanoparticles are used as particles (B), and the pores 22 existing inside the silica-based porous film obtained by pyrolyzing the particles are independent pores, and a plurality of voids are present.
  • One hole 22 is present separately.
  • the conventional silica-based porous film obtained by a method of laminating inorganic nanoparticles which is a general method for producing a silica-based porous film
  • voids between the particles form connection holes.
  • the inside of the film is composed of connecting holes, even if a dense layer is formed on the outermost surface, moisture and the like are likely to permeate into the interface between the glass and the film, so that the moisture and heat resistance tends to be insufficient.
  • the silica-based porous film 14 is applied with a coating liquid described later (that is, a coating liquid containing the compound (A1), the compound (A2), the particles (B), and the liquid medium (C)) and subjected to a heat treatment process.
  • a coating liquid described later that is, a coating liquid containing the compound (A1), the compound (A2), the particles (B), and the liquid medium (C)
  • the outermost surface dense layer 14b and other regions specifically, layers in the silica-based porous film 14 up to the glass plate 12 below the outermost surface dense layer 14b.
  • the composition of the matrix 21 is different from the layer in the region where the pores 22 having a diameter of 20 nm or more are distributed, and may be called the main body layer 14c of the silica-based porous film.
  • the matrix 21 constituting the outermost surface dense layer 14b is substantially composed of a heat-treated product of the compound (A2) and includes a structure derived from the compound (a2) (for example, a non-hydrolyzable group Y).
  • the matrix 21 constituting the other region described above is substantially composed of a heat-treated product of the compound (A1) and does not contain or contains very little a structure derived from the compound (a2).
  • Average film thickness of outermost surface dense layer 14b (hereinafter, also referred to as “outermost surface dense layer average film thickness”) d, that is, from the outermost surface 14a to the uppermost part of holes 22 having a diameter of 20 nm or more existing under the outermost surface 14a
  • the average value d of the distance is preferably 10 to 80 nm, and more preferably 13 to 60 nm.
  • the outermost surface dense layer average film thickness d is 10 nm or more, the effect of suppressing moisture in the outside air from reaching the glass is good. If the average thickness d of the outermost surface dense layer is 80 nm or less, the refractive index of the entire film can be kept low, and the antireflection performance is good.
  • the measuring method of the average thickness of the outermost dense layer is as shown in the examples described later.
  • the average thickness d of the outermost dense layer depends on the molar ratio ((a1) / (a2)) between the compound (a1) and the compound (a2) in the coating solution described later, the average primary particle diameter of the particles (B), and the like. Can be adjusted.
  • the outermost surface dense layer 14b is mainly formed from the compound (A2). Therefore, if the total amount of the compound (A1) and the compound (A2) is the same, the smaller the (a1) / (a2) (that is, the higher the ratio of the compound (a2)), the more the outermost surface dense layer average film The thickness d tends to increase. Further, as the average primary particle size of the particles (B) is larger, only the compound (A2) is likely to float, and the average thickness d of the outermost surface dense layer tends to increase.
  • the ratio of the outermost surface dense layer average film thickness d (nm) to the average total film thickness (nm) of the silica-based porous film 14 takes into consideration the desired outermost surface dense layer average film thickness d, average total film thickness, and the like. Although it can be appropriately set and is not particularly limited, it is preferably 8 to 40%, more preferably 10 to 30%.
  • the average total film thickness of the silica-based porous film 14 is preferably 40 to 300 nm, and more preferably 80 to 200 nm. When the average total film thickness of the silica-based porous film 14 is 40 nm or more, light interference occurs in the visible light region, and antireflection performance is exhibited. If the average total film thickness of the silica-based porous film 14 is 300 nm or less, the film can be formed without generating cracks. The method for measuring the average total film thickness is as shown in the examples described later.
  • the refractive index of the silica-based porous film 14 is in the range of 1.10 to 1.38, and preferably in the range of 1.15 to 1.35. If the refractive index of the silica-based porous film 14 is 1.38 or less, sufficient pores 22 are present in the silica-based porous film 14, and the reflectance of the silica-based porous film 14 is sufficiently low, Excellent anti-reflection performance. If the refractive index of the silica type porous membrane 14 is 1.10 or more, the porosity of the silica type porous membrane 14 will not become high too much, and durability will improve.
  • the measuring method of the refractive index is the same as the measuring method of “upper layer refractive index” shown in the examples described later.
  • the arithmetic average roughness (Sa) of the outermost surface 14a of the silica-based porous membrane 14 is preferably 3.0 nm or less, and more preferably 2.5 nm or less. If the outermost surface 14a has smoothness with an arithmetic average roughness (Sa) of 3.0 nm or less, durability, such as wear resistance, is improved. In addition, the antifouling property is improved such that the dirt is difficult to adhere and the attached dirt is easy to remove, and the usefulness as an antireflection film is improved. A film having many open pores on the surface or a film obtained by using core-shell type particles or hollow particles is not preferable because of high arithmetic average roughness (Sa). The method of measuring the arithmetic average roughness (Sa) is as shown in the examples described later.
  • the average reflectance of light having a wavelength of 400 to 1100 nm incident on the surface of the silica-based porous film 14 at an incident angle of 5 ° (hereinafter also referred to as “average reflectance (5 ° incidence)”) is 2.0% or less. It is preferable that it is 1.7% or less. If the average reflectance (5 ° incidence) of the silica-based porous film 14 is 2.0% or less, the antireflection performance required for a solar cell cover glass or the like is sufficiently satisfied.
  • the incident angle in this specification is an angle formed by the incident direction of light and the normal line of the surface of the silica-based porous film.
  • the measuring method of the average reflectance (5 ° incidence) is as shown in the examples described later.
  • the average transmittance of light having a wavelength of 400 to 1100 nm incident on the surface of the article 10 with a silica-based porous membrane on the silica-based porous membrane 14 side at an incident angle of 0 ° (hereinafter also referred to as “average transmittance (0 ° incidence)”). .) Is preferably 94.0% or more, more preferably 94.5% or more. If the average transmittance (0 ° incidence) of the article 10 with a silica-based porous film is 94.0% or more, the light transmittance required for a cover glass of a solar cell is sufficiently satisfied.
  • the average transmittance of an article with a silica-based porous film using another light-transmitting substrate instead of the glass plate 12 in the article with a silica-based porous film 10 may be 94.0% or more as described above. preferable.
  • the measuring method of the average transmittance (0 ° incidence) is as shown in the examples described later.
  • the article 10 with a silica-based porous film can be manufactured by forming a silica-based porous film 14 on a glass plate 12.
  • a coating liquid containing a matrix precursor (A) shown below, particles (B) that can be removed from the matrix, and a liquid medium (C) is used as glass. It is applied to the surface of the plate 12 and heat-treated.
  • the matrix 21 is formed from the matrix precursor (A) by heat-treating the coating film of the coating solution. If the particles (B) can be removed by heat treatment, the particles (B) are removed by the heat treatment, and the silica-based porous film 14 is formed.
  • the heat treatment temperature when forming the matrix 21 is set to the thermal decomposition temperature of the thermally decomposable material.
  • the particles (B) are vaporized, pass through the fine pores in the matrix 21 and are released to the outside of the matrix 21, and the silica-based porous film 14 is formed.
  • the heat treatment for forming the matrix 21 may be performed at a temperature lower than the above-described thermal decomposition temperature after the coating film is formed, and after the film formation, the heat treatment at a temperature equal to or higher than the thermal decomposition temperature may be performed again.
  • the silica-based porous film 14 is subjected to a removal treatment according to the material constituting the particles (B) before or after the matrix 21 is formed by the heat treatment. Can be formed.
  • the matrix precursor (A) includes a compound (a1) represented by the following general formula (a1), at least one compound (A1) selected from the group consisting of a hydrolyzate and a partial condensate thereof, and the following general formula: A compound (a2) represented by (a2), and at least one compound (A2) selected from the group consisting of a hydrolyzate and a partial condensate thereof.
  • SiX 4 (a1) Y n SiX 4-n (a2) [Wherein, X represents a hydrolyzable group, Y represents a non-hydrolyzable group in which the dielectric constant of Y—OH is 35 F / m or less, and n represents an integer of 1 to 3. ]
  • X represents a hydrolyzable group.
  • the hydrolyzable group is a group that can convert a Si—X group into a Si—OH group by hydrolysis.
  • Examples of X include halogen atoms (for example, chlorine atoms), alkoxy groups, acyloxy groups, aminoxy groups, amide groups, ketoximate groups, hydroxyl groups, epoxy groups, glycidyl groups, isocyanate groups, and the like.
  • An alkoxy group is particularly preferable because the hydrolysis polycondensation reaction can be easily controlled.
  • the alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
  • Four Xs which compound (a1) has may be the same or different. The same group is preferable in terms of availability, ease of control of the hydrolysis polycondensation reaction, and the like.
  • the compound (a1) include, for example, tetraalkoxysilane (for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.). These may be used alone or in combination of two or more.
  • the outermost surface dense layer 14b is formed by causing phase separation by using two or more kinds of matrix precursors (compounds (A1) and (A2)) having different dielectric constants. .
  • the larger the difference in the dielectric constant between the compound (A1) having a large dielectric constant and the compound (A2) having a small dielectric constant the more the phase separation is caused, and the average film thickness d of the outermost surface dense layer 14b is increased.
  • the hydrolyzable group included in the compound (a1) is an alkoxy group
  • the smaller the carbon number of the alkoxy group the faster the hydrolysis proceeds, and thus the easier the conversion to Si—OH proceeds.
  • the dielectric constant of the compound (A1) is increased (that is, the dielectric constant is Si—X ⁇ Si—OH), the phase separation with the compound (A2) having a low dielectric constant is significantly caused.
  • the compound (a1) is preferably a tetraalkoxysilane having 1 or 2 carbon atoms in the alkoxy group, and particularly preferably tetramethoxysilane, among tetraalkoxysilanes.
  • the hydrolyzate and partial condensate of compound (a1) can be obtained by a conventional method.
  • the compound (a1) has high reactivity, and a hydrolysis reaction or a partial condensation reaction can proceed only by adding water to the compound (a1). Therefore, a hydrolyzate or a partial condensate can be obtained by mixing the compound (a1) and water.
  • the amount of water added is preferably at least 4 moles of the compound (a1).
  • An acid or an alkali can be used as the catalyst.
  • the acid examples include inorganic acids (for example, nitric acid, sulfuric acid, hydrochloric acid, etc.) and organic acids (for example, formic acid, oxalic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.).
  • Examples of the alkali include ammonia, sodium hydroxide, potassium hydroxide and the like.
  • the catalyst is preferably an acid from the viewpoint of long-term storage stability of the hydrolyzate or partial condensate of compound (a1).
  • the obtained reaction solution is usually used as it is or after appropriately diluted to prepare the coating solution. Therefore, the catalyst used for the hydrolysis is preferably one that does not hinder the dispersion of the particles (B).
  • the temperature at which the compound (a1) is subjected to hydrolysis and partial polycondensation reaction is preferably 5 to 80 ° C., more preferably 10 to 70 ° C. If it is 5 degreeC or more, a hydrolysis polycondensation reaction will fully advance, and if it is 80 degrees C or less, hydrolysis polycondensation reaction control is easy.
  • n represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.
  • Examples of the hydrolyzable group for X include the same groups as described above. When n is 1 or 2, the plurality of Xs that the compound (a2) has may be the same or different. The same group is preferable in terms of availability, ease of controlling the hydrolysis reaction, and the like.
  • Y represents a non-hydrolyzable group having a dielectric constant of Y—OH of 35 F / m or less.
  • the non-hydrolyzable group is a functional group whose structure does not change under the condition that the Si—X group becomes a Si—OH group by hydrolysis.
  • the dielectric constant of the hydrolyzate of compound (a1) and the partial condensate Si (OH) 4 and the hydrolyzate and partial condensate Y n Si (OH) 4-n of compound (a2) Although it should be, it is difficult to measure the dielectric constant of the hydrolyzate and partial condensate itself of each compound. Therefore, the dielectric constant of similar compounds was applied and modeled for verification.
  • HO—OH hydrogen peroxide
  • Y—OH hydrolyzate and partial condensate of compound (a2).
  • a literature value may be used for the dielectric constant of Y—OH, but it can be measured by the following measuring method.
  • the dielectric constant of Y-OH is determined by applying an electric field to the sample by a bridge circuit using a network analyzer (manufactured by Agilent Technologies, PNA microwave vector network analyzer) in accordance with JIS-R1627. And the phase was calculated from the measured values.
  • Y includes a perfluoropolyether group, a perfluoroalkyl group, an alkyl group, an aryl group (such as a phenyl group), and the like.
  • the compound (a2) include, for example, monoalkyltrialkoxysilane (methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, etc.), Dialkyl dialkoxysilane (dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, etc.), trialkylmonoalkoxysilane (trimethylmethoxysilane, trimethylethoxysilane, Triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tripropylethoxysilane), monoaryltrialkoxys
  • monoalkyltrialkoxysilanes and monoaryltrialkoxysilanes are preferable and monoaryltrialkoxysilanes are more preferable because they are easily available and do not generate an inert gas during thermal decomposition.
  • the hydrolyzate and partial condensate of compound (a2) can be obtained in the same manner as the hydrolyzate and partial condensate of compound (a1).
  • the compounds (a1) and (a2) may be mixed in advance to perform a cohydrolysis polycondensation reaction.
  • the ratio of the content of the compound (A1) and the compound (A2) is converted into the molar ratio ((a1) / (a2)) of the compound (a1) and the compound (a2).
  • it is within the range of 0.1 to 3.0, and preferably within the range of 0.2 to 2.0.
  • the smoothness of the outermost surface 14a is high, and arithmetic mean roughness Sa can be 3.0 nm or less. Excellent moisture resistance and dirt removal properties can be obtained when the number of holes on the outermost surface is small, and excellent wear resistance can be obtained when the smoothness is high.
  • the value of (a1) / (a2) is less than 0.1, since the amount of (a2) is too large, the thickness of the outermost surface dense layer 14b becomes too thick and the antireflection performance becomes insufficient. By setting the value of (a1) / (a2) to 0.1 or more, sufficient antireflection performance can be obtained.
  • the average molecular weight of the hydrolyzate and partial condensate of compound (a1), (a2), or the cohydrolyzate and partial condensate of (a1) and (a2) is preferably in the range of 200 to 2000, and 300 to 1500 The range of is more preferable. If the average molecular weight is 200 or more, volatilization of unreacted components is suppressed, and if it is 2000 or less, sufficient transparency can be secured.
  • the average molecular weight can be controlled by the amount of water added, the reaction temperature, the content of the precursor (A), and the like.
  • the average molecular weight is a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (GPC).
  • the content of the matrix precursor (A) in the coating solution is not particularly limited as long as the coating solution can be applied, but as a solid content concentration in terms of SiO 2 with respect to the total amount (100% by mass) of the coating solution. 0.2 to 20% by mass is preferable, and 0.5 to 15% by mass is more preferable. If it is 0.2% by mass or more, the hydrolysis polycondensation reaction proceeds sufficiently, and if it is 20% by mass or less, the hydrolysis polycondensation reaction can be easily controlled and the long-term storage stability is good.
  • SiO 2 in terms of solids are solids when all the Si matrix precursor contained in the coating liquid (A) was converted to SiO 2.
  • the particles (B) are particles that can be removed from the matrix, for example, particles that can be removed by heat treatment, particles that can be removed by plasma treatment, particles that can be removed by solvent immersion, particles that can be removed by acid or alkali immersion, Examples thereof include particles that can be removed by light irradiation. Since heat treatment is required to form the outermost surface dense layer 14b, the particles (B) are preferably particles that can be removed by heat treatment. Before or after the heat treatment, plasma treatment, solvent immersion, acid or alkali immersion, Alternatively, the outermost surface dense layer 14b may be formed by heat treatment after removal by light irradiation.
  • Examples of particles that can be removed by heat treatment include particles made of a thermally decomposable material or a thermally sublimable material.
  • the thermal decomposition temperature of the thermally decomposable material is preferably 100 to 800 ° C, more preferably 200 to 700 ° C.
  • Examples of the thermally decomposable material include carbon, organic polymer, and surfactant micelle. Among these, carbon or an organic polymer is preferable from the viewpoint of stability over time.
  • the thermal decomposition temperature of carbon in air is about 500 ° C.
  • the thermal decomposition temperature of the organic polymer in air varies depending on the type and molecular weight of the organic polymer, but is generally about 200 to 600 ° C.
  • the thermal decomposition temperature of the organic polymer can be measured by differential thermal-thermogravimetric simultaneous measurement (TG-DTA).
  • the particles that can be removed by the heat treatment may be core-shell particles coated with an inorganic oxide such as SiO 2 that is not removed by the heat treatment. If the shell is thick, irregularities derived from particles are likely to be formed on the surface of the film, and the shell thickness is preferably 5 nm or less because insufficient wear resistance and dirt are likely to adhere. From the viewpoint of antireflection performance, it is more preferable that a component that cannot be removed by heating is not included.
  • the organic polymer is not particularly limited as long as synthesis of nanoparticles having a desired particle size can be obtained, but (meth) acrylic monomers, styrene monomers, diene monomers, imide monomers, amide monomers. Homopolymers or copolymers of monomers selected from the group consisting of (hereinafter also referred to as “specific monomer group”) are preferred.
  • Acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Pentyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, ( (Meth) acrylic acid dodecyl, (meth) acrylic acid phenyl, (meth) acrylic acid methoxyethyl, (meth) acrylic acid ethoxyethyl, (meth) acrylic acid propoxyethyl, (meth) acrylic acid butoxyethyl, (meth) acrylic acid Ethoxy
  • styrene monomers include alkyl styrene; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, fluorostyrene, chloro.
  • Examples include styrene, bromostyrene, dibromostyrene, chloromethylstyrene, nitrostyrene, acetylstyrene, methoxystyrene, ⁇ -methylstyrene, vinyltoluene, sodium p-styrenesulfonate, and the like.
  • Examples of the diene monomer include butadiene, isoprene, cyclopentadiene, 1,3-pentadiene, dicyclopentadiene, and the like.
  • imide monomers examples include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 6-aminohexyl succinimide, 2-aminoethyl succinimide, and the like.
  • amide monomers include acrylamide derivatives such as acrylamide and N-methylacrylamide, allylamine derivatives such as N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide, and acrylamide derivatives such as acrylamide and N-methylacrylamide.
  • aminostyrenes such as N-aminostyrene.
  • the copolymer may be a copolymer of two or more monomers selected from the specific monomer group.
  • at least one selected from the specific monomer group and at least one monomer other than the monomer selected from the specific monomer group may be copolymerized.
  • Examples of the other monomers include divinylbenzene, vinyl acetate, vinylpyridine, acrylic acid, methacrylic acid, tetrahydrophthalic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, methylene Malonic acid, monoethyl itaconate, monobutyl itaconate, monomethyl maleate, monoethyl maleate, monobutyl maleate, monopropyl maleate, monooctyl maleate, carboxyalkyl vinyl ether, carboxyalkyl vinyl ester, bicyclo [2,2,1] Hept-2-ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Acrylic acid such as an
  • the thermal decomposition temperature of the homopolymer or copolymer is preferably 200 to 600 ° C, more preferably 300 to 500 ° C.
  • organic polymer in addition to the homopolymer or copolymer of the specific monomer group, polyethylene glycol, polypropylene glycol, polyisobutylene glycol, polyethylene oxide-polypropylene oxide diblock polymer, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock A polymer, polyvinyl alcohol, silicone or the like can also be used.
  • the particles that can be removed by the plasma treatment can be decomposed and removed by irradiating the film made of the matrix precursor (A) and the particles (B) with plasma.
  • Examples of the material of the particles include the organic polymers described above.
  • the particles that can be removed by immersion in the solvent can be dissolved and removed by immersing the film made of the matrix precursor (A) and the particles (B) in the solvent.
  • Examples of the material of the particles include diglyme, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetate, ethyl acetoacetate, N-methyl-2-pyrrolidinone, 2-pyrrolidinone, 1,3-dimethyl- Polystyrene as soluble in solvents such as 2-imidazolidinone, dimethyl sulfoxide, toluene, xylene, benzene, trichlene, mineral spirit, benzol, xylol, ⁇ -butyrolactone, tetrahydrofuran, methyl ethyl ketone, acetone, dichloromethane, chloroform, methylene chloride And polymethyl acrylate.
  • solvents such as 2-imidazolidinone, dimethyl sulfoxide, toluene, xylene, benzene, trichlene, mineral spirit, benzol, xylol
  • Particles that can be removed by acid or alkali immersion can be dissolved and removed by immersing a film composed of the matrix precursor (A) and particles (B) in acid or alkali.
  • the material of the particles include zinc oxide, basic zinc carbonate, calcium carbonate and the like which can be dissolved in acids such as hydrochloric acid, nitric acid, and sulfuric acid.
  • Zinc oxide etc. are mentioned as what melt
  • the particles that can be removed by light irradiation can be removed by irradiating light (for example, ultraviolet rays or the like) to the film composed of the matrix precursor (A) and the particles (B) and dissolving them.
  • Examples of the material of the particles include zinc oxide and cadmium sulfide.
  • the particles (B) are preferably made of a thermally decomposable material in that the particles (B) can be removed simultaneously with the heat treatment when the matrix precursor (A) is used as a matrix, and the production process becomes simple. .
  • a carbon particle a commercially available thing may be used and what was manufactured by the manufacturing method of a well-known carbon nanoparticle may be used.
  • As an organic polymer particle a commercially available thing may be used and what was manufactured by the manufacturing method of a well-known organic polymer nanoparticle may be used.
  • a dispersion in which organic polymer nanoparticles are dispersed can be obtained by a known emulsion polymerization method.
  • an aqueous dispersion of organic polymer nanoparticles can be obtained by adding a monomer to water containing a surfactant, mixing to form micelles, and adding a polymerization initiator for polymerization.
  • the average primary particle diameter of the particles (B) is 20 to 130 nm, preferably 30 to 100 nm.
  • the average primary particle diameter of the particles (B) is at 20nm or more, can form a silica-based porous membrane having pores with a diameter of 20nm, If it is 130nm or less, the number of outermost surface open pores 13/10 6 nm 2 or less. Further, when the average primary particle diameter of the particles (B) is in the range of 20 to 130 nm, the average pore diameter tends to be in the range of 15 to 100 nm.
  • the average primary particle size in this specification is 100 particles randomly selected from an image obtained by observation with a transmission electron microscope, the particle size of each particle is measured, and the particle size of 100 particles is determined. It is average.
  • the particles (B) one type may be used alone, or two or more types having different materials and average primary particle diameters may be used in combination.
  • the content of the particles (B) in the coating solution is such that the mass ratio ((A) / (B)) between the content of the matrix precursor (A) in terms of SiO 2 and the content of the particles (B) is 0.
  • the amount is preferably in the range of 0.3 to 4.0, and more preferably in the range of 0.5 to 3.0.
  • the porosity in the silica-based porous film 14 is sufficiently high, and the refractive index of the silica-based porous film 14 is sufficiently low (eg, 1.38). The following).
  • (A) / (B) is 0.3 or more, the porosity in the silica-based porous film 14 does not become too high, and the durability is excellent.
  • the liquid medium (C) is a liquid in which the matrix precursor (A) is dissolved and the particles (B) are dispersed, and even a single liquid is a mixed liquid in which two or more kinds of liquids are mixed. May be. Since water is required for hydrolysis of the compounds (a1) and (a2), the liquid medium (C) preferably contains at least water. Water and other liquids may be used in combination. Examples of the other liquid include alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.).
  • alcohols methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.
  • ketones acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • Cellosolves methyl cellosolve, ethyl cellosolve, etc.
  • esters methyl acetate, ethyl acetate, etc.
  • glycol ethers ethylene glycol monoalkyl ether, etc.
  • nitrogen-containing compounds N, N-dimethylacetamide, N, N -Dimethylformamide, N-methylpyrrolidone, etc.
  • sulfur-containing compounds dimethylsulfoxide, etc.
  • the solvent for the matrix precursor (A) alcohols are preferable, and methanol and ethanol are particularly preferable.
  • any of alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds, etc. may be used as the dispersion medium for the particles (B). Good.
  • the coating solution may contain other components other than the matrix precursor (A) and the particles (B) as long as the effects of the present invention are not impaired.
  • the other component include a curing catalyst (metal chelate, metal alcoholate, organotin, etc.) for improving the reactivity of the matrix precursor (A).
  • Examples of the method for preparing the coating liquid include a method of mixing a solution of the matrix precursor (A) and a dispersion of the particles (B). More specifically, the following methods ( ⁇ ) to ( ⁇ ) are used. Is mentioned. Among these, the method ( ⁇ ) is preferable because the compound (a2) tends to float on the surface of the coating film when the coating solution is applied to the surface of the glass plate 12. Moreover, it is preferable to add the dispersion liquid of particle
  • the coating liquid As a coating method of the coating liquid, known wet coating methods (for example, spin coating method, spray coating method, dip coating method, die coating method, curtain coating method, screen coating method, ink jet method, flow coating method, gravure coating method, Bar coating method, flexo coating method, slit coating method, roll coating method, sponge coating method, etc.) can be used.
  • the coating temperature is preferably 10 to 100 ° C, more preferably 20 to 80 ° C.
  • heat treatment may be performed at 80 ° C. or higher, but is preferably 100 ° C. or higher, and more preferably 200 to 700 ° C.
  • the heat treatment temperature is 100 ° C. or higher, the matrix 21 is densified and the durability is improved.
  • the heat treatment temperature is 700 ° C. or lower, the alkali diffusion from the glass can be kept low, and the moisture resistance is good.
  • the heat treatment is performed at a temperature equal to or higher than the thermal decomposition temperature of the thermally decomposable material.
  • the particles (B) can be removed.
  • the heat treatment temperature is preferably (thermal decomposition temperature + 100 ° C.) or higher, more preferably (thermal decomposition temperature + 50 ° C.) or higher.
  • heat treatment for using the matrix precursor (A) as the matrix 21 may be performed at a temperature lower than the thermal decomposition temperature before the heat treatment.
  • the heat treatment may also serve as a step of strengthening the glass.
  • tempered glass When using glass for solar cell applications, tempered glass is used from the viewpoint of safety.
  • the tempered glass has a compressive stress on the surface, has a higher strength than a general float plate glass, and is excellent in safety because it becomes granular even when broken.
  • a method for strengthening the glass there is a heat strengthening method in which the glass is heated to 600 to 700 ° C. and then air is blown to the surface to quench the glass.
  • a glass plate a glass plate subjected to a chemical strengthening method in which ion exchange is performed on the surface of a glass plate by impregnating a glass plate containing sodium ions with a molten salt containing potassium ions at 300 to 500 ° C. Can also be used.
  • the particles (B) are removed by a removal method other than the heat treatment before or after the heat treatment.
  • the removal method other than the heat treatment include plasma treatment, solvent immersion, acid or alkali immersion, and light irradiation as mentioned in the description of the particles (B).
  • a method of irradiating a film comprising a matrix precursor (A) and particles (B) with plasma a method of immersing the film in a solvent, a method of immersing the film in an acid or an alkali, the film And a method of irradiating with light.
  • particles (B) made of a thermally decomposable material such as carbon and organic polymer, and remove the particles (B) by heat treatment.
  • the coating solution is applied onto the surface of an article such as the glass plate 12, preheated as necessary, heat-treated, and a series of steps of removing particles (B) is performed once.
  • the two-layer structure in which the distribution state of the vacancies 22 is different that is, the outermost surface dense layer b, the outermost surface dense layer b in which the vacancies 22 having a diameter of 20 nm or more do not exist,
  • a silica-based porous film 14 having a layer in which pores 22 having a diameter of 20 nm or more exist can be formed. This is considered to be due to the following reason.
  • the dielectric constant of HO—OH with respect to the Si—OH group is 89.2 F / m.
  • the interface free energy of the hydrolyzate or partial condensate of compound (a2) is the hydrolyzate of compound (a1) (Si (OH) 4 ).
  • the compound (A2) floats in the coating film, and as a result, the upper phase (compound (A2) phase) And the lower phase (compound (A1) phase).
  • the particles (B) have an average primary particle size that is somewhat large, they do not float and remain on the lower phase side as they are. Therefore, by subjecting the coating film to heat treatment, the compounds (A1) and (A2) are used as matrices, respectively, and subjected to removal treatment according to the material of the particles (B) simultaneously with the heat treatment or before or after the heat treatment.
  • a silica-based porous film 14 having pores 22 having a shape corresponding to the shape of (B) is formed.
  • the outermost surface dense layer 14b and other regions are the matrix 21. It is thought that the composition in is different. That is, the matrix 21 constituting the outermost surface dense layer 14b is substantially made of a heat-treated product of the compound (A2) and includes a structure derived from the compound (A2) (for example, a non-hydrolyzable group Y). The matrix 21 constituting the other region is substantially composed of a heat-treated product of the compound (A1) and does not include or includes very little structure derived from the compound (A2).
  • the refractive index of the silica type porous membrane 14 formed can be 1.38 or less.
  • the arithmetic mean roughness of the silica type porous membrane 14 formed can be 3.0 nm or less. As the arithmetic average roughness is smaller, the wear resistance, antifouling property and the like are improved, and the usefulness as an antireflection film is improved.
  • a coating liquid in which hollow silica fine particles are dispersed in a matrix precursor solution is applied and heat-treated.
  • the size of the hollow silica fine particles is small, it is possible to form a silica-based porous film having a surface open pore number of 13/10 6 nm 2 or less.
  • the size of the hollow silica fine particles is increased to make the refractive index 1.38 or less (for example, the inner pore diameter is 20 nm or more)
  • pores having a diameter of 20 nm or more are formed between the hollow silica fine particles, A hole opens in the outermost surface.
  • the shape of the hollow silica fine particles is reflected on the outermost surface, the arithmetic average roughness (Sa) tends to be larger than 3 nm.
  • FIG. 3 is a cross-sectional view showing a second embodiment of an article with a silica-based porous film having the silica-based porous film of the present invention on the surface of the article.
  • An article 20 with a silica-based porous film of the present embodiment includes a glass plate 12, an undercoat layer 16 formed on the surface of the glass plate 12, and a silica-based porous film 14 formed on the surface of the undercoat layer 16. And have.
  • the undercoat layer 16 has a function as an alkali barrier layer or a wide band low refractive index layer.
  • the undercoat layer 16 includes a layer composed only of a matrix mainly composed of silica, a layer having a plurality of pores in a matrix mainly composed of silica, and a silica solid in a matrix mainly composed of silica. Examples thereof include a layer having particles and a layer having silica hollow particles in a matrix mainly composed of silica.
  • the matrix containing silica as a main component include a heat-treated product of sol-gel silica (hydrolyzate or partial condensate of alkoxysilane), a heat-treated product of silazane, and the like, and a heat-treated product of sol-gel silica is preferable.
  • the thickness of the undercoat layer is preferably 10 to 500 nm.
  • the refractive index of the undercoat layer is preferably 1.30 to 1.50, more preferably 1.35 to 1.46.
  • the compound (a1), the compound (a2), and other known alkoxysilanes can be used, for example, tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxy).
  • alkoxysilane having a perfluoropolyether group perfluoropolyether triethoxysilane, etc.
  • alkoxysilane having a perfluoroalkyl group perfluoroethyltriethoxysilane, etc.
  • alkoxysilane having a vinyl group vinyltriethoxysilane, vinyltriethoxysilane, etc.
  • acryloyl alkoxysilane having an oxy group (3-acryloyloxy propyl trimethoxysilane and the like) and the like.
  • the article 20 with a silica-based porous film forms, for example, a coating liquid (hereinafter also referred to as a lower layer coating liquid) and a silica-based porous film 14 for forming the undercoat layer 16 on the glass plate 12.
  • a coating liquid hereinafter also referred to as a lower layer coating liquid
  • the heat treatment may be performed only after the upper layer coating solution is applied, or may be performed after the lower layer coating solution is applied and after the upper layer coating solution is applied.
  • the glass plate 12 may be heated to a heat treatment temperature in advance, and a lower layer coating solution and an upper layer coating solution may be sequentially applied to the surface of the glass plate 12.
  • the heat treatment temperature is preferably 50 to 300 ° C, more preferably 100 to 200 ° C.
  • the upper layer coating solution and the formation procedure of the silica-based porous film 14 using the same are the same as those in the first embodiment.
  • Lower layer coating solution As a lower layer coating solution, a matrix precursor solution (sol-gel silica solution, silazane solution, etc.), a mixture of particles (B) or a dispersion of hollow particles and a matrix precursor solution, or dispersion of silica solid particles Examples thereof include a mixture of a liquid and a matrix precursor solution.
  • the lower layer coating solution may contain a surfactant for improving leveling properties, a metal compound for improving durability of the coating film, and the like.
  • the matrix precursor examples include sol-gel silica (alkoxysilane hydrolyzate or partial condensate), silazane and the like, and sol-gel silica is preferable.
  • sol-gel silica alkoxysilane hydrolyzate or partial condensate
  • silazane silazane
  • sol-gel silica is preferable.
  • the alkoxysilane the compound (a1), the compound (a2), and other known alkoxysilanes can be used.
  • tetraalkoxysilane tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.
  • An alkoxysilane having a perfluoropolyether group perfluoropolyethertriethoxysilane, etc.
  • an alkoxysilane having a perfluoroalkyl group perfluoroethyltriethoxysilane, etc.
  • an alkoxysilane having a vinyl group vinyltrimethoxysilane, Vinyltriethoxysilane, etc.
  • Examples of the solvent for the matrix precursor include those similar to the liquid medium (C), and a mixed solvent of water and alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.) is preferable.
  • a dispersion medium for the dispersion liquid of particles (B) hollow particles, or silica solid particles, water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds, etc. And the same as those mentioned in the liquid medium (C).
  • the coating temperature of the coating solution for forming the undercoat layer 16 is preferably room temperature to 200 ° C., more preferably room temperature to 150 ° C.
  • the silica-based porous film 14 is formed by performing a series of steps of applying the coating liquid on the glass plate 12, heat-treating, and removing the particles (B) once.
  • the silica-based porous film 14 may be a film formed by performing the above process a plurality of times.
  • grains (B)) of the coating liquid used at each process may be the same, or may differ.
  • the articles 10 and 20 with the silica-based porous film may have a layer other than the undercoat layer 16 between the glass plate 12 and the silica-based porous film 14.
  • the other layers include a fingerprint removing layer, an antistatic layer, a water-repellent antifouling layer, a hydrophilic antifouling layer, an ultraviolet shielding layer, an infrared shielding layer, and a wavelength conversion layer.
  • it is most preferable that no other layer is interposed between the glass plate 12 and the silica-based porous film 14 as in the article 10 with the silica-based porous film.
  • item which provides the silica type porous membrane of this invention on the surface is not limited to a glass plate.
  • various base materials such as an organic resin film, an organic resin plate, and an organic-inorganic hybrid substrate may be used.
  • the article provided with the silica-based porous film of the present invention is preferably made of a transparent material such as glass or organic resin, and a glass plate is preferred.
  • the silica-based porous film of the present invention has a refractive index as low as 1.38 or less, and is excellent in durability such as moist heat resistance and wear resistance. For this reason, it is useful as an antireflection film for various articles such as glass plates.
  • the silica-based porous film of the present invention is preferably disposed on the outermost layer of the article with the silica-based porous film.
  • Articles with a silica-based porous film having a silica-based porous film on the surface thereof according to the present invention are transparent parts for vehicles (headlight covers, side mirrors, front transparent substrates, side transparent substrates, rear transparent substrates, instrument panels, etc.
  • Meter architectural window, show window, display (notebook PC, monitor, LCD, PDP, ELD, CRT, PDA, etc.), LCD color filter, touch panel substrate, pickup lens, optical lens, spectacle lens, camera parts, Video parts, CCD cover substrates, optical fiber end faces, projector parts, copying machine parts, transparent substrates for solar cells, mobile phone windows, backlight unit parts (for example, light guide plates, cold cathode tubes, etc.), backlight unit parts (for example, , Prism, transflective film, etc.), LCD brightness enhancement Film, organic EL light-emitting element parts, inorganic EL light-emitting element parts, phosphor light-emitting element parts, optical filters, end faces of optical parts, illumination lamps, lighting fixture covers, amplified laser light sources, antireflection films, polarizing films, agricultural films Useful as such.
  • examples 1 to 14 described later examples 1 to 9 are examples, and examples 10 to 14 are comparative examples.
  • the measurement method and evaluation method used in each example are shown below.
  • the dispersion of particles (B) was diluted to 0.1% by mass with water, then sampled on a collodion membrane, and observed with a transmission electron microscope (Hitachi, Ltd., model: H-9000). The particles (B) were randomly selected and the average value obtained by measuring the diameter of each particle was defined as the average primary particle size of the particles (B).
  • the matrix precursor (A) was diluted to 0.5% with tetrahydrofuran and then measured using a high-speed GPC apparatus (manufactured by Tosoh Corporation, model: HLC-8320GPC).
  • the reflectance of light incident at an incident angle of 5 ° on the surface of the upper glass (silica porous membrane) side of the produced glass plate with the silica porous membrane was measured with a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100). The average reflectance (%) in the wavelength range of 400 to 1100 nm was determined. In addition, in order to prevent the back surface light reflection of a glass plate, the back surface was painted black and measured.
  • the transmittance of light incident at an incident angle of 0 ° on the surface of the manufactured glass plate with silica-based porous film (silica-based porous film) is measured with a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100). The average transmittance (%) in the wavelength range of 400 to 1100 nm was determined. In addition, in order to prevent the back surface light diffusion of the glass plate, the measurement was performed by attaching quartz glass to the back surface with anisole.
  • the average total film thickness and the average thickness of the outermost surface dense layer were observed with a scanning electron microscope SEM (manufactured by Hitachi, Ltd., model: S-4300), respectively, of the cross section of the produced glass plate with a silica-based porous film. From the image obtained in this manner, the thickness of each of the silica-based porous film and the outermost surface dense layer was measured at 100 locations, and the average value thereof was calculated.
  • the average pore diameter in the upper layer (silica porous membrane) of the produced glass plate with a silica-based porous membrane was measured with a scanning electron microscope SEM (manufactured by Hitachi, Ltd., model: S-4300). The diameter was measured and the average value was calculated.
  • the number of open holes on the outermost surface is determined by scanning electron microscope SEM (manufactured by Hitachi Ltd., model: S-4300) on the outermost surface (silica porous film) side of the manufactured glass plate with silica porous film.
  • SEM scanning electron microscope
  • the number of openings having a diameter of 20 nm or more present in the region of 1000 nm ⁇ 1000 nm was determined from the observed and obtained images.
  • the refractive index of the produced silica-based porous film was determined by measuring the produced glass plate with the silica-based porous film with an ellipsometer (manufactured by JA Woollam, model: M-2000DI), and having a refractive index of 589.3 nm. The rate was determined. In addition, in order to prevent the back surface light reflection of a glass plate, the back surface was painted black and measured.
  • the arithmetic average roughness (Sa) of the outermost surface on the upper layer (silica-based porous film) side of the produced glass plate with a silica-based porous film was measured using a scanning probe microscope apparatus (SII Nano Technology, SPA400DFM). The measurement range was 10 ⁇ m ⁇ 10 ⁇ m.
  • the following moisture resistance test was performed on the manufactured glass plate with a silica-based porous film.
  • the produced glass plate with a porous silica film is put into a constant temperature and humidity chamber at 85 ° C. and a relative humidity of 85%, and after holding for 1000 hours, the transmittance is measured to obtain the average transmittance at a wavelength of 400 to 1100 nm. It was. From the average transmittance before and after the test, the change in transmittance due to the moisture resistance test was determined.
  • the average transmittance (0 ° incidence) at a wavelength of 400 to 1100 nm was determined by the same procedure as described above.
  • the amount of change in the average transmittance before and after the moisture resistance test was determined.
  • the amount of change is preferably from 0 to 1.0, particularly preferably from 0 to 0.5.
  • the following abrasion test was done about the manufactured glass plate with a silica type porous membrane.
  • the surface of the produced glass plate with a silica-based porous film was subjected to 1000 reciprocating abrasions with a 1 kg load with felt, and then the transmittance was measured to determine the average transmittance at a wavelength of 400 to 1200 nm. From the average transmittance before and after the test, the change in transmittance due to the abrasion test was obtained.
  • the average transmittance (0 ° incidence) at a wavelength of 400 to 1100 nm was determined by the same procedure as described above.
  • the amount of change in average transmittance before and after the wear test was determined.
  • the amount of change is preferably 0 to 1.0 or less, particularly preferably 0 to 0.5.
  • particle dispersion The particle dispersion used in each example was prepared by the following procedure. ⁇ Preparation of particle dispersions A to F> An amount (g) of sodium dodecyl lactate (SDS) and water shown in Table 1 were charged into a 200 mL glass container and stirred. The amount (g) of methyl methacrylate (MMA) shown in Table 1 was added thereto and stirred to emulsify. Thereto, ammonium persulfate (APS) in the amount (g) shown in Table 1 was added as a polymerization initiator, heated to 70 ° C., and held for 1 hour to obtain particle dispersions A to F.
  • SDS sodium dodecyl lactate
  • MMA methyl methacrylate
  • APS ammonium persulfate
  • ⁇ Preparation of particle dispersion G A quantity (g) of hexadecyltrimethylammonium bromide (C16TAB) and water shown in Table 1 and water were charged into a glass container having a capacity of 200 mL and stirred. The amount (g) of styrene shown in Table 1 was added thereto, stirred and emulsified. As a polymerization initiator, 2,2′-azobis (isobutylamidine) dihydrochloride (AIBA) in the amount (g) shown in Table 1 was added, heated to 70 ° C., and held for 1 hour to disperse the particles. Liquid G was obtained.
  • AIBA 2,2′-azobis (isobutylamidine) dihydrochloride
  • Table 2 shows the solid content concentration (% by mass), the dispersion medium, the particle material, and the average primary particle size (nm) for the obtained particle dispersions A to G.
  • PMMA indicates poly (methyl methacrylate) and PS indicates polystyrene.
  • HNO 3 aq. Represents a nitric acid aqueous solution having a concentration of 60%
  • TEOS represents tetraethoxysilane
  • PTMS represents phenyltrimethoxysilane
  • TMOS represents tetramethoxysilane
  • MTMS represents methyltrimethoxysilane.
  • Table 3 also shows the average molecular weight of the matrix precursor contained in each matrix precursor solution.
  • the dielectric constant of Y—OH is 2.9 F / m when Y is a phenyl group (Y—OH is phenol), and 33.1 F / m when Y is a methyl group (Y—OH is methanol). m.
  • the solid content concentration of the matrix precursor is a solid content concentration in terms of SiO 2 .
  • the upper layer coating solution was prepared by mixing the particle dispersion of the type and blending amount shown in Table 5, the matrix precursor solution of the type and blending amount shown in Table 5, and isopropanol. After applying the upper layer coating solution on the surface of a glass plate (soda lime glass, manufactured by Asahi Glass Co., Ltd., size: 100 mm ⁇ 100 mm, thickness: 3.2 mm) by spin coating (rotation speed: 500 rpm ⁇ 20 seconds), A silica-based porous film was formed by heat treatment at 650 ° C. for 5 minutes to obtain a glass plate with a silica-based porous film.
  • Example 5 An upper layer coating solution and a lower layer coating solution were prepared by mixing the particle dispersion of the types and blending amounts shown in Table 5, the matrix precursor solution of the types and blending amounts shown in Table 5, and isopropanol. After applying the lower layer coating liquid on the surface of a glass plate (soda lime glass, manufactured by Asahi Glass Co., Ltd., size: 100 mm ⁇ 100 mm, thickness: 3.2 mm) by spin coating (rotation speed: 500 rpm ⁇ 20 seconds), An undercoat layer was formed by heat treatment at 200 ° C. for 1 minute.
  • the upper layer coating solution was prepared by mixing the particle dispersions of the types and blending amounts shown in Tables 5 to 6, the matrix precursor solutions of the types and blending amounts shown in Tables 5 to 6, and isopropanol.
  • a glass plate sina lime glass, manufactured by Asahi Glass Co., Ltd., size: 100 mm ⁇ 100 mm, thickness: 3.2 mm
  • spin coating rotating speed: 500 rpm ⁇ 20 seconds
  • a silica-based porous film was formed by heat treatment (only in Example 9 at 450 ° C. for 30 minutes, and in other examples at 650 ° C. for 5 minutes) to obtain a glass plate with a silica-based porous film.
  • FIGS. 4 to 13 show scanning electron micrographs of (a) the top surface and (b) cross section of the glass plates with silica-based porous membranes of Examples 1, 3, 5, 7, 9, 10 to 14, respectively.
  • Example 10 in which the average primary particle diameter of the PMMA particles was 15 nm, the change in average transmittance due to the moisture resistance test was large, and the durability was poor. This is considered to be because the outermost surface dense layer was not formed because the average primary particle diameter of the PMMA particles was small.
  • Example 11 in which the average primary particle diameter of the PMMA particles was 143 nm, the change in average transmittance by the moisture resistance test and the change in average transmittance by the wear test were both large, and the durability was poor. This is thought to be due to the fact that large-sized open pores were generated due to the large average primary particle size of the PMMA particles.
  • Example 5 with a two-layered silica-based porous membrane, and Example 6 with a non-porous undercoat layer provided between a glass plate and a silica-based porous membrane also have an average transmittance by a moisture resistance test and an abrasion test. There was little change and the durability was excellent.
  • Examples 13, 12, 7, 3 in which a film was formed under the same conditions using an upper coating solution having the same composition except that the ratio of the compound (a1) and the compound (a2) contained in the matrix precursor solution was different. , 8 is compared, the molar ratio of TEOS as the compound (a1) and PTMS as the compound (a2) is (a1) / (a2) 0.25 to 1.5 (20/80 to 60/40).
  • the change in average transmittance due to the moisture resistance test and wear test was small, and the durability was excellent.
  • Example 13 in which the compound (a2) was not used in combination the change in average transmittance due to the moisture resistance test was large, and the durability was poor.
  • Example 5 shows an average of the moisture resistance test and the wear test.
  • the change in transmittance was small and the durability was excellent.
  • Example 14 using the matrix precursor solution M not containing the compound (a1) the holes were continuous holes as shown in FIG. Further, the refractive index was as high as 1.42, the average reflectance was high, the average transmittance was low, and the antireflection performance was not sufficient. Furthermore, the durability against the abrasion test was also poor.
  • the pores having a diameter of 20 nm or more inside the film were independent holes.
  • the porous structure can be maintained for a long period of time, and the silica-based porous film having excellent antireflection performance and durability, the silica-based porous film It is possible to provide an article with a silica-based porous film and a production method capable of easily producing the article with a silica-based porous film.

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CN106772755A (zh) * 2017-02-27 2017-05-31 合肥京东方光电科技有限公司 一种偏光片和液晶显示设备
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US10800700B2 (en) 2015-03-06 2020-10-13 Nippon Sheet Glass Company, Limited Coated glass sheet and method for producing same
EP3649091B1 (fr) 2017-07-07 2022-02-16 Saint-Gobain Glass France Procede d'obtention d'un substrat de verre texture revetu d'un revetement de type sol-gel antireflet

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US10173920B2 (en) 2014-06-19 2019-01-08 Corning Incorporated Aluminosilicate glasses
US11001521B2 (en) 2014-06-19 2021-05-11 Corning Incorporated Aluminosilicate glasses
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JP2016085240A (ja) * 2014-10-22 2016-05-19 旭化成株式会社 光学塗膜、光学塗膜の製造方法、及び反射防止膜
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WO2018143371A1 (ja) * 2017-02-06 2018-08-09 富士フイルム株式会社 塗布組成物、反射防止膜及びその製造方法、積層体、並びに、太陽電池モジュール
CN106772755A (zh) * 2017-02-27 2017-05-31 合肥京东方光电科技有限公司 一种偏光片和液晶显示设备
US11016333B2 (en) 2017-02-27 2021-05-25 Boe Technology Group Co., Ltd. Polarizer and liquid crystal display device having porous protective layer
EP3649091B1 (fr) 2017-07-07 2022-02-16 Saint-Gobain Glass France Procede d'obtention d'un substrat de verre texture revetu d'un revetement de type sol-gel antireflet

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