CN113946000B - Method for manufacturing optical member, and optical member - Google Patents
Method for manufacturing optical member, and optical member Download PDFInfo
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- CN113946000B CN113946000B CN202110712332.2A CN202110712332A CN113946000B CN 113946000 B CN113946000 B CN 113946000B CN 202110712332 A CN202110712332 A CN 202110712332A CN 113946000 B CN113946000 B CN 113946000B
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- functional film
- silicate
- optical member
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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
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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
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
Abstract
The present invention provides an optical member including a functional film excellent in hydrophilicity and hardness, and a method for manufacturing the same. The method for producing an optical member is a method for producing an optical member including a light-transmitting member and a functional film covering the light-transmitting member, and includes a functional film forming step of forming the functional film by applying a functional film forming coating liquid on the light-transmitting member. The coating liquid for forming a functional film contains photocatalyst particles, a binder raw material and a solvent. The binder material comprises silicate monomers and silicate oligomers. The ratio of the mass of the silicate oligomer to the total of the mass of the silicate monomer and the mass of the silicate oligomer is 3.5 mol% or more and 28.0 mol% or less.
Description
Technical Field
The present invention relates to a method for manufacturing an optical member and an optical member.
Background
The optical member includes, for example, a light-transmissive member and a functional film covering the surface of the light-transmissive member. The functional film has, for example, hydrophilicity.
There is known an inorganic hydrophilic coating liquid comprising: (a) An aqueous solution containing an amorphous silicate compound, which is obtained by subjecting a tetrafunctional silicon compound having a purity of 99.0 mass% or more to hydrolytic condensation at a temperature of from normal temperature to 170 ℃ or lower in an aqueous medium in the presence of an alkaline compound; (b) water; and optionally (c) 30 mass% or less of an alcohol, ketone, surfactant, or a combination of two or more thereof (for example, patent document 1). In the inorganic hydrophilic coating liquid, the concentration of the solid content derived from the aqueous solution containing the amorphous silicate compound is 0.01 mass% or more and 2.0 mass% or less. The pH value of the inorganic hydrophilic coating liquid is more than 5 and less than 8. The inorganic hydrophilic coating liquid can be used to form the functional film.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] International publication No. 2013/001975
Disclosure of Invention
However, the functional film formed from the inorganic hydrophilic coating liquid described in patent document 1 tends to have insufficient hardness.
The present invention has been made in view of the above problems, and an object thereof is to provide an optical member including a functional film excellent in hydrophilicity and hardness.
An exemplary method for manufacturing an optical member according to the present invention is a method for manufacturing an optical member including a light-transmitting member and a functional film covering the light-transmitting member, and includes a functional film forming step of forming the functional film by applying a functional film forming coating liquid on the light-transmitting member. The coating liquid for forming a functional film contains photocatalyst particles, a binder raw material and a solvent. The binder material comprises silicate monomers and silicate oligomers. The ratio of the mass of the silicate oligomer to the total of the mass of the silicate monomer and the mass of the silicate oligomer is 3.5 mol% or more and 28.0 mol% or less.
An exemplary optical member of the present invention is formed by the method of manufacturing an optical member.
The present invention can provide an optical member including a functional film excellent in hydrophilicity and hardness.
The above and other features, elements, steps, features and advantages of the present invention will be more clearly understood from the following detailed description of the preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
Fig. 1 is a schematic view of an optical member formed by an example of a method for manufacturing an optical member according to an embodiment of the present invention.
Fig. 2 is a schematic view of an optical member formed by modification 1 of the method for manufacturing an optical member according to the embodiment of the present invention.
Fig. 3 is a graph showing the relationship between the ratio (α) of silicate oligomer and the contact angle for the functional film formed in the example.
Fig. 4 is a graph showing the relationship between the ratio (α) of silicate oligomer and indentation hardness for the functional film formed in the example.
Fig. 5 is a graph showing the relationship between the ratio (α) of silicate oligomer and the gel fraction for the sample film formed in the example.
FIG. 6 is a photograph showing the result of the wiping experiment performed in the example.
[ description of symbols ]
1. 11: optical component
2. 12: light-transmitting member
2a: substrate material
2b: antireflection film
3. 13: functional film
Detailed Description
Hereinafter, embodiments of the present invention will be described with appropriate reference to the drawings. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and description thereof will not be repeated. The dimensions of the various elements in the drawings are not necessarily the same as the dimensions of the actual elements.
In the present specification, "thickness" means an average thickness. The "thickness of the antireflection film" is measured by a scanning electron microscope (for example, "JSM-7900F" manufactured by japan electronics corporation). The "thickness of the functional film" is measured by a contact film thickness measuring device (e.g., "DekTakXT-S" manufactured by Bruker).
< method for producing optical Member >
The method for manufacturing an optical member according to the first embodiment of the present invention is a method for manufacturing an optical member including a light-transmissive member and a functional film covering the light-transmissive member, and includes a functional film forming step of forming the functional film by applying a functional film forming coating liquid onto the light-transmissive member. The coating liquid for forming a functional film contains photocatalyst particles, a binder raw material and a solvent. The binder material comprises silicate monomers and silicate oligomers. The ratio of the mass of the silicate oligomer to the total of the mass of the silicate monomer and the mass of the silicate oligomer (hereinafter, may be referred to as the ratio (α) of the silicate oligomer) is 3.5 mol% or more and 28.0 mol% or less.
The optical member formed by the method of manufacturing an optical member of the present embodiment is suitable, for example, as an optical member used in an optical unit (particularly an optical unit used outdoors) including one or more optical members. The optical member is particularly suitable as an optical member (hereinafter, sometimes referred to as a first optical member) located closest to the object side among one or more lenses included in the optical unit. In the case of using the optical member as the first optical member, the optical member is generally used in a state in which the functional film side faces the object side. Specifically, the optical member is suitable as a lens for a lens unit of an in-vehicle camera for monitoring the surroundings of a vehicle.
The optical member includes a functional film. The functional film is a hydrophilic film having photocatalytic activity. With the optical member, even if water adheres to the functional film, water droplets are less likely to form because the adhered water wets and spreads thinly on the functional film. Therefore, the optical member can suppress a decrease in optical performance caused by the adhesion of water droplets. Here, the known functional film can be formed using a known coating liquid for forming a functional film containing photocatalyst particles and silicate oligomer, for example. The known functional film formed from the known coating liquid for forming a functional film contains photocatalyst particles and a binder. The binder comprises silicate hardening substance. The photocatalyst particles and the cured silicate are excellent in hydrophilicity. The known functional film can exhibit excellent hydrophilicity by containing photocatalyst particles and a cured silicate. On the other hand, the known functional film tends to have insufficient hardness. Therefore, when the surface is rubbed in order to remove dirt (for example, mud and dust) adhering to the surface, the known functional film tends to easily cause scratches on the surface.
The inventors found that: by using a coating liquid for forming a functional film, which contains a silicate monomer and a silicate oligomer and has a silicate oligomer ratio (α) of a certain or more, a functional film having excellent hardness can be formed. The reason for this phenomenon can be judged to be: by adding both silicate monomers and silicate oligomers to the functional film-forming coating liquid, hardening (e.g., hydrolytic condensation) of silicate is efficiently performed. On the other hand, the present inventors found that: when the ratio (α) of silicate oligomer in the coating liquid for forming a functional film is equal to or greater than a predetermined value, the hydrophilicity of the formed functional film is reduced. The occurrence of the phenomenon can be judged for the following reason. First, in the formation of the functional film, the silicate monomer and the silicate oligomer contained in the coating liquid for forming the functional film are not completely cured, and a part remains in an unreacted state. Therefore, when the proportion (α) of the silicate oligomer of the coating liquid for forming a functional film is increased, the amount of the silicate oligomer remaining in the functional film is also increased. Here, the silicate oligomer is less hydrophilic than the silicate monomer. As described above, the functional film formed from the coating liquid for forming a functional film, in which the ratio (α) of the silicate oligomer is equal to or greater than a certain value, contains a relatively large amount of silicate oligomer, and therefore has low hydrophilicity. The present invention is based on the above findings. That is, in the method for producing an optical member according to the present embodiment, a functional film having excellent hardness can be formed because a coating liquid for forming a functional film is used which contains a silicate monomer and a silicate oligomer and has a proportion (α) of 3.5 mol% or more. In the method for producing an optical member according to the present embodiment, the ratio (α) of the silicate oligomer in the coating liquid for forming a functional film is 28.0 mol% or less, so that a functional film excellent in hydrophilicity can be formed. The functional film has excellent hardness, and therefore is less likely to cause scratches (excellent scratch resistance) even if the surface is rubbed.
Hereinafter, a method for manufacturing an optical member according to the present embodiment will be further described with reference to the drawings. Fig. 1 is a schematic view of an optical member 1 formed by an example of a method for manufacturing an optical member according to the present embodiment. The optical member 1 includes a light-transmissive member 2 and a functional film 3 covering the light-transmissive member 2.
[ light-transmitting Member ]
The light-transmitting member 2 has a base material 2a and an antireflection film 2b covering the base material 2 a. However, as shown in modification 1 described later, the light-transmitting member of the optical member formed by the method of manufacturing an optical member of the present embodiment may include a single member. The light-transmitting member 2 has light transmittance. That is, the light-transmitting member 2 transmits light. The light-transmitting member 2 may be transparent or translucent.
The light-transmitting member 2 is, for example, lens-shaped. When the light-transmitting member 2 has a lens shape, the surface of the light-transmitting member 2 on the side of the antireflection film 2b is, for example, a convex surface. When the light-transmitting member 2 has a lens shape, the radius of curvature of the lens surface of the light-transmitting member 2 is preferably 10mm or more and 15mm or less. When the radius of curvature of the light-transmitting member 2 is less than 10mm, it tends to be difficult to adjust the thickness of the functional film 3. When the radius of curvature of the light-transmitting member 2 exceeds 15mm, it tends to be difficult to impart a desired angle of view to the optical member 1.
(substrate)
The base material 2a contains glass or resin as a main component, for example.
(antireflection film)
The antireflection film 2b suppresses reflection of light. Specifically, the optical member 1 includes the antireflection film 2b to suppress reflection of light entering the light-transmitting member 2 from the functional film 3 in the light-transmitting member 2.
The antireflection film 2b may have a one-layer structure or a multilayer structure. The antireflection film 2b contains, for example, a metal or a metal oxide. The antireflection film 2b is, for example, a vapor deposited film or a sputtered film.
The thickness of the antireflection film 2b is preferably 200nm to 400 nm. When the thickness of the antireflection film 2b is less than 200nm, a sufficient antireflection effect tends to be obtained. When the thickness of the antireflection film 2b exceeds 400nm, productivity of the optical member 1 tends to be lowered.
[ functional film ]
The functional film 3 covers the surface of the light-transmitting member 2 on the antireflection film 2b side. The functional film 3 contains photocatalyst particles and a binder. The functional film 3 has photocatalytic activity. Specifically, the functional film 3 has hydrophilicity. The static contact angle of the functional film 3 with respect to pure water is preferably 30.0 ° or less, more preferably 20.0 ° or less, and still more preferably 10.0 ° or less.
The thickness of the functional film 3 is preferably 15nm to 200nm, more preferably 20nm to 180 nm. The hardness of the functional film 3 is further improved by the thickness of the functional film 3 being 15nm or more. The optical characteristics of the optical member 1 are improved by the thickness of the functional film 3 being 200nm or less.
(photocatalyst particles)
The photocatalyst particles include photocatalyst primary particles containing a photocatalyst. The photocatalyst particles may also contain photocatalyst secondary particles composed of photocatalyst primary particles. The photocatalyst particles may contain a component other than the photocatalyst as long as they contain the photocatalyst. Examples of the component other than the photocatalyst include components having an electron capturing effect. Examples of the component having an electron capturing effect include: gold, silver, copper, platinum, palladium, iron, nickel, cobalt, zinc, and copper oxide. The content of the photocatalyst in the photocatalyst particles is preferably 90% by mass or more, more preferably 99% by mass or more, and still more preferably 100% by mass.
Examples of the photocatalyst contained in the photocatalyst particles include: titanium oxide, strontium titanate, zinc oxide, silicon carbide, gallium phosphate, cadmium sulfide, cadmium selenide, and molybdenum trisulfide. The photocatalyst particles preferably contain titanium oxide. The photocatalytic activity of the functional film 3 is further improved by containing titanium oxide in the photocatalyst particles.
Examples of the titanium oxide include: anatase titanium oxide, rutile titanium oxide, and brookite titanium oxide. The titanium oxide is preferably anatase-type titanium oxide from the viewpoint of photocatalytic activity.
The average particle diameter of the photocatalyst particles is preferably 1nm to 20nm, more preferably 5nm to 15 nm. The light transmittance of the optical member 1 is improved by the photocatalyst particles having an average particle diameter of 1nm to 20nm.
(adhesive)
The binder contains a silicate hardening substance. The silicate cured product is produced by a curing reaction (e.g., a hydrolytic condensation reaction) of a silicate monomer and a silicate oligomer.
[ method for producing optical Member ]
A method of manufacturing the optical member 1 will be described. The method for manufacturing the optical member 1 includes: an antireflection film forming step of forming an antireflection film 2b on a base material 2a to obtain a light-transmitting member 2; and a functional film forming step of forming the functional film 3 by applying a functional film forming coating liquid to the light-transmitting member 2 (specifically, to the surface on the side of the antireflection film 2 b). However, in the method for manufacturing the optical member 1, a commercially available light-transmitting member 2 may be used. In this case, the antireflection film forming step may be omitted.
[ antireflection film Forming Process ]
In this step, the method for forming the antireflection film 2b is not particularly limited, and known antireflection film forming methods (for example, sputtering and vapor deposition) can be used.
[ functional film Forming Process ]
The coating liquid for forming a functional film used in the present step contains photocatalyst particles, a binder raw material and a solvent. The functional film-forming coating liquid may further contain other components. The binder material comprises silicate monomers and silicate oligomers.
In addition, the binder raw material may contain only silicate monomers and silicate oligomers, and may also contain other components (e.g., silica). The total content of the silicate monomer and the silicate oligomer in the binder raw material is preferably 80% by mass or more, more preferably 99% by mass or more, and still more preferably 100% by mass.
Silicate monomers are silicate compounds that do not have a siloxane bond (Si-O-Si) in the molecule. Silicate oligomers are silicate compounds having 1 or more (e.g., 2 or more and 6 or less) siloxane bonds in the molecule.
The molecular weight of the silicate monomer is preferably 120 to 210. By setting the molecular weight of the silicate monomer to 120 or more and 210 or less, the hardness of the functional film 3 is further improved. The molecular weight of the silicate oligomer is preferably 200 to 1000, more preferably 600 to 850. By setting the molecular weight of the silicate oligomer to 200 or more and 1000 or less, the hardness of the functional film 3 is further improved. In addition, in the case where the adhesive contains a plurality of silicate monomers, the molecular weight of the silicate monomers is an exponential average molecular weight. Similarly, where the binder comprises a plurality of silicate oligomers, the molecular weight of the silicate oligomer is the exponential average molecular weight.
The silicate monomer preferably contains a compound represented by the following general formula (1) (hereinafter, may be referred to as compound (1)). The silicate oligomer preferably contains a compound represented by the following general formula (2) (hereinafter, may be referred to as compound (2)). By containing the compound (1) in the silicate monomer, the silicate oligomer contains the compound (2), and the hardness and hydrophilicity of the functional film 3 are further improved.
Si(OR 1 ) n (OH) (4-n) …(1)
Si m O (m-1) (OR 2 ) (2m+2) …(2)
In the general formula (1), R 1 Represents an organic group having 1 to 8 carbon atoms. n represents an integer of 1 to 4 inclusive. In the general formula (2), R 2 An alkyl group having 1 to 4 carbon atoms. m represents an integer of 2 to 6.
In the general formula (1), when n represents an integer of 2 or more, a plurality of R' s 1 May be the same as or different from each other, but are preferably the same as each other. In the general formula (2), a plurality of R 2 May be the same as or different from each other, but are preferably the same as each other. The details of the compound (1) and the compound (2) are described below.
(Compound (1))
In the general formula (1), R is 1 Examples of the organic group having 1 to 8 carbon atoms include an alkyl group having 1 to 4 carbon atoms and an alkoxysilane group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Examples of the alkoxysilane group having 1 to 8 carbon atoms include trimethoxysilane group and triethoxysilane group. As R 1 The organic group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
The compound (1) is preferably a compound represented by the following general formula (1') (hereinafter, may be referred to as an ethyl silicate monomer). N in the following formula (1') has the same meaning as n in the formula (1).
Si(OC 2 H 5 ) n (OH) (4-n) …(1′)
The silicate monomer may also comprise a mixture of two or more compounds (1). In this case, the average value of n in the general formula (1) in the mixture of the compound (1) is preferably 2.0 to 4.0, more preferably 3.0 to 4.0.
The method of calculating the average value of n in the general formula (1) will be described by way of example. It is assumed that the mixture of the compounds (1) includes the compound (1) in which n represents 1, the compound (1) in which n represents 2, the compound (1) in which n represents 3, and the compound (1) in which n represents 4 in the general formula (1) in the same mole, respectively. In this case, in the mixture of the compound (1), the average value of n in the general formula (1) is 2.5.
(Compound (2))
In the general formula (2), R is 2 Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (i) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. As R 2 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group.
The compound (2) is preferably a compound represented by the following general formula (2') (hereinafter, sometimes referred to as an ethyl silicate oligomer). M in the following formula (2') has the same meaning as m in the formula (2).
Si m O (m-1) (OC 2 H 5 ) (2m+2) …(2′)
The silicate oligomer may comprise a mixture of two or more compounds (2). In this case, the average value of m in the general formula (2) in the mixture of the compounds (2) is preferably 4.0 to 6.0, more preferably 4.5 to 5.5.
The method of calculating the average value of m in the general formula (2) will be described by way of example. It is assumed that the mixture of the compounds (2) includes the compound (2) in which m represents 2, the compound (2) in which m represents 3, the compound (2) in which m represents 4, the compound (2) in which m represents 5, and the compound (2) in which m represents 6 in the general formula (2) in the same mole, respectively. In this case, in the mixture of the compounds (2), the average value of m in the general formula (2) is 4.0.
The proportion (α) of the silicate oligomer is 3.5 mol% or more and 28.0 mol% or less, preferably 5.0 mol% or more and 28.0 mol% or less, and more preferably 10.0 mol% or more and 20.0 mol% or less. The functional film 3 exhibits excellent hardness by the proportion (α) of the silicate oligomer being 3.5 mol% or more. The functional film 3 exhibits excellent hydrophilicity by the proportion (α) of the silicate oligomer being 28.0 mol% or less.
The solvent of the functional film forming coating liquid is preferably an aqueous solvent. The aqueous solvent contains water and optionally additives. Examples of the additive include an organic acid, an alcohol compound, and ammonia. The content of the additive in the aqueous solvent is preferably more than 0% by mass and 20% by mass or less. As the organic acid, there may be mentioned: formic acid, acetic acid, propionic acid, succinic acid, citric acid and malic acid. Examples of the alcohol compound include: methanol, ethanol, isopropanol, n-propanol, and butanol.
As a coating method of the functional film forming coating liquid, a wet process is preferable. Examples of the wet process include: spin coating, roll coating, bar coating, dip coating, spray coating, and combinations thereof (e.g., dip spin coating). As the wet process, spin coating, dip coating or dip spin coating is preferable.
In the case of applying the functional film-forming coating liquid by spin coating or dip spin coating, the rotation speed is preferably 500rpm to 10000 rpm.
The concentration of the photocatalyst particles in the functional film-forming coating liquid in terms of solid content is preferably 1.0% by mass or more and 15.0% by mass or less, more preferably 2.0% by mass or more and 6.0% by mass or less. The concentration of the binder raw material in the functional film forming coating liquid in terms of solid content is preferably 85.0 mass% or more and 99.0 mass% or less, more preferably 94.0 mass% or more and 98.0 mass% or less. The solid content concentration of the functional film-forming coating liquid is preferably 0.1% by mass or more and 10.0% by mass or less, more preferably 0.2% by mass or more and 1.0% by mass or less.
In this step, the surface of the light-transmitting member 2 on the antireflection film 2b side may be subjected to surface treatment before the functional film forming coating liquid is applied. Examples of the surface treatment include: plasma treatment, electron beam treatment, corona treatment, and flame (flame) treatment. As the plasma treatment, for example, a high-frequency discharge plasma treatment or an atmospheric pressure glow discharge plasma treatment can be cited. These surface treatments may be used in combination of plural ones.
In this step, it is preferable to apply a coating liquid for forming a functional film and then heat-treat the resultant film. The removal of volatile components in the functional film-forming coating liquid and the hardening reaction can be promoted by the heat treatment. The heating conditions may be, for example, a treatment temperature of 60 ℃ to 200 ℃ and a treatment time of 10 minutes to 10 hours.
< modification 1>
Next, an optical member 11 formed by modification 1 of the method for manufacturing an optical member according to the present embodiment will be described with reference to fig. 2. The optical member 11 of fig. 2 is a modification 1 of the optical member 1 of fig. 1. The optical member 11 includes a light-transmissive member 12 and a functional film 13 covering the light-transmissive member 12.
The method of manufacturing the optical member 11 in fig. 2 is different from the method of manufacturing the optical member 1 in fig. 1 in that only the light-transmitting member 12 is a single member. Therefore, the description repeated with the manufacturing method of the optical member 1 is omitted. The light-transmitting member 12 is a member corresponding to the base material 2a of the optical member of fig. 1. The optical member 11 does not include the antireflection film 2b, and thus can be manufactured at a lower cost than the optical member 1 of fig. 1.
[ other modifications ]
As described above, the method of manufacturing the optical member according to the present embodiment will be described with reference to the drawings. However, the method of manufacturing the optical member of the present embodiment is not limited to the method of manufacturing the optical member 1 of fig. 1 and the method of manufacturing the optical member 11 of fig. 2.
The optical member formed by the method of manufacturing an optical member according to the present embodiment may further include other structures than the light-transmitting member and the functional film. The functional film preferably has a single-layer structure, but may have a multilayer structure. The functional films are preferably coated on the entire surfaces of the light-transmitting members, but the entire surfaces may not be necessarily coated.
< second embodiment: optical component ]
The optical member of the second embodiment of the present invention can be formed by the method for manufacturing an optical member of the first embodiment. The optical member formed by the method for manufacturing an optical member according to the first embodiment is described above in detail, and thus, a repetitive description is omitted.
Examples (example)
< production of optical Member A >
The optical members of examples 1 to 4 and comparative examples 1 to 3 were produced by the following methods. In the production of each optical member, the 1 st coating liquid and the 2 nd coating liquid are prepared as coating liquids for forming functional films. The following describes the details of the 1 st coating liquid and the 2 nd coating liquid.
(1 st coating liquid)
A1 st coating liquid was prepared by mixing an ethyl silicate monomer (tetraethyl orthosilicate (tetraethyl orthosilicate, TEOS) manufactured by Ml. Chemical industry Co., ltd., purity: 99.9 mass% or more), a photocatalyst dispersion liquid containing anatase-type titanium oxide particles (cloth Luo Sika (Sagan Coat) (registered trademark) TO-85 manufactured by Japan photocatalyst center Co., ltd., solid content: 0.85 mass%, solvent: water) and water so as TO obtain the following composition. The 1 st coating liquid contains silicate monomer (solid content conversion concentration: 96 mass%), titanium oxide particles as photocatalyst particles (solid content conversion concentration: 4 mass%), and solvent (water) (solid content concentration: 0.45 mass%). In the ethyl silicate monomer, the average value of n in the general formula (1) is about 4.0. The ethyl silicate monomer contained in the 1 st coating liquid had a number average molecular weight of about 208. The average particle diameter of the titanium oxide particles contained in the 1 st coating liquid was 10nm.
(coating liquid 2)
As the 2 nd coating liquid, a solution containing an ethyl silicate oligomer and a solvent (ethyl silicate 40, solid content concentration: 0.34% by mass, solvent: ethanol, manufactured by Kelcet (COLCOAT) Co., ltd.) was prepared. The ethyl silicate oligomer contained in the coating liquid of the 2 nd is a mixture of a plurality of ethyl silicate oligomers having different values of m in the general formula (2). In the ethyl silicate oligomer contained in the coating liquid of the 2 nd, the average value of m in the general formula (2) was 5.0. The number average molecular weight of the ethyl silicate oligomer contained in the coating liquid 2 was 745.2.
Example 1
The optical member of example 1 was manufactured by the following method. First, a lens (TAFD-5G, composition: glass, diameter 12.9mm, manufactured by Haoya (HOYA) Co., ltd.) was prepared as a base material. One of the lenses is concave (radius of curvature 3 mm) and the other is convex (radius of curvature 12 mm). Then, an antireflection film is formed on the convex surface of the lens. The antireflection film contains SiO 2 Layer, tiO 2 Layer and Ta 2 O 5 A layer. The total thickness of the antireflection film was about 300nm. Thus, a light-transmitting member including a base material and an antireflection film was obtained. Then, the surface of the light-transmitting member on the antireflection film side was subjected to surface treatment (30 seconds). As the surface treatment, plasma treatment using a plasma surface modifying apparatus is performed.
Subsequently, 8.1g of the 1 st coating liquid and 1.9g of the 2 nd coating liquid were mixed. The obtained mixed solution was used as a coating solution for forming a functional film. In the coating liquid for forming a functional film, the mass of the silicate oligomer (8.6X10) -6 Molar) relative to the total mass of silicate monomers and silicate oligomers (1.8X10) -4 Molar) was 4.9 mol%.
The functional film forming coating liquid is applied to the antireflection film of the light-transmitting member after the plasma treatment by spin coating. A spin coater (MS-B100 manufactured by Mikasa Co., ltd.) was used for the spin coating method. The coating conditions were a spin speed of 8000rpm and a spin time of 30 seconds. After the coating, a heating treatment was performed at 120℃for 30 minutes. Thereby, a functional film is formed on the light-transmitting member. As a result, the optical member of example 1 in which the base material, the antireflection film, and the functional film were laminated in this order was obtained.
The thickness of the functional film of the optical member of example 1 was measured using a contact film thickness measuring apparatus ("DekTakXT-S" manufactured by Bruker). The functional film of the optical member of example 1 had a thickness of 20nm.
Examples 2 to 4 and comparative examples 1 to 3
The optical members of examples 2 to 4 and comparative examples 1 to 3 were produced by the same method as the method for producing the optical member of example 1, except that the following modifications were made. In the production of the optical members of examples 2 to 4 and comparative examples 1 to 3, the 1 st coating liquid and the 2 nd coating liquid were mixed in the proportions shown in table 1 below in the production of the coating liquid for forming a functional film. In the production of the optical member of comparative example 1, the 1 st coating liquid was directly used as the coating liquid for forming the functional film.
< evaluation of hydrophilicity of functional film >
For the optical members of examples 1 to 4 and comparative examples 1 to 3, the static contact angle (hereinafter, may be simply referred to as "contact angle") of the functional film with respect to pure water was measured. For the measurement of the contact angle, an automatic contact angle meter ("DMo-601" manufactured by the company, inc.) was used as a measurement machine. The measurement environment was set at a temperature of 23.+ -. 3 ℃ and a relative humidity of 50%.+ -. 10%. The measurement results are shown in table 1 below. In this example, it can be judged that the contact angle of the functional film is 15 ° or less.
Fig. 3 is a graph showing the relationship between the ratio (α) of silicate oligomer in the functional film and the contact angle for each optical member.
In table 1 below, "1 st coating liquid [ mass% ]" and "2 nd coating liquid [ mass% ]" represent the mass ratios of the 1 st coating liquid and the 2 nd coating liquid, respectively, for preparing the coating liquid for forming a functional film. "proportion (α) [ mol% ]" means the proportion (α) of silicate oligomer in the functional film. These descriptions are also the same as those in tables 2 and 3 below.
TABLE 1
As shown in table 1 and fig. 3, the ratio (α) of silicate oligomer in the functional films of the optical members of comparative example 1 and examples 1 to 4 was 28.0 mol% or less. The contact angle of the functional film of the optical member of comparative example 1 and examples 1 to 4 was good. On the other hand, the ratio (α) of silicate oligomer in the functional films of the optical members of comparative examples 2 and 3 exceeded 28.0 mol%. The contact angle of the functional films of the optical members of comparative examples 2 and 3 was not good.
< production of optical Member B >
The optical members of examples 1 to 4 and comparative examples 1 to 3 were manufactured again.
< evaluation of hardness of functional film >
The hardness of the functional films of the optical members of examples 1 to 4 and comparative examples 1 to 3 was measured. Specifically, a nanoindentation (ultra-fine indentation hardness) test according to "International organization for standardization (International Standardization Organization, ISO) 14577-1" was performed on a functional film of each optical member using a Nanoindenter (ENT-NEXUS manufactured by Elionix Co., ltd.). In the nanoindentation test, the indentation depth was set to 50nm. The hardness of the functional film of each optical member is shown in table 2 below. In this example, if the indentation hardness of the functional film is 1000N/mm 2 As described above, it can be judged to be good.
Fig. 4 is a graph showing the relationship between the ratio (α) of silicate oligomer in the functional film and the indentation hardness for each optical member.
TABLE 2
As shown in table 2 and fig. 4, the ratio (α) of silicate oligomer in the functional films of the optical members of examples 1 to 4 was 3.5 mol% or more and 28.0 mol% or less. The functional films of the optical members of examples 1 to 4 were excellent in hardness. On the other hand, the proportion (α) of silicate oligomer in the functional film of the optical member of comparative example 1 was less than 3.5 mol%. The functional film of the optical member of comparative example 1 was not good in hardness. The ratio (α) of silicate oligomer in the functional films of the optical members of comparative examples 2 and 3 was more than 28.0 mol%. The functional films of the optical members of comparative examples 2 and 3 were excellent in hardness, but as described above, it was judged that the contact angles of the functional films were not excellent.
From the above results, it was found that when the proportion (α) of silicate oligomer in the functional film of the optical member was 3.5 mol% or more, both the hydrophilicity and hardness of the functional film were good.
< evaluation of gel fraction of adhesive >
The relation between the ratio (α) of silicate oligomer in the binder raw material and the hardening rate of the binder raw material was studied by the following method. First, a sample coating liquid containing a binder raw material (silicate monomer and silicate oligomer) and containing no photocatalyst particles was prepared. As sample coating liquids, 5 sample coating liquids having different ratios (α) of silicate oligomers were prepared. The formation of a sample film was performed using each sample coating liquid, and the gel fraction of the adhesive of the formed sample film was measured. Here, it can be determined that the higher the hardening speed of the adhesive raw material contained in the sample coating liquid, the higher the gel fraction of the adhesive of the formed sample film. Therefore, the gel fraction of the adhesive of the sample film is set as an index for estimating the curing rate of the adhesive raw material contained in the sample coating liquid. Then, how the curing rate (gel fraction) of the binder raw material changes when the ratio (α) of the silicate oligomer in the binder raw material is increased or decreased was examined. In this study, the adhesive raw material was cured under mild conditions for the purpose of easily estimating the curing rate of the adhesive raw material. The results are shown in table 3 below.
First, an ethyl silicate monomer (tetraethyl orthosilicate (TEOS) manufactured by Multimole chemical industry Co., ltd., "purity: 99.9 mass% or more) and water were mixed so as to have the following composition, to prepare a 1' coating liquid. The 1 st coating liquid contains a silicate monomer and a solvent (water) (solid content: 0.45 mass%).
Then, the 1 st coating liquid and the 2 nd coating liquid were prepared in the proportions shown in table 3 below, thereby preparing sample coating liquids a to E.
Then, the sample coating liquids a to E to be evaluated were coated on the glass substrate after the plasma treatment by spin coating. A spin coater (MS-B100 manufactured by Mikasa Co., ltd.) was used for the spin coating method. The coating conditions were a spin speed of 8000rpm and a spin time of 30 seconds. After coating, the mixture was allowed to stand at room temperature (23 ℃) for 130 hours. Thereby, a sample film was formed on the glass substrate. The thickness of the sample film was measured using a contact film thickness measuring apparatus ("DekTakXT-S" manufactured by Bruker). The thickness of the sample film was 20nm.
Then, the mass (mass a) of the glass substrate on which the sample film was formed was measured. Then, the value obtained by removing the mass of the glass substrate from the mass a is set as "the mass of the adhesive". Then, the glass substrate on which the sample film was formed was immersed in toluene at 23℃for 24 hours. After the dipping treatment, the glass substrate on which the sample film was formed was sufficiently washed and dried, and then the mass (mass B) thereof was measured. Then, the value obtained by removing the mass of the glass substrate from the mass B is set as "the mass of the gel component". The gel fraction of the adhesive was determined based on the following formula.
Gel fraction [ mass% ] = 100 x mass of gel component [ g ]/mass of binder [ g ]
Fig. 5 is a graph showing the relationship between the ratio (α) of silicate oligomer and the gel fraction for each sample film.
TABLE 3
As shown in table 3 and fig. 5, the gel fraction increases as the ratio (α) of silicate oligomer increases in the formation of the sample film. In particular, when the proportion (α) of the silicate oligomer is increased from 0.0% by mass to 3.9% by mass, the gel fraction increases sharply. From the above, it was found that the curing rate of the binder raw material can be improved by setting the ratio (α) of the silicate oligomer to 3.5 mass% or more. In addition, in the coating liquid for forming a functional film containing the photocatalyst particles, it can be judged that the curing rate of the binder raw material can be increased by setting the ratio (α) of the silicate oligomer to 3.5 mass% or more, as in the sample coating liquid containing no photocatalyst particles. In examples 1 to 4, the reason why the functional film of the optical member was excellent in hardness was judged to be: the binder raw material of the coating liquid for forming a functional film is efficiently cured.
Further, the sample film is formed by hardening the sample coating liquid under mild conditions. Therefore, the gel fraction of the sample film was relatively low and less than 60 mass%. On the other hand, the functional films of the optical members of each of the examples and comparative examples were formed by hardening the coating liquid for forming the functional film at high temperature. Therefore, it is assumed that the gel fraction of the functional films of the optical members of examples and comparative examples is close to 100 mass%.
< evaluation of scratch resistance of functional film >
The optical members of example 3 and comparative example 1 were manufactured again. Wiping tests were performed on the functional films of the respective optical members. Specifically, the surface of the functional film of each optical member was photographed (photographing magnification: 20 times) by a laser microscope ("OLS 5000", manufactured by Olympus corporation). Then, the surface of the functional film of each optical member was gently rubbed 10 times with a paper wiper ("Kaydry (registered trademark)") manufactured by Critia (CRECIA) Inc., japan. After the wiping test, the surface of the functional film of each optical member was photographed by the laser microscope.
Fig. 6 shows a laser micrograph of the surface of the functional film of each optical member taken in the wiping test. "A1", "A2", "B1" and "B2" of fig. 6 are respectively as follows. In fig. 6, "A1", "A2", "B1" and "B2" are all equal magnification. The "S" of fig. 6 indicates a flaw generated on the surface of the functional film.
A1: comparative example 1 (before wiping test)
A2: comparative example 1 (after wiping test)
B1: example 3 (before wiping test)
B2: example 3 (after wiping test)
As is clear from fig. 6, the optical member of example 3 did not cause scratches on the surface of the functional film even when the wiping test was performed. On the other hand, the optical member of comparative example 1 was scratched on the surface of the functional film by performing the wiping test.
From the above, it can be determined that the scratch resistance of the functional film is improved when the proportion (α) of the silicate oligomer in the functional film of the optical member is 3.5 mol% or more and 28.0 mol% or less.
[ Industrial applicability ]
The present invention is suitable for providing an optical member for a sensor or a camera.
Claims (4)
1. A method for manufacturing an optical member, which comprises a light-transmitting member and a functional film covering the light-transmitting member, and
the method for producing an optical member includes a functional film forming step of forming a functional film by applying a functional film forming coating liquid onto the light-transmitting member,
the coating liquid for forming the functional film contains photocatalyst particles, a binder raw material and a solvent,
the binder stock comprises silicate monomers and silicate oligomers,
the ratio of the mass of the silicate oligomer to the total of the mass of the silicate monomer and the mass of the silicate oligomer is 3.5 mol% or more and 28.0 mol% or less,
the total content of silicate monomers and silicate oligomers in the binder raw material is 80 mass% or more.
2. The method for producing an optical member according to claim 1, wherein the silicate monomer comprises a compound represented by the following general formula (1),
the silicate oligomer comprises a compound represented by the following general formula (2);
Si(OR 1 ) n (OH) (4-n) …(1)
Si m O (m-1) (OR 2 ) (2m+2) …(2)
in the general formula (1), R 1 An organic group having 1 to 8 carbon atoms, n is an integer of 1 to 4,
in the general formula (2), R 2 An alkyl group having 1 to 4 carbon atoms, and m is an integer of 2 to 6.
3. The method for producing an optical member according to claim 1 or 2, wherein the silicate monomer has a molecular weight of 120 or more and 210 or less,
the molecular weight of the silicate oligomer is 200 to 1000.
4. An optical member formed by the method for manufacturing an optical member according to any one of claims 1 to 3.
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| CN101276004A (en) * | 2007-03-29 | 2008-10-01 | 富士胶片株式会社 | Protective film, polarizing plate, and liquid crystal display device |
| JP2012185352A (en) * | 2011-03-07 | 2012-09-27 | Nof Corp | Display optical filter |
| CN106054532A (en) * | 2015-04-17 | 2016-10-26 | 台湾永光化学工业股份有限公司 | Negative photosensitive polysiloxane composition |
| CN109337106A (en) * | 2018-08-27 | 2019-02-15 | 明基材料有限公司 | Hard conating optical film, polarizer and image display |
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| JP2610155B2 (en) * | 1987-10-24 | 1997-05-14 | 伊藤光学工業株式会社 | Anti-reflection treatment liquid, anti-reflection treatment method, and anti-reflection treatment optical component for optical parts |
| JP3027675B2 (en) * | 1993-09-21 | 2000-04-04 | ホーヤ株式会社 | Optical member having cured coating |
| EP1535731A4 (en) * | 2002-07-24 | 2005-11-02 | Tdk Corp | Functional film for transfer having functional layer, object furnished with functional layer and process for producing the same |
| JP2008150457A (en) * | 2006-12-15 | 2008-07-03 | Nicca Chemical Co Ltd | Wiping up type hydrophilization treatment agent, method for forming hydrophilic protective membrane and hydrophilic protective membrane |
| WO2008143186A1 (en) * | 2007-05-18 | 2008-11-27 | Nissan Chemical Industries, Ltd. | Coating solution for formation of low refractive index coating film, method for production of the same, and anti-reflection material |
| JP5761346B2 (en) * | 2011-06-29 | 2015-08-12 | 信越化学工業株式会社 | Inorganic hydrophilic coating liquid, hydrophilic coating obtained therefrom and member using the same |
| JP6099587B2 (en) * | 2014-03-17 | 2017-03-22 | 富士フイルム株式会社 | Aqueous coating agent, film, film production method, laminate, and solar cell module |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101276004A (en) * | 2007-03-29 | 2008-10-01 | 富士胶片株式会社 | Protective film, polarizing plate, and liquid crystal display device |
| JP2012185352A (en) * | 2011-03-07 | 2012-09-27 | Nof Corp | Display optical filter |
| CN106054532A (en) * | 2015-04-17 | 2016-10-26 | 台湾永光化学工业股份有限公司 | Negative photosensitive polysiloxane composition |
| CN109337106A (en) * | 2018-08-27 | 2019-02-15 | 明基材料有限公司 | Hard conating optical film, polarizer and image display |
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