WO2022260143A1 - セキュリティカメラ用防曇膜付きガラス物品、セキュリティカメラ、及びセキュリティカメラ用防曇膜付きガラス物品の製造方法 - Google Patents

セキュリティカメラ用防曇膜付きガラス物品、セキュリティカメラ、及びセキュリティカメラ用防曇膜付きガラス物品の製造方法 Download PDF

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Publication number
WO2022260143A1
WO2022260143A1 PCT/JP2022/023353 JP2022023353W WO2022260143A1 WO 2022260143 A1 WO2022260143 A1 WO 2022260143A1 JP 2022023353 W JP2022023353 W JP 2022023353W WO 2022260143 A1 WO2022260143 A1 WO 2022260143A1
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WO
WIPO (PCT)
Prior art keywords
film
glass
fogging film
security camera
glass article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/023353
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
清美 林
夕希 寺岡
和晃 大家
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to CN202280041471.XA priority Critical patent/CN117858852A/zh
Priority to EP22820322.0A priority patent/EP4353693A4/en
Priority to US18/568,203 priority patent/US20240280733A1/en
Priority to JP2023527931A priority patent/JPWO2022260143A1/ja
Publication of WO2022260143A1 publication Critical patent/WO2022260143A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0075—Cleaning of glass
    • 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
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/006—Other surface treatment of glass not in the form of fibres or filaments by irradiation by plasma or corona discharge
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B17/00—Details of cameras or camera bodies; Accessories therefor
    • G03B17/02—Bodies
    • G03B17/08—Waterproof bodies or housings
    • G—PHYSICS
    • G08—SIGNALLING
    • G08B—SIGNALLING SYSTEMS, e.g. PERSONAL CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B13/00—Burglar, theft or intruder alarms
    • G08B13/18—Actuation by interference with heat, light, or radiation of shorter wavelength; Actuation by intruding sources of heat, light, or radiation of shorter wavelength
    • G08B13/189—Actuation by interference with heat, light, or radiation of shorter wavelength; Actuation by intruding sources of heat, light, or radiation of shorter wavelength using passive radiation detection systems
    • G08B13/194—Actuation by interference with heat, light, or radiation of shorter wavelength; Actuation by intruding sources of heat, light, or radiation of shorter wavelength using passive radiation detection systems using image scanning and comparing systems
    • G08B13/196—Actuation by interference with heat, light, or radiation of shorter wavelength; Actuation by intruding sources of heat, light, or radiation of shorter wavelength using passive radiation detection systems using image scanning and comparing systems using television cameras
    • G08B13/19617—Surveillance camera constructional details
    • G08B13/19632—Camera support structures, e.g. attachment means, poles
    • 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
    • C03C2217/75—Hydrophilic and oleophilic coatings

Definitions

  • the present invention relates to a glass article with an anti-fog film for security cameras, a security camera, and a method for manufacturing a glass article with an anti-fog film for security cameras.
  • Patent Literature 1 discloses an anti-fogging film containing a polyvinyl acetal resin, which is a water-absorbing resin, and a silica component such as colloidal silica.
  • an object of the present invention is to provide a glass article with an anti-fogging film suitable for use in security cameras.
  • the present invention comprising a glass substrate and an anti-fog coating on the surface of the glass substrate; It was immersed in water at 25° C. for 100 hours and then removed from the water, and the anti-fogging film was exposed for 30 seconds to water vapor generated from water at 90° C. to 100° C. placed at a distance of 60 mm vertically downward from the anti-fogging film.
  • QR code In a test to determine whether information in a QR code placed 110 mm away from the anti-fogging film in the downward direction can be read using a camera from the side opposite to the side on which the anti-fogging film is formed, Can read information of QR code having a size of 40 mm square, Provided is a glass article with an anti-fogging film for security cameras.
  • the QR code encodes the character string "Rank: B" as the information according to the Japanese Industrial Standard (JIS) X 0510: 2018, with a symbol size of 21 ⁇ 21 modules and a level H error correction specification. It is a two-dimensional code.
  • the present invention provides comprising a glass substrate and an anti-fog coating on the surface of the glass substrate;
  • the antifogging film contains an organic polymer having a betaine structure, It is immersed in water at 25° C. for 100 hours and then removed from the water, and the anti-fogging film is exposed for 30 seconds to water vapor generated from water at 90° C. to 100° C. placed at a distance of 60 mm vertically downward from the anti-fogging film.
  • a transparent continuous film is formed on the surface of the antifogging film exposed to the water vapor when the test is performed.
  • a glass article with an anti-fogging film for security cameras are provided.
  • the present invention provides camera and a glass article with an anti-fogging film for a security camera according to the present invention, which is placed in front of the lens of the camera; Provide security cameras.
  • the present invention provides A method for producing a glass article with an anti-fogging film for a security camera, comprising a glass substrate and an anti-fogging film on the surface of the glass substrate, comprising: applying a coating liquid containing an organic polymer having a betaine structure to the surface of a glass substrate; Heating the glass substrate coated with the coating liquid at a temperature of 90 to 190 ° C.
  • a method for manufacturing a glass article with an anti-fogging film for a security camera is provided.
  • a glass article with an anti-fogging film suitable for maintaining the imaging function of a security camera is provided.
  • FIG. 3 is a cross-sectional view showing another example of the glass article with an antifogging film according to the present embodiment.
  • 1 is a schematic diagram showing an example of a security camera according to this embodiment;
  • FIG. 4 is a schematic diagram showing another example of the security camera according to the embodiment;
  • It is a schematic diagram for demonstrating the outline
  • It is another schematic diagram for demonstrating the outline
  • QR code size 15 mm ⁇ 15 mm, recorded information “Rank: SS” used for high-temperature steam evaluation. It is an example of a QR code (size 20 mm ⁇ 20 mm, recorded information “Rank: S”) used for high-temperature steam evaluation. It is an example of a QR code (size 30 mm ⁇ 30 mm, recorded information “Rank: A”) used for high-temperature steam evaluation. It is an example of a QR code (size 40 mm ⁇ 40 mm, recorded information “Rank: B”) used for high-temperature steam evaluation.
  • the term "main component” means the component with the highest content.
  • the “principal surface” of a plate-like article means two surfaces facing opposite sides separated by a predetermined distance called thickness.
  • an inorganic component typically a silica component such as colloidal silica
  • a silica component such as colloidal silica
  • a water-absorbent polymer to compensate for a decrease in abrasion resistance.
  • a glass article with an anti-fogging film that achieves both anti-fogging properties and high wear resistance is suitable for use as window glass for automobiles.
  • glass articles used with security cameras do not require high levels of abrasion resistance. It is appropriate that glass articles with an anti-fog film for security cameras be developed from a different perspective from glass articles with an anti-fog film for automobiles.
  • the anti-fog film does not interfere with the security camera's imaging function even if it is exposed to harsh environments for a long period of time.
  • the glass article with an anti-fogging film according to the present embodiment was obtained by further studies from such a viewpoint, and even if the anti-fogging film is exposed to a severe environment, it transmits light without scattering it at a high level. It can exert the function to make
  • FIG. 1 is a cross-sectional view showing a glass article with an anti-fogging film according to this embodiment.
  • a glass article 1 with an antifogging film includes a plate-like glass substrate 10 , that is, a glass substrate, and an antifogging film 11 formed on the surface of the glass substrate 10 .
  • the anti-fogging film 11 is formed on at least part of the surface of the glass substrate 10 , for example, the main surface of the glass substrate 10 .
  • the antifogging film 11 may be formed on both main surfaces 10a and 10b of the plate-like glass substrate 10, but as shown in FIG. 1, it is formed only on one main surface 10a. may
  • the shape and material of the glass substrate 10 are not particularly limited.
  • the glass substrate 10 is, for example, a glass plate.
  • the glass composition constituting the glass plate is not particularly limited, and may be soda-lime glass, aluminosilicate glass, borosilicate glass, alkali-free glass, or multi-component glass called C glass, E glass, or the like.
  • the multicomponent glass contains SiO2 as a main component, and a group consisting of components other than SiO2 , such as B2O3 , Al2O3 , MgO, CaO, Li2O, Na2O , and K2O . It further contains at least one oxide selected from the above.
  • the glass plate may be made of silica glass.
  • the glass plate may be float glass.
  • Float glass is formed by a so-called float method. Since float glass is formed in a float bath with one main surface in contact with molten tin, tin diffuses to the main surface. Thus, float glass has a tin-diffused surface layer on one major surface, called the bottom surface, and this surface layer is absent on the other major surface, called the top surface. Stated from another point of view, in float glass, the concentration of tin on one major surface is higher than the concentration of tin on the other major surface.
  • the glass plate may be formed by a manufacturing method other than the float method, such as an overflow down-draw method.
  • the major surface 10a may be the top surface, but is preferably the bottom surface. Since the bottom surface has more hydroxyl groups than the top surface, it is suitable as a surface for forming an antifogging film with excellent water resistance.
  • the thickness of the glass plate is, for example, 0.5 to 7.0 mm, and may be 0.5 to 5.0 mm.
  • the thickness of the glass plate which is non-tempered glass, is preferably 3.5 mm or more. However, in the case of tempered glass, if the thickness is 1.8 mm or more, the glass plate can have sufficient impact resistance.
  • the tempered glass may be air-cooled tempered glass or chemically tempered glass.
  • the glass substrate 10 may be in the shape of a flat plate whose main surface is flat. However, the main surface of the glass substrate may be curved.
  • the glass substrate may be obtained by bending a flat glass substrate.
  • the glass base material may be a molded body directly molded from a molten material so as to have a curved surface without passing through a flat glass substrate. An example of such a compact is shown in FIG.
  • the main surfaces of the glass substrate 20 shown in FIG. 2 are both curved surfaces, one main surface 20a being concave and the other main surface 20b being convex.
  • An anti-fogging film 21 is formed on the main surface 20a, which is a concave surface.
  • the main surface 20a faces the lens of a security camera (not shown).
  • the glass substrate 20 has a dome shape, and the interior of the dome shape can be used as a space for housing the lens of the security camera (see FIG. 4). In other words, the glass substrate 20 has a concave surface facing the space that houses the lens of the security camera.
  • a base film may be formed on the main surface of the glass substrate.
  • the base film is interposed between the surface of the glass base material and the anti-fogging film.
  • the base film is not particularly limited, but may be, for example, a barrier film that prevents elution of alkali metals from glass.
  • the barrier film is composed of, for example, a silica film.
  • a film other than the anti-fogging film may be formed on the other main surface.
  • films include antireflection films, water-repellent films, hydrophilic films, colored films, and the like.
  • the film thickness of the antifogging films 11 and 21 is not limited to a specific value, and is 1.0 to 1000 nm, preferably 10 to 500 nm, particularly preferably 30 to 150 nm.
  • the antifogging films 11 and 21 contain, for example, an organic polymer having a betaine structure.
  • a betaine structure has a positive charge and a negative charge at positions that are not adjacent to each other in the same molecule, and a positively charged atom is not directly bonded to a dissociable hydrogen atom.
  • positively charged atoms include a nitrogen atom, a sulfur atom, and a phosphorus atom.
  • An oxygen atom can be exemplified as an atom having a negative charge.
  • the betaine structure may be a polymer of betaine monomers as described below. Although the molecular weight of the organic polymer is not particularly limited, the weight average molecular weight may be 100,000 or more.
  • the organic polymer may have a main chain and a side chain containing a betaine structure.
  • the backbone may comprise a linear carbon chain, eg a linear alkyl group.
  • the organic polymer may have a structure in which multiple side chains are attached to one main chain.
  • the organic polymer may further contain a silicon atom attached to one end of the main chain.
  • the organic polymer may be bonded to the surface of the glass substrate via silicon atoms. This bond can be formed by reaction of silanol groups with hydroxyl groups on the surface of the glass substrate.
  • a backbone chemically bonded to the surface of the glass substrate via silicon atoms can extend upward from the surface of the glass substrate to form a so-called polymer brush.
  • the anti-fogging film can be a monomolecular film composed of an organic polymer whose side chains contain a betaine structure.
  • the organic polymer may be supplied to the surface of the glass substrate, for example, as a compound represented by formula (I) below.
  • R in formula (I) is an organic group containing a betaine structure.
  • R may comprise a polymer of betaine monomers.
  • betaine monomers are sulfoxybetaine monomers, carboxybetaine monomers, and phosphorylbetaine monomers. Each of these betaine monomers may be used alone, or two or more of them may be used in combination.
  • R may include the main chain described above and side chains containing betaine structures.
  • X in formula (I) is a hydroxyl group, a hydrolyzable group, or a halogen atom.
  • hydrolyzable groups include at least one selected from the group consisting of alkoxyl groups, acetoxy groups, alkenyloxy groups, and amino groups.
  • Alkoxyl groups include alkoxyl groups having 1 to 4 carbon atoms, specifically methoxy, ethoxy, propoxy and butoxy groups.
  • the hydrolyzable group is preferably an alkoxyl group, more preferably an alkoxyl group having 1 to 4 carbon atoms.
  • a halogen atom is, for example, chlorine.
  • a sulfoxybetaine monomer is represented, for example, by the following formula (II).
  • R 1 is a (meth)acryloylaminoalkyl group having an alkyl group of 1 to 4 carbon atoms or a (meth)acryloyloxyalkyl group having an alkyl group of 1 to 4 carbon atoms.
  • R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (meth)acryloyl in which the alkyl group has 1 to 4 carbon atoms; It is an oxyalkyl group.
  • R 4 is an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 1 to 4 carbon atoms.
  • a carboxybetaine monomer is represented, for example, by the following formula (III).
  • R 8 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 10 is a (meth)acryloyloxyalkyl group having 1 to 4 carbon atoms in the alkyl group.
  • R 11 is an alkylene group having 1 to 4 carbon atoms.
  • a phosphoryl betaine monomer is represented, for example, by the following formula (IV).
  • R 12 is a (meth)acryloyloxyalkyl group having 1 to 4 carbon atoms in the alkyl group.
  • R 13 is an alkylene group having 1 to 4 carbon atoms.
  • R 14 , R 15 and R 16 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the betaine monomer may have a structure represented by formula (V) below.
  • R 20 may be a (meth)acryloyloxyalkyl group having 11 carbon atoms in the alkyl group.
  • organic polymer having a main chain and multiple side chains a silicon atom bonded to the end of the main chain, and a side chain containing a betaine structure, for example, LAMBIC 771W manufactured by Osaka Organic Chemical Industry Co., Ltd. is used. can.
  • the organic polymer having a betaine structure may be the main component of the antifogging film.
  • the anti-fogging film may appropriately contain ultraviolet absorbers, infrared absorbers, leveling agents (surface conditioners), light stabilizers, and the like. However, these components are desirably added in an amount of 5% by mass or less, more preferably 3% by mass or less, and particularly 1% by mass or less of the antifogging film. Since high abrasion resistance is not required, the antifogging film may or may not contain colloidal silica or other silica fine particles.
  • the content of silica fine particles in the antifogging film may be, for example, 10 to 60% by mass, but may be limited to less than 5% by mass, further less than 3% by mass, and particularly less than 1% by mass.
  • the content of oxide fine particles including silica fine particles may also be at the same level as described above for silica fine particles.
  • the antifogging film may or may not contain oxide fine particles typified by silica fine particles.
  • the antifogging film according to the present embodiment exerts a function of transmitting transmitted light at a high level without scattering even after being placed in a harsh environment for the antifogging film, for example, in contact with water for a long period of time. sell.
  • the anti-fogging film has transparency, water resistance, and hydrophilicity.
  • An anti-fogging film with insufficient water resistance may elute its components when in contact with water for a long period of time.
  • the anti-fogging film is hydrophilic enough to retain water as a continuous film on its surface, transmitted light can be transmitted without excessive scattering.
  • the glass article with an anti-fogging film according to this embodiment can transmit transmitted light without excessive scattering.
  • the anti-fogging coated glass article may have a haze ratio of, for example, 5% or less, further 3% or less, particularly 1% or less, and in some cases 0.4% or less.
  • the haze ratio is specified in JIS K 7136:2018.
  • both water resistance and hydrophilicity can be achieved. These properties can be evaluated by a method called hot steam evaluation, which is described in detail in the Examples section.
  • hot steam evaluation which is described in detail in the Examples section.
  • high-temperature and excessive water vapor is supplied to the anti-fogging film with the anti-fogging film facing vertically downward.
  • a transparent continuous film of water is formed on the surface of the anti-fogging film, which is hydrophilic and excellent in water resistance, in the portion directly exposed to water vapor.
  • Whether or not it is a "transparent continuous film” can be determined by visually confirming that continuity as a film is ensured and that the film is not clouded. Cloudiness of the film can be caused by whitening of the film due to insufficient water resistance or condensation on the film surface due to insufficient anti-fogging properties.
  • On the surface of the film lacking hydrophilicity water is not retained as a continuous film, but is dispersed and deposited as water droplets. A film with insufficient water resistance is observed to be whitened by contact with high-temperature steam, and elution of film components and film defects may occur. Hydrophilicity of a surface is generally evaluated by the contact angle of water.
  • the transparent continuous film may cover 80% or more, or even 90% or more of the surface of the antifogging film exposed to water vapor.
  • the glass article with an antifogging film according to the present embodiment preferably has a QR code "A” having a size of 30 mm square, more preferably a size of 20 mm square, even after being immersed in water at room temperature for 100 hours.
  • QR code "S” having a size more preferably a QR code "SS” having a size of 15 mm square, and particularly preferably a QR code "SSS” having a size of 10 mm square. It can exhibit hydrophilicity.
  • Alkali cleaning is cleaning using an alkaline cleaning liquid.
  • the alkaline cleaning liquid is, for example, an aqueous solution containing a water-soluble alkali metal salt.
  • the cleaning liquid may contain other components such as, for example, a surfactant.
  • Plasma cleaning is cleaning that is exposed to plasma. Plasma cleaning may be cleaning using plasma under a reduced pressure atmosphere or cleaning using atmospheric pressure plasma (AP plasma cleaning). Alkaline cleaning and plasma cleaning may be performed alone or both. In one preferred form, alkaline cleaning and AP plasma cleaning are performed. Thereby, the organic polymer can be more strongly bonded to the surface of the glass substrate.
  • the glass substrate is float glass
  • the surface of the float glass to which the coating liquid is to be applied is the bottom surface
  • at least the bottom surface is subjected to alkali cleaning. Both alkali cleaning and plasma cleaning may be performed on the bottom surface.
  • the surface of the float glass to which the coating liquid is to be applied is the top surface
  • the top surface is subjected to both alkaline cleaning and plasma cleaning.
  • the anti-fogging film can be formed by applying a coating liquid for forming the anti-fogging film onto the surface of a glass substrate and heating the glass substrate on which a coating film has been formed with the coating liquid.
  • a coating liquid for forming the anti-fogging film onto the surface of a glass substrate and heating the glass substrate on which a coating film has been formed with the coating liquid.
  • Conventionally known materials and methods may be used for the solvent used for preparing the coating liquid and the coating method for the coating liquid. Examples of application methods are spin coating, roll coating, spray coating, dip coating, flow coating, screen printing and brush coating.
  • the coating may optionally be dried prior to heating.
  • the heating temperature of the glass substrate on which the coating film is formed is, for example, 90°C or higher, preferably 100°C or higher, and in some cases 120°C or higher.
  • the heating temperature of the coating film is 190° C. or lower, preferably 180° C. or lower, and particularly preferably 160° C. or lower.
  • the heating time is not particularly limited, but may be 5 to 60 minutes, 5 to 45 minutes, 10 to 45 minutes, or 15 to 30 minutes.
  • [Security camera] 3 and 4 show an example of a security camera provided with glass articles 1 and 2 with an anti-fogging film according to this embodiment.
  • Security cameras 51 and 52 shown in FIGS. 3 and 4 comprise cameras 31 and 41, housings 30 and 40 for fixing the cameras, and glass articles 1 and 2 with anti-fogging films.
  • Light entering the lenses of the cameras 31 and 41 from the outside is transmitted through the glass articles 1 and 2 with anti-fogging films.
  • An antifogging film is formed on the side facing the cameras 31 and 41 .
  • ⁇ Anti-fogging evaluation using high-temperature steam As shown in FIG. 5A, a glass article with an anti-fogging film is placed above a stainless steel heat-retaining cup 80 holding boiled water 70 so that the surface on which the anti-fogging film 11 is formed faces the heat-retaining cup 80 side. 1 was held horizontally. The temperature of water 70 was maintained at 90-100° C. while supplying steam. The distance D 1 between the antifogging film and the water surface was 60 mm.
  • the internal space of the heat insulating cup 80 has a cylindrical shape with an opening having a diameter of 64 mm, and the volume of the water 70 is about 130 cc.
  • the antifogging film-attached glass article 1 was held on the heat-retaining cup 80 for 30 seconds, and high-temperature steam was supplied to the antifogging film 11 .
  • the heat retaining cup 80 was removed, and a mount 95 on which a predetermined QR code 90 was printed was placed instead.
  • the distance D 2 between the antifogging film 11 and the mount 95 was set to 110 mm.
  • the QR code 90 was photographed with the camera 100 from above through the glass article 1 with the antifogging film, and it was confirmed whether the information possessed by the QR code 90 could be read.
  • the distance D3 between the glass substrate 10 and the lens 101 of the camera 100 was set to 80 mm.
  • the removal of the heat insulating cup 80 that is, the stoppage of the supply of high-temperature steam to the photographing of the QR code was performed within 30 seconds.
  • QR code SSS 10 mm x 10 mm
  • information "Rank: SSS” Fig. 6A
  • QR code "SS” 15 mm x 15 mm
  • information "Rank: SS” Fig. 6B
  • QR code "S” 20 mm x 20 mm
  • information "Rank: S” Fig. 6C
  • information "Rank: A” Fig. 6D
  • the QR code "SSS” described in FIG. 6A encodes the above character string as information in accordance with JIS X 0510:2018, with a symbol size of 25 ⁇ 25 modules and level H error correction specifications.
  • the QR code "SS” to QR code “B” described in FIGS. 6B to 6E conform to JIS X 0510:2018, and the above characters as information according to the specifications of the symbol size of the 21 ⁇ 21 module and the error correction of level H. Encoded columns.
  • Each character string is composed of half-width characters (1-byte code) instead of full-width characters.
  • the camera used was Sony's smartphone "Xperia XZ2" (model name: SO-03K, OS: Android (registered trademark) (ver.10)).
  • the QR code reading function of the LINE (registered trademark) application (ver.11.7.2) was used to read the QR code.
  • Example 1 Preparation of coating liquid
  • a coating liquid was prepared by mixing 20% by mass of LAMBIC 771W (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 80% by mass of purified water.
  • a float glass (size: 50 mm ⁇ 50 mm, thickness: 1.1 mm) was used as the glass plate, which had been pre-washed by alkaline washing.
  • the coating liquid was applied to the bottom surface of the float glass by a spin coating method (1500 rpm, 10 seconds) to form a coating film.
  • the float glass on which the coating film was formed was heated in an oven at 100° C. for 15 minutes to obtain a glass article with an anti-fogging film.
  • a 25% potassium hydroxide aqueous solution (LBC-1, manufactured by Leybold) was used as a cleaning liquid for the alkali cleaning.
  • Example 2 A glass article with an anti-fogging film according to Example 2 was obtained in the same manner as in Example 1 except for the following points.
  • the float glass was pre-cleaned by alkaline cleaning and then further cleaned by atmospheric pressure plasma cleaning (AP plasma cleaning).
  • AP plasma cleaning a controller CSM-SSC1 (nozzle: CSM-BG, output: 1000 W, processing time: 10 seconds) manufactured by CSM was used.
  • Example 3-6 Glass articles with antifogging films according to Examples 3 to 6 were obtained in the same manner as in Example 1, except that the heating conditions were changed to those shown in Table 1.
  • the film thickness of the antifogging film was measured by SEM.
  • the film thickness of the antifogging films according to Examples 1 to 6 was about 55 nm.
  • Example 7 A glass article with an antifogging film according to Example 7 was obtained in the same manner as in Example 1, except that the conditions in the spin coating method were changed to 300 rpm and 10 seconds. In Example 7, the film thickness of the antifogging film was about 395 nm.
  • Example 8 A glass article with an antifogging film according to Example 8 was obtained in the same manner as in Example 1, except that the coating liquid was dropped onto the glass plate instead of the spin coating method.
  • Example 9 A glass article with an antifogging film according to Example 8 was obtained in the same manner as in Example 2, except that the coating liquid was applied to the top surface of the float glass.
  • Comparative Examples 1 to 5 were carried out in the same manner as in Example 1, except that the cleaning of the float glass, the method of applying the coating liquid, and the heating conditions of the float glass with the coating film formed thereon were changed as shown in Table 2.
  • Example 8 in which the anti-fogging film was formed by dropping, the film thickness was slightly thickened to about 330 nm.
  • the glass article with an anti-fog film according to each example had a high-temperature steam evaluation of "SSS" after the water immersion test (100 hours).
  • SSS high-temperature steam evaluation of "SSS" after the water immersion test (100 hours).
  • the transparent continuous film that received the evaluation "SSS" in each example covered 90% or more of the surface of the antifogging film exposed to water vapor, more specifically, substantially all of the surface. was On the other hand, in Comparative Examples 4 and 5, fogging occurred on the film due to dew condensation, and even the largest QR code could not be read.

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PCT/JP2022/023353 2021-06-11 2022-06-09 セキュリティカメラ用防曇膜付きガラス物品、セキュリティカメラ、及びセキュリティカメラ用防曇膜付きガラス物品の製造方法 Ceased WO2022260143A1 (ja)

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CN202280041471.XA CN117858852A (zh) 2021-06-11 2022-06-09 用于安防照相机的带有防雾膜的玻璃物品、安防照相机及用于安防照相机的带有防雾膜的玻璃物品的制造方法
EP22820322.0A EP4353693A4 (en) 2021-06-11 2022-06-09 GLASS ITEM FOR SECURITY CAMERAS EQUIPPED WITH ANTI-FOG FILM, SECURITY CAMERA AND METHOD FOR MANUFACTURING THE GLASS ITEM FOR SECURITY CAMERAS EQUIPPED WITH ANTI-FOG FILM
US18/568,203 US20240280733A1 (en) 2021-06-11 2022-06-09 Antifog-film-attached glass article for security cameras, security camera, and method for manufacturing antifog-film-attached glass article for security cameras
JP2023527931A JPWO2022260143A1 (https=) 2021-06-11 2022-06-09

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US20240279486A1 (en) * 2021-06-11 2024-08-22 Nippon Sheet Glass Company, Limited Antifog-film-attached transparent article for security cameras and security camera

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