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WO2016136041A1 - Film hydrophile et son procédé de fabrication, stratifié, matériau de protection pour caméra de surveillance et caméra de surveillance - Google Patents

Film hydrophile et son procédé de fabrication, stratifié, matériau de protection pour caméra de surveillance et caméra de surveillance Download PDF

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Publication number
WO2016136041A1
WO2016136041A1 PCT/JP2015/081384 JP2015081384W WO2016136041A1 WO 2016136041 A1 WO2016136041 A1 WO 2016136041A1 JP 2015081384 W JP2015081384 W JP 2015081384W WO 2016136041 A1 WO2016136041 A1 WO 2016136041A1
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WIPO (PCT)
Prior art keywords
hydrophilic film
coating
hydrophilic
surveillance camera
siloxane
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English (en)
Japanese (ja)
Inventor
優介 畠中
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin

Definitions

  • the present invention relates to a hydrophilic film, a manufacturing method thereof, a laminate, a protective material for a surveillance camera, and a surveillance camera.
  • Equipment or building materials that are installed indoors or outdoors and used for a long period of time are used by being exposed to various environments, so that dust, dust, gravel, etc. gradually accumulate or get wet in rainwater during wind and rain. Equally, planned functions and performance may be impaired.
  • surveillance cameras are widely used for crime prevention in homes or as security systems for commercial buildings or outdoors.
  • surveillance cameras are stationary devices that include an imaging device such as a charge coupled device (CCD) camera and a protective cover, and are typically used for a long period of time once installed.
  • the protective cover plays a role of protecting the imaging device from rainwater, gravel, or the like while having light transmittance that enables photographing.
  • the protective cover of the surveillance camera is required to be maintenance-free that does not require cleaning over a long period of time in order to always capture a stable image while protecting the imaging device.
  • devices that are generally installed outdoors, such as surveillance cameras tend to lose light transmittance gradually as water drops, dust, dust, or sand adhere to the surface of the device with long-term use. It is in.
  • dust, dust, sand, etc. are likely to accumulate on the surface of the protective cover, and depending on the size or amount of the deposit, there is a concern that not only the light transmission will be significantly reduced, but also that the expected image cannot be recorded. Arise. Therefore, a technique for preventing adhesion of water, dust, dust, sand, or the like to the surface of the device exposed to the outdoor environment has been studied.
  • building materials such as garage roofs for cars or bicycles, soundproof walls for roads, etc. are also used outdoors. It is the same.
  • the water contact angle is 5 to 30 degrees
  • the centerline average roughness Ra of the surface is 0.01 to 0.06 ⁇ m
  • the main component There is disclosed a camera cover having a hydrophilic coat of an inorganic material made of silicone on the outer surface of a resin substrate. This camera cover is supposed to prevent water droplets and dirt from adhering to ensure the sharpness of the image.
  • JP 2013-203774 A discloses an antifogging and antifouling agent for organic substrates containing an organosilica sol, an organic solvent, and boric acid.
  • This anti-fogging and antifouling agent for organic substrates is said to impart an inorganic cured coating film having high hydrophilicity, hardness, adhesion strength to the organic substrate and water resistance and excellent antifouling and antifogging performance.
  • JP 2006-52352 A discloses a hydrolyzate of tetraalkoxysilane and / or a condensate thereof, a metal compound capable of interacting with a silanol group, an alkylene oxide unit, and an HLB (Hydrophile).
  • An aqueous hydrophilization treatment agent comprising a nonionic surfactant having a Lipophile Balance) of 10 to 15, acidic colloidal silica, and a hydrophilic organic solvent is disclosed.
  • 2000-212511 discloses a hydrophilic film provided with a cured coating of a hydrophilic inorganic paint containing a silane-modified surfactant having a terminal reactive group in an inorganic paint mainly composed of a silicone resin.
  • a painted product is disclosed.
  • One embodiment of the present invention has been made in view of the above situation, and provides a hydrophilic film excellent in scratch resistance and hydrophilicity, a method for manufacturing the same, a laminate, a protective material for a surveillance camera, and a surveillance camera.
  • the purpose is to achieve this purpose.
  • ⁇ 1> A hydrophilic film containing a siloxane binder and silica particles, wherein the surface area difference ⁇ S and the surface roughness Ra on the surface satisfy the relationship of the following formula 1.
  • ⁇ S [(S X ⁇ S 0 ) / S 0 ] ⁇ 100 Equation 2
  • S 0 represents the projected area viewed from the perpendicular direction of the hydrophilic film
  • S X represents the actual surface area of the surface of the hydrophilic film in the projected area represented by S 0 .
  • ⁇ 2> The hydrophilic film according to ⁇ 1>, wherein the surface roughness Ra is 100 nm or less.
  • ⁇ 3> The hydrophilic film according to ⁇ 1> or ⁇ 2>, wherein the surface roughness Ra is 10 nm or less.
  • ⁇ 4> The hydrophilic film according to any one of ⁇ 1> to ⁇ 3>, wherein the surface area difference ⁇ S is 0.1% or more.
  • ⁇ 5> The hydrophilic film according to any one of ⁇ 1> to ⁇ 4>, further containing an antistatic agent.
  • ⁇ 6> The hydrophilic film according to ⁇ 5>, wherein at least one of the antistatic agents is an ionic surfactant.
  • R 1 , R 2 , R 3 , and R 4 each independently represent a monovalent organic group having 1 to 6 carbon atoms.
  • n represents an integer of 2 to 20.
  • hydrophilic film according to any one of ⁇ 1> to ⁇ 9>, wherein an average primary particle diameter of the silica particles is 2 nm to 100 nm.
  • Equation 1 ⁇ S is a percentage obtained by Equation 2 below.
  • ⁇ S [(S X ⁇ S 0 ) / S 0 ] ⁇ 100 Equation 2
  • S 0 represents the projected area viewed from the perpendicular direction of the hydrophilic film
  • S X represents the actual surface area of the surface of the hydrophilic film in the projected area represented by S 0 .
  • hydrophilic film according to ⁇ 11> further comprising a preparation step of preparing a coating liquid by mixing water, a siloxane oligomer, and silica particles having an average primary particle diameter of 2 nm to 100 nm.
  • Production method. ⁇ 13> The method for producing a hydrophilic film according to ⁇ 12>, wherein the preparation step further comprises preparing a coating solution by mixing a catalyst that promotes a condensation reaction of the siloxane oligomer.
  • ⁇ 14> A laminate having a base material and the hydrophilic film according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 15> A surveillance camera protective material comprising the laminate according to ⁇ 14>.
  • ⁇ 16> The surveillance camera protective material according to ⁇ 15>, wherein the base material in the laminate has a hemispherical shape, a semi-ellipsoidal shape, a planar shape, a prismatic shape, or a cylindrical shape.
  • ⁇ 18> A surveillance camera comprising the surveillance camera protective material according to any one of ⁇ 15> to ⁇ 17>.
  • a hydrophilic film excellent in scratch resistance and hydrophilicity a method for producing the same, a laminate, a protective material for a surveillance camera, and a surveillance camera are provided.
  • a numerical range indicated by using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the hydrophilic film contains a siloxane binder and silica particles, and the surface area difference ⁇ S and the surface roughness Ra on the surface satisfy the relationship of the following formula 1.
  • ⁇ S 0.5Ra Formula 1
  • ⁇ S is a percentage obtained by Equation 2 below.
  • ⁇ S [(S X ⁇ S 0 ) / S 0 ] ⁇ 100 Equation 2
  • S 0 represents the projected area viewed from the perpendicular direction of the hydrophilic film
  • S X represents the actual surface area of the surface of the hydrophilic film in the projected area represented by S 0 .
  • the unit of S 0 and S X may be the same unit (for example, ⁇ m).
  • a hydrophilic membrane refers to a membrane having a water contact angle of 40 ° or less.
  • the water contact angle is a value obtained by measuring 5 times by using a contact angle meter M553G-XM (manufactured by Shiro Sangyo Co., Ltd.) by dropping 1 ⁇ l of pure water on the surface of the hydrophilic membrane and calculating by the ⁇ / 2 method. Arithmetic mean value.
  • the surface roughness Ra is a value measured according to JIS B0601: 2001 using an atomic force microscope (AFM).
  • S X is a value measured by an atomic force microscope (AFM).
  • the surface area difference ⁇ S of the hydrophilic film is expressed by the above formula 2.
  • the surface area difference ⁇ S indicates that the closer the numerical value approaches 0%, the smaller the difference between the numerical values of S X and S 0 . That is, as ⁇ S approaches 0%, the surface of the hydrophilic film becomes flat with less unevenness.
  • the actual surface area represented by S X refers to the total area along the concavo-convex surface measured by an atomic force microscope (AFM).
  • the projected area represented by S 0 refers to an apparent area in the two-dimensional direction of the xy axis that is projected from the perpendicular direction of the hydrophilic film and ignores irregularities on the surface of the hydrophilic film.
  • the value of the measurement range (projected area viewed from the perpendicular direction of the hydrophilic film) on the xy axis when measuring S X can be used as S 0 .
  • the surface area difference ⁇ S can be adjusted to a predetermined range depending on the average primary particle diameter of the silica particles, the ratio of the silica particles to the siloxane binder, and the drying conditions (specifically, drying temperature and drying time) at the time of film formation. .
  • the surface area difference ⁇ S is preferably 0.1% or more.
  • the state where the surface area difference ⁇ S is 0.1% or more is a state where a part of the silica particles is exposed on the surface of the hydrophilic film. When the surface of the film is in this state, the hydrophilicity and scratch resistance of the silica particles can be effectively expressed.
  • the surface area difference ⁇ S is more preferably 0.1% or more and 50% or less, and further preferably 0.1% or more and 5% or less from the same point as described above.
  • the surface roughness Ra can be measured according to JIS B0601: 2001 using an atomic force microscope (AFM) (manufactured by Seiko Instruments Inc., SPA-400).
  • AFM atomic force microscope
  • the surface roughness Ra is preferably 100 nm or less, and more preferably 10 nm or less, from the viewpoint of scratch resistance.
  • the film has excellent scratch resistance and hydrophilicity.
  • the surface area difference ⁇ S and the surface roughness Ra satisfy the relationship of Formula 1, the film has excellent scratch resistance and hydrophilicity.
  • the surface area difference ⁇ S is 5% or less. That is, in the case of the surfaces having the same surface roughness, it is shown that the one with less unevenness is more effective for achieving both scratch resistance and hydrophilicity.
  • the water contact angle of the hydrophilic film is preferably 30 ° or less, more preferably 25 ° or less, and further preferably 15 ° or less. When the water contact angle is in the above range, the surface of the hydrophilic film is more excellent in hydrophilicity.
  • the water contact angle is as described above.
  • the hydrophilic film can achieve the above effect.
  • the surface area difference ⁇ S and the surface roughness Ra satisfy the relationship of the above formula 1, so that the hydrophilic film has a surface with small unevenness. Therefore, for example, when the surface of the hydrophilic film is rubbed with a contaminant such as gravel attached, the area where the hydrophilic film and the contaminant are in contact with each other is increased, and the stress at the time of contact is dispersed. Further, since the unevenness is small, the accumulation of contaminants can be suppressed.
  • the hydrophilic film is considered to be a film that is difficult to be scratched and soiled (that is, excellent in scratch resistance and antifouling property).
  • the hydrophilic film contains a siloxane binder and silica particles (preferably, the siloxane binder is formed by a condensation reaction of siloxane oligomers), the surface of the silica particles in the formed film has a high density of silanol groups. Exists. Therefore, it is considered that the formed hydrophilic film is excellent in hydrophilicity.
  • the hydrophilicity of a film for example, the larger the numerical value of the surface roughness Ra, the more the hydrophilicity appears (for example, Wenzel's formula), and the smaller the numerical value of the surface roughness Ra (surface). It was thought that the hydrophilicity etc. were inferior so that it became flat. However, it is considered that excellent hydrophilicity can be obtained even if the numerical value of the surface roughness Ra is small, by adopting the above-described configuration for the hydrophilic film of one embodiment of the present invention. From the above, it is considered that the hydrophilic film is excellent in scratch resistance and hydrophilicity.
  • the hydrophilic film contains at least one siloxane binder.
  • the hydrophilic film can hold silica particles, and both scratch resistance and hydrophilicity can be achieved.
  • the siloxane binder preferably contains at least one compound obtained by a condensation reaction of a siloxane oligomer.
  • siloxane oligomer a partial hydrolysis condensate obtained by using one kind of silane compound and a partial cohydrolysis condensate obtained by using two or more kinds of silane compounds can be used.
  • these compounds may be referred to as “partial (co) hydrolysis condensates”.
  • the silane compound is a compound having a hydrolyzable silyl group and / or a silanol group. The silyl group is hydrolyzed to become a silanol group, and the silanol group is dehydrated and condensed to produce a siloxane bond.
  • dimers of the silane compound as described above (1 mol of water was allowed to act on 2 mol of the silane compound to remove 2 mol of alcohol to form disiloxane units.
  • Compound) to 100-mer, preferably dimer to 50-mer, more preferably dimer to 20-mer, and a part (co) of which two or more silane compounds are used as raw materials. It is also possible to use hydrolysis condensates.
  • Such a partial (co) hydrolysis condensate may be a compound commercially available as a silicone alkoxy oligomer (for example, commercially available from Shin-Etsu Chemical Co., Ltd.). Based on the law, a compound produced by reacting hydrolyzable silane compound with less than an equivalent amount of hydrolyzed water and then removing by-products such as alcohol and hydrochloric acid may be used.
  • the siloxane oligomer preferably has an alkoxysilyl group at the molecular end.
  • a tetrafunctional or bifunctional siloxane oligomer can be used, including a tetrafunctional siloxane oligomer having four alkoxysilyl groups in the molecule.
  • tetrafunctional siloxane oligomers are preferable from the viewpoint of the reactivity of the condensation reaction.
  • the hydrophilic film preferably contains at least one siloxane binder formed from the compound represented by the general formula (1).
  • membrane can improve the hydrophilic property of a surface more by including the siloxane binder formed from the compound represented by General formula (1).
  • R 1 , R 2 , R 3 , and R 4 each independently represent a monovalent organic group having 1 to 6 carbon atoms.
  • n represents an integer of 2 to 20.
  • the monovalent organic group having 1 to 6 carbon atoms in R 1 , R 2 , R 3 and R 4 may be linear, branched or cyclic. .
  • Examples of the monovalent organic group include an alkyl group and an alkenyl group, and an alkyl group is preferable.
  • Examples of the alkyl group when R 1 , R 2 , R 3 , or R 4 represents an alkyl group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n- Examples thereof include a pentyl group, an n-hexyl group, and a cyclohexyl group.
  • R 1 to R 4 are more preferably each independently an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 or 2 carbon atoms. More preferably.
  • N in the general formula (1) is an integer of 2 to 20.
  • n is preferably 3 to 12, and more preferably 5 to 10. When n is 20 or less, the viscosity of the coating solution does not become too high, and a hydrophilic film with high uniformity is formed by coating.
  • n 2 or more
  • the reactivity of the siloxane compound is easily controlled, and for example, a hydrophilic film having excellent surface hydrophilicity is formed by coating.
  • examples of the specific siloxane compound are described by R 1 to R 4 and n in the general formula (1). However, it is not limited to these exemplary compounds.
  • the siloxane oligomer is hydrolyzed at least partially by coexisting with water.
  • a hydrolyzate of a siloxane oligomer is a compound in which at least a part of an alkoxy group bonded to a silicon atom of a siloxane oligomer is substituted with a hydroxy group by a reaction between the siloxane oligomer and water, and a hydroxy group that is a hydrophilic group. Due to the group, for example, a hydrophilic film formed through coating and drying becomes a film having good surface hydrophilicity.
  • the hydrolysis reaction it is not always necessary to react all the alkoxy groups of the siloxane oligomer, but for example, from the viewpoint that the hydrophilicity of the coating film obtained by applying and drying the coating liquid for forming a hydrophilic film becomes better. It is preferable that more alkoxy groups are hydrolyzed.
  • the amount of water required for the hydrolysis is the same molar amount as the alkoxy group of the siloxane oligomer, but it is preferable to carry out the hydrolysis with a large excess of water from the viewpoint of allowing the hydrolysis reaction to proceed efficiently.
  • the siloxane binder contained in the hydrophilic film is obtained by condensing at least a part of the hydroxy groups of the hydrolyzate of the siloxane oligomer and condensing the siloxane oligomer.
  • the hydrophilic film may contain only one type of siloxane binder or two or more types.
  • the weight average molecular weight of the siloxane oligomer is preferably in the range of 300 to 1500, more preferably in the range of 500 to 1200.
  • the weight average molecular weight can be measured by gel permeation chromatography (GPC). Specifically, HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation) is used, TSKgel, SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID ⁇ 15 cm) are used as columns, and tetrahydrofuran is used as an eluent. It can be measured using (THF). The conditions are as follows: the sample concentration is 0.5 mass%, the flow rate is 0.6 ml / min, the sample injection amount is 10 ⁇ l, the measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. it can.
  • GPC gel permeation chromatography
  • the calibration curves are “polystyrene standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. , “F-4”, “F-40”, “F-128”, and “F-700” prepared from 10 samples can be used.
  • the content of the siloxane binder in the hydrophilic film is preferably 1% by mass to 80% by mass, more preferably 3% by mass to 75% by mass with respect to the total solid content of the hydrophilic film, and 5% by mass to 70%. More preferred is mass%.
  • the content of the siloxane binder is within the above range, the water contact angle on the surface of the hydrophilic film is suppressed to be low, and the film is difficult to get dirty, and even when dirty, the film can be easily removed.
  • silica particles examples include fumed silica and colloidal silica.
  • Fumed silica can be obtained by reacting a compound containing a silicon atom with oxygen and hydrogen in the gas phase.
  • silicon compound used as a raw material examples include silicon halide (for example, silicon chloride).
  • Colloidal silica can be synthesized by a sol-gel method in which a raw material compound is hydrolyzed and condensed.
  • the raw material compound for colloidal silica include alkoxy silicon (for example, tetraethoxysilane) and halogenated silane compound (for example, diphenyldichlorosilane).
  • the shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, a plate shape, a needle shape, a bead shape, or a shape in which two or more of these are combined.
  • spherical as used herein includes not only true spheres but also spheroids and oval shapes.
  • the silica particles preferably have an average primary particle diameter of 100 nm or less, from the viewpoint of easy adjustment to a range in which the surface area difference ⁇ S and the surface roughness Ra of the hydrophilic film satisfy the relationship of the above formula 1, and are 50 nm or less. More preferably, it is more preferably 30 nm or less, and particularly preferably 15 nm or less. Moreover, the minimum of the average primary particle diameter of a silica particle is although it does not specifically limit, 2 nm or more is preferable from a viewpoint similar to the above. Silica particles having different sizes or shapes may be mixed.
  • the average primary particle diameter of the silica particles is obtained by observing with a transmission electron microscope, measuring the projected area of the particles for 300 or more particles from the obtained photograph, and determining the equivalent circle diameter from the projected area.
  • the shape of a silica particle is not spherical, it calculates
  • the content of silica particles is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and still more preferably 20% by mass to 85% by mass with respect to the total solid content of the hydrophilic film. .
  • a hydrophilic film having hydrophilicity can be formed while being excellent in hardness, scratch resistance, and impact resistance.
  • content of a silica particle is the range of a fixed ratio with respect to content of the above-mentioned siloxane binder. That is, the ratio of the silica particles to the siloxane binder in the hydrophilic film is preferably 0.1 to 1.8, more preferably 0.1 to 1.5, more preferably 0.1 More preferably, it is -1.2.
  • the ratio of the silica particles to the siloxane binder is in the above range, the relationship between the surface area difference ⁇ S of the hydrophilic film and the surface roughness Ra can be easily adjusted to a range satisfying the above formula 1.
  • the hydrophilic film may contain an antistatic agent, a surfactant, a catalyst for promoting the condensation reaction of the siloxane oligomer, and other components.
  • the hydrophilic film preferably contains at least one antistatic agent.
  • an antistatic agent By containing an antistatic agent, antistatic properties are imparted to the hydrophilic film.
  • the antistatic agent together with a siloxane binder and silica particles, the effect of preventing adhesion to contaminants is great, and the antifouling property is dramatically improved. improves.
  • the antistatic agent can be appropriately selected from compounds having an antistatic function, and may be either a compound showing surface activity or a compound not showing surface activity.
  • examples of the antistatic agent include ionic surfactants and metal oxide particles. Since an ionic surfactant has a property of easily segregating in the vicinity of the film surface of a coating film when a hydrophilic film is formed by coating, for example, the effect can be expected with a small amount of addition.
  • metal oxide particles may be required to be added in a relatively large amount in order to impart antistatic properties to the hydrophilic film, but are suitable for enhancing the scratch resistance of the hydrophilic film because it is an inorganic substance. ing.
  • ionic surfactants include alkyl sulfates (eg, sodium dodecyl sulfate, sodium lauryl sulfate, etc.), alkyl benzene sulfonates (eg, sodium dodecyl benzene sulfonate, sodium lauryl benzene sulfonate, etc.), alkyl sulfosuccinates.
  • an ionic surfactant exhibits an antifouling function against pollutants
  • one embodiment of the present invention is based on such knowledge, and an ionic surfactant is used as an antistatic agent in a hydrophilic film. It is a preferable aspect to contain the surfactant. By including an ionic surfactant, the antifouling property and water washability of the hydrophilic membrane are further enhanced.
  • the metal oxide particles may be used by mixing particles having different sizes, shapes, or materials.
  • the shape of the particles is not particularly limited, and may be spherical, plate-shaped, or needle-shaped.
  • the average primary particle size is preferably 100 nm or less, and preferably 50 nm or less. More preferably, it is more preferably 30 nm or less.
  • the content of the ionic surfactant is preferably 50% by mass or less, more preferably 20% by mass or less, based on the total solid content of the hydrophilic film. Preferably, 10 mass% or less is more preferable.
  • the content of the ionic surfactant is within the above range, the antifouling property of the hydrophilic film can be enhanced while suppressing aggregation of the silica particles.
  • content of an ionic surfactant is 0.05 mass% or more from a viewpoint of the antifouling property improvement effect of a hydrophilic film
  • the content of metal oxide particles is preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass with respect to the total solid content of the hydrophilic film. % Or less is more preferable.
  • the content of the metal oxide particles is within the above range, the antistatic property can be effectively imparted without impairing the film formability when the hydrophilic film is formed by coating.
  • it is preferable that content of a metal oxide particle is 1 mass% or more from a viewpoint of the antifouling property improvement effect of a hydrophilic film
  • the hydrophilic film further contains a surfactant.
  • the surfactant is contained together with the siloxane binder and the silica particles, thereby exhibiting the ability to prevent the adhesion of contaminants (particularly gravel, etc.) and excellent antifouling properties.
  • the surfactant here does not include the compound having an antistatic function (for example, an ionic surfactant) mentioned as the above-mentioned antistatic agent.
  • the hydrophilic film contains a surfactant, not only the antifouling property of the hydrophilic film is increased, but also the coating property when the hydrophilic film is formed by coating, for example, can be improved.
  • the surface tension of the coating film also decreases, and the uniformity of the coating film is further improved.
  • the surfactant examples include nonionic surfactants.
  • an ionic surfactant When an ionic surfactant is used as the aforementioned antistatic agent, if the ionic surfactant is excessively added to the film as described above, the electrolytic mass in the system increases and silica particles are aggregated. Since it is easy to invite, it is preferable to use a nonionic surfactant together.
  • the nonionic surfactant does not necessarily need to be used in combination with the ionic surfactant, and may contain a nonionic surfactant alone as the surfactant.
  • nonionic surfactant examples include polyalkylene glycol monoalkyl ether, polyalkylene glycol monoalkyl ester, polyalkylene glycol monoalkyl ester / monoalkyl ether, and the like.
  • specific examples of the nonionic surfactant include polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, and polyethylene glycol monostearyl ester.
  • the content of the surfactant in the hydrophilic film is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more based on the total solid content of the hydrophilic film. Moreover, 50.0 mass% or less is preferable with respect to the total solid of a hydrophilic film
  • content of the surfactant is 30.0% by mass or less, the phenomenon that the surfactant is segregated on the film surface is suppressed, which is advantageous in that the hardness of the film is maintained well.
  • condensation promotion catalyst there is no restriction
  • an acid catalyst, an alkali catalyst, and an organometallic catalyst are mentioned.
  • the acid catalyst include nitric acid, hydrochloric acid, sulfuric acid, acetic acid, chloroacetic acid, formic acid, oxalic acid, and toluenesulfonic acid.
  • the alkali catalyst include sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide.
  • organometallic catalysts include aluminum chelate compounds such as aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), and aluminum ethylacetoacetate diisopropylate; zirconium tetrakis (acetylacetonate) And zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate); titanium chelate compounds such as titanium tetrakis (acetylacetonate) and titanium bis (butoxy) bis (acetylacetonate); and dibutyltin diacetate , Organotin compounds such as dibutyltin dilaurate, and dibutyltin dioctiate.
  • aluminum chelate compounds such as aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), and aluminum ethylacetoacetate diisoprop
  • nitric acid is preferable as the acid catalyst
  • sodium hydroxide is preferable as the alkali catalyst
  • an aluminum chelate compound or a zirconium chelate compound is preferable as the organometallic catalyst.
  • an organometallic catalyst is more preferable, and an aluminum chelate compound is particularly preferable.
  • the content of the condensation accelerating catalyst in the hydrophilic membrane is preferably from 0.1% by mass to 20% by mass, more preferably from 0.2% by mass to 15% by mass, based on the total solid content of the hydrophilic membrane. More preferably, the content is 3% by mass to 10% by mass.
  • the content of the condensation accelerating catalyst is within the above range, it is easy to form a hydrophilic film having scratch resistance. Moreover, it is excellent also in the formation property of a hydrophilic film
  • the hydrophilic film can further contain additives such as a binder component (binder additive component) other than the siloxane binder, if necessary, as other components.
  • a binder component binder additive component
  • binder addition component for example, polyurethane, acrylic resin, polyphosphate, metaphosphate, etc., terminal polar groups (for example, hydroxyl group, carboxy group, phosphate group, sulfonate group, amino group, etc.)
  • the binder additive component in the hydrophilic film, the adhesion between the hydrophilic film and the substrate (particularly, the polycarbonate substrate) is improved.
  • a binder-added component having a hydroxyl group, a carboxy group, or a phosphate group at the terminal is preferable.
  • Polyurethane, acrylic resin, and polyphosphorus Acid salts are more preferred.
  • polyurethane which has a soft segment / hard segment structure comprised by a polyol skeleton and a polyisocyanate skeleton is mentioned.
  • a commercially available polyurethane may be used.
  • acrylic resins include acrylic acid homopolymers (polyacrylic acid), acrylic acid derivatives such as acrylic acid and esters of acrylic acid, and methacrylic acid derivatives such as methyl methacrylate.
  • polyacrylic acid is preferable, polyacrylic acid having a weight average molecular weight of 20 to 5 million is preferable, polyacrylic acid having 10,000 to 2 million is more preferable, and polyacrylic acid having 250,000 to 1 million is preferable. Acid is more preferred.
  • the polyphosphate include sodium polyphosphate and potassium polyphosphate. The weight average molecular weight can be measured by the method described above.
  • the content of the binder additive component in the hydrophilic film is preferably 0.001% by mass to 0.1% by mass and more preferably 0.001% by mass to 0.01% by mass with respect to the total solid content of the hydrophilic film. Preferably, 0.002% by mass to 0.008% by mass is more preferable. When the content of the binder additive component is within the above range, it is easy to form a hydrophilic film having excellent adhesion to the substrate.
  • the hydrophilic film contains silicon and oxygen as main components of the solid content, and has a small carbon content.
  • a hydrophilic film formed by forming a coating film using a hydrophilic film-forming coating solution and drying it can be used in various environments exposed to outdoor wind and rain. Even when placed on the film, the influence of light and heat on the film can be kept to a minimum.
  • the proportion of carbon in the total solid content is preferably 3% by mass or less, more preferably 2.5% by mass or less, and further preferably 2% by mass or less.
  • the organic compound containing carbon is preferably a compound having a low weight average molecular weight.
  • the content of the organic compound having a weight average molecular weight of 1100 or more is preferably 0.2% by mass or less, and 0% by mass with respect to the total solid content of the hydrophilic film. That is, it is more preferable that it is not contained except for inevitable impurities.
  • the content of the organic compound having a weight average molecular weight of 1100 or more is in the above range, the compatibility of the solid content in the hydrophilic film becomes better, and the coating film is formed using the hydrophilic film forming coating solution. The film formability can be further improved.
  • the “organic compound having a weight average molecular weight of 1100 or more” does not include the above-described siloxane binder. Moreover, a weight average molecular weight can be measured by the above-mentioned method.
  • the thickness of the hydrophilic film is preferably in the range of 20 nm to 600 nm, more preferably in the range of 50 nm to 350 nm, and still more preferably in the range of 100 nm to 250 nm.
  • the hydrophilic film is excellent in scratch resistance and hydrophilicity.
  • the hydrophilic film is suitable as a protective material for objects installed outdoors (for example, surveillance cameras, protective materials for protecting lighting, garage roofing materials, protective materials for signs, wall materials).
  • a hydrophilic film By attaching a hydrophilic film, adhesion of contaminants is suppressed.
  • the hydrophilic film has good hydrophilicity, when a contaminant adheres to the surface, it can be easily removed by washing away the contaminant (for example, washing with water). There is also an effect that it is easy to be washed away by rain water or the like during rainy weather.
  • the hydrophilic film is excellent in scratch resistance, it is possible to prevent the film from being damaged when the contaminant is wiped off.
  • the physical properties of the hydrophilic film are listed below.
  • the surface resistance value of the hydrophilic film is preferably 1 ⁇ 10 12 ⁇ / square or less, more preferably 1 ⁇ 10 11 ⁇ / square or less, and 1 ⁇ 10 10 ⁇ / square or less. Is more preferable. When the surface resistance of the hydrophilic film is within the above range, the hydrophilic film has a more excellent antifouling property.
  • the surface resistance value is measured using Hiresta MCP-HT450 (manufactured by Mitsubishi Chemical Analytech).
  • the hydrophilic film is preferably excellent in light transmittance.
  • the integrating sphere transmittance is more preferably 95.5% or more. Integral sphere transmittance of the hydrophilic membrane is determined by measuring the integral sphere transmittance of the base material on which the hydrophilic membrane is not formed and the base material on which the hydrophilic membrane is formed with reference to the white plate of barium sulfate. By subtracting the integrated sphere transmittance of the base material on which the hydrophilic film is not formed from the integrated sphere transmittance of the formed base material, the light transmittance improvement for the base material is calculated. The integrating sphere transmittance is measured using a transmission spectrophotometer with an integrating sphere.
  • the light transmittance improvement is obtained as an average value in the wavelength region of 400 nm to 1400 nm.
  • the transmittance of the hydrophilic membrane was determined by measuring the integrating sphere transmittance of the base material on which the hydrophilic membrane was formed with reference to the integrating sphere transmittance of the base material on which the hydrophilic membrane was not formed.
  • the transmittance is a value measured by a self-recording spectrophotometer (UV2400-PC, manufactured by Shimadzu Corporation).
  • the hydrophilic film is produced by applying a coating liquid containing a siloxane binder and silica particles having an average primary particle diameter of 2 nm or more and 100 nm or less to the substrate, and applying the coating liquid on the substrate by the coating process. And a drying step of drying the coated film at a temperature of 20 ° C. or higher and 150 ° C. or lower. Moreover, it is preferable that the manufacturing method of a hydrophilic film
  • membrane has the preparation process which prepares a coating liquid further.
  • the ratio of the silica particles to the siloxane binder is 0.1 to 1.8 on a mass basis, and the surface area difference ⁇ S and the surface roughness on the surface.
  • Ra satisfies the relationship of the following formula 1.
  • ⁇ S ⁇ 0.5Ra Formula 1 In Equation 1, ⁇ S is a percentage obtained by Equation 2 below.
  • ⁇ S [(S X ⁇ S 0 ) / S 0 ] ⁇ 100 Equation 2
  • S 0 represents the projected area viewed from the perpendicular direction of the hydrophilic film, and S X represents the actual surface area of the surface of the hydrophilic film in the projected area represented by S 0 .
  • membrane has a preparation process which prepares a coating liquid.
  • the coating liquid used in the method for producing the hydrophilic film can be appropriately selected from coating liquids containing a siloxane binder and silica particles having an average primary particle diameter of 2 nm to 100 nm.
  • a coating solution is prepared by mixing water, a siloxane oligomer, and silica particles having an average primary particle size of 2 nm to 100 nm.
  • a preparation process prepares a coating liquid by further mixing the catalyst (condensation promotion catalyst) which accelerates
  • the coating liquid is prepared by bringing a siloxane oligomer into contact with water to prepare a mixed liquid containing a hydrolyzate of the siloxane oligomer, and then adding silica particles having an average primary particle diameter of 2 nm to 100 nm to the mixed liquid.
  • the method of doing is mentioned.
  • the hydrolysis reaction of the siloxane oligomer proceeds even at room temperature (25 ° C.), but in order to promote the reaction, after preparing a mixed solution by bringing the siloxane oligomer into contact with water, the obtained mixed solution is heated at 30 ° C. to 50 ° C. You may heat to about degreeC. A longer reaction time for the hydrolysis reaction is preferred because the reaction proceeds more.
  • the hydrolysis reaction of the siloxane oligomer is a reversible reaction. Therefore, when water is removed from the mixed solution, the hydrolyzate of the siloxane oligomer starts with a condensation reaction between hydroxy groups and proceeds.
  • the addition amount of the siloxane oligomer is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and more preferably 0.5% by mass to 20% by mass with respect to the total mass of the coating solution. % Is more preferable.
  • the amount of silica particles added is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less with respect to the total mass of the coating solution. When the proportion of the silica particles in the coating solution is within the above range, it is advantageous in that the dispersibility of the silica particles in the solution is enhanced and aggregation is prevented.
  • the coating solution may further contain a condensation accelerating catalyst, an antistatic agent, a surfactant, and a binder additive component.
  • the coating solution contains the siloxane oligomer and the condensation accelerating catalyst, the condensation reaction of the siloxane oligomer is promoted and the formation of the siloxane binder is promoted. Thereby, a hydrophilic film
  • the condensation accelerating catalyst is the same as the condensation accelerating catalyst in the hydrophilic membrane described above, and the preferred embodiment is also the same.
  • the amount of the condensation accelerating catalyst added to the coating solution is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 15% by mass, and 0.3% with respect to the total solid content of the coating solution. More preferably, the content is 10% by mass to 10% by mass.
  • the content of the condensation accelerating catalyst is within the above range, a hydrophilic film having scratch resistance is easily formed. Moreover, it is excellent also in the formation property of a hydrophilic film
  • the condensation accelerating catalyst is also useful for hydrolysis of siloxane oligomers.
  • the hydrolysis reaction and condensation reaction of the alkoxy group bonded to silicon of the siloxane oligomer are in an equilibrium relationship. If there is a lot of moisture in the system, the reaction proceeds in the direction of hydrolysis, and if the moisture in the system is low, the reaction Proceeds in the direction of condensation. Since the catalyst for promoting the condensation reaction of the alkoxy group promotes the reaction in both directions, the hydrolysis reaction can be promoted in a state where there is a lot of moisture in the system. The presence of the catalyst allows the hydrolysis of the siloxane oligomer to proceed more reliably under milder conditions.
  • the catalyst used for the hydrolysis reaction of the siloxane oligomer is kept in the system as it is to be used as a component of the coating liquid for forming a hydrophilic film and used as it is as a condensation catalyst for the siloxane oligomer.
  • the coating liquid may contain an antistatic agent. Since the coating liquid contains an antistatic agent, it is possible to form a hydrophilic film imparted with antistatic properties, and the formed hydrophilic film is antifouling because the adhesion of contaminants to the film is suppressed. Will improve.
  • an antistatic agent it is the same as the antistatic agent in the above-mentioned hydrophilic film
  • the content of the ionic surfactant in the coating liquid is preferably 1.0% by mass or less based on the total mass of the coating liquid. More preferably, it is 8 mass% or less, More preferably, it is 0.5 mass% or less.
  • the proportion of the ionic surfactant in the coating solution is within the above range, the antifouling property of the hydrophilic film can be enhanced while suppressing aggregation of the silica particles.
  • the content of the metal oxide particles in the coating solution is preferably 30% by mass or less, and 20% by mass or less with respect to the total mass of the coating solution. More preferably, it is more preferably 10% by mass or less.
  • the ratio of the metal oxide particles in the coating liquid is within the above range, the dispersibility of the metal oxide particles in the liquid is enhanced, which is advantageous in preventing aggregation and the like.
  • the coating solution contains a surfactant
  • the wettability of the coating solution to the substrate is improved.
  • the surfactant is the same as the surfactant in the hydrophilic film described above, and the preferred embodiment is also the same.
  • the content of the surfactant in the coating solution is preferably 0.01% by mass or more, preferably 0.02% by mass or more, and more preferably 0.03% by mass or more with respect to the total mass of the coating solution.
  • content of the surfactant is within the above range, the wettability to the substrate is more excellent.
  • 15 mass% or less is preferable with respect to the total solid of a coating liquid, content of surfactant is 10.0 mass% or less, More preferably, it is 5 mass% or less.
  • the coating liquid may contain a binder additive component.
  • a binder addition component it is the same as the binder addition component in the above-mentioned hydrophilic film
  • the content of the binder additive component in the coating solution is preferably 0.001% by mass to 0.1% by mass, more preferably 0.001% by mass to 0.01% by mass, based on the total solid content of the coating solution. 0.002 mass% to 0.008 mass% is more preferable.
  • an antistatic agent when an antistatic agent, a surfactant and a binder additive component are added, a part or all of them may be added in the step of obtaining a hydrolyzate of a siloxane oligomer.
  • the coating liquid does not contain a photopolymerization initiator and a thermal polymerization initiator.
  • a photopolymerization initiator and a thermal polymerization initiator By not using a photopolymerization initiator and a thermal polymerization initiator, light irradiation or heat treatment can be omitted when forming the hydrophilic film.
  • the conditions for preparing the coating liquid are not particularly limited, but from the viewpoint of suppressing the aggregation of silica particles due to pH and the concentration of coexisting components, the silica particles are preferably added in the latter half of the process of preparing the coating liquid. More preferably, it is added last.
  • the silica particles are used as a dispersion (specifically, a dispersion in which silica particles are previously dispersed in an aqueous solvent, or a commercially available silica particle dispersion)
  • the pH of the dispersion and the solvent used in the coating solution It is preferable to adjust the pH of the dispersion of silica particles and the solvent of the coating solution to the same or close values by making the pH both acidic or basic.
  • membrane has an application
  • coating method which apply
  • the well-known method of spray coating, brush coating, roller coating, bar coating, dip coating (dip coating) can be applied.
  • the coating amount of the coating liquid is not particularly limited, and can be appropriately set in consideration of operability and the like according to the solid content concentration in the coating liquid, the desired film thickness, and the like.
  • the coating amount of the coating solution is preferably 0.1 mL / m 2 to 1000 mL / m 2 , more preferably 0.5 mL / m 2 to 500 mL / m 2 , and 1 mL / m 2 to 200 mL / m 2. 2 is more preferable.
  • the coating amount of the coating liquid is within the above range, the coating accuracy is good and the surface area difference ⁇ S and the surface roughness Ra can be easily adjusted.
  • membrane has a drying process which dries the coating film apply
  • the coating film formed by applying the coating liquid is heated to a temperature of 20 ° C. or more and 150 ° C. and dried, whereby the surface area difference ⁇ S and the surface roughness Ra are expressed by the above formula 1
  • the formed hydrophilic film is excellent in scratch resistance and hydrophilicity.
  • the coating film may be dried using a heating device.
  • the heating device is not particularly limited as long as it can be heated to a target temperature, and any known heating device can be used.
  • As the heating device an oven, an electric furnace, or the like, or a heating device uniquely manufactured according to the production line can be used.
  • the coating film can be dried using, for example, the above-described heating device so that the surface temperature of the coating film is 20 ° C. or higher and 150 ° C. or lower.
  • the drying time can be, for example, a heating time of about 1 minute to 60 minutes.
  • the drying condition of the coating film is preferably a drying condition in which the coating film is heated at a surface temperature of 20 ° C. or higher and 150 ° C. or lower for 1 minute to 60 minutes, and is heated at a surface temperature of 40 ° C. or higher and 150 ° C. or lower for 1 minute to 60 minutes. More preferably, the drying condition is heating for 1 to 30 minutes at a surface temperature of 60 ° C.
  • the drying condition is heating for 1 to 10 minutes at a surface temperature of 90 ° C. to 150 ° C.
  • the drying of the coating film is preferably performed in a short time at a high temperature from the viewpoint of maintaining the surface shape of the coating film.
  • the surface temperature can be measured with an infrared thermometer.
  • the coating film after drying preferably has a film thickness of 20 nm or more. When the film thickness is 20 nm or more, the coating film after drying is more excellent in scratch resistance.
  • the coating film after drying preferably has a thickness of 20 nm to 600 nm, more preferably 50 nm to 350 nm, and particularly preferably 100 nm to 250 nm.
  • the laminate has at least a base material and the hydrophilic film according to one embodiment of the present invention described above. Since the laminate has the hydrophilic film according to the embodiment of the present invention, the laminate is excellent in scratch resistance and hydrophilicity.
  • hydrophilic film membrane in a laminated body is the hydrophilic film
  • Base material There is no restriction
  • Glass is widely used as a substrate, and is suitable as a substrate for forming a laminate.
  • a resin material is also suitable as the base material.
  • a resin material is often used for a base material such as a protective material for a monitoring camera.
  • the resin materials polycarbonate and polymethyl methacrylate are preferable because they are excellent in durability against light and heat.
  • the substrate may be a composite material.
  • any of a composite material including glass and a resin material, in which glass and a resin material are mixed and combined, or a resin composite material in which a plurality of types of resin materials are kneaded or bonded may be used.
  • the thickness of the substrate is not particularly limited and may be appropriately selected depending on the intended use or intended purpose, and may be, for example, 0.05 mm to 10 mm.
  • Laminates are for surveillance cameras, protective materials for protecting lighting (so-called protective covers), roof materials for garages for vehicles such as automobiles and bicycles, protective materials for signs such as road signs, and highway shoulder installations. Or it is used suitably for uses, such as a noise barrier for railroads. Especially, it can apply suitably for the use of the protective material (what is called a camera cover) for the surveillance camera which protects an imaging device.
  • protective material what is called a camera cover
  • the surveillance camera protective material includes at least the laminate according to the embodiment of the present invention. Since the laminate has the hydrophilic film according to one embodiment of the present invention described above, it is excellent in scratch resistance and hydrophilicity. Accordingly, the protective material for a surveillance camera is, for example, an imaging device for a surveillance camera that is easily exposed to a harsh outdoor environment for a long period of time, has excellent light transmission and transparency over a long period of time, and requires long-term durability. It is useful as a protective material for protecting the imaging surface.
  • the shape of the substrate in the laminate As the shape of the substrate in the laminate, a hemispherical shape, a semi-ellipsoidal shape (including a so-called dome shape), a planar shape, a prismatic shape, or a cylindrical shape is preferable.
  • the ellipsoid refers to a shape obtained by extending the ellipse into three dimensions so as to be symmetric with respect to the xy plane, the yz plane, and the zx plane.
  • the diameter of the circle of the opening surface may be in the range of 10 mm to 1000 mm, for example.
  • the same material as the base material in the above-described laminate of one embodiment of the present invention can be used.
  • a resin material is preferable and polycarbonate and polymethyl methacrylate are more preferable from the viewpoint of adhesion to the hydrophilic film of one embodiment of the present invention.
  • the surveillance camera includes the monitoring camera protective material according to the embodiment of the present invention described above for protecting the imaging apparatus. Therefore, the surveillance camera is excellent in scratch resistance and hydrophilicity. Therefore, the surveillance camera is useful as a surveillance camera that is easily exposed to a harsh outdoor environment for a long period of time, maintains excellent light transmission and transparency over a long period of time, and requires long-term durability.
  • one embodiment of the present invention will be described more specifically by way of examples. However, one embodiment of the present invention is not limited to the following examples unless it exceeds the gist thereof.
  • aluminum bis (ethylacetoacetate) mono (acetylacetonate) 0.94 g of a 1% by mass isopropanol solution (catalyst for promoting condensation reaction of siloxane oligomer) was added and mixed.
  • the ratio of silica particles to siloxane binder in the hydrophilic film is 0.5 on a mass basis.
  • a camera cover (laminate) for a surveillance camera which was an acrylic plate having a hydrophilic film, was produced.
  • the laminate on which the hydrophilic film is formed is cut to a size of 1 cm ⁇ 1 cm, set on a horizontal sample stage on a piezo scanner, the cantilever is approached to the sample surface, and the atomic force is reduced. When it reached the working area, it was scanned in the XY directions. During scanning, irregularities on the surface of the hydrophilic film were captured by the displacement of the piezo in the Z direction. The measurement was performed at 512 points ⁇ 512 points in a surface area of 5 ⁇ m ⁇ 5 ⁇ m. Three-dimensional data was obtained from the measured results. Note that the actual surface area that is actually measured by the cantilever and S X, the area of the measurement range (5 ⁇ m ⁇ 5 ⁇ m) was S 0.
  • the relationship between the surface area difference ⁇ S and the surface roughness Ra was determined using the numerical values obtained above. In Table 2, it is represented by ⁇ S / Ra, and satisfies the formula 1 when the value of ⁇ S / Ra is 0.5 or less.
  • B A natural ocher pigment adheres to the surface of the hydrophilic film, and the adhesion area is 10% or less of the total area.
  • C A natural ocher pigment adheres to the surface of the hydrophilic film, and the adhesion area exceeds 10% of the total area and is 50% or less.
  • D Although natural ocher pigment adheres to the surface of the hydrophilic film and the transparency of the hydrophilic film is maintained, the adhesion area exceeds 50% of the total area.
  • E Natural ocher pigment adheres to the entire surface of the hydrophilic film, and part or all of the surface is opaque.
  • Example 2 Comparative Examples 1 to 4 and Comparative Examples 6 to 7
  • a hydrophilic film was prepared in the same manner as in Example 1 except that various components, base materials, and drying conditions were changed as shown in Table 2.
  • a camera cover (laminate) for a surveillance camera was produced in the same manner as in Example 1, and measured and evaluated. The results of measurement and evaluation are shown in Table 2.
  • Example 5 A hydrophilic film was prepared in the same manner as in Example 1 except that EXCELPURE manufactured by China Automotive Industry Co., Ltd. was used as the coating solution. Further, a camera cover (laminate) for a surveillance camera was produced in the same manner as in Example 1, and measured and evaluated. The results of measurement and evaluation are shown in Table 2.
  • Snowtex (registered trademark) OYL average primary particle size: 50 nm to 80 nm, manufactured by Nissan Chemical Industries, Ltd. -Acrylic plate ... Planar shape, plate size: 300 mm x 450 mm, thickness: 1 mm, made by Ebara Kogyo Co., Ltd.-Dome substrate ... Semi-ellipsoidal shape (dome shape), maximum outer diameter: 150 mm, maximum height: 130 mm, thickness: 3mm, polymethylmethacrylate molding member, K camera type made by Sugawara Kogyo Co., Ltd. (transparent)
  • any camera cover for a surveillance camera was colorless and transparent, and exhibited good scratch resistance and hydrophilicity.
  • the surface of the camera cover for the surveillance camera was inferior in both scratch resistance and hydrophilicity.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un film hydrophile qui comporte un liant siloxane et des particules de silice et dont une surface présente une différence de zone de surface ΔS et une rugosité de surface Ra qui satisfont à la relation 1 suivante ; un procédé de fabrication du film hydrophile ; un stratifié ; un matériau de protection pour des caméras de surveillance ; une caméra de surveillance. Relation 1 : ΔS≤0,5 Ra. Dans la relation 1, ΔS représente le pourcentage déterminé par l'équation 2 suivante. Équation 2 : ΔS=[(SX-S0)/S0]×100. Dans l'équation 2, S0 représente la surface projetée du film hydrophile vu dans la direction perpendiculaire, et SX représente la zone de surface réelle du film hydrophile présentant la surface projetée exprimée par S0.
PCT/JP2015/081384 2015-02-27 2015-11-06 Film hydrophile et son procédé de fabrication, stratifié, matériau de protection pour caméra de surveillance et caméra de surveillance Ceased WO2016136041A1 (fr)

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JPWO2018092543A1 (ja) 2016-11-15 2019-10-17 富士フイルム株式会社 積層体及びその製造方法、並びに、防曇コート用組成物
JPWO2018092544A1 (ja) 2016-11-15 2019-10-17 富士フイルム株式会社 積層体
WO2019159974A1 (fr) * 2018-02-14 2019-08-22 富士フイルム株式会社 Stratifié anticondensation et son procédé de fabrication
JP7200233B2 (ja) * 2018-05-11 2023-01-06 富士フイルム株式会社 コート剤、防曇膜、防曇膜の製造方法、及び積層体
JP2020157626A (ja) * 2019-03-27 2020-10-01 キヤノン株式会社 光学部材およびその保護方法
JP7542260B2 (ja) * 2021-05-31 2024-08-30 日本ペイント・サーフケミカルズ株式会社 水性親水化組成物および物品

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JP2006052352A (ja) * 2004-08-13 2006-02-23 Nippon Paint Co Ltd 水性親水化処理剤
WO2015012021A1 (fr) * 2013-07-24 2015-01-29 富士フイルム株式会社 Agent anti-salissure à base d'eau, couche anti-salissure, corps stratifié et module de pile solaire
WO2015141240A1 (fr) * 2014-03-17 2015-09-24 富士フイルム株式会社 Agent de revêtement aqueux, film, procédé de production d'un film, stratifié, et module de cellule photovoltaïque

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JPH1161042A (ja) * 1997-08-08 1999-03-05 Matsushita Electric Works Ltd 高親水性無機塗料、それを用いた塗装品およびそれらの用途
JP2006052352A (ja) * 2004-08-13 2006-02-23 Nippon Paint Co Ltd 水性親水化処理剤
WO2015012021A1 (fr) * 2013-07-24 2015-01-29 富士フイルム株式会社 Agent anti-salissure à base d'eau, couche anti-salissure, corps stratifié et module de pile solaire
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