WO2019082768A1 - Agent de revêtement, film antibuée, procédé de production de film antibuée, et stratifié - Google Patents

Agent de revêtement, film antibuée, procédé de production de film antibuée, et stratifié

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Publication number
WO2019082768A1
WO2019082768A1 PCT/JP2018/038694 JP2018038694W WO2019082768A1 WO 2019082768 A1 WO2019082768 A1 WO 2019082768A1 JP 2018038694 W JP2018038694 W JP 2018038694W WO 2019082768 A1 WO2019082768 A1 WO 2019082768A1
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WO
WIPO (PCT)
Prior art keywords
coating agent
boiling point
mass
agent according
antifogging film
Prior art date
Application number
PCT/JP2018/038694
Other languages
English (en)
Japanese (ja)
Inventor
米澤　裕之
優介 畠中
明希 中道
北村　拓也
Original Assignee
富士フイルム株式会社
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 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2019082768A1 publication Critical patent/WO2019082768A1/fr

Links

Classifications

    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • the present disclosure relates to a coating agent, an antifogging film, a method of producing an antifogging film, and a laminate.
  • Japanese Patent No. 4648667 discloses a hydrolyzate of tetraalkoxysilane and / or a condensate thereof, a metal compound capable of interacting with a silanol group, an alkylene oxide unit
  • An aqueous hydrophilization treatment agent comprising a nonionic surfactant having an HLB (Hydrophile Lipophile Balance) of 10 to 15, an acidic colloidal silica, and a hydrophilic organic solvent is disclosed.
  • HLB Hydrophile Balance
  • JP-A-2016-164265 contains a siloxane binder and a silica particle, and the surface area difference ⁇ S on the surface and the surface roughness Ra satisfy the predetermined relationship.
  • a membrane is disclosed.
  • a problem to be solved by an embodiment of the present invention is to provide a coating agent capable of forming an antifogging film having low haze and excellent in antifogging properties and staining resistance.
  • another problem to be solved by another embodiment of the present invention is to provide an antifogging film having a low haze and being excellent in antifogging properties and staining resistance, a method for producing the antifogging film, and a laminate.
  • the haze represents the degree to which the light beam incident on the hydrophilic film is diffused, and indicates the ratio of the diffuse transmittance in the total light transmittance as a percentage.
  • stain resistance refers to suppression of deposition of contaminants in the hydrophilic film and maintenance of antifogging performance.
  • R 1 , R 2 , R 3 and R 4 each independently represent a C 1-6 monovalent organic group.
  • n represents an integer of 1 to 20.
  • ⁇ 2> The coating agent according to ⁇ 1>, further comprising a nonionic surfactant.
  • ⁇ 4> The coating agent according to any one of ⁇ 1> to ⁇ 3>, wherein the average primary particle diameter of the silica particles is 10 nm to 20 nm.
  • ⁇ 5> The coating agent according to any one of ⁇ 1> to ⁇ 4>, wherein the content of the silica particles is 50% by mass or more based on the total solid content of the coating agent.
  • ⁇ 6> The coating agent according to any one of ⁇ 1> to ⁇ 5>, wherein the boiling point of the high boiling point solvent is 140 ° C. or higher.
  • ⁇ 7> The coating agent according to any one of ⁇ 1> to ⁇ 6>, wherein the boiling point of the high boiling point solvent is 150 ° C. or higher.
  • ⁇ 8> The coating agent according to any one of ⁇ 1> to ⁇ 7>, wherein the high boiling point solvent is a glycol ether solvent.
  • ⁇ 9> The coating agent according to any one of ⁇ 1> to ⁇ 8>, wherein the high boiling point solvent is a solvent having a branched alkyl group.
  • ⁇ 10> The coating agent according to any one of ⁇ 1> to ⁇ 9>, wherein the content of the high boiling point solvent is 20% by mass to 40% by mass with respect to the total mass of the coating agent.
  • ⁇ 11> The coating agent according to any one of ⁇ 1> to ⁇ 10>, wherein the content of the resin having an acid group is 30% by mass to 45% by mass with respect to the silica particles.
  • ⁇ 12> The coating agent according to any one of ⁇ 1> to ⁇ 11>, further comprising water.
  • the antifogging film whose haze is 2.0 or less including the condensation product of the hydrolyzate of a compound represented by ⁇ 14> following General formula (1), a silica particle, and resin which has an acidic radical.
  • R 1 , R 2 , R 3 and R 4 each independently represent a C 1-6 monovalent organic group.
  • n represents an integer of 1 to 20.
  • a method of producing an antifogging film comprising:
  • ⁇ 16> A laminate having a base material and an antifogging film formed on the base material and formed of the coating agent according to any one of ⁇ 1> to ⁇ 12>.
  • a substrate and a condensation product of a hydrolyzate of a compound represented by the following general formula (1), provided on the substrate, a silica particle, and a resin having an acid group, A laminate having an antifogging film having a haze of 2.0 or less.
  • R 1 , R 2 , R 3 and R 4 each independently represent a C 1-6 monovalent organic group.
  • n represents an integer of 1 to 20.
  • a coating agent capable of forming an antifogging film having low haze and excellent antifogging properties and stain resistance.
  • an antifogging film having a low haze and excellent antifogging properties and stain resistance, a method for producing the antifogging film, and a laminate are provided.
  • a numerical range indicated by using “to” means a range including numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless there is a particular mention of the plurality of components present in the composition. It means the total amount.
  • the upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
  • the term "solids" in the present disclosure means components excluding solvents, and liquid components such as low molecular weight components other than solvents are also included in the "solids" in the present disclosure.
  • solvent means water, an organic solvent, and a mixed solvent of water and an organic solvent.
  • the Hydrophile-Lipophile Balance value may be described as an HLB value.
  • the coating agent according to the present disclosure includes a hydrolyzate of the compound represented by General Formula (1), silica particles, a high boiling point solvent having a boiling point of 120 ° C. or more, and a resin having an acid group.
  • the compound represented by the general formula (1) is hereinafter also referred to as a specific siloxane compound, and the hydrolyzate of the specific siloxane compound is also referred to as a specific siloxane hydrolyzate.
  • the coating agent containing each of the components described above can form an antifogging film having low haze and excellent antifogging properties and stain resistance. The reason why such an effect is exerted is presumed as follows. However, the coating agent according to the present disclosure is not limited by the following reasons.
  • a coating agent containing silica particles is used.
  • a hydrophilic film is formed by applying a coating agent containing silica particles to a material to be coated and drying the applied coating agent, but uneven aggregation of the silica particles occurs in the drying step from the application step, The formed film may become whitish and haze may increase.
  • the unevenness derived from the uneven aggregation of the silica particles is formed on the surface of the hydrophilic film, the haze is increased due to the surface unevenness.
  • one of the antifogging properties of the hydrophilic film is obtained by the voids formed between the silica particles, but if the void size is not uniform in the hydrophilic film, the incident light is diffused. The haze may increase and the antifogging performance itself may decrease.
  • a void having a large size is locally formed between silica particles in the hydrophilic film, water vapor is absorbed in the big void and becomes cloudy, which may cause the haze to increase.
  • contaminants such as hydrocarbon gas and silicone oil are gradually taken in and accumulated, resulting in antifogging. There is a problem that the performance is degraded.
  • the coating agent according to the present disclosure includes a coating solution containing a silica particle by including a resin having a high boiling point solvent and an acid group together with the hydrolyzate of the compound represented by the general formula (1) and the silica particle.
  • the film-forming behavior in the drying step is controlled, the surface smoothness is high, and a film with almost uniform pore size (that is, an antifogging film) can be formed. Therefore, the formed antifogging film has a low haze and is excellent in antifogging properties and stain resistance.
  • the inclusion of a high boiling point solvent improves the leveling property of the coating film of the coating agent, and enhances the smoothness of the formed film (that is, the antifogging film).
  • the dispersibility of the silica particles is enhanced, and non-uniform aggregation can be suppressed, and the silica particles are adsorbed to the resin having an acid group to be immobilized and be fixed between the silica particles. It is believed that this is due to the uniformity of the void size.
  • the coating agent containing the high boiling point solvent dries slowly, the adsorption of the acid groups and the silica particles in the resin having an acid group in the coating film of the coating agent and the silica particles by the resin having an acid group It is inferred that the immobilization of H.sub.2O.sub.3 is sufficiently facilitated, and the homogenization of the pore size between the silica particles can be enhanced.
  • the coating agent according to the present disclosure includes a specific siloxane hydrolyzate (i.e., a hydrolyzate of a specific siloxane compound).
  • the specific siloxane compound has a structure in which at least a part is hydrolyzed by coexistence with water. Specifically, at least a portion of OR 1 , OR 2 , OR 3 and OR 4 bonded to a silicon atom in the following general formula (1) is substituted with a hydroxy group by reacting a specific siloxane compound with water. Be done.
  • the specific siloxane hydrolyzate refers to a compound in which at least a portion of OR 1 , OR 2 , OR 3 and OR 4 in the general formula (1) is substituted with a hydroxy group.
  • the coating agent contains the specific siloxane hydrolyzate
  • the antifogging film formed by the coating agent has good retention of the silica particles described later, the scratch resistance is enhanced, and the hydroxyl group of the specific siloxane hydrolyzate is As a result, the hydrophilicity is good.
  • the hydrophilicity of the antifogging film is increased, water droplets can be changed to a water film on the surface of the antifogging film, so that the antifogging property is further improved.
  • R 1 , R 2 , R 3 and R 4 each independently represent a C 1-6 monovalent organic group.
  • n represents an integer of 1 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.
  • R 1 , R 2 , R 3 or R 4 represents an alkyl group
  • examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl and n- Examples thereof include pentyl group, n-hexyl group and cyclohexyl group.
  • R 1 to R 4 are each independently more preferably an alkyl group having 1 to 4 carbon atoms, and is an alkyl group having 1 or 2 carbon atoms. It is further preferred that
  • N in the general formula (1) represents an integer of 1 to 20.
  • n 1 or more, the reactivity of the specific siloxane compound can be easily controlled, and, for example, a film having excellent surface hydrophilicity can be formed.
  • n 20 or less, the viscosity of the coating agent does not become too high, and the handling property and the uniform coating property become good.
  • n is preferably 3 to 12, and more preferably 5 to 10, from the viewpoint of facilitating control of the hydrolysis reaction.
  • a commercial item can be used as a specific siloxane compound.
  • Examples of commercially available products of specific siloxane compounds include MKC (registered trademark) Silicate MS 51 (R 1 , R 2 , R 3 and R 4 : methyl group, average of n: 5) of Mitsubishi Chemical Corporation, MKC Trademarks Silicate MS 56 (R 1 , R 2 , R 3 and R 4 : methyl, average of n: 11), MKC® Silicate MS 57 (R 1 , R 2 , R 3 and R 4 : Methyl group, average of n: 13], MKC (registered trademark) silicate MS 56 S [R 1 , R 2 , R 3 , and R 4 : methyl group, average of n: 16], MKC (registered trademark) methyl silicate 53 A [ R 1 , R 2 , R 3 and R 4 : methyl group, average of n: 7], MKC (registered trademark) ethyl silicate 40 [R 1 , R 2
  • the specific siloxane hydrolyzate does not necessarily have to react with all the end groups of the specific siloxane compound (ie, -OR 1 , -OR 2 , -OR 3 or -OR 4 ), for example, it may be caused by a coating agent From the viewpoint of further increasing the hydrophilicity of the formed antifogging film, it is preferable that more terminal groups be hydrolyzed.
  • the weight average molecular weight of the specific siloxane compound is preferably in the range of 300 to 1,500, and more preferably in the range of 500 to 1,200.
  • the weight average molecular weight can be measured by gel permeation chromatography (GPC). Specifically, using HLC-8120GPC, SC-8020 (Tosoh Corp.) and using two columns of TSKgel and SuperHM-H (Tosoh Corp., 6.0 mm ID ⁇ 15 cm) as a column and tetrahydrofuran as an eluent It can be measured using (THF). As conditions, the sample concentration is 0.5% by mass, the flow rate is 0.6 ml / min, the sample injection amount is 10 ⁇ l (microliter), the measurement temperature is 40 ° C., and a differential refractometer (RI) detector is used. Can be done. The calibration curve is available from Tosoh Corp.
  • GPC gel permeation chromatography
  • polystyrene standard sample TSK standard “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 coating agent according to the present disclosure may contain only one type of specific siloxane hydrolyzate, or may contain two or more types.
  • the coating agent according to the present disclosure includes the specific siloxane hydrolyzate.
  • Coating agents according to the present disclosure can include partial co-hydrolysis obtained with two or more silane compounds.
  • the two or more types of silane compounds may be specific siloxane compounds having different structures from each other, and the specific siloxane compounds and the specific siloxane compounds may be a combination of other siloxane compounds having different structures.
  • the hydrolyzate obtained from two or more types of siloxane compounds is also referred to as "(co) hydrolyzate", and the compound obtained by condensing these is also referred to as "condensate of (co) hydrolyzate”.
  • the silane compound refers to a compound having at least one selected from a hydrolyzable silyl group and a silanol group, and the silyl group is hydrolyzed to form a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond Generates.
  • the content of the specific siloxane hydrolyzate in the coating agent is preferably 1% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and more preferably 15% by mass to 35% by mass with respect to the total solid content of the coating agent. % Is more preferred.
  • the content of the specific siloxane hydrolyzate is in the above range, the contact angle of pure water on the surface of the antifogging film formed with the coating agent is suppressed to a low level, and the stain resistance to waterborne stains and stains It becomes easy to remove dirt.
  • the coating agent according to the present disclosure contains silica particles.
  • the silica particles have the function of enhancing the scratch resistance of the hydrophilic film formed by the coating agent and further exhibiting hydrophilicity. That is, the silica particles play a role as a hard filler, and the hydroxyl groups on the particle surface act to contribute to the improvement of the hydrophilicity of the hydrophilic film.
  • 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.
  • a silicon compound used as a raw material a halogenated silicon (for example, silicon chloride) etc. are mentioned, for example.
  • Colloidal silica can be synthesized by a sol-gel method in which a raw material compound is hydrolyzed and condensed.
  • alkoxy silicon for example, tetraethoxysilane
  • a halogenated silane compound for example, diphenyl dichlorosilane
  • 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, and a shape in which two or more of these are combined.
  • spherical as used herein includes not only true spheres but also shapes such as spheroids and ovals.
  • Silica particles are also available as commercial products.
  • Commercially available silica particles include EERONIC's AEROSIL (registered trademark) series, Nissan Chemical's Snowtex (registered trademark) series (such as Snowtex O), and NALCO's NALCO (registered trademark) series (such as NALCO 8699) And the like), Quarton (registered trademark) PL series of Sakai Chemical Industry Co., Ltd. (eg, PL-1), and the like.
  • the average primary particle diameter of the silica particles is preferably 100 nm or less, more preferably 50 nm or less, and preferably 30 nm or less, from the viewpoint that the film properties of the formed hydrophilic film are good and the haze is lowered. Is more preferable, and 20 nm or less is particularly preferable.
  • the lower limit of the average primary particle diameter of the silica particles is not particularly limited, but is preferably 2 nm or more from the viewpoint of handleability, and 10 nm or more from the viewpoint of easy formation of voids for exhibiting antifogging performance. More preferable.
  • the average primary particle size of the silica particles is preferably 10 nm to 20 nm from the viewpoint of the improvement of the antifogging property and the stain resistance.
  • the average primary particle size of the silica particles is determined by the following method. That is, when the shape of the silica particles is spherical or substantially spherical in cross section, the dispersed silica particles are observed with a transmission electron microscope, and the projected area of the particles is measured for 300 or more particles from the obtained photograph. The circle equivalent diameter is determined from the projected area, and the obtained circle equivalent diameter is taken as the average primary particle diameter of the silica particles. If the shape of the silica particles is not spherical or substantially spherical, other methods such as dynamic light scattering are used to determine the average primary particle size of the silica particles.
  • the coating agent according to the present disclosure may contain only one type of silica particles, or may contain two or more types. When two or more types of silica particles are included, particles having different sizes or shapes may be included.
  • the hydrophilicity of the antifogging film formed by the coating agent is good, and the hardness of the antifogging film, the scratch resistance and the like are excellent.
  • 30 mass% or more is preferable, 40 mass% or more is more preferable, 45 mass% or more is more preferable, 50 mass% or more is especially preferable.
  • the upper limit of the content of the silica particles is preferably 85% by mass, and not more than 75% by mass, based on the total solid content of the coating layer, from the viewpoint of maintaining antifogging performance and securing the temporal stability of the coating agent. Is more preferable, and 65% by mass is more preferable.
  • the coating agent according to the present disclosure includes a high boiling point solvent having a boiling point of 120 ° C. or higher (hereinafter, also simply referred to as a high boiling point solvent).
  • a high boiling point solvent having a boiling point of 120 ° C. or higher
  • the boiling point of the high-boiling point solvent is preferably 140 ° C. or higher, and more preferably 150 ° C.
  • the upper limit of the boiling point of the high boiling point solvent is preferably 230 ° C., more preferably 220 ° C., and still more preferably 210 ° C. from the viewpoint of suppressing drying defects of the coated film by the coating agent.
  • Examples of the high boiling point solvent include the following.
  • the numerical value in the parentheses after the high boiling point solvent shown below shows a boiling point.
  • Alcohol solvents such as 1,3-butanediol (207 ° C.), 1,4-butanediol (228 ° C.), benzyl alcohol (205 ° C.), terpionel (217 ° C.);
  • Glycol solvents such as ethylene glycol (197 ° C.), diethylene glycol (244 ° C.), triethylene glycol (287 ° C.), propylene glycol (187 ° C.), dipropylene glycol (230 ° C.); Diethylene glycol monomethyl ether (194 ° C), diethylene glycol monoethyl ether (202 ° C), diethylene glycol monobutyl ether (231 ° C), triethylene glycol monomethyl ether (249 ° C), propylene glycol monomethyl ether (121 ° C), propylene glycol monobutyl ether
  • propylene glycol monomethyl ether propionate 160 ° C.
  • Methyl cellosolve ethylene glycol monomethyl ether, 125 ° C
  • ethyl cellosolve ethylene glycol monoethyl ether 135 ° C
  • butyl cellosolve ethylene glycol monobutyl ether, 171 ° C
  • ethylene glycol mono-tert-butyl ether 153 ° C
  • tripropylene glycol monomethyl ether 243 ° C
  • dipropylene glycol monomethyl ether 188 ° C
  • Glycol ether solvents such as diethylene glycol dimethyl ether (162 ° C.), diethylene glycol ethyl methyl ether (176 ° C.), diethylene glycol isopropyl methyl ether (179 ° C.), triethylene glycol dimethyl ether (216 ° C.); Ester solvents such as ethylene glycol monomethyl ether acetate (145 ° C.), diethylene glycol monoethyl ether acetate (217 ° C.), ethyl acetate (154 ° C.), ethyl lactate (154 ° C.), 3-methoxybutyl acetate (172 ° C.); Ketone solvents such as diacetone alcohol (169 ° C.), cyclohexanone (156 ° C.) and cyclopentanone (131 ° C.); Etc.
  • Ether solvents such as diethylene glycol dimethyl ether (162 ° C.), diethylene glycol ethyl methyl ether
  • the alcohol-based solvent in the present disclosure refers to a solvent having a structure in which one carbon atom of hydrocarbon is substituted by one hydroxy group.
  • the glycol-based solvent in the present disclosure refers to a solvent having a structure in which two or more carbon atoms of a hydrocarbon each have a hydroxy group substituted.
  • the glycol ether solvent in the present disclosure refers to a solvent having a structure having one hydroxy group and at least one ether group in one molecule.
  • the ether-based solvent in the present disclosure refers to a solvent having a structure having at least one ether group without having a hydroxy group or an ester group in one molecule.
  • the ester solvent in the present disclosure refers to a solvent having a structure having at least one ester group in one molecule.
  • the ketone-based solvent in the present disclosure refers to a solvent having a structure having at least one ketone group in one molecule.
  • the high boiling point solvent contained in the coating agent it is preferable to use a glycol ether solvent from the viewpoint of low surface energy and enhanced leveling of the coating film by the coating agent. Further, for the same reason as above, it is preferable to use a solvent having a branched alkyl group as the high boiling point solvent contained in the coating agent.
  • the coating agent according to the present disclosure may contain only one type of high boiling point solvent, or may contain two or more types.
  • a glycol ether solvent as one of them.
  • the glycol ether solvent is preferably used in a range of 10% by mass to 40% by mass, and more preferably in a range of 15% by mass to 30% by mass, based on all high boiling point solvents.
  • a ketone solvent as one of them. By including the ketone solvent, the adhesion between the antifogging film formed by the coating agent and the substrate is improved.
  • the ketone solvent is preferably used in the range of 5% by mass to 40% by mass, and more preferably in the range of 5% by mass to 15% by mass, based on the total high boiling point solvent.
  • the coating agent according to the present disclosure contains two or more high boiling point solvents, it is particularly preferable to include both a glycol ether solvent and a ketone solvent.
  • the ketone-based solvent as the high boiling point solvent is a ketone-based solvent having an SP value (solubility parameter) of 10.0 MPa 1/2 or more from the viewpoint of being able to form an antifogging film having more excellent transparency.
  • SP value solubility parameter
  • the upper limit of the SP value of the ketone-based solvent is not particularly limited, and is, for example, 13.0 MPa 1/2 or less from the viewpoint of coating property to a base material, for example, surface failure such as repelling hardly occurs. Is preferred.
  • high boiling point solvents and the ketone solvents having an SP value of 10.0 MPa 1/2 or more are shown below, but are not limited thereto.
  • the numerical values in parentheses after the following specific examples indicate SP values (unit: MPa 1/2 ). That is, diacetone alcohol (10.2) and cyclopentanone (10.4).
  • the above-mentioned SP value is a value represented by the square root of molecular aggregation energy.
  • F It is a value calculated by the method described in Fedors, Polymer Engineering Science, 14, p147-p154 (1974).
  • 15 mass% or more is preferable with respect to the total mass of a coating agent, and, as for content of the high boiling point solvent in a coating agent, 20 mass% or more is more preferable. Moreover, 60 mass% or less is preferable, as for the upper limit of content of the high boiling point solvent in the coating agent which concerns on this indication, 50 mass% or less is more preferable, and 40 mass% or less is still more preferable.
  • the content of the high boiling point solvent in the coating agent according to the present disclosure is preferably 20% by mass to 40% by mass.
  • the coating agent according to the present disclosure includes a resin having an acid group.
  • the acid group in the resin having an acid group is not particularly limited as long as it has an adsorption ability to silica particles, and examples thereof include a carboxy group, a sulfonic acid group, and a phosphoric acid group.
  • the acid value of the resin having an acid group is preferably 180 mg KOH / g or less, and preferably 100 mg KOH, from the viewpoints of expression of adsorption performance to silica particles, improvement of dispersibility of silica particles, and equalization of void size among silica particles. It is more preferable that it is / g or less.
  • the lower limit of the acid value is not particularly limited, but is preferably 3 mg KOH / g or more.
  • the acid value of the resin having an acid group can be measured by titration of an indicator, and specifically, according to the method described in JIS K 0070, the acid component in 1 g of solid content of the resin having an acid group is neutralized The number of mg of potassium hydroxide to be obtained can be measured and calculated.
  • the weight average molecular weight (Mw) of the resin having an acid group is 1,000 to 200,000, from the viewpoint of expression of adsorption performance to silica particles, improvement of dispersibility of silica particles, uniformization of void size among silica particles, etc. More preferably, it is 1000 to 50000, and still more preferably 5000 to 30000.
  • Resins having an acid group are also commercially available.
  • DISPERBYK (registered trademark) -2015 Acid group: carboxy group, acid value: 10 mgKOH / g) of BIC Chemie Japan KK
  • DISPERBYK (registered trademark)-2010 Acid group: carboxy group, acid value: 20 mg KOH / g
  • DISPERBYK (registered trademark)-194 ((acid group: carboxy group, acid value: 70 mg KOH / g), Toho synthesis ( Aron (registered trademark) A-6012 (acid group: sulfonic acid group, weight average molecular weight: 10000), Aron (registered trademark) A-6001 (acid group: carboxy group, pH: 7 to 9 (aqueous solution concentration)) , Weight average molecular weight: 8000), Aron (registered trademark) SD-10 (
  • the coating agent according to the present disclosure may contain only one type of resin having an acid group, or may contain two or more types.
  • 20 mass% or more is preferable with respect to a silica particle, as for content of resin which has an acidic radical in a coating agent, 25 mass% or more is more preferable, and 30 mass% or more is still more preferable.
  • the upper limit of the content of the resin having an acid group in the coating agent is preferably 60% by mass or less, more preferably 50% by mass or less, and 45% by mass or less based on the silica particles. More preferable.
  • the content of the resin having an acid group in the coating agent is preferably 30% by mass to 45% by mass with respect to the silica particles.
  • content of resin which has an acidic radical in coating agent is 3 with respect to a silica particle. % By mass or more is preferable, 5% by mass or more is more preferable, and 8% by mass or more is more preferable. Moreover, when using together resin which has an acidic radical, and resin which does not have an acidic radical, 25 mass% or less is preferable and the upper limit of content of resin which has an acidic radical in a coating agent is 23 mass% or less More preferably, 20% by mass or less is more preferable.
  • the coating agent according to the present disclosure may contain, in addition to the specific siloxane hydrolyzate, the silica particles, the high boiling point solvent, and the resin having an acid group, other known components as long as the effects of the present disclosure are not impaired. Good. Other components include nonionic surfactants, condensation catalysts that promote the condensation reaction of a specific siloxane hydrolyzate, solvents other than high boiling point solvents, resins having no acid group, additives, etc. It is not limited to the ingredients of
  • the coating agent according to the present disclosure preferably contains a nonionic surfactant.
  • the coating agent according to the present disclosure includes the nonionic surfactant, so that the surface tension of the coating agent is reduced, so that the coating property of the coating agent can be enhanced, and furthermore, the antifogging film formed from the coating agent Surface smoothness can be further enhanced.
  • the antifogging film contains a nonionic surfactant, the adhesion preventing property of the contaminant can be enhanced.
  • the nonionic surfactant is non-ionic, the electrolytic mass in the system does not increase, aggregation of the silica particles can be suppressed, and antifogging can be improved.
  • nonionic surfactants include polyalkylene glycol monoalkyl ethers, polyalkylene glycol monoalkyl esters, and polyalkylene glycol monoalkyl esters / monoalkyl ethers.
  • specific examples of the nonionic surfactant include polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, polyethylene glycol monostearyl ester and the like.
  • the HLB value i.e., hydrophilic-lipophilic balance value
  • the HLB value is 15 or more from the viewpoint of forming an antifogging film which is excellent in hydrophilicity and adhesion preventing property of contaminants. It is preferable to use a large nonionic surfactant (hereinafter, also referred to as a "specific nonionic surfactant").
  • a specific nonionic surfactant e.g, hydrocarbon gas, silicone oil, etc.
  • the hydrophilicity of the formed antifogging film is further improved, and adhesion of a contaminant (eg, hydrocarbon gas, silicone oil, etc.) as a hydrophobic component is achieved. Preventability is good.
  • the HLB value of the specific nonionic surfactant is preferably 15.5 or more, more preferably 16 or more, still more preferably 17 or more, and particularly preferably 18 or more.
  • the upper limit of the HLB value of the specific nonionic surfactant is not particularly limited, and is preferably, for example, 20 or less.
  • the HLB value of the surfactant in the present disclosure is a value which is defined by the following formula (I) according to the Griffin method (all revision new surfactant introduction, p 128) and is obtained by arithmetic.
  • Surfactant HLB value (molecular weight of hydrophilic group portion / surfactant molecular weight) ⁇ 20 (I)
  • nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene aryl ether, polyoxyalkylene alkyl aryl ether, sorbitan derivative, formalin condensate of polyoxyalkylene aryl ether, polyoxyalkylene alkyl Examples include formalin condensates of aryl ethers, polyethylene glycol and the like. Among these, polyoxyalkylene alkyl ethers are particularly preferable as the specific nonionic surfactant.
  • the alkyl group of the polyoxyalkylene alkyl ether in the specific nonionic surfactant includes, for example, a linear alkyl group having 1 to 36 carbon atoms or a branched alkyl group having 3 to 36 carbon atoms.
  • the oxyalkylene moiety of the polyoxyalkylene alkyl ether is preferably polyoxyethylene from the viewpoint of being able to form an antifogging film which is particularly excellent in hydrophilicity.
  • the number of polyoxyethylene structural units possessed by the specific nonionic surfactant is preferably 6 or more, more preferably 10 or more, still more preferably 15 or more, and particularly preferably 20 or more. preferable.
  • the number of polyoxyethylene structural units can be, for example, 100 or less from the viewpoint of solubility.
  • a surfactant represented by the following formula (II) is preferable.
  • m represents an integer of 6 to 100.
  • R represents a linear alkyl group having 1 to 36 carbon atoms or a branched alkyl group having 3 to 36 carbon atoms.
  • a commercial item can be used as a specific nonionic surfactant.
  • specific nonionic surfactants include EMALEX (registered trademark) 715 (HLB value: 15.6), EMALEX (registered trademark) 720 (HLB value: 16.5), and EMALEX of Nippon Emulsion Co., Ltd. (Registered trademark) 730 (HLB value: 17.5), EMALEX (registered trademark) 750 (HLB value: 18.4) (all trade names are polyoxyethylene lauryl ether), and Leodol TW-P120 of Kao Corporation. (Trade name, polyoxyethylene sorbitan monopalmitate, HLB value: 15.6), PEG2000 (trade name, HLB value: 19.9) of Sanyo Chemical Industries, Ltd., and the like.
  • the coating agent which concerns on this indication contains a nonionic surfactant
  • a nonionic surfactant only 1 type of nonionic surfactant may be included, and 2 or more types may be included.
  • the coating agent according to the present disclosure contains a nonionic surfactant (preferably, a specific nonionic surfactant), the content of the nonionic surfactant in the coating agent is 0.01 relative to the total solid content. It is preferable that it is mass% or more and 15 mass% or less, It is more preferable that it is 0.1 mass% or more and 10 mass% or less, It is still more preferable that it is 1 mass% or more and 10 mass% or less.
  • membrane formed becomes it favorable that it is the said range, and the adhesion prevention property of the contaminant which is a hydrophobic component becomes favorable.
  • the coating agent according to the present disclosure preferably contains a condensation catalyst (hereinafter, also simply referred to as “condensation catalyst”) that promotes the condensation reaction of the specific siloxane hydrolyzate.
  • a condensation catalyst hereinafter, also simply referred to as “condensation catalyst” that promotes the condensation reaction of the specific siloxane hydrolyzate.
  • the condensation catalyst is not particularly limited as long as it promotes the condensation reaction of the specific siloxane hydrolyzate, and examples thereof include an acid catalyst, an alkali catalyst, and an organometallic catalyst.
  • acid catalysts include nitric acid, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, chloroacetic acid, formic acid, oxalic acid, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, dinonylnaphthalene monosulfonic acid, dinonylnaphthalene disulfonic acid , Dodecylbenzene sulfonic acid, polyphosphate, metaphosphate and the like.
  • alkaline catalysts include sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide, sodium hydrogen carbonate, urea and the like.
  • organic metal catalyst include metal chelate compounds (aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate, zirconium tetrakis Zirconium chelate compounds such as acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), titanium chelate compounds such as titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), etc .; Organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dicutiate, etc., aluminum ethylate, aluminum
  • phosphoric acid, toluene sulfonic acid, polyphosphate or metaphosphate is preferable as an acid catalyst
  • baking soda or urea is preferable as an alkali catalyst
  • an aluminum chelate compound is preferable as an organic metal catalyst.
  • Metal chelate compounds such as titanium chelate compounds or zirconium chelate compounds are preferred.
  • organometallic catalysts more preferred are organometallic catalysts, and particularly preferred are aluminum chelate compounds.
  • the content of the condensation catalyst is preferably 0.1% by mass to 40% by mass, and more preferably 1% by mass to 30% by mass with respect to the total solid content. More preferably, 5% by mass to 20% by mass.
  • the content of the condensation catalyst is in the above range, an antifogging film having scratch resistance is easily formed. Moreover, it is excellent also in the formation property of an antifogging film.
  • the coating agent according to the present disclosure preferably contains a solvent other than the high boiling point solvent.
  • solvents other than high boiling point solvents water and organic solvents having a boiling point of less than 120 ° C. can be mentioned.
  • the coating agent according to the present disclosure preferably contains water.
  • Water contributes to the hydrolysis reaction of the specific siloxane compound as described above.
  • As water ion-exchanged water, pure water, distilled water and the like are preferable from the viewpoint of less impurities.
  • the content of water in the coating agent is preferably in the range of 5% by mass to 60% by mass, more preferably in the range of 10% by mass to 55% by mass, and more preferably 10% by mass to 35%
  • the range of% is more preferable.
  • Organic solvents having a boiling point of less than 120 ° C. include methanol, ethanol, butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, n-propanol, 2-propanol, tert-butanol, 2-butanol and the like Alcohol solvents; Glycol ether solvents such as dipropylene glycol methyl ether; Ether solvents such as isopropyl ether, 1,4-dioxane, tert-butyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, diethyl ether; Ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, methyl isobuty
  • the organic solvent having a boiling point of less than 120 ° C. may be used alone or in combination of two or more.
  • the adhesion between the antifogging film formed by the coating agent and the substrate can be improved by using a ketone-based solvent as one of them.
  • a ketone-based solvent used here, acetone (10.0) and acetylacetone (10.3) having an SP value of 10.0 MPa 1/2 or more are preferable.
  • the numerical value in parentheses is the SP value.
  • the ketone-based solvent is preferably used in the range of 1% by mass to 15% by mass, and more preferably in the range of 3% by mass to 10% by mass, based on all solvents.
  • the coating agent according to the present disclosure contains an organic solvent having a boiling point of less than 120 ° C.
  • the content of the organic solvent having a boiling point of less than 120 ° C. is 20% by mass to 75% by mass based on the total mass of the coating agent The range of 25% by mass to 65% by mass is more preferable.
  • the coating agent according to the present disclosure may contain a resin having no acid group, if necessary, in addition to the components described above. Coating property and film-forming property can be improved by containing resin which does not have an acidic radical.
  • resin which does not have an acidic radical it refers to resin which does not have an acidic radical which resin which has the above-mentioned acidic radical (namely, an acidic radical which has adsorption performance to a silica particle) in the molecule.
  • Specific examples of the resin having no acid group include acrylic resin, cellulose resin, vinyl alcohol resin, vinyl pyrrolidone resin, urethane resin, vinyl acetal resin and the like, among which vinyl pyrrolidone resin is preferable.
  • the vinyl pyrrolidone resin may be a homopolymer of vinyl pyrrolidone or a copolymer of vinyl pyrrolidone and vinyl acetate.
  • the content of the resin having no acid group is relative to the total mass of the resin having an acid group and the resin having no acid group.
  • the range of 30% by mass to 85% by mass is preferable, and the range of 45% by mass to 80% by mass is more preferable.
  • the coating agent according to the present disclosure may further contain other additives as necessary in addition to the components described above.
  • Other additives include, for example, an adhesion aiding agent used for the purpose of improving the film property of an antifogging film formed by a coating agent, improving adhesion with a substrate, etc., and improving the effect of preventing adhesion of contaminants.
  • UV absorbers that prevent deterioration due to light, and antioxidants that prevent deterioration due to heat.
  • the coating agent according to the present disclosure is prepared by mixing the specific siloxane hydrolyzate, the silica particles, the high boiling point solvent, and the resin having an acid group, and, if necessary, the optional components described above. Specifically, for example, first, the specific siloxane compound is mixed with water to form a hydrolyzate of the specific siloxane compound, and a hydrolyzate containing the specific siloxane hydrolyzate is prepared. Subsequently, a silica particle, a high boiling point solvent, and a resin having an acid group are added to the obtained hydrolysis solution. In addition, when preparing a hydrolysis liquid, you may use the condensation catalyst which is an arbitrary component as stated above other than a specific siloxane compound and water, and the organic solvent whose boiling point is less than 120 degreeC.
  • the storage container for the coating agent according to the present disclosure is not particularly limited, and may be a metal container, a resin container such as polyethylene or polypropylene, or a glass container. It is also good.
  • the storage temperature of the coating agent according to the present disclosure is preferably 0 ° C. or more and 50 ° C. or less.
  • the antifogging film according to the present disclosure is formed by the coating agent according to the present disclosure described above.
  • an antifogging film is formed by the coating agent, at least a part of the hydroxy groups of the specific siloxane hydrolyzate are bonded to each other between molecules, and the specific siloxane hydrolyzate is condensed. Therefore, the antifogging film formed by the coating agent contains a condensate of a specific siloxane hydrolyzate.
  • an antifogging film with low haze can be formed. That is, the antifogging film according to the present disclosure includes a condensate of a specific siloxane hydrolyzate, silica particles, and a resin having an acid group, and can achieve a haze of 2.0% or less.
  • the condensation product of the specific siloxane hydrolyzate contained in the antifogging film according to the present disclosure is a condensation product of the "specific siloxane hydrolyzate" described in the section of the coating agent.
  • the silica particles and the resin having an acid group contained in the antifogging film according to the present disclosure are the same as the “silica particles” and the "resin having an acid group” described in the section of the coating agent It is.
  • the antifogging film according to the present disclosure has a void between silica particles in the antifogging film.
  • the presence of voids inside the antifogging film develops antifogging performance.
  • “the antifogging film has a void therein” means that the porosity of the antifogging film is 5% or more.
  • the porosity is preferably 10% or more and 50% or less from the viewpoint of contamination resistance and suppression of water dripping.
  • the porosity is a value measured using an automatic porosimeter (manufactured by Shimadzu Corporation, Autopore IV 9520).
  • the thickness of the antifogging film may be determined depending on the application etc., but is preferably 2 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to less than 20 ⁇ m, and still more preferably 2 ⁇ m to less than 10 ⁇ m.
  • the thickness of the antifogging film can be measured by an optical interference type film thickness meter, and for example, Hamamatsu Photonics Co., Ltd. Optical Gauge series C13027 or the like is used.
  • the antifogging film according to the present disclosure has a haze of 2.0% or less.
  • the haze of the antifogging film is preferably as small as possible from the viewpoint of transparency, but when the thickness of the antifogging film is in the range of 0.05 ⁇ m or more and 10 ⁇ m or less, the haze is preferably 2.0% or less, 1 .7% or less is preferable, 1.2% or less is preferable, and 0.5 or less is more preferable.
  • the haze is a measurement value obtained using a haze meter (model number: NDH 5000, Nippon Denshoku Kogyo Co., Ltd.).
  • the method for producing the antifogging film according to the present disclosure is not particularly limited as long as the antifogging film according to the present disclosure can be produced.
  • the method for producing an antifogging film according to the present disclosure includes, for example, applying a coating agent according to the present disclosure to a material to be coated (hereinafter referred to as application step) and drying the applied coating agent. (Hereinafter referred to as a drying step). The coating step and the drying step will be described below.
  • the coating agent according to the present disclosure is applied to the material to be coated.
  • the material to be coated may be a base material in a laminate to be described later, or may be a temporary support which is peeled from the antifogging film after the production of the antifogging film.
  • the coating method may be determined according to the shape, size, thickness of the coating film, etc. of the material to be coated, for example, spray coating, brush coating, roller coating, bar coating, dip coating (so-called dip coating)
  • spray application is preferable when applying to a three-dimensional structure having various surface shapes such as curved surface and unevenness.
  • the setting method of a to-be-coated material is not specifically limited.
  • the direction of the material to be coated can be applied while appropriately changing the direction such as the horizontal direction or the vertical direction with respect to the application direction.
  • the distance to the coating material is preferably 10 mm or more and 1,000 mm or less.
  • any of a pumping type, a suction type, and a gravity type can be used.
  • the nozzle diameter of the spray nozzle is preferably 0.1 mm ⁇ or more and 1.8 mm ⁇ or less, and the air pressure is preferably 0.02 MPa or more and 0.60 MPa or less. By applying under such conditions, the applied film thickness can be made more uniform. In order to form a more suitable coating film by spray coating, it is necessary to adjust the amount of air, the amount of ejection of the coating agent, the pattern opening, and the like.
  • the amount of air is preferably 5 L / min to 600 L / min, and the amount of coating agent ejection is preferably 5 L / min to 600 L / min,
  • the pattern opening is preferably 40 mm or more and 450 mm or less.
  • the temperature condition is preferably 15 ° C. or more and 35 ° C. or less, and the humidity condition is preferably 80% RH or less.
  • the cleanliness is not particularly limited. For example, from the viewpoint of suppressing surface failure due to fine particles (that is, particles) in the coating environment, cleanliness of class 10,000 or more is preferable, and cleanliness of class 1,000 or more It is more preferable that
  • the application amount of the coating agent is not particularly limited, and can be appropriately set in consideration of operability and the like according to the concentration of solid content in the coating agent, the desired layer thickness of the antifogging film, and the like.
  • the coating amount of the coating agent is preferably 1 mL / m 2 or more and 400 mL / m 2 or less, more preferably 2 mL / m 2 or more and 100 mL / m 2 or less, and 4 mL / m 2 or more and 40 mL / m 2 more preferably 2 or less, particularly preferably 6 mL / m 2 or more 20 mL / m 2 or less. Coating accuracy will become favorable as it is the above-mentioned range.
  • the coating agent applied on the material to be coated is dried. Drying of the coating agent may be performed 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 in addition to an oven, an electric furnace, etc., a heating device manufactured independently according to the production line can be used.
  • the drying conditions of the coating agent are not particularly limited, and can be appropriately set in consideration of the curability of the coating film. Drying of the coating agent may be performed under constant temperature conditions in which a predetermined set temperature is kept constant, or temperature conditions may be changed stepwise. As drying conditions of the coating agent in the former case, drying conditions in which the surface temperature is 20 ° C. to 150 ° C. and heating is performed for 1 minute to 60 minutes are preferable, and the surface temperature is 40 ° C. to 150 ° C. Drying conditions of heating for 1 minute to 60 minutes are more preferable, and drying conditions of heating the surface temperature at 60 ° C. or more and 150 ° C. or less and heating for 1 minute to 60 minutes are more preferable.
  • Drying of the coating agent in the latter case is preferably performed separately in pre-drying and main drying.
  • predrying conditions conditions in which the surface temperature is 20 ° C. or more and 60 ° C. or less and heating is performed for 5 seconds to 10 minutes are preferable.
  • the surface temperature can be measured by an infrared thermometer or the like.
  • the air volume of dry air can be suitably set up in consideration of the optimal temperature at the time of reaching a coated material.
  • coated the coating agent may be directly put on a base (namely, flat), and may be dried, and you may stand and dry. , May be hung and dried.
  • the antifogging film is formed on the material to be coated.
  • a laminate according to the present disclosure has a substrate, and an antifogging film formed on the substrate and formed of the coating agent according to the present disclosure described above.
  • the antifogging film formed by the coating agent according to the present disclosure contains a condensate of a specific siloxane hydrolyzate and has a low haze. Therefore, the laminate according to the present disclosure includes a substrate, a condensate of a specific siloxane hydrolyzate provided on the substrate, a silica particle, and a resin having an acid group, and the haze is 2.0% or less And an antifogging film.
  • the laminate according to the present disclosure has a substrate.
  • the material of the substrate is not particularly limited, and can be appropriately selected and used from various materials such as glass, resin (including plastic), metal, and ceramics, and preferably resin.
  • a resin substrate When the laminate is applied to, for example, a protective material of a light of a car and a protective material of a surveillance camera, it is preferable to use a resin substrate.
  • the material of the base material is a resin
  • the base material it is excellent in durability against light and heat, and laminated while maintaining the transparency of the base between the antifogging film and the adhesion.
  • it is an acrylic resin base material, a polycarbonate base material, or a polyethylene terephthalate base material from the viewpoint that a body can be formed, and an acrylic resin base material or a polycarbonate group from the viewpoint that a laminate excellent in adhesion can be formed.
  • a composite material formed of a plurality of materials can also be used as a material of a base material.
  • the material of the base material may be a composite material in which glass and a resin material are mixed and formed by mixing glass and a resin material, or a resin composite material in which a plurality of resin materials are kneaded or bonded. Good.
  • the thickness and shape of the substrate are not particularly limited, and are appropriately set according to the application target. Moreover, surface treatment may be given to the surface of a substrate if needed. There is no restriction
  • the laminate according to the present disclosure has an antifogging film.
  • the antifogging film may be provided on part of the substrate or may be provided on the entire surface. Moreover, the antifogging film may be in direct contact with the substrate or may not be in direct contact with the substrate.
  • the antifogging film in the laminate according to the present disclosure is the same as the antifogging film according to the present disclosure, and the preferred embodiments are also the same.
  • the laminate according to the present disclosure can be used in various applications. Specifically, for example, protective materials for protecting surveillance cameras, lights, sensor lamps and the like (so-called protective covers); roof materials of garages of vehicles such as automobiles and motorcycles; signs such as road signs; highway road shoulders Soundproof walls for installation, railways, etc .; Body of vehicles such as automobiles and motorcycles; Protective materials such as window glass, mirrors and lights of automobiles (for example, lenses); Tools for protecting eyes such as goggles and protective glasses A shield material of a helmet; an inner lens of a head mount display; and the like, which can be suitably used in order to impart functions such as antifogging properties.
  • protective covers for protecting surveillance cameras, lights, sensor lamps and the like
  • roof materials of garages of vehicles such as automobiles and motorcycles
  • signs such as road signs
  • Body of vehicles such as automobiles and motorcycles
  • Protective materials such as window glass, mirrors and lights of automobiles (for example, lenses
  • the laminate according to the present disclosure can be more suitably used as a protective material for automobile lights (headlights, tail lamps, door mirror blinker lights, etc.) and protective materials for surveillance cameras.
  • a car includes a light unit configured to include a light and a lens for protecting the light.
  • a transparent substrate such as glass or plastic used in this light unit has one of the dew points below the surface due to the difference in temperature and humidity between the inner and outer surfaces sandwiching the substrate, or Water in the atmosphere adheres as water droplets when the temperature and humidity changes rapidly (when boiling water vapor contacts the substrate, when it moves from a low temperature part to a high temperature and high humidity environment, etc.), the substrate surface becomes dew condensation Do.
  • so-called “clouding” may occur due to the scattering of light due to the condensed water droplets.
  • cloudsiness occurs in headlights, rear lights, etc.
  • the appearance is significantly impaired.
  • fogging also occurs in the protective cover of a surveillance camera having a protective cover (i.e., a housing-integrated surveillance camera), and in this case, the visibility and safety are significantly impaired.
  • the laminate according to the present disclosure has a low haze and is excellent in transparency, and thus does not impair the appearance, function and performance of the light and surveillance camera of an automobile, and is excellent in antifogging properties and contamination resistance, Antifogging can be maintained over the
  • the manufacturing method of the laminated body which concerns on this indication should just manufacture the laminated body of this indication, and is not specifically limited.
  • the method for producing a laminate according to the present disclosure includes, for example, a step of applying a coating agent according to the present disclosure described above (hereinafter referred to as a coating step) on a substrate and a step of drying the applied coating agent And drying step).
  • a coating step a coating agent according to the present disclosure described above
  • the application process and the drying process in the manufacturing method of a laminated body are the same as the application process and the drying process in the manufacturing method of the anti-fog film
  • Example 1 Preparation of Hydrolyzate The following components were mixed to obtain a mixture.
  • Ethanol solvent other than high boiling point solvent
  • MKC registered trademark
  • Silicate MS 51 specific siloxane compound
  • Ion-exchanged water solvent other than high boiling point solvent
  • 100 A mass part was gradually added, and finally 6 mass parts of acetic acid (100%) were added, and it stirred at room temperature (25 degreeC, the same hereafter) for 24 hours or more.
  • the specific siloxane compound was hydrolyzed in the obtained mixture, and the hydrolysis liquid containing the specific siloxane hydrolyzate was obtained.
  • the coating agent was prepared by mixing the following components.
  • the obtained coating agent was named coating agent 1 of Example 1.
  • the above hydrolysis solution 100 parts by mass Snowtex (registered trademark) OXS (silica particles): 480 parts by mass DISPERBYK (registered trademark)-2015 (resin having an acid group): 63 parts by mass ion exchanged water (high Solvent other than boiling point solvent): 296 parts by mass Ethanol (solvent other than high boiling point solvent): 817 parts by mass Propylene glycol monomethyl ether (high boiling point solvent): 744 parts by mass
  • the obtained coating agent 1 was applied to one side of a polycarbonate substrate (Asahi Glass Co., Ltd., Carboglass C-110, thickness: 0.5 mm) as a base material using a spray gun (Anest Iwata Co., Ltd.)
  • the solution was painted with W-101-101G), allowed to stand at 30 ° C. for 1 minute, and dried at 120 ° C. for 20 minutes to form an antifogging film having a thickness of 300 nm after drying on a substrate.
  • a laminate in which the antifogging film was formed on the substrate was obtained.
  • Examples 2 to 41 and Comparative Examples 1 to 4 Preparation of hydrolyzate by appropriately changing the components used, the types of components, and the amounts used so as to obtain the composition of solid content, the composition of solvent, and the concentration of solid content described in Tables 2 to 5 below.
  • the coating agents 2 to 41 and C 1 to C 4 of Examples 2 to 41 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that the coating agents were prepared.
  • the composition of the solid content and the composition of the solvent are each 100% by mass in total.
  • the solid concentration is the percentage of the total solid content in the coating agent.
  • the condensation catalyst and the nonionic surfactant described in Tables 2 to 5 below were used at the time of preparation of the coating agent.
  • all high boiling point solvents were used at the time of preparation of a coating agent.
  • the coating agent was prepared using polyvinyl alcohol instead of the resin having an acid group.
  • “(PVA)” was described in the column of resin having an acid group.
  • the coating agent was prepared using n-butyl alcohol instead of the high boiling point solvent.
  • “(nBA)” was described in the column of high boiling point solvents.
  • an antifogging film was formed on the polycarbonate substrate in the same manner as in Example 1 except that Coating agent 1 was replaced by Coating agents 2 to 41 and C1 to C4, respectively, and Examples 2 to 41 and Comparative Example One to four laminates were obtained.
  • Comparative Example 5 The aqueous
  • -Silica particles- -ST-OXS Snowtex (registered trademark) OXS (water dispersion of silica particles, solid content 10%, average primary particle size 4 nm to 6 nm, Nissan Chemical Industries, Ltd.)
  • -ST-O33 Snowtex (registered trademark) O33 (water dispersion of silica particles, solid content 15%, average primary particle size 10 nm to 15 nm, Nissan Chemical Industries, Ltd.)
  • -ST-OUP Snowtex (registered trademark) OUP (water dispersion of silica particles, solid content 15%, average primary particle diameter 40 nm to 100 nm, Nissan Chemical Industries, Ltd.)
  • -Resin with acid group- -BYK-2015 DISPERBYK (registered trademark)-2015 (aqueous solution of resin having a carboxy group, solid content 40%, acid value: 10 mg KOH / g, BIC Chemie Japan Ltd.)
  • A-6012 ARON (registered trademark)
  • A-6012 an aqueous solution of a resin having a sulfonic acid group, solid content 40%, weight average molecular weight: 10000, Toagosei Co., Ltd.
  • TEGO 651 TEGO® Dispers 651 (an aqueous solution of a resin having a phosphate group, solid content 30%, acid value: 30 mg KOH / g, Evonik)
  • -EUDRAGIT L100 EUDRAGIT (registered trademark) L 100 (copolymer of methacrylic acid and methyl methacrylate, solid content 100%, weight average molecular weight 125000, Evonik) -Resin used in Comparative Example
  • -Condensation catalyst- ⁇ AL-D Aluminum chelate D (aluminum chelate compound, 76% aqueous solution, Kawaken Fine Chemicals Co., Ltd.)
  • -Nonionic surfactant- -EMA 715 EMALEX (registered trademark) 715 (HLB value: 15.6, Nippon Emulsion Co., Ltd.)
  • -EMA 730 EMALEX (registered trademark) 730 (HLB value: 17.5, Nippon Emulsion Co., Ltd.)
  • -EMA 750 EMALEX (registered trademark) 750 (HLB value: 18.4, Nippon Emulsion Co., Ltd.)
  • -Resin without acid group- K-30 Pitzcor® K-30 (a homopolymer of vinyl pyrrolidone, solid content 100%, weight average molecular weight: 45000, Dai-ichi Kogyo Seiyaku Co., Ltd.)
  • S-630 PVP / VA S-630 (Copolymer of vinyl pyrrolidone and vinyl acetate, solid content 100%, weight average molecular weight: 51000, Ashland Japan Ltd.)
  • E-735 PVP / VA E-735 (registered trademark) (ethanol solution of copolymer of vinyl pyrrolidone and vinyl acetate, solid content 50%, weight average molecular weight: 38,000, Ashland Japan Co., Ltd.)
  • the haze of the produced laminate was measured using a haze meter NDH 5000 (Nippon Denshoku Kogyo Co., Ltd.). In addition, the measurement of haze measured toward the light source to the anti-fog film side. The smaller the haze value, the better the transparency of the laminate.
  • the haze is preferably 2.0% or less. In addition, when the haze of a laminated body is 2.0% or less, it can be said that the haze of antifog film itself is 2.0% or less.
  • the coating agents obtained in the examples have smaller haze, excellent initial antifogging properties, and stain resistance (that is, contaminants) than the coating agents obtained in the comparative examples.
  • Example 1 and Example 6 From the comparison between Example 1 and Example 6, it is understood that the initial antifogging property and the stain resistance are enhanced by setting the content of the silica particles to the total solid content in the coating agent to 50% by mass or more. This is considered to be attributable to the fact that the amount of the voids formed between the silica particles in the antifogging film is optimized because the content of the silica particles is in the above range. From the comparison of Example 7, Example 8, and Example 9, by using the high boiling point solvent having a high boiling point, the film forming property is enhanced, and as a result, the antifogging film having low haze and excellent initial antifogging property is obtained. It is understood that it can be obtained.
  • Example 9 From the comparison of Example 9, Example 10, and Example 11, it can be seen that a glycol ether solvent is preferable as the high boiling point solvent, and a solvent having a branched alkyl group is preferable. From the comparison of Example 9, Example 12, and Example 13, by setting the content of the high boiling point solvent to 20% by mass to 40% by mass with respect to the total mass of the coating agent, the leveling of the coating film of the coating agent is performed. It can be seen that the antifogging film having a high haze and a low haze can be obtained.
  • Example 9 and Example 14 From the comparison between Example 9 and Example 14, by setting the content of the resin having an acid group to 30% by mass or more with respect to the silica particles, the aggregation in the drying step of the silica particles is suppressed, and the haze is low It turns out that a cloudy film is obtained.
  • Example 9 and Example 15 by setting the content of the resin having an acid group to 45% by mass or less with respect to the silica particles, voids between the silica particles formed in the antifogging film It can be seen that an antifogging film excellent in initial antifogging properties and contamination resistance can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un agent de revêtement et son application, l'agent de revêtement comprenant : un hydrolysat d'un composé représenté par la formule générale (1) ; des particules de silice ; un solvant à point d'ébullition élevé ayant un point d'ébullition de 120 °C ou plus ; et une résine ayant un groupe acide. Dans la formule générale (1), R1, R2, R3, et R4 représentent chacun d'une manière indépendante un groupe organique monovalent ayant 1 à 6 atomes de carbone, et n représente un entier de 1 à 20.
PCT/JP2018/038694 2017-10-25 2018-10-17 Agent de revêtement, film antibuée, procédé de production de film antibuée, et stratifié WO2019082768A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114667219A (zh) * 2019-11-15 2022-06-24 三井化学株式会社 层叠体、层叠体的制造方法、防雾膜形成用组合物、防雾膜及防雾膜形成用组合物套组
WO2022255096A1 (fr) * 2021-05-31 2022-12-08 日本ペイント・サーフケミカルズ株式会社 Composition aqueuse d'hydrophilisation et article

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JP2001040251A (ja) * 1999-05-26 2001-02-13 Nof Corp 汚れ防止処理剤、汚れ防止処理方法および汚れ防止処理物品
WO2011052677A1 (fr) * 2009-11-02 2011-05-05 互応化学工業株式会社 Résine polyester de type hybride, composition de résine filmogène, et film et textile polyester
JP2012192595A (ja) * 2011-03-16 2012-10-11 Toray Advanced Film Co Ltd 親水性積層フッ素樹脂フィルム
JP2014015543A (ja) * 2012-07-09 2014-01-30 Nissan Chem Ind Ltd 低屈折率コーティング組成物
WO2015147278A1 (fr) * 2014-03-28 2015-10-01 三菱マテリアル株式会社 Composition liquide filmogène
WO2017217474A1 (fr) * 2016-06-17 2017-12-21 富士フイルム株式会社 Composition filmogène et procédé de fabrication de stratifié
JP2018119073A (ja) * 2017-01-26 2018-08-02 石原ケミカル株式会社 親水性コーティング組成物

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Publication number Priority date Publication date Assignee Title
JP2001040251A (ja) * 1999-05-26 2001-02-13 Nof Corp 汚れ防止処理剤、汚れ防止処理方法および汚れ防止処理物品
WO2011052677A1 (fr) * 2009-11-02 2011-05-05 互応化学工業株式会社 Résine polyester de type hybride, composition de résine filmogène, et film et textile polyester
JP2012192595A (ja) * 2011-03-16 2012-10-11 Toray Advanced Film Co Ltd 親水性積層フッ素樹脂フィルム
JP2014015543A (ja) * 2012-07-09 2014-01-30 Nissan Chem Ind Ltd 低屈折率コーティング組成物
WO2015147278A1 (fr) * 2014-03-28 2015-10-01 三菱マテリアル株式会社 Composition liquide filmogène
WO2017217474A1 (fr) * 2016-06-17 2017-12-21 富士フイルム株式会社 Composition filmogène et procédé de fabrication de stratifié
JP2018119073A (ja) * 2017-01-26 2018-08-02 石原ケミカル株式会社 親水性コーティング組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114667219A (zh) * 2019-11-15 2022-06-24 三井化学株式会社 层叠体、层叠体的制造方法、防雾膜形成用组合物、防雾膜及防雾膜形成用组合物套组
CN114667219B (zh) * 2019-11-15 2024-03-15 三井化学株式会社 层叠体、层叠体的制造方法、防雾膜形成用组合物、防雾膜及防雾膜形成用组合物套组
WO2022255096A1 (fr) * 2021-05-31 2022-12-08 日本ペイント・サーフケミカルズ株式会社 Composition aqueuse d'hydrophilisation et article

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