WO2024070969A1 - Film mince antibactérien et antiviral et produit optique - Google Patents

Film mince antibactérien et antiviral et produit optique Download PDF

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Publication number
WO2024070969A1
WO2024070969A1 PCT/JP2023/034566 JP2023034566W WO2024070969A1 WO 2024070969 A1 WO2024070969 A1 WO 2024070969A1 JP 2023034566 W JP2023034566 W JP 2023034566W WO 2024070969 A1 WO2024070969 A1 WO 2024070969A1
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water
antibacterial
mass
meth
thin film
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PCT/JP2023/034566
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English (en)
Japanese (ja)
Inventor
紘子 鈴木
宏寿 高橋
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東海光学株式会社
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides

Definitions

  • the present invention relates to an antibacterial and antiviral thin film that exhibits antibacterial and antiviral properties, or at least both antibacterial and antiviral properties, and optical products such as non-prescription eyeglass lenses and eyeglass lenses including sunglass lenses.
  • a coating composition capable of forming an anti-fogging cured film, which has the property of suppressing fogging, on the surface of an article is known, as described in Japanese Patent No. 6340539 (Patent Document 1).
  • This coating composition contains a (meth)acrylic resin (A) having structural units (a-1) to (a-4) derived from four types of monomers, a polyol compound (B), and a polyfunctional isocyanate compound (C), each in a specified range of mass %.
  • This coating composition is constructed as follows. That is, the structural unit (a-1) of (A) has an amide group, and is easy to hold and absorb moisture. (C) contributes to the formation of a cured film by crosslinking with (A).
  • the structural unit (a-2) of (A) has a polycaprolactone structure, and its flexible chemical skeleton improves the flexibility and elasticity of the cured film, and improves the scratch resistance of the cured film.
  • the structural unit (a-4) of (A) has a polydimethylsiloxane chain, and improves the slipperiness of the cured film, and improves the scratch resistance of the cured film.
  • the structural unit (a-3) of (A) is a hydroxyalkyl (meth)acrylate, which is harder than (a-2) in the cured film, and which adjusts the flexibility provided mainly by (a-2) to provide a well-balanced elasticity.
  • the applicant of the present application conceived the idea that the cured film could have antibacterial and antiviral properties while proceeding with improvements to the above-mentioned coating composition and anti-fog cured film with the aim of improving the scratch resistance and slipperiness.
  • the main object of the present invention is to provide an antibacterial and antiviral thin film, which is a thin film having antibacterial and antiviral properties, and an optical product having antibacterial and antiviral properties.
  • the antibacterial and antiviral thin film has a porous layer having a plurality of holes.
  • the physical thickness of the porous layer may be 6 ⁇ m or more.
  • the antifogging performance duration per unit thickness obtained by dividing the antifogging performance duration obtained by a steam test of the porous layer by the physical thickness of the porous layer may be 4 seconds/ ⁇ m or more.
  • the steam test may be performed by continuously applying steam related to natural evaporation at 40° C. to the surface of the porous layer side, and measuring the time from the start of application to the start of fogging as the antifogging performance duration.
  • the present specification also discloses an optical product, which comprises the antibacterial and antiviral thin film and a substrate.
  • the main effect of the present invention is to provide an antibacterial and antiviral thin film, which is a thin film having antibacterial and antiviral properties, and an optical product having antibacterial and antiviral properties.
  • FIG. 1 is a schematic cross-sectional view of an anti-fogging plastic eyeglass lens according to an embodiment of the present invention.
  • Example 1-2 was used as the subject of an ink penetration test, and the photographs are black and white photographs of the test subjects taken from the front side when the ink was dried.
  • the ink penetration test was conducted using Example 1-2, and the black and white photographs were taken from the back side of the test subjects immediately after wiping off the ink.
  • the ink penetration test was conducted using Example 1-2, and the black and white photographs were taken from the back side of the test subjects immediately after wiping off each ink with acetone.
  • FIG. 1 is a schematic cross-sectional view of an anti-fogging plastic eyeglass lens according to an embodiment of the present invention.
  • Example 1-2 was used as the subject of an ink penetration test, and the photographs are black and white photographs of the test subjects taken from the front side when the ink was dried.
  • the ink penetration test was conducted using Example 1-2, and the black and white photographs were taken
  • FIG. 1 is a schematic diagram showing an antibacterial and antiviral thin film and Escherichia coli when the physical thickness of the water-absorbing layer, which is an antibacterial and antiviral thin film having a large number of pores, is sufficient.
  • 1 is a schematic diagram showing a thin film and E. coli when the physical thickness of a water-absorbing layer, which is a thin film having a large number of pores, is not sufficient.
  • a group (atomic group) when a group (atomic group) is represented in a chemical formula or the like without specifying whether it is substituted or unsubstituted, it includes both those that have no substituent and those that have a substituent.
  • an alkyl group includes not only an alkyl group that has no substituent (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group).
  • (meth)acrylic includes both acrylic and methacrylic. The same applies to similar expressions such as (meth)acrylate.
  • a structural unit derived from the monomer (a-1) may be referred to as a structural unit (a-1).
  • a structural unit (a-1) may be referred to as a structural unit (a-1).
  • similar notations such as a structural unit derived from the monomer (a-2).
  • the explanations of various physical properties in the embodiments of the present invention include properties that have actually been confirmed as well as properties that are reasonably inferred from chemical structures, etc.
  • the applicant of the present application has improved the coating composition capable of forming an anti-fog cured film on the surface of an article in Japanese Patent No. 6340539 with the aim of improving scratch resistance and slipperiness, and has filed a patent application for an anti-fog plastic eyeglass lens in which an improved anti-fog cured film is formed on the plastic eyeglass lens.
  • the application is Japanese Patent Application No. 2021-164985, and was not disclosed at the time of filing this application.
  • the applicant of the present application found, while improving the coating composition and the cured film, that the improved cured film has at least one of antibacterial and antiviral properties, or antibacterial and antiviral properties.
  • the following first aspect relates to an antifogging thin film as such an antifogging cured film. Furthermore, the applicant of the present application has found that not only the specific antifogging cured film according to the above-mentioned improvement, but also any predetermined antifogging thin film can have antibacterial and antiviral properties. The second and subsequent embodiments described below relate to those predetermined antifogging thin films.
  • the antibacterial and antiviral thin film 1 according to the first embodiment has a water-absorbing layer 4 as a porous layer, and a water-repellent layer 6 .
  • the optical product 10 according to the first embodiment includes the antibacterial and antiviral thin film 1 and a substrate 12 .
  • the optical product 10 is, for example, a spectacle lens.
  • the water-repellent layer 6 may be omitted.
  • an antibacterial and antiviral thin film 1 is formed on a film-forming surface M (air side) that is disposed on one or more surfaces of a substrate 12 .
  • the base material 12 is made of, for example, plastic.
  • the substrate 12 is, for example, a spectacle lens substrate.
  • the material of the substrate 12 is preferably at least any one of an allyl-based resin including polydiethylene glycol bisallyl carbonate known as CR-39, a thiourethane-based resin, an episulfide-based resin, polymethyl methacrylate, a copolymer of polymethyl methacrylate, polycarbonate, cellulose acetate, polyethylene terephthalate, polyvinyl chloride, an acrylic resin, and a polyurethane resin.
  • an allyl-based resin including polydiethylene glycol bisallyl carbonate known as CR-39, a thiourethane-based resin, an episulfide-based resin, polymethyl methacrylate, a copolymer of polymethyl methacrylate, polycarbonate, cellulose acetate, polyethylene terephthalate, polyvinyl chloride, an acrylic resin, and a polyurethane resin.
  • the water-absorbing layer 4 of the antibacterial and antiviral thin film 1 is a water-absorbent resin layer.
  • the water absorbing layer 4 is formed on the film forming surface M of the substrate 12 .
  • the water-absorbing layer 4 is formed from a composition containing the following components: That is, the composition contains a (meth)acrylic resin (A), a polyfunctional isocyanate compound (B), and an epoxide (C).
  • the (meth)acrylic resin (A) has a structural unit derived from a monomer (a-1) represented by the following general formula (1), a structural unit derived from a monomer (a-2) represented by the following general formula (2), a structural unit derived from a hydroxyalkyl (meth)acrylate (a-3), and a structural unit derived from a monomer (a-4) represented by the following general formula (3).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 and R 3 are a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms
  • R 2 and R 3 may be the same or different.
  • R4 is a hydrogen atom or a methyl group
  • n1 is an integer of 1 or more and 5 or less.
  • R5 is a hydrogen atom or a methyl group
  • R6 is a divalent organic group
  • n2 is an integer of 0 or 1 or more.
  • (Meth)acrylic resin (A) contains 20% by mass or more and 65% by mass or less of structural units derived from monomer (a-1), 10% by mass or more and 40% by mass or less of structural units derived from monomer (a-2), and 1% by mass or more and 10% by mass or less of structural units derived from monomer (a-4), relative to 100% by mass of all structural units constituting the resin.
  • the polyfunctional isocyanate compound (B) is a compound having two or more isocyanate groups in one molecule.
  • the isocyanate groups include isocyanate groups protected with a leaving group.
  • the number of functional groups in the polyfunctional isocyanate compound is preferably 2 to 6 per molecule, and more preferably 2 to 4 per molecule.
  • the epoxide (C) is an organic compound having a plurality of epoxy groups.
  • the epoxide (C) preferably has two epoxy groups, and more preferably has a straight chain of carbon atoms, with an epoxy group at each of both ends.
  • the epoxide (C) preferably has one or more hydroxyl groups in order to suppress liberation from other components.
  • the composition may further contain other components, such as additives used in preparing a composition (paint).
  • additives used in preparing a composition such as additives used in preparing a composition (paint).
  • a curing catalyst for example, at least one of a curing catalyst, an ultraviolet absorbing agent, a light stabilizer, a surfactant, a leveling agent, and an antifoaming agent may be used.
  • the water absorbing layer 4 is formed by applying such a composition to the film forming surface M and polymerizing it.
  • the configuration of the water-absorbing layer 4 may be considered to be specified by the manufacturing method of applying the composition, and even if this is the case, it is considered that such specification is permissible because there are so-called impossible or impractical circumstances.
  • polymers of this composition combining various monomers, and it is not practical to directly identify the water-absorbing layer 4 by its structure or characteristics by listing specific examples in order to distinguish it from other polymers.
  • Patent Document 1 discloses a patent for an invention of a cured film formed from a specific composition (see claim 7 of the patent).
  • the water-repellent layer 6 is disposed on the water-absorbent layer 4 (on the air side, the side opposite the substrate 12).
  • the physical thickness of the water-repellent layer 6 is preferably equal to or less than the physical thickness of the water-absorbing layer 4.
  • the physical thickness of the water-repellent layer 6 is preferably 0.5 nm or more and 20 nm or less, and more preferably 1 nm or more and 10 nm or less.
  • the main component of the water-repellent layer 6 is at least one of amino-modified silicone and mercapto-modified silicone. Here, the main component means that it accounts for the majority in terms of mass %.
  • the water-repellent layer 6 is preferably the uppermost layer of the water-absorbent layer 4 and is the layer disposed closest to the air.
  • one or more other layers may be disposed on the water-repellent layer 6.
  • one or more other layers may be disposed between the water-absorbing layer 4 and the water-repellent layer 6.
  • One or more other layers may be disposed between the substrate 12 and the water-absorbing layer 4.
  • the layer between the substrate 12 and the water-absorbing layer 4 may be a primer layer (undercoat layer). When a primer layer or the like is formed on the surface of the substrate 12, the surface of the primer layer or the like may be treated as the surface of the substrate 12.
  • the primer layer may be a connecting layer disposed to improve the adhesion between the water-absorbing layer 4 and the substrate 12.
  • the primer layer is, for example, a urethane-based resin, an acrylic-based resin, a methacrylic-based resin, an organic silicon-based resin, or the like.
  • the primer layer is formed, for example, by a dip method in which the substrate 12 is immersed in a primer liquid.
  • the primer layer may be formed by any of a spray method, a roll coating method, and a spin coating method.
  • the water-repellent layer 6 is formed from a water-repellent agent containing at least one of amino-modified silicone and mercapto-modified silicone as a main component.
  • the amount of the water repellent agent is set so that the water repellent layer 6 exhibits water repellency while preventing the adsorption or absorption of moisture into the water absorbing layer 4 from being impeded.
  • the water-repellent layer 6 is preferably formed by drying the substrate 12 with the water-absorbing layer 4 to which the water-repellent agent has been adhered, and more preferably, is formed by heating and drying the substrate 12 with the water-absorbing layer 4 to which the water-repellent agent has been adhered.
  • a cleaning treatment is performed on the substrate 12 with the water-absorbing layer 4 as a pretreatment.
  • the cleaning treatment is, for example, at least one of cleaning with an ultrasonic cleaner, cleaning with a plasma cleaner, and degreasing with an acid-alkali or the like.
  • ultrasonic treatment with an ultrasonic cleaner ultrasonic waves act on the substrate 12 with the water-absorbing layer 4.
  • plasma treatment with a plasma cleaner plasma acts on the substrate 12 with the water-absorbing layer 4.
  • a similar pretreatment may be performed before the formation of at least one of the water-absorbing layer 4 and other layers.
  • the configuration of the water-repellent layer 6 may be considered to be specified by the manufacturing method of forming it from the water-repellent agent, and even if this is the case, it is considered that such a specification is permissible because there are so-called impossible or impractical circumstances.
  • there are a wide variety of molecular structures of the water-repellent layer 6 derived from the water-repellent agent and it is not practical to directly identify the water-repellent layer 6 by its structure or characteristics by listing specific examples in order to distinguish it from other structures.
  • the (meth)acrylic resin (A), which is one of the components of the composition for the water-absorbing layer 4, will now be described in further detail.
  • the structural unit (a-1) has an amide group, is highly hydrophilic, and easily holds moisture. Therefore, moisture that adheres to the upper part of the water absorption layer 4 is absorbed into the water absorption layer 4. This prevents the antibacterial and antiviral thin film 1 from fogging. In other words, the structural unit (a-1) imparts antifogging properties to the antibacterial and antiviral thin film 1. It is also known that amide groups form a porous structure with a complex network mediated by hydrogen bonds as they are polymerized. In other words, the inclusion of the structural unit (a-1) imparts a porous structure that exhibits moisture adsorption or moisture absorption properties to the antibacterial and antiviral thin film 1.
  • the structural unit (a-2) has a so-called polycaprolactone structure.
  • the polycaprolactone structure contributes to improving the flexibility and elasticity of the water-absorbing layer 4 due to its flexible chemical skeleton.
  • the structural unit (a-4) has a polydimethylsiloxane chain.
  • the polydimethylsiloxane chain contributes to improving the slipperiness of the water absorption layer 4.
  • the structural units (a-2) and (a-4) of the water absorbent layer 4 exert an absorbing effect by their flexibility and elasticity against an external force applied to the water absorbent layer 4, while exerting an action of releasing the force by their slipperiness, thereby suppressing the adhesion of scratches. That is, the water absorbent layer 4 is endowed with tear resistance.
  • the structural unit (a-2) has a hydroxyl group at its terminal, and therefore undergoes a crosslinking reaction with the polyfunctional isocyanate compound (B), thereby contributing to the formation of the water absorbing layer 4.
  • the crosslinking reaction between the (meth)acrylic resin (A) and the polyfunctional isocyanate compound (B) occurs only in the structural unit (a-2)
  • the water absorption layer 4 becomes too soft and, while exhibiting sufficient flexibility, lacks elasticity. Therefore, by including the structural unit (a-3), which is harder than the structural unit (a-2), as a component of the (meth)acrylic resin (A), a water-absorbing layer 4 having a good balance between flexibility and elasticity can be obtained.
  • the structural unit (a-3) contains a hydroxyl group.
  • the structural unit (a-2) has a polycaprolactone structure, which increases the flexibility and elasticity of the water-absorbing layer 4 while also increasing the frictional resistance of the water-absorbing layer 4.
  • the structural unit (a-4) imparts slipperiness to the water absorbent layer 4 through the polydimethylsiloxane chain and reduces the frictional resistance of the water absorbent layer 4, but since the abundance ratio of the structural unit (a-4) is smaller than the abundance ratio of the structural unit (a-2), it is difficult to obtain sufficiently low frictional resistance even if sufficient tear resistance is obtained.
  • the equivalent ratio (NCO/OH) which is the ratio of isocyanate groups to hydroxyl groups, to a specific range less than 1 while the ratios of the structural units (a-2) and (a-3) having hydroxyl groups are balanced, the hardness of the water absorption layer 4 is improved to such an extent that the frictional resistance is sufficiently reduced.
  • the equivalent ratio (NCO/OH) is less than 1, the number of isocyanate groups is less than the number of hydroxyl groups.
  • the number of isocyanate groups is less than the number of hydroxyl groups, the number of isocyanate groups not involved in crosslinking is reduced.
  • the crosslink density of the water absorption layer 4 is increased, the hardness of the water absorption layer 4 is improved, and the frictional resistance is reduced.
  • the equivalent ratio (NCO/OH) is too small, the number of crosslinking points that are the basis for forming the water-absorbing layer 4 becomes too small, resulting in insufficient strength of the water-absorbing layer 4. Therefore, there is a lower limit to the equivalent ratio (NCO/OH).
  • the (meth)acrylic resin (A) is typically obtained by polymerization of the monomers (a-1), (a-2), (a-3) and (a-4). It is not necessary that all of the constituent units of the (meth)acrylic resin (A) are constituent units derived from (meth)acrylic monomers. That is, the (meth)acrylic resin (A) may contain a portion of constituent units derived from monomers that are not (meth)acrylic. However, in order to fully obtain the effect derived from the (meth)acrylic structure, it is preferable that 50% by mass or more of the constituent units of the (meth)acrylic resin (A) are constituent units derived from (meth)acrylic monomers.
  • the constituent units of the (meth)acrylic resin (A) are constituent units derived from (meth)acrylic monomers, and it is even more preferable that 100% by mass of the constituent units of the (meth)acrylic resin (A) are constituent units derived from (meth)acrylic monomers.
  • Monomer (a-1) is not particularly limited as long as it has the structure of the above general formula (1).
  • Examples of monomer (a-1) include (meth)acrylamide, N-methylacrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-n-propyl(meth)acrylamide, and N-isopropyl(meth)acrylamide.
  • the monomer (a-1) may be at least one type, or may be a combination of two or more types.
  • the (meth)acrylic resin (A) may be obtained by carrying out a polymerization reaction using two or more types of the monomers listed above.
  • the monomer (a-1) contains N,N-dimethyl(meth)acrylamide or N,N-diethyl(meth)acrylamide.
  • the constituent units derived from the monomer (a-1) in the (meth)acrylic resin (A) are contained in an amount of 20% by mass or more and 65% by mass or less, more preferably 35% by mass or more and 60% by mass or less, and even more preferably 40% by mass or more and 55% by mass or less, based on the total constituent units of the resin.
  • the content of the structural units derived from the monomer (a-1) is less than 20% by mass, it is difficult to form a water-absorbing layer 4 that exhibits anti-fogging performance suitable for practical use.
  • the content of the structural units derived from the monomer (a-1) exceeds 65% by mass, the proportion of structural units derived from other monomers decreases relatively, and the balance of the composition as a whole becomes relatively poor.
  • Monomer (a-2) is not particularly limited as long as it has the structure of the above general formula (2).
  • An example of monomer (a-2) is the "Placcel F" series manufactured by Daicel Corporation.
  • the constituent units derived from the monomer (a-2) in the (meth)acrylic resin (A) are contained in an amount of 10 mass % or more and 40 mass % or less, more preferably 20 mass % or more and 38 mass % or less, and even more preferably 25 mass % or more and 35 mass % or less, based on the total constituent units of the resin.
  • the content of the structural units derived from the monomer (a-2) is less than 10% by mass, the flexibility of the water-absorbing layer 4 becomes insufficient.
  • the (meth)acrylic resin (A) may contain multiple kinds of repeating units derived from the monomer (a-2).
  • the (meth)acrylic resin (A) may be obtained by polymerization in a state in which two or more kinds of compounds belonging to the above-mentioned "PLACCEL F" series are contained.
  • the monomer (a-3) is a hydroxyalkyl (meth)acrylate.
  • the monomer (a-3) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. Among these, hydroxyethyl (meth)acrylate is preferred.
  • the constituent units derived from the monomer (a-3) of (A) in the (meth)acrylic resin are contained in an amount of preferably 1 mass % or more and 30 mass % or less, more preferably 2 mass % or more and 20 mass % or less, and even more preferably 3 mass % or more and 15 mass % or less, based on the total constituent units of the (meth)acrylic resin (A).
  • the monomer (a-3), like the monomer (a-2), has a hydroxyl group and undergoes a crosslinking reaction with the polyfunctional isocyanate compound (B) to form the water absorption layer 4.
  • the water absorption layer 4 is not formed by causing a crosslinking reaction with only the monomer (a-2), but is formed by causing a crosslinking reaction with the polyfunctional isocyanate compound (B) together with the monomer (a-3) to form the water absorption layer 4, and the water absorption layer 4 has various physical properties.
  • the (meth)acrylic resin (A) contains structural units derived from the monomer (a-2) and the monomer (a-3), it has hydroxyl groups as a whole, i.e., it is a resin having a hydroxyl value. Therefore, the (meth)acrylic resin (A) can react with the polyfunctional isocyanate compound (B) to form a crosslinked structure.
  • the hydroxyl value of the (meth)acrylic resin (A) is preferably 40 mgKOH/g or more and 150 mgKOH/g or less, more preferably 70 mgKOH/g or more and 140 mgKOH/g or less, and even more preferably 90 mgKOH/g or more and 130 mgKOH/g or less.
  • the hydroxyl value refers to the number of mg of potassium hydroxide required to neutralize acetic acid bonded to hydroxyl groups when 1 g of a sample is acetylated.
  • the crosslinked structure is appropriately controlled by reacting with the polyfunctional isocyanate compound (B). Therefore, the water absorption layer 4 becomes hard while maintaining its flexibility and elasticity. Therefore, the water absorption layer 4 can have a higher degree of both scratch resistance and reduced frictional resistance.
  • Monomer (a-4) is not particularly limited as long as it has the structure of the above general formula (3).
  • Examples of monomer (a-4) include Silaplane "FM-0711", “FM-0721”, and “FM-0725” manufactured by JNC Corporation, “X-22-174DX” and “X-22-2426” manufactured by Shin-Etsu Chemical Co., Ltd., and "AK-5" and "AK-32” manufactured by Toagosei Co., Ltd.
  • the (meth)acrylic resin (A) may contain a plurality of repeating units derived from the monomer (a-4).
  • the (meth)acrylic resin (A) may be obtained by carrying out a polymerization reaction using two or more of the monomers listed above.
  • the structural units derived from the monomer (a-4) in the (meth)acrylic resin (A) are contained in an amount of 1 mass % or more and 10 mass % or less, more preferably 2 mass % or more and 8 mass % or less, and even more preferably 3 mass % or more and 7 mass % or less, based on the total structural units of the resin.
  • the content of the structural units derived from the monomer (a-4) is less than 1 mass %, it is difficult to obtain a water absorbing layer 4 having sufficient scratch resistance.
  • the content of the structural units derived from the monomer (a-4) is more than 10 mass %, it is difficult to synthesize a homogeneous (meth)acrylic resin (A). This is because the monomer (a-1) has an amide group and is extremely hydrophilic with high affinity for water, whereas the monomer (a-4) is relatively hydrophobic, and therefore the two are difficult to mix with each other.
  • the (meth)acrylic resin (A) may or may not contain an arbitrary structural unit (a-5) other than the structural units (a-1), (a-2), (a-3), and (a-4).
  • the structural unit (a-5) include structural units derived from the monomers represented below.
  • R is a hydrogen atom or a methyl group
  • R' is an alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.
  • monomers are methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate.
  • the (meth)acrylic resin (A) may contain a plurality of repeating units corresponding to the structural unit (a-5).
  • the (meth)acrylic resin (A) may be obtained by carrying out a polymerization reaction using two or more of the above monomers.
  • the content thereof is preferably from 1 mass % to 40 mass %, more preferably from 3 mass % to 30 mass %, and even more preferably from 5 mass % to 20 mass %, based on all structural units of the (meth)acrylic resin (A).
  • the weight average molecular weight (Mw) of the (meth)acrylic resin (A) is not particularly limited, but is preferably from 10,000 to 100,000, more preferably from 20,000 to 70,000, and even more preferably from 30,000 to 60,000. If the weight average molecular weight is 10,000 or more, anti-fogging performance is easily imparted, and if the weight average molecular weight is 100,000 or less, paintability is easily imparted.
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • the glass transition temperature of the (meth)acrylic resin (A) is not particularly limited, but is preferably 20°C or higher and 120°C or lower, more preferably 30°C or higher and 110°C or lower, and even more preferably 35°C or higher and 100°C or lower.
  • the glass transition temperature of the (meth)acrylic resin (A) can be determined by various methods. For example, the glass transition temperature can be determined based on the Fox formula. For monomers whose glass transition temperature is unknown, such as special monomers and polyfunctional monomers, the glass transition temperature can be determined using only monomers whose glass transition temperature is known.
  • the (meth)acrylic resin (A) is typically obtained by a polymerization reaction.
  • the polymerization reaction may be any of various methods such as radical polymerization, cationic polymerization, and anionic polymerization, among which radical polymerization is preferred.
  • the polymerization may be any of solution polymerization, suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferred from the viewpoint of precise control of the polymerization.
  • the polymerization initiator for radical polymerization may be a known one.
  • the polymerization initiator include azo-based initiators such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2-methylpropionitrile), and 2,2-azobis(2,4-dimethylvaleronitrile), peroxide-based initiators such as benzoyl peroxide, t-butylperoxyoctanoate, diisobutyl peroxide, di(2-ethylhexyl)peroxypivalate, decanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and t-butylperoxybenzoate, and redox-based initiators in which an oxidizing agent and a reducing agent are combined, such as hydrogen peroxide and an iron(II) salt, or a persulfate and sodium hydrogen sulfite.
  • the blending amount of the polymerization initiator is not particularly limited, but is preferably 0.001 parts by mass or more and 10 parts by mass or less, when the total mixed solution of the monomers to be polymerized is 100 parts by mass.
  • the polymerization reaction may be carried out in one stage or in two or more stages.
  • the temperature of the polymerization reaction is not particularly limited, but is typically 50°C or higher and 200°C or lower, and preferably 80°C or higher and 150°C or lower.
  • the polyfunctional isocyanate compound (B), which is one of the components of the composition relating to the water-absorbing layer 4, will be described in further detail.
  • the polyfunctional isocyanate compound (B) undergoes a crosslinking reaction with the hydroxyl groups of the structural units (a-2) and (a-3) contained in the (meth)acrylic resin (A).
  • the polyfunctional isocyanate compound (B) is a compound having two or more isocyanate groups, including an isocyanate group protected by a leaving group, in one molecule.
  • the number of functional groups in the polyfunctional isocyanate compound (B) is preferably 2 to 6 per molecule, more preferably 2 to 4 per molecule.
  • polyfunctional isocyanate compound (B) examples include aliphatic diisocyanates such as lysine isocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-(or 2,6)-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-(isocyanatomethyl)cyclohexane; and tri- or higher functional isocyanates such as lysine triisocyanate.
  • aliphatic diisocyanates such as lysine isocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate
  • cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, isophor
  • biuret type, isocyanurate type, adduct type, and the like are known as polymers thereof. Any of these can be used as the composition, and among these, it is particularly preferable to use a biuret type polyfunctional isocyanate compound. This is because the structure of the biuret type is softer than that of the isocyanurate type, but harder than that of the adduct type, and has a more appropriate hardness.
  • the polyfunctional isocyanate compound (B) may be a so-called blocked isocyanate. That is, a part or all of the isocyanate groups of the polyfunctional isocyanate compound (B) may be in the form of a blocked isocyanate group blocked by a protecting group.
  • the blocked isocyanate group is formed by blocking the isocyanate group with an active hydrogen compound such as an alcohol-based, phenol-based, lactam-based, oxime-based, or active methylene-based compound.
  • an active hydrogen compound such as an alcohol-based, phenol-based, lactam-based, oxime-based, or active methylene-based compound.
  • a polyfunctional isocyanate compound (B) having a blocked isocyanate group is preferred.
  • polyfunctional isocyanate compound (B) examples include the "Duranate” series manufactured by Asahi Kasei Corporation, the “Sumidur” series manufactured by Sumika Bayer Urethane Co., Ltd., and the “Coronate” series manufactured by Nippon Polyurethane Co., Ltd.
  • the content of the polyfunctional isocyanate compound (B) in the composition is not particularly limited, but is preferably blended according to an equivalent ratio (NCO)/(OH), and more specifically, is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 7 parts by mass or more and 75 parts by mass or less, and even more preferably 10 parts by mass or more and 70 parts by mass or less, per 100 parts by mass of the (meth)acrylic resin (A).
  • NCO equivalent ratio
  • OH equivalent ratio
  • the epoxide (C) is an organic compound having a plurality of epoxy groups.
  • the epoxide (C) is, for example, at least one of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol #200 diglycidyl ether, polyethylene glycol #400 diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol #400 diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and bisphenol A PO2 mol adduct diglycidyl ether.
  • the epoxide (C) having a hydroxyl group is, for example, glycerin diglycidyl ether.
  • the epoxide (C) for example, the "Epolite” series manufactured by Kyoeisha Chemical Co., Ltd. Of these, the epoxide (C) having a hydroxyl group is "Epolite 80MF".
  • the content of the epoxide (C) in the composition is not particularly limited, but is preferably determined so that sufficient adhesion of the water-absorbing layer 4 is obtained without excessively impairing the water-absorbing property, etc., of the water-absorbing layer 4.
  • the content of the epoxide (C) in the composition is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 3 parts by mass or more and 8 parts by mass or less, and even more preferably 5 parts by mass or more and 7 parts by mass or less, relative to 100 parts by mass of the (meth)acrylic resin (A) and the polyfunctional isocyanate compound (B) combined.
  • the content of the epoxide (C) falls within this numerical range, the adhesion of the water absorbing layer 4 becomes sufficient without excessively impairing other performances.
  • the composition is typically used in a state in which each component is dissolved or dispersed in a solvent.
  • the solvent is an organic solvent in one embodiment.
  • the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, and isobutanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate, and glycol ether solvents such as propylene glycol monomethyl acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
  • the amount of the solvent used is not particularly limited, but is preferably an amount such that the concentration of solids (non-volatile
  • the composition can form a cured film having further improved flexibility and elasticity and excellent physical properties.
  • the ratio of the amount of isocyanate groups to the amount of hydroxyl groups in the composition is appropriately adjusted, the physical properties of the water absorbing layer 4 finally obtained will be more excellent.
  • the molar amount (equivalent ratio (NCO)/(OH)) of the isocyanate groups including the blocked isocyanate groups contained in the polyfunctional isocyanate compound (B) relative to the hydroxyl groups contained in the (meth)acrylic resin (A) is preferably in the range of 0.15 or more and 0.55 or less.
  • the reason for this is that, first, when the equivalent ratio (NCO)/(OH) is less than 0.15, even if all the isocyanate groups (NCO) contained in the composition undergo a crosslinking reaction, the crosslink density is insufficient and it is difficult to reach the level required for the water absorption layer 4.
  • the equivalent ratio (NCO)/(OH) exceeds 0.55, the number of isocyanate groups relative to the hydroxyl groups becomes too high, making it difficult to obtain a required crosslink density for the entire water absorption layer 4.
  • the reason for this is that when the number of isocyanate groups relative to the hydroxyl groups is relatively high, for example, in one molecule of a polyfunctional isocyanate compound, it is easy for a situation to occur in which an isocyanate group involved in a reaction and an isocyanate group not involved in the reaction are generated within the molecule, and as a result, the crosslink density is relatively low, making it difficult for the water absorption layer 4 to have sufficient functions such as antifogging property and solvent resistance.
  • the equivalent ratio (NCO)/(OH) is more preferably 0.25 or more and 0.50 or less, and further preferably 0.35 or more and 0.45 or less.
  • the hydroxyl value of the (meth)acrylic resin (A) is preferably in the range of 80 mgKOH/g to 190 mgKOH/g, more preferably 100 mgKOH/g to 150 mgKOH/g, and even more preferably 110 mgKOH/g to 140 mgKOH/g.
  • the hydroxyl value in such a range, the flexibility and elasticity of the water-absorbing layer 4 are further improved, and a water-absorbing layer 4 having even more excellent physical properties is formed.
  • the composition may be of one-part type, that is, all components other than the solvent are substantially uniformly mixed, that is, dissolved or dispersed, in the solvent.
  • the polyfunctional isocyanate compound (B) is a blocked isocyanate, a one-component type is preferred.
  • the composition may also be of a two-liquid type. If the composition is of a two-liquid type, the storage stability of the composition can be further improved.
  • the composition may be composed of (1) a first liquid containing a (meth)acrylic resin (A) and not containing a polyfunctional isocyanate compound (B), and (2) a second liquid containing a polyfunctional isocyanate compound (B) and not containing a (meth)acrylic resin (A), and the first liquid and the second liquid are stored in separate containers, and the first liquid and the second liquid may be mixed immediately before use (coating).
  • Components other than the (meth)acrylic resin (A) and the polyfunctional isocyanate compound (B) may be contained in the first liquid, the second liquid, or prepared in other containers.
  • the polyfunctional isocyanate compound (B) is not a blocked isocyanate, that is, when the isocyanate group is present in the form of -NCO in the system, the composition is preferably of a two-liquid type.
  • the upper limit of the physical thickness of the water absorbing layer 4 is preferably 50 ⁇ m, and more preferably 30 ⁇ m. By setting the upper limit of the physical film thickness in this range, a good appearance can be obtained with reduced deterioration in optical performance compared to the case where the base material 12 is used alone, and costs can also be reduced.
  • the main component of the water-repellent layer 6 is, for example, reactive silicone.
  • the reactive silicone is a compound in which a reactive functional group has been introduced into polydimethylsiloxane (silicone) obtained by polycondensation of an organosilicon compound, and is preferably at least one of amino-modified silicone and mercapto-modified silicone.
  • the reactive silicone contains an amino group and a mercapto group, it has a good reactivity with the water absorption layer 4 having an ester bond.
  • silicone having a silanol group and fluoroalkylsilane have a relatively poor reactivity with the water absorption layer 4 and are inferior in terms of water repellency.
  • the functional group equivalent weight of the amino-modified silicone and the mercapto-modified silicone is preferably 5,000 or more and 100,000 or less, and more preferably 10,000 or more and 60,000 or less.
  • the amino-modified silicone is, for example, at least one of "KF-869” and "KF-8021" manufactured by Shin-Etsu Chemical Co., Ltd. These are side-chain type amino-modified silicones and diamine-modified types.
  • KF-8021 viscosity 15000 mm2 per second at 25°C, functional group equivalent 55000 g/mol
  • KF-869 viscosity 1500 mm2 per second, functional group equivalent 3800 g/mol
  • the water-repellent layer 6 can be formed by applying a solution prepared by mixing the above components in a non-reactive solvent to the surface of the water-absorbing layer 4 by a wet method such as dipping, spraying, roll coating, or spin coating.
  • a non-reactive solvent include aliphatic hydrocarbon solvents such as hexane, heptane, and cyclohexane, and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These solvents may be used alone or in combination.
  • the physical thickness of the water-repellent layer 6 is preferably 0.5 nm to 20 nm, and more preferably 10 nm or less in order to suppress the effect on the water absorption properties of the water-absorbing layer 4 .
  • the contact angle of the surface of the water-repellent layer 6 with water is preferably 100 degrees or more.
  • the size of the contact angle depends on the degree to which water-soluble components such as surfactants contained in the water-absorbing layer 4 remain, and the degree to which the modified silicone adheres to the surface of the water-absorbing layer 4.
  • the substrate 12 with the water-absorbing layer 4 may be treated with at least one of water and alcohol to remove the water-soluble components, or the reactivity may be increased by a surface activation treatment.
  • Such treatment is preferably a physical treatment, for example at least one of plasma treatment and ultraviolet treatment, and among these, plasma treatment is more preferable.
  • the antifogging performance duration (seconds/ ⁇ m) per unit thickness of the antibacterial and antiviral thin film 1 obtained by the steam test is preferably 4 or more.
  • the unit thickness is 1 ⁇ m.
  • the steam test is performed by continuously applying steam due to natural evaporation at 40°C to the surface of the water absorption layer 4 (film-forming surface M, water-repellent layer 6). The time from the start of the application of the steam until the surface starts to fog up is measured, and this time is treated as the anti-fogging performance duration.
  • the anti-fogging performance duration indirectly grasps the porous structure of the water absorption layer 4, which is difficult to directly confirm the shape of using a microscope or the like, that is, the size and distribution of the pores in the water absorption layer 4, and the anti-fogging performance duration per unit film thickness makes it possible to grasp whether the porous structure of the water absorption layer 4 is sufficiently suitable for exhibiting antibacterial and antiviral properties.
  • the lower limit of the physical thickness of the water absorbing layer 4 is preferably 6 ⁇ m or more, and more preferably 10 ⁇ m or more. The porous structure of the water-absorbing layer 4 is maintained even when the water-repellent layer 6 is added, and the water-absorbing layer 4 with the water-repellent layer 6 has a porous structure.
  • the antibacterial and antiviral thin film 1 has a porous structure. If the antifogging performance duration is long, the water absorption capacity of the water absorption layer 4 or the water absorption layer 4 to which the water repellent layer 6 is added is high. If the water absorption capacity is high, the density of the holes in the porous structure for water absorption is considered to be high. The increase in the density of the holes is due to at least one of an increase in the number of holes and an increase in the area of the holes.
  • the antifogging performance duration can be an index of antibacterial and antiviral properties.
  • the antifogging performance duration tends to increase monotonically in proportion to an increase in the physical film thickness of the water-absorbing layer 4 or an increase in the physical film thickness of the water-absorbing layer 4 to which the water-repellent layer 6 has been added. Therefore, from the viewpoint of more appropriately relating the antifogging performance duration to the density of holes in the porous structure, it is preferable to grasp the antifogging performance duration per unit physical film thickness of the antibacterial and antiviral thin film 1.
  • the second embodiment is similar to the first embodiment, except for the composition of the water-absorbing layer.
  • the same members and parts as those in the first embodiment are given the same reference numerals, and descriptions thereof will be omitted as appropriate.
  • composition of the water-absorbing layer in the second embodiment is a mixture of hydrophilic acrylic resin monomers and polyvinyl alcohol (PVA) monomers, for example "X-12-1372A" manufactured by Shin-Etsu Chemical Co., Ltd.
  • PVA polyvinyl alcohol
  • the specific monomer names and amounts of the hydrophilic acrylic resin, the amount of polyvinyl alcohol, and the types and amounts of additives in such compositions are the know-how of the material manufacturer, and therefore the applicant would not be able to know them, and furthermore, it may be impossible for the applicant to thoroughly investigate them by introducing an analyzer, even with great effort.
  • This second form of the composition can be cured in the same manner as the first form to obtain a thin film in the second form, and when such a thin film is cured on the substrate 12, an optical product in the second form can be obtained.
  • the compositions of the second form given as examples above are commercially available as materials for forming hydrophilic functional films, and by adjusting at least one of the physical film thickness and the duration of antifogging performance of a thin film formed using the composition of the second form, an antibacterial and antiviral thin film 1 having a porous structure for exhibiting sufficient antibacterial and antiviral properties can be obtained.
  • the third embodiment is similar to the first embodiment, except for the composition of the water-absorbing layer.
  • the same members and parts as those in the first embodiment are given the same reference numerals, and descriptions thereof will be omitted as appropriate.
  • composition of the water-absorbing layer in the third embodiment contains a polyol compound (D) in addition to the (meth)acrylic resin (A), polyfunctional isocyanate compound (B), and epoxide (C) that are components of the composition in the first embodiment.
  • the composition in the third form is cured in the same manner as the composition in the first form to obtain a thin film in the third form, and when such a thin film is cured on the substrate 12, an optical product in the third form is obtained.
  • an antibacterial and antiviral thin film 1 having a porous structure for exhibiting sufficient antibacterial and antiviral properties can be obtained.
  • the polyol compound (D) in the composition of the third embodiment reacts with the (meth)acrylic resin and the polyfunctional isocyanate compound to form a cured film.
  • the number of hydroxyl groups contained in one molecule of the polyol compound is 2 or more, preferably 2 to 6, and more preferably 2 to 4.
  • the polyol compound preferably contains at least one polyol compound selected from the group consisting of polycaprolactone polyol, polycarbonate polyol, and polyether polyol. These chemical structures are moderately flexible and elastic. This can further increase the flexibility and elasticity of the cured film.
  • the polycaprolactone polyol can be any compound that has a caprolactone ring-opening structure and two or more hydroxyl groups in one molecule, and specific examples include polyols represented by any of the following general formulas (P-1) to (P-3).
  • R represents a divalent organic group.
  • the divalent organic group include linear alkylene groups such as at least one of -CH 2 - and -C 2 H 4 -, branched alkylene groups such as -CH 2 -C(CH 3 ) 2 -CH 2 -, and ether-containing groups such as -C 2 H 4 -O-C 2 H 4 -.
  • Each X is independently a linear or branched alkylene group having preferably 3 to 7 carbon atoms, more preferably 4 to 6 carbon atoms.
  • Each of m and n independently represents an integer of 1 or more.
  • Each of m and n is preferably an integer of 2 to 20. The sum of m and n is preferably 4 to 35.
  • R represents a trivalent organic group.
  • the trivalent organic group include a structure in which three hydrogen atoms have been removed from a linear or branched alkane.
  • Each X is independently a linear or branched alkylene group having preferably 3 to 7 carbon atoms, more preferably 4 to 6 carbon atoms.
  • Each of l, m, and n independently represents an integer of 1 or more.
  • Each of l, m, and n is preferably an integer of 2 to 20. The sum of l, m, and n is preferably 3 to 40.
  • R represents a tetravalent organic group.
  • the tetravalent organic group include a structure in which four hydrogen atoms have been removed from a linear or branched alkane.
  • Each X is independently a linear or branched alkylene group having preferably 3 to 7 carbon atoms, more preferably 4 to 6 carbon atoms.
  • k, l, m and n each independently represent an integer of 1 or more.
  • Each of k, l, m and n is preferably an integer of 2 to 20.
  • the sum of k, l, m and n is preferably 4 to 50.
  • polycaprolactone polyols include, for example, Daicel Corporation's Plaxel 200 series, Plaxel 300 series, and Plaxel 400 series.
  • the polycarbonate polyol can be used without any particular limitation so long as it is a compound having a carbonate group represented by --O--(C.dbd.O)--O-- and two or more hydroxyl groups in one molecule.
  • Polycarbonate polyols can be obtained by reacting one or more polyol raw materials (polyhydric alcohols) with at least one of a carbonate ester and phosgene.
  • the polyol raw material is not particularly limited, and examples thereof include aliphatic polyols, polyols having an alicyclic structure, aromatic polyols, etc. In the present embodiment, from the viewpoint of flexibility of the cured film, aliphatic polyols not having an alicyclic structure are preferred.
  • carbonate esters examples include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonate esters such as diphenyl carbonate, and cyclic carbonate esters such as ethylene carbonate.
  • aliphatic carbonate esters are preferred from the viewpoint of availability and ease of production, and dimethyl carbonate is particularly preferred.
  • polycarbonate polyols for example, the Plaxel series manufactured by Daicel Corporation and the Duranol (trade name) series manufactured by Asahi Kasei Corporation can be used.
  • the polyether polyol can be used without any particular limitation so long as it is a compound having an ether bond (-O-) and two or more hydroxyl groups in one molecule.
  • Specific examples of the compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, bisphenol A, bis( ⁇ -
  • polyamines such as ethylene diamine, propylene diamine, toluene diamine, metaphenylene diamine, diphenylmethane diamine, xylylene diamine, or the like, which are used as an initiator and have two or more, preferably 2 to 3, active hydrogen groups, such as polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, or the like; or polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, and tetrahydrofuran, or the like.
  • active hydrogen groups such as polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, or the like; or
  • the polyol compound (D) may be a compound corresponding to two or more of polycaprolactone polyol, polycarbonate polyol, and polyether polyol.
  • the polyol compound (D) may be a polyether polyester polyol having an ether bond and an ester bond.
  • the polyol compound may contain a plurality of types of polycaprolactone polyol, polycarbonate polyol, and polyether polyol.
  • the hydroxyl value of the polyol compound is preferably 50 to 500 mgKOH/g, more preferably 100 to 350 mgKOH/g, and particularly preferably 150 to 250 mgKOH/g.
  • the weight average molecular weight (Mw) of the polyol compound (D) is preferably 450 to 2500, more preferably 500 to 1500, and particularly preferably 500 to 700.
  • the content of polyol compound (D) in the composition is usually 5 to 200 parts by mass, preferably 15 to 180 parts by mass, and more preferably 20 to 150 parts by mass, per 100 parts by mass of the (meth)acrylic resin. By setting the content within this range, it is possible to obtain sufficient performance derived from polyol compound (D) while also achieving a good balance with other components.
  • the polyol compound (D) preferably contains a polycaprolactone polyol among the above-mentioned polycaprolactone polyols, polycarbonate polyols, and polyether polyols, and among the polycaprolactone polyols, it is particularly preferable to contain a polycaprolactone diol, which is a compound having a caprolactone structure and two hydroxyl groups.
  • the (meth)acrylic resin contained in the composition of the present embodiment has the structure of the above-mentioned general formula (2), i.e., a caprolactone structure, and therefore the polyol compound (D) tends to have good compatibility with the resin, and the anti-fogging performance tends to be improved without excessively increasing the crosslink density.
  • the polyol compound (D) reacts with the (meth)acrylic resin (A) and the polyfunctional isocyanate compound (B) to form a third type of water-absorbing layer.
  • the polyol compound (D) reacts by penetrating between the (meth)acrylic resin (A) and the polyfunctional isocyanate compound (B), acting as a bridge and widening the gaps for water absorption while maintaining sufficient crosslink density as a water-absorbing layer.
  • the composition does not contain the epoxide (C).
  • the composition contains the (meth)acrylic resin (A), the polyfunctional isocyanate compound (B), and the polyol compound (D).
  • the respective contents and the like of the first to third embodiments described above may be used.
  • an antibacterial and antiviral thin film 1 having a porous structure that exhibits sufficient antibacterial and antiviral properties can be obtained by adjusting at least one of the physical film thickness and the duration of antifogging performance for a thin film formed from a composition that imparts antifogging properties, i.e., that allows the thin film to adsorb or absorb moisture without causing fogging.
  • Example 1 belongs to the first aspect.
  • Example 1 includes Example 1-1 and Example 1-2.
  • Example 1-1 and Example 1-2 are similar to each other except for the physical film thicknesses and the characteristics based on the physical film thicknesses.
  • Example 1 was formed as follows.
  • the substrate 12 was made of thiourethane ("MR-8" manufactured by Mitsui Chemicals, Inc.) having a refractive index of 1.60, and was a spectacle lens substrate having a diopter of S-2.00.
  • the composition of the first form was applied by dipping to the convex surface (film-forming surface M) of the substrate 12 by further heating at 130°C for 2 hours to harden the applied composition, thereby forming a water-absorbing layer 4 on the film-forming surface M.
  • the solvent was propylene glycol monomethyl ether (PGM).
  • PGM propylene glycol monomethyl ether
  • a water-repellent layer 6 made of amino-modified silicone ("KF-8021" manufactured by Shin-Etsu Chemical Co., Ltd.) was formed on the water-absorbing layer 4 by dipping using a non-reactive solvent as the solvent.
  • the (meth)acrylic resin (A) of the first type of composition has a structural unit (a-1) that is 50 mass% dimethylacrylamide (DMAA), a structural unit (a-2) that is 35 mass% polycaprolactone-modified hydroxyethyl acrylate (“PLACCEL FA2D” manufactured by Daicel Corporation), a structural unit (a-3) that is 10 mass% 2-hydroxylethyl methacrylate (HEMA), and a structural unit (a-4) that is 5 mass% one-end methacrylate-modified polydimethylsiloxane (“Silaplane FM-0721" manufactured by JNC Corporation).
  • DMAA dimethylacrylamide
  • PLACCEL FA2D polycaprolactone-modified hydroxyethyl acrylate
  • HEMA 2-hydroxylethyl methacrylate
  • a-4 that is 5 mass% one-end methacrylate-modified polydimethylsiloxane
  • the polyfunctional isocyanate compound (B) in the composition of the first embodiment is a biuret type of hexamethylene diisocyanate ("24A-100" manufactured by Asahi Kasei Corporation) and is 18 parts by mass per 100 parts by mass of the (meth)acrylic resin (A).
  • the epoxide (C) of the composition of the first type is glycerin diglycidyl ether ("Epolight 80M” manufactured by Kyoeisha Chemical Co., Ltd.), and is 6 parts by mass (approximately 6% by mass of the solid content of the composition) per 100 parts by mass of the (meth)acrylic resin (A) and the polyfunctional isocyanate compound (B).
  • residual OH Vol. The amount of residual hydroxyl groups in the composition of Example 1 (hereinafter, “residual OH Vol.”) is 20% or more and less than 30% (20-30%), and the amount of hydroxyl groups in the resin (hereinafter, “resin OH Vol.”) is medium (medium). Since the applicant is not a material manufacturer, the residual OH Vol. requires a lot of time and cost for analysis, and only information on a wide range of states can be obtained. Meanwhile, since the resin OH Vol. requires a lot of time and cost for analysis of the elements of the resin, the relative magnitude can be grasped.
  • Example 1-1 In the physical film thickness of Example 1-1, the target film thickness, which is the physical film thickness intended at the time of film formation, was 10 ⁇ m, and the actual film thickness, which is the physical film thickness actually measured, was 10.65 ⁇ m. In the physical film thickness of Example 1-2, the target film thickness was 13 ⁇ m, and the actually measured film thickness was 13.33 ⁇ m. The physical thickness of the water-repellent layer 6 in Example 1 was set to 7 nm.
  • Example 2 belongs to the first aspect.
  • Example 2 includes Example 2-1 and Example 2-2.
  • Example 2-1 and Example 2-2 are similar to each other except for the physical film thicknesses and the characteristics based on the physical film thicknesses.
  • Example 2 was formed similarly to Example 1 with the following exceptions. That is, in Example 2, the polyfunctional isocyanate compound (B) in the composition of the first form was 10.8 parts by mass per 100 parts by mass of the (meth)acrylic resin (A), which was reduced by 40% compared to 18 parts by mass in Example 1.
  • Example 2 has a water-repellent layer 6 on a water-absorbing layer 4, similar to Example 1.
  • the target film thickness was 6 ⁇ m
  • the actually measured film thickness was 6.85 ⁇ m.
  • the target film thickness of Example 2-2 the target film thickness was 10 ⁇ m, and the actually measured film thickness was 9.61 ⁇ m.
  • Example 3 belongs to the second aspect.
  • Example 3 includes Example 3-1 and Example 3-2.
  • Example 3-1 and Example 3-2 are similar to each other except for the physical film thicknesses and the characteristics based on the physical film thicknesses.
  • Example 3 was formed as follows. That is, a titanium-based catalyst was added to the second type composition, "X-12-1372A" manufactured by Shin-Etsu Chemical Co., Ltd., in an amount of 1% by mass on the film-forming surface M of the substrate 12, which was the same as in Example 1, and the composition was applied by the dipping method in the same manner as in Example 1 and then cured to form a water-absorbing layer 4. In addition, a water-repellent layer, the same as in Example 1, was formed on the water-absorbing layer 4.
  • Example 3-1 In the physical film thickness of Example 3-1, the target film thickness was 6 ⁇ m, and the actually measured film thickness was 7.61 ⁇ m. In the physical film thickness of Example 3-2, the target film thickness was 10 ⁇ m, and the actually measured film thickness was 14.96 ⁇ m.
  • the fourth embodiment belongs to the third embodiment.
  • Example 4 was formed as follows. That is, the composition of the third embodiment was applied by dipping to the same substrate 12 as in Example 1, and the applied composition was cured by heating at 130° C. for 2 hours, thereby forming a water-absorbing layer 4 on the film-forming surface M. The solvent was PGM. Moreover, the same water-repellent layer 6 as in Example 1 was formed on the water-absorbing layer 4.
  • the (meth)acrylic resin (A) of the composition of the third embodiment is as follows. That is, the structural unit (a-1) is DMAA, which accounts for 50% by mass in the (meth)acrylic resin (A).
  • the structural unit (a-2) is polycaprolactone-modified hydroxyethyl acrylate ("Placcel FA2D” manufactured by Daicel Corporation), which accounts for 35% by mass in the (meth)acrylic resin (A). Furthermore, the structural unit (a-3) is HEMA, which accounts for 10% by mass in the (meth)acrylic resin (A). Furthermore, the structural unit (a-4) is one-terminal methacrylate-modified polydimethylsiloxane ("Silaplane FM-0721" manufactured by JNC Corporation), which accounts for 5% by mass in the (meth)acrylic resin (A).
  • the polyfunctional isocyanate compound (B) in the composition of the third embodiment is a biuret type of hexamethylene diisocyanate ("24A-100" manufactured by Asahi Kasei Corporation) and accounts for 18 parts by mass per 100 parts by mass of the (meth)acrylic resin (A).
  • the epoxide (C) of the composition of the third form is glycerin diglycidyl ether ("Epolight 80M” manufactured by Kyoeisha Chemical Co., Ltd.) and accounts for 6 parts by mass per 100 parts by mass of the (meth)acrylic resin (A) and the polyfunctional isocyanate compound (B).
  • the polyol compound (D) of the composition of the third embodiment is polycaprolactone diol ("Placcel 205U” manufactured by Daicel Corporation, molecular weight 530, hydroxyl value 207 to 217 mgKOH/g), and accounts for 30 parts by mass per 100 parts by mass of the (meth)acrylic resin (A).
  • the target film thickness was 10 ⁇ m
  • the actually measured film thickness was 10.50 ⁇ m.
  • Comparative Example 1 includes Comparative Example 1-1 and Comparative Example 1-2. Comparative Example 1-1 and Comparative Example 1-2 are similar to each other except for the physical film thicknesses and the characteristics based on the physical film thicknesses. Except for the physical film thickness, the comparative example 1 was formed in the same manner as in the example 1. As in the example 1, the comparative example 1 has a water repellent layer 6 on a water absorbing layer. In the physical film thickness of Comparative Example 1-1, the target film thickness was 3 ⁇ m, and the actually measured film thickness was 3.29 ⁇ m. In the physical film thickness of Comparative Example 1-2, the target film thickness was 6 ⁇ m, and the actually measured film thickness was 5.88 ⁇ m.
  • Comparative Example 2 includes Comparative Example 2-1 and Comparative Example 2-2. Comparative Example 2-1 and Comparative Example 2-2 are similar to each other except for the physical film thicknesses and the characteristics based on the physical film thicknesses. Comparative Example 2 was formed as follows. That is, a polyurethane resin forming composition based on a polyurethane monomer ("Visgard Premium Plus" manufactured by FSI Coating Technologies) was applied by dipping to the film forming surface M of the same substrate 12 as in Example 1, and then heat cured at 130° C. for 2 hours to form a water absorption layer. In addition, a water repellent layer 6 similar to that in Example 1 was formed on the water absorption layer.
  • a polyurethane resin forming composition based on a polyurethane monomer ("Visgard Premium Plus" manufactured by FSI Coating Technologies) was applied by dipping to the film forming surface M of the same substrate 12 as in Example 1, and then heat cured at 130° C. for 2 hours to form a water absorption layer.
  • the target film thickness of Comparative Example 2-1 was 6 ⁇ m, and the actually measured film thickness was 7.24 ⁇ m.
  • the target film thickness was 10 ⁇ m, and the actually measured film thickness was 9.42 ⁇ m.
  • the breath whitening test is a test in which breath is applied to the surface of the test subject on the film-formed surface M for 2 seconds to check whether the lens becomes cloudy and white.
  • the results of the breath whitening test were marked as "x” if the lens became cloudy and marked as "o” if the lens did not become cloudy.
  • a steam test was carried out, the antifogging performance duration was measured, and the antifogging performance duration per unit film thickness was calculated.
  • the steam test was carried out as follows. That is, first, a bottle with a lid and water was placed in a thermostatic chamber in which the temperature inside the chamber was maintained at 40°C, and the bottle was heated to 40°C by waiting for a predetermined time to elapse. The opening of the bottle was 30 mm, the capacity of the bottle was 120 ml, and the amount of water was 100 ml.
  • the bottle was taken out of the thermostatic chamber, the lid of the opening was removed, and the test object was set in a state in which the convex surface (the surface on the film-forming surface M side) of the test object was facing downward and in contact with the opening.
  • the time from the time the test object was set to the time when it started to fog up, that is, the anti-fogging performance duration (seconds), was measured.
  • the anti-fogging performance duration reached 180 seconds (3 minutes), the anti-fogging performance duration was deemed sufficient, and the steam test was terminated ( ⁇ 180).
  • the anti-fogging performance duration (seconds) of each test object was divided by the actual film thickness ( ⁇ m) of the water-absorbing layer 4 in the test object to calculate the anti-fogging performance duration per unit film thickness (seconds/ ⁇ m).
  • the lid of the bottle may be omitted. At least one of the size and shape of the opening of the bottle may be other than those described above, so long as the test object is placed on it. Furthermore, other steam generating structures may be used, so long as the steam from natural evaporation at 40°C is continuously applied to the test object, i.e., the steam is continuously applied to the test object.
  • the line below the breath whitening test shows the duration of anti-fogging performance, and the line below that shows the duration of anti-fogging performance per unit film thickness.
  • the duration of the antifogging performance is less than 40 seconds, and the duration of the antifogging performance per unit film thickness is less than 4 seconds/ ⁇ m.
  • the anti-fogging performance duration of Comparative Example 1-1 was 13.06 seconds, and the anti-fogging performance duration per unit film thickness was 3.97 seconds/ ⁇ m
  • the anti-fogging performance duration of Comparative Example 1-2 was 23.45 seconds
  • the anti-fogging performance duration per unit film thickness was 3.98 seconds/ ⁇ m
  • the anti-fogging performance duration of Comparative Example 2-1 was 24.65 seconds
  • the anti-fogging performance duration per unit film thickness was 3.40 seconds/ ⁇ m
  • the anti-fogging performance duration of Comparative Example 2-2 was 36.91 seconds
  • the anti-fogging performance duration per unit film thickness was 3.92 seconds/ ⁇ m.
  • the antifogging performance duration is 40 seconds or more, and the antifogging performance duration per unit film thickness is 4 or more.
  • the antifogging performance duration of Example 1-1 is 50.54 seconds, and the antifogging performance duration per unit thickness is 4.74 seconds/ ⁇ m
  • the antifogging performance duration of Example 1-2 is 62.91 seconds
  • the antifogging performance duration per unit thickness is 4.72 seconds/ ⁇ m
  • the antifogging performance duration of Example 2-1 is 42.53 seconds
  • the antifogging performance duration per unit thickness is 6.21 seconds/ ⁇ m
  • the antifogging performance duration of Example 2-2 is 75.22 seconds
  • the antifogging performance duration per unit thickness is 7.83 seconds/ ⁇ m.
  • the antifogging performance duration of Example 3-1 is 105.75 seconds, and the antifogging performance duration per unit thickness is 13.90 seconds/ ⁇ m, the antifogging performance duration of Example 3-2 is ⁇ 180 seconds, and the antifogging performance duration per unit thickness is ⁇ 12 seconds/ ⁇ m, and the antifogging performance duration of Example 4 is 48.57 seconds, and the antifogging performance duration per unit thickness is 4.63 seconds/ ⁇ m.
  • the duration of anti-fogging performance is longer and the duration of anti-fogging performance per unit film thickness is longer than in Comparative Examples 1 and 2.
  • Examples 1 to 4 are superior in anti-fogging performance and anti-fogging performance per unit film thickness than in Comparative Examples 1 and 2.
  • the surface condition of the antibacterial and antiviral thin film 1 (film-forming surface M side) including the water-absorbing layer 4 and water-repellent layer 6 in Example 1-2 was examined by measuring the pore distribution and ink penetration tests, assuming that the surface condition is capable of adsorbing or absorbing moisture due to the distribution of numerous pores, thereby suppressing clouding due to moisture.
  • many spectacle lenses have an inorganic anti-reflection multilayer film having a SiO 2 film as the layer closest to the air on the surface of the spectacle lens substrate via a hard coat film.
  • the inorganic anti-reflection multilayer film is formed by a vacuum deposition method. Therefore, the fact that there is no significant difference from the above-mentioned various values in the SiO 2 film leads to the fact that there is no significant difference from the above-mentioned various values in a general spectacle lens.
  • the antibacterial and antiviral thin film 1 of Example 1-2 has an antifogging property and a structure that adsorbs or absorbs moisture, this result suggests the following various points.
  • the size of the pores in the antibacterial and antiviral thin film 1 is so small that it is difficult to confirm the difference from the SiO2 film by mercury intrusion porosimetry. Because such a difference does not appear by mercury intrusion porosimetry, the pore diameter, which is the diameter when the pores are regarded as cylindrical, i.e., the width of the pores, is expected to be at least 100 nm or less.
  • the antibacterial and antiviral thin film 1 and the substrate 12 are both made of plastic, they may expand during mercury injection, generating pores caused by external pressure, that is, pseudo-pores.
  • the dye ink was a black water-based dye ink contained in an aqueous dye ink cartridge "XFR-AD” for brush pens manufactured by Pentel Co., Ltd.
  • the pigment ink was a black water-based pigment ink contained in an aqueous pigment ink cartridge "XFRP-A” for brush pens manufactured by Pentel Co., Ltd. That is, first, each ink was put into a beaker without dilution, the tip of a cotton swab was soaked in each ink, and a line was drawn on the surface of the test object with the cotton swab.
  • each ink was dried by leaving it for one minute indoors, and then the line of each ink was wiped dry with a nonwoven fabric (Ozu Sangyo Co., Ltd.'s "Pure Leaf”). Next, the remaining line of each ink was wiped with the same type of nonwoven fabric soaked in an organic solvent (acetone).
  • Figure 2 is a grayscale photograph of the test object taken from the front side when each ink was dried.
  • Figure 3 is a grayscale photograph of the test object taken from the back side immediately after wiping each ink dry.
  • Figure 4 is a grayscale photograph of the test object taken from the back side immediately after wiping each ink with acetone.
  • the upper lines are dye inks and the lower lines are pigment inks.
  • the pigment ink of the test subject was removed by dry wiping, and the dye ink of the test subject remained after the dry wiping.
  • the remaining dye ink of the test subject remained even after wiping with acetone. That is, the pigment ink did not soak into the surface of the test subject, but the dye ink did soak into the surface.
  • the particle size distribution of each ink was measured by a dynamic light scattering particle size distribution measuring device (Dynamic Light Scattering; DLS).
  • the particle size distribution of the dye ink was approximately normal in a graph with the horizontal axis representing particle size (nm) and the vertical axis representing the proportion (percentage) of the number of particles, and was within the range of 2 nm to 15 nm, with the maximum value at 5.1 nm (approximately 25%).
  • the particle size distribution of the pigment ink was approximately normal in the same graph as for the pigment ink, and was within the range of 40 nm to 300 nm with a maximum value (approximately 23%) at 85.3 nm.
  • the pore size in the antibacterial and antiviral thin film 1 of Example 1-2 is about 30 nm ⁇ 10 nm in pore diameter.
  • the pore width in the antibacterial and antiviral thin film 1 of Example 1-2 is 20 nm or more and 40 nm or less.
  • the antibacterial performance was tested against Staphylococcus aureus and Escherichia coli in accordance with ISO 22196:2007.
  • the antibacterial activity value R is defined by the following formula (1).
  • R log(B/C) (1)
  • B is the average number of viable bacteria (units) in the test subject (reference) after 24 hours
  • C is the average number of viable bacteria (units) in the antibacterial film after 24 hours
  • log is the common logarithm.
  • the antibacterial activity value R is ⁇ 2.0, it is judged that the antibacterial performance is insufficient, and the antibacterial performance is rated as " ⁇ ". Furthermore, when the antibacterial properties of both Staphylococcus aureus and Escherichia coli are " ⁇ ", the overall antibacterial performance is rated as " ⁇ ", when either one of the antibacterial properties of Staphylococcus aureus and Escherichia coli is " ⁇ " and the other is " ⁇ ", the overall antibacterial performance is rated as " ⁇ ", and when the antibacterial properties of both Staphylococcus aureus and Escherichia coli are " ⁇ ", the overall antibacterial performance is rated as " ⁇ ".
  • the antiviral performance was tested against influenza A virus in accordance with ISO 21702:2019.
  • the antiviral activity value R' is defined by the following formula (1').
  • R' log(B'/C') (1')
  • B' is the average number (pieces) of live viruses in the test subject (reference) after 24 hours
  • C' is the average number (pieces) of live viruses in the antiviral membrane after 24 hours
  • log is common logarithm.
  • Examples 1 to 4 have a large number of pores with a size of about 30 nm ⁇ 10 nm, which enables adsorption or absorption of moisture, and thus have antifogging properties as well as antibacterial and antiviral properties. Note that Examples 1 to 4 do not contain any inorganic antibacterial agent (e.g., silver ion-supported zeolite) or organic antibacterial component (e.g., quaternary ammonium salt). On the other hand, it is generally known that objects having a fine uneven structure like an insect's wing have a certain degree of antibacterial and antiviral properties.
  • inorganic antibacterial agent e.g., silver ion-supported zeolite
  • organic antibacterial component e.g., quaternary ammonium salt
  • the mechanism by which the antibacterial and antiviral properties are exerted has not been fully elucidated, but there is a theory that it is related to the distance between adjacent convex parts (the width of the concave part) and the height of the convex parts (the depth of the concave part) in the fine uneven structure. There is also a theory that the antibacterial properties are sufficient when the height of the convex parts is greater than a certain threshold value.
  • Fig. 5 is a schematic diagram showing the antibacterial and antiviral thin film 1 and E. coli E when the physical thickness of the antibacterial and antiviral thin film 1 (water absorption layer 4) having a large number of pores P is sufficient as in Examples 1 to 4.
  • Fig. 6 is a schematic diagram showing the thin film and E. coli E when the physical thickness of the thin film TF (water absorption layer) having a large number of pores P is not sufficient as in Comparative Examples 1 and 2.
  • E. coli has an E. coli body EB and one or more flagella EW extending from it. The size of the E.
  • the thickness of the flagella EW is about 20-30 nm in diameter, and the length of the flagella EW is about 10 ⁇ m.
  • E. coli moves by the rotation of the flagella EW. 5, in Examples 1 to 4, the physical thickness of the antibacterial and antiviral thin film 1 is sufficient, and the depth of the pores P is sufficient, allowing the entire flagellum EW of E. coli E to enter the pores P. It is believed that E. coli E with the entire flagellum EW entering the pores P will no longer be able to move using the flagellum EW.
  • viruses are about 10 to 1000 nm in size and do not move on their own like E. coli E.
  • the width of the pores P was about 30 nm ⁇ 10 nm, which is similar to the size of a virus, and it is believed that the virus is captured by the pores P.
  • Staphylococcus aureus does not have flagella and has multiple globules in its body resembling a bunch of grapes, with the size of each globule being similar to that of a virus, and it is thought that Staphylococcus aureus is captured in the pores P.
  • the antifogging performance duration and the antifogging performance duration per unit film thickness are small, it can be said that the antifogging performance is low and the pores P are not evenly distributed. In that case, even if the physical film thickness of the thin film is sufficient, the pores P for capturing E. coli E and the like are insufficient, and it is considered that the antibacterial and antiviral properties are reduced. In contrast, when the antifogging performance duration and the antifogging performance duration per unit film thickness are greater than a certain level (a predetermined threshold value), it can be said that the antifogging properties are high and the pores P are more evenly distributed. Therefore, when the physical film thickness of the antibacterial and antiviral thin film 1 is sufficient, it is considered that there are sufficient pores P that capture E. coli E and the like, and sufficient antibacterial and antiviral properties can be obtained.
  • a certain level a predetermined threshold value
  • the water-absorbing layer 4 or the porous layer which has a plurality of pores P capable of adsorbing or absorbing moisture and does not cause fogging by adsorbing moisture in some or all of the pores P, can be considered as a bacteria/virus capture layer that captures at least one of bacteria and viruses. Even if the water-repellent layer 6 is provided together with the water-absorbing layer 4 in the antibacterial and antiviral thin film 1, as long as the physical film thickness is 20 nm or less, the multiple pores P effective for capturing at least one of bacteria and viruses will not all be blocked.
  • the antibacterial and antiviral thin film 1 provided with the water-repellent layer 6 has antibacterial and antiviral properties, and also has better maintainability, such as being easier to wipe off dirt on the surface.
  • the antibacterial and antiviral thin films 1 of Examples 1 to 4 have a water absorption layer 4 having a plurality of pores P, the physical film thickness of the water absorption layer 4 is 6 ⁇ m or more, and the antifogging performance duration per unit film thickness (1 ⁇ m) obtained by dividing the antifogging performance duration obtained by a steam test of the water absorption layer 4 by the physical film thickness (actually measured film thickness, unit ⁇ m) of the water absorption layer 4 is 4 seconds/ ⁇ m or more.
  • the steam test is performed by continuously applying steam related to natural evaporation at 40° C. to the surface on the water absorption layer 4 side and measuring the time from the start of application to the start of fogging as the antifogging performance duration. Therefore, Examples 1 to 4 provide an antibacterial and antiviral thin film 1 having antibacterial and antiviral properties.
  • the width of the pores P in the antibacterial and antiviral thin films 1 of Examples 1 to 4 is 20 nm or more and 40 nm or less. Therefore, the antibacterial and antiviral thin films 1 of Examples 1 to 4 exhibit better antibacterial and antiviral properties. Furthermore, the antibacterial and antiviral thin films 1 of Examples 1 to 4 have a water-repellent layer 6 containing at least one of amino-modified silicone and mercapto-modified silicone as a main component, and the physical film thickness of the water-repellent layer 6 is 7 nm, which is 20 nm or less. Therefore, the antibacterial and antiviral thin films 1 of Examples 1 to 4 have sufficient antibacterial and antiviral properties, as well as sufficient scratch resistance and slipperiness. In addition, the optical products 10 of Examples 1 to 4 include the above-mentioned antibacterial and antiviral thin film 1 and a substrate 12. Thus, Examples 1 to 4 provide the optical products 10 having antibacterial and antiviral properties.
  • the water-absorbing layer is obtained from a composition comprising
  • the (meth)acrylic resin (A) has, relative to 100 mass% of all structural units, a proportion of structural units derived from the monomer (a-1) of 20 mass% or more and 65 mass% or less, a proportion of structural units derived from the monomer (a-2) of 10 mass% or more and 40 mass%
  • R 1 is a hydrogen atom or a methyl group
  • R 2 and R 3 are a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and R 2 and R 3 may be the same or different.
  • R4 is a hydrogen atom or a methyl group
  • n1 is an integer of 1 or more and 5 or less.
  • R5 is a hydrogen atom or a methyl group
  • R6 is a divalent organic group
  • n2 is 0 or an integer of 1 or more.
  • (Invention 2) The antibacterial and antiviral thin film described in (Invention 1), characterized in that a ratio of the polyfunctional isocyanate compound (B) is 5 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the (meth)acrylic resin (A).
  • (Invention 3) The antibacterial and antiviral thin film described in (Invention 1), wherein the epoxide (C) is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic resin (A) and the polyfunctional isocyanate compound (B) combined.
  • (Invention 4) The antibacterial and antiviral thin film according to (Invention 1), wherein the epoxide (C) has one or more hydroxyl groups.
  • the antibacterial and antiviral thin film described in (Invention 1) is characterized in that it further has a water-repellent layer on the water-absorbing layer, the water-repellent layer mainly composed of at least one of amino-modified silicone and mercapto-modified silicone.
  • 1 antibacterial and antiviral thin film
  • 4 water-absorbing layer (porous layer)
  • 6 water-repellent layer
  • 10 optical product
  • 12 substrate
  • M film-forming surface

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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un film mince antibactérien et antiviral qui est un film mince ayant des propriétés antibactériennes et antivirales, et un produit optique. [Solution] Un film mince antibactérien et antiviral 1 qui comprend une couche d'absorption d'eau 4 ayant une pluralité de trous P, l'épaisseur de film physique de la couche d'absorption d'eau 4 étant supérieure ou égale à 6 µm, une durée de performance antibuée par épaisseur de film unitaire (1 µm) obtenue en divisant une durée de performance antibuée obtenue par un test de vapeur de la couche d'absorption d'eau 4 par une épaisseur de film physique de la couche d'absorption d'eau 4 (épaisseur de film mesurée (µm)) étant supérieure ou égale à 4 secondes/µm. Le test de vapeur est réalisé en appliquant en continu de la vapeur générée par vaporisation naturelle à 40 °C sur la surface du côté de la couche d'absorption d'eau 4 pour mesurer, en tant que durée de performance antibuée, la durée depuis le début de l'application jusqu'à l'apparition de la buée.
PCT/JP2023/034566 2022-09-29 2023-09-22 Film mince antibactérien et antiviral et produit optique WO2024070969A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001145982A (ja) * 1999-09-08 2001-05-29 Toto Ltd 吸湿性防曇フィルム及びその製造方法
JP2008260718A (ja) * 2007-04-12 2008-10-30 Nippon Sheet Glass Co Ltd 抗菌性多孔質薄膜の製造方法
JP2010167388A (ja) * 2009-01-26 2010-08-05 Emprie Technology Development LLC ナノポーラス表面を有する製品の製造方法
JP2013103990A (ja) * 2011-11-14 2013-05-30 Nippon Synthetic Chem Ind Co Ltd:The 樹脂組成物および、それを用いてなるフィルム、防曇用フィルム、抗菌用フィルム、並びにコーティング剤
JP2019094468A (ja) * 2017-11-28 2019-06-20 ナトコ株式会社 塗料組成物、硬化膜、硬化膜を備えた物品
CN114854075A (zh) * 2022-06-06 2022-08-05 江阴诚公转印包装材料有限公司 一种果蔬专用保鲜呼吸膜及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001145982A (ja) * 1999-09-08 2001-05-29 Toto Ltd 吸湿性防曇フィルム及びその製造方法
JP2008260718A (ja) * 2007-04-12 2008-10-30 Nippon Sheet Glass Co Ltd 抗菌性多孔質薄膜の製造方法
JP2010167388A (ja) * 2009-01-26 2010-08-05 Emprie Technology Development LLC ナノポーラス表面を有する製品の製造方法
JP2013103990A (ja) * 2011-11-14 2013-05-30 Nippon Synthetic Chem Ind Co Ltd:The 樹脂組成物および、それを用いてなるフィルム、防曇用フィルム、抗菌用フィルム、並びにコーティング剤
JP2019094468A (ja) * 2017-11-28 2019-06-20 ナトコ株式会社 塗料組成物、硬化膜、硬化膜を備えた物品
CN114854075A (zh) * 2022-06-06 2022-08-05 江阴诚公转印包装材料有限公司 一种果蔬专用保鲜呼吸膜及其制备方法

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