Radical polymerization anti-fogging coating agent

Abstract

The present invention provides a radical polymerizable anti-fogging coating agent that yields a cured product with excellent anti-fogging properties and scratch resistance, as well as superior durability of anti-fogging properties and appearance, and a laminate having an anti-fogging coating layer obtained from the coating agent. [Solution] The radical polymerizable anti-fogging coating agent of the present invention comprises (A) a (meth)acryloyl compound represented by the following general formula (1), (B) a bifunctional or more (meth)acryloyl compound (excluding (meth)acryloyl compound (A)), (C) inorganic particles, and (D) a nonionic surfactant, wherein the radical polymerizable anti-fogging coating agent contains (A) the (meth)acryloyl compound in an amount of 20% to 60% by mass per 100% by mass of solid content. TIFF2026069906000009.tif48153

Description

Technical Field

[0001] The present invention relates to a radically polymerizable anti-fog coating agent, a film composed of a cured product of the coating agent, and an anti-fog coating laminate provided with a resin layer composed of a cured product of the coating agent on a substrate.

Background Art

[0002] Conventionally, when plastic materials, glass, etc. are used in a place with high temperature and high humidity or an atmosphere with a large temperature difference or humidity difference, if the surface temperature becomes lower than the dew point temperature, moisture in the atmosphere condenses on the surface to form fine water droplets and adheres, causing fogging. In particular, plastic materials are used in a wide range of fields such as automotive parts, building materials, household appliances, packaging materials, lenses, etc. due to advantages such as light weight, processability, and transparency. However, in applications where anti-fog performance is required, it has been difficult to use for the same reasons as above. To solve these situations, a method of applying an anti-fog composition composed of a non-reactive surfactant to the surface of a substrate is often used. However, there are problems such as poor practicality, for example, the anti-fog property can be easily impaired by simply wiping and cleaning the coated surface lightly.

[0003] Various proposals have been made as methods for solving the above problems. For example, a method (Patent Document 1) has been proposed in which a resin composition containing a (meth)acrylate of a predetermined polyglycerin alkylene oxide adduct is applied to the surface of a substrate and radically polymerized to form an anti-fog film and impart anti-fog properties.

[0004] The present inventors have proposed a method (Patent Document 2) in which a radically polymerizable composition containing poly(meth)acrylate, inorganic particles, and a surfactant is applied to the surface of a substrate, a transparent film for lamination is overlapped on the coated surface, irradiated with radiation such as UV to resinify, and then the transparent film for lamination is peeled off to form a film and impart anti-fog properties.

[0005] Furthermore, a method has been proposed (Patent Document 3) in which a composition consisting of poly(meth)acrylate, urethane poly(meth)acrylate, inorganic particles, and a nonionic surfactant is applied to the surface of a substrate, and radical polymerization is carried out to form an anti-fogging film on the surface and impart anti-fogging properties. Furthermore, the present inventors have proposed a method (Patent Document 4) for imparting antifouling (easy cleaning) and antifogging properties by concentrating and fixing anionic hydrophilic groups on the surface (segregation gradient). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2010-260917 [Patent Document 2] Japanese Patent Publication No. 2022-051202 [Patent Document 3] Japanese Patent Publication No. 2022-152737 [Patent Document 4] International Publication No. 2015 / 087810 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The methods described in Patent Documents 1 to 4 can maintain anti-fogging properties for a longer period than methods that involve applying surfactants, and also allow for short-time polymerization (coating) using radiation sources such as ultraviolet (UV) light. However, even when using the compositions and methods described in these documents, the resulting anti-fog layer could be scratched during cleaning such as dry wiping, or condense and fog up in low-temperature environments, leaving room for improvement. The object of this invention is to provide a radical polymerizable anti-fog coating agent that provides a coating layer with excellent anti-fogging performance and scratch resistance, as well as superior durability of anti-fogging properties and appearance. [Means for solving the problem]

[0008] The inventors selected a specific (meth)acryloyl compound and a bifunctional or more (meth)acryloyl compound from among many compounds, and found that a radical polymerizable anti-fogging coating agent containing these compounds can solve the above problems, thus completing the present invention. The present invention can be shown as follows.

[0009] [1](A) A (meth)acryloyl compound represented by the following general formula (1), (B) A (meth)acryloyl compound with two or more functions (excluding the (A) (meth)acryloyl compound mentioned above) (C) Inorganic particles and (D) Nonionic surfactants, A radical polymerizable anti-fogging coating agent, comprising: A radical polymerizable anti-fogging coating agent comprising the above-mentioned radical polymerizable anti-fogging coating agent in an amount of 20% to 60% by mass of the (A)(meth)acryloyl compound in 100% by mass of the solid content of the radical polymerizable anti-fogging coating agent. [ka] (In the formula, n1 to n6 independently represent integers from 1 to 33. R1 to R6 independently represent a hydrogen atom or a methyl group.) [2] The (B) difunctional or greater (meth)acryloyl compound is a difunctional or greater poly(meth)acrylate having a urethane bond or isocyanurate ring structure in one molecule [the radical polymerizable anti-fogging coating agent according to 1]. [3] The (B) (meth)acryloyl compounds with two or more functionalities, Tris{(meth)acryloyloxyethyl}isocyanurate, A bifunctional urethane di(meth)acrylate obtained by reacting hexamethylene diisocyanate with polyethylene glycol mono(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, A tetrafunctional urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate with glycerin-1,3-di(meth)acrylate, A hexafunctional urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate and pentaerythritol tri(meth)acrylate, A hexafunctional urethane poly(meth)acrylate obtained by reacting N,N′,N′′-tris(isocyanatohexyl)isocyanurate and glycerin-1,3-di(meth)acrylate, A nonafunctional urethane poly(meth)acrylate obtained by reacting N,N′,N′′-tris(isocyanatohexyl)isocyanurate and pentaerythritol tri(meth)acrylate, A decafunctional urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate and dipentaerythritol penta(meth)acrylate, A 15-functional urethane poly(meth)acrylate obtained by reacting N,N′,N′′-tris(isocyanatohexyl)isocyanurate and dipentaerythritol penta(meth)acrylate, and The radical-polymerizable anti-fogging coating agent according to [1], comprising one or more selected from triallyl isocyanurate. [4] The radical-polymerizable anti-fogging coating agent according to any one of [1] to [3], wherein the (C) inorganic particles contain silica. [5] The radical-polymerizable anti-fogging coating agent according to any one of [1] to [4], wherein the weight average molecular weight of the (D) nonionic surfactant is 900 or more. [6] The radical-polymerizable anti-fogging coating agent according to any one of [1] to [5], wherein the (D) nonionic surfactant has two or more oxyalkylene structures in the molecule. [7] In 100% by mass of the solid content of the radical-polymerizable anti-fogging coating agent, The (B) difunctional or higher (meth)acryloyl compound is 20% by mass or more and 50% by mass or less, The (C) inorganic particles are 10% by mass or more and 35% by mass or less, The radical-polymerizable anti-fogging coating agent according to any one of [1] to [6], containing the (D) nonionic surfactant in an amount of 1% by mass or more and 10% by mass or less. [8] The radical-polymerizable anti-fogging coating agent according to [1], wherein the ratio (A / (A + B)) of the content (parts by mass) of the (A) (meth)acryloyl compound and the (B) polyfunctional (meth)acryloyl compound is 0.20 or more and 0.99 or less. [9] A film comprising a cured product of the radical-polymerizable anti-fogging coating agent according to any one of [1] to [8].

[10] A substrate, An anti-fogging coating layer provided on at least one surface of the substrate and comprising a cured product of the radical-polymerizable anti-fogging coating agent according to any one of [1] to [8], An anti-fogging coating laminate comprising:

Advantages of the Invention

[0010] According to the present invention, there can be provided a radical-polymerizable anti-fogging coating agent that gives a cured product excellent in anti-fogging property, scratch resistance, and further excellent in the persistence of anti-fogging property and appearance. In other words, the radical-polymerizable anti-fogging coating agent of the present invention is excellent in the balance of these properties.

Modes for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present invention will be described. Also, for example, "1 to 10" represents "1 or more and 10 or less" unless otherwise specified.

[0012] <Radical-Polymerizable Anti-Fogging Coating Agent> The radical-polymerizable anti-fogging coating agent of the present embodiment (hereinafter also referred to as an anti-fogging coating agent) comprises (A) a (meth)acryloyl compound represented by the following general formula (1), (B) a polyfunctional (meth)acryloyl compound (excluding the (meth)acryloyl compound (A)), (C) inorganic particles, (D) a nonionic surfactant, and contains the (A) (meth)acryloyl compound in an amount of 20% by mass or more and 60% by mass or less in 100% by mass of the solid content of the radical-polymerizable anti-fogging coating agent.

[0013] The mechanism by which the radical polymerizable anti-fogging coating agent of this embodiment can exert the effects of the present invention is not clear, but it is presumed to be as follows. First, it is believed that as the radical polymerizable anti-fogging coating agent of this embodiment hardens, the (D) nonionic surfactant is encapsulated within the network formed by the crosslinking reaction between the acrylic components (A) and (B). Then, since the (D) nonionic surfactant encapsulated within this network is slowly released onto the surface of the cured product, a cured product with excellent anti-fogging properties, as well as superior durability of anti-fogging properties and appearance, can be obtained. Furthermore, by including (C) inorganic particles in the acrylic components (A) and (B), it is possible to improve hardness (improve scratch resistance) while maintaining initial and long-term anti-fogging properties. This is because the (C) inorganic particles are encapsulated within the network, and the hardness of these fine particles allows for improvement of hardness (improve scratch resistance) without changing the crosslinking density.

[0014] [(A)(meth)acryloyl compounds] (A)(meth)acryloyl compounds are represented by the following general formula (1). [ka]

[0015] Compounds of general formula (1) have a polyglycerol skeleton in their main chain. Since this polyglycerol skeleton has a strong affinity for (D) nonionic surfactants, it is thought that the dispersibility and interaction force within the network are improved, resulting in improved transparency and the ability to release (D) nonionic surfactants more slowly. As a result, cured products with excellent appearance and anti-fogging durability can be obtained.

[0016] As a polyglycerin skeleton, the tetraglycerin skeleton, in which the 2,3-propylene dioxide structure repeats four times, is the most preferred in terms of antifogging properties, their durability, productivity, and coating properties. In the case of triglycerin skeletons (3 repeats), diglycerin skeletons (2 repeats), and glycerin skeletons (1 repeat), which have fewer repeats of the 2,3-propylene dioxide structure than the tetraglycerin skeleton, the antifogging properties tend to decrease.

[0017] In the case of polyglycerin skeletons with a larger number of repeating 2,3-propylene dioxide structures than the tetraglycerin skeleton, such as the pentaglycerin skeleton (5 repeats), hexaglycerin skeleton (6 repeats), octaglycerin skeleton (8 repeats), and undecaglycerin skeleton (12 repeats), it is difficult to produce the desired structure, and the viscosity may increase or the material may become solid. As a result, the obtained anti-fogging coating agent may undergo phase separation or become highly viscous, leading to an inability to obtain a uniform anti-fogging coating agent and anti-fogging coating film, or a decrease in coating properties. In other words, the most preferred form of polyglycerin as the main chain is the tetraglycerin skeleton (4 repeats of the 2,3-propylene dioxide structure).

[0018] In general formula (1), the number of repeating ethylene oxide structures in the side chains, n1 to n6, independently represent integers from 1 to 33. Preferably, they are in the range of 2 to 20, and more preferably, in the range of 4 to 16. Also, if expressed as n1+n2+n3+n4+n5+n6, they are in the range of 6 to 198, preferably in the range of 12 to 120, and even more preferably in the range of 24 to 96.

[0019] In general formula (1), R1 to R6 independently represent either a hydrogen atom or a methyl group. From the viewpoint of radical polymerization reactivity, hydrogen atoms are preferred over methyl groups, while from the viewpoint of heat resistance, methyl groups are preferred.

[0020] Here, the component ratios of the radical polymerizable anti-fog coating agent in this embodiment are expressed as solid content ratios (mass%) unless otherwise specified. Furthermore, unless otherwise specified, these component ratios do not include solvents, initiators, leveling agents, and other additives added after the preparation (manufacturing) of the radical polymerizable anti-fog coating agent. The individual component ratios of the radical polymerizable anti-fog coating agent are solid content ratios (mass%) relative to the total solid content of components (A) to (D) at 100% by mass.

[0021] The content of the (meth)acryloyl compound represented by general formula (1) that constitutes the anti-fogging coating agent of this embodiment is in the range of 20 to 60% by mass, based on the weight ratio of solids excluding solvents, etc., relative to 100% by mass of the solids content of the anti-fogging coating agent, more preferably 20 to 55% by mass, and even more preferably 35 to 55% by mass. (A) If the content of component (A) is 20% by mass or more, anti-fogging properties can be further improved, and if it is 60% by mass or less, scratch resistance can be further improved. In other words, by including component (A) within the above range, anti-fogging properties and scratch resistance can be further improved, and an excellent balance of these properties can be achieved.

[0022] [(B) (meth)acryloyl compounds with two or more functions] The (B) (meth)acryloyl compound of this embodiment is a compound having two or more poly(meth)acryloyl groups, and includes monomers and oligomers. (B) The upper limit of the number of (meth)acryloyl groups in a (meth)acryloyl compound with two or more functions is preferably 24 or less, more preferably 20 or less, and even more preferably 16 or less. (B) Two- or more functional (meth)acryloyl compounds do not include the (meth)acryloyl compounds represented by the general formula (1) described above in (A).

[0023] By including compound (B) together with compound (A), the crosslinking density is improved, and the scratch resistance of the cured product can be enhanced. Specifically, by selecting compound (B) and setting the mixing ratio of compound (A) and compound (B), the slow release rate of the nonionic surfactant (D) can be controlled, making it possible to design cured products with superior anti-fogging properties and appearance.

[0024] In this embodiment, the (meth)acryloyl group refers to an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a maleimide group, an acryloylthio group, and a methacrylthio group. Among these (meth)acryloyl groups, the acrylate group and the methacrylate group are preferred from the viewpoint of color and odor, and the acrylate group is more preferred from the viewpoint of high radical polymerization.

[0025] Incidentally, (meth)acrylate group refers to acrylate group and methacrylate group, and (meth)acrylate refers to a compound having at least one acrylate group or methacrylate group in one molecule. Poly(meth)acrylate refers to a compound having a total of two or more acrylate groups and methacrylate groups in one molecule, and these can be used individually or in combination of two or more types.

[0026] Examples of (B) difunctional or greater (meth)acryloyl compounds used in this embodiment include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin-1,3-di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, and difunctional (meth)acrylates such as 2,2-bis-[4-((meth)acryloxy-polyethoxy)phenyl]-propane (ethylene oxide-added bisphenol); Trifunctional methacrylates such as pentaerythritol tri(meth)acrylate and trimethylolpropane tri(meth)acrylate; Examples include tetrafunctional or more (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and these can be used individually or in combination of two or more. In this embodiment, among the compounds described above, it is preferable to use dipentaerythritol hexa(meth)acrylate.

[0027] Similarly to the above, a preferred (B) bifunctional or greater (meth)acryloyl compound is a bifunctional or greater poly(meth)acrylate (b) having a urethane bond or isocyanurate ring structure within one molecule. By using poly(meth)acrylate (b), a urethane structure or isocyanurate ring structure is included in the network structure, resulting in a cured product with excellent antifogging and scratch resistance, as well as superior durability of antifogging and appearance, and further improvements in heat resistance, weather resistance, crack resistance, etc.

[0028] As poly(meth)acrylate(b), for example, a trifunctional poly(meth)acrylate having an isocyanurate ring structure, such as tris{(meth)acryloyloxyethyl}isocyanurate; A bifunctional urethane di(meth)acrylate obtained by reacting hexamethylene diisocyanate with polyethylene glycol mono(meth)acrylate; A tetrafunctional urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate with glycerin-1,3-di(meth)acrylate; A hexafunctional urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate with pentaerythritol tri(meth)acrylate; A hexafunctional urethane poly(meth)acrylate obtained by reacting N,N′,N′′-tris(ishicyanatohexyl)isocyanurate (HDI-Trimer) with glycerin-1,3-di(meth)acrylate; A 9-functional urethane poly(meth)acrylate obtained by reacting N,N′,N′′-tris(ishicyanatohexyl)isocyanurate (HDI-Trimer) with pentaerythritol tri(meth)acrylate; A decaf urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate with dipentaerythritol penta(meth)acrylate; Examples include 15-functional urethane poly(meth)acrylates obtained by reacting N,N′,N′′-tris(isecyanatohexyl) isocyanurate (HDI-Trimer) with dipentaerythritol penta(meth)acrylate; and these can be used individually or in combination of two or more. Furthermore, triallyl isocyanurate is an example of a compound that imparts reactivity and scratch resistance equivalent to that of a bifunctional or more poly(meth)acrylate (b) having a urethane bond or isocyanurate ring structure within a single molecule, and can be used as a bifunctional or more poly(meth)acrylate (b) in the same way as the aforementioned trifunctional poly(meth)acrylate having an isocyanurate ring structure.

[0029] The (B) (meth)acryloyl compound of this embodiment may further include a monofunctional (meth)acryloyl compound having one (meth)acryloyl group, together with the above-mentioned compound, in order to reduce viscosity and improve operability. Examples of monofunctional (meth)acryloyl compounds include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate; Hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; (Meth)acrylates having an alicyclic structure, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; Examples include (meth)acrylates having an aromatic ring structure such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, and phenoxypolyalkylene oxy(meth)acrylate; and these can be used individually or in combination of two or more.

[0030] The content of the (B) bifunctional or greater (meth)acryloyl compound constituting the anti-fogging coating agent of this embodiment is preferably in the range of 20 to 50% by mass, more preferably 20 to 48% by mass, and even more preferably 22 to 46% by mass, based on a weight ratio of solids excluding solvents, etc., relative to 100% by mass of the solids content of the anti-fogging coating agent. If the content of component (B) is 20% by mass or more, durability (duration of anti-fogging) can be further improved, and if it is 50% by mass or less, anti-fogging can be further improved. In other words, by including component (B) within the above range, anti-fogging and the duration of anti-fogging can be further improved, and an excellent balance of these properties can be achieved.

[0031] [(C) Inorganic particles] In this embodiment, (C) inorganic particles refer to particles whose main component is inorganic material or diamond. Examples include particles made of metal oxides, such as silicon oxide particles (silica particles), zirconium oxide particles (zirconia particles), aluminum oxide particles (alumina particles), titanium oxide particles (titania particles), tin oxide particles, and antimony oxide particles. Diamond particles may also be used to improve aesthetics. These may be used individually or in combination of two or more types.

[0032] In this embodiment, (C) inorganic particles preferably contain silica. By using silica, hardness can be further improved while maintaining anti-fogging properties and the durability of anti-fogging properties, and scratch resistance can be further improved.

[0033] (C) The average particle size of inorganic particles is generally in the range of 5 to 50 nm, preferably in the range of 10 to 30 nm. If the average particle size of inorganic particles exceeds the lower limit, hardness is improved. If the average particle size of inorganic particles falls below the upper limit, dispersibility and transparency are improved. The average particle size of inorganic particles can be measured by dynamic scattering using laser light.

[0034] The inorganic particles (C) constituting the anti-fogging coating agent of this embodiment are preferably in the range of 10 to 35% by mass, more preferably 12 to 30% by mass, and even more preferably 15 to 30% by mass, based on a solid content weight ratio excluding solvents, etc., relative to 100% by mass of the solid content of the anti-fogging coating agent. When the content of component (C) is 10% by mass or more, scratch resistance is further improved, and when it is 35% by mass or less, appearance defects such as cracks are suppressed and anti-fogging properties are further improved. In other words, by including component (C) within the above range, scratch resistance, appearance, and anti-fogging properties can be further improved, and an excellent balance of these properties can be achieved.

[0035] [(D) Nonionic surfactant] The anti-fogging coating agent of this embodiment contains (D) a nonionic surfactant. (D) Nonionic surfactants have excellent solubility, transparency (including the transparency of the anti-fogging film itself as well as the suppression of whitening during bleed-out), and anti-fogging properties.

[0036] (D) Examples of nonionic surfactants include nonionic surfactants having two or more oxyalkylene structures in the molecule. (D) Nonionic surfactants specifically consist of repeating units (oxyalkylene structures) represented by the following general formula (a).

[0037] [ka]

[0038] In general formula (a), A represents an alkylene group having 2 to 5 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. Specifically, A can be an ethylene group, a propylene group, a butylene group, a pentylene group, or the like. n is not particularly restricted, but for example, it is an integer between 2 and 30, preferably between 2 and 20.

[0039] In this embodiment, the (D) nonionic surfactant is preferably a nonionic surfactant having two or more oxyalkylene structures (polyoxyalkylene structures), namely a polyoxyethylene structure and a polyoxypropylene structure, and more preferably a nonionic surfactant having a polyoxyethylene structure. (D) The nonionic surfactant has two or more oxyalkylene structures in its molecule, which gives it superior affinity to (A) the (meth)acryloyl compound represented by general formula (1), which has a polyglycerol backbone in its main chain. Therefore, (D) the nonionic surfactant is slowly released onto the surface of the cured product, resulting in a cured product with superior durability in terms of anti-fogging properties. Furthermore, from the viewpoint of anti-fogging properties, it is preferable that these nonionic surfactants do not have a (meth)acryloyl structure and an ethylenically unsaturated bond structure.

[0040] (D) More specifically, examples of nonionic surfactants include nonionic surfactants having a polyoxyalkylene alkyl ether and a polyoxyalkylene alkyl ester structure, and preferably, nonionic surfactants having a polyoxyalkylene alkyl ether structure. Examples of polyoxyalkylene alkyl ethers include polyoxyethylene alkyl ether, polyoxyalkylene alkenyl ether, and polyoxyethylene polyoxypropylene alkyl ether.

[0041] More specifically, examples of nonionic surfactants having a polyoxyalkylene alkyl ether structure include polyoxyalkylene branched decyl ether, polyoxyalkylene dodecyl ether, polyoxyalkylene tridecyl ether, and nonionic surfactants having a polyoxyalkylene oleyl cetyl ether structure.

[0042] (D) In ​​nonionic surfactants, the number of repeating oxyalkylene structural units is not particularly limited, but is, for example, 1 or more, preferably 2 or more. The number of repeating oxyethylene structural units is, for example, 30 or less, preferably 20 or less.

[0043] (D) The molecular weight of the nonionic surfactant (GPC measurement, weight-average molecular weight in polystyrene equivalent) is, for example, 500 or more, preferably 900 or more, more preferably 1000 or more, for example, 10000 or less, preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less. If the molecular weight of the nonionic surfactant exceeds the lower limit mentioned above, the anti-fogging durability tends to improve. Furthermore, if the molecular weight of the nonionic surfactant falls below the upper limit mentioned above, it can exhibit suitable anti-fogging properties.

[0044] (D) Nonionic surfactants may, if necessary, contain anionic hydrophilic groups or cationic hydrophilic groups in appropriate proportions. Examples of anionic hydrophilic groups include sulfo groups, carboxyl groups, phosphate groups, O-sulfate groups (-O-SO3-), N-sulfate groups (-NH-SO3-), and salts thereof. Examples of anionic hydrophilic salts include sodium salts, potassium salts, and ammonium salts. Examples of cationic hydrophilic groups include quaternary ammonium groups and their salts, and examples of counteranions that form these salts include fluoroions, chlorions, bromions, iodines, phosphate ions, and sulfonates.

[0045] The nonionic surfactant (D) contained in the anti-fogging coating agent of this embodiment is preferably in the range of 1 to 10% by mass, more preferably in the range of 2 to 6% by mass, and even more preferably in the range of 3 to 5% by mass, based on a weight ratio of solids excluding solvents, etc., relative to 100% by mass of the solids of the anti-fogging coating agent. When the content of component (D) is 10% by mass or less, appearance defects such as blue-out are further suppressed, and when it is 1% by mass or more, anti-fogging properties are further improved. In other words, by including component (D) within the above range, appearance and anti-fogging properties can be further improved, and an excellent balance of these properties can be achieved.

[0046] [(E) Polymerization initiator] The radical polymerizable anti-fogging coating agent of this embodiment may contain (E) a polymerization initiator as an optional component.

[0047] The polymerization initiator (E) used in this embodiment is an additive that cleaves upon heating or irradiation with radiation (such as UV light) to generate radicals, and initiates radical polymerization with these cleaved radicals. From the viewpoint of productivity (polymerization rate), radiation polymerization (such as UV light) tends to be preferable to thermal polymerization. Therefore, known photopolymerization initiators that cleave and generate radicals upon irradiation with radiation (such as UV light) are preferably used as initiators. In some cases, known thermal polymerization initiators that cleave and generate radicals upon heating may also be used in combination.

[0048] Examples of photopolymerization initiators include alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, α-acyloxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, and anthraquinone compounds. These can be used individually or in combination of two or more. From the viewpoint of reactivity, alkylphenone compounds and acylphosphine oxide compounds are preferred as photopolymerization initiators.

[0049] Commercially available photopolymerization initiators can be used. Examples of commercially available products include Omnirad127, Omnirad184, Omnirad1173, Omnirad500, Omnirad819, and OmniradTPO (all manufactured by IGM Resins B.V.). Other examples of commercially available products include EsaCure ONE, EsaCure KIP100F, EsaCure KT37, and EsaCure KTO46 (all manufactured by Lambertie).

[0050] (E) The content of the polymerization initiator is, for example, 0.2% by mass or more, preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the radical polymerizable anti-fogging coating agent of this embodiment. Alternatively, the content of the polymerization initiator is, for example, 10% by mass or less, preferably 6.0% by mass or less, and more preferably 4.0% by mass or less, relative to the total solid content of the radical polymerizable anti-fogging coating agent.

[0051] [(F) Solvent] The radical polymerizable anti-fogging coating agent of this embodiment may further contain (F) a solvent as an optional component. Examples of (F) solvents include water and known organic solvents, but water is not actively used because it may separate from other components.

[0052] (F) The solvent content is set appropriately according to the purpose and application. For example, when the radical polymerizable anti-fog coating agent of this embodiment contains a solvent, the solid content concentration of the radical polymerizable anti-fog coating agent is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. Alternatively, the solid content concentration of the radical polymerizable anti-fog coating agent of this embodiment is, for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 65% ​​by mass or less.

[0053] [Other ingredients] The radical polymerizable anti-fogging coating agent of this embodiment may contain, in addition to the above-mentioned components (A) to (D), and as optional components (E) polymerization initiator and (F) solvent, other components as needed. Examples of other components include polymerization accelerators, thickeners, defoamers, foaming agents, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, and flame retardants. These can be used individually or in combination of two or more types. The radical polymerizable anti-fogging coating agent of this embodiment basically does not contain allyl monomers or oligomers, vinyl monomers or oligomers, or styryl monomers or oligomers, excluding triallyl isocyanurate. This is because these monomers or oligomers do not react easily with radiation such as UV. However, this does not exclude the inclusion of these monomers to the extent that it does not affect the effects of the present invention.

[0054] A more preferred form of the radical polymerizable anti-fogging coating agent of this embodiment is that the radical polymerizable anti-fogging coating agent contains, (A) A (meth)acryloyl compound represented by the following general formula (1) is preferably contained in an amount of 20 to 60% by mass, more preferably 20 to 55% by mass, and even more preferably 35 to 55% by mass, (B) A (meth)acryloyl compound with two or more functionalities is preferably contained in an amount of 20-50% by mass, more preferably 20-48% by mass, and even more preferably 22-46% by mass. (C) Inorganic particles are preferably contained in an amount of 10-35% by mass, more preferably 12-30% by mass, and even more preferably 15-30% by mass. (D) A nonionic surfactant is preferably contained in an amount of 1 to 10% by mass, more preferably 2 to 6% by mass, and even more preferably 3 to 5% by mass. These ranges can be combined as appropriate. The radical polymerizable anti-fogging coating agent of this embodiment, by containing each component in the above amounts, can produce a cured product that is superior in anti-fogging properties and scratch resistance, as well as superior in the durability of its anti-fogging properties and appearance.

[0055] Furthermore, a more preferred form of the radical polymerizable anti-fogging coating agent of this embodiment is one in which the ratio (parts by mass) of the content (A) of the (meth)acryloyl compound represented by the following general formula (1) and (B) of the (meth)acryloyl compound with two or more functionalities (A / (A+B)) is preferably 0.20 or more and 0.99 or less, more preferably 0.30 or more and 0.80 or less, and even more preferably 0.33 or more and 0.70 or less.

[0056] The radical polymerizable anti-fogging coating agent of this embodiment contains components (A) and (B) in the above-mentioned content ratio. As a result, the nonionic surfactant (D), which is encapsulated within the network formed by the crosslinking reaction between acrylic components (A) and (B), is slowly released to the surface of the cured product through the network. This provides more effective initial and long-term anti-fogging properties, and also suppresses excessive release (excessive release from the inside), resulting in a cured product with a superior appearance. Furthermore, if the ratio (A / (A+B)) exceeds 0.99, the crosslinking density decreases, and the surfactant encapsulated within the network is released all at once, making it impossible to maintain anti-fogging properties for a long period of time. For example, surface cleaning such as rinsing with water immediately causes the anti-fogging properties to be lost. On the other hand, if the ratio (A / (A+B)) is less than 0.20, the crosslinking density increases, and the surfactant encapsulated within the network is not released onto the surface of the cured product, resulting in no anti-fogging properties. In contrast, by including components (A) and (B) in the above-mentioned content ratio, a balanced blending ratio is achieved between crosslink density and strength, and as a result, it is believed that an appropriate release rate of the nonionic surfactant (D) and a high level of scratch resistance of the resulting cured product are ensured. Therefore, by satisfying the above content ratio, a cured product with superior anti-fogging and scratch resistance, as well as superior durability of anti-fogging and appearance, can be obtained. Furthermore, controlling the properties using the above (A / (A+B)) ratio tends to be easier when a trifunctional or more (meth)acryloyl compound is selected as component (B) than when a bifunctional (meth)acryloyl compound is selected.

[0057] [Method for producing a radical polymerizable anti-fogging coating agent] The radical polymerizable anti-fog coating agent of this embodiment is obtained by mixing the above components by a known method. This radical polymerizable anti-fog coating agent of this embodiment can produce a cured resin in a short time by radiation polymerization using ultraviolet light (UV) or the like, and the cured resin has excellent anti-fog properties and scratch resistance, as well as excellent durability of anti-fog properties and appearance.

[0058] <film> In this embodiment, an anti-fog film can be obtained by pouring a radical polymerizable anti-fog coating agent onto a flat surface using a casting machine, spreading it to a uniform thickness, evaporating and drying the solvents contained in the coating agent, polymerizing and curing it by heating or irradiation with ultraviolet (UV) light, and then peeling it off the flat surface. The thickness of the self-supporting anti-fog film can be, for example, 1 to 1000 μm, preferably 5 to 500 μm, and more preferably 10 to 300 μm.

[0059] <Anti-fog coated laminate> The anti-fog coated laminate of this embodiment comprises a substrate and an anti-fog coating layer provided on at least one surface of the substrate, the anti-fog coating layer being made of a cured product of the aforementioned radical polymerizable anti-fog coating agent.

[0060] Examples of substrates include organic substrates, inorganic substrates, and composite substrates. An organic substrate refers to a substrate made of organic material. Examples of materials for organic substrates include plastics, paper, and pulp, with plastics being preferred. Examples of plastics include polymethyl (meth)methacrylate, polycarbonate, polyallyl carbonate, polyethylene terephthalate (PET), polyacetylcellulose, acrylonitrile-butadiene-styrene copolymer (ABS), polyolefin, polystyrene, polyurethane, epoxy, poly(meth)acrylate, vinyl chloride, polyimide, polyamide, and silicone. These may be used individually, in combination of two or more, or laminated as desired.

[0061] The term "inorganic substrate" refers to a substrate made of inorganic materials. Examples of materials for inorganic substrates include glass, silica, metals, and metal oxides, with glass, metals, and metal oxides being preferred. Examples of metals include aluminum, gold, silver, copper, nickel, zinc, titanium, cobalt, indium, and chromium. Examples of metal oxides include oxides of the above metals. Specifically, examples of metal oxides include aluminum oxide and titanium oxide. These may be used individually, in combination of two or more, or layered as desired.

[0062] Typical composite substrates include GFRP (Glass Fiber Reinforced Plastic), which is a composite of organic and inorganic materials, but CFRP (Carbon Fiber Reinforced Plastics), which is a composite of organic materials, is another example.

[0063] The shape of the substrate is not particularly limited. Examples of substrate shapes include plate-like, film-like, sheet-like, lens-like, bottle-like, and cup-like shapes. Preferably, the substrate shapes are plate-like, film-like, and sheet-like.

[0064] Furthermore, the above-mentioned substrate may be surface-treated by known methods. Examples of surface treatments include corona discharge treatment, glow discharge treatment, plasma treatment, ozone treatment, flame treatment, chemical oxidation treatment, anchor coating treatment, and primer coating treatment (undercoating treatment).

[0065] Among these surface treatments, primer coating treatment tends to be preferred. In primer coating treatment, known primers are used, such as urethane primers, epoxy primers, polyester primers, and acrylic primers.

[0066] The thickness of the substrate is, for example, 3 μm or more, preferably 10 μm or more. Alternatively, the thickness of the substrate may be, for example, 50 mm or less, preferably 10 mm or less, and more preferably 3 mm or less.

[0067] Transparent substrates are preferred as the base material. The transmittance of the transparent substrate is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, and even more preferably 92% or more, based on the average transmittance of visible light (380-780 nm). Typically, the transmittance of the substrate is 100% or less.

[0068] The anti-fog coated laminate of this embodiment can be manufactured, for example, by applying the radical polymerizable anti-fog coating agent of this embodiment to at least one surface of the substrate, evaporating (drying) the solvent by heating, and then curing the radical polymerizable anti-fog coating agent on the substrate by heating or irradiation with radiation such as ultraviolet light (UV) to form a resin layer (anti-fog coating layer).

[0069] The application method is not particularly limited and includes known methods. Examples of application methods include bar coating, spin coating, dip coating, spray coating, flow coating, brush coating, gravure coating, reverse roll coating, knife coating, and kiss coating.

[0070] The drying method is not particularly limited and known methods can be used. For example, when heating to evaporate the solvent, the drying temperature is at least the dew temperature. For example, 10°C or higher, preferably 20°C or higher. For example, 200°C or lower, preferably 100°C or lower. The drying time is, for example, 30 seconds or more, preferably 1 minute or more. For example, 24 hours or less, preferably 12 hours or less, and more preferably 1 hour or less.

[0071] Methods for curing the radical polymerizable anti-fogging coating agent of this embodiment include, for example, curing by heat polymerization and radiation polymerization, but for polymerization in a shorter time, polymerization curing by radiation irradiation is preferred. Examples of radiation include alpha rays, beta rays, gamma rays, X-rays, electron beams, ultraviolet rays, and visible light, among which radiation with wavelengths of 0.0001 nm to 800 nm is preferred. Ultraviolet (UV) radiation is a more preferred type of radiation. Preferred peak wavelengths for ultraviolet radiation are, for example, 200 nm or more, preferably 230 nm or more, more preferably 240 nm or more, and even more preferably 250 nm or more. Also, preferred peak wavelengths for ultraviolet radiation are, for example, 450 nm or less, preferably 445 nm or less, more preferably 430 nm or less, and even more preferably 400 nm or less.

[0072] The irradiation time is set appropriately within the range that allows the radical polymerizable anti-fogging coating agent of this embodiment to cure. For example, the irradiation energy is 5 mJ / cm². 2 Preferably, 10 mJ / cm 2 More preferably, 50 mJ / cm 2 That concludes the explanation. Furthermore, the light irradiation energy is, for example, 1000 mJ / cm². 2 Preferably, 500 mJ / cm² 2 The following applies:

[0073] The main embodiment of the method for manufacturing the anti-fog coated laminate is a method for obtaining an anti-fog coated laminate in which an anti-fog coating layer is formed on the surface of the substrate by applying a radical polymerizable anti-fog coating agent to a substrate, drying it, and then heating or irradiating it with UV or other radiation.

[0074] In addition to the above-described embodiments for manufacturing the main anti-fog coated laminate, another method involves applying a radical polymerizable anti-fog coating agent to a substrate, drying the anti-fog coating layer, covering the surface with a transparent coating material, and then curing the transparent coating material by irradiating it with radiation to form an anti-fog coating layer between the coating material and the substrate. This transparent coating may be peeled off after radiation irradiation, or it may be peeled off immediately before use or after application as a protective film for the anti-fog coating layer.

[0075] Furthermore, the transparent coating material used above may be a coating material with a smooth surface, or a coating material having a surface structure such as a moth-eye may be used to transfer the surface structure (such as a moth-eye) of the coating material onto the surface of the anti-fog coating layer.

[0076] The anti-fog coating layer described above is placed as the outermost layer on one or both sides of the substrate during practical use. The resulting laminate of this embodiment has anti-fog and scratch-resistant properties due to the anti-fog coating layer.

[0077] The thickness of the anti-fog coating layer is, for example, 1 μm or more, preferably 3 μm or more. The thickness of the coating layer is, for example, 100 μm or less, preferably 80 μm or less.

[0078] If the anti-fog coating layer is formed on one side of the substrate, an adhesive layer and a separator film may be placed on the opposite side.

[0079] The above-mentioned anti-fog coating layer and laminate may also provide antistatic properties in addition to excellent anti-fogging and scratch resistance.

[0080] The anti-fog film (self-supporting film) and anti-fog coated laminate of this embodiment may be used directly as a component or attached to the surface of various components. Applications include, for example, eyeglasses, sunglasses, displays, display covers, sensors, sensor covers, cameras, camera covers, lenses, lens covers, instruments, instrument covers, face shields, helmet shields, lamps, lamp covers, windows, mirrors, and other optical articles and optical components.

[0081] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted as long as they do not impair the effects of the present invention. [Examples]

[0082] The present invention will be described below based on examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are based on mass.

[0083] In this invention, the physical properties were evaluated by the following method. <Rating> (1) Exterior The external appearance was evaluated visually.

[0084] (2) Anti-fogging properties Two anti-fog coated laminates (a laminate of an anti-fog coating layer and a base film) were placed with the anti-fog coating layer facing outwards (towards the air), and the edges of the two laminates were joined together using a 100 μm thick ultra-transparent double-sided adhesive sheet (manufactured by Nitoms Co., Ltd.) to create a sample with anti-fog coatings on both sides. The obtained sample was kept in a refrigerator at 0-5°C for 30 minutes or more, then left to stand at room temperature (23-25°C, 45-55% RH) and visually evaluated based on the following evaluation criteria. (Evaluation Criteria) ○: The anti-fog coating layer did not fog up. ×: The anti-fog coating layer became cloudy.

[0085] (3) Durability after washing with water The surface of the anti-fog coating layer of the anti-fog coated laminate was washed with running tap water for 5 seconds, dried with an air gun, and then, in a room with a temperature of 23-25°C and humidity of 45-55%RH, exhaled air was blown onto the surface of the anti-fog coated laminate from a distance of about 5 cm to evaluate whether or not the surface of the anti-fog coating layer fogged up. This cycle was repeated until fogging was confirmed. Table 1 shows the number of cycles required for fogging to be confirmed. A higher number of cycles before fogging was confirmed indicated higher water washing durability. Water wash durability was confirmed by accelerated testing, which showed that after the (D) nonionic surfactant slow-released onto the surface of the anti-fog coating layer is washed away by water, the (D) nonionic surfactant is slow-released again onto the same surface, and the presence of this (D) nonionic surfactant suppresses fogging. In other words, in the above test, the more cycles there are, the higher the water wash durability and the better the duration of the anti-fog performance.

[0086] (4) Scratch resistance Steel wool #0000 was placed on the surface of the anti-fog coating layer of the anti-fog coated laminate, and a 300g load was applied to the steel wool, causing it to move back and forth 10 times. The condition of the scratches in the area that underwent this back-and-forth motion was visually assessed based on the following evaluation criteria. (Evaluation Criteria) Rank 1: The entire back-and-forth surface is scratched, and the anti-fog coating layer is peeling off completely. Rank 2: The entire front and rear section has deep scratches, but the anti-fog coating layer remains intact. Rank 3: Has several to dozens of thick scratches. Rank 4: The item has several to dozens of thin, fine scratches. Rank 5: Almost no visible scratches.

[0087] [Example 1] (Manufacturing of anti-fogging coating agents) (A) 20.0 parts of SA-TE60 (n1+n2+n3+n4+n5+n6=60, R1~R6: hydrogen atoms, molecular weight approximately 3300) from Sakamoto Pharmaceutical Co., Ltd. as a (meth)acryloyl compound represented by general formula (1), (B) 28.5 parts of NK Ester A-9300S and 17.0 parts of NK Oligo UA-122P from Shin Nakamura Chemical Co., Ltd. as bifunctional or more (meth)acryloyl compounds, (C) inorganic particles (D) 64.1 parts (30.0 parts in terms of solids) of Nissan Chemical's PGM-AC-2140Y (2-methoxypropanol solution) with a solids content of 46.8% by mass, (D) 4.5 parts of Noigen LP100 from Daiichi Kogyo Seiyaku as a nonionic surfactant, and (F) 34.1 parts of PGM (1-methoxy-2-propanol) and 65.9 parts of ethyl acetate as solvents were mixed and dissolved to obtain 200.0 parts of a uniform anti-fogging coating agent with a solids content of 50% by mass. Furthermore, 3 parts of Orminard 127 (manufactured by IGM resins B.V.) as a polymerization initiator (UV polymerization initiator) were added to this anti-fogging coating agent to make a coating solution.

[0088] (Formation of an anti-fog coating layer and a laminate having an anti-fog coating layer) The above coating solution was applied to the surface of Toyobo's easy-adhesion PET film CosmoShine A4160 (film thickness 100 μm) as a base material using a bar coater #12, dried in an 80°C oven for 5 minutes, and passed through a UV conveyor equipped with an electrodeless discharge lamp H-bulb to obtain an anti-fog coated laminate in which an 8 μm anti-fog coating layer was formed on the surface of the base material. The illuminance when the UV lamp is fully open is 300 mW / cm². 2 The cumulative light intensity is 350 mJ / cm². 2 This was the result (measured with Ushio Inc. UIT-150). Table 1 shows the mixing ratios of the anti-fog coating compositions, and Table 2 shows the evaluation results of the anti-fog layer of the anti-fog coating laminate obtained from those compositions.

[0089] [Examples 2-11 and Comparative Examples 1-6] A laminate (film) having an anti-fog coating layer was obtained according to the composition described in Table 1 and in the same manner as in Example 1. The evaluation results of the obtained film are shown in Table 2. Comparative Example 4 corresponds to the composition described in Example 1 of Japanese Patent Publication No. 2022-051202, Comparative Example 5 corresponds to the composition described in Example 1 of Japanese Patent Publication No. 2022-152737, and Comparative Example 6 corresponds to the composition before methanol distillation described in Example 1A of International Publication No. 2015 / 087810.

[0090] [Table 1]

[0091] The details of the abbreviations in Table 1 are as follows. • SA-TE60: Polyacrylate manufactured by Sakamoto Pharmaceutical Co., Ltd. • A-9300S: Polyacrylate (tris{acryloyloxyethyl}isocyanurate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. • UA-122P: Urethane polyacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (a bifunctional urethane diacrylate obtained by reacting hexamethylene diisocyanate and polyethylene glycol monoacrylate) • UA-33H: Urethane polyacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (a 9-functional urethane polyacrylate obtained by reacting N,N′,N′′-tris(ishicyanatohexyl) isocyanurate with pentaerythritol triacrylate) • U-15HA: Urethane polyacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (a 15-functional urethane polyacrylate obtained by reacting N,N′,N′′-tris(ishicyanatohexyl) isocyanurate with dipentaerythritol pentaacrylate) A-600: Polyfunctional acrylic monomer, polyethylene glycol diacrylate, EO unit count 14, manufactured by Shin Nakamura Chemical Industry Co., Ltd.

[0092] • A-GLY-9E: A compound represented by the following chemical formula. [ka]

[0093] • DPHA: Dipentaerythritol hexaacrylate • U-6LPA: A hexafunctional urethane polyacrylate obtained by reacting hexamethylene diisocyanate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. with pentaerythritol triacrylate. • U-10HA: Urethane polyacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (a 10-functional urethane polyacrylate obtained by reacting hexamethylene diisocyanate with dipentaerythritol pentaacrylate) • UA-306H: Urethane acrylate, urethane reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate, manufactured by Kyoeisha Chemical Co., Ltd.

[0094] · A-9530: Compound represented by the following chemical formula [ka]

[0095] SPA-K: Potassium 3-acryloyloxypropylsulfonate • 2140Y: Silica particles manufactured by Nissan Chemical Industries, Ltd., product name PGM-AC-2140Y (solids content 46.8%, 2-methoxypropanol solvent dispersion) LP-100: Nonionic surfactant (polyoxyalkylene alkyl ether), weight-average molecular weight 1154, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. LP-70: Nonionic surfactant (polyoxyalkylene alkyl ether), weight-average molecular weight 984, manufactured by Daiichi Kogyo Seiyaku. • DS-Na: Sodium distearyl sulfosuccinate • S-EED: Hindered amine-based light stabilizer (manufactured by Clariant Japan Co., Ltd.) • PGM: 2-Methoxypropanol • AcOEt: Ethyl acetate • MeOH: methanol

[0096] [Table 2]

[0097] The results in Table 2 revealed the following: The radical polymerizable anti-fogging coating agents of Examples 1 to 11 exhibited excellent anti-fogging and scratch resistance, as well as superior durability of anti-fogging properties and appearance, resulting in cured products with an excellent balance of these characteristics. On the other hand, Comparative Example 1, a radical polymerizable anti-fogging coating agent with a low content of (A)(meth)acryloyl compound, exhibited inferior anti-fogging properties and durability of anti-fogging compared to the examples. Furthermore, Comparative Examples 2 and 3, which had a high content of (A)(meth)acryloyl compound and did not satisfy the configuration of the present invention, exhibited inferior durability of anti-fogging and scratch resistance compared to the examples. Furthermore, the radical polymerizable anti-fogging coating agents of Comparative Examples 4-6 exhibited inferior anti-fogging properties compared to the examples.

Claims

1. (A) A (meth)acryloyl compound represented by the following general formula (1), (B) A (meth)acryloyl compound with two or more functions (excluding the (A) (meth)acryloyl compound mentioned above) (C) Inorganic particles and (D) Nonionic surfactants, A radical polymerizable anti-fogging coating agent, comprising: A radical polymerizable anti-fogging coating agent comprising 20% ​​to 60% by mass of the (A) (meth)acryloyl compound in 100% by mass of the solid content of the radical polymerizable anti-fogging coating agent. 【Chemistry 1】 (In the formula, n １ ~n ６ Each of these independently represents an integer from 1 to 33. １ ~R ６ (Each represents either a hydrogen atom or a methyl group independently.)

2. The radical polymerizable anti-fogging coating agent according to claim 1, wherein the (B) bifunctional or greater (meth)acryloyl compound is a bifunctional or greater poly(meth)acrylate having a urethane bond or isocyanurate ring structure within one molecule.

3. The (B) above-mentioned (meth)acryloyl compound with two or more functionalities, Tris{(meth)acryloyloxyethyl}isocyanurate, A bifunctional urethane di(meth)acrylate obtained by reacting hexamethylene diisocyanate with polyethylene glycol mono(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, A tetrafunctional urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate with glycerin-1,3-di(meth)acrylate, A hexafunctional urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate with pentaerythritol tri(meth)acrylate. A hexafunctional urethane poly(meth)acrylate obtained by reacting N,N',N''-tris(isecyanatohexyl) isocyanurate with glycerin-1,3-di(meth)acrylate. A 9-functional urethane poly(meth)acrylate obtained by reacting N,N',N''-tris(isecyanatohexyl) isocyanurate with pentaerythritol tri(meth)acrylate. A decahedral urethane poly(meth)acrylate obtained by reacting hexamethylene diisocyanate with dipentaerythritol penta(meth)acrylate. A 15-functional urethane poly(meth)acrylate obtained by reacting N,N',N''-tris(isecyanatohexyl) isocyanurate with dipentaerythritol penta(meth)acrylate, and The radical polymerizable anti-fogging coating agent according to claim 1, comprising one or more selected from triallyl isocyanurates.

4. The radical polymerizable anti-fogging coating agent according to claim 1, wherein the (C) inorganic particles include silica.

5. The radical polymerizable anti-fogging coating agent according to claim 1, wherein the weight-average molecular weight of the (D) nonionic surfactant is 900 or more.

6. The radical polymerizable anti-fogging coating agent according to claim 1, wherein the (D) nonionic surfactant has two or more oxyalkylene structures in its molecule.

7. In the 100% by mass solid content of the aforementioned radical polymerizable anti-fogging coating agent, The above (B) a bifunctional or more (meth)acryloyl compound in an amount of 20% by mass or more and 50% by mass or less, The (C) inorganic particles are present in an amount of 10% by mass or more and 35% by mass or less. The radical polymerizable anti-fogging coating agent according to claim 1, comprising the (D) nonionic surfactant in an amount of 1% by mass or more and 10% by mass or less.

8. The radical polymerizable anti-fogging coating agent according to claim 1, wherein the ratio (parts by mass) of the content (A) (meth)acryloyl compound and the content (B) of the bifunctional or more (meth)acryloyl compound (A / (A+B)) is 0.20 or more and 0.99 or less.

9. A film comprising a cured product of a radical polymerizable anti-fogging coating agent according to any one of claims 1 to 8.

10. Substrate and An anti-fog coating layer provided on at least one surface of the substrate, comprising a cured product of a radical polymerizable anti-fog coating agent according to any one of claims 1 to 8, A laminate with an anti-fog coating.

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