Anti-reflective film, and anti-reflective film for exterior glass application.

Abstract

To provide an antireflection film including a low refractive index layer formed, using a paint that has as a binder a silane compound having a hydrolyzable group, on top of hard coat layer formed using a paint that has as a binder an active energy ray curable resin, the antireflection film having weatherproofness allowing for it to be pasted to the outdoor side of window glass.SOLUTION: The hard coat layer is formed using a paint containing: (B1-a) a polymerizable compound having a silsesquioxane skeleton: and (B1-b) urethane (meth)acrylate. The paint preferably further contains: (B1-d) a compound having one or more cationic polymerizable group and one or more radical polymerizable group in one molecule. The paint, in one embodiment, contains: (B2) a high refractive index particle.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an antireflection film. More specifically, it relates to an antireflection film (hereinafter sometimes abbreviated as "antireflection film for external window application") used by being laminated on the outdoor side of glass such as window glass.

Background Art

[0002] Conventionally, resin films have been used by being laminated on glass for the purpose of protecting glass such as window glass of buildings, windows of automobiles, and display panels of image display devices, and preventing scattering. Conventionally, when a resin film is laminated on the window glass of a building, from the viewpoints of weather resistance and abrasion resistance, and further, when the resin film is laminated on the outdoor side of the window glass, there is a problem that the eyes get fatigued by the reflected light when exposed to direct sunlight. Therefore, it is common to laminate it on the indoor side. However, when laminating on the indoor side, there are problems such as the need for a work space indoors; it may be impossible to secure a sufficient work space and work may be restricted; etc. Therefore, there is a demand for a resin film that can be laminated on the outdoor side of window glass, preferably having weather resistance and abrasion resistance, and having an antireflection function. The same applies to the case of laminating a resin film on the window of an automobile. From the same viewpoints, there is a demand for a resin film that can be laminated on the outside of the window and preferably has weather resistance and abrasion resistance, and has an antireflection function. In recent years, image display devices have been developed for applications used in places exposed to direct sunlight such as car navigation and digital signage. On the other hand, when an image display device is used in a place exposed to direct sunlight, it has been pointed out that there is a disadvantage that the contrast decreases and the image does not look clear. Therefore, also in the case of laminating a resin film on the display panel of an image display device, from the same viewpoints, there is a demand for a resin film having weather resistance, preferably weather resistance and abrasion resistance, and having an antireflection function.

[0003] Furthermore, as resin films with anti-reflective properties (anti-reflective films), those having a low refractive index layer, a hard coat layer, and a film substrate in order from the surface facing the incident sunlight in actual use conditions, or having a low refractive index layer, a high refractive index layer, and a film substrate, are widely used. When developing an anti-reflective film for external application to glass, the inventors considered that a paint with a silane compound having hydrolyzable groups as a binder would be suitable for forming the low refractive index layer from the viewpoint of weather resistance. They also considered that a paint with an active energy ray curable resin as a binder would be suitable for forming the hard coat layer and the high refractive index layer because it has high hardness, a short curing time, and high productivity. However, experiments conducted by the inventors revealed that when a low refractive index layer was formed using a paint with a silane compound having hydrolyzable groups as a binder on top of a hard coat layer or high refractive index layer formed using a paint with an active energy ray curable resin as a binder, the weather resistance was insufficient, and there was a problem that the paint film was prone to peeling. Furthermore, we concluded that the peeling of the paint film was caused by the deterioration of the hard coat layer and the high refractive index layer. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-164255 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] An object of the present invention is to provide a weather-resistant anti-reflective film that can be applied to the exterior side of window glass. A further object of the present invention is to provide a weather-resistant anti-reflective film that can be applied to the exterior side of window glass, having a hard coat layer and a high refractive index layer formed using a paint with a hydrolyzable silane compound as a binder on top of a surface formed using a paint with an active energy ray curable resin as a binder. Another further object of the present invention is to provide a weather-resistant anti-reflective film with high transparency that can be applied to the exterior side of window glass. [Means for solving the problem]

[0006] As a result of diligent research, the inventors have found that the above problem can be solved by using a specific anti-reflective film.

[0007] In other words, the embodiments of the present invention are as follows. [1]. The material has layers of a low refractive index layer, a hard coat layer, and a film substrate in this order; the low refractive index layer is formed using a paint containing (A1) a silane compound having a hydrolyzable group and (A2) low refractive index particles; the hard coat layer is formed using a paint containing (B1) an active energy ray curable resin; where the above component (B1) the active energy ray curable resin is (B1-a) Silsesquioxane Anti-reflective film comprising a polymerizable compound having a skeleton and (B1-b) urethane (meth)acrylate. [2]. The amount of component (B1-b) urethane (meth)acrylate is 30 to 99% by mass, where the total amount of all components of component (B1) active energy ray curable resin is 100% by mass; [1] Anti-reflective film as described in item [1]. [3]. The number of (meth)acryloyl groups in the above component (B1-b) urethane (meth)acrylate is 1 to 10 per 1000 units of polystyrene-based number-average molecular weight, determined from the differential molecular weight distribution curve measured by gel permeation chromatography; the anti-reflective film according to item [1] or [2]. [4]. The above component (B1) active energy ray curable resin further comprises (B1-c) hydroxyl group-containing (meth)acrylate; the anti-reflective film according to any one of items [1] to [3]. [5]. The material has layers of a low refractive index layer, a hard coat layer, and a film substrate in this order; the low refractive index layer is formed using a paint containing (A1) a silane compound having a hydrolyzable group and (A2) low refractive index particles; the hard coat layer is formed using a paint containing (B1) an active energy ray curable resin and (B3) a compound having two or more isocyanate groups in one molecule; where the above component (B1) active energy ray curable resin is (B1-a) Silsesquioxane Anti-reflective film comprising a polymerizable compound having a skeleton and (B1-c)hydroxyl group-containing (meth)acrylate. [6]. The amount of the above component (B3) compound having two or more isocyanate groups in one molecule is 1 to 40 parts by mass per 100 parts by mass of the above component (B1) active energy ray curable resin; the amount of the above component (B1-c) hydroxyl group-containing (meth)acrylate is 1 to 40% by mass, with the total amount of all components of the above component (B1) active energy ray curable resin being 100% by mass; the anti-reflective film as described in item [5]. [7]. The above component (B1-a) Silsesquioxane The amount of polymerizable compound having a skeleton is 1 to 70% by mass, where the total amount of all components of the active energy ray curable resin (B1) is 100% by mass; the anti-reflective film according to any one of items [1] to [6]. [8]. The above component (B1) active energy ray curable resin further comprises (B1-d) a compound having one or more cationic polymerizable groups and one or more radical polymerizable groups in one molecule; the anti-reflective film according to any one of items [1] to [7]. [9]. The above component (B1) active energy ray curable resin further comprises (B1-e) alkyl (meth)acrylate; the anti-reflective film according to any one of items [1] to [8].

[10] . An anti-reflective film having layers of a low refractive index layer, a hard coat layer, an anchor coat, and a film substrate in this order; the anchor coat is formed using a paint containing a polymer comprising a polymer containing a (meth)acrylate-derived structural unit having one or more skeletons selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton in one molecule; the anti-reflective film according to any one of items [1] to [9].

[11] . The anti-reflective film according to any one of items [1] to

[10] , wherein the hard coat layer further contains (B2) high refractive index particles.

[12] . The anti-reflective film according to any one of items [1] to

[11] , wherein the low refractive index layer further comprises fine particles of an inorganic compound that functions as an antibacterial or antiviral agent.

[13] . Articles containing anti-reflective film as described in any one of items [1] to

[12] . [Effects of the Invention]

[0008] The anti-reflection film of the present invention has excellent weather resistance. In one preferred embodiment, the anti-reflection film of the present invention has a low refractive index layer formed using a paint with a silane compound having a hydrolyzable group as a binder on the surface of a hard coat layer or a high refractive index layer formed using a paint with an active energy ray curable resin as a binder, so that the productivity is high. Also, it has excellent weather resistance. In one of the other preferred embodiments, the anti-reflection film of the present invention has excellent weather resistance and transparency. Therefore, the anti-reflection film of the present invention can be suitably used as an anti-reflection film for external attachment to glass.

Embodiments for Carrying out the Invention

[0009] In this specification, the term "resin" is used as a term that also includes a resin mixture containing two or more resins and a resin composition containing components other than the resin. In this specification, the term "film" is used interchangeably or replaceably with "sheet". In this specification, the terms "film" and "sheet" are used for those that can be industrially wound into a roll. The term "plate" is used for those that cannot be industrially wound into a roll. Also, in this specification, laminating one layer on top of another layer in order includes both directly laminating those layers and laminating them with one or more other layers such as an anchor coat intervening between those layers.

[0010] In this specification, the term "above" related to a numerical range is used to mean a certain numerical value or more than a certain numerical value. For example, "above 20%" means 20% or more than 20%. The term "below" related to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, "below 20%" means 20% or less than 20%. Also, the symbol "~" related to a numerical range is used to mean a certain numerical value, more than a certain numerical value and less than another certain numerical value, or another certain numerical value. Here, the other certain numerical value is a numerical value greater than the certain numerical value. For example, "10~90%" means 10%, more than 10% and less than 90%, or 90%. Further, the upper limit and the lower limit of a numerical range can be arbitrarily combined, and an arbitrarily combined embodiment should be construed as being read. For example, from the description such as "usually above 10%, preferably above 20%. On the other hand, usually below 40%, preferably below 30%." or "usually 10~40%, preferably 20~30%." related to the numerical range of a certain characteristic, it should be construed that the numerical range of that certain characteristic is 10~40%, 20~30%, 10~30%, or 20~40% in one embodiment.

[0011] Unless otherwise specified or except in the case of examples, all numerical values used in this specification and the claims should be understood to be modified by the term "about". Without intending to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed in light of significant figures and by applying ordinary rounding methods.

[0012] 1. Anti-reflective film: The anti-reflective film of the present invention has a low refractive index layer, a hard coat layer, and a film substrate layer in this order. In one embodiment of the present invention, the anti-reflective film has a low refractive index layer, a hard coat layer, an anchor coat, and a film substrate layer in this order. In one preferred embodiment, the hard coat layer may be a hard coat layer having a high refractive index (hereinafter referred to as the "high refractive index layer"). In this specification, the term "hard coat layer" includes the "high refractive index layer (hard coat layer having a high refractive index)" unless otherwise specified. Each layer will be described below.

[0013] (A) Low refractive index layer: The anti-reflective film of the present invention has a low refractive index layer, which typically forms the surface on which sunlight or ambient light enters during actual use. Here, "actual use" refers to the state in which the anti-reflective film is laminated to glass such as window glass of a building, car windows, or display panels of an image display device, and is used for the protection and shatter prevention of the glass.

[0014] The refractive index (RL) of the low refractive index layer described above is usually 1.5 or less, preferably 1.45 or less, and more preferably 1.4 or less, from the viewpoint of enabling the anti-reflective film to exhibit good anti-reflective properties. On the other hand, from the viewpoint of the transparency of the anti-reflective film, it may be preferably 1.2 or more, more preferably 1.25 or more, more preferably 1.28 or more, and even more preferably 1.3 or more.

[0015] The above refractive index (RL) is measured using an Abbe refractometer according to Method A of JIS K7142:2008, with the sodium D line (wavelength 589.3 nm), 1-bromonaphthalene as the contact fluid, the surface of the sample that was on the biaxially oriented polypropylene resin film side during sample preparation in contact with the prism, and the bar coater operation direction of the sample being in the direction of the length of the test piece. For the sample, the coating used to form the above low refractive index layer is applied to the surface of a 20 μm thick biaxially oriented polypropylene resin film using a bar coater so that the thickness after curing is 2 μm, and the coating obtained after drying and curing is peeled off from the biaxially oriented polypropylene resin film and used.

[0016] As a paint used to form the low refractive index layer described above, a paint using a silane compound having a hydrolyzable group as a binder is preferred from the viewpoint of weather resistance of the anti-reflective film. The paint for forming a low refractive index layer using a silane compound having a hydrolyzable group as a binder (hereinafter sometimes abbreviated as "paint (A)") will be described below.

[0017] The above-mentioned paint (A) comprises (A1) a silane compound having a hydrolyzable group, and is a paint capable of forming a low refractive index layer having a refractive index (RL) within the range described above. In one typical embodiment, the above-mentioned paint (A) comprises (A1) a silane compound having a hydrolyzable group, and (A2) low refractive index particles.

[0018] (A1) Silane compounds having hydrolyzable groups: The above component (A1) condenses and hardens upon heat, etc., to form a polymer with a silicone skeleton (siloxane bond (Si-O-Si)) as its main structure, and functions to form a coating film (cured coating film). In addition, the silane compound of component (A1) having a hydrolyzable group functions as a binder, encapsulating the low refractive index particles of component (A2).

[0019] Examples of hydrolyzable groups in component (A1) include alkoxy groups such as methoxy, ethoxy, propoxy, and isopropoxy groups; acyloxy groups such as acetoxy groups; and halogen groups such as chloro groups. Among these, alkoxy groups are preferred as hydrolyzable groups in component (A1) from the viewpoint of controllability of the hydrolysis reaction.

[0020] Examples of the above component (A1) include hydrolyzable organosilicon compounds, (partial) hydrolysates of said compounds, and (partial) condensates thereof. Here, (partial) hydrolysate means a partial hydrolysate, a hydrolysate, or a mixture of a partial hydrolysate and a hydrolysate. Here, (partial) condensate means a partial condensate, a condensate, or a mixture of a partial condensate and a condensate.

[0021] The hydrolysis or partial hydrolysis of the above-mentioned hydrolyzable organosilicon compounds can be carried out by known methods. For example, a method for hydrolyzing or partially hydrolyzing the above-mentioned hydrolyzable organosilicon compounds can be used. This method involves mixing a predetermined amount of water, typically about 0.1 to 2 moles per mole of hydrolyzable groups in the above-mentioned hydrolyzable organosilicon compounds, with a mixture of the above-mentioned hydrolyzable organosilicon compounds and an organic solvent such as diacetone alcohol, and then optionally adding a catalyst, such as an acid or alkali such as phosphoric acid, acetic acid, and formic acid, and reacting the mixture while stirring at a predetermined temperature, typically room temperature (23°C) to about 100°C.

[0022] The condensation or partial condensation of the above-mentioned hydrolyzable organosilicon compounds can be carried out by known methods. For example, a method for condensing or partially condensing the above-mentioned hydrolyzable organosilicon compounds can be performed by the method described above to obtain a (partial) hydrolyzate, and then optionally adding a silanol condensation catalyst, such as a metal chelate compound, an organic acid metal salt, or a metal compound having a hydrolyzable group, and reacting while stirring at a predetermined temperature, typically around 50°C to below the boiling point of the organic solvent.

[0023] Examples of the hydrolyzable organosilicon compounds include alkoxymonosilane compounds, compounds in which one or more hydrogen atoms in the alkoxymonosilane compound are substituted with fluorine atoms, bis(alkoxysilyl)alkyl compounds, compounds in which one or more hydrogen atoms in the bis(alkoxysilyl)alkyl compound are substituted with fluorine atoms, and alkoxysilane compounds such as oligomers or prepolymers of one or more of these.

[0024] Examples of the above alkoxymonosilane compounds include tetraalkoxysilane, alkyltrialkoxysilane, and dialkyldialkoxysilane. Examples of the above tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane. Examples of the above alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane. Examples of the above dialkyldialkoxysilane include dimethyldimethoxysilane and dimethyldiethoxysilane.

[0025] Examples of compounds in which one or more hydrogen atoms in the above-mentioned alkoxymonosilane compound are substituted with fluorine atoms include compounds having the structure of the following general formula (1).

[0026] R-SiX3(1)

[0027] In formula (1), X is an alkoxy group. R is an alkyl group in which one or more hydrogen atoms, preferably three or more, are substituted with fluorine atoms. The number of carbon atoms in R is usually 1 to 20, preferably 3 to 12. In one of the preferred embodiments, R may have the structure of the following general formula (1-1).

[0028] CF3(CF2)n(CH2)2- (1-1)

[0029] In equation (1-1), n ​​is usually an integer between 0 and 17, preferably between 0 and 9.

[0030] Examples of compounds in which one or more hydrogen atoms in the above-mentioned alkoxymonosilane compounds are substituted with fluorine atoms include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,4,4,5,5,5-heptafluoropentyltrimethoxysilane, 3,3,4,4,5,5,5-heptafluoropentyltriethoxysilane, 1H,1H,2H,2H-heptadecafluorodecyltrimethoxysilane, 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyltrimethoxysilane, and 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyltriethoxysilane.

[0031] Examples of the bis(alkoxysilyl)alkyl compounds mentioned above include compounds having the structure of the following general formula (2).

[0032] R' 3-n -SiXn-R-SiX'm-R” 3-m (2)

[0033] In formula (2), R is a hydrocarbon group. The hydrocarbon group may be a straight chain or a branched chain, and may contain an aromatic ring, an aliphatic cyclic group, an ether group, an ester group, a nitrogen atom, or an oxygen atom. The number of carbon atoms in the hydrocarbon group is usually 1 to 20, preferably 2 to 12. X and X' are alkoxy groups. R' and R'' are alkyl groups. n and m are integers from 1 to 3.

[0034] Examples of the above-mentioned bis(alkoxysilyl)alkyl compounds include bis(alkoxysilyl)alkanes such as 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,4-bis(trimethoxysilyl)butane, 1-dimethyldimethoxysilyl-4-trimethoxysilylbutane, 1,4-bis(dimethyldimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,7-bis(trimethoxysilyl)heptane, 1,8-bis(trimethoxysilyl)octane, 1,9-bis(trimethoxysilyl)nonane, and 1,10-bis(trimethoxysilyl)decane; and bis(alkoxysilyl)alkanes having an amine group such as bis[3-(trimethoxysilyl)propyl]amine.

[0035] Examples of compounds in which one or more hydrogen atoms of the above-mentioned bis(alkoxysilyl)alkyl compound are substituted with fluorine atoms include compounds having the structure of the following general formula (3).

[0036] R' 3-n -SiXn-R-SiX'm-R” 3-m (3)

[0037] In formula (3), X and X' are alkoxy groups, R' and R'' are alkyl groups, and n and m are integers from 1 to 3. R is a hydrocarbon group in which one or more, preferably two or more, hydrogen atoms are substituted with fluorine atoms. The hydrocarbon group may be linear or branched, and may contain aromatic rings, aliphatic cyclic groups, ether groups, ester groups, nitrogen atoms, or oxygen atoms. The number of carbon atoms in the hydrocarbon group is usually 1 to 20, preferably 2 to 12. In one of the preferred embodiments, R may have the structure of the following general formula (3-1).

[0038] -(CH2)2-(CF2)n-(CH2)2- (3‐1)

[0039] In equation (3-1), n ​​is a natural number, preferably a natural number between 1 and 20, and more preferably a natural number between 2 and 12.

[0040] Examples of compounds in which one or more hydrogen atoms of the above bis(alkoxysilyl)alkyl compounds are substituted with fluorine atoms include 3,3,4,4-tetrafluoro-1,6-bis(trimethoxysilyl)hexane, 3,3,4,4,5,5,6,6-octafluoro-1,8-bis(trimethoxysilyl)octane, 3,3,4,4,5,5,6,6-octafluoro-1,8-bis(triethoxysilyl)octane, 1H,1H,2H,2H,9H,9H,10H,10H-dodecafluoro-1,10-bis(trimethoxysilyl)decane, and 1H,1H,2H,2H,11H,11H,12H,12H-hexadecafluoro-1,12-bis(trimethoxysilyl)dodecane.

[0041] As for the above component (A1), from the viewpoint of lowering the refractive index of the base resin and further improving the anti-reflective function, a compound in which one or more hydrogen atoms in the alkoxymonosilane compound are substituted with a fluorine atom, and a compound in which one or more hydrogen atoms in the bis(alkoxysilyl)alkyl compound are substituted with a fluorine atom are preferred.

[0042] As the above component (A1), one or a mixture of two or more of these can be used.

[0043] (A2) Low refractive index particles: The above-mentioned component (A2), low refractive index particles, are particles that lower the refractive index of the coating film formed using the above-mentioned paint (A). Examples of the above-mentioned component (A2) include particles (solid particles) of low refractive index materials such as silica, magnesium fluoride, fluorine resin, and silicone resin, as well as hollow particles.

[0044] The hollow particles described above are particles that have an outer shell layer and an interior that is porous or hollow (single-pore). Because these hollow particles contain air (refractive index 1.0) in the pores of the porous or hollow (single-pore) structure, they have a great effect in lowering the refractive index of the coating film.

[0045] The material constituting the hollow particles described above is not particularly limited, as long as it forms the structure described above. Examples of materials constituting the hollow particles include low refractive index materials such as silica, magnesium fluoride, fluorine resin, and silicone resin. Among these, silica is preferred from the viewpoint of productivity when manufacturing the hollow particles.

[0046] The average particle size of component (A2) is determined appropriately, taking into account the thickness of the low refractive index layer and the productivity of manufacturing the low refractive index particles. The average particle size of component (A2) is usually 1 to 150 nm, preferably 5 to 100 nm, more preferably 10 to 80 nm, and even more preferably 15 to 60 nm.

[0047] In this specification, the average particle size is defined as the particle size at which the cumulative total from the smallest particle size to the largest particle size in the particle size distribution curve, measured by the laser diffraction-scattering method using a laser diffraction-scattering particle size analyzer, reaches 50% by mass. As the laser diffraction-scattering particle size analyzer, for example, the "MT3200II (product name)" from Nikkiso Co., Ltd. can be used.

[0048] Among the above components (A2), hollow particles are preferred, and hollow silica (hollow silica particles) is more preferred. One or a mixture of two or more of these can be used as component (A2).

[0049] The amount of component (A2) to be blended is determined appropriately, taking into consideration the type of component (A2) and from the viewpoint of keeping the refractive index (RL) within the above range. The amount of component (A2) to be blended is usually 10 to 200 parts by mass, preferably 20 to 100 parts by mass, and more preferably 30 to 80 parts by mass, per 100 parts by mass of component (A1), from the viewpoint of keeping the refractive index (RL) within the above range.

[0050] The above-mentioned paint (A) may further contain a solvent from the viewpoint of productivity when forming a wet coating using the above-mentioned paint (A). Examples of the above-mentioned solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellsolve, ethyl cellsolve, diacetone alcohol, and acetone. One or more of these solvents or mixtures thereof can be used.

[0051] The amount of solvent blended is determined appropriately from the viewpoint of productivity when forming a wet coating using the paint (A), and from the viewpoint of productivity in the process of drying the wet coating and recovering the solvent after forming the wet coating using the paint (A). From the viewpoint of productivity when forming a wet coating using the paint (A), the amount of solvent blended is preferably 600 parts by mass or more, more preferably 1200 parts by mass or more, and even more preferably 1800 parts by mass or more, with the sum of the blended amounts of component (A1) and component (A2) being 100 parts by mass. On the other hand, from the viewpoint of productivity in the process of drying the wet coating and recovering the solvent after forming the wet coating using the paint (A), the amount of solvent blended is preferably 6000 parts by mass or less, more preferably 4000 parts by mass or less, and even more preferably 3000 parts by mass or less.

[0052] In one embodiment, the above-mentioned paint (A) may further contain (A3) fine particles of an inorganic compound that functions as an antibacterial or antiviral agent. The above-mentioned component (A3) works to impart antibacterial and antiviral properties to the low refractive index layer.

[0053] Examples of the above component (A3) that function as an antibacterial or antiviral agent include fine particles of copper compounds, silver compounds, tin compounds, molybdenum compounds, and zinc compounds. Examples of the above copper compounds include cuprous halides such as cuprous chloride (CuCl), cuprous bromide (CuBr), and cuprous iodide (CuI), and cuprous compounds such as cuprous thiocyanate (CuSCN); and cupric compounds such as cupric carbonate (CuCO3), cupric oxide (CuO), and cupric chloride (CuCl2). Examples of the above silver compounds include silver halides such as silver iodide (AgI). Examples of the above tin compounds include tin tetraiodide (SnI4). Examples of the above molybdenum compounds include molybdenum oxide (MoO3), molybdenum-silver composite oxide, molybdenum-zinc composite oxide, and molybdenum-copper composite oxide. Examples of the zinc compounds mentioned above include zinc oxide compounds such as zinc oxide (ZnO).

[0054] Other compounds that function as antibacterial or antiviral agents in the above component (A3) include, for example, potassium aluminum sulfate, silver-sodium-hydrogen-zirconium phosphate, silver-magnesium-aluminum-phosphate glass (FCN registration number 433 with the U.S. Food and Drug Administration), silver-magnesium-calcium-phosphate-boric acid glass (FCN registration number 432 with the U.S. Food and Drug Administration), and silver-zinc-magnesium-aluminum-calcium-sodium-boric acid-phosphate glass (FCN registration number 432 with the U.S. Food and Drug Administration). Examples of fine particles include silver-magnesium-sodium-phosphate glass (FCN registration number 434 from the U.S. Food and Drug Administration), silver-magnesium-zinc-aluminum-calcium-sodium-boric acid-phosphate glass (FCN registration number 1981 from the U.S. Food and Drug Administration), silver zeolite (CAS number 0130328-18-6), silver-copper zeolite (CAS number 0130328-19-7), silver-zinc zeolite (CAS number 0130328-20-0), and copper-tin alloys.

[0055] The average particle size of the inorganic compound fine particles of component (A3) that function as an antibacterial or antiviral agent may be typically 1 μm or less, preferably 300 nm or less, more preferably 150 nm or less, and even more preferably 120 nm or less, from the viewpoint of the thickness of the low refractive index layer, the productivity of forming the low refractive index layer, and transparency. On the other hand, there is no particular lower limit to the average particle size of component (A3), but from the viewpoint of productivity in producing the inorganic compound fine particles that function as an antibacterial or antiviral agent, it may be typically 1 nm or more.

[0056] In this specification, the average particle size is defined as the particle size at which the cumulative total from the smallest particle size to the largest particle size in the particle size distribution curve, measured by the laser diffraction-scattering method using a laser diffraction-scattering particle size analyzer, reaches 50% by mass. As the laser diffraction-scattering particle size analyzer, for example, the "MT3200II (product name)" from Nikkiso Co., Ltd. can be used.

[0057] Of the above components (A3), cuprous halide compounds and silver halide compounds are preferred as fine particles of inorganic compounds that function as antibacterial or antiviral agents, from the viewpoint of antibacterial properties, antiviral properties, and maintaining a refractive index within a predetermined range. One or more of these can be used as fine particles of inorganic compounds that function as antibacterial or antiviral agents.

[0058] The amount of the above component (A3), which is a fine particle of an inorganic compound that functions as an antibacterial or antiviral agent, should be appropriately selected considering its type, from the viewpoint of ensuring that its function is reliably expressed, and from the viewpoint of suppressing problems caused by excessive amounts.

[0059] The amount of the above component (A3), fine particles of an inorganic compound that functions as an antibacterial or antiviral agent, is usually 1 part by mass or more, preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the above component (A1), a silane compound having a hydrolyzable group, from the viewpoint of reliably exhibiting antibacterial or antiviral properties. On the other hand, the amount of the above component (A3) is usually 100 parts by mass or less, preferably 60 parts by mass or less, and more preferably 30 parts by mass or less, from the viewpoint of maintaining the paint's coatability and the transparency of the coating film, as well as maintaining the refractive index within a predetermined range.

[0060] The above-mentioned paint (A) may further contain optional components other than the above-mentioned components (A1) to (A3), to the extent that it does not contradict the purpose of the present invention. Examples of the above-mentioned optional components include organic compounds that function as defoaming agents, leveling agents, surfactants, thixotropic agents, antistatic agents, antifouling agents, printability improvers, antioxidants, weather-resistant stabilizers, light-resistant stabilizers, ultraviolet absorbers, heat stabilizers, antibacterial agents or antiviral agents, and dyes. One or a mixture of two or more of these optional components may be used. The amount of the above-mentioned optional components may be 10 parts by mass or less, or about 0.01 to 10 parts by mass, per 100 parts by mass of component (A1).

[0061] The above paint (A) can be obtained by mixing and stirring these components.

[0062] The method for forming the low refractive index layer on the surface of the hard coat layer is not particularly limited, and known web coating methods can be used. From the viewpoint of applying the paint productively using a roll-to-roll method, preferred web coating methods include, for example, rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating. Among these methods, rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferred from the viewpoint of applying the paint productively using a roll-to-roll method, rod coating is more preferred from the viewpoint of making the thickness of the coating film uniform, and rod coating using a Meyer bar as the rod (hereinafter sometimes abbreviated as "Meyer bar method") is even more preferred.

[0063] The thickness of the low refractive index layer is determined appropriately, taking into consideration the desired reflectance and the productivity of forming the low refractive index layer. From the viewpoint of reducing reflectance, the thickness of the low refractive index layer may be 300 nm or less, preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. On the other hand, from the viewpoint of productivity of forming the low refractive index layer, it may be 10 nm or more, preferably 20 nm or more, more preferably 40 nm or more, and even more preferably 60 nm or more.

[0064] (B) Hard coat layer: The anti-reflective film of the present invention has a hard coat layer. The hard coat layer serves to increase the surface hardness of the anti-reflective film. In one preferred embodiment, the hard coat layer may be a high refractive index layer. The refractive index (RH) of the high refractive index layer is usually 1.55 or higher, preferably 1.6 or higher, and more preferably 1.65 or higher, from the viewpoint of increasing the refractive index difference with the refractive index (RL) of the low refractive index layer and exhibiting good anti-reflective function in the anti-reflective film. On the other hand, from the viewpoint of the transparency of the anti-reflective film, it is preferably 2.0 or lower, more preferably 1.9 or lower, and even more preferably 1.8 or lower.

[0065] The above refractive index (RH) is measured using an Abbe refractometer according to Method A of JIS K7142:2008, with the sodium D line (wavelength 589.3 nm), 1-bromonaphthalene as the contact solution, the surface of the sample that was on the biaxially oriented polypropylene resin film side during sample preparation in contact with the prism, and the bar coater operation direction of the sample being the longitudinal direction of the test piece. For the sample, the coating used to form the above high refractive index layer is applied to the surface of a 20 μm thick biaxially oriented polypropylene resin film using a bar coater so that the thickness after curing is 2 μm, and the coating obtained after drying and curing is peeled off from the biaxially oriented polypropylene resin film and used.

[0066] As a paint used to form the hard coat layer described above, a paint using an active energy ray-curable resin as a binder is preferred because it has high hardness, a short curing time, and high productivity. Below, a paint for forming a hard coat layer using an active energy ray-curable resin as a binder (hereinafter sometimes abbreviated as "paint (B)") will be described.

[0067] The above-mentioned paint (B) is a paint that contains (B1) an active energy ray curable resin and is capable of forming a coating film (cured coating film). In one preferred embodiment, the above-mentioned paint (B) may contain (B1) an active energy ray curable resin and (B3) a compound having two or more isocyanate groups in one molecule.

[0068] When the hard coat layer is a high refractive index layer, the paint (B) is a paint that includes (B1) an active energy ray curable resin and can form a high refractive index layer with a refractive index (RH) within the range described above. In one preferred embodiment, the paint (B) may include (B1) an active energy ray curable resin and (B2) high refractive index particles. In another preferred embodiment, the paint (B) may include (B1) an active energy ray curable resin, (B2) high refractive index particles and (B3) a compound having two or more isocyanate groups in one molecule.

[0069] (B1) Active energy ray curable resin: The above component (B1) polymerizes and hardens upon irradiation with active energy rays such as ultraviolet rays or electron beams, forming a coating film (cured coating film). Furthermore, if the above hard coat layer is a high refractive index layer, the above component (B1), an active energy ray curable resin, acts as a binder, encapsulating the above component (B2), a high refractive index particle.

[0070] In an embodiment in which a low refractive index layer is formed on the surface of a hard coat layer formed using a paint with an active energy ray curable resin as a binder, using a paint with a hydrolyzable silane compound as a binder, the above component (B1) is preferably (B1-a) from the viewpoint of suppressing and preventing cracking of the low refractive index layer. Silsesquioxane It contains a polymerizable compound having a skeleton. In one preferred embodiment, component (B1) is (B1-a) Silsesquioxane It may contain a polymerizable compound having a skeleton and (B1-b) urethane (meth)acrylate. If the above paint (B) contains the above components (B1), (B2), and (B3), then in one preferred embodiment, component (B1) is (B1-a) Silsesquioxane The material may contain polymerizable compounds having a skeleton, and (B1-c)hydroxyl group-containing (meth)acrylates.

[0071] (B1-a) Polymerizable compounds having a silsesquioxane skeleton: The above component (B1-a) SilsesquioxanePolymerizable compounds with a skeleton have a main chain consisting of siloxane bonds (Si-O-Si), and their unit composition formula is "(RSiO 1.5 The compound has a skeleton represented by ")n" and contains one or more, preferably two or more, photopolymerizable functional groups in one molecule. Here, R is an organic group. The above photopolymerizable functional group is a functional group that polymerizes by irradiation with active energy rays. Examples of the above photopolymerizable functional group include acryloyl group, methacryloyl group, vinyl group, thiol group, epoxy group, and cyclic ether group such as oxetanyl group.

[0072] The above component (B1-a) Silsesquioxane Polymerizable compounds with a skeletal structure improve weather resistance (particularly by suppressing the decrease in adhesion between the low refractive index layer and the hard coat layer).

[0073] Examples of the above component (B1-a) include those described in International Publication No. 2010 / 024119, International Publication No. 2010 / 044321, and International Publication No. 2018 / 131565. A commercially available example of the above component (B1-a) is "MAC-SQ HDM (product name)" from Toagosei Co., Ltd. Silsesquioxane Compounds having a skeleton and a methacryloyl group), and "OX-SQ HDX (trade name)" Silsesquioxane Examples include compounds having a skeleton and an oxetanyl group. One or more of these can be used as component (B1-a).

[0074] The amount of component (B1-a) is appropriately determined from the viewpoint of improving weather resistance, and in particular from the viewpoint of suppressing a decrease in adhesion between the low refractive index layer and the hard coat. The amount of component (B1-a) is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, with the total amount of all components of the active energy ray curable resin of component (B1) being 100% by mass, from the viewpoint of improving weather resistance, and in particular from the viewpoint of suppressing a decrease in adhesion between the low refractive index layer and the hard coat layer. On the other hand, from the viewpoint of curability of the coating film, it is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 35% by mass or less, and most preferably 25% by mass or less.

[0075] (B1-b) Urethane (meth)acrylate: The above component (B1-b) urethane (meth)acrylate is a compound having a urethane structure (-NH-CO-O-) or a derivative thereof, which has one or more (meth)acryloyl groups in one molecule. In this specification, (meth)acryloyl group means acryloyl group or methacryloyl group.

[0076] The above component (B1-b) improves weather resistance (particularly by reducing and preventing the occurrence of microcracks in the low refractive index layer).

[0077] While not intending to be bound by theory, it is hypothesized that when a low refractive index layer is formed on a hard coat layer formed using a paint with a silane compound containing hydrolyzable groups as a binder, the weather resistance is insufficient and the paint film is prone to peeling, which is due to the deterioration of the hard coat layer. Originally, there is a difference in mobility between the hard coat layer formed using a paint with an active energy ray curable resin as a binder and the low refractive index layer formed using a paint with a silane compound containing hydrolyzable groups as a binder, and stress is easily applied between the two. When the hard coat layer deteriorates, the mobility of the hard coat layer decreases further, and the difference in mobility between the hard coat layer and the low refractive index layer becomes even larger, resulting in strong stress being applied between the two. As a result, microcracks may form in the low refractive index layer, or the adhesion or interlayer strength between the low refractive index layer and the hard coat layer may decrease, leading to paint film peeling.

[0078] Therefore, in the present invention, by reducing the difference in mobility between the low refractive index layer and the hard coat layer by methods such as introducing a urethane structure, the stress acting between them is suppressed, and the above component (B1-a) Silsesquioxane By using a polymerizable compound with a skeletal structure, the reduction in adhesion or interlayer strength between the low refractive index layer and the hard coat layer is suppressed, thereby solving the weather resistance problem.

[0079] The above component (B1-b) is not particularly limited as long as it has the characteristics described above. Typically, the above component (B1-b) may be produced using compounds having two or more isocyanate groups (-N=C=O) in one molecule, polyol compounds, and hydroxyl group-containing (meth)acrylates, i.e., it may contain constituent units derived from these compounds. In this specification, (meth)acrylate means acrylate or methacrylate.

[0080] Examples of compounds having two or more isocyanate groups in one molecule include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, methylene bis-4-cyclohexyl isocyanate, and diphenylmethane diisocyanate, which have two isocyanate groups in one molecule; and trimethylolpropane adducts of compounds having two isocyanate groups in one molecule, such as the trimethylolpropane adduct of tolylene diisocyanate, the trimethylolpropane adduct of hexamethylene diisocyanate, and the trimethylolpropane adduct of isophorone diisocyanate. Examples include compounds having three isocyanate groups in one molecule; isocyanurates of compounds having two isocyanate groups in one molecule, such as the isocyanurate of tolylene diisocyanate, the isocyanurate of hexamethylene diisocyanate, and the isocyanurate of isophorone diisocyanate, which have three isocyanate groups in one molecule; biuretes of compounds having two isocyanate groups in one molecule, such as the biuret of hexamethylene diisocyanate, which have three isocyanate groups in one molecule; and urethane crosslinking agents such as these blocked isocyanates.

[0081] As the compounds having two or more isocyanate groups in one molecule, one or a mixture of two or more of these can be used.

[0082] Examples of the above-mentioned polyol compounds include polyether polyols, polyester polyols, and polycarbonate polyols.

[0083] Examples of the above-mentioned polyether polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyalkylene oxides such as polyethylene oxide and polypropylene oxide; copolymers of ethylene oxide and propylene oxide; copolymers of ethylene oxide and tetrahydrofuran; copolymers of divalent phenol compounds and polyoxyalkylene glycols; and copolymers of divalent phenols with one or more alkylene oxides having 2 to 4 carbon atoms (e.g., ethylene oxide, propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide).

[0084] Examples of the above-mentioned polyester polyols include poly(ethylene adipate), poly(butylene adipate), poly(neopentyl adipate), poly(hexamethylene adipate), poly(butylene azelaate), poly(butylene sebacate), and polycaprolactone.

[0085] Examples of the polycarbonate polyols mentioned above include poly(butanediol carbonate), poly(hexanediol carbonate), and poly(nonanediol carbonate).

[0086] As the above polyol compounds, one or a mixture of two or more of these can be used.

[0087] Examples of the hydroxyl group-containing (meth)acrylates mentioned above include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate; glycol-based (meth)acrylates such as dipropylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; glycerin-based (meth)acrylates such as glycerin di(meth)acrylate; modified glycidyl-based (meth)acrylates such as fatty acid-modified glycidyl (meth)acrylate; and 2-hydroxyethyl Examples include phosphorus atom-containing (meth)acrylates such as acryloyl phosphate; (meth)acrylic acid adducts of esters or ester derivatives such as 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate; pentaerythritol-based (meth)acrylates such as pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate; and caprolactone-modified (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, and caprolactone-modified dipentaerythritol penta(meth)acrylate.

[0088] As the hydroxyl group-containing (meth)acrylates mentioned above, one or a mixture of two or more of these can be used.

[0089] The number-average molecular weight (Mn) in polystyrene terms, determined from the differential molecular weight distribution curve (hereinafter sometimes abbreviated as GPC curve) measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) of the above component (B1-b), may be 500 or more, preferably 800 or more, from the viewpoint of weather resistance. On the other hand, from the viewpoint of coating properties, it may be 50,000 or less, preferably 30,000 or less.

[0090] The polystyrene-based mass-average molecular weight (Mw) obtained from the GPC curve measured by GPC of the above component (B1-b) may be 1000 or more, preferably 1500 or more, and more preferably 2000 or more, from the viewpoint of weather resistance. On the other hand, from the viewpoint of coating properties, it may be 100,000 or less, preferably 50,000 or less.

[0091] The number of (meth)acryloyl groups in the above component (B1-b) may be preferably 1 or more, more preferably 1.5, per 1000 units of polystyrene-based number-average molecular weight (Mn) determined from the GPC curve, from the viewpoint of paint curability. On the other hand, from the viewpoint of weather resistance, it may be preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, even more preferably 3 or less, and most preferably 2.5 or less.

[0092] The measurement of GPC was performed using a high-performance liquid chromatography system "HLC-8320 (trade name)" of Tosoh Corporation as a system (a system including a degasser, a liquid delivery pump, an autosampler, a column oven, and a RI (differential refractive index) detector); as GPC columns, two Shodex GPC columns "KF-806L (trade name)", one each of "KF-802 (trade name)" and "KF-801 (trade name)", a total of four columns were connected in the order of KF-806L, KF-806L, KF-802, and KF-801 from the upstream side and used; tetrahydrofuran (without stabilizer) for high-performance liquid chromatography of Wako Pure Chemical Industries, Ltd. was used as the mobile phase; it can be carried out under the conditions of a flow rate of 1.0 milliliter / minute, a column temperature of 40 °C, a sample concentration of 1 milligram / milliliter, and a sample injection volume of 100 microliters. The elution amount at each retention volume can be determined from the detection amount of the RI detector assuming that the molecular weight dependence of the refractive index of the measurement sample is absent. Also, a calibration curve from the retention volume to the polystyrene-equivalent molecular weight can be created using commercially available standard polystyrene. Note that it should be appropriately selected so that the measured value is interpolated in the calibration curve. The analysis program can use "TOSOH HLC-8320GPC EcoSEC (trade name)" of Tosoh Corporation. For the theory of GPC and the actual measurement, reference books such as "Size Exclusion Chromatography, High-Performance Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, First Printing, December 10, 1991" by Kyoritsu Shuppan Co., Ltd., and "Synthetic Polymer Chromatography, Editors: Hajime Ohtani, Tatsuya Takasaki (the upper part of '崎' is '立'), First Edition, First Printing, July 25, 2013" by Ohmsha, Ltd. can be referred to.

[0093] Figure 2 shows the differential molecular weight distribution curves of the components (B1-b1) used in the example. Two sharp peaks are observed in the relatively low molecular weight region, and the polystyrene-equivalent molecular weights at the top of these peaks are 280 and 610, respectively, from the low molecular weight side. A peak for the main component is observed on the higher molecular weight side of these two peaks, and the polystyrene-equivalent molecular weight at the top of this peak is 2400. The overall number-average molecular weight (Mn) is 1000, the mass-average molecular weight (Mw) is 2900, and the Z-average molecular weight (Mz) is 4700. Furthermore, since there are 2 (meth)acryloyl groups per molecule, the number of (meth)acryloyl groups per 1000 units of polystyrene-equivalent number-average molecular weight (Mn), as determined from the GPC curve, is 2.

[0094] The amount of component (B1-b) is determined appropriately from the viewpoint of improving weather resistance, particularly from the viewpoint of suppressing a decrease in adhesion between the low refractive index layer and the hard coat layer, and from the viewpoint of reducing and preventing fine cracks that occur in the low refractive index layer. The amount of component (B1-b) is usually 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more, with the total amount of all components of the active energy ray curable resin (B1) being 100% by mass, from the viewpoint of improving weather resistance, particularly from the viewpoint of reducing and preventing fine cracks that occur in the low refractive index layer. On the other hand, from the viewpoint of improving weather resistance, particularly from the viewpoint of suppressing a decrease in adhesion between the low refractive index layer and the hard coat layer, it is usually 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0095] (B1-c) Hydroxyl group-containing (meth)acrylate: The above-mentioned active energy ray curable resin component (B1) may preferably further contain the above-mentioned component (B1-c) hydroxyl group-containing (meth)acrylate. The above-mentioned component (B1-c) is a compound having one or more hydroxyl groups and one or more (meth)acryloyl groups in one molecule.

[0096] The above component (B1-c), a hydroxyl group-containing (meth)acrylate, has one or more hydroxyl groups per molecule, and is therefore thought to enhance the adhesion or interlayer strength between the low refractive index layer and the hard coat layer, thus being useful for improving weather resistance.

[0097] Furthermore, if the above-mentioned paint (B) contains the above-mentioned component (B1) an active energy ray curable resin and the above-mentioned component (B3) a compound having two or more isocyanate groups in one molecule, or if the above-mentioned component (B1) an active energy ray curable resin, the above-mentioned component (B2) high refractive index particles, and the above-mentioned component (B3) a compound having two or more isocyanate groups in one molecule, it is considered that the above-mentioned component (B1-c) hydroxyl group-containing (meth)acrylate forms a urethane structure with its hydroxyl group and the isocyanate group of the above-mentioned component (B3), thereby improving weather resistance (in particular, reducing and preventing fine cracks that occur in the low refractive index layer).

[0098] The above paint (B) contains the above component (B1), where the above component (B1) is the above component (B1-a) Silsesquioxane Embodiments comprising a polymerizable compound having a skeleton and component (B1-b) urethane (meth)acrylate, and embodiments in which the coating (B) comprises component (B1) and component (B3), wherein component (B1) comprises component (B1-a) and component (B1-c), share common or corresponding technical features in that the hard coat layer contains a structural unit derived from component (B1-a) and has a urethane structure.

[0099] The above paint (B) comprises the above component (B1) and the above component (B2), where the above component (B1) is the above component (B1-a) SilsesquioxaneEmbodiments comprising a polymerizable compound having a skeleton and component (B1-b) urethane (meth)acrylate, and embodiments in which the coating (B) comprises component (B1), component (B2), and component (B3), wherein component (B1) comprises component (B1-a) and component (B1-c), share common or corresponding technical features in that the high refractive index layer contains a structural unit derived from component (B1-a) and has a urethane structure.

[0100] Furthermore, in the embodiment for forming the anchor coat described above, the component (B1-c) hydroxyl group-containing (meth)acrylate improves adhesion to the anchor coat, particularly when a paint containing a compound having two or more isocyanate groups in one molecule is used as the paint for forming the anchor coat, as in the example described later.

[0101] Examples of the above component (B1-c) include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate; glycol-based (meth)acrylates such as dipropylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; glycerin-based (meth)acrylates such as glycerin di(meth)acrylate; modified glycidyl-based (meth)acrylates such as fatty acid-modified glycidyl (meth)acrylate; and 2-hydroxyethyl acrylo Examples include phosphorus atom-containing (meth)acrylates such as yl phosphate; (meth)acrylic acid adducts of esters or ester derivatives such as 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate; pentaerythritol-based (meth)acrylates such as pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate; and caprolactone-modified (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, and caprolactone-modified dipentaerythritol penta(meth)acrylate.

[0102] As the above component (B1-c), one or a mixture of two or more of these can be used.

[0103] When using the above component (B1-c), its blending amount should be determined appropriately from the viewpoint of ensuring its effectiveness. The blending amount of the above component (B1-c) may be 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, with the total blending amount of all components of the above component (B1) active energy ray curable resin being 100% by mass, from the viewpoint of ensuring its effectiveness. On the other hand, from the viewpoint of curability of the coating film, it may be 40% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.

[0104] (B1-d) Compounds having one or more cationic polymerizable groups and one or more radical polymerizable groups in one molecule: The above-mentioned active energy ray curable resin component (B1) may preferably further contain a compound having one or more cationic polymerizable groups and one or more radical polymerizable groups in one molecule of component (B1-d). By including component (B1-d), the adhesion or interlayer strength between the low refractive index layer and the hard coat layer can be further improved.

[0105] While not intended to be bound by theory, the following considerations explain why including the above component (B1-d) can further improve the adhesion or interlayer strength between the low refractive index layer and the hard coat layer. When a radical generator is used as a photopolymerization initiator in the above paint (B), the above component (B1-d) polymerizes to form a coating film through the reaction of radical polymerizable groups. On the other hand, many of the cationic polymerizable groups remain unreacted. Then, when a wet coating film is formed using the above paint (A) on the surface of the cured coating film formed using the above paint (B), and cured by heat, the remaining cationic polymerizable groups also react. As a result, the curing reaction of the low refractive index layer and the curing reaction of the above hard coat layer occur simultaneously, further improving the adhesion or interlayer strength between the two layers.

[0106] Examples of radical polymerizable groups include acryloyl groups and methacryloyl groups. Examples of cationic polymerizable groups include epoxy groups, cyclic ether groups such as oxetanyl groups, and vinyl ether groups.

[0107] Examples of the above component (B1-d) include (3-ethyloxetan-3-yl)methyl (meth)acrylate and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

[0108] As the above component (B1-d), one or a mixture of two or more of these can be used.

[0109] When using the above component (B1-d), its blending amount should be determined appropriately from the viewpoint of ensuring its effectiveness. The blending amount of the above component (B1-d) may be 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more, with the total blending amount of all components of the above component (B1) active energy ray curable resin being 100% by mass, from the viewpoint of ensuring its effectiveness. On the other hand, from the viewpoint of curability of the coating film, it may be 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0110] (B1-e)alkyl (meth)acrylate: The above component (B1) active energy ray curable resin may preferably further contain the above component (B1-e) alkyl (meth)acrylate. The above component (B1-e) is an ester of (meth)acrylic acid between an aliphatic alkyl monoalcohol which may have an alkyl branched, cyclic hydrocarbon group, or ether group. The number of carbon atoms in the above aliphatic alkyl monoalcohol is usually 1 to 20, preferably 2 to 16, and more preferably 3 to 12. The above aliphatic alkyl monoalcohol may preferably be a primary alcohol.

[0111] The above component (B1-e) enhances the mobility of the hard coat layer and, consequently, improves its weather resistance (in particular, it reduces and prevents fine cracks that occur in the low refractive index layer).

[0112] Examples of the above component (B1-e) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and octyl (meth)acrylate.

[0113] As the above component (B1-e), one or a mixture of two or more of these can be used.

[0114] When using the above component (B1-e), its amount should be determined appropriately from the viewpoint of ensuring its effectiveness. The amount of component (B1-e) should be 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, with the total amount of all components of the active energy ray curable resin (B1) being 100% by mass, from the viewpoint of ensuring its effectiveness. On the other hand, from the viewpoint of curability of the coating film, it should be 40% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.

[0115] The above-mentioned active energy ray curable resin component (B1) may contain other active energy ray curable resins other than components (B1-a) to (B1-e) to the extent that it does not contradict the objectives of the present invention. The sum of the amounts of components (B1-a) to (B1-e) in component (B1) may be 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98 to 100% by mass, with the total amount of all components in component (B1) being 100% by mass.

[0116] (B2) High refractive index particles: The above component (B2), high refractive index particles, are particles that increase the refractive index of the coating film formed using the above paint (B).

[0117] Examples of the above component (B2) include metal oxides such as titanium oxide, zinc oxide, indium oxide, tin oxide, zirconium oxide, and aluminum oxide; and composite oxides obtained by doping these metal oxides with other elements such as antimony and tin.

[0118] It is preferable to use a component (B2) in which the surface of high refractive index particles has been treated with a silane coupling agent such as vinylsilane and aminosilane; a titanate coupling agent; an aluminate coupling agent; an organic compound having reactive functional groups such as ethylenically unsaturated bonding groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, or epoxy groups; and a surface treatment agent such as fatty acids and fatty acid metal salts. The interaction between component (B2) and component (B1) is strengthened, and the weather resistance of the coating film can be improved. Among these, as a surface treatment agent, an organic compound having a reactive functional group is preferred, an organic compound having an ethylenically unsaturated bonding group is more preferred, and an organic compound having a (meth)acryloyl group is even more preferred.

[0119] The average particle size of component (B2) is determined appropriately, taking into consideration the viewpoint of maintaining the transparency of the coating film and the productivity when manufacturing high refractive index particles. The average particle size of component (B2) is usually 1 to 300 nm, preferably 5 to 200 nm, more preferably 10 to 150 nm, and even more preferably 15 to 100 nm. The method for measuring the average particle size and its definition are described above in the description of component (A2) low refractive index particles.

[0120] As the above component (B2), one or a mixture of two or more of these can be used.

[0121] When using component (B2) as described above, the amount to be blended is determined appropriately, taking into consideration the type of component (B2) and from the viewpoint of keeping the refractive index (RH) within the range described above. The amount of component (B2) blended is usually 10 to 300 parts by mass, preferably 30 to 200 parts by mass, more preferably 45 to 150 parts by mass, and even more preferably 60 to 120 parts by mass, per 100 parts by mass of the active energy ray curable resin component (B1), from the viewpoint of keeping the refractive index (RH) within the range described above.

[0122] (B3) Compounds having two or more isocyanate groups in one molecule: The above paint (B) may further contain a compound having two or more isocyanate groups (-N=C=O) in one molecule of component (B3). Component (B3) enhances the curability of component (B1). In an embodiment in which component (B1) contains component (B1-c) hydroxyl group-containing (meth)acrylate as an active energy ray curable resin, the hydroxyl groups of component (B1-c) and the isocyanate groups of component (B3) form a urethane structure, thereby improving weather resistance (particularly reducing and preventing fine cracks that occur in the low refractive index layer).

[0123] The above component (B3) includes, for example, compounds having two isocyanate groups in one molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, methylene bis-4-cyclohexyl isocyanate, and diphenylmethane diisocyanate; and trimethylolpropane adducts of compounds having two isocyanate groups in one molecule, such as trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, and trimethylolpropane adduct of isophorone diisocyanate, which have three isocyanate groups in one molecule. Compounds having isocyanate groups; isocyanurates of compounds having two isocyanate groups in one molecule, such as the isocyanurate of tolylene diisocyanate, the isocyanurate of hexamethylene diisocyanate, and the isocyanurate of isophorone diisocyanate, which have three isocyanate groups in one molecule; biuretes of compounds having two isocyanate groups in one molecule, such as the biuret of hexamethylene diisocyanate, which have three isocyanate groups in one molecule; and urethane crosslinking agents such as these blocked isocyanates.

[0124] From the viewpoint of weather resistance, the above component (B) is preferably a trimethylolpropane adduct compound of a compound having two isocyanate groups in one molecule and having three isocyanate groups in one molecule, an isocyanurate compound of a compound having two isocyanate groups in one molecule and having three isocyanate groups in one molecule, and a biuret compound of a compound having two isocyanate groups in one molecule and having three isocyanate groups in one molecule. More preferably, the trimethylolpropane adduct compound of hexamethylene diisocyanate and having three isocyanate groups in one molecule, an isocyanurate compound of hexamethylene diisocyanate and having three isocyanate groups in one molecule, and a biuret compound of hexamethylene diisocyanate and having three isocyanate groups in one molecule.

[0125] While there is no intention to be bound by theory, these structures have the structural characteristic of having isocyanate groups at widely spaced positions at the ends of the hexamethylene chain, which is thought to result in an appropriate crosslinking density and excellent weather resistance. Therefore, it is considered that structures having a similar structural characteristic of having isocyanate groups at widely spaced positions at the ends of the alkyl chain can be used in a similarly favorable manner.

[0126] As the above component (B3), one or a mixture of two or more of these can be used.

[0127] When using the above component (B3), the amount to be blended is determined appropriately from the viewpoint of ensuring that the effects of using component (B3) are obtained and from the viewpoint of preventing the isocyanate groups in component (B3) from remaining unreacted in the coating film. The amount of component (B3) blended is usually 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the active energy ray curable resin of component (B1). On the other hand, from the viewpoint of preventing the isocyanate groups from remaining unreacted in the coating film, it is usually 40 parts by mass or less, preferably 30 parts by mass or less.

[0128] (B4) Photopolymerization initiator: The above paint (B) may preferably further contain (B4) a photopolymerization initiator. The above component (B4) photopolymerization initiator is a compound that generates active species such as radicals when irradiated with active energy rays. By generating active species such as radicals, the above component (B4) polymerizes and cures the above component (B1) active energy ray curable resin.

[0129] Examples of the above component (B4) include benzophenone compounds such as benzophenone, methyl-o-benzoyl benzoate, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, o-methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl} Examples include acetophenone compounds such as -2-methyl-propan-1-one; alkylphenone compounds such as α-hydroxyalkylphenone and acetophenone dimethyl ketal; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; biimidazole compounds; titanocene compounds; oxime ester compounds; oxime phenyl acetate compounds; hydroxyketone compounds; triazine compounds; and aminobenzoate compounds.

[0130] Among the above components (B4), from the viewpoint of reliably curing the coating film, compounds that generate radicals upon irradiation with active energy rays are preferred, and acetophenone compounds, alkylphenone compounds, and acylphosphine oxide compounds are more preferred.

[0131] As the above component (B4), one or a mixture of two or more of these can be used.

[0132] When using the above component (B4), the amount to be blended is determined appropriately from the viewpoint of ensuring the effectiveness of the above component (B4) and from the viewpoint of the color tone of the coating film. From the viewpoint of ensuring the effectiveness of the above component (B4), the amount to be blended of the above component (B4) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the above component (B1) active energy ray curable resin. On the other hand, from the viewpoint of the color tone of the coating film, it is usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less.

[0133] The above-mentioned paint (B) may further contain a silane coupling agent. The silane coupling agent is a silane compound having one or more hydrolyzable groups and one or more organic polymerizable functional groups in one molecule. This can improve the adhesion or interlayer strength between the high refractive index layer and the adjacent layer.

[0134] Examples of the hydrolyzable groups include alkoxy groups such as methoxy and ethoxy groups; acyloxy groups such as acetoxy groups; and halogen groups such as chloro groups. Examples of the organic polymerizable functional groups include vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, amino groups, mercapto groups, isocyanate groups, ureido groups, and isocyanurate groups. The silane coupling agent may contain one or more of these hydrolyzable groups and one or more of these organic polymerizable functional groups in one or more molecules.

[0135] Examples of the silane coupling agents mentioned above include vinyl group-containing silane coupling agents (silane compounds having vinyl group and hydrolyzable group), epoxy group-containing silane coupling agents (silane compounds having epoxy group and hydrolyzable group), (meth)acryloxy group-containing silane coupling agents (silane compounds having (meth)acryloxy group and hydrolyzable group), amino group-containing silane coupling agents (silane compounds having amino group and hydrolyzable group), mercapto group-containing silane coupling agents (silane compounds having mercapto group and hydrolyzable group), isocyanate group-containing silane coupling agents (silane compounds having isocyanate group and hydrolyzable group), ureido group-containing silane coupling agents (silane compounds having ureido group and hydrolyzable group), and isocyanurate group-containing silane coupling agents (silane compounds having isocyanurate group and hydrolyzable group).

[0136] As the silane coupling agent described above, one or a mixture of two or more of these can be used.

[0137] When using the above-mentioned silane coupling agent, the amount to be blended should be determined appropriately from the viewpoint of ensuring the effectiveness of use and the pot life of the paint. From the viewpoint of ensuring the effectiveness of use of component (B4), the amount of the above-mentioned silane coupling agent to be blended should be typically 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of the above-mentioned active energy ray curable resin (B1). On the other hand, from the viewpoint of the pot life of the paint, it should be typically 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less.

[0138] The above-mentioned paint (B) may further contain a solvent from the viewpoint of productivity when forming a wet coating using the above-mentioned paint (B). Examples of the above-mentioned solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellsolve, ethyl cellsolve, diacetone alcohol, and acetone. One or more of these solvents or mixtures thereof can be used.

[0139] The above-mentioned coating (B) may further contain optional components other than the above-mentioned components (B1) to (B4), the above-mentioned solvent, and the above-mentioned silane coupling, to the extent that it does not contradict the purpose of the present invention. Examples of the above-mentioned optional components include defoaming agents, leveling agents, surfactants, thixotropic agents, antistatic agents, printability improvers, antioxidants, weather-resistant stabilizers, light-resistant stabilizers, ultraviolet absorbers, heat stabilizers, and dyes. One or more of these optional components may be used. When using the above-mentioned optional components, the amount used may be typically 10 parts by mass or less, or about 0.01 to 10 parts by mass, per 100 parts by mass of component (B1).

[0140] The above paint (B) can be obtained by mixing and stirring these components.

[0141] The method for forming the hard coat layer on the surface of the film substrate using the above-mentioned paint (B) is not particularly limited, and known web coating methods can be used. Examples of web coating methods include rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, dip coating, spray coating, spin coating, air knife coating, and die coating. Among these methods, rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferred from the viewpoint of applying the paint productively using a roll-to-roll method, rod coating is more preferred from the viewpoint of making the thickness of the coating film uniform, and rod coating using a Meyer bar as the rod (hereinafter sometimes abbreviated as "Meyer bar method") is even more preferred.

[0142] The thickness of the hard coat layer (except in the case of a high refractive index layer in this paragraph) is determined appropriately considering the desired surface hardness and productivity in forming the hard coat layer. From the viewpoint of surface hardness, the thickness of the hard coat layer may be 1 μm or more, preferably 2 μm or more. On the other hand, from the viewpoint of maintaining good flexibility of the anti-reflective film, making it easy to handle as a film roll, and suppressing curling, it may be 60 μm or less, preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less.

[0143] The thickness of the high refractive index layer described above is determined appropriately, taking into consideration the desired reflectivity and the productivity of forming the high refractive index layer. From the viewpoint of anti-reflective function, the thickness of the high refractive index layer may be 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 1.5 μm or more. On the other hand, from the viewpoint of maintaining good flexibility of the anti-reflective film, making it easy to handle as a film roll, and suppressing curling, the thickness may be 60 μm or less, preferably 30 μm or less, more preferably 20 μm or less, even more preferably 10 μm or less, and most preferably 5 μm or less.

[0144] (C) Anchor Coat: In one embodiment, the anti-reflective film of the present invention may have layers of a low refractive index layer, a hard coat layer, an anchor coat, and a film substrate in this order. In this embodiment, the hard coat layer is usually formed directly on the surface of the anchor coat. In another embodiment, the anchor coat is formed directly on the surface of the film substrate.

[0145] In one preferred embodiment, the anti-reflective film of the present invention may have layers of a low refractive index layer, a high refractive index layer, an anchor coat, and a film substrate in this order. In this embodiment, the high refractive index layer is usually formed directly on the surface of the anchor coat. In another embodiment, the anchor coat is formed directly on the surface of the film substrate.

[0146] The anchor coating agent used to form the above-mentioned anchor coat is not particularly limited, and any anchor coating agent can be used. Examples of such anchor coating agents include polyester-based, acrylic-based, polyurethane-based, acrylic urethane-based, and polyester urethane-based anchor coating agents.

[0147] In one preferred embodiment, the above anchor coating agent may include a polymer (resin or oligomer) containing a constituent unit derived from (meth)acrylate having one or more skeletons selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton in one molecule (C1). The amount of constituent units derived from (meth)acrylate having one or more skeletons selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton in one molecule of the polymer is usually 1 mol% or more, preferably 3 mol% or more, more preferably 7 mol or more, and even more preferably 10 mol% or more, with the total amount of constituent units derived from all constituent monomers being 100 mol%. On the other hand, from the viewpoint of improving adhesion as an anchor coating agent and curability, it is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol or less. In one more preferred embodiment, the above-described anchor coating agent may mainly contain the above-described component (C1) (usually 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more in terms of solid content). By using such an anchor coating agent, the weather resistance of the anti-reflective film can be further improved.

[0148] Examples of anchor coating agents containing the above component (C1) include those described in paragraphs 0074 to 0095 of Japanese Patent Application Publication No. 2018-203989 as anchor coating agents containing a polymer (resin or oligomer) derived from a (meth)acrylate having one or more skeletons selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton in one molecule of component (P).

[0149] As the anchor coating agent described above, one or a mixture of two or more of these can be used.

[0150] The above-mentioned anchor coating agent may further contain a solvent, from the viewpoint of productivity when forming a wet coating film using the above-mentioned anchor coating agent. Examples of the solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellosolve, ethyl cellosolve, diacetone alcohol, and acetone. One or more of these solvents or mixtures thereof can be used.

[0151] The above-mentioned anchor coating agent may, to the extent that it does not contradict the objectives of the present invention, optionally contain one or more optional components such as antioxidants, weather-resistant stabilizers, light-resistant stabilizers, ultraviolet absorbers, heat stabilizers, antistatic agents, surfactants, infrared shielding agents, leveling agents, thixotropic agents, anti-fouling agents, printability improvers, colorants, inorganic particles, and organic particles. When using the above optional components, the amount blended may be typically 10 parts by mass or less, or about 0.01 to 10 parts by mass, per 100 parts by mass of the base resin of the anchor coating agent.

[0152] The above-mentioned anchor coating agent can be obtained by mixing and stirring these components.

[0153] The method for forming the anchor coat using the above-mentioned anchor coating agent is not particularly limited, and known web coating methods can be used. From the viewpoint of applying the coating productively using a roll-to-roll method, preferred web coating methods include, for example, rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating.

[0154] The thickness of the anchor coat is determined appropriately from the viewpoint of adhesion to the hard coat layer and the film substrate layer, maintaining good flexibility of the anti-reflective film and making it easy to handle as a film roll, and suppressing curling. From the viewpoint of adhesion to the hard coat layer and the film substrate layer, the thickness of the anchor coat is usually 0.1 μm or more, preferably 0.5 μm or more. If the anchor coating agent contains the above component (C1), from the viewpoint of weather resistance, it is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 2.5 μm or more. On the other hand, from the viewpoint of maintaining good flexibility of the anti-reflective film and making it easy to handle as a film roll, and suppressing curling, it is usually 60 μm or less, preferably 30 μm or less, more preferably 20 μm or less, even more preferably 10 μm or less, and most preferably 5 μm or less.

[0155] (D) Layer of film substrate: The above-mentioned film substrate layer consists of any resin film and is a film substrate layer for forming a low refractive index layer, a hard coat layer, an anchor coat, etc., on its surface.

[0156] Examples of the above-mentioned resin films include polyvinyl chloride resins; polyester resins such as aromatic polyesters and aliphatic polyesters; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; acrylic resins; polycarbonate resins; poly(meth)acrylimide resins; styrene resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene-butadiene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene-ethylene-ethylene-propylene-styrene copolymer; cellulose resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; and other resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulfone. These films include unoriented films, uniaxially oriented films, and biaxially oriented films. These films also include laminated films formed by stacking one or more of these films in two or more layers.

[0157] When the anti-reflective film of the present invention is used in applications where transparency is required, such as a film for external application on glass for the purpose of protecting and preventing shattering of window glass of buildings and automobile windows; or as an anti-reflective film for the purpose of protecting and preventing shattering of the display panel of an image display device used in a place exposed to direct sunlight, such as an image display device, particularly a car navigation system and digital signage, a transparent resin film having high transparency is preferred as the resin film, and a transparent resin film having high transparency and being uncolored is more preferred.

[0158] The total light transmittance of the above transparent resin film (measured in accordance with JIS K7361-1:1997 using the NDH2000 turbidimeter (product name) manufactured by Nippon Denshoku Industries Co., Ltd.) is usually 80% or higher, preferably 85% or higher, more preferably 88% or higher, and even more preferably 90% or higher. A higher total light transmittance is preferable.

[0159] The yellowness index of the above transparent resin film (measured in accordance with JIS K7105:1981 using a colorimeter "SolidSpec-3700 (product name)" manufactured by Shimadzu Corporation) is usually 5 or less, preferably 3 or less, more preferably 2 to -2, and even more preferably 1 to -1.

[0160] Examples of the transparent resin films mentioned above include cellulose ester resins such as triacetylcellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymers; acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane-(meth)methyl acrylate copolymers; aromatic polycarbonate resins; poly(meth)acrylimide resins; polyolefin resins such as polypropylene and 4-methylpentene-1; polyamide resins; polyarylate resins; polymer-type urethane acrylate resins; and polyimide resins. These films include unoriented films, uniaxially oriented films, and biaxially oriented films. These films also include laminated films obtained by laminating one or more of these types in two or more layers.

[0161] When the anti-reflective film of the present invention is used in applications where transparency is not required, such as decorative films for glass, the resin film may be colored, opaque, or transparent.

[0162] The thickness of the resin film described above is determined appropriately, taking into account the application and handling of the anti-reflective film. When the anti-reflective film of the present invention is used in applications that do not require high rigidity, the thickness may be 10 μm or more, preferably 30 μm or more, and more preferably 50 μm or more, from the viewpoint of handling and conforming to the standards for glass shatterproof films. On the other hand, from the viewpoint of economic efficiency, the thickness may be 250 μm or less, preferably 150 μm or less, and more preferably 100 μm or less. When the anti-reflective film of the present invention is used in applications that require high rigidity, the thickness may be 200 μm or more, preferably 300 μm or more, and more preferably 400 μm or more. On the other hand, from the viewpoint of meeting the demand for thinner articles, the thickness may be 1500 μm or less, preferably 1000 μm or less, and more preferably 700 μm or less.

[0163] The anti-reflective film of the present invention may further have any layer other than the low refractive index layer, the hard coat layer (high refractive index layer), the anchor coat, and the film substrate layer. The anti-reflective film of the present invention includes, for example, a low refractive index layer, a hard coat layer, an anchor coat, a film substrate layer, and an adhesive layer, in order from the surface facing the incident sunlight in actual use; a low refractive index layer, a high refractive index layer, an anchor coat, a film substrate layer, and an adhesive layer; a low refractive index layer, a hard coat layer, an anchor coat, a film substrate layer, a functional layer, and an adhesive layer; a low refractive index layer, a high refractive index layer, an anchor coat, a film substrate layer, a functional layer, and an adhesive layer; a low refractive index layer, a hard coat layer, an anchor coat, a functional layer, a film substrate layer, and an adhesive layer; a low refractive index layer, a high refractive index layer, an anchor coat, a functional layer, a film substrate layer, a functional layer, and an adhesive layer; a low refractive index layer, a high refractive index layer, an anchor coat, a functional layer, a film substrate layer, a functional layer, and an adhesive layer; a low refractive index layer, a hard coat layer, an anchor coat, a film substrate layer, Examples include: having an anchor coat and an adhesive layer; having a low refractive index layer, a high refractive index layer, an anchor coat, a film substrate layer, an anchor coat and an adhesive layer; having a low refractive index layer, a hard coat layer, an anchor coat, a film substrate layer, an anchor coat, a functional layer and an adhesive layer; having a low refractive index layer, a high refractive index layer, an anchor coat, a film substrate layer, an anchor coat, a functional layer and an adhesive layer; having a low refractive index layer, a hard coat layer, an anchor coat, a functional layer, an anchor coat, a film substrate layer, an anchor coat and an adhesive layer; having a low refractive index layer, a high refractive index layer, an anchor coat, a functional layer, an anchor coat, a film substrate layer, an anchor coat and an adhesive layer; and having a low refractive index layer, a high refractive index layer, an anchor coat, a functional layer, an anchor coat, a film substrate layer, an anchor coat, a functional layer and an adhesive layer; and so on.

[0164] The adhesive layer described above serves to bond the anti-reflective film of the present invention to the glass. The adhesive used to form the adhesive layer is not limited to any adhesive other than having sufficient adhesive strength to glass, and any adhesive can be used. A transparent adhesive that has sufficient adhesive strength to glass and is transparent is preferred. Examples of such transparent adhesives include acrylic adhesives, urethane adhesives, and silicone adhesives. One or more of these can be used as the transparent adhesive.

[0165] The above adhesive may contain an ultraviolet absorber. This can improve the weather resistance of the adhesive strength. The amount of ultraviolet absorber to be added is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the base resin of the adhesive, since the anti-reflective film of the present invention is usually laminated to the outdoor side of window glass.

[0166] Alternatively, in other embodiments, the amount of the ultraviolet absorber may be preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 10 to 25 parts by mass, per 100 parts by mass of the base resin of the adhesive. This takes into consideration that, for example, in casement windows such as outward-opening windows and double-hinged windows, when the window is open, it may receive sunlight from the side that is normally (when the window is closed) facing indoors.

[0167] The coating for forming the adhesive layer described above may further contain a solvent, from the viewpoint of productivity when forming a wet coating using the coating. Examples of the solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellsolve, ethyl cellsolve, diacetone alcohol, and acetone. One or more of these solvents or mixtures thereof can be used.

[0168] The above adhesive may optionally contain additional components other than the adhesive component, to the extent that it does not contradict the objectives of the present invention. Examples of such optional components include photopolymerization initiators, compounds having two or more isocyanate groups in one molecule, antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weather-resistant stabilizers, light-resistant stabilizers, ultraviolet absorbers, heat stabilizers, pigments, inorganic particles, and organic particles. When using the above optional components, the amount blended may typically be about 0.01 to 50 parts by mass, or about 1 to 30 parts by mass, relative to 100 parts by mass of the base resin of the adhesive.

[0169] The coating for forming the adhesive layer described above can be obtained by mixing and stirring these components.

[0170] As a method for forming the above-mentioned adhesive layer, known web coating methods can be used. As a method for forming the above-mentioned adhesive layer, for example, a known web coating method such as roll coating, gravure coating, reverse coating, die coating, dip coating, spray coating, spin coating, and air knife coating can be used to form the adhesive layer on the adhesive layer forming surface of the anti-reflective film, either directly or via an anchor coating. As a method for forming the above-mentioned adhesive layer, for example, an adhesive layer can be formed on the surface of any film substrate (for example, a biaxially oriented polyethylene terephthalate resin film or a biaxially oriented polypropylene resin film) using a known web coating method such as roll coating, gravure coating, reverse coating, die coating, dip coating, spray coating, spin coating, and air knife coating, and then transferred to the adhesive layer forming surface of the anti-reflective film, either directly or via an anchor coating.

[0171] The thickness of the adhesive layer described above is determined appropriately from the viewpoint of adhesive strength and thinning. From the viewpoint of adhesive strength, the thickness of the adhesive layer may be 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more. On the other hand, from the viewpoint of thinning, it may be 100 μm or less, preferably 60 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

[0172] Examples of the above-mentioned functional layers include those having functions such as infrared shielding, infrared reflection, electromagnetic wave shielding, electromagnetic wave reflection, field of view control (blinding), and field of view angle control.

[0173] The above functional layers are not limited to one layer, but may consist of two or more layers. If there are two or more functional layers, the number of types is not limited to one, but may consist of two or more types.

[0174] The thickness of the above functional layer is selected appropriately, taking into consideration the function to be provided and the method of forming the layer.

[0175] The visible light transmittance of the anti-reflective film of the present invention is preferably 80% or more, more preferably 85% or more, even more preferably 88% or more, and most preferably 90% or more. A higher visible light transmittance is preferable. Such an anti-reflective film can be suitably used as an anti-reflective film for purposes such as protection, shatter prevention, ultraviolet shielding, and infrared shielding of window glass of buildings and automobile windows. Such an anti-reflective film can also be suitably used as an anti-reflective film for purposes such as protection and shatter prevention of the display panel of image display devices used in places exposed to direct sunlight, such as car navigation systems and digital signage.

[0176] The above visible light transmittance is measured in accordance with JIS A5759:2016, 6.4 Visible Light Transmittance Test, with the side of the anti-reflective film opposite to the low refractive index layer side being the bonding surface to the glass plate, and the film surface of the test piece facing the light source.

[0177] The minimum reflectivity of the anti-reflective film of the present invention is preferably 2% or less, more preferably 1.5% or less, and even more preferably 1% or less. A lower minimum reflectivity is preferable. Such an anti-reflective film can be suitably used as an anti-reflective film for purposes such as protecting window glass of buildings and automobile windows, preventing shattering, shielding against ultraviolet rays, and shielding against infrared rays. Such an anti-reflective film can also be suitably used as an anti-reflective film for purposes such as protecting the display panel of an image display device used in a location exposed to direct sunlight, such as car navigation systems and digital signage, and preventing shattering.

[0178] The above minimum reflectance is measured according to the minimum reflectance test (c) of the following example.

[0179] Figure 1 is a conceptual cross-sectional view showing an example of the anti-reflective film of the present invention. In actual use (when the anti-reflective film of the present invention is attached to a car window or the like), the film has, in order from the surface facing the incident sunlight, a low refractive index layer 1, a high refractive index layer 2, an anchor coat 3, a film substrate layer 4, a coating 5 having an infrared shielding function, and an adhesive layer 6.

[0180] 2. Goods: In one embodiment, the article of the present invention includes the anti-reflective film of the present invention. In this embodiment, the article of the present invention typically has the anti-reflective film of the present invention covering at least part or all of the surface on which sunlight enters under actual use conditions. Examples of articles of the present invention in this embodiment include window panes of buildings and windows of automobiles.

[0181] In one of the other embodiments, the article of the present invention may be an article that uses a resin plate (including a laminate; hereinafter the same) as a base material instead of the resin film. Examples of the article of the present invention in this embodiment include an article in which the resin plate is used as a base material and the hard coat layer and the low refractive index layer are formed in this order on at least one side thereof; an article in which the resin plate is used as a base material and the high refractive index layer and the low refractive index layer are formed in this order on at least one side thereof; an article in which the resin plate is used as a base material and the anchor coat, the hard coat layer and the low refractive index layer are formed in this order on at least one side thereof; and an article in which the resin plate is used as a base material and the anchor coat, the high refractive index layer and the low refractive index layer are formed in this order on at least one side thereof. Articles of the present invention in this embodiment, in particular, in which a resin plate having high transparency is used as the resin plate, can be suitably used as a component or article to replace glass, for example, in window glass of buildings and windows of automobiles.

[0182] In articles using a transparent resin plate as a base material instead of the resin film described above, the low refractive index layer can be formed using the same paint as the paint used to form the low refractive index layer in the anti-reflective film of the present invention.

[0183] The hard coat layer in an article using a transparent resin plate as a base material instead of the resin film described above can be formed using the same paint as the paint used to form the hard coat layer in the anti-reflective film of the present invention.

[0184] In the case of an article using a transparent resin plate as a base material instead of the resin film described above, the high refractive index layer can be formed using the same paint as the paint for forming the high refractive index layer that the anti-reflective film of the present invention has in one of its preferred embodiments.

[0185] The anchor coat for an article using a transparent resin plate as a base material instead of the resin film described above can be formed using the same paint as the paint used to form the anchor coat, which is one embodiment of the anti-reflective film of the present invention.

[0186] Examples of the above-mentioned resin plates include resin plates obtained by extruding or injection molding a thermoplastic resin, and resin plates obtained by injecting a curable resin into a mold and then curing it. Examples of the above-mentioned thermoplastic resins include polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymers; acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane-(meth)methyl acrylate copolymers; aromatic polycarbonate resins; poly(meth)acrylimide resins; and polystyrene resins such as polystyrene. Examples of the above-mentioned curable resins include acrylic curable resins and polyester curable resins.

[0187] The shape of the resin plate may be a flat plate (rectangular parallelepiped), a plate with a desired curve, or a plate with irregularities on its surface. When the article of the present invention is used as window glass for a building, the shape of the resin plate may be a flat plate (rectangular parallelepiped). When the article of the present invention is used as a window for an automobile, particularly a front windshield or rear window, the shape of the resin plate may have a desired curve. [Examples]

[0188] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0189] Measurement method (i) Total light transmittance, haze: In accordance with JIS K7136:2000, the total light transmittance and haze were measured using the NDH2000 turbidimeter (product name) manufactured by Nippon Denshoku Industries Ltd., under the condition that light was incident from the low refractive index layer side of the anti-reflective film. At this time, the measurement sample used was the same as that used in the following test (b) visible light transmittance (i.e., laminated with plate glass according to JIS A5759:2016 6.4 visible light transmittance test).

[0190] (b) Visible light transmittance: In accordance with JIS A5759:2016, section 6.4 Visible Light Transmittance Test, a spectrophotometer "Solid Spec-3700 (product name)" from Shimadzu Corporation was used to measure the visible light transmittance (unit: %) under the condition that the side of the anti-reflective film opposite to the low refractive index layer side was the bonding surface with the glass plate, and the film surface of the test piece was facing the light source.

[0191] (h) Minimum reflectance: Using the "SolidSpec-3700" spectrophotometer and the "Absolute Reflectance Measurement Device, Incident Angle 5°" reflection unit from Shimadzu Corporation, and following the instructions for the spectrophotometer, under the condition of 5° specular reflection (the reflection unit was placed in front of the integrating sphere), a black adhesive sheet was attached to the side of the anti-reflective film opposite to the low refractive index layer side. The reflectance spectrum of visible light (wavelength 380-780 nm) was measured, and the lowest reflectance was read from the spectrum obtained by smoothing it using a polynomial approximation method, as the minimum reflectance (unit: %). The above black adhesive sheet was obtained by mixing 20 parts by mass of black acrylic adhesive masterbatch "Black-OT-1338" from Resino Color Industries, Ltd. and 100 parts by mass of adhesive "LKU-01" from Fujikura Chemicals, Ltd. onto one side of a 25 μm thick biaxially oriented polyethylene terephthalate resin film "E5431 (product name)" from Toyobo Co., Ltd., and coating the mixture with an applicator so that the thickness after drying was 35 μm. The L* value of the above black adhesive sheet, determined by color measurement from the surface of the adhesive layer, was 3.13. The L* value was determined in accordance with JIS Z 8722:2009, using a spectrophotometer "CM600d" from Konita Minolta Japan, Inc., measuring the XYZ coordinates under standard light D65 illumination, geometric condition c, and conditions including specular reflection components, and converting these to L*a*b* coordinates.

[0192] (ii) Board layout test: In accordance with JIS K5600-5-6:1999, 100 grid-like cuts (1 grid = 1 mm x 1 mm) were made on the low refractive index layer side of the anti-reflective film. Then, adhesion test tape was applied to the grid, rubbed with a finger, and peeled off. The evaluation criteria followed Table 1 of the above JIS standard. Classification 0: The edges of the cut are perfectly smooth, and there are no peeling marks in any of the grid lines. Classification 1: Small paint peeling at the intersection of cuts. The affected area at the cross-cut does not clearly exceed 5%. Classification 2: The paint film is peeling along the edges of the cuts and / or at the intersections. The affected area in the cross-cut is clearly more than 5%, but never exceeds 15%. Classification 3: The paint film is partially or completely peeling along the edges of the cuts, and / or peeling in various parts of the grain, partially or completely. The affected area in the cross-cut section is clearly more than 15% but not more than 35%. Classification 4: The paint film is partially or completely peeling along the edges of the cuts, and / or several areas are partially or completely peeling. The affected area in the cross-cut is clearly more than 35% but not more than 65%. Classification 5: When the degree of peeling exceeds Classification 4.

[0193] (e) Exterior: A 10cm x 10cm sample was taken from the anti-reflective film, and the side with the low refractive index layer was visually observed by a person with corrected visual acuity of 1.0, either with the naked eye or using a magnifying glass (10x), and evaluated according to the following criteria. A: No cracks were observed even when using a magnifying glass. B: No cracks were visible to the naked eye. However, when a magnifying glass was used, the areas where cracks had occurred were discovered. C: No cracks were visible to the naked eye. However, cracks were observed when using a magnifying glass. D: Cracks were visible to the naked eye.

[0194] (h) Accelerated weathering test: In accordance with JIS A5759:2016, Section 6.10, Weather Resistance, and using the Sunshine Carbon Arc Lamp Weathering Tester (SWOM) "Sunshine Weather Meter S300 (product name)" manufactured by Suga Test Instruments Co., Ltd. as specified in JIS B7753:2007, the test specimen was set so that the low refractive index layer of the anti-reflective film was the irradiated surface, and the conditions shown in Table 11 of JIS A5759:2016, Section 6.10, Weather Resistance, namely, an irradiance of 255 ± 25.5 W / m², were used. 2(The specifications for the glass filter were a spectral transmittance of 2% or less at 275nm and 90% or more at 400nm), and the film was treated for 1000 hours under the conditions of 18 minutes of water spraying every 120 minutes, a black panel temperature of 63±3℃, and a relative humidity of 50±5%. Using the treated anti-reflective film, the following evaluations were performed: (b) Visible light transmittance after the accelerated weathering test (f-1) according to the above test (b) Visible light transmittance; (c) Minimum reflectance after the accelerated weathering test (f-2) according to the above test (c) Minimum reflectance; (d) Cross-pattern test after the accelerated weathering test (f-3) according to the above test (d) Cross-pattern test; and (e) Appearance after the accelerated weathering test (f-4) according to the above test (e) Appearance.

[0195] Raw materials used (A1) Silane compounds having hydrolyzable groups: (A1-1) "X-12-2510A (trade name)," an organosilane compound from Shin-Etsu Chemical Co., Ltd., having a hydrolyzable group in which one or more hydrogen atoms are substituted with fluorine atoms. Solid content: 3% by mass.

[0196] (A2) Low refractive index particles: (A2-1) Hollow silica dispersion "THRULYA4320 (product name)" from JGC Catalysts & Chemicals Co., Ltd. The amount of hollow silica in the dispersion is 20% by mass. The average particle size of the hollow silica is 60 nm.

[0197] (A3) Optional ingredients: (A3-1) Toagosei Co., Ltd.'s acrylic-silicone copolymer-based anti-fouling agent "Cymac US270 (product name)". Solids content 100% by mass. (A3-2) Microparticles of inorganic compounds that function as antibacterial or antiviral agents: Commercially available cuprous iodide (CuI) powder (manufactured by Wako Pure Chemical Industries, Ltd.) was pre-dispersed in ethanol, then crushed and dispersed using a bead mill to obtain a cuprous iodide slurry with an average particle size of 120 nm. This slurry was then adjusted to a solid content (cuprous iodide content in the slurry) of 11% by mass. (A3-3) 3-aminopropyltriethoxysilane "KBE903 (product name)" from Shin-Etsu Chemical Co., Ltd.

[0198] (A) Paint for forming a low refractive index layer (indicated as Paint (A) in the table): (A-1) 3333 parts by mass of component (A1-1) (100 parts by mass in terms of solid content), 200 parts by mass of component (A2-1) (40 parts by mass in terms of solid content), and 4.2 parts by mass of component (A3-1) were mixed and stirred, and diluted to a solid content concentration of 4% by mass using a mixed solvent of 2-methoxyethanol, 1-methoxy-2-propanol, and methyl isobutyl ketone in a volume ratio of 2:1:1 to obtain coating (A-1) for forming a low refractive index layer. (A-2) 3333 parts by mass of component (A1-1) (100 parts by mass in terms of solids), 200 parts by mass of component (A2-1) (40 parts by mass in terms of solids), 4.2 parts by mass of component (A3-1), 100 parts by mass of component (A3-2) (11 parts by mass of solids), and 6 parts by mass of component (A3-3) were mixed and stirred, and diluted to a solids concentration of 4% by mass using a mixed solvent of 2-methoxyethanol, 1-methoxy-2-propanol, and methyl isobutyl ketone in a volume ratio of 2:1:1 to obtain coating for forming a low refractive index layer (A-2).

[0199] (B1-a) Silsesquioxane Polymerizable compounds with a skeleton: (B1-a1) Toagosei Co., Ltd. Silsesquioxane A compound "MAC-SQ HDM (trade name)" having a skeleton and a methacryloyl group, with a solid content of 50% by mass.

[0200] (B1-b) Urethane (meth)acrylate: (B1-b1) Daicel Ornex Corporation's polyfunctional urethane (meth)acrylate "EBECRYL284 (product name)". Solid content 100% by mass, number of functional groups 2, number average molecular weight 1000, mass average molecular weight 2900, Z average molecular weight 4700, number of (meth)acryloyl groups per 1000 number average molecular weight 2. (B1-b2) Daicel Ornex Corporation's polyfunctional urethane (meth)acrylate "EBECRYL4101 (product name)". Solids content 100% by mass, number of functional groups 3, number average molecular weight 1100, mass average molecular weight 2800, Z average molecular weight 4900, number of (meth)acryloyl groups per 1000 number average molecular weight 2.7. (B1-b3) Daicel Ornex Corporation's polyfunctional urethane (meth)acrylate "KRM8200 (product name)". Solid content 100% by mass, number of functional groups 6, number average molecular weight 470, mass average molecular weight 810, Z average molecular weight 1300, number of (meth)acryloyl groups per 1000 number average molecular weight 13. (B1-b4) Shin Nakamura Chemical Industry Co., Ltd.'s polyfunctional urethane (meth)acrylate "UA-1100H (product name)". Solids content 100% by mass, number of functional groups 6, number average molecular weight 440, mass average molecular weight 880, Z average molecular weight 1600, number of (meth)acryloyl groups per 1000 number average molecular weight 14. (B1-b5) Art Resin UN-952 (product name), a polyfunctional urethane (meth)acrylate from Negami Kogyo Co., Ltd., has a solid content of 60% by mass, 10 functional groups, a number average molecular weight of 2500, a mass average molecular weight of 9100, a Z average molecular weight of 23000, and 4 (meth)acryloyl groups per 1000 number average molecular weight. (B1-b6) Art Resin UN-954 (product name), a polyfunctional urethane (meth)acrylate from Negami Kogyo Co., Ltd., has a solid content of 60% by mass, 6 functional groups, a number average molecular weight of 2000, a mass average molecular weight of 4800, a Z average molecular weight of 9600, and 3 (meth)acryloyl groups per 1000 number average molecular weight.

[0201] (B1-c) Hydroxyl group-containing (meth)acrylate: (B1-c1)4-Hydoxybutylacrylate.

[0202] (B1-d) Compounds having one or more cationic polymerizable groups and one or more radical polymerizable groups in one molecule: (B1-d1) (3-ethyloxetan-3-yl)methyl acrylate "OXE-10 (trade name)" from Osaka Organic Chemical Industry Co., Ltd.

[0203] (B1-e)alkyl (meth)acrylate: (B1-e1)n-butyl acrylate.

[0204] (B2) High refractive index particles: (B2-1) Zirconium oxide methyl isobutyl ketone dispersion "ZRMIBK15WT%-P01 (product name)" from CIK Nanotech Co., Ltd. The amount of zirconium oxide in the dispersion is 15% by mass. The average particle size of zirconium oxide is 30 nm.

[0205] (B3) Compounds having two or more isocyanate groups in one molecule: (B3-1) Natco Corporation's hexamethylene diisocyanate biuret compound "No. 21 curing agent (product name)".

[0206] (B4) Photopolymerization initiator: (B4-1) IGM Resins' acylphosphine oxide-based photopolymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) "Omnirad 819 (trade name)". (B4-2) IGM Resins' α-hydroxyalkylphenone-based photopolymerization initiator (1-hydroxycyclohexyl-phenyl ketone) "Omnirad 184 (trade name)".

[0207] (B5) Other ingredients: (B5-1) BASF Japan Ltd.'s benzotriazole-based UV absorber, 2-(2H-benzotriazole-2-yl)-4-methylphenol "TINUVIN P (trade name)". (B5-2) Shin-Etsu Chemical Co., Ltd.'s amine-based silane coupling agent, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane "KBM-6803 (trade name)". (B5-3) 1-Methoxy-2-propanol (labeled "PGM" in the table). (B5-4) Nissan Chemical Corporation's silica nanoparticle propylene glycol monomethyl ether dispersion "PGM-AC-2140Y (product name)". Solid content 42% by mass, average particle size 15 nm.

[0208] (B) Paint for forming a high refractive index layer (indicated as Paint (B) in the table): (B-1) 36 parts by mass of component (B1-a1) (18 parts by mass in terms of solid content), 73 parts by mass of component (B1-b1), 9 parts by mass of component (B1-d1), 747 parts by mass of component (B2-1) (112 parts by mass in terms of zirconium oxide), 6 parts by mass of component (B4-1), 2 parts by mass of component (B4-2), 4 parts by mass of component (B5-1), and 100 parts by mass of component (B5-3) were mixed and stirred to obtain coating (B-1) for forming a high refractive index layer. In the table, values ​​are shown in terms of solid content, except for the solvent and component (B2-1). The value for component (B2-1) is shown in terms of zirconium oxide.

[0209] (B-2)~(B-22): High refractive index layer-forming coatings (B-2) to (B-22) were obtained in the same manner as the high refractive index layer-forming coating (B-1) described above, except that the formulation was changed as shown in Table 1. In the table, values ​​are listed on a solid content basis for all components except the solvent and the above component (B2-1). The value for the above component (B2-1) is listed on a zirconium oxide basis.

[0210] (C1) Polymer for anchor coat formation: 32 parts by mass (14 mol%) of (C1-1)2-(2-hydroxy-5-(2-(methacryloyloxy)-ethyl)phenyl)-2H-benzotriazole, 54 parts by mass (76 mol%) of methyl methacrylate, 5 parts by mass (5 mol%) of 2-hydroxyethyl methacrylate, and 9 parts by mass (5 mol%) of caprolactone methacrylate were placed in a reactor equipped with a reflux condenser and a stirrer, and reacted with a mixed solvent of methyl ethyl ketone, n-butyl acetate, and toluene (volume ratio 1:1:2) as a diluent, and 2,2'-azobisisobutyronitrile as a catalyst under a nitrogen atmosphere at a temperature of 70-80°C for 10 hours to obtain polymer (C1-1) for anchor coating.

[0211] (C2) Compounds having two or more isocyanate groups in one molecule: (C2-1) "Coronate HX (product name)" from Tosoh Corporation.

[0212] (C) Anchor coating agent (paint for forming anchor coat. Indicated as AC agent in the table): (C-1) 100 parts by mass of the above component (C1-1) and 20 parts by mass of the above component (C2-1) were mixed and stirred, and diluted to a solid content concentration of 50% by mass using a mixed solvent of methyl ethyl ketone, n-butyl acetate, and toluene (volume ratio 1:1:2) to obtain an anchor coating agent.

[0213] (D) Film substrate: (D-1) Lumirror (product name), a 50 μm thick, double-sided, easily bondable, biaxially oriented polyethylene terephthalate resin film from Toray Industries, Inc.

[0214] (E) Paint for forming adhesive layer: (E-1) 100 parts by mass of Toyo Chem Co., Ltd.'s acrylic adhesive "Olivine BPS5296 (product name)", 0.5 parts by mass (0.2 parts by mass in terms of solid content) of Toyo Chem Co., Ltd.'s isocyanate curing agent "Olivine BXX4773 (product name)", 20 parts by mass of Cipro Chemical Co., Ltd.'s benzophenone-based ultraviolet absorber (2,2',4,4'-tetrahydroxybenzophenone) "SEESORB106 (product name)", and 70 parts by mass of ethyl acetate were mixed and stirred to obtain adhesive layer forming coating (E-1).

[0215] Example 1 (1) On one side of the film substrate (D-1), the anchor coat forming paint (C-1) was applied using a film Mayer bar coating apparatus so that the thickness after curing was 3 μm, and the anchor coat was formed by drying and curing in a drying oven. (2) On the surface of the anchor coat formed in step (1) above, the high refractive index layer forming paint (B-1) was applied using a film Mayer bar coating apparatus to a thickness of 2 μm after curing, dried in a drying oven, and then cured by irradiation with ultraviolet light to form a high refractive index layer. (3) On the surface of the high refractive index layer formed in step (2) above, the low refractive index layer forming paint (A-1) was applied using a film Mayer bar coating apparatus so that the thickness after curing was 0.1 μm, and the low refractive index layer was formed by drying and curing in a drying oven. (4) Next, the adhesive layer forming paint (E-1) is applied to the surface of the film substrate (D-1) opposite to the anchor coat forming surface to a dry thickness of 25 μm, and dried in a drying oven to form an adhesive layer, thereby obtaining an anti-reflective film having, in order from the surface facing the incident sunlight in actual use, a low refractive index layer, a high refractive index layer, an anchor coat, a film substrate layer, and an adhesive layer. (5) The above tests (a) to (f) were carried out. The results are shown in Table 1.

[0216] Examples 2-22 An anti-reflective film was obtained in the same manner as in Example 1, except that one of the materials shown in Tables 1 to 4 was used instead of (B-1) above as the coating for forming the high refractive index layer. Tests (a) to (f) above were performed. The results are shown in one of Tables 1 to 4.

[0217] [Table 1]

[0218] [Table 2]

[0219] [Table 3]

[0220] [Table 4]

[0221] The anti-reflective film of the present invention exhibited excellent weather resistance. Furthermore, the transparency and anti-reflective properties of the anti-reflective film of the present invention were also good. Therefore, it was concluded that the anti-reflective film of the present invention can be suitably used as an anti-reflective film for exterior application to glass.

[0222] Example 23 An anti-reflective film was obtained in the same manner as in Example 1, except that (A-2) was used instead of (A-1) as the coating for forming the low refractive index layer. Tests (a) to (f) above were performed. The results were as follows: Test (a) Total light transmittance 90%, haze 1.5%; Test (b) Visible light transmittance 90%; Test (c) Minimum reflectance 0.6%; Test (d) Checkerboard test classification 0; Test (e) Appearance rank A; Test (f) Visible light transmittance after accelerated weathering test 90%, minimum reflectance 0.6%, checkerboard test classification 1, appearance rank B.

[0223] Regarding the anti-reflective film of Example 23, the Japan Textile Products Quality Technology Center, in accordance with ISO 210702, tested its antiviral activity against influenza A / Hong Kong / 8 / 68(H3N2) virus, using the anti-reflective film of Example 1 as a control. The test conditions were as follows: host cells were MDCK cells (canine kidney-derived cells), washout solution was SCDLP medium, standing temperature was 25°C, standing time was 24 hours, sample size was 5cm x 5cm, adhesive film was polyethylene film, and the inoculation amount of the test virus suspension was 0.4 ml. The samples were also pre-treated according to the Sustainability Standards of the Japan Society of International Antimicrobial Agents before being subjected to the test. When pre-treated according to water resistance treatment category 0 of the standards, the antiviral activity value was 4.4 or higher. When pre-treated according to light resistance treatment category 2 of the above standards, the antiviral activity value was 3.7 or higher.

[0224] Here, the antiviral activity value (R) is the viral infectivity titer (PFU (Plaque-forming unit) / cm³) of the control after standing. 2 Ut is the common logarithm of ) and the viral infectivity titer (PFU / cm²) after the sample has been left standing. 2When At is the common logarithm of ), it is defined by the following equation. R = Ut - At

[0225] Furthermore, the antiviral activity of the anti-reflective film of Example 23 against feline calicivirus (Strain(F-9)) was tested. The test conditions were the same as those for the antiviral activity test against influenza A / Hong Kong virus described above, except that the host cell was changed to CRFK cells (cat kidney-derived cells) and the washout was changed to SCDLP medium supplemented with Fetal Bovine Serum to a final concentration of 10%. When pre-treated with the above water-resistant treatment category 0, the antiviral activity value was 2.2. When pre-treated with the above light-resistant treatment category 2, the antiviral activity value was 3.6.

[0226] It has been found that by including fine particles of an inorganic compound that functions as an antibacterial or antiviral agent in a coating for forming a low refractive index layer, the anti-reflective film of the present invention can be further imparted with antibacterial or antiviral properties.

[0227] Preparation of coating (1) for forming a hard coat layer 36 parts by mass of component (B1-a1) (18 parts by mass in terms of solid content), 73 parts by mass of component (B1-b1), 9 parts by mass of component (B1-d1), 119 parts by mass of component (B5-4) (50 parts by mass in terms of solid content), 6 parts by mass of component (B4-1), 2 parts by mass of component (B4-2), 4 parts by mass of component (B5-1), and 160 parts by mass of component (B5-3) were mixed and stirred to obtain a coating (1) for forming a hard coat layer.

[0228] Preparation of coating (2) for forming a hard coat layer 36 parts by mass of component (B1-a1) (18 parts by mass in terms of solid content), 73 parts by mass of component (B1-b1), 9 parts by mass of component (B1-d1), 6 parts by mass of component (B4-1), 2 parts by mass of component (B4-2), 4 parts by mass of component (B5-1), and 150 parts by mass of component (B5-3) were mixed and stirred to obtain a coating (2) for forming a hard coat layer.

[0229] Example 24 An anti-reflective film was obtained in the same manner as in Example 1, except that the hard coat layer forming paint (1) was used instead of the high refractive index layer forming paint (B-1) and (A-2) was used instead of (A-1) as the low refractive index layer forming paint. Tests (a) to (f) were performed. The results were as follows: Test (a) Total light transmittance 90%, haze 1.5%; Test (b) Visible light transmittance 90%; Test (c) Minimum reflectance 2.0%; Test (d) Check pattern test classification 0; Test (e) Appearance rank A; Test (f) Visible light transmittance after accelerated weathering test 90%, minimum reflectance 2.0%, check pattern test classification 1, appearance rank B.

[0230] Example 25 An anti-reflective film was obtained in the same manner as in Example 1, except that the hard coat layer forming paint (2) was used instead of the high refractive index layer forming paint (B-1), and (A-2) was used instead of (A-1) as the low refractive index layer forming paint. Tests (a) to (f) above were performed. The results were as follows: Test (a) Total light transmittance 90%, haze 1.5%; Test (b) Visible light transmittance 90%; Test (c) Minimum reflectance 2.0%; Test (d) Check pattern test classification 0; Test (e) Appearance rank A; Test (f) Visible light transmittance after accelerated weathering test 90%, minimum reflectance 2.0%, check pattern test classification 1, appearance rank A.

[0231] Example 26 (1) On one side of the film substrate (D-1), the anchor coat forming paint (C-1) was applied using a film Mayer bar coating apparatus so that the thickness after curing was 3 μm, and the anchor coat was formed by drying and curing in a drying oven. (2) On the surface of the anchor coat formed in step (1) above, the low refractive index layer forming paint (A-2) was applied using a film Mayer bar coating apparatus so that the thickness after curing was 0.1 μm, and the low refractive index layer was formed by drying and curing in a drying oven. (3) Next, the coating material (E-1) for forming the adhesive layer was applied onto the surface of the film substrate (D-1) opposite to the surface where the anchor coat is formed, so that the dry thickness became 25 μm, and dried in a drying oven to form an adhesive layer. Thus, an antireflection film having, in the order from the surface on the side where sunlight is incident in the actual use state, a low refractive index layer, an anchor coat, a layer of the film substrate, and an adhesive layer was obtained.

[0232] Regarding the antireflection films of Examples 24 to 26, the pencil hardness of the surface of the low refractive index layer was measured in accordance with JIS K 5600-5-4:1999 under the conditions of a test length of 25 mm and a load of 750 g using a pencil "Uni (trade name)" of Mitsubishi Pencil Co., Ltd. At this time, the determination of whether or not scratches occurred was made by visually observing the surface of the low refractive index layer at a position 50 cm away from the fluorescent lamp under the fluorescent lamp. The results were 2H for Example 24, H for Example 25, and F for Example 26.

[0233] It was confirmed that by providing a hard coat layer, the surface hardness of the antireflection film can be increased.

[0234] As described above, since the antireflection film of the present invention has good characteristics, it can be similarly suitably used for a transparent resin plate (including a laminate) that substitutes for glass such as window glass of a building and a window of an automobile. Those skilled in the art will immediately understand this.

[0235] In addition, examples of embodiments of articles using a resin plate (including a laminate; hereinafter the same) as a substrate instead of the resin film, for example, a transparent resin plate (including a laminate) that substitutes for glass such as window glass of a building and a window of an automobile, are summarized as follows. [1]. A transparent resin plate having a low refractive index layer, a hard coat layer, and a substrate layer in this order; the low refractive index layer is formed using a paint containing (A1) a silane compound having a hydrolyzable group and (A2) low refractive index particles; the hard coat layer is formed using a paint containing (B1) an active energy ray curable resin; where the above component (B1) the active energy ray curable resin is (B1-a) Silsesquioxane bone A transparent resin plate comprising a polymerizable compound having a specific grade, and (B1-b) urethane (meth)acrylate. [2]. The amount of component (B1-b) urethane (meth)acrylate is 30 to 99% by mass, where the total amount of all components of component (B1) active energy ray curable resin is 100% by mass; [1] The transparent resin sheet as described in item [1]. [3]. The number of (meth)acryloyl groups in the above component (B1-b) urethane (meth)acrylate is 1 to 10 per 1000 units of polystyrene-based number-average molecular weight, determined from the differential molecular weight distribution curve measured by gel permeation chromatography; the transparent resin plate as described in item [1] or [2]. [4]. The above component (B1) active energy ray curable resin further comprises (B1-c) hydroxyl group-containing (meth)acrylate; a transparent resin sheet according to any one of items [1] to [3]. [5]. The material has layers of a low refractive index layer, a hard coat layer, and a film substrate in this order; the low refractive index layer is formed using a paint containing (A1) a silane compound having a hydrolyzable group and (A2) low refractive index particles; the hard coat layer is formed using a paint containing (B1) an active energy ray curable resin and (B3) a compound having two or more isocyanate groups in one molecule; where the above component (B1) active energy ray curable resin is (B1-a) Silsesquioxane A transparent resin sheet containing a polymerizable compound having a skeleton and (B1-c)hydroxyl group-containing (meth)acrylate. [6]. The amount of the above component (B3) compound having two or more isocyanate groups in one molecule is 1 to 40 parts by mass per 100 parts by mass of the above component (B1) active energy ray curable resin; the amount of the above component (B1-c) hydroxyl group-containing (meth)acrylate is 1 to 40% by mass, with the total amount of all components of the above component (B1) active energy ray curable resin being 100% by mass; the transparent resin plate as described in item [5]. [7]. The above component (B1-a) Silsesquioxane The amount of polymerizable compound having a skeleton is 1 to 70% by mass, where the total amount of all components of the active energy ray curable resin (B1) is 100% by mass; a transparent resin plate as described in any one of items [1] to [6]. [8]. The above component (B1) active energy ray curable resin further comprises (B1-d) a compound having one or more cationic polymerizable groups and one or more radical polymerizable groups in one molecule; a transparent resin plate according to any one of items [1] to [7]. [9]. The above component (B1) active energy ray curable resin further comprises (B1-e) alkyl (meth)acrylate; a transparent resin plate according to any one of items [1] to [8].

[10] . A transparent resin plate having layers of a low refractive index layer, a hard coat layer, an anchor coat, and a film substrate in this order; the anchor coat is formed using a paint containing a polymer comprising a polymer containing a (meth)acrylate-derived structural unit having one or more skeletons selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton in one molecule; the transparent resin plate according to any one of items [1] to [9].

[11] . A transparent resin plate according to any one of items [1] to

[10] , wherein the hard coat layer further contains (B2) high refractive index particles.

[12] . A transparent resin plate according to any one of items [1] to

[11] , wherein the low refractive index layer further contains fine particles of an inorganic compound that functions as an antibacterial or antiviral agent.

[13] . Window glass for buildings or windows for automobiles containing a transparent resin sheet as described in any one of items [1] to

[12] . [Brief explanation of the drawing]

[0236] [Figure 1] This is a conceptual cross-sectional view showing an example of the anti-reflective film of the present invention. [Figure 2] This is the GPC curve for the above component (B1-b1) used in the example. [Explanation of Symbols]

[0237] 1: Low refractive index layer 2: High refractive index layer 3: Anchor Coat 4: Layer of film substrate 5: Coating film with infrared shielding function 6: Adhesive layer

Claims

1. It has a low refractive index layer, a hard coat layer, and a film substrate layer in this order; Here, the low refractive index layer and the hard coat layer are directly laminated. The low refractive index layer is formed using a paint containing (A1) a silane compound having a hydrolyzable group and (A2) low refractive index particles; The above hard coat layer is formed using a paint containing (B1) an active energy ray curable resin; Here, the above component (B1), an active energy ray curable resin, Assuming the total amount of all components of the above component (B1), the active energy ray curable resin, is 100% by mass, (B1-a) Polymerizable compound having a silsesquioxane skeleton, 5% by mass or more, and (B1-b) Contains 30% by mass or more of urethane (meth)acrylate; anti-reflective film.

2. The amount of the polymerizable compound having a silsesquioxane skeleton (component (B1-a)) is 10% by mass or more, with the total amount of all components of the active energy ray curable resin being 100% by mass; the anti-reflective film according to claim 1.

3. The number of (meth)acryloyl groups in the above component (B1-b) urethane (meth)acrylate is 1 to 10 per 1000 units of polystyrene-based number-average molecular weight, determined from the differential molecular weight distribution curve measured by gel permeation chromatography; the anti-reflective film according to claim 1 or 2.

4. The above component (B1) active energy ray curable resin further comprises (B1-c) hydroxyl group-containing (meth)acrylate; the anti-reflective film according to any one of claims 1 to 3.

5. The anti-reflective film according to any one of claims 1 to 4, wherein the hard coat layer is formed using a paint containing the above components (B1) an active energy ray curable resin and (B3) a compound having two or more isocyanate groups in one molecule.

6. The above component (B1) active energy ray curable resin further comprises (B1-d) a compound having one or more cationic polymerizable groups and one or more radical polymerizable groups in one molecule; the anti-reflective film according to any one of claims 1 to 5.

7. The above component (B1) active energy ray curable resin further comprises (B1-e) alkyl (meth)acrylate; the anti-reflective film according to any one of claims 1 to 6.

8. It has layers of a low refractive index layer, a hard coat layer, an anchor coat, and a film substrate in this order; The above anchor coat is formed using a paint containing a polymer comprising a polymer having (C1) one or more structural units derived from a (meth)acrylate, each molecule having one or more skeletons selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton; the anti-reflective film according to any one of claims 1 to 7.

9. The anti-reflective film according to any one of claims 1 to 8, wherein the hard coat layer further comprises (B2) high refractive index particles.

10. The anti-reflective film according to any one of claims 1 to 9, wherein the low refractive index layer further comprises fine particles of an inorganic compound that functions as an antibacterial or antiviral agent.

11. An article comprising the anti-reflective film according to any one of claims 1 to 10.

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