Anti-reflective film and low refractive index resin composition

Abstract

This invention provides an anti-reflective film that exhibits low reflection from external light sources, resulting in excellent visibility, while also possessing equivalent levels of scratch resistance and water repellency without the use of PFAS. [Solution] An anti-reflective hard coat film is provided, in which a hard coat layer and a low refractive index layer are laminated in that order on a light-transmitting base film, the low refractive index layer contains amine-modified (meth)acrylate, hollow silica fine particles, alumina fine particles, and a silicone-based leveling agent as essential components, and the silicone-based leveling agent contains polyether-modified polydimethylsiloxane and polyester-modified polydimethylsiloxane.

Description

Technical Field

[0001] The present invention relates to an antireflection film and a low refractive index resin composition used therefor.

Background Art

[0002] Antireflection films are widely used in image display devices such as liquid crystal displays and organic EL displays because they have the characteristics of less reflection of external light sources such as fluorescent lamps and good visibility. In particular, in the case of devices that input to an image display surface such as a touch panel with a touch pen, higher abrasion resistance and scratch resistance have come to be required.

[0003] As an antireflection film, a laminated structure that reduces the reflected light itself by canceling out the light reflected on the surface of the antireflection layer (low refractive index layer) and the light reflected at the interface between the antireflection layer and the layer adjacent to the antireflection layer (for example, a hard coat layer) is well known. For example, in the past, the applicant has invented an antireflection film having a low refractive index layer composed of a binder resin, hollow silica, alumina fine particles, and a fluorine-based silicone compound having a reactive functional group (Patent Document 1). This antireflection film had excellent characteristics of less reflection of external light sources and good antifouling properties and abrasion resistance.

[0004] Organic fluorine compounds such as the "fluorine-based silicone compound having a reactive functional group" used here (hereinafter referred to as PFAS) have high water repellency and improve scratch resistance, and also have the effect of reducing the reflectance because of their low refractive index, and are widely adopted in the low refractive index layer of antireflection films. However, this PFAS is regarded as having problems of being hardly decomposable and bioaccumulative, and there is a movement to regulate its use mainly in Europe. Therefore, there has been a demand for an antireflection film that has a low reflectance without using PFAS and can obtain the same level of water repellency and scratch resistance.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] Patent No. 7354087 [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide an anti-reflective film that has low reflection from external light sources and excellent visibility, as well as equivalent levels of scratch resistance and water repellency without the use of PFAS. [Means for solving the problem]

[0007] To solve the above problems, the invention of claim 1 provides an anti-reflective hard coat film in which a hard coat layer and a low refractive index layer are laminated in this order on a light-transmitting substrate film, the low refractive index layer contains amine-modified (meth)acrylate (A), hollow silica fine particles (B), alumina fine particles (C), and a silicone-based leveling agent (D) as essential components, and (D) contains polyether-modified polydimethylsiloxane (d1) and polyester-modified polydimethylsiloxane (d2).

[0008] The invention of claim 2 provides an anti-reflective hard coat film according to claim 1, characterized in that the amount of polyether-modified polydimethylsiloxane (d1) blended is 15 to 45% by weight relative to the total amount of solids of the silicone-based leveling agent (D).

[0009] The invention of claim 3 provides an anti-reflective film according to claim 1 or 2, characterized in that the amount of the silicone-based leveling agent (D) is 13 to 23% by weight relative to the total amount of the low refractive index layer.

[0010] The invention of claim 4 provides a low refractive index resin composition for anti-reflective films, comprising an amine-modified (meth)acrylate (A), hollow silica fine particles (B), alumina fine particles (C), and a silicone-based leveling agent (D) as essential components, wherein (D) comprises a polyether-modified polydimethylsiloxane (d1) and a polyester-modified polydimethylsiloxane (d2). [Effects of the Invention]

[0011] The film of the present invention exhibits good visibility due to minimal reflection from external light sources, and also possesses equivalent water repellency and scratch resistance without the use of PFAS. Therefore, it is useful as an environmentally friendly anti-reflective film for use in image display devices such as touch panels. [Best Mode for Carrying Out the Invention]

[0012] The anti-reflective film of the present invention has a structure in which a low refractive index layer (hereinafter referred to as the low refractive index layer), which is a cured product of a low refractive index resin composition (hereinafter referred to as the low refractive index resin composition), is laminated on a hard coat layer (hereinafter referred to as the HC layer) laminated on a light-transmitting substrate film. In this specification, (meth)acrylate includes both acrylate and methacrylate.

[0013] The low-refractory resin composition used in the present invention contains, in addition to a binder resin that disperses each component, an amine-modified (meth)acrylate (A), hollow silica fine particles (B), nanoalumina particles (C), and a silicone-based leveling agent (D) containing polyether-modified polydimethylsiloxane (d1) and polyester-modified polydimethylsiloxane (d2) as essential components.

[0014] The amine-modified (meth)acrylate (A) used in this invention is added to mitigate polymerization inhibition by oxygen during UV curing and to improve the degree of curing. (A) is a compound having at least one amino group and at least one acryloyl group or methacryloyl group. To avoid curing inhibition by oxygen, exposure in an environment with an inert gas such as nitrogen is a well known method. However, in production processes involving high-speed transport, it is difficult to completely eliminate the effect of oxygen adhering to the exposed material, and the addition of (A) significantly improves curability. The amino group may be a primary, secondary, or tertiary amino group, but a tertiary amino group is preferred in terms of curing acceleration properties.

[0015] Examples of (A) include amino(meth)acrylate, amine-modified aliphatic(meth)acrylate, amine-modified polyether(meth)acrylate, amine-modified polyester(meth)acrylate, amine-modified epoxy(meth)acrylate, and amine-modified urethane(meth)acrylate, which can be used individually or in combination of two or more. Among these, amine-modified polyetheracrylate is preferred due to its high reactivity.

[0016] The number of functional groups in (A) above is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 4. By keeping it within this range, surface hardness and scratch resistance can be improved without increasing curing shrinkage. A commercially available product is EBECRYL80 (product name: manufactured by Daicel Ornex, a tertiary amine with tetrafunctional properties).

[0017] The amount of (A) is preferably 0.8 to 9% by weight, more preferably 1.0 to 8% by weight, and particularly preferably 1.2 to 6% by weight, relative to the total solid content of the low-refractory resin composition. A concentration of 0.8% by weight or more ensures sufficient scratch resistance, while a concentration of 9% by weight or less ensures good optical properties with low haze. Furthermore, the amount of (A) added relative to 100 parts by weight of the binder resin is preferably 5 to 70 parts by weight, more preferably 8 to 50 parts by weight, and particularly preferably 10 to 40 parts by weight.

[0018] The hollow silica fine particles (B) used in the present invention are blended for the purpose of reducing the refractive index of the low refractive layer. (B) has a function of reducing its refractive index while maintaining the coating strength of the low refractive layer, and is silica particles having cavities containing air with a refractive index of 1 inside. While the refractive index of solid silica particles is about 1.45, the refractive index of (B) decreases as the occupancy rate of the internal cavities increases, and is about 1.15 to 1.40.

[0019] The primary average particle diameter of the above (B) is preferably 5 to 100 nm, more preferably 20 to 80 nm, and particularly preferably 40 to 70 nm. By setting it within this range, good dispersibility can be obtained without impairing the transparency of the low refractive index layer. Particularly when it is 40 to 70 nm, it is possible to increase the occupancy rate of the cavities and efficiently lower the refractive index while ensuring the thickness of the outer shell that does not cause insufficient strength. The average particle diameter is defined as the median diameter (d = 50) measured by the laser diffraction / scattering method in accordance with JIS Z8825-1.

[0020] The blending amount of the above (B) is preferably 30 to 60% by weight, more preferably 35 to 55% by weight, and particularly preferably 40 to 52% by weight based on the total solid content of the low refractive resin composition. By setting it at 30% by weight or more, the refractive index can be made sufficiently low to reduce the reflectance, and by setting it at 60% by weight or less, sufficient abrasion resistance can be ensured. Examples of commercially available products include Thruia 4320 (trade name: manufactured by JGC Catalysts and Chemicals Ltd., solid content 20.5%, primary average particle diameter 60 nm).

[0021] The nanoalumina particles (C) used in the present invention are blended for the purpose of increasing the hardness of the low refractive layer and improving the abrasion resistance. The primary average particle diameter of (C) is preferably 5 to 100 nm, more preferably 10 to 90 nm. By setting it at 5 nm or more, an improvement in abrasion resistance can be expected, and by setting it at 100 nm or less, an increase in haze can be suppressed and sufficient total light transmittance can be ensured.

[0022] It is preferable that the above (C) uses in combination two types of particles with different average particle diameters, a smaller particle diameter (c1) and a larger particle diameter (c2). By using in combination two types of particle diameters, the blendable amount of (C) can be increased, and the abrasion resistance can be further improved. In this case, the primary average particle diameter of (c1) is preferably 5 to 40 nm, and more preferably 10 to 30 nm. Also, the primary average particle diameter of (c2) is preferably 50 to 100 nm, and more preferably 60 to 90 nm.

[0023] The blending amount of the above (C) is preferably 8 to 20% by weight, more preferably 10 to 18% by weight, and particularly preferably 11 to 15% by weight based on the total solid content of the low-refractive resin composition. By setting it to 8% by weight or more, sufficient abrasion resistance can be ensured, and by setting it to 20% by weight or less, a sufficiently low reflectance can be ensured. Also, when (c1) and (c2) are used in combination, the blending ratio of (c1) with respect to the whole of (C) is preferably 40 to 70% by weight, and more preferably 50 to 60% by weight.

[0024] The silicone leveling agent (D) used in the present invention is blended for the purpose of improving the leveling property during coating and improving the abrasion resistance and water repellency of the cured film. Although PFAS exhibits the same effect even with a small amount of addition, the applicant has repeatedly tried and found that by using in combination polyether-modified polydimethylsiloxane (d1) and polyester-modified polydimethylsiloxane (d2) as (D) together with the above (A), an effect equivalent to that of PFAS can be obtained.

[0025] Examples of the above (D) include polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane, polyester-modified polysiloxane, polyether-modified polysiloxane, etc. Among these, the present composition contains at least a polyether-modified polysiloxane compound (d1) and a polyester-modified polydimethylsiloxane (d2) as essential components.

[0026] Examples of (d1) include compounds having polyether side chains such as ethylene oxide or propylene oxide in the side chains of the polydimethylsiloxane main chain. The incorporation of (d1) can particularly improve scratch resistance and water repellency. Furthermore, by having reactive functional groups that can polymerize with binder resins such as acryloyl groups, the cured film does not peel off over time due to bleeding, etc., and the effects of scratch resistance and water repellency can be sustained for a longer period of time.

[0027] Examples of (d2) include compounds having a polyester side chain formed by reacting a dicarboxylic acid component with a glycol in the side chain of a polydimethylsiloxane main chain. The incorporation of (d2) can particularly improve scratch resistance and leveling properties. In particular, the improved leveling properties stabilize the coating appearance and suppress the increase in haze. Furthermore, by having a reactive functional group that can polymerize with a binder resin, such as an acryloyl group, the film does not peel off over time due to bleeding after curing, and the scratch resistance effect can be sustained for a longer period of time.

[0028] The amount of (D) containing (d1) and (d2) is preferably 13 to 23% by weight, more preferably 15 to 22% by weight, and particularly preferably 16 to 21% by weight, relative to the total solid content of the low-refractory resin composition. A concentration of 13% by weight or more ensures sufficient scratch resistance and water repellency, while a concentration of 23% by weight or less ensures good appearance and optical properties without excessive addition.

[0029] The amount of (d1) added is preferably 15 to 50% by weight, more preferably 20 to 40% by weight, and particularly preferably 24 to 35% by weight relative to the total amount of (D). By setting it within this range, scratch resistance and water repellency can be improved, and sufficient nail scratch resistance and water contact angle can be ensured. A commercially available product of (d1) is BYK-UV3590 (product name: manufactured by BYK Chemie, an acryloyl group-containing polyethylene-modified polydimethylsiloxane compound), etc.

[0030] The amount of (d2) added is preferably 50 to 85% by weight, more preferably 55 to 80% by weight, and particularly preferably 60 to 76% by weight, relative to the total amount of (D). By setting it within this range, scratch resistance and leveling properties can be improved, and sufficient appearance and optical properties can be ensured. A commercially available example of (d2) is BYK-UV3570 (product name: manufactured by BYK Chemie, an acryloyl group-containing polyester-modified polydimethylsiloxane compound).

[0031] There are no particular limitations on the binder resin of the low-refractory resin composition of the present invention. For example, oligomers include urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polycarbonate (meth)acrylate, acrylic (meth)acrylate, diene (meth)acrylate, etc., which can be used alone or in combination of two or more types.

[0032] In addition to oligomers, low molecular weight binders may be used as components. Examples include (meth)acrylates having functional groups such as aliphatic, alicyclic, polyether skeletons, hydroxyl groups, and amino groups, as well as acrylamide compounds, which can be used alone or in combination of two or more. Examples include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate (hereinafter referred to as DPHA).

[0033] The amount of binder resin added is preferably 5 to 25% by weight, and more preferably 10 to 20% by weight, relative to the total solid content of the low-refractory resin composition. Within this range, sufficient curability, good dispersibility, and various properties after curing can be ensured.

[0034] In the low-refractory resin composition of the present invention, it is preferable to use a photopolymerization initiator. A photopolymerization initiator generates radicals upon irradiation with ultraviolet light or electron beams, and these radicals trigger the polymerization reaction. General-purpose photopolymerization initiators such as benzyl ketal, acetophenone, and phosphine oxide can be used. By arbitrarily selecting the light absorption wavelength of the polymerization initiator, curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, examples include 2,2-dimethoxy-1,2-diphenylethane-1-one as a benzyl ketal, 1-hydroxycyclohexyl-phenyl-ketone and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one as α-hydroxyacetophenones, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one as an α-aminoacetophenone, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide as acylphosphine oxides, which can be used individually or in combination of two or more.

[0035] Among the aforementioned photopolymerization initiators, it is preferable to include an α-hydroxyacetophenone-based initiator that is less prone to yellowing. Examples of commercially available products include Omnirad127, Omnirad184, and Omnirad2959 (trade name: manufactured by IGM Resins). Among these, Omnirad127D (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one), which has high reactivity, is particularly preferred. Unlike most conventional photocleavage-type polymerization initiators, Omnirad127D has two cleavage sites per molecule. Therefore, after cleavage by active energy ray irradiation, it can react with polymerizable monomers at multiple points, resulting in very good reaction curing properties, especially in thin films, and allowing for a high molecular weight of the polymer product.

[0036] The amount of the photopolymerization initiator is preferably 5 to 25 parts by weight, more preferably 10 to 20 parts by weight, and particularly preferably 12 to 18 parts by weight, per 100 parts by weight of the radical polymerizable portion of the low-refractory resin composition.

[0037] The low-refractory resin composition of the present invention may optionally contain ultraviolet absorbers, antioxidants, adhesion promoters, bluing agents, defoaming agents, thickeners, anti-precipitation agents, antistatic agents, anti-fogging agents, antibacterial agents, antiviral agents, organic fine particles, etc., to the extent that it does not impair performance.

[0038] The antireflective film of the present invention can be obtained by laminating the low-reflectivity layer, obtained by curing the above-mentioned low-reflectivity resin composition, onto an HC layer laminated on a light-transmitting substrate film. The HC resin composition for forming the HC layer may include a compound having polymerizable functional groups and a photopolymerization initiator. In addition, additives such as leveling agents and fillers such as silica fine particles may be included to improve the appearance, optical properties, and other physical properties of the cured film.

[0039] Examples of compounds having polymerizable functional groups include oligomers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polycarbonate (meth)acrylate, acrylic (meth)acrylate, and diene (meth)acrylate, which can be used individually or in combination of two or more. Among these, urethane (meth)acrylate (hereinafter referred to as urea) is preferred because it has excellent scratch resistance due to the cohesive force of hydrogen bonds derived from urethane bonds.

[0040] Low molecular weight binders may be used as components other than oligomers. Examples include (meth)acrylates having functional groups such as aliphatic, alicyclic, polyether skeletons, hydroxyl groups, and amino groups, as well as acrylamide compounds, which can be used alone or in combination of two or more. Examples include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate (hereinafter referred to as DPHA).

[0041] When coating a low-refractory resin composition, it may be diluted with a solvent to improve coating properties. Examples of diluent solvents include alcohol-based solvents such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol (hereinafter referred to as isobutanol), and diacetone alcohol; ketone-based solvents such as acetone, methyl ethyl ketone (hereinafter referred to as MEK), methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; and ether-based solvents such as PGM, diethyl ether, and diisopropyl ether. These can be used individually or in combination of two or more. When diluting, the solid content is exemplified as 1 to 40%, but there is no particular requirement, and it can be set appropriately to achieve a viscosity that is easy to coat.

[0042] Examples of light-transmitting substrate films to which the HC resin composition is applied include polyester film, triacetylcellulose film, polycarbonate film, polysulfone film, nylon film, cycloolefin film, acrylic film, polyimide film, ABS film, polyolefin film, PVC film, and PVA film. Among these, biaxially oriented polyester film is preferred in terms of weather resistance, processability, and dimensional stability. The film thickness should generally be between 25 μm and 500 μm.

[0043] The base film may be subjected to surface treatments such as primer treatment, sandblasting, solvent treatment to create surface irregularities, or corona discharge treatment, chromic acid treatment, or ozone / ultraviolet irradiation treatment to improve adhesion with the HC resin composition.

[0044] The method for applying the HC resin composition and the low-refractory resin composition is not particularly limited and can be formed by known coating methods such as spray coating, roll coating, die coating, air knife coating, blade coating, spin coating, reverse coating, gravure coating, and wire bar coating, or by printing methods such as gravure printing, screen printing, offset printing, and inkjet printing.

[0045] The film thickness of the HC resin composition can be exemplified as 1 μm to 10 μm when dry, but is not limited thereto. The film thickness of the low-refractory layer coated on the HC layer is preferably 50 to 200 nm when dry, and more preferably 80 to 150 nm. If the thickness of the low-refractory layer is within this range, it is possible to sufficiently lower the reflectivity of the film.

[0046] When curing HC resin compositions and low-refractory resin compositions, suitable light sources for ultraviolet irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, LED lamps, and electrodeless ultraviolet lamps. The irradiation atmosphere may be air or an inert gas such as nitrogen or argon. Furthermore, heating the coating film with a back roll or an IR heater during ultraviolet irradiation can further improve curing performance. The irradiation conditions include an irradiation intensity of 500 mW / cm². 2 ~3000mW / cm 2 Exposure dose: 50-400 mJ / cm² 2 Examples are given, but this is not an exhaustive list.

[0047] The present invention will be described in detail below with reference to examples and comparative examples, but these are merely examples and the invention is not limited to them. Unless otherwise specified, measurements were taken under conditions of room temperature of 25°C and relative humidity of 65%. The amounts of ingredients are expressed in parts by weight on a solid content basis. [Examples]

[0048] HC resin composition Z-876-21L (Product name: Aica Kogyo Co., Ltd., hard coating agent containing hexafunctional urea, photopolymerization initiator, and colloidal nanosilica, solids content 40%)

[0049] Low flexure resin composition As a binder resin, KAYARAD DPHA (product name: manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) is used, as (A) EBECRYL80 (product name: manufactured by Daicel Ornex Co., Ltd., amine-modified polyether acrylate, 100% solids content, a tetrafunctional tertiary amino group compound) is used, as (B) Thruria 4320 (product name: manufactured by JGC Catalysts & Chemicals Co., Ltd., 20.5% solids content, 1 (c1) ALMIBK30WT%-M47 (product name: CIK Nanotech, solids content 30%, average particle size 20nm, MIBK dilution) is used as (c2) ALMIBK30WT%-M146 (product name: CIK Nanotech, solids content 30%, average particle size 80nm, MIBK dilution) is used as (c2) BYK-UV3590 (product name: BYK A polyether-modified polysiloxane containing an acryloyl group (manufactured by Chemie) was used as (d2), BYK-UV3570 (trade name: BYK Chemie, polyether-modified polysiloxane containing an acryloyl group) was used as (d2), Omnirad127D (trade name: IGM Resins) was used as a photopolymerization initiator, and X-71-1203M (trade name: Shin-Etsu Chemical Co., Ltd., fluorine-containing fluorine compound) was used as a fluorine-based leveling agent in the formulations shown in Tables 1 to 3. Each formulation was diluted with 68 parts of a mixed solvent of isobutanol and MEK (isobutanol:MEK = 35:65), and stirred until uniformly dissolved and dispersed to obtain a low-diffraction resin composition (solids content approximately 3%).

[0050] Table 1 JPEG2026072137000001.jpg114163

[0051] Table 2 JPEG2026072137000002.jpg116166

[0052] Table 3 JPEG2026072137000003.jpg83135

[0053] The evaluation method was as follows:

[0054] Preparation of the HC layer Using HC resin composition Z-876-21L, it was applied to PET film 100U403 (product name: Toray Industries, Ltd., thickness 100 μm, with easy-adhesion layer) to a dry film thickness of 3 μm, and dried at 80°C for 1 minute. Afterwards, it was heated with a high-pressure mercury lamp at 1300 mW / cm². 2 , cumulative light intensity 200 mJ / cm 2 An HC film was created by curing under these conditions.

[0055] Preparation of anti-reflective film On the HC layer prepared above, the low-reactivity resin composition was applied to a dry film thickness of 100 nm, dried at 80°C for 1 minute, and then heated with a high-pressure mercury lamp at 1300 mW / cm². 2 , cumulative light intensity 200 mJ / cm 2 The material was cured under conditions of a nitrogen atmosphere to form a low-refractory layer.

[0056] Total light transmittance was measured using a Haze-GARD2 haze meter manufactured by Toyo Seiki Seisakusho in accordance with JIS K7361-1. Evaluation was rated as ○ for 92% or higher and × for less than 92%.

[0057] Haze: Measured using Haze-GARD2 manufactured by Toyo Seiki Seisakusho Co., Ltd., in accordance with JIS K7136. 1.5% or less was marked with ○, and over 1.5% with ×.

[0058] Minimum reflectance: Using the anti-reflective film described above, the side opposite the coated surface was scratched with sandpaper, filled with a black pigment marker, and then black PET was bonded to make the reflectance of the opposite side 0%. Then, the reflectance of the HC side was plotted at 1 nm intervals in the range of 300 nm to 780 nm using a spectrophotometer to measure the lowest reflectance, with a value of 1.5% or less marked as ○ and a value greater than 1.5% marked as ×.

[0059] Water contact angle: Following the static drop method of JIS R 3257:1999, water was dropped onto the optical laminate at room temperature using a DMs-400 manufactured by Kyowa Interface Science Co., Ltd., and the contact angle was measured after standing for 30 seconds. Under normal conditions, a value of 108° or higher was marked as ○, and a value of less than 108° was marked as ×.

[0060] Scratch resistance: A load of 1000g / cm2 was placed on steel wool #0000 and moved back and forth 2000 times. Visual inspection indicated that no scratches occurred (○) and scratches occurred (×).

[0061] Evaluation results Table 4 JPEG2026072137000004.jpg95135

[0062] Evaluation results Table 5 JPEG2026072137000005.jpg95135

[0063] Evaluation results Table 6 JPEG2026072137000006.jpg83135

[0064] The examples showed no problems in any aspect, including total light transmittance, haze, minimum reflectance, water contact angle, and scratch resistance, and were all satisfactory.

[0065] On the other hand, Comparative Example 1, which did not contain (A), had poor scratch resistance; Comparative Example 2, which did not contain (B), had poor minimum reflectance and water contact angle; and Comparative Examples 3 and 6, which did not contain (C) and (D), had low water contact angles and poor scratch resistance. Furthermore, Comparative Example 4, which contained (d1) alone, had high haze, and Comparative Example 5, which contained (d2) alone, had a low water contact angle; all of these were unsuitable for the present invention.

Claims

1. A light-transmitting substrate film is laminated in the order of a hard coat layer and a low refractive index layer. The low refractive index layer contains amine-modified (meth)acrylate (A), hollow silica nanoparticles (B), alumina nanoparticles (C), and a silicone-based leveling agent (D) as essential components. An anti-reflective hard coat film characterized in that (D) comprises a polyether-modified polydimethylsiloxane (d1) and a polyester-modified polydimethylsiloxane (d2).

2. The anti-reflective hard coat film according to claim 1, characterized in that the amount of the polyether-modified polydimethylsiloxane (d1) is 15 to 45% by weight relative to the total amount of solids of the silicone-based leveling agent (D).

3. The anti-reflective film according to either claim 1 or 2, characterized in that the amount of the silicone-based leveling agent (D) is 13 to 23% by weight relative to the total amount of the low refractive index layer.

4. A low refractive index resin composition for anti-reflective films, comprising amine-modified (meth)acrylate (A), hollow silica fine particles (B), alumina fine particles (C), and a silicone-based leveling agent (D) as essential components, wherein (D) comprises polyether-modified polydimethylsiloxane (d1) and polyester-modified polydimethylsiloxane (d2).

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