TWI647487B - Antiglare laminate - Google Patents

Abstract

The present invention provides an antiglare laminate having excellent antiglare properties and antiglare, a display device including the antiglare laminate, a curable resin composition and a coating film therefor.

The present invention is an anti-glare laminate comprising a transparent substrate and a hard coat layer disposed on at least one of the outermost layers of the transparent substrate, wherein the hard coat layer contains a curable resin and a fine particle component. The fine particle component has irregularities on the surface by containing the fine particle component, and the fine particle component has at least three peaks in the particle diameter distribution, and the average particle of the fine particle having the particle diameter belonging to the first peak region among the at least three peaks The diameter is set to A (μm), the average particle diameter of the fine particles whose particle diameter belongs to the second peak region smaller than A is B (μm), and the particle diameter belongs to the third peak including m peaks smaller than A and larger than B. When the average particle diameter of the fine particles in the region is Cm (μm), the following formula is satisfied. 1≦A≦5, 0.001≦B≦0.3, (2×B)≦Cm≦(0.5×A), where m is an integer of 1 or more.

Description

Anti-glare laminate

The present invention relates to an anti-glare laminate.

Liquid crystal display devices are widely used in flat panel displays such as personal computers, mobile phones, and portable game machines. In such a liquid crystal display device, an anti-glare film is attached to the surface in order to prevent deterioration of visibility due to reflection of light from the outside.

As the anti-glare film, it is known that light is scattered and scattered by providing a concavo-convex structure on the surface. For example, Patent Document 1 discloses an anti-glare film formed by forming a hard coat layer having particles having an average particle diameter of 0.6 to 20 μm, fine particles having an average particle diameter of 1 to 500 nm, and a hard coat resin as a main component on a transparent base film. . Further, Patent Document 2 discloses an optical film including an antiglare layer containing a binder resin, organic fine particles, and inorganic fine particles on a light-transmitting substrate.

In recent years, mobile terminals such as smart phones and small screen sizes are gradually adopting high-definition liquid crystal display devices having a resolution of 200 ppi or more with respect to the screen size. Furthermore, the so-called ppi is pixel/inch, which means the number of pixels per 1 inch.

In the high-definition liquid crystal display device, since the size of each pixel is small, a so-called glare phenomenon is likely to occur. The phenomenon of glare is a phenomenon in which a pixel of a liquid crystal is enlarged due to a lens effect when an anti-glare film having an uneven layer is attached to a surface of a liquid crystal display device, and it is a phenomenon that appears to be glittering.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-286083

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2014-59334

The anti-glare film disclosed in Patent Document 1 includes a hard coat layer containing two types of particles. Such an anti-glare film is effective for anti-glare property, but is not effective for glare generated in a high-definition liquid crystal display device.

Further, the optical film disclosed in Patent Document 2 includes an antiglare layer containing two types of particles of organic fine particles and inorganic fine particles. Although such an optical film is effective for anti-glare property or rainbow unevenness and interference fringe, it is not effective for glare generated in a high-definition liquid crystal display device.

The present invention has been accomplished in view of such circumstances. An object of the present invention is to provide an antiglare laminate having excellent antiglare properties and antiglare, a display device including the antiglare laminate, a curable resin composition and a coating film therefor.

The inventors of the present invention have studied the uneven structure of the surface of the hard coat layer in order to prevent such glare, particularly glare generated in a high-definition liquid crystal display device. As a result, it has been found that the degree of irregularity of the uneven structure on the surface of the hard coat layer can be appropriately controlled by using three or more kinds of fine particles having different average particle diameters. The present invention has been achieved based on such insights. That is, the present invention has the following constitution.

(1) An anti-glare laminate body having a transparent substrate and disposed thereon A hard coat layer of at least one of the outermost layers of the transparent substrate, wherein the hard coat layer contains a curable resin and a fine particle component, and the fine particle component has irregularities on the surface, and the fine particle component is attached to the particle The diameter distribution has at least three peaks, and among the at least three peaks, the average particle diameter of the fine particles belonging to the first peak region is A (μm), and the particle diameter belongs to the second peak region smaller than A. When the average particle diameter of the fine particles is B (μm) and the average particle diameter of the fine particles having the third peak region including the m peaks smaller than A and larger than B is Cm (μm), respectively, the following formula is satisfied. :1≦A≦5, 0.001≦B≦0.3, (2×B)≦Cm≦(0.5×A), where m is an integer of 1 or more.

(2) The antiglare laminate according to the above (1), wherein the hard coat layer has a skewness of 1.0 to 4.0.

(3) The anti-glare laminate according to (1) or (2) above, wherein the haze is 2 to 10%, and the total light transmittance is 88% or more.

(4) The anti-glare laminate according to any one of the above (1) to (3), wherein the glossiness is 60 to 90%.

(5) The anti-glare laminate according to any one of the above (1), wherein the transparent substrate has a retardation of 3,000 to 30,000.

(6) The anti-glare layered body according to any one of the above-mentioned (1), wherein the number of the fine particles having the particle diameter of the first peak region is N ₁ and the particle diameter is The number of the fine particles belonging to the second peak region smaller than A is N ₂ , and the number of the fine particles belonging to the third peak region including the m peaks smaller than A and larger than B is N ₃ , and N _{1 is} satisfied. :N ₂ :N ₃ =1:30:5~1:50000:100 ratio.

(7) A display device comprising any one of (1) to (6) above Anti-glare laminate body.

(8) A curable resin composition for forming an antiglare hard coat layer, wherein the curable resin composition contains a curable resin and a fine particle component, and the fine particle component is in a particle size distribution At least three or more peaks, and an average particle diameter of the fine particles belonging to the first peak region of the at least three or more peaks is A (μm), and an average of the fine particles having a particle diameter of less than the second peak region of A When the particle diameter is B (μm) and the average particle diameter of the fine particles having the third peak region including the m peaks smaller than A and larger than B is Cm (μm), the following formula is satisfied: 1≦ A ≦ 5, 0.001 ≦ B ≦ 0.3, (2 × B) ≦ Cm ≦ (0.5 × A), where m is an integer of 1 or more.

(9) The curable resin composition according to the above (8), wherein the number of the fine particles belonging to the first peak region is N ₁ and the particle diameter is smaller than the second peak region of A. when the set number of N _2, belonging to the above average particle diameter is less than a and greater than m comprising fine particles of a peak 3 area of the peak B is set to the number N _3, satisfies _{N 1: N 2: N 3} = 1: 30 : 5~1:50000:100 ratio.

(10) A coating film obtained by curing the curable resin composition according to (8) or (9) above.

The anti-glare laminate of the present invention and the display device including the anti-glare laminate are excellent in anti-glare property and anti-glare. Further, the curable resin composition of the present invention and the coating film can provide a hard coat layer of an antiglare laminate which is excellent in antiglare property and antiglare.

Hereinafter, embodiments of the present invention will be specifically described. However, the embodiments of the present invention are not limited to the following embodiments.

This embodiment is useful for a high definition display device. The so-called high definition display device in the present embodiment means a display device of 200 ppi or more. Further, if it is further a display device of 250 ppi or more, it is further preferable.

(Composition of anti-glare laminate)

The anti-glare laminate of the present embodiment has a transparent substrate and a hard coat layer provided on at least one of the outermost layers. In addition to the transparent substrate and the hard coat layer, other layers such as a pinned layer, a refractive index adjusting layer, and a protective layer may be laminated between the transparent substrate and the hard coat layer as needed.

The hard coat layer may be formed on the outermost layer on the front side (outer side) of the transparent substrate, or on the outermost layer on the back side (anti-outside side) of the transparent substrate, and may be formed on the outermost layer on both sides.

(transparent substrate)

The transparent substrate is a transparent substrate for forming a hard coat layer. As a material for forming a transparent substrate, a material excellent in optical transparency, mechanical strength, solvent resistance, and the like is preferable. Further, the transparent substrate may be an organic material or an inorganic material.

Examples of the organic material include a polypropylene resin, a polyethylene resin, a cyclic polyolefin resin, a polyamide resin, a polyester resin, a polyacryl resin, a polyvinyl chloride resin, and a nylon resin. A cellulose resin such as a urethane resin or triacetyl cellulose. Among these, polyethylene terephthalate, polyethylene naphthalate, polytetramethylene terephate, polypropylene naphthalate, polyparaphenylene are preferred. Dicarboxylic acid three A polyester resin such as polytrimethylene terephtalate or polybutylene terephthalate. Further, polyethylene terephthalate is more preferably used from the viewpoint of transparency, weather resistance, solvent resistance, rigidity, and cost. The organic material may be used by mixing two or more organic materials or laminating them.

Examples of the inorganic material include soda lime glass, borosilicate glass, quartz glass, and tempered glass (aluminum silicate glass). Among these, tempered glass (aluminum silicate glass) is preferred.

Various additives may also be included in the transparent substrate. Examples of the additive include an antioxidant, a heat-resistant stabilizer, an ultraviolet absorber, a pigment, a dye, an antistatic agent, a nucleating agent, a coupling agent, and the like.

In order to improve the adhesion between the transparent substrate and the hard coat layer, the transparent substrate may be subjected to a surface treatment. Examples of the surface treatment include surface oxidation treatment such as corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone, and ultraviolet irradiation treatment.

The thickness of the transparent substrate is preferably from 1 to 1,000 μm, more preferably from 5 to 500 μm, still more preferably from 50 to 250 μm, from the viewpoint of ensuring mechanical strength, curl resistance, workability and the like.

Regarding the transparent substrate, the retardation is preferably from 3,000 to 30,000 in view of the reason for the reduction of the rainbow pattern described later. The delay is preferably 5000~25000.

(hard coating)

The hard coat layer is provided on at least one outermost layer of the transparent substrate, and contains a curable resin and a fine particle component, and has irregularities on the surface by containing the fine particle component. By forming a hard coat layer on the surface of the transparent substrate, scratch resistance or abrasion resistance can be imparted. Further, the hard coat layer can impart antifouling properties, slipperiness, water repellency, and the like to sebum, cosmetics, and the like to the surface of the transparent substrate.

The curable resin may be a thermosetting type or an active energy ray hardening type. In order to suppress the occurrence of curl during production as much as possible, an active energy ray hardening type is preferred. The active energy ray refers to free radiation such as ultraviolet rays, electron beams, visible rays, and gamma rays.

Examples of the thermosetting resin include a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, and an amino alcohol. Acid resin, enamel resin, polyoxyalkylene resin, and the like.

Examples of the active energy ray-curable resin include an acrylic curable resin and an urethane curable resin. Further, as the active energy ray, ultraviolet rays are preferred in terms of ease of handling or processing.

The active energy ray-curable acrylic curable resin is a polymer comprising a curable composition of a monomer or oligomer having an acrylic polymerizable unsaturated group. As the acrylic monomer or oligomer having a polymerizable unsaturated group, it is monofunctional or polyfunctional.

Specific examples of the monofunctional monomer having an acrylic polymerizable unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, ( N-decyl methacrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate Base ester, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, (methyl) (Meth) acrylate such as cyclohexyl acrylate or benzyl (meth) acrylate. These may be used alone or in combination of two or more.

Further, specific examples of the monofunctional oligomer having an acrylic polymerizable unsaturated group include ethoxylated o-phenylphenol acrylate, methoxy polyethylene glycol acrylate, and phenoxy polyethyl acrylate. Glycol acrylate and the like.

In order to make the composition of the monomer or oligomer having an acrylic polymerizable unsaturated group to be curable, it is preferred to contain a polyfunctional (meth) acrylate as an acrylic monomer having a polymerizable unsaturated group. Or oligomers. Examples of the polyfunctional (meth) acrylate include dipropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and poly Ethylene glycol di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, modified bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(a) Bifunctional (meth) acrylate such as acrylate or polyethylene glycol di(meth) acrylate; pentaerythritol tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, three Trifunctional (meth) acrylate such as hydroxymethylpropane ethoxy tris(meth) acrylate, polyether tri(meth) acrylate, glyceryl propoxy tri(meth) acrylate; pentaerythritol tetra ( Methyl) acrylate, pentaerythritol ethoxy tetra(meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol A tetrafunctional or higher (meth) acrylate such as hydroxypenta(meth)acrylate or dipentaerythritol hexa(meth)acrylate. These polyfunctional acrylates may be used alone or in combination of two or more. In order to secure the hardness as the hard coat layer, a tetrafunctional or higher (meth) acrylate is preferably used.

The active energy ray-curing type urethane-based curable resin is a polymer of urethane acrylate monomer or oligomer. As the urethane acrylate oligomer, it is a polyoxyalkylene group or a saturated polyester segment or both of them are bonded via an urethane bond and have an acrylonitrile group at both ends.

In order to form a thermosetting or active energy ray-curable acrylic curable resin, it is necessary to add a polymerization initiator to the above-mentioned monomer or oligomer having a polymerizable unsaturated group to prepare a thermosetting or active energy ray. A composition of hardenability.

As the thermal polymerization initiator, a known one can be used. For example, a peroxide compound such as benzamidine peroxide or ditributyl peroxide can be mentioned. The amount of the thermal polymerization initiator to be added is preferably from 1 to 10% by mass based on the monomer or oligomer having a polymerizable unsaturated group.

Further, as the active energy ray polymerization initiator, various known photopolymerization initiators can be used. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl Methyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2 (hydroxyl) -2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, propiophenone, dichlorobenzophenone, 2-methyl Bismuth, 2-ethyl hydrazine, 2-tert-butyl fluorene, 2-amino hydrazine, 2-methyl 9-oxo sulphur 2-ethyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur Benzene dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoate and the like. These active energy ray polymerization initiators may be used alone or in combination of two or more. The amount of the active energy ray polymerization initiator to be added is preferably from 1 to 10% by mass based on the monomer or oligomer having a polymerizable unsaturated group.

Further, in addition to the photopolymerization initiator, a photosensitizer may be further contained. Examples of the photosensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.

In the hard coat layer, a softening component may also be included as needed. If it contains a soft component, it can prevent cracks during processing. The soft component is preferably a (meth) acrylate having one or more polymerizable unsaturated groups in the molecule. Examples of the (meth) acrylate include tricyclodecane hydroxymethyl bis (meth) acrylate, ethylene oxide modified di(meth) acrylate of bisphenol F, and bisphenol A. Ethylene oxide modified di(meth)acrylate, isomeric cyanuric acid modified ethylene di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol II Bifunctional (meth) acrylate such as methyl acrylate; trimethylolpropane tri(meth) acrylate, trimethyl propane propylene oxide modified tri(meth) acrylate, trimethyl propane 3-functional (meth) acrylate such as ethylene oxide modified tri(meth) acrylate; ethyl methacrylate; (meth) acrylate polyester; polyether (meth) acrylate Ester and the like. In particular, a trifunctional (meth) acrylate or ethyl methacrylate (meth) acrylate is more preferred. These (meth) acrylates may be used alone or in combination of two or more.

Further, the hard coat layer may contain components other than the above insofar as it does not impair the effects of the embodiment. Examples of the component that can be added to the hard coat layer include a dispersant, a softening component, an antibacterial agent, a fluorine-based antifouling agent, a fluorine-based slipper or a ruthenium-based slip agent, a leveling agent, an antistatic agent, and an ultraviolet absorbing agent. Agents, heat stabilizers, antioxidants, etc. The dispersing agent contains a user in order to uniformly disperse the fine particles described later in the coating liquid for forming the hard coat layer.

The thickness of the hard coat layer is preferably from 0.5 to 8.0 μm. The thickness of the hard coat layer is more preferably from 0.5 to 5.0 μm, further preferably from 1.0 to 4.0 μm, most preferably from 1.0 to 3.5 μm.

(microparticles)

The fine particle component contained in the hard coat layer has at least three peaks in the particle size distribution. In the particle size distribution, the peak value is a particle diameter in which the horizontal axis is the particle diameter and the vertical axis is the number of particles, and the number of particles becomes a maximum value.

The present inventors have found that when a fine particle component having at least three peaks in the particle diameter distribution is used as the fine particle component contained in the hard coat layer, and the particle diameter of each peak is within a specific numerical range, the present invention can be appropriately The irregularity of the uneven structure on the surface of the hard coat layer was controlled, and it was found that the anti-glare property and the anti-glare of the anti-glare laminate body can be achieved.

In other words, the fine particle component must have at least three or more peaks in the particle size distribution, and the average particle diameter of the fine particles having the particle diameter belonging to the first peak region among the at least three or more peaks is A (μm). The average particle diameter of the fine particles having the diameter in the second peak region is B (μm), and the average particle diameter of the fine particles having the particle diameter belonging to the third peak region including m peaks smaller than A and larger than B is Cm (μm). When the formula is satisfied, the following formula is satisfied. 1≦A≦5, 0.001≦B≦0.3, (2×B)≦Cm≦(0.5×A), where m is an integer of 1 or more.

The particle size distribution of the microparticles was measured by the following method. A particle image was obtained by photographing the surface layer of the hard coat layer using a transmission electron microscope. For the maximum length (Dmax: the maximum length of 2 points on the contour of the particle image) and the maximum length of the maximum length (DV-max: between the two lines when the particle image is sandwiched by two straight lines parallel to the maximum length The shortest length is measured, and the multiplied average value (Dmax × DV-max) ^{1/2 is} set as the particle diameter. According to this method, the particle size distribution can be approximated based on 100 measured values. In order to more accurately study the particle size distribution, it is preferred to measure the particle size of as many particles as possible.

Here, the peak region means a particle diameter distribution in which the vertical axis is the number of fine particles and the horizontal axis is the particle diameter of the fine particles, and one of the peaks in the particle diameter distribution (the number of fine particles is prominent) The point is the center of the horizontal axis direction, and there is a certain area in the direction of the horizontal axis of the fine particles. The peak region should be interpreted according to technical common sense. For example, the peak region may be selected such that one of the peaks in the particle size distribution is the center of the horizontal axis direction, and the self-particle diameter is smaller than the peak value and the closest to the peak value (the first minimum value). a curve having a particle diameter larger than the peak value and closest to the peak value (second minimum value), a horizontal axis of the particle size distribution map, a vertical axis defining the first minimum value as a constant, and the second minimum The value is set to be surrounded by the vertical axis of the constant. Further, in the graph of the particle size distribution, when the distance or the region from the maximum value to the minimum value is not clear, for example, a maximum value may be used and the distance from the inflection point on the way from the maximum value to the minimum value. 2 times the approximate value of the distance from the maximum value to the minimum value.

According to the above formula, in the particle size distribution of the fine particle component, the average particle diameter of the fine particles having the particle diameter belonging to the first peak region is A (μm), and the average particle diameter of the fine particles having the particle diameter belonging to the second peak region smaller than A When B (μm) is set, the number of particles having a particle diameter smaller than A and larger than B is one or more.

When the number of particles having a particle diameter smaller than A and larger than B is one, the average particle diameter of the fine particles belonging to the peak region is C1 (μm). When the number of particles having a particle diameter of less than A and greater than B is two, the average particle diameter of the fine particles belonging to the peak regions is C1 (μm) and C2 (μm), respectively. Similarly, as the particle diameter is smaller than A and the number of peaks larger than B, that is, m is increased to 3, 4, etc., the average particle diameters of the microparticles belonging to the peak regions are defined as C3 (μm) and C4 (μm, respectively). )Wait. At this time, the total average particle diameter of the particle diameter smaller than A and larger than B is expressed as Cm (μm).

The average particle diameter A (μm) of the fine particles having the particle diameter of the first peak region is 1 ≦ A ≦ 5. Such microparticles are primarily involved in imparting anti-glare properties to the hardcoat layer. The average particle diameter B (μm) of the fine particles having a particle diameter of less than the second peak region of A was 0.001 ≦ B ≦ 0.3. Such microparticles are primarily involved in the inhibition of glare. The average particle diameter Cm (μm) of the fine particles belonging to the third peak region containing m peaks smaller than A and larger than B is (2 × B) ≦ Cm ≦ (0.5 × A). Such microparticles are primarily involved in the inhibition of glare.

Further, it is preferable that the fine particle component is a particle size distribution, and the number of the fine particles having the particle diameter belonging to the first peak region is N ₁ , and the number of the fine particles having the particle diameter belonging to the second peak region smaller than A is N. _2. When the number of particles having a particle diameter belonging to the third peak region of less than A and greater than the m peaks of B is N ₃ , N ₁ :N ₂ :N ₃ =1:30:5~1 is satisfied: 50,000:100 ratio. When the relative number of the fine particles belonging to the three or more peak regions is within the ratio range, the anti-glare property and the anti-glare of the anti-glare laminate can be improved to a higher degree. More preferably, it satisfies the _{ratio of} N ₁ :N ₂ :N ₃ =1:1000:5 to 1:50000:50. Further preferably, the _{ratio of} N ₁ :N ₂ :N ₃ =1:1000:5 to 1:30000:50 is satisfied. The number of the fine particles belonging to the peak region can be measured together with the particle size distribution of the fine particles by the above-described method using a transmission electron microscope.

The fine particles may be inorganic fine particles or organic fine particles. As the inorganic fine particles, for example, metal oxide fine particles such as cerium oxide, titanium oxide, zirconium oxide, or aluminum oxide can be used, and those having higher hardness are preferable. As the organic fine particles, for example, an acrylic resin, polystyrene, polyoxyalkylene, melamine resin, or benzoquinone can be used. Resin, resin particles such as polytetrafluoroethylene, cellulose acetate, polycarbonate, and polyamide.

Further, in order to uniformly disperse the fine particles in the hard coat layer, the surface of the fine particles may be subjected to surface treatment. As a method of surface treatment, for example, a given boundary A surfactant, and a method of imparting a functional group such as a hydroxyl group or a carboxylic acid.

The content of the fine particles in the hard coat layer is also dependent on the thickness of the hard coat layer, and is preferably from 10 to 500% by mass, and more preferably from 50 to 300% by mass, from the viewpoint of glare and anti-glare property.

Further, from the viewpoint of reducing glare, the difference in refractive index between the fine particles and the hard coat layer is preferably 0.1 or less, more preferably 0.01 or less.

When the average particle diameters A, B, and Cm of the fine particles satisfy the above formula, they are effective not only for anti-glare property and anti-glare, but also for preventing the prevention of rainbow lines and preventing blushing.

The so-called rainbow pattern refers to the interference pattern which appears due to the difference in refractive index between the transparent substrate and the hard coat layer. By appropriately controlling the degree of unevenness on the surface of the hard coat layer, the appearance of the Moire pattern can be alleviated.

The so-called whitishness refers to the phenomenon that whitening appears when the light of the anti-glare laminate is seen. Unlike the anti-glare property evaluated by the diffusion of reflected light, it was evaluated by the diffusion of the transmitted light. By appropriately controlling the degree of unevenness on the surface of the hard coat layer, whitening can be reduced.

(Characteristics of anti-glare laminates)

The antiglare laminate of the present embodiment preferably has a degree of skew of the hard coat layer of 1.0 to 4.0. In this case, it is more excellent in anti-glare properties and anti-glare properties. Here, the degree of skewness is an index of the degree of deflection of the unevenness on the surface of the hard coat layer. The measurement was carried out in accordance with JIS B0601-2001. Indicates the degree of skew of the symmetry of the height distribution when the average plane is centered. When the skewness is 0, the height distribution of the unevenness of the surface is symmetrical with respect to the average line. If the skewness is a positive value, it indicates the following tendency: the height distribution is relative to the flat Both are deflected toward the lower side, and the bumps are sharp.

The haze of the antiglare laminate of the present embodiment is preferably from 2 to 10%, more preferably from 4 to 8%. By setting the haze to a range of 2 to 10%, the level of anti-glare can be made more effective. The so-called haze is an indicator of the transparency of the laminate, also known as Haze. It is the ratio of diffuse penetrating light to total light penetrating light. In general, if the haze becomes large, it looks white and blurred. The haze can be controlled by appropriately changing the degree of unevenness on the surface of the hard coat layer.

In the antiglare layered body of the present embodiment, the total light transmittance is preferably 88% or more, and more preferably 90% or more from the viewpoint of improving the visibility of the display device.

The antiglare laminate of the present embodiment preferably has a gloss of 60 to 90%, more preferably 60 to 80%. The anti-glare property can be further improved by setting the gloss to a range of 60 to 90%. Here, the gloss was evaluated in the form of a 60-degree specular reflectance.

(Production method)

The anti-glare laminate of the present embodiment can be formed by applying a curable resin composition for forming an anti-glare hard coat layer on a transparent substrate, and then drying the hard coat layer, followed by hardening the hard coat layer to form a hard layer. The coating is applied to the coating. In other words, the hard coat layer of the anti-glare laminate of the present embodiment is a coating film obtained by curing the curable resin composition. The manufacturing steps can also be carried out continuously in a roll-to-roll manner.

The curable resin composition of the present embodiment is characterized in that it contains a curable resin and a fine particle component, and the fine particle component has a peak of at least three or more in a particle size distribution, and the particles are at least three or more peaks. Trail belongs to the first The average particle diameter of the fine particles in the peak region is A (μm), the average particle diameter of the fine particles having the particle diameter of the second peak region smaller than A is B (μm), and the particle diameter is included to be smaller than A and larger than B. When the average particle diameter of the fine particles in the third peak region of the m peaks is Cm (μm), the following formula is satisfied. 1≦A≦5, 0.001≦B≦0.3, (2×B)≦Cm≦(0.5×A), where m is an integer of 1 or more.

Further, the curable resin composition of the present embodiment is preferably one in which the number of the fine particles having the particle diameter in the first peak region is N ₁ and the particle diameter is in the second peak region smaller than A. when the number is set to N _2, belonging to the above-described particle diameter of fine particles a comprises less than 3 and greater than m-th peak area of the peak of B is set to the number N _3, satisfies _{N 1: N 2: N 3} = 1: 30 : 5~1:50000:100 ratio. More preferably, it satisfies the _{ratio of} N ₁ :N ₂ :N ₃ =1:1000:5 to 1:50000:50. Further preferably, the _{ratio of} N ₁ :N ₂ :N ₃ =1:1000:5 to 1:30000:50 is satisfied.

The description of the above-described contents of the curable resin composition of the present embodiment is as described above, and thus the description thereof will be omitted.

In order to set the fine particle component contained in the curable resin composition of the present embodiment to have a peak value of at least three or more of the predetermined average particle diameters of the above formula, the average particle diameter ( Μm) Three or more kinds of fine particles in the numerical range of the above A, B, and Cm are obtained by adding to a curable resin composition at a predetermined mixing ratio. In other words, the fine particle component contained in the curable resin composition can be added by appropriately mixing ratios of three or more kinds of fine particles having different average particle diameters, and the particle size distribution of the fine particle component is as described above. The method for setting the ratio of the number of fine particles belonging to each peak region to the above ratio is also the same.

As the solvent of the curable resin composition, for example, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, n-hexane, n-butyl alcohol, methyl Isobutyl ketone, methyl butyl ketone, ethyl butyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, N- Methyl-2-pyrrolidone and the like. These may be used alone or in combination of two or more.

Examples of the coating method of the curable resin composition include a knife coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, and a rod. A method of a knife coater, a lip coater, a die coater, a curtain coater, a printer, and the like.

The coating film is dried by heating the transparent substrate having the coating film. It is usually carried out under the conditions of a heating temperature of 60 to 100 ° C and a heating time of 1 to 5 minutes. The drying is carried out by a heating dryer or a vacuum dryer or the like.

Then, the uncured coating film is hardened. When the uncured coating film contains a thermosetting resin, it is heated and hardened by using a heating furnace or an infrared lamp. When the uncured coating film contains an active energy ray-curable resin, it is hardened by irradiation with an active energy ray. As the active energy ray, ultraviolet rays are preferred in terms of versatility. As the light source of ultraviolet rays, for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, or the like can be used. The hardening by irradiation with an active energy ray is preferably carried out in an environment filled with an inert gas such as nitrogen. The step of hardening can be divided into two stages of a pre-hardening step and a formal hardening step.

The anti-glare layer system of the present embodiment is possible to achieve both anti-glare property and anti-glare in a display device including the laminate. In particular, in the high-definition liquid crystal display device of 200 to 400 ppi and further 250 to 400 ppi, the features of the anti-glare laminate of the present embodiment can be further exhibited.

[Examples]

This embodiment will be further specifically described by way of the following examples.

As the coating liquid for a hard coat layer, the following materials were used.

(1) Acrylic resin: Acrylic ultraviolet curable resin; manufactured by Kyoeisha Chemical Co., Ltd.; trade name: Light acrylate DPE-6A; solid content 100%

(2) cerium oxide microparticles

(i) a solution obtained by dispersing cerium oxide fine particles having an average particle diameter of 0.01 μm in a mass% of 30% by mass in methyl ethyl ketone (manufactured by Nissan Chemical Co., Ltd.; trade name: organic cerium oxide sol )

(ii) a solution obtained by dispersing cerium oxide fine particles having an average particle diameter of 0.1 μm in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd.; trade name: organic cerium oxide sol)

(iii) a solution obtained by dispersing cerium oxide fine particles having an average particle diameter of 0.2 μm in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd.; trade name: organic cerium oxide sol)

(iv) a solution obtained by dispersing cerium oxide fine particles having an average particle diameter of 0.3 μm in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd.; trade name: organic cerium oxide sol)

(v) a solution obtained by dispersing cerium oxide microparticles having an average particle diameter of 0.5 μm in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd.; trade name: organic cerium oxide sol)

(vi) A solution obtained by dispersing cerium oxide fine particles having an average particle diameter of 0.8 μm in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd.; trade name: organic cerium oxide sol)

(vii) cerium oxide microparticles having an average particle diameter of 1 μm (manufactured by Nippon Shokubai Co., Ltd.; trade name: SEAHOSTAR)

(viii) cerium oxide microparticles having an average particle diameter of 2 μm (manufactured by Nippon Shokubai Co., Ltd.; trade name: SEAHOSTAR)

(ix) cerium oxide microparticles having an average particle diameter of 4 μm (manufactured by Corefront); Product Name: sicastar)

(x) cerium oxide microparticles having an average particle diameter of 10 μm (manufactured by Corefront Co., Ltd.; trade name: sicastar)

For the cerium oxide microparticles (vii) to (x), a solution obtained by dispersing it in MEK so as to be 30% by mass is used.

(3) Dispersing agent: manufactured by BYK-Chemie Japan; trade name: DISPERBYK102

(4) Photopolymerization initiator: manufactured by BASF; trade name: IRGACURE 184

The coating materials HC1 to HC14 for each of the hard coat layers used in Examples 1 to 9 and Comparative Examples 1 to 5 were prepared by mixing and stirring the compositions described in Table 1 using MEK. Further, the amount of cerium oxide described in Table 1 is a numerical value as a part by mass of the solid portion. In the case of actual use, it is used in the form of a dispersion (30% by mass) dispersed in MEK.

As the transparent substrate, the following were used. (1) PET film a: manufactured by Toyobo Co., Ltd., A4100, film thickness 100 μm, retardation 2500 nm. (2) PET film b: Polyethylene terephthalate was dissolved at 290 ° C, and extruded into a sheet shape by a film forming mold, followed by water cooling. Thereafter, it was adhered to a rotating quench drum and cooled to prepare an unstretched film. The unstretched film was preliminarily heated at 120 ° C for 1 minute using a biaxial stretching test apparatus (manufactured by Toyo Seiki Co., Ltd.), and then extended to a stretching ratio of 4.5 times at 120 ° C, and then 90 degrees with respect to the extending direction thereof. The direction extends to a magnification of 1.5 times. The obtained PET film b-based film had a thickness of 100 μm and a retardation of 9000 nm. Further, the delay was measured using KOBURA-WPR manufactured by Oji Scientific Instruments Co., Ltd.

(Example 1)

The coating liquid for coating hard coat layer HC1 having the composition described in Table 1 was applied onto the surface of one side of the PET film a by a bar coater, and dried, and then irradiated with ultraviolet rays of 300 mJ/cm ² to be hardened. This obtains the anti-glare laminate 1 . The number of microparticles N ₁ :N ₂ :N ₃ is 1:24355:13. The hardened hard coat layer had a thickness of 2.4 μm.

(Example 2)

The coating liquid for coating hard coat layer HC2 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 2. The number of microparticles N ₁ :N ₂ :N ₃ is 1:24391:12. The hardened hard coat layer had a thickness of 2.5 μm.

(Example 3)

The coating liquid for hard coat layer HC3 having the composition described in Table 1 was applied to the surface of one side of the PET film b by a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 3. The number of microparticles N ₁ :N ₂ :N ₃ is 1:23587:22. The hardened hard coat layer had a thickness of 2.4 μm.

(Example 4)

The coating liquid for hard coat layer HC4 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 4. The number of microparticles N ₁ :N ₂ :N ₃ is 1:240:6. The hardened hard coat layer had a thickness of 2.5 μm.

(Example 5)

The coating liquid for coating hard coat layer HC5 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 5. The number of microparticles N ₁ :N ₂ :N ₃ is 1:300:33. The hardened hard coat layer had a thickness of 2.6 μm.

(Example 6)

The coating liquid for hard coat layer HC6 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 6. The number of microparticles N ₁ :N ₂ :N ₃ is 1:41474:15. The hardened hard coat layer had a thickness of 2.3 μm.

(Example 7)

The coating liquid for hard coat layer HC7 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 7. The number of microparticles N ₁ :N ₂ :N ₃ is 1:43:11. The hardened hard coat layer had a thickness of 2.6 μm.

(Example 8)

The coating liquid for hard coat layer HC8 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 8. The number of microparticles N ₁ :N ₂ :N ₃ is 1:869:13. The hardened hard coat layer had a thickness of 2.3 μm.

(Example 9)

The coating liquid for hard coat layer HC9 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 9. The number of microparticles N ₁ :N ₂ :N ₃ is 1:842:13. The hardened hard coat layer had a thickness of 2.4 μm.

(Comparative Example 1)

The coating liquid for coating hard coating layer HC10 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 10. The number of microparticles N ₁ :N ₂ :N ₃ is 1:486:13. The hardened hard coat layer had a thickness of 2.7 μm.

(Comparative Example 2)

The coating liquid for hard coat layer HC11 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 11. The number of microparticles N ₁ :N ₂ :N ₃ is 1:125:0. The hardened hard coat layer had a thickness of 2.5 μm.

(Comparative Example 3)

The coating liquid for hard coat layer HC12 having the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 12. The number of microparticles N ₁ :N ₂ :N ₃ is 1:46:2. The hardened hard coat layer had a thickness of 2.4 μm.

(Comparative Example 4)

The coating liquid for coating hard coating layer HC13 of the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 13. The number of microparticles N ₁ :N ₂ :N ₃ is 1:86:6. The hardened hard coat layer had a thickness of 2.4 μm.

(Comparative Example 5)

The coating liquid for coating hard coat layer HC14 of the composition described in Table 1 was applied to the surface of one side of the PET film a using a bar coater, and thereafter, an antiglare layered body was obtained in the same manner as in Example 1. 14. The number of microparticles N ₁ :N ₂ :N ₃ is 1:12:10. The hardened hard coat layer had a thickness of 2.6 μm.

The following characteristics and effects were evaluated using the produced anti-glare laminates 1 to 14. The evaluation results are shown in Table 2.

(1) Skewness

The skewness is an index of the degree of skew of the symmetry between the mountain portion and the valley portion in the roughness curve of the surface of the hard coat layer, and is measured in accordance with JIS B0601-2001. The measuring apparatus was a VK-X100 manufactured by KEYENCE Corporation.

(2) Haze, full light transmittance

The haze and total light transmittance were measured using a haze meter NDH4000 manufactured by Electrochromic Co., Ltd.

(3) Glossiness

A gloss meter (GM-3D) manufactured by Murakami Color Technology Research Institute was used. A black plastic tape (Nitto plastic tape, PROSELF No. 21 (wide width)) was attached to the opposite side of the hard coat layer to measure the gloss of 60 degrees.

(4) glare

The glare was visually evaluated on a 264 (pixel/inch) liquid crystal display. If it is good, it is set to "○ mark", and if it is good, it is set to "○ mark", and if it is bad, it is set to "x mark".

(5) Anti-glare

The light of the fluorescent lamp was reflected in the state in which the anti-glare laminated body was attached to the black plastic plate via the adhesive, and the light diffusion of the anti-glare laminated body was visually evaluated. If it is good, it is set to "○ mark", and if it is good, it is set to "○ mark", and if it is bad, it is set to "x mark".

(6) Rainbow

(a) The anti-glare laminate was bonded to a black acrylic plate via a transparent adhesive, and visually confirmed to interfere with the grain. (b) The anti-glare laminate was inserted between the polarizing plates in the orthogonally polarized state, and the rainbow pattern was visually confirmed. (a), (b) The case where no rainbow pattern is seen is set to "◎ mark", (a) no rainbow pattern is seen, but (b) the case where rainbow pattern is seen is set to "○ mark", (a) (b) The case where the rainbow pattern can be confirmed is "× mark".

(7) whitish

The anti-glare laminated body is placed at a position of 0.5 m from the observer, and the liquid crystal display placed at a position of 1 m from the observer is observed, and the contrast of the image displayed on the liquid crystal display is set to "○ mark", and the screen is displayed. It seems that the whitish situation is set to "× mark".

As can be seen from Table 2, the anti-glare laminated body 1 to the anti-glare laminated body 9 of Examples 1 to 9 are all excellent in anti-glare property, anti-glare property, and are less likely to cause rainbow or whitening. In Example 3, since the retardation of the transparent substrate was as high as 9000, the suppression effect of the rainbow pattern was particularly excellent. In the eighth embodiment, since the degree of skew is small, the anti-glare property and the glare are better grades than the other embodiments. On the other hand, in the embodiment 9, since the skewness is large, the glare is a better level than the other embodiments.

In Comparative Example 1, the average particle diameter A of the fine particles having the largest average particle diameter exceeded 5 μm, which was inferior in glare. In Comparative Example 2, there was no average particle diameter Cm of fine particles having an average particle diameter between A and B, which was inferior in glare. In Comparative Example 3, the average particle diameter C1 of the fine particles having an average particle diameter between A and B exceeded (0.5 × A) = 1 μm, which was inferior in glare. In Comparative Example 4, the average particle diameter C1 of the fine particles having an average particle diameter between A and B was less than (2 × B) = 0.4 μm, which was inferior in glare. In Comparative Example 5, the average particle diameter B of the fine particles having the smallest average particle diameter exceeded 0.3 μm, which was inferior in terms of glare and blushing.

Claims (10)

An anti-glare laminate comprising a transparent substrate and a hard coat layer provided on at least one of the outermost layers of the transparent substrate, wherein the hard coat layer contains a curable resin and a fine particle component, and comprises The fine particle component has irregularities on the surface, and the fine particle component has at least three peaks in the particle diameter distribution, and among the at least three peaks, the average particle diameter of the fine particles having the particle diameter in the first peak region is set. The average particle diameter of the fine particles having the particle diameter of the second peak region smaller than A is B (μm), and the particle diameter belongs to the third peak region including m peaks smaller than A and larger than B. When the average particle diameter of the fine particles is Cm (μm), the following formula is satisfied: 1≦A≦5, 0.001≦B≦0.3, (2×B)≦Cm≦(0.5×A), where m is An integer greater than one. The anti-glare laminate according to claim 1, wherein the hard coat layer has a skewness of 1.0 to 4.0. The anti-glare layer body of claim 1 or 2 has a haze of 2 to 10% and a total light transmittance of 88% or more. The anti-glare laminate according to any one of claims 1 to 3, which has a gloss of 60 to 90%. The anti-glare laminate according to any one of claims 1 to 4, wherein the transparent substrate has a retardation of from 3,000 to 30,000. The anti-glare laminate according to any one of claims 1 to 5, wherein the number of the fine particles having the particle diameter belonging to the first peak region is N ₁ and the particle diameter is the second peak region smaller than A. When the number of the fine particles is N ₂ and the number of the fine particles belonging to the third peak region including the m peaks smaller than A and larger than B is N ₃ , N ₁ : N ₂ : N ₃ =1 is satisfied: 30:5~1:50000:100 ratio. A display device comprising the anti-glare laminate of any one of claims 1 to 6. A curable resin composition for forming an anti-glare hard coat layer, wherein the curable resin composition contains a curable resin and a fine particle component, and the fine particle component has at least three or more particle size distributions The peak value of the above-mentioned at least three or more peaks, the average particle diameter of the fine particles having the particle diameter belonging to the first peak region is A (μm), and the average particle diameter of the fine particles having the particle diameter belonging to the second peak region smaller than A When B (μm) is used and the average particle diameter of the fine particles having the third peak region including the m peaks smaller than A and larger than B is Cm (μm), the following formula is satisfied: 1≦A≦ 5, 0.01 ≦ B ≦ 0.3, (2 × B) ≦ Cm ≦ (0.5 × A), where m is an integer of 1 or more. The curable resin composition of claim 8, wherein the number of the fine particles having the particle diameter belonging to the first peak region is N ₁ and the number of the fine particles having the particle diameter of the second peak region smaller than A is set. N ₂ , when the number of the particles having the third peak region including the m peaks smaller than A and greater than B is N ₃ , satisfying N ₁ :N ₂ :N ₃ =1:30:5~1 :50000:100 ratio. A coating film obtained by hardening a curable resin composition of claim 8 or 9.