WO2016030738A1

WO2016030738A1 - Anti-glare laminate

Info

Publication number: WO2016030738A1
Application number: PCT/IB2015/001433
Authority: WO
Inventors: 賢大久保; 誠司瀬口
Original assignee: 王子ホールディングス株式会社
Priority date: 2014-08-26
Filing date: 2015-08-25
Publication date: 2016-03-03
Also published as: TW201614275A; TWI647487B; JPWO2016030738A1

Abstract

The present invention provides an anti-glare laminate having excellent anti-glare properties and glare-preventing properties, a display device provided with the anti-glare laminate, a curable resin composition for same, and a coating film. More specifically, the present invention provides an anti-glare laminate comprising a transparent substrate and a hard-coat layer that is provided on the outermost layer on at least one side of the transparent substrate, the hard-coat layer comprising a curable resin and microparticle components and having an uneven surface due to the inclusion of the microparticle components, the microparticle components having at least three peaks in the particle size distribution thereof, and for the three or more peaks, when the average particle size of the microparticles for which the particle size belongs to the first peak area is A (μm), the average particle size of the microparticles for which the particle size belongs to the second peak area is B (μm), and the average particle size of the microparticles for which the particle size is smaller than A but bigger than B and belongs to the third peak area comprising m peaks is Cm (μm), the following formula is satisfied. 1≤A≤5, 0.001≤B≤0.3, (2XB)≤Cm≤(0.5XA), wherein m is an integer of at least 1.

Description

Antiglare laminate

The present invention relates to an antiglare laminate.
This application claims the priority based on Japanese Patent Application No. 2014-171385 for which it applied on August 26, 2014, and uses the content here.

Liquid crystal display devices are widely used for flat panel displays such as personal computers, mobile phones, and portable game devices. In such a liquid crystal display device, an antiglare film may be attached to the surface in order to prevent a decrease in visibility due to light reflected from the outside.

As an antiglare film, a film that scatters reflection of light by providing an uneven structure on the surface is known. For example, in Patent Document 1, a hard coat layer mainly composed of 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 is formed on a transparent substrate film. An antiglare film is disclosed. 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, in small-sized mobile terminals such as smartphones, the resolution with respect to the screen size has increased, and high-definition liquid crystal display devices of 200 ppi or more are being adopted. Note that ppi is pixel / inch and means the number of pixels per inch.

In a high-definition liquid crystal display device, since the size of each pixel is small, a so-called glare phenomenon is likely to occur. The glare phenomenon is a phenomenon that occurs when an anti-glare film with a concavo-convex layer is attached to the surface of a liquid crystal display device, because the pixels of the liquid crystal are enlarged by the lens effect. Say.

Japanese Laid-Open Patent Publication No. 11-286083 Japanese Unexamined Patent Publication No. 2014-59334

The antiglare film disclosed in Patent Document 1 is provided with a hard coat layer containing two types of particles, large and small. Such an anti-glare film is effective for anti-glare properties, but cannot be said to be effective for glare generated in a high-definition liquid crystal display device.

The optical film disclosed in Patent Document 2 is provided with an antiglare layer containing two kinds of particles, organic fine particles and inorganic fine particles. Such an optical film is effective for anti-glare properties, azimuth blur, and interference fringes, but cannot be said to be effective for glare generated in a high-definition liquid crystal display device.

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

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

(1) An antiglare laminate having a transparent substrate and a hard coat layer provided on at least one outermost layer thereof,
The hard coat layer contains a curable resin and a fine particle component, and has irregularities on the surface by containing the fine particle component,
The fine particle component has at least three or more peaks in the particle size distribution,
Of the at least three or more peaks, the average particle size of the fine particles belonging to the first peak region is A (μm), and the average particle size of the fine particles belonging to the second peak region having a particle size smaller than A is B ( μm), and when the average particle diameter of fine particles belonging to the third peak region including m peaks smaller than A and larger than B is Cm (μm), the following equation is satisfied: An antiglare laminate.
1 ≦ A ≦ 5,
0.001 ≦ B ≦ 0.3,
(2 × B) ≦ Cm ≦ (0.5 × A),
Here, m is an integer of 1 or more.

(2) The antiglare laminate as described in (1) above, wherein the skewness of the hard coat layer is 1.0 to 4.0.

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

(5) The antiglare laminate according to any one of (1) to (4), wherein the retardation of the transparent substrate is 3,000 to 30,000.

(6) the number of particles belonging to the particles first peak region and N _1, the number of fine particles that the particle diameter belonging to A is less than the second peak region and N _2, the particle diameter is smaller than A B When the number of fine particles belonging to the third peak region including m larger peaks is N ₃ , the ratio of N ₁ : N ₂ : N ₃ = 1: 30: 5 to 1: 50,000: 100 is set. 6. The antiglare laminate according to any one of (1) to (5), wherein the antiglare laminate is satisfied.

(7) A display device comprising the antiglare laminate according to any one of (1) to (6).

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

(9) than said first number of particles belonging to the peak area as N _1, the number of fine particles that the particle diameter belonging to A is less than the second peak region and N _2, the particle diameter is smaller than A B Satisfying the ratio of N ₁ : N ₂ : N ₃ = 1: 30: 5 to 1: 50,000: 100, where N ₃ is the number of fine particles belonging to the third peak region including large m peaks The curable resin composition as described in (8) above, wherein

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

The display device provided with the antiglare laminate of the present invention and the antiglare laminate is excellent in antiglare properties and glare prevention. Moreover, the curable resin composition and coating film of the present invention can provide a hard coat layer of an antiglare laminate excellent in antiglare property and glare prevention.

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

This embodiment is useful in a high-definition display device. The high-definition display device in this embodiment refers to a display device of 200 ppi or more. Furthermore, it is more preferable that it is a display apparatus of 250 ppi or more.

(Configuration of antiglare laminate)
The antiglare laminate of the present embodiment has a transparent substrate and a hard coat layer provided on the outermost layer on at least one side thereof. In addition to the transparent substrate and the hard coat layer, other layers such as an anchor layer, a refractive index adjusting layer, and a protective layer may be laminated between the transparent substrate and the hard coat layer as necessary.

The hard coat layer may be formed on the outermost layer on the front side (external world side) of the transparent base material, or may be formed on the outermost layer on the back side (anti-external side) of the transparent base material. It may be formed in the outermost layer.

(Transparent substrate)
A transparent base material becomes a transparent base material which forms a hard-coat layer. The material for forming the transparent substrate is preferably a material excellent in optical transparency, mechanical strength, solvent resistance, and the like. The transparent substrate may be an organic material or an inorganic material.

Examples of organic materials include polypropylene resins, polyethylene resins, cyclic polyolefin resins, polyamide resins, polyester resins, polyacrylic resins, polyvinyl chloride resins, nylon resins, urethane resins, and triacetyl cellulose. Cellulosic resins such as Among these, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polypropylene naphthalate, polytrimethylene terephthalate, and polybutylene terephthalate are preferable. Furthermore, it is more preferable to use polyethylene terephthalate from the viewpoints of transparency, weather resistance, solvent resistance, rigidity, and cost. The organic material may be used by mixing or laminating two or more kinds of organic materials.

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

The transparent base material may contain various additives. Examples of the additive include an antioxidant, a heat stabilizer, an ultraviolet absorber, a pigment, a dye, an antistatic agent, a nucleating agent, and a coupling agent.

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 corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, and surface oxidation treatment such as ozone / ultraviolet irradiation treatment.

The thickness of the transparent substrate is preferably 1 to 1,000 μm, more preferably 5 to 500 μm, and more preferably 50 to 250 μm from the viewpoints of ensuring mechanical strength, curling prevention, workability, and the like. It is more preferable.

The transparent substrate preferably has a retardation of 3,000 to 30,000 for the reason of reducing the rainbow pattern described later. The retardation is more preferably 5,000 to 25,000.

(Hard coat layer)
The hard coat layer is provided on the outermost layer on at least one side of the transparent substrate, 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 and scratch resistance can be imparted. Furthermore, the hard coat layer can impart antifouling properties, finger slipping properties, water repellency, and the like to sebum and cosmetics on the surface of the transparent substrate.

The curable resin may be a thermosetting type or an active energy ray curable type. In order to suppress the occurrence of curling during production as much as possible, the active energy ray curable type is preferable. Active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, visible rays, and γ rays.

Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, and the like.

Examples of the active energy ray-curable resin include acrylic curable resins and urethane curable resins. Moreover, as an active energy ray, an ultraviolet ray is preferable from the viewpoint of easy handling and processing.

The active energy ray-curable acrylic curable resin is a polymer of a curable composition comprising a monomer or oligomer having an acrylic polymerizable unsaturated group. Monomers and oligomers having an acrylic polymerizable unsaturated group include monofunctional and polyfunctional ones.

Specific examples of the monofunctional monomer having an acrylic polymerizable unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meta ) N-undecyl acrylate, n-dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylate Le methoxyethyl acrylate, ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) (meth) acrylic acid esters of benzyl acrylate and the like. These may be used individually by 1 type and may use 2 or more types together.

Specific examples of the monofunctional oligomer having an acrylic polymerizable unsaturated group include ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate, and the like.

In order for a composition comprising a monomer or oligomer having an acrylic polymerizable unsaturated group to be curable, a polyfunctional (meth) acrylic ester is used as the monomer or oligomer having an acrylic polymerizable unsaturated group. It is preferable to contain. Examples of polyfunctional (meth) acrylic acid esters include dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. , Bifunctional (meth) acrylates such as propylene oxide modified neopentyl glycol di (meth) acrylate, modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, polyether tri (meth) acrylate , Trifunctional (meth) acrylates such as glycerin propoxytri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propionic acid modified dipentaerythritol Examples include tetra- or higher functional (meth) acrylates such as penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These polyfunctional acrylates may be used individually by 1 type, and can also be used in combination of 2 or more type.
In order to ensure the hardness as the hard coat layer, it is preferable to use a tetrafunctional or higher (meth) acrylic ester.

The active energy ray-curable urethane-based curable resin is a polymer of urethane acrylate monomer or oligomer. As a urethane acrylate oligomer, a polyoxyalkylene segment and / or a saturated polyester segment are linked via a urethane bond, and acryloyl groups are present at both ends.

In order to obtain a thermosetting or active energy ray-curable acrylic curable resin, a polymerization initiator is added to the monomer or oligomer having the polymerizable unsaturated group, and the thermosetting or active energy ray curing is performed. It is necessary to make the composition of the nature.

As the thermal polymerization initiator, known ones can be used. Examples thereof include peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide. The addition amount of the thermal polymerization initiator is preferably 1 to 10% by mass relative to the monomer or oligomer having a polymerizable unsaturated group.

Also, 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, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 -One, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, propi Phenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, and the like. One of these active energy ray polymerization initiators may be used alone, or two or more thereof may be used in combination. The addition amount of the active energy ray polymerization initiator is preferably 1 to 10% by mass relative to the monomer or oligomer having a polymerizable unsaturated group.

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

The hard coat layer may contain a flexible component as necessary. When the flexible component is contained, generation of cracks during processing can be prevented. As the flexible component, (meth) acrylates having one or more polymerizable unsaturated groups in the molecule are preferable. Examples of (meth) acrylates include tricyclodecanemethylol di (meth) acrylate, ethylene oxide modified di (meth) acrylate of bisphenol F, ethylene oxide modified di (meth) acrylate of bisphenol A, and ethylene oxide modified of isocyanuric acid. Bifunctional (meth) acrylates such as di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide modified tri (meth) acrylate of trimethylpropane , Trifunctional (meth) acrylates such as ethylene oxide modified tri (meth) acrylate of trimethylpropane, urethane (meth) acrylate, polyester (meth ) Acrylates, polyether (meth) acrylate. In particular, trifunctional (meth) acrylate and urethane (meth) acrylate are more preferable. These (meth) acrylates can be used singly or in combination of two or more.

In addition, the hard coat layer may contain components other than those described above as long as the effects of the present embodiment are not impaired. Components that can be added to the hard coat layer include, for example, a dispersant, a flexible component, an antibacterial agent, a fluorine antifouling agent, a fluorine lubricant or a silicone lubricant, a leveling agent, an antistatic agent, an ultraviolet absorber, and a heat stabilizer. Agents, antioxidants and the like. The dispersant includes those used to uniformly disperse fine particles described later in the coating liquid for forming the hard coat layer.

The thickness of the hard coat layer is preferably 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, and most preferably from 1.0 to 3.5 μm.

(Fine particles)
The fine particle component contained in the hard coat layer has at least three or more peaks in the particle size distribution. In the particle size distribution, the peak is the particle size when the number of particles reaches a maximum value in a chart in which the horizontal axis represents the particle size and the vertical axis represents the number of particles.

The present inventors use a fine particle component having at least three or more peaks in the particle size distribution as the fine particle component contained in the hard coat layer, and when the particle diameter of each peak is in a specific numerical range, It has been found that the randomness of the concavo-convex structure on the surface of the hard coat layer can be appropriately controlled, and it is possible to achieve both the antiglare property and the glare prevention of the antiglare laminate.

That is, the fine particle component has at least three or more peaks in the particle size distribution, and among the at least three or more peaks, the average particle diameter of the fine particles belonging to the first peak region is A (μm). And the average particle diameter of the fine particles belonging to the second peak area is B (μm), and the average particle diameter of the fine particles belonging to the third peak area including m peaks whose particle diameter is smaller than A and larger than B is When the diameter is Cm (μm), it is necessary to satisfy the following formula.
1 ≦ A ≦ 5,
0.001 ≦ B ≦ 0.3,
(2 × B) ≦ Cm ≦ (0.5 × A),
Here, m is an integer of 1 or more.

The particle size distribution of the fine particles is measured by the following method.
Using a transmission electron microscope, the surface layer of the hard coat layer is photographed to obtain a particle image. The maximum length (Dmax: maximum length at two points on the contour of the particle image) and the maximum vertical length (DV-max: two lines when the particle image is sandwiched between two straight lines parallel to the maximum length) ) Is measured, and the geometric mean value (Dmax × DV-max) ^1/2 is defined as the particle diameter. By this method, the particle size distribution can be approximately obtained from 100 measured values. In order to investigate the particle size distribution more accurately, it is preferable to measure the particle size of as many fine particles as possible.

Here, the peak area is a particle size distribution chart in which the vertical axis represents the number of fine particles and the horizontal axis represents the particle diameter of the fine particles, and one peak in the particle size distribution (the point where the number of fine particles protrudes) is horizontal. It means a certain region in the horizontal axis direction where fine particles exist as the center in the axial direction. The peak area is a term that should be interpreted according to common general technical knowledge. The peak area is, for example, from a minimum value (first minimum value) closest to the peak having a particle diameter smaller than the peak with a certain peak in the particle size distribution as the center in the horizontal axis direction. The particle diameter is larger and the curve from the peak to the nearest minimum value (second minimum value), the horizontal axis of the particle size distribution diagram, the vertical axis with the first minimum value as a constant, It can be regarded as a region surrounded by a vertical axis having the second minimum value as a constant. In the particle size distribution chart, when the distance or region from the maximum value to the minimum value is not clear, for example, one maximum value and an inflection point on the way from the maximum value to the minimum value. Twice the distance can be used as an approximate value of the distance from the maximum value to the minimum value.

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

When the number of peaks having a particle diameter smaller than A and larger than B is one, the average particle diameter of fine particles belonging to the peak region is defined as C1 (μm). When the number of peaks having a particle diameter smaller than A and larger than B is two, the average particle diameters of the fine particles belonging to those peak regions are C1 (μm) and C2 (μm), respectively. Similarly, as the number of peaks whose particle diameter is smaller than A and larger than B, that is, m increases to 3, 4, etc., the average particle diameters of the fine particles belonging to those peak regions are respectively set to C3 (μm) and C4 ( μm) etc.
Here, the average particle diameter of peaks having a particle diameter smaller than A and larger than B is collectively expressed as Cm (μm).

The average particle diameter A (μm) of the fine particles whose particle diameter belongs to the first peak region is 1 ≦ A ≦ 5. Such fine particles are exclusively involved in imparting antiglare properties to the hard coat layer.
The average particle diameter B (μm) of the fine particles belonging to the second peak region having a particle diameter smaller than A is 0.001 ≦ B ≦ 0.3. Such fine particles are exclusively involved in suppressing glare.
The average particle diameter Cm (μm) of the fine particles belonging to the third peak region including m peaks smaller than A and larger than B is (2 × B) ≦ Cm ≦ (0.5 × A). It is. Such fine particles are exclusively involved in suppressing glare.

Furthermore, in the particle size distribution, the fine particle component has N _{1 as} the number of fine particles belonging to the first peak region, and N _{2 as} the number of fine particles belonging to the second peak region whose particle size is smaller than A. N ₁ : N ₂ : N ₃ = 1: 30: 5 to 1:50 where N ₃ is the number of fine particles belonging to the third peak region including m peaks smaller than A and larger than B. It is preferable to satisfy a ratio of 1,000,100. When the relative number of fine particles belonging to three or more kinds of peak regions is within the range of this ratio, it becomes possible to improve the antiglare property and glare prevention of the antiglare laminate at a higher level. . It is more preferable to satisfy the ratio of N ₁ : N ₂ : N ₃ = 1: 1,000: 5 to 1: 50,000: 50. More preferably, the ratio of N ₁ : N ₂ : N ₃ = 1: 1,000: 5 to 1: 30,000: 50 is satisfied.
The number of fine particles belonging to the peak region can be measured together with the particle size distribution of the fine particles by the method using the 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 silicon dioxide, titanium dioxide, zirconium oxide, and aluminum oxide can be used, and those having high hardness are preferable.
As the organic fine particles, for example, resin particles such as acrylic resin, polystyrene, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, cellulose acetate, polycarbonate, and polyamide can be used.

Further, the surface of the fine particles may be surface-treated for the purpose of uniformly dispersing the fine particles in the hard coat layer. Examples of the surface treatment method include methods such as imparting a functional group such as a hydroxyl group and a carboxylic acid in addition to imparting a surfactant.

The content of the fine particles in the hard coat layer depends on the thickness of the hard coat layer, but from the viewpoint of glare and antiglare properties, the total content is preferably 10 to 500% by mass, and 50 to 300% by mass. It is more preferable that

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, and more preferably 0.01 or less.

When the average particle diameters A, B, and Cm of the fine particles satisfy the above formula, it is effective not only for preventing glare and glare, but also for preventing rainbow patterns and whiteness.

The rainbow pattern is an interference pattern that appears due to a 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, it is possible to mitigate the expression of interference patterns.

WHITE is a phenomenon that appears whitish when the transmitted light of the antiglare laminate is viewed. Unlike the antiglare property, which is evaluated by the diffused state of reflected light, it is evaluated by the diffused state of transmitted light. Whitiness can be reduced by appropriately controlling the degree of unevenness on the surface of the hard coat layer.

(Characteristics of antiglare laminate)
In the antiglare laminate of the present embodiment, it is preferable that the skewness of the hard coat layer is 1.0 to 4.0. At this time, in the antiglare property and glare prevention, it becomes a thing of the more superior performance.
Here, the skewness is an index of the degree of uneven unevenness of the hard coat layer surface. It is measured according to JIS B0601-2001. This represents the degree of symmetry deviation of the height distribution with the average plane as the center. When the skewness is 0, it indicates that the height distribution of the surface irregularities is symmetric with respect to the average line. When the skewness is a positive numerical value, the height distribution is biased downward with respect to the average surface, indicating that the unevenness tends to be sharp.

In the antiglare laminate of this embodiment, the haze is preferably 2 to 10%, and more preferably 4 to 8%. By setting the haze in the range of 2 to 10%, the antiglare level can be made more effective.
The haze is an index related to the transparency of the laminate and is also referred to as haze. This is the ratio of diffuse transmitted light to total light transmitted. In general, when haze increases, it appears whitish and blurry. It can be controlled by appropriately changing the degree of unevenness on the surface of the hard coat layer.

In the antiglare laminate of this 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.

In the antiglare laminate of the present embodiment, the gloss is preferably 60 to 90%, and more preferably 60 to 80%. By making the glossiness in the range of 60 to 90%, the antiglare property can be further improved. Here, the glossiness is evaluated as a 60-degree specular reflectance.

(Production method)
In the antiglare laminate of this embodiment, a curable resin composition for forming an antiglare hard coat layer is applied on a transparent substrate, and then the hard coat layer is dried, and then the hard coat layer Can be cured to form a hard coat layer coating. That is, the hard coat layer of the antiglare laminate of this embodiment is a coating film obtained by curing a curable resin composition. The manufacturing process can also be performed continuously in a roll-to-roll manner.

The curable resin composition of this embodiment contains a curable resin and a fine particle component, and the fine particle component has at least three or more peaks in the particle size distribution, and among the at least three or more peaks. The average particle diameter of the fine particles belonging to the first peak area whose particle diameter is A (μm), the average particle diameter of the fine particles belonging to the second peak area whose particle diameter is smaller than A is B (μm), and the particle diameter A curable resin composition satisfying the following formula when the average particle diameter of the fine particles belonging to the third peak region including m peaks smaller than A and larger than B is Cm (μm), respectively. It is a thing.
1 ≦ A ≦ 5,
0.001 ≦ B ≦ 0.3,
(2 × B) ≦ Cm ≦ (0.5 × A),
Here, m is an integer of 1 or more.

Further, in the curable resin composition of the present embodiment, the number of fine particles belonging to the first peak region where the particle size belongs to N ₁ and the number of fine particles belonging to the second peak region where the particle size is smaller than A is defined as N _1. When N ₂ and the number of fine particles belonging to the third peak region including m peaks smaller than A and larger than B are N ₃ , N ₁ : N ₂ : N ₃ = 1: 30: It is preferable to satisfy a ratio of 5 to 1: 50,000: 100. It is more preferable to satisfy the ratio of N ₁ : N ₂ : N ₃ = 1: 1,000: 5 to 1: 50,000: 50. More preferably, the ratio of N ₁ : N ₂ : N ₃ = 1: 1,000: 5 to 1: 30,000: 50 is satisfied.

Since the above description of the curable resin composition of the present embodiment is as described above, the description thereof is omitted.

In order for the fine particle component contained in the curable resin composition of the present embodiment to have at least three or more peaks having a predetermined average particle size satisfying the above formula in the particle size distribution, an average It can be obtained by adding three or more kinds of fine particles having a particle diameter (μm) in the numerical ranges of A, B, and Cm to the curable resin composition at a predetermined blending ratio.
That is, the fine particle component contained in the curable resin composition can have the above-mentioned particle size distribution of the fine particle component by adding three or more kinds of fine particles having different average particle sizes at an appropriate blending ratio. .
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.

Examples of the solvent for the curable resin composition include 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 are used. These may be used alone or in combination of two or more.

Examples of the coating method of the curable resin composition include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and a printing machine. The method used is mentioned.

The coating film is dried by heating the transparent substrate having the coating film. Usually, the heating is performed under conditions of a heating temperature of 60 to 100 ° C. and a heating time of 1 to 5 minutes. Drying is performed by a heat dryer or a vacuum dryer.

Next, the uncured coating film is cured. When the uncured coating film contains a thermosetting resin, it is heated and cured using a heating furnace or an infrared lamp. When the uncured coating film contains an active energy ray-curable resin, it is cured by irradiation with active energy rays.
As the active energy ray, ultraviolet rays are preferable from the viewpoint of versatility. As the ultraviolet light source, 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.
Curing by irradiation with active energy rays is preferably performed in an environment filled with an inert gas such as nitrogen. The curing process may be performed in two stages, a preliminary curing process and a main curing process.

The antiglare laminate of the present embodiment enables both antiglare properties and glare prevention in a display device including the laminate. In particular, in a high-definition liquid crystal display device of 200 to 400 ppi, and further 250 to 400 ppi, the characteristics can be further exhibited.

This embodiment will be described more specifically with reference to the following examples.

The following materials were used as the coating liquid for the hard coat layer.
(1) Acrylic resin: acrylic UV curable resin, manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate DPE-6A, solid content 100%
(2) Silica fine particles (i) A solution in which silica fine particles having an average particle size of 0.01 μm are dispersed in MEK (methyl ethyl ketone) at 30% by mass (trade name: Organosilica sol, manufactured by Nissan Chemical Co., Ltd.)
(Ii) A solution in which silica fine particles having an average particle diameter of 0.1 μm are dispersed in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd., trade name: organosilica sol)
(Iii) Solution in which silica fine particles having an average particle size of 0.2 μm are dispersed in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd., trade name: organosilica sol)
(Iv) A solution in which silica fine particles having an average particle size of 0.3 μm are dispersed in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd., trade name: organosilica sol)
(V) Solution in which silica fine particles having an average particle size of 0.5 μm are dispersed in MEK at 30% by mass (product name: organosilica sol, manufactured by Nissan Chemical Industries, Ltd.)
(Vi) A solution in which silica fine particles having an average particle diameter of 0.8 μm are dispersed in MEK at 30% by mass (manufactured by Nissan Chemical Co., Ltd., trade name: organosilica sol)
(Vii) Silica fine particles having an average particle diameter of 1 μm (manufactured by Nippon Shokubai Co., Ltd., trade name: Seahoster)
(Viii) Silica fine particles having an average particle diameter of 2 μm (manufactured by Nippon Shokubai Co., Ltd., trade name: Seahoster)
(Ix) Silica fine particles having an average particle diameter of 4 μm (manufactured by Corefront Corporation, trade name: sicastar)
(X) Silica fine particles having an average particle diameter of 10 μm (manufactured by Corefront Corporation, trade name: sicastar)
For silica fine particles (vii) to (x), a solution dispersed in MEK so as to be 30% by mass was used.
(3) Dispersant: manufactured by Big Chemie Japan, trade name: DISPERBYK102
(4) Photopolymerization initiator: manufactured by BASF, trade name: IRGACURE184

Using the above materials, using MEK as a solvent, mixing and stirring with the compositions shown in Table 1, and then coating liquid HC1 for each hard coat layer used in Examples 1 to 9 and Comparative Examples 1 to 5 ~ HC14 was produced. In addition, the quantity of the silica described in Table 1 is a numerical value of the mass part as solid content. When actually used, it is used as a dispersion (30% by mass) dispersed in MEK.

The following were used as the transparent substrate.
(1) PET film a: manufactured by Toyobo Co., Ltd., A4100, film thickness 100 μm, retardation was 2,500 nm.
(2) PET film b: Polyethylene terephthalate was dissolved at 290 ° C., extruded through a film-forming die into a sheet, and then cooled with water. Then, it was made to contact | adhere on the rotating quenching drum, it cooled, and the unstretched film was produced. This unstretched film is preheated at 120 ° C. for 1 minute using a biaxial stretching test apparatus (manufactured by Toyo Seiki Co., Ltd.), and then stretched at 120 ° C. to a stretch ratio of 4.5 times. The film was stretched at a stretching ratio of 1.5 times in the direction of 90 degrees. The obtained PET film b had a film thickness of 100 μm and a retardation of 9,000 nm.
In addition, retardation was measured using Oji Scientific Instruments company make, KOBURA-WPR.

(Example 1)
By applying the coating liquid HC1 for the hard coat layer having the composition shown in Table 1 to the surface of one side of the PET film a using a bar coater, drying, and then irradiating with 300 mJ / cm ² of ultraviolet rays and curing. The antiglare laminate 1 was obtained. The number of fine particles, N ₁ : N ₂ : N ₃ , was 1:24, 355: 13. The thickness of the hard coat layer after curing was 2.4 μm.

(Example 2)
After applying the coating liquid HC2 for hard coat layer having the composition described in Table 1 to the surface on one side of the PET film a using a bar coater, the antiglare laminate 2 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N ₃ , was 1:24, 391: 12. The thickness of the hard coat layer after curing was 2.5 μm.

(Example 3)
After applying the hard coat layer coating solution HC3 having the composition shown in Table 1 to the surface of one side of the PET film b using a bar coater, the antiglare laminate 3 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N ₃ was 1:23, 587: 22. The thickness of the hard coat layer after curing was 2.4 μm.

Example 4
After applying the coating liquid HC4 for hard coat layer having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 4 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N _3, was 1: 240: 6. The thickness of the hard coat layer after curing was 2.5 μm.

(Example 5)
After applying the hard coat layer coating liquid HC5 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 5 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N _3, was 1: 300: 33. The thickness of the hard coat layer after curing was 2.6 μm.

(Example 6)
After applying the hard coat layer coating liquid HC6 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 6 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N ₃ was 1:41, 474: 15. The thickness of the hard coat layer after curing was 2.3 μm.

(Example 7)
After applying the hard coat layer coating solution HC7 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 7 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N ₃ , was 1:43:11. The thickness of the hard coat layer after curing was 2.6 μm.

(Example 8)
After applying the coating liquid HC8 for hard coat layer having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 8 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N _3, was 1: 869: 13. The thickness of the hard coat layer after curing was 2.3 μm.

Example 9
After applying the coating liquid HC9 for hard coat layer having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 9 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N _3, was 1: 842: 13. The thickness of the hard coat layer after curing was 2.4 μm.

(Comparative Example 1)
After applying the hard coat layer coating solution HC10 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 10 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N _3, was 1: 486: 13. The thickness of the hard coat layer after curing was 2.7 μm.

(Comparative Example 2)
After applying the hard coat layer coating solution HC11 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 11 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N _3, was 1: 125: 0. The thickness of the hard coat layer after curing was 2.5 μm.

(Comparative Example 3)
After applying the hard coat layer coating solution HC12 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 12 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N _3, was 1: 46: 2. The thickness of the hard coat layer after curing was 2.4 μm.

(Comparative Example 4)
After applying the hard coat layer coating solution HC13 having the composition shown in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 13 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N _3, was 1: 86: 6. The thickness of the hard coat layer after curing was 2.4 μm.

(Comparative Example 5)
After applying the hard coat layer coating solution HC14 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 14 was obtained in the same manner as in Example 1. . The number of fine particles, N ₁ : N ₂ : N ₃ , was 1:12:10. The thickness of the hard coat layer after curing was 2.6 μm.

The following properties and effects were evaluated using the produced antiglare laminates 1 to 14. The evaluation results are shown in Table 2.

(1) Skewness In the roughness curve of the irregularities on the surface of the hard coat layer, it is an index of the degree of symmetry deviation between the peaks and valleys, and was measured according to JIS B0601-2001. As a measuring device, VK-X100 manufactured by Keyence Corporation was used.

(2) Haze and total light transmittance Haze and total light transmittance were measured using a haze meter NDH4000 manufactured by Denshoku Co., Ltd.

(3) Glossiness A gloss meter (GM-3D) manufactured by Murakami Color Research Laboratory was used. A black vinyl tape (Nitto vinyl tape, PROSELF No. 21 (wide)) was applied to the opposite surface of the hard coat layer, and the 60 ° gloss was measured.

(4) Glitter The image was installed on a liquid crystal display of 264 (pixel / inch), and the glare was visually evaluated. When it was good, it was marked with “◎”, when it was slightly good, it was marked with “◯”, and when it was poor, it was marked with “x”.

(5) Antiglare property With the antiglare laminate adhered to a black plastic plate via an adhesive, a fluorescent lamp was reflected, and the light diffusion state of the antiglare laminate was visually evaluated. When it was good, it was marked with “◎”, when it was slightly good, it was marked with “◯”, and when it was poor, it was marked with “x”.

(6) Rainbow pattern (a) The antiglare laminate is bonded to a black acrylic plate via a transparent adhesive, and the interference pattern is visually confirmed.
(B) The antiglare laminate is inserted between polarizing plates in a crossed Nicol state, and a rainbow pattern is visually confirmed.
If a rainbow pattern is not seen in both (a) and (b),
In (a), no rainbow pattern is seen, but in (b), it is “○”
When a rainbow pattern could be confirmed in both (a) and (b), it was marked “x”.

(7) Whitish The anti-glare laminate is installed at a position of 0.5m from the observer, and the liquid crystal display installed at the position of 1m from the observer is observed, and the contrast of the image displayed on the liquid crystal display is When it was good, it was marked with “○”, and when the screen appeared white, it was marked with “×”.

As can be seen from Table 2, the antiglare laminate 1 to the antiglare laminate 9 of Examples 1 to 9 all have good antiglare and antiglare properties, such as rainbow patterns and whitening. It was hard to produce a gap. In Example 3, since the retardation of the transparent substrate was as high as 9,000, the effect of suppressing the rainbow pattern was particularly excellent. In Example 8, since the skewness was small, the antiglare property and the glare were slightly better than those in the other examples. On the other hand, in Example 9, since the skewness was large, the glare was slightly better than in the other examples.

In Comparative Example 1, the average particle diameter A of the fine particles having the maximum average particle diameter exceeded 5 μm, which was inferior to glare. In Comparative Example 2, the average particle diameter Cm of the fine particles having an average particle diameter between A and B does not exist, and the glare is inferior. 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 to glare. In Comparative Example 4, the average particle size C1 of the fine particles having an average particle size between A and B was less than (2 × B) = 0.4 μm, which was inferior to glare. In Comparative Example 5, the average particle diameter B of the fine particles having the smallest average particle diameter exceeded 0.3 μm, and the glare and whitish color were inferior.

Claims

An antiglare laminate having a transparent substrate and a hard coat layer provided on the outermost layer on at least one side thereof,
The hard coat layer contains a curable resin and a fine particle component, and has irregularities on the surface by containing the fine particle component,
The fine particle component has at least three or more peaks in the particle size distribution,
Among the at least three or more peaks, the average particle diameter of the fine particles belonging to the first peak area having a particle diameter of A (μm) and the average particle diameter of the fine particles belonging to the second peak area smaller than A is selected. Is B (μm), and when the average particle diameter of the fine particles belonging to the third peak region including m peaks smaller than A and larger than B is Cm (μm), the following formula is satisfied. An antiglare laminate characterized by the above.
1 ≦ A ≦ 5,
0.001 ≦ B ≦ 0.3,
(2 × B) ≦ Cm ≦ (0.5 × A),
Here, m is an integer of 1 or more.
The antiglare laminate according to claim 1, wherein the skewness of the hard coat layer is 1.0 to 4.0.
The antiglare laminate according to claim 1 or 2, wherein the haze is 2 to 10% and the total light transmittance is 88% or more.
The antiglare laminate according to any one of claims 1 to 3, wherein the glossiness is 60 to 90%.
The antiglare laminate according to any one of claims 1 to 4, wherein the retardation of the transparent substrate is 3,000 to 30,000.
The number of fine particles that the particle diameter belongs to the first peak region and N 1, the number of fine particles that the particle diameter belonging to A is less than the second peak region and N 2, the particle size is smaller than than A B Satisfying the ratio of N 1 : N 2 : N 3 = 1: 30: 5 to 1: 50,000: 100, where N 3 is the number of fine particles belonging to the third peak region including large m peaks The antiglare laminate according to any one of claims 1 to 5, wherein the antiglare laminate is provided.
A display device comprising the antiglare laminate according to any one of claims 1 to 6.
A curable resin composition for forming an antiglare hard coat layer,
The curable resin composition contains a curable resin and a fine particle component,
The fine particle component has at least three or more peaks in the particle size distribution,
Among the at least three or more peaks, the average particle diameter of the fine particles belonging to the first peak area having a particle diameter of A (μm) and the average particle diameter of the fine particles belonging to the second peak area smaller than A is selected. Is B (μm), and when the average particle diameter of the fine particles belonging to the third peak region including m peaks smaller than A and larger than B is Cm (μm), the following formula is satisfied. A curable resin composition characterized by that.
1 ≦ A ≦ 5,
0.01 ≦ B ≦ 0.3,
(2 × B) ≦ Cm ≦ (0.5 × A),
Here, m is an integer of 1 or more.
The number of fine particles that the particle diameter belongs to the first peak region and N 1, the number of fine particles that the particle diameter belonging to A is less than the second peak region and N 2, the particle size is smaller than than A B Satisfying the ratio of N 1 : N 2 : N 3 = 1: 30: 5 to 1: 50,000: 100, where N 3 is the number of fine particles belonging to the third peak region including large m peaks The curable resin composition according to claim 8.
A coating film obtained by curing the curable resin composition according to claim 8 or 9.