JP2009061686A - Antiglare laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare laminate excellent in a surface hardness, transparency, gloss and antiglare property, particularly to provide an antiglare laminate excellent in visibility, gloss and antiglare property, which can be used in a highly refined LCD and PDP such as recent high vision display and full-spec high vision display. <P>SOLUTION: The antiglare laminate comprises an antiglare hard coat layer (B) laminated on at least one surface of a substrate material (A), wherein a half width of a projection distribution in which projection frequency against projection height is plotted is 500 to 1,500 nm on a surface of the antiglare hard coat layer (B). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical laminate. More specifically, the present invention relates to an antiglare laminate used on the surface of an image display element such as a liquid crystal display (LCD), a plasma display (PDP), a cathode ray tube display (CRT), etc., and particularly an antiglare property used on the surface of a high-definition display. It relates to a laminate.

  In displays such as LCD, PDP, and CRT, light is incident on the screen from the outside, and this light is reflected to make it difficult to see the display image (referred to as glare or glare), especially in recent flat panel displays. As the screen becomes larger and the pixels become finer due to high definition, it is becoming increasingly important to solve the above problems. In order to solve such a problem, various anti-glare treatments have been applied to various displays so far. As one of them, for example, a hard coat film used for a polarizing plate in a liquid crystal display device, a hard coat film for protecting various displays, and the like are subjected to an antiglare treatment for roughening the surface. The antiglare treatment method for this hard coat film is generally (1) a method of roughening the surface by adding particles to the hard coat layer (Patent Documents 1 to 3), and (2) forming a hard coat layer. It can be roughly classified into methods (Patent Documents 4 and 5) for roughening the surface during curing. Of these two methods, the former (1) the method of roughening the surface by mixing particles in the hard coat layer is the mainstream, and the whiteness of the obtained hard coat film is used as the particles. Silica particles are mainly used from the viewpoints of lowness and good dispersibility when mixed in a coating liquid for forming a hard coat layer.

Japanese Patent Laid-Open No. 10-180950 JP 2002-36452 A JP 2003-266582 A JP 2006-137835 A JP 2003-26832 A

  However, the antiglare hard coat films obtained by the methods of Patent Documents 1 to 3 are all low in transparency and do not achieve the visibility required for LCDs, PDPs and the like that have recently been refined. Absent. In particular, in very high-definition LCDs and PDPs such as recent high-definition displays or full-spec high-definition displays, anti-glare hard coat films with higher visibility are required. Furthermore, in such LCDs and PDPs, the blackness of the screen is regarded as important in order to increase the contrast and sharpness of the image, and even when an antiglare hard coat film is applied to the outermost surface of the screen. There is a need for an antiglare hard coat film that does not impair the blackness of the screen. Further, in order to obtain a high-quality image, an antiglare hard coat film having an excellent glossiness is required.

  On the other hand, in general, when the amount of added particles is increased to increase the antiglare property or the particle size of the particles is increased, the haze of the antiglare hard coat film is increased and the glossiness is increased. As a result, the display becomes inferior in visibility, and the blackness of the screen is deteriorated and the image is inferior in quality. On the other hand, although the visibility, screen blackness, and glossiness are improved by reducing the amount of particles added or by reducing the particle size of the particles, the antiglare property is inferior. There's a problem.

  In order to avoid these problems, even if silica particles and fine particles are used in combination as in Patent Document 2, the haze, glossiness and antiglare property do not satisfy recently required characteristics. Further, as described in Patent Documents 4 and 5, in the method of roughening the surface at the time of curing for forming the hard coat layer, in addition to the above problems, the operation is complicated, visibility, glossiness, There is a problem that the dazzle varies.

  This invention is made | formed in view of the said background art, The objective is to provide the anti-glare laminated body excellent in surface hardness, transparency, glossiness, and anti-glare property. In particular, it is to provide an antiglare laminate having excellent visibility, glossiness and antiglare properties, which can be used for high definition LCDs and PDPs such as recent high-definition displays and full-spec high-definition displays. .

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object is achieved by an antiglare laminate having a specific surface shape, and have reached the present invention. That is, the present invention relates to an antiglare laminate in which the antiglare hard coat layer (B) is laminated on at least one surface of the base material (A), and a projection is formed on the surface of the antiglare hard coat layer (B). It is an anti-glare laminate having a half-value width of the protrusion distribution in which the protrusion frequency with respect to the height is plotted is 500 nm or more and 1500 nm or less.

  Furthermore, the present invention provides that the 60 degree gloss on the surface of the hard coat layer (B) is 100 or more and 150 or less, the haze is 0.5% or more and 3.5% or less, and the antiglare hard coat layer. (B) 0.5% to 5.0% by weight of particles (C) having an average particle diameter of 1 μm to 5 μm and 0.3% of particles (D) having an average particle diameter of 5 nm to 60 nm. The particles (D) are aggregated in the antiglare hard coat layer (B), and the thickness T of the antiglare hard coat layer (B) includes: wt% or more and 6.0 wt% or less. The ratio T / d (C) of the particles (C) to the average particle diameter d (C) is 0.5 or more and 3.0 or less, and the antireflection on the antiglare hard coat layer (B). Outstanding anti-glare by adopting at least any one of the layers (E). Can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-glare laminated body excellent in surface hardness, transparency, glossiness, and anti-glare property can be provided. In particular, even when used in recent high-definition displays, it is possible to provide an antiglare laminate having excellent glossiness and excellent antiglare properties without deteriorating its visibility.

<Anti-glare laminate>
The antiglare laminate of the present invention is an antiglare laminate in which a hard coat layer (B) described later is laminated on at least one surface of a substrate (A) described later.

  In the present invention, on the surface of the hard coat layer (B) in the antiglare laminate, it is necessary that the half width of the projection distribution in which the projection frequency is plotted with respect to the projection height is 500 nm or more and 1500 nm or less. By setting the full width at half maximum in the above numerical range, excellent transparency, glossiness, and antiglare properties can be obtained. If the full width at half maximum is too low, the glossiness tends to increase too much, and the antiglare property is inferior. On the other hand, when the full width at half maximum is too high, haze increases and glossiness tends to decrease, and the transparency and glossiness are inferior. From such a viewpoint, the full width at half maximum is more preferably 550 nm to 1200 nm, particularly preferably 700 nm to 1000 nm.

  The height of the protrusion distribution is preferably 5000 (Counts) or more and 29500 (Counts) or less. It is preferable that the height of the protrusion distribution is in the above numerical range because the balance between transparency and glossiness and antiglare properties becomes good. If the height of the protrusion distribution is too large, the transparency and the glossiness tend to decrease, which is not preferable. On the other hand, if it is too small, the antiglare property tends to be low, which is not preferable. From such a viewpoint, the height of the protrusion distribution is more preferably 8000 (Counts) or more and 25000 (Counts) or less, and particularly preferably 10000 (Counts) or more and 20000 (Counts) or less.

  The method for setting the half-value width of the protrusion distribution on the surface of the antiglare hard coat layer (B) is not particularly limited, but by adding specific particles to the antiglare hard coat layer (B). It may be achieved by separating the antiglare hard coat layer (B) and utilizing the layer separation, or the surface of the antiglare hard coat layer (B) is chemically treated. May be achieved by mechanical or physical treatment. Among these, the method of adding specific particles is preferable because it can be performed stably and relatively easily. As a particularly preferable embodiment, an embodiment in which the antiglare hard coat layer (B) contains particles (C) and particles (D) described later can be mentioned.

  Such an antiglare laminate preferably has a surface waviness component on the surface of the antiglare hard coat layer (B), and by making such an aspect, the half width of the protrusion distribution is within the above numerical range. Becomes easy. The surface waviness component refers to gentle irregularities present on the surface of the antiglare hard coat layer (B), which are different from sharp protrusions. According to the present inventors' cross-sectional observation, when the antiglare hard coat layer (B) has such a surface undulation component, the particles (D) described later in the antiglare hard coat layer (B). Aggregates or aggregates of particles (D) further aggregated are observed. Therefore, the surface waviness component is presumed to be formed by an aggregate of particles (D) described later, or an aggregate in which aggregates of particles (D) are further aggregated. The size of the surface waviness component is preferably 10 μm or more and 90 μm or less, more preferably 20 μm or more and 85 μm or less, and particularly preferably 30 μm or more and 50 μm or less. By setting the size of the surface waviness component within the above numerical range, it becomes easier to set the half width of the projection distribution within the above numerical range, and the effect of improving transparency and antiglare property can be further enhanced.

  The antiglare laminate of the present invention preferably has a 60 degree glossiness of 100 or more and 150 or less on the surface of the hard coat layer (B). When the 60 ° glossiness is in the above numerical range, the glossiness and antiglare property are excellent. In particular, excellent glossiness and antiglare properties can be obtained for recent high-definition displays and full-spec high-definition displays. Furthermore, the blackness of the screen is improved, the contrast and sharpness of the image are improved, and the high-quality image is enhanced. When the 60 ° glossiness is too low, the transparency and glossiness tend to decrease, and the effect of improving visibility is reduced, which is not preferable. In particular, recent high-definition displays and full-spec high-definition displays are inferior in screen blackness and image quality. On the other hand, when the 60 degree glossiness is too high, the antiglare property tends to be lowered, and the effect of improving the antiglare property is lowered, which is not preferable. From such a viewpoint, the 60 degree glossiness is more preferably 112 or more and 140 or less, and particularly preferably 117 or more and 133 or less.

  The antiglare laminate of the present invention preferably has a haze of 0.5% to 3.5%. If the haze is 3.5% or more, the transparency tends to be low, and the effect of improving the visibility is low, which is not preferable. In particular, when used for recent high-definition displays and full-spec high-definition displays, the screen is inferior in blackness, which is not preferable. Although the haze is preferably low, in general, it is necessary to reduce the amount of particles added to the base material or the hard coat layer in order to reduce the haze, or to reduce the particle size. The lower limit is preferably 0.5% or more because problems such as the material being easily scratched occur. From such a viewpoint, the haze is more preferably 0.7% or more and 2.7% or less, further preferably 0.9% or more and 1.9% or less, and particularly preferably 1.1% or more and 1.6% or less. It is.

  The antiglare laminate of the present invention preferably has a pencil hardness of H or higher on the surface of the antiglare hard coat layer (B). More preferably, it is 2H or higher, and higher is preferable from the viewpoint of improving the surface height.

<Base material (A)>
As a base material (A) in this invention, it can select and use from the well-known plastic film conventionally used as a base material of the hard coat film for optics. Examples of such plastic films include polyester films made of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., polyolefin films made of polyethylene, polypropylene, etc., cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film. , Polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, poly Etherimide film, polyimide film, film Containing resin film, nylon film, acrylic resin film or the like. Among these plastic films, a polyester film is preferable because of excellent mechanical properties, heat resistance, transparency, processing suitability, and the like, and a polyester film made of polyethylene terephthalate is particularly preferable. A biaxially stretched film is particularly preferable.

  There is no restriction | limiting in particular in the thickness of a base material (A), Although it selects suitably according to a condition, Usually, they are 25 micrometers or more and 500 micrometers or less, Preferably they are 50 micrometers or more and 250 micrometers or less. It is preferable for the thickness to be in the above numerical range because the effect of improving transparency is enhanced. In addition, the rigidity is good and the handleability is excellent.

  The base material (A) in the present invention can be subjected to a surface treatment for the purpose of improving the adhesion to the hard coat layer (B) laminated thereon. Such surface treatments include surface roughening treatments such as sandblasting and solvent treatment, and surface oxidation treatments such as corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, etc. Etc. Moreover, a primer process can also be given to the single side | surface or both surfaces of a base material (A).

<Anti-glare hard coat layer (B)>
The antiglare hard coat layer (B) in the present invention is made of an activated energy ray curable resin. Examples of the activated energy beam curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin is preferable from the viewpoint of handleability. As such an ultraviolet curable resin, it can be appropriately selected from conventionally known ones. This ultraviolet curable resin generally contains a photopolymerizable monomer as a basic component, and further contains a photopolymerizable prepolymer, a photopolymerization initiator and the like as desired.

  Examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neo Pentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) phosphate Acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diventaerythritol tri (meth) acrylate, propionic acid modified dipentaeryth Litol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol Examples include hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. One type of these photopolymerizable monomers may be used alone, or two or more types may be used in combination.

  Examples of the photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, polyol acrylate, and the like. Such a polyester acrylate-based prepolymer is obtained by, for example, esterifying hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to an acid with (meth) acrylic acid. The epoxy acrylate-based prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. The urethane acrylate prepolymer can be obtained, for example, by esterifying, with (meth) acrylic acid, a polyurethane oligomer obtained by a reaction between polyether polyol or polyester polyol and polyisocyanate. Furthermore, the polyol acrylate-based prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. These photopolymerizable prepolymers may be used alone or in combination of two or more. Moreover, the compounding quantity is preferably 40 parts by mass or less, and more preferably 4 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the photopolymerizable monomer.

  Examples of the photopolymerization initiator include 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-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzofe , 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. These may be used alone or in combination of two or more. Moreover, the compounding quantity has preferable 0.2-10 mass parts with respect to 100 mass parts of said photopolymerizable monomers.

  The thickness of the antiglare hard coat layer (B) in the present invention is preferably 2 μm to 10 μm, more preferably 3 μm to 8 μm, and particularly preferably 4 μm to 7 μm. If the thickness is less than 2 μm, the effect of improving the surface hardness is lowered, which is not preferable. Specifically, the pencil hardness tends to be lower than H, and the steel wool scratch resistance tends to be inferior. On the other hand, when the thickness exceeds 10 μm, the surface hardness tends to increase, but the added particles tend to hardly form protrusions, and the protrusion height becomes too low, resulting in an effect of improving the antiglare property. Since it becomes low, it is not preferable.

As a preferable aspect of the antiglare hard coat layer (B) in the present invention, the particle (C) described later is 0.5 wt% or more and 5.0 wt% or less, and the particle (D) described later is 0.3 wt%. % And 6.0% by weight or less, and the particles (D) are aggregated in the antiglare hard coat layer (B).
Furthermore, as will be described later, the ratio T / d (C) when the thickness of the antiglare hard coat layer (B) is T and the average particle diameter of particles (C) described later is d (C). Is preferably 0.5 or more and 3.0 or less.

<Particle (C)>
In the present invention, it is preferable that the antiglare hard coat layer (B) contains 0.5% by weight or more and 5.0% by weight or less of particles (C) having an average particle diameter of 1 μm or more and 5 μm or less.
The average particle diameter of the particles (C) is preferably 1 μm to 5 μm, more preferably 1.5 μm to 4.5 μm, still more preferably 2 μm to 4 μm, and particularly preferably 2.5 μm to 3.5 μm. . If the average particle size is less than 1 μm, the effect of improving the antiglare property is lowered, which is not preferable. On the other hand, if it exceeds 5 μm, the transparency and glossiness tend to be low, such being undesirable.

  Further, the content of the particles (C) in the antiglare hard coat layer (B) is preferably 0.5% by weight or more and 5.0% by weight or less based on the weight of the antiglare hard coat layer (B). More preferably, it is 0.7 wt% or more and 3.5 wt% or less, particularly preferably 0.9 wt% or more and 2.5 wt% or less. If the content is less than 0.5% by weight, the effect of improving the antiglare property is lowered, which is not preferable. On the other hand, if it exceeds 5.0% by weight, the transparency and gloss tend to be low, such being undesirable.

  By setting the average particle size and content of the particles (C) within the above numerical range, the half width of the protrusion distribution on the surface of the antiglare hard coat layer (B) can be easily set within the numerical range defined by the present invention. This is preferable.

The particles (C) in the present invention include inorganic particles such as silica particles, hollow silica particles, alumina particles, TiO ₂ particles, polymethyl (meth) acrylate particles, crosslinked polymethyl (meth) acrylate particles, and crosslinked methyl (meth) acrylate- Preferred examples include resin particles such as styrene copolymer particles, polystyrene particles, crosslinked polystyrene particles, melamine resin particles, benzoguanamine particles, polycarbonate particles, and polyvinyl chloride particles, and resin particles are preferred. Among these, crosslinked polymethyl (meth) acrylate particles are preferable, and crosslinked polymethyl (meth) acrylate particles having a refractive index of 1.49 to 1.51 are more preferable. By setting the refractive index within the above numerical range, the effect of improving transparency can be enhanced. This is particularly effective when an acrylic hard coat having a refractive index of 1.49 to 1.51 is used.

Such particles (C) are preferably monodispersed and have a uniform particle diameter, and those that do not form aggregates in the antiglare hard coat layer (B) are also preferred.
The average particle diameter of the particles (C) is the ratio T / d when the thickness of the antiglare hard coat layer (B) is T and the average particle diameter of the particles (C) is d (C). An embodiment in which (C) is 0.5 or more and 3.0 or less is preferable. It is preferable that the above ratio T / d (C) is in the above numerical range because it is excellent in transparency, glossiness, and antiglare property. If the above ratio is too small, the protrusion height on the surface of the antiglare hard coat layer (B) tends to be too high, and the glossiness tends to be low, such being undesirable. On the other hand, when the ratio is too large, projections tend not to be formed on the surface of the antiglare hard coat layer (B), and the antiglare property tends to be low, such being undesirable. From such a viewpoint, the ratio T / d (C) is more preferably 0.7 or more and 2.4 or less, and particularly preferably 1.4 or more and 1.8 or less.

<Particle (D)>
In the present invention, an embodiment in which the antiglare hard coat layer (B) contains particles (D) having an average particle size of 5 nm to 60 nm in an amount of 0.3 wt% to 6.0 wt% is preferable.
The average particle diameter of the particles (D) is preferably 5 nm to 60 nm, more preferably 9 nm to 45 nm, and particularly preferably 15 nm to 30 nm. When the average particle size is less than 5 nm, the effect of improving the antiglare property is lowered, which is not preferable. On the other hand, if it exceeds 60 nm, the transparency and glossiness tend to be low, such being undesirable.

  Further, the content of the particles (D) in the antiglare hard coat layer (B) is preferably 0.3% by weight or more and 6.0% by weight or less based on the weight of the antiglare hard coat layer (B). It is. By setting the content within the above numerical range, the particles (D) can easily form aggregates in the antiglare hard coat layer (B), and the balance between transparency and glossiness and antiglare properties is further improved. It will be good. If the content is too small, the effect of improving the antiglare property is lowered, which is not preferable. On the other hand, if the amount is too large, the transparency and the glossiness tend to be low, such being undesirable. From such a viewpoint, the content of the particles (D) is more preferably 0.5% by weight or more and 5.0% by weight or less, and particularly preferably 1.0% by weight or more and 4.0% by weight or less.

  By setting the average particle diameter and content of the particles (D) within the above numerical range, the half width of the protrusion distribution on the surface of the antiglare hard coat layer (B) can be set within the numerical range defined by the present invention. Since it becomes easy, it is preferable.

The particles (D) in the present invention include inorganic particles such as silica particles, hollow silica particles, alumina particles, TiO ₂ particles, polymethyl (meth) acrylate particles, crosslinked polymethyl (meth) acrylate particles, and crosslinked methyl (meth) acrylate- Preferred examples include resin particles such as styrene copolymer particles, polystyrene particles, crosslinked polystyrene particles, melamine resin particles, benzoguanamine particles, polycarbonate particles, and polyvinyl chloride particles, and inorganic particles are preferred. Among these, silica particles are preferable, and the silica particles are more preferably monodispersed and uniform in particle size.

  In the present invention, an embodiment in which the particles (D) are aggregated in the antiglare hard coat layer (B) is preferable. By setting it as such an aspect, it becomes easy to make the half value width of the protrusion distribution on the surface of the antiglare hard coat layer (B) within the numerical range defined by the present invention. The “aggregation” in the present invention refers to an aspect in which a plurality of monodispersed primary particles are aggregated to form secondary particles, and in particular, the number of primary particles is 50% or more, preferably 80% or more. The case where the particles are involved in the formation of secondary particles is shown.

  In order to achieve the above-described embodiment, the particles (D) that have been aggregated in advance may be used, or the coating solution in which the particles (D) that are the dispersion form the antiglare hard coat layer (B). The agglomerates may be formed in at least any one of the step of preparing, storing, coating, or drying. Among these, a mode in which the particles (D) as the dispersion form an aggregate in the step of preparing the coating liquid or the step of storing is preferable because the characteristics of the antiglare hard coat layer (B) are stabilized.

  The following method can be mentioned as an example of the method of obtaining the aggregate of such particle | grains (D). That is, the dispersion solution in which the particles (D) are dispersed using the solvent (X) as a dispersion solvent is about 3 times the volume of the solvent (Y) different from the solvent (X) or the solvent (Y) as the solvent. Or the aggregate of particle | grains (D) can be obtained by adding to the solution used as a dispersion solvent, or a dispersion solution. For example, when silica particles having an average particle diameter of 20 nm are used as the particles (D), an aggregate of the particles (D) can be obtained by using toluene as the solvent (X) and methyl ethyl ketone as the solvent (Y). Thus, a solvent that is a relatively good solvent for the particles (D) may be used as the solvent (X), and a solvent that is a relatively poor solvent may be used as the solvent (Y).

  Further, after adding the particles (D), the aggregate is preferably stored at room temperature for 1 hour or more, more preferably 6 hours or more and 240 hours or less, particularly preferably 12 hours or more and 72 hours or less. It can be obtained stably and the size of the aggregate becomes more uniform.

  As described above, the antiglare hard coat layer (B) in the antiglare laminate of the present invention preferably has a surface undulation component on the surface thereof, but the surface undulation component is an antiglare hard coat layer ( B) is presumed to be formed by the presence of aggregates of particles (D) or aggregates of aggregates of particles (D). By making the surface of the antiglare hard coat layer (B) in such an embodiment, gentle irregularities are formed in places where the particles (C) do not exist, and the antiglare is achieved without reducing the transparency improving effect. The improvement effect of property can be improved. If the particles (D) are not aggregated, the irregularities formed by the particles (D) are generally sharp protrusions, no surface waviness component is present, and the effect of improving transparency and antiglare properties is enhanced at the same time. That is, only one of the improvement effects can be enhanced.

  The aspect in which the aggregates of the particles (D) are present in the antiglare hard coat layer (B) as described above is the projection frequency relative to the projection height on the surface of the antiglare hard coat layer (B). It can be mentioned as a preferable method for setting the half-value width of the plotted protrusion distribution to 500 nm or more and 1500 nm or less.

<Antireflection layer (E)>
In the present invention, for the purpose of imparting antireflection properties, an antireflection layer (E) composed of a siloxane-based film, a fluorine-based film or the like can be provided on the surface of the antiglare hard coat layer (B). . The thickness of the antireflection layer (E) is preferably 0.01 μm or more and 1 μm or less. By providing this antireflection layer (E), it is possible to eliminate the reflection of light from the sun, fluorescent lamps, etc. on the screen, and the total light transmittance can be reduced by reducing the reflectance on the screen surface. And transparency is improved. Furthermore, the antistatic property can be improved by selecting the type of the antireflection layer (E).

<Other layers>
In the present invention, an adhesive for adhering an antiglare laminate to an adherend such as a liquid crystal display on the surface of the substrate (A) opposite to the antiglare hard coat layer (B). A layer can be formed. As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, those conventionally used frequently for optical applications, for example, acrylic pressure-sensitive adhesive, urethane pressure-sensitive adhesive, and silicone-based pressure-sensitive adhesive are preferably used. The thickness of this pressure-sensitive adhesive layer is usually 5 to 100 μm, preferably 10 to 50 μm.

  Furthermore, a release film can be provided on the pressure-sensitive adhesive layer as necessary. Examples of such a release film include papers such as glassine paper, coated paper, and laminated paper, and various plastic films coated with a release agent such as silicone resin. The thickness of the release film is not particularly limited, but is usually 20 to 100 μm.

<Method for producing antiglare laminate>
The antiglare laminate of the present invention is prepared by preparing a coating liquid for forming the antiglare hard coat layer (B), and coating the coating liquid on the substrate (A) to form a coating film. After the coating film is dried, it can be produced by curing by irradiation with an activation energy ray. When coating the coating liquid on the substrate (A), a conventionally known coating method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like is used. Can do.

Examples of the activation energy rays include ultraviolet rays and electron beams. Ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like, and the irradiation amount is usually 100 to 500 mJ / cm ² . At this time, it is also possible to purge with nitrogen. By purging with nitrogen, it is possible to prevent curing inhibition due to oxygen damage on the surface of the antiglare hard coat layer (B), and to increase the surface hardness. On the other hand, the electron beam is obtained by an electron beam accelerator or the like, and the irradiation amount is usually 150 to 350 kV. Among these activation energy rays, ultraviolet rays are particularly preferable from the viewpoint of handleability. In addition, when using an electron beam, it can be hardened without adding a polymerization initiator.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples. The properties of the antiglare laminate were evaluated according to the following methods.

(1) Average particle diameter of particles A sample was fixed on a sample stage for a scanning electron microscope, and a surface of the sample was set to 0. 0 on a sample surface using a sputtering apparatus (manufactured by JEOL Ltd .: trade name JIS-1100 type ion sputtering apparatus). Ion etching treatment was performed for 5 minutes under conditions of 0.25 kV and 1.25 mA under a vacuum of 13 Pa. Next, gold sputtering was performed with the same apparatus, and observation was performed at 10,000 to 50,000 times using a scanning electron microscope, and particles and particles (D) corresponding to particles (C) were observed with Luzex 500 manufactured by Japan Regulator Co., Ltd. ), The area equivalent particle size of at least 100 particles was determined, and the average value was defined as the average particle size (unit: μm or nm) of the particles.
The measurement was carried out at any five locations on the surface of the antiglare hard coat layer (B) of the antiglare laminate, and the average value thereof was taken as the measurement value.

(2) Determination of presence / absence of aggregation Similar to the above (1), the sample surface after the ion etching treatment was observed 10,000 to 50,000 times using a scanning electron microscope, and determined visually.
In the determination, the particle (D) was discriminated from the particle size, and the case where 50% or more of the particles (D) were present in an aggregated state based on the number of the observed particles (D) was determined to be aggregated.

(3) Size of surface waviness component Using a non-contact optical roughness meter (manufactured by ZYGO, trade name: NewView 5022), scanning was performed on a 250 μm × 250 μm region at a magnification of 10 times. In the obtained surface profile, sharp projections having a size corresponding to that of the particle (C) were omitted, and the other convex portions on the gentle irregularities were individually observed. About the convex part in the gentle unevenness observed, since it was approximately elliptical, the major axis and minor axis were measured, and the average value thereof was taken as the size (unit: μm) of the surface waviness component.
The measurement was performed on the surface of the antiglare hard coat layer (B) of the antiglare laminate, and the above operation was performed on at least 10 convex portions of the gentle irregularities, and the average value thereof was taken as the measurement value.

(4) Thickness of the antiglare hard coat layer (B) The cross section of the sample was observed with an optical microscope, and the thickness (unit: μm) was measured.
The measurement was carried out at any five locations of the sample, and the average value thereof was taken as the measurement value.

(5) Half width and height of protrusion distribution Using a non-contact optical roughness meter (manufactured by ZYGO, trade name: NewView 5022), a region of 250 μm × 250 μm was scanned at a magnification of 10 times to obtain a surface profile It was. From the obtained surface profile, a protrusion distribution was obtained by plotting the height of the protrusion (unit: nm) on the horizontal axis and the frequency (unit: Counts) on the vertical axis by Histogram Plot. From the obtained protrusion distribution, the height (unit: Counts) of the graph was obtained. In addition, the width of the protrusion distribution at the half height of the peak height of the obtained protrusion distribution was defined as a half width (unit: nm). In addition, about the median value in processus | protrusion distribution, it followed the automatic calculation process of the computer.
The measurement was carried out at any five locations on the surface of the antiglare hard coat layer (B) of the antiglare laminate, and the average value thereof was taken as the measurement value.

(6) Haze A haze meter (manufactured by Nippon Denshoku Industries Co., Ltd .: trade name NDH2000) was used and measured according to JIS K6714.
The measurement was carried out at any five locations in the antiglare laminate, and the average value thereof was taken as the measurement value.

(7) 60 degree glossiness A digital variable angle photometer (manufactured by Konica Minolta Co., Ltd .: trade name gloss meter GM-268) was used and measured according to JIS K7105.
The measurement was carried out at any five locations on the surface of the antiglare hard coat layer (B) of the antiglare laminate, and the average value thereof was taken as the measurement value.

(8) Pencil hardness It implemented based on JISK5600-5-4.
Evaluation was performed on the surface of the antiglare hard coat layer (B) of the antiglare laminate.

[Example 1]
(Dispersion solution of particles (C))
A powder of crosslinked acrylic particles having an average particle size of 3 μm (manufactured by Soken Chemical Co., Ltd .: trade name MX300) was dispersed in a methyl ethyl ketone solution to obtain a dispersion solution of particles (C) (solid content concentration 10% by weight).

(Dispersion solution of particles (D))
A dispersion solution (trade name: SIT10WT%, manufactured by CI Kasei Co., Ltd.) in which silica particles having an average particle diameter of 20 nm are dispersed in toluene was used as it was to obtain a dispersion solution of particles (D) (solid content concentration: 10% by weight). .

(Preparation of coating solution)
Under stirring, 110 parts by mass of methyl ethyl ketone was added to 100 parts by mass of an acrylate ultraviolet curable resin (manufactured by JSR Corporation: trade name Desolite Z7501, solid concentration 50% by weight, methyl ethyl ketone solution). Thereto was added 5.1 parts by mass of the dispersion solution of particles (C) obtained above, and further 3.0 parts by mass of the dispersion solution of particles (D). Obtained. In the case of Example 1, the obtained coating liquid contains 1.0% by weight of particles (C) and 0.6% by weight of particles (D) based on the solid content concentration of the coating liquid.
The obtained coating liquid was further allowed to stand at room temperature for 12 hours.

(Creation of antiglare laminate)
The coating liquid obtained above was used as a base material (A) on a 100 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd .: trade name O3L86W-100), and the thickness after drying and curing was 4. The coating was applied to 5 μm and dried at 80 ° C. for 2 minutes to obtain a dried coating film. Next, this dried coating film was irradiated with ultraviolet rays under a condition of a light amount of 200 mJ / cm ² using an ultraviolet irradiation device (FusionUV Systems Japan Co., Ltd .: product name Fusion H bulb) to cure the dried coating film. An antiglare laminate was obtained. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Example 2]
The addition amount of the dispersion solution of particles (C) (solid content concentration of 10% by weight) is 5.2 parts by mass, and the addition amount of the dispersion solution of particles (D) (solid content concentration of 10% by weight) is 15.6 parts by mass. Except that, an antiglare laminate was obtained in the same manner as in Example 1. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Example 3]
An antiglare laminate was obtained in the same manner as in Example 2 except that coating was performed so that the thickness of the dried and cured coating film was 5.0 μm. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Example 4]
The added amount of the dispersion solution of particles (C) (solid content concentration 10% by weight) is 5.4 parts by mass, and the added amount of the dispersion solution of particles (D) (solid content concentration 10% by weight) is 32.3 parts by mass. Except that, an antiglare laminate was obtained in the same manner as in Example 1. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Example 5]
Using crosslinked acrylic particles having an average particle size of 4 μm as particles (C) and silica particles having an average particle size of 40 nm as particles (D), coating was performed so that the thickness of the coating film after drying and curing was 6.5 μm. Except for this, an antiglare laminate was obtained in the same manner as in Example 4. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Example 6]
Using crosslinked acrylic particles having an average particle diameter of 5 μm as particles (C) and silica particles having an average particle diameter of 10 nm as particles (D), the amount of dispersion of the particles (C) (solid content concentration 10% by weight) added is 5. 1 part by mass, the amount of addition of the dispersion solution of particles (D) (solid content concentration 10% by weight) was 1.5 parts by mass, and the thickness of the coating film after drying / curing was 4.0 μm. Except for this, an antiglare laminate was obtained in the same manner as in Example 1. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Example 7]
Using crosslinked acrylic particles having an average particle diameter of 2 μm as particles (C) and silica particles having an average particle diameter of 50 nm as particles (D), the amount of dispersion of the particles (C) (solid content concentration 10% by weight) is 16. An antiglare laminate was obtained in the same manner as in Example 1 except that 5 parts by mass and the addition amount of the dispersion solution of particles (D) (solid content concentration 10% by weight) were 33.0 parts by mass. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Example 8]
Cross-linked acrylic particles having an average particle diameter of 2 μm are used as the particles (C), the added amount of the dispersion solution of particles (C) (solid content concentration 10% by weight) is 27.2 parts by mass, the dispersion solution of particles (D) (solid) Anti-glare laminate in the same manner as in Example 1 except that the coating amount was 16.3 parts by mass and the coating thickness after drying / curing was 5.0 μm. Got the body. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Comparative Example 1]
Silica particles having an average particle diameter of 4 nm are used as the particles (D), the added amount of the dispersion solution of particles (C) (solid content concentration 10% by weight) is 5.1 parts by mass, and the dispersion solution of particles (D) (solid content) An antiglare laminate was obtained in the same manner as in Example 1 except that the amount added was 1.0 part by mass and the coating liquid was not left after preparation and was applied immediately. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Comparative Example 2]
An anti-glare laminate was obtained in the same manner as in Example 2 except that the coating liquid was not left after preparation and was applied immediately. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

[Comparative Example 3]
Silica particles having an average particle diameter of 70 nm are used as the particles (D), the amount of the dispersion solution of particles (C) (solid content concentration: 10% by weight) is 5.4 parts by mass, and the dispersion solution of particles (D) (solid content) An antiglare laminate was obtained in the same manner as in Example 1 except that the amount added was 38.0 parts by mass. The properties of the antiglare hard coat layer (B) and the antiglare laminate in the obtained antiglare laminate are shown in Table 1.

  The antiglare laminate obtained in Examples 1 to 8 has an appropriate half-value width of the protrusion distribution, that is, has an excellent surface shape, high transparency, and appropriate gloss. Met.

  The anti-glare laminates obtained in Comparative Examples 1 and 2 are because the particles (D) are not aggregated, or the half width of the protrusion distribution is inappropriate, that is, the surface shape is inferior, and the transparency Although it was high, the glossiness was too high and the antiglare property was poor.

  In the antiglare laminate obtained in Comparative Example 3, the half-value width of the protrusion distribution is inappropriate, that is, the surface shape is inferior because of the excessive addition amount of the particles (D), that is, the antiglare property is inferior. Although it was excellent, it was inferior in transparency and glossiness.

[Example 9]
(Preparation of curable resin solution)
As a solvent, ethyl acetate 500 mass parts, hexafluoropropylene (HFP) 120 mass parts, perfluoropropyl vinyl ether (FPVE) 53.2 mass parts, ethyl vinyl ether (EVE) 48.7 mass parts, hydroxybutyl vinyl ether (HBVE) 26. 4 parts by mass and 1.0 part by mass of lauroyl peroxide (LPO) as a polymerization initiator were charged and reacted at 60 ° C. for 20 hours in an autoclave to obtain a fluorine-containing olefin resin solution containing a hydroxyl group. From the obtained fluorine-containing olefin resin solution, a polymer was precipitated using methanol, and a fluorine-containing olefin resin was obtained by vacuum drying.

  Next, in a glass separable flask equipped with a stirrer, 1620 parts by mass of methyl ethyl ketone (MEK) as a solvent, 100 parts by mass of the fluorine-containing olefin resin obtained above, and a methoxylated methyl melamine (a crosslinkable compound as a thermally crosslinkable resin) Made by Mitsui Cytec Co., Ltd .: trade name Cymel 303) 30 parts by mass, dipentaerythritol pentaacrylate (DPPA) (manufactured by Sartomer) as an ultraviolet-crosslinkable resin 60 parts by mass, and 2-methyl-1- [4 as a photopolymerization initiator -(Methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals: trade name Irgacure 907), 2 parts by weight of p-toluenesulfonic acid as a thermal acid catalyst were charged at 23 ° C. Was stirred for 1 hour to obtain a curable resin solution. The resulting curable resin solution had a solid content concentration of 10% by weight and a viscosity of 30 cps.

On the anti-glare hard coat layer (B) of the anti-glare laminate obtained in Example 2, the curable resin solution prepared above was applied with a Meyer bar so that the thickness after drying was 100 nm. Then, heat curing treatment is performed at 140 ° C. for 2 minutes, and then UV irradiation is performed using a UV irradiation device (FusionUV Systems Japan Co., Ltd .: trade name Fusion H bulb) under the condition of a light amount of 150 mJ / cm ² and dried. The coating film was cured to obtain an antiglare laminate having an antireflection layer (E).

  The antiglare laminate provided with the antireflection layer (E) obtained in Example 9 was improved in antiglare properties by the antireflection layer (E), and reflection of sunlight, fluorescent lamps and the like was reduced. Furthermore, since transparency was improved, visibility was improved.

  Moreover, when the anti-glare laminate obtained in Examples 1 to 9 was attached to a commercially available plasma panel display of pull spec hi-vision via an adhesive, it was excellent in visibility and the screen was black enough. In addition, because of the glossiness, it was excellent in the quality of the image.

Claims (7)

  An antiglare laminate in which an antiglare hard coat layer (B) is laminated on at least one surface of a substrate (A), and the protrusion frequency relative to the protrusion height on the surface of the antiglare hard coat layer (B) An anti-glare laminate having a half-value width of the protrusion distribution plotted with a value of 500 nm or more and 1500 nm or less.   The antiglare laminate according to claim 1, wherein the 60-degree glossiness on the surface of the hard coat layer (B) is 100 or more and 150 or less.   The antiglare laminate according to claim 1 or 2, wherein the haze is 0.5% to 3.5%.   The antiglare hard coat layer (B) comprises 0.5 to 5.0% by weight of particles (C) having an average particle diameter of 1 to 5 μm and particles having an average particle diameter of 5 to 60 nm ( D) is contained in an amount of 0.3% by weight to 6.0% by weight, and the particles (D) are aggregated in the antiglare hard coat layer (B). The anti-glare laminate according to item.   The ratio T / d (C) between the thickness T of the antiglare hard coat layer (B) and the average particle diameter d (C) of the particles (C) is 0.5 or more and 3.0 or less. The anti-glare laminated body of any one of -4.   The antiglare laminate according to any one of claims 1 to 5, wherein an antireflection layer (E) is provided on the antiglare hard coat layer (B).   The display apparatus using the anti-glare laminated body of any one of Claims 1-6 for the whole surface.