WO2012147527A1 - 反射防止フィルム、偏光板及び画像表示装置 - Google Patents

反射防止フィルム、偏光板及び画像表示装置 Download PDF

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Publication number
WO2012147527A1
WO2012147527A1 PCT/JP2012/060000 JP2012060000W WO2012147527A1 WO 2012147527 A1 WO2012147527 A1 WO 2012147527A1 JP 2012060000 W JP2012060000 W JP 2012060000W WO 2012147527 A1 WO2012147527 A1 WO 2012147527A1
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Prior art keywords
refractive index
fine particles
low refractive
silica fine
index layer
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PCT/JP2012/060000
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English (en)
French (fr)
Japanese (ja)
Inventor
真理子 林
智之 堀尾
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大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to KR1020177021088A priority Critical patent/KR101871135B1/ko
Priority to CN201280017337.2A priority patent/CN103460079B/zh
Priority to JP2013512005A priority patent/JP6011527B2/ja
Priority to KR1020137022588A priority patent/KR20140006922A/ko
Publication of WO2012147527A1 publication Critical patent/WO2012147527A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/107—Porous materials, e.g. for reducing the refractive index

Definitions

  • the present invention relates to an antireflection film, a polarizing plate, and an image display device.
  • Image display surface in image display devices such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), electroluminescence display (ELD), field emission display (FED), touch panel, tablet PC, electronic paper
  • CTR cathode ray tube display
  • LCD liquid crystal display
  • PDP plasma display
  • ELD electroluminescence display
  • FED field emission display
  • touch panel tablet PC
  • electronic paper it is required to reduce the reflection due to the light rays emitted from the external light source and to improve the visibility.
  • an antireflection film having an antireflection layer As an antireflection film having an antireflection layer, a structure in which a low refractive index layer having a refractive index lower than that of a light-transmitting substrate is provided on the outermost surface is conventionally known.
  • a low refractive index layer has a low refractive index in order to enhance the antireflection performance of the antireflection film, and since it is provided on the outermost surface, it has antifouling performance, scratch prevention, etc. It is required to have high hardness and excellent optical properties such as transparency.
  • an antireflection film having a low refractive index layer formed on the outermost surface for example, in Patent Document 1, a coating liquid containing hollow silica fine particles and a binder resin such as acrylate is used, and the inside is hollow.
  • An antireflection film having a low refractive index layer having a structure containing silica fine particles is disclosed.
  • the display quality required for image display devices has become very high, and the antireflection performance by the antireflection film has also been required at a higher level.
  • the conventional antireflection film provided with a low refractive index layer containing hollow silica fine particles does not have sufficient antireflection performance and cannot sufficiently meet the recent demand for high display quality. It was.
  • Patent Document 2 discloses a method of blending a fluorine atom-containing polymer or monomer with a material for a low refractive index layer. Since the fluorine atom-containing polymer or monomer is a material having a low refractive index, a low refractive index layer containing these may lower the refractive index more than a conventional low refractive index layer containing hollow silica fine particles. Is possible. However, the conventional low refractive index layer containing a fluorine atom-containing polymer or monomer has a problem that the hardness of the low refractive index layer becomes insufficient when these compounds are contained to such an extent that the refractive index is sufficiently reduced. was there.
  • an antireflection film having a sufficient surface hardness, a low refractive index layer having a lower refractive index, and having high antireflection performance has been demanded. Furthermore, since such an antireflection film is usually placed on the outermost surface of the image display device, it is also required to have excellent slipperiness.
  • the present invention has a sufficient antifouling performance, surface hardness, and a uniform surface, and has a low refractive index layer having a sufficiently low refractive index, and has excellent antireflection performance. It is an object to provide an antireflection film having a polarizing plate, a polarizing plate using the antireflection film, and an image display device.
  • the present invention is an antireflection film in which a hard coat layer is formed on a light-transmitting substrate and a low refractive index layer is formed on the hard coat layer.
  • Acrylic resin, hollow silica fine particles, reactive silica fine particles and antifouling agent, and the reactive silica fine particles in the low refractive index layer are near the interface on the hard coat layer side and / or the hard coat. It is an antireflection film characterized by being unevenly distributed in the vicinity of the interface opposite to the layer.
  • the reactive silica fine particles in the low refractive index layer are unevenly distributed in the vicinity of the interface opposite to the hard coat layer side, and the hard coat layer is an interface on the low refractive index layer side. It is preferable to have reactive silica fine particles aligned in the interface direction in the vicinity. Further, the content of the reactive silica fine particles in the low refractive index layer is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin.
  • the hollow silica fine particles have an average particle diameter of 40 to 80 nm, and the blending ratio with respect to (meth) acrylic resin (content of hollow silica fine particles / content of (meth) acrylic resin) is 0.
  • the antifouling agent is preferably a compound containing a reactive functional group and a fluorine atom and / or a silicon atom.
  • the (meth) acrylic resin includes pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) ), A polymer or copolymer of at least one monomer selected from the group consisting of acrylate, dipentaerythritol tetra (meth) acrylate, and isocyanuric acid tri (meth) acrylate.
  • the low refractive index layer preferably further contains a fluorine atom-containing resin.
  • the content of the reactive silica fine particles in the hard coat layer is preferably 15 to 60 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin.
  • This invention is also a polarizing plate provided with a polarizing element, Comprising:
  • the said polarizing plate is provided with the above-mentioned antireflection film on the surface of a polarizing element, It is also a polarizing plate characterized by the above-mentioned.
  • the present invention is also an image display device comprising the above-described antireflection film or the above-described polarizing plate. The present invention is described in detail below.
  • the present invention is an antireflection film in which a hard coat layer is formed on a light-transmitting substrate and a low refractive index layer is formed on the hard coat layer.
  • the present inventors have included the reactive silica fine particles in the hard coat layer and further the reactive silica fine particles and the hollow silica fine particles in the low refractive index layer.
  • the reactive silica fine particles in the low refractive index layer are unevenly distributed in the vicinity of the interface opposite to the hard coat layer, and the hollow silica fine particles in the low refractive index layer are densely packed.
  • the inventors have found that the present invention is effective and have completed the present invention.
  • each layer constituting the antireflection film of the present invention will be described in detail.
  • the low refractive index layer is lower than the refractive index of components other than the low refractive index layer, such as a light-transmitting base material and a hard coat layer constituting the antireflection film of the present invention. What is the refractive index.
  • the low refractive index layer contains (meth) acrylic resin, hollow silica fine particles, reactive silica fine particles, and an antifouling agent.
  • the hollow silica fine particles serve to lower the refractive index while maintaining the layer strength of the low refractive index layer.
  • “hollow silica fine particles” refers to a structure in which gas is filled and / or a porous structure containing a gas, and the gas occupancy rate compared to the original refractive index of silica fine particles.
  • the silica fine particles whose refractive index decreases in proportion to Further, in the present invention, the form of silica fine particles, the structure, the aggregation state, and the dispersion inside the coating film formed by using the composition for low refractive index layer, which will be described later, used when forming the low refractive index layer.
  • silica fine particles capable of forming a nanoporous structure inside and / or at least part of the surface are also included.
  • the hollow silica fine particles are contained in a densely packed state in the low refractive index layer. For this reason, the surface uniformity of the low refractive index layer is excellent, and the antireflection film of the present invention is excellent in surface hardness.
  • the “closely packed state” means that there are almost no reactive silica fine particles to be described later between adjacent hollow silica fine particles, and a state similar to the closest packed structure is formed. Means.
  • the hollow silica fine particles are contained in a densely packed state in the low refractive index layer because the reactive silica fine particles contained in the low refractive index layer are hard in the low refractive index layer as will be described later. This is presumably because it is unevenly distributed in the vicinity of the interface on the coat layer side or in the vicinity of the interface on the side opposite to the hard coat layer. That is, the low refractive index layer comprises a composition containing hollow silica fine particles, reactive silica fine particles and a monomer component of (meth) acrylic resin (hereinafter also referred to as a composition for low refractive index layer) on the hard coat layer.
  • the coating film is formed by applying to the film, and the coating film is dried and cured.
  • the reactive silica fine particles contained in the coating film move to the vicinity of the interface on the hard coat layer side or the vicinity of the interface on the opposite side of the hard coat layer as described later. For this reason, in the formed coating film, there is almost no reactive silica fine particles between adjacent hollow silica fine particles, and as a result, the hollow silica fine particles in the low refractive index layer to be formed are closely packed. It is presumed that it will be in the state.
  • hollow silica fine particles are not particularly limited, and for example, silica fine particles prepared by using the technique disclosed in JP-A-2001-233611 are preferable. Since hollow silica fine particles are easy to manufacture and have high hardness themselves, when mixed with an organic binder to form a low refractive index layer, the layer strength is improved and the refractive index is adjusted to be low. It becomes possible to do.
  • hollow silica fine particles In addition to the above-mentioned hollow silica fine particles, it is manufactured and used for the purpose of increasing the specific surface area, used for packing columns, adsorbents that adsorb various chemical substances on the porous surface, and for fixing catalysts. Porous fine particles, or dispersions or aggregates of hollow fine particles intended to be incorporated into a heat insulating material or a low dielectric material. As such a specific example, it has a structure in which porous silica fine particles aggregated from the product names Nippil and Nipgel manufactured by Nippon Silica Kogyo Co., Ltd. as a commercial product, and silica fine particles manufactured by Nissan Chemical Industries, Ltd. are linked in a chain shape. Colloidal silica UP series (trade name) may be mentioned. Among these, those within the preferred particle diameter range of the present invention can be used.
  • the average particle diameter of the hollow silica fine particles is preferably 10 to 100 nm. When the average particle diameter of the hollow silica fine particles is within this range, excellent transparency can be imparted to the low refractive index layer.
  • a more preferred lower limit is 40 nm, a more preferred upper limit is 80 nm, a still more preferred lower limit is 45 nm, a still more preferred upper limit is 75 nm, a most preferred lower limit is 50 nm, and a most preferred upper limit is 70 nm.
  • the average particle diameter of the hollow silica fine particles means a value measured by a dynamic light scattering method in the case of the hollow silica fine particles alone.
  • the average particle diameter of the hollow silica fine particles in the low refractive index layer is determined by observing the cross section of the low refractive index layer with a STEM or the like, and selecting 30 arbitrary hollow silica fine particles. It is a value measured and calculated as the average value.
  • the porosity of the hollow silica fine particles is preferably 1.5 to 80.0%. If it is less than 1.5%, the refractive index of the low refractive index layer cannot be sufficiently lowered, and the antireflection performance of the antireflection film of the present invention may be insufficient. If it exceeds 80.0%, the strength of the hollow silica fine particles may be lowered, and the strength of the entire low refractive index layer may be insufficient.
  • the void ratio of the hollow silica fine particles has a more preferable lower limit of 6.4%, a more preferable upper limit of 76.4%, a still more preferable lower limit of 20.0%, and a further preferable upper limit of 55.0%.
  • the low refractive index layer can have a sufficiently low refractive index and can have excellent strength.
  • the porosity of the hollow silica fine particles is measured by measuring the diameter and the thickness of the outer shell portion excluding the void portions by cross-sectional STEM observation of the hollow silica fine particles, and the hollow silica fine particles are spherical.
  • the volume of the void portion of the hollow silica fine particle and the volume of the hollow silica fine particle when there is no void portion are calculated, and ⁇ (the volume of the void portion of the hollow silica fine particle) / (the void portion is absent) (Volume of hollow silica fine particles) ⁇ ⁇ 100.
  • the low refractive index layer includes a plurality of hollow silica fine particles having different average particle diameters and thicknesses of the outer shell portion
  • the porosity of each hollow silica fine particle calculated by the method described above, and each hollow silica fine particle The average value calculated from the blending ratio is used as the porosity of the hollow silica fine particles (hereinafter, such porosity is also referred to as “average porosity”).
  • each hollow silica fine particle preferably has a porosity in the above-described range.
  • the average porosity of the hollow silica fine particles is preferably 10.0 to 40.0%.
  • the refractive index of the low refractive index layer cannot be sufficiently lowered, and the antireflection performance of the antireflection film of the present invention may be insufficient. If it exceeds 40.0%, the strength of the hollow silica fine particles may be lowered, and the strength of the entire low refractive index layer may be insufficient.
  • a more preferred lower limit is 15.0%, and a more preferred upper limit is 35.0%.
  • the porosity in this range the low refractive index layer can have a sufficiently low refractive index and can have excellent strength. From the viewpoint of low refractive index and strength, the more preferable lower limit of the average porosity of the hollow silica fine particles is 20.0%, and the more preferable upper limit is 30.0%.
  • the hollow silica fine particles have a blending ratio (content of hollow silica fine particles / content of (meth) acrylic resin) with respect to the (meth) acrylic resin described later contained in the low refractive index layer of 0.90 to It is preferably 1.60.
  • the blending ratio is less than 0.90, the refractive index of the low refractive index layer is not sufficiently low, and the antireflection performance of the antireflection film of the present invention may be insufficient.
  • the blending ratio exceeds 1.60, the surface uniformity of the low refractive index layer is insufficient, and the surface hardness of the antireflection film of the present invention may be insufficient.
  • a more preferable lower limit of the blending ratio is 1.00, and a more preferable upper limit is 1.50. By being in this range, it can be set as the antireflection film provided with the more excellent antireflection performance, surface uniformity, and surface hardness. Further, the surface hardness (scratch resistance) is improved by increasing the surface uniformity of the low refractive index layer.
  • the hollow silica fine particles preferably have a close-packed structure laminated in two steps in the thickness direction of the low refractive index layer.
  • the transparency, surface uniformity, low refractive index, etc. of the antireflection film of the present invention can be made extremely excellent.
  • the reactive silica fine particles are unevenly distributed in the vicinity of the interface on the hard coat layer side to be described later of the low refractive index layer and / or in the vicinity of the interface on the side opposite to the hard coat layer to be described later. It plays a role of lowering and increasing the surface hardness.
  • the reactive silica fine particles are unevenly distributed in the vicinity of the interface on the hard coat layer side of the low refractive index layer and in the vicinity of the interface on the side opposite to the hard coat layer, both the surface hardness and the antifouling property can be improved. .
  • the reactive silica fine particles are unevenly distributed in the vicinity of the interface on the hard coat layer side of the low refractive index layer, an antifouling agent described later is unevenly distributed in the vicinity of the interface opposite to the hard coat layer of the low refractive index layer, Since the amount of antifouling agent present on the outermost surface is increased compared to the case where reactive silica is present on the outermost surface, the antifouling performance of the antireflection film of the present invention is extremely excellent.
  • the reactive silica fine particles are unevenly distributed in the vicinity of the interface opposite to the hard coat layer of the low refractive index layer, the surface hardness of the low refractive index layer can be further improved by the uneven distribution of the reactive silica fine particles.
  • the low refractive index layer is in a state where the hollow silica fine particles are densely packed as described above, the surface hardness is improved by the excellent surface uniformity of the low refractive index layer. Can also be planned. As a result, the antireflection film of the present invention has excellent scratch resistance.
  • the phrase “is unevenly distributed in the vicinity of the interface on the hard coat layer side or in the vicinity of the interface on the side opposite to the hard coat layer described later” means that the reactive silica fine particles are dense in the low refractive index layer. It means that it exists below (hard coat layer side) or above (opposite side of the hard coat layer) of the above-mentioned hollow silica fine particles in a state of being filled.
  • the thickness of the low refractive index layer is divided into three equal parts, and the 1/3 region, 2/3 region, 3 /
  • the 1/3 region contains 70% or more of the reactive silica fine particles
  • the reactive silica fine particles are unevenly distributed in the vicinity of the interface on the hard coat layer side.
  • the / 3 region contains 70% or more of the reactive silica fine particles, it is determined that the reactive silica fine particles are unevenly distributed in the vicinity of the interface opposite to the hard coat layer.
  • Reactive silica in which a total of 70% or more of the reactive silica fine particles are unevenly distributed in the 1/3 region and the 3/3 region, and each of the 1/3 region and the 3/3 region is unevenly distributed.
  • the amount of fine particles is larger than the amount of reactive silica fine particles contained in the 2/3 region, the reactive silica fine particles are in the vicinity of the interface on the hard coat layer side of the low refractive index layer and on the side opposite to the hard coat layer. Judged to be unevenly distributed near the interface.
  • the state where such reactive silica fine particles are unevenly distributed is easily determined by cross-sectional observation (STEM, TEM) of the low refractive index layer when the antireflection film of the present invention is cut in the thickness direction. be able to.
  • the reason why the reactive silica fine particles are unevenly distributed in the vicinity of the hard coat layer side interface and / or the vicinity of the hard coat layer side interface in the low refractive index layer is not clear.
  • the amount of reactive silica fine particles in the low refractive index layer can be adjusted by adjusting the amount of reactive silica fine particles added in the hard coat layer. It is possible to control the uneven distribution. That is, when the hard coat layer does not contain reactive silica fine particles, forming a low refractive index layer on the hard coat layer causes the reactive silica fine particles of the low refractive index layer to be unevenly distributed near the hard coat layer side interface. Can do.
  • the hard coat layer contains reactive silica fine particles in a range of more than 25 parts by weight and less than 60 parts by weight with respect to 100 parts by weight of the resin component constituting the hard coat layer, on the hard coat layer
  • the reactive silica fine particles of the low refractive index layer can be unevenly distributed in the vicinity of the interface opposite to the hard coat layer.
  • the reactive silica fine particles of the low refractive index layer can be unevenly distributed in the vicinity of the hard coat layer side interface of the low refractive index layer and in the vicinity of the interface opposite to the hard coat layer.
  • reactive silica fine particles commercially available products can be used, for example, MIBK-SDL, MIBK-SDMS, MIBK-SD (all are manufactured by Nissan Chemical Industries, Ltd.), DP1021SIV, DP1039SIV, DP1117SIV (all above, any Also available from JGC Catalysts & Chemicals Co., Ltd.).
  • the average particle diameter of the reactive silica fine particles is preferably 1 to 25 nm.
  • the thickness is less than 1 nm, aggregation is likely to occur, and sufficient strength may not be obtained in the low refractive index layer obtained when the filling degree is low.
  • it exceeds 25 nm surface irregularities are formed in the low refractive index layer, and sufficient strength may not be obtained.
  • the more preferable lower limit of the average particle diameter of the reactive silica fine particles is 5 nm, and the more preferable upper limit is 20 nm.
  • the average particle diameter of the reactive silica fine particles means a value measured by cross-sectional observation (average value of 30 particles) such as BET method or STEM.
  • the content of the reactive silica fine particles in the low refractive index layer is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin described later.
  • the amount is less than 5 parts by mass, the surface hardness of the low refractive index layer cannot be sufficiently increased, and the antireflection film of the present invention may be inferior in scratch resistance.
  • the amount exceeds 60 parts by mass the amount of reactive silica fine particles that are not unevenly distributed in the low refractive index layer increases, and the hollow silica fine particles do not become the above-described densely packed state, resulting in low refraction.
  • the uniformity of the surface of the index layer may be inferior and may cause an increase in reflectivity.
  • the minimum with more preferable content of the said reactive silica fine particle is 10 mass parts, and a more preferable upper limit is 50 mass parts.
  • the (meth) acrylic resin functions as a binder component for the hollow silica fine particles and reactive silica fine particles described above in the low refractive index layer.
  • “(meth) acryl” means acryl or methacryl.
  • Examples of the (meth) acrylic resin include polymers or copolymers of (meth) acrylic monomers, and the (meth) acrylic monomer is not particularly limited.
  • pentaerythritol tri (meth) acrylate dipenta Erythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, isocyanuric acid tri (meth) acrylate, etc.
  • pentaerythritol tri (meth) acrylate dipenta Erythritol hexa (meth) acrylate
  • pentaerythritol tetra (meth) acrylate dipentaerythritol penta (meth) acrylate
  • trimethylolpropane tri (meth) acrylate dipentaerythritol tetra (meth) acrylate
  • these (meth) acrylate monomers may be modified in part of the molecular skeleton, and have been modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. Things can also be used.
  • These (meth) acrylic monomers may be used alone or in combination of two or more. These (meth) acrylic monomers satisfy the refractive index range as described later and are excellent in curing reactivity, and can improve the hardness of the resulting low refractive index layer. Of these, (meth) acrylic resins having 3 or more functional groups are preferably used.
  • the (meth) acrylic resin (after curing) preferably has a refractive index of 1.47 to 1.53. It is practically impossible to make the refractive index less than 1.47. If it exceeds 1.53, a low refractive index layer having a sufficiently low refractive index may not be obtained.
  • the (meth) acrylic monomer preferably has a weight average molecular weight of 250 to 1,000. If it is less than 250, the number of functional groups decreases, and the hardness of the resulting low refractive index layer may be reduced. If it exceeds 1000, the functional group equivalent (number of functional groups / molecular weight) is generally small, so that the crosslink density is low and a low refractive index layer having sufficient hardness may not be obtained.
  • the weight average molecular weight of the said (meth) acryl monomer can be calculated
  • the measurement column may be used in combination with a commercially available column such as a column for tetrahydrofuran or a column for chloroform.
  • a commercially available column such as a column for tetrahydrofuran or a column for chloroform.
  • Examples of the commercially available column include Shodex GPC KF-801, GPC-KF800D (both are trade names, manufactured by Showa Denko KK) and the like.
  • an RI (differential refractive index) detector and a UV detector may be used. Using such a solvent, a column, and a detector, the weight average molecular weight can be appropriately measured by a GPC system such as Shodex GPC-101 (manufactured by Showa Denko).
  • the low refractive index layer further contains an antifouling agent.
  • the antireflective film of the present invention has antifouling performance.
  • the reactive silica fine particles in the low refractive index layer are on the interface on the hard coat layer side.
  • the antifouling performance of the antireflection film of the present invention is particularly excellent because the content ratio of the antifouling agent in the vicinity of the interface opposite to the hard coat layer of the low refractive index layer is increased. Become.
  • the antifouling agent is the same as the reactive silica fine particles described above. It is unevenly distributed in the vicinity of the interface opposite to the hard coat layer, and in this case as well, the antifouling performance by the antifouling agent can be improved to some extent.
  • the reason why the antifouling agent is unevenly distributed to some extent in the vicinity of the interface opposite to the hard coat layer is not clear, but for example, when a coating film formed on the hard coat layer is formed, the coating film is formed as described above.
  • the reactive silica fine particles move in this, and it is assumed that the movement of the reactive silica fine particles has an influence.
  • an antifouling performance is obtained by including an antifouling agent in the low refractive index layer.
  • the antifouling agent is preferably a compound containing a reactive functional group and a fluorine atom and / or a silicon atom. By containing such an antifouling agent, the antifouling performance of the low refractive index layer to be formed can be further improved.
  • a reactive fluorine compound for example, a fluorine-containing monomer having an ethylenically unsaturated bond can be widely used.
  • olefins for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, and the like).
  • 2,2,2-trifluoroethyl (meth) acrylate 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2 -(Perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, methyl ⁇ -trifluoro (meth) acrylate, etc.
  • a fluorinated polymer having a fluorinated alkylene group or a fluorinated alkyl group in the main chain and the side chain is particularly preferably used because the problem of bleeding out from the low refractive index layer hardly occurs.
  • a reactive silicone compound is mentioned, for example.
  • Examples of the compound containing the reactive functional group and a fluorine atom and a silicon atom include a silicone-containing vinylidene fluoride copolymer obtained by reacting the reactive silicone compound with the reactive fluorine compound. It is done.
  • the content of the antifouling agent is appropriately determined depending on the antifouling performance of the target low refractive index layer, but with respect to a total of 100 parts by mass of the hollow silica fine particles and the (meth) acrylic resin described above,
  • the amount is preferably 1 to 20 parts by mass. If it is less than 1 part by mass, it may not be possible to impart sufficient antifouling performance to the low refractive index layer to be formed. If it exceeds 20 parts by mass, the added antifouling agent will bleed out from the low refractive index layer. There are things to do.
  • the effect of simply adding the antifouling agent is not seen, the manufacturing cost is increased, the hardness and appearance of the obtained low refractive index layer are lowered, and the reflectance may be increased.
  • the minimum with more preferable content of the said antifouling agent is 2 mass parts, and a more preferable upper limit is 15 mass parts.
  • a compound not containing a reactive functional group may be added and used together with a compound containing the reactive functional group and a fluorine atom and / or a silicon atom.
  • the low refractive index layer preferably has a refractive index of less than 1.45.
  • the antireflection performance of the antireflection film of the present invention is insufficient, and it may not be possible to cope with the high-level display quality of recent image display devices.
  • a more preferred lower limit is 1.25, and a more preferred upper limit is 1.43.
  • the low refractive index layer has the following formula (II): 120 ⁇ n A d A ⁇ 145 (II) It is preferable from the viewpoint of low reflectivity.
  • the low refractive index layer preferably has a haze value of 1% or less. If it exceeds 1%, the light transmittance of the antireflection film of the present invention may be reduced, which may cause a reduction in display quality of the image display device. More preferably, it is 0.5% or less.
  • the haze value is a value obtained in accordance with JIS K7136.
  • the low refractive index layer preferably has a hardness of H or higher, more preferably 2H or higher, according to a pencil hardness test according to JIS K5600-5-4 (1999). Furthermore, it is preferable that the low refractive index layer does not cause scratches in a scratch resistance test in which a friction load of 300 g / cm 2 using # 0000 steel wool is used and the friction is made 10 times.
  • the low refractive index layer is prepared by preparing a composition for a low refractive index layer containing the hollow silica fine particles, reactive silica fine particles, a monomer component of (meth) acrylic resin and an antifouling agent, and the like. It can form using the coating liquid for layers.
  • the said composition for low refractive index layers contains a solvent.
  • the solvent is preferably a mixed solvent of methyl isobutyl ketone (MIBK) and propylene glycol monomethyl ether (PGME) or propylene glycol monomethyl ether acetate (PGMEA).
  • MIBK methyl isobutyl ketone
  • PGME propylene glycol monomethyl ether
  • PGMEA propylene glycol monomethyl ether acetate
  • the said composition for low refractive index layers may contain the other solvent, if it is a range which does not inhibit formation of the low refractive index layer of the structure mentioned above.
  • other solvents include alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, iso-butanol, t-butanol, and benzyl alcohol; acetone, methyl ethyl ketone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone Ketones such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, and PGMEA; aliphatic hydrocarbons such as hexane and cyclohexane; methylene chloride, chloroform, tetrach
  • the said composition for low refractive index layers may contain the other component further as needed.
  • the other components include photopolymerization initiators, leveling agents, polymerization accelerators, viscosity modifiers, antiglare agents, antistatic agents, ultraviolet absorbers, and resins (monomers, oligomers, polymers) other than those described above. Is mentioned.
  • the composition for a low refractive index layer contains a resin system having a radical polymerizable unsaturated group
  • acetophenones for example, trade name Irgacure 184 (manufactured by BASF)
  • 1-hydroxy-cyclohexyl-phenyl-ketone 1,3-bis(trimethyl)-2-hydroxy-cyclohexyl-phenyl-ketone
  • benzophenones 1, 4-hydroxy-cyclohexyl-phenyl-ketone
  • benzophenones 1, thioxanthones
  • benzoin 1,4-benzin methyl ether
  • the photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, A metallocene compound, benzoin sulfonic acid ester, etc. are mentioned, These may be used independently and 2 or more types may be used together.
  • Irgacure 369 Irgacure 127, Irgacure 907, Esacure ONE, Speedcure MBB, Speedcure PBZ, and KAYACURE DETX-S are preferable.
  • Irgacure 127 (2-Hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one manufactured by BASF
  • Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone manufactured by BASF).
  • the addition amount of the photopolymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the resin component contained in the low refractive index layer coating solution.
  • leveling agents, polymerization accelerators, viscosity modifiers, antiglare agents, antistatic agents, ultraviolet absorbers, and resins (monomers, oligomers, polymers) other than those described above can be used.
  • the method for preparing the composition for the low refractive index layer is not particularly limited.
  • the hollow silica fine particles, the reactive silica fine particles, the monomer component of the (meth) acrylic resin, the antifouling agent, and the solvent It can be obtained by mixing components such as a photopolymerization initiator added as necessary.
  • a known method such as a paint shaker or a bead mill can be used.
  • the composition for a low refractive index layer is a coating film formed by applying the composition for a low refractive index layer on a hard coat layer to be described later, and the coating film is cured by irradiation with ionizing radiation and / or heating. Can be formed.
  • preferable drying conditions for the coating film are 40 to 80 ° C. and 10 seconds to 2 minutes. By drying the coating film under such conditions, the low refractive index layer having the above-described structure can be suitably formed.
  • the method for applying the low refractive index layer composition is not particularly limited. For example, spin coating, dipping, spraying, gravure coating, die coating, bar coating, roll coater, meniscus coater, etc. There are various methods.
  • Hard coat layer The antireflection film of the present invention has a hard coat layer between the light-transmitting substrate and the low refractive index layer.
  • the “hard coat layer” means a layer showing a hardness of 2H or more in a pencil hardness test specified in JIS K5600-5-4 (1999). The pencil hardness is more preferably 3H or more.
  • the film thickness (when cured) of the hard coat layer is preferably 1 to 30 ⁇ m, and more preferably 2 to 15 ⁇ m.
  • the hard coat layer preferably contains reactive silica fine particles.
  • the reactive silica fine particles in the low refractive index layer described above are unevenly distributed in the vicinity of the interface opposite to the hard coat layer.
  • the reactive silica fine particles include the same reactive silica fine particles as those in the low refractive index layer described above.
  • the content of reactive silica fine particles in the hard coat layer is preferably 15 to 60 parts by mass with respect to 100 parts by mass of the resin component constituting the hard coat layer. If it is less than 15 parts by mass, the hardness of the hard coat layer may be insufficient, and if it exceeds 60 parts by mass, the adhesiveness with the light-transmitting substrate and the adhesiveness with the low refractive index layer are insufficient.
  • the hard coat layer may be easily broken, or the total light transmittance may be lowered and the haze degree may be increased.
  • a more preferred lower limit is 20 parts by mass, and a more preferred upper limit is 55 parts by mass.
  • the hard coat layer preferably has reactive silica fine particles contained in a state aligned in the interface direction near the interface on the low refractive index layer side.
  • the reactive silica fine particles aligned in this way, the low refractive index layer having the above-described structure can be obtained more suitably.
  • the state of alignment in the interface direction near the interface on the low refractive index layer side means that the reactive silica fine particles are aligned along the interface direction in the vicinity of the interface of the hard coat layer with the low refractive index layer.
  • the aligned state is preferably adjacent to each other, and more preferably, the upper ends of the reactive silica fine particles are in contact with the interface of the hard coat layer with the low refractive index layer and aligned along the interface in a state adjacent to each other. (FIG. 1).
  • the said hard-coat layer also contains the reactive silica fine particle contained at random other than the state which aligned as mentioned above.
  • the hard coat layer examples include those formed by the composition for hard coat layer containing the reactive silica fine particles, a resin, and other optional components.
  • a transparent resin is preferably used.
  • an ionizing radiation curable resin, an ionizing radiation curable resin and a solvent-drying resin (during coating) are resins that are cured by ultraviolet rays or electron beams. The resin added to adjust the solid content is dried, and a mixture with a resin that forms a film), a thermosetting resin, or the like, preferably an ionizing radiation curable resin.
  • the ionizing radiation curable resin include those having an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, polyhydric alcohol, and the like. Monomers such as (meth) allylates of functional compounds, oligomers or prepolymers may be mentioned.
  • the (meth) acrylic resin used in the low refractive index layer is also used in the hard coat layer, and among them, a (meth) acrylic resin having 3 or more functional groups is preferable.
  • the ionizing radiation curable resin is used as an ultraviolet curable resin
  • a photopolymerization initiator examples include acetophenones, benzophenones, Michler benzoyl benzoate, ⁇ -amyloxime ester, tetramethylchuram monosulfide, thioxanthones, and the like.
  • Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone manufactured by BASF) is preferable.
  • a mixture of photosensitizers and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.
  • a non-reactive polymer may be used by mixing with the ionizing radiation curable resin.
  • the non-reactive polymer include polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polyolefin, polystyrene, polyamide, polyimide, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, and polycarbonate.
  • thermosetting resin examples include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin. And polysiloxane resin.
  • hardening agents such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc. can be further added and used.
  • the hard coat layer is formed by applying the composition for hard coat layer prepared using each of the above-mentioned materials on the light-transmitting substrate, and if necessary, dried, and irradiated with ionizing radiation. Alternatively, it can be formed by curing by heating or the like.
  • the preparation method of the said composition for hard-coat layers, the formation method of a coating film, etc. can mention the method similar to the low-refractive-index layer mentioned above.
  • the hard coat layer may further contain a high hardness / low curl material such as a known antistatic agent or high refractive index agent.
  • the antireflection film of the present invention has a light transmissive substrate.
  • the light transmissive substrate preferably has smoothness and heat resistance and is excellent in mechanical strength.
  • Specific examples of the material forming the light-transmitting substrate include, for example, polyester (polyethylene terephthalate, polyethylene naphthalate), cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, polyester, polyamide, polyimide, polyethersulfone, poly Examples thereof include thermoplastic resins such as sulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, acrylic base material (PMMA), and polyurethane.
  • polyester (polyethylene terephthalate, polyethylene naphthalate) and cellulose triacetate are used.
  • the light-transmitting substrate preferably uses the thermoplastic resin as a flexible film-like body, but uses a plate of these thermoplastic resins depending on the use mode in which curability is required. It is also possible, or a glass plate plate may be used.
  • examples of the light transmissive substrate include an amorphous olefin polymer (Cyclo-Olefin-Polymer: COP) film having an alicyclic structure.
  • This is a base material in which a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and the like are used.
  • the thickness of the light transmissive substrate is preferably 3 to 300 ⁇ m, more preferably the lower limit is 20 ⁇ m and the upper limit is 100 ⁇ m. When the light-transmitting substrate is a plate-like body, the thickness may exceed these thicknesses.
  • the light-transmitting substrate is called an anchor agent or a primer in addition to physical treatment such as corona discharge treatment and oxidation treatment in order to improve adhesiveness when forming the hard coat layer or the like thereon. Application of the paint may be performed in advance.
  • the antireflection film of the present invention having a structure in which the hard coat layer is formed between the light transmissive substrate and the low refractive index layer is further provided between the hard coat layer and the light transmissive substrate.
  • a structure in which an antistatic layer comprising a known antistatic agent and a binder resin is formed may be used.
  • the antireflection film of the present invention includes other hard coat layers different from the above-described hard coat layer, antifouling layer, high refractive index layer, medium refractive index layer, etc. as optional layers as necessary. It may be.
  • the antifouling layer, the high refractive index layer, and the medium refractive index layer are prepared by adding a commonly used antifouling agent, a high refractive index agent, a medium refractive index agent, a low refractive index agent or a resin, Each layer may be formed by a known method.
  • the total light transmittance of the antireflection film of the present invention is preferably 90% or more. If it is less than 90%, color reproducibility and visibility may be impaired when it is mounted on the display surface.
  • the total light transmittance is more preferably 93% or more, and still more preferably 95% or more.
  • the haze of the antireflection film of the present invention is preferably less than 1%, and more preferably less than 0.5%.
  • the method for producing an antireflection film of the present invention includes the steps of forming the hard coat layer by applying the above-described hard coat layer composition on the light-transmitting substrate, and the above-described hard coat layer.
  • coating the composition for low refractive index layers and forming a low refractive index layer is mentioned.
  • the method for forming the hard coat layer and the low refractive index layer is as described above.
  • the antireflection film of the present invention can be made into a polarizing plate by providing the antireflection film according to the present invention on the surface of the polarizing element opposite to the surface where the low refractive index layer is present in the antireflection film. .
  • a polarizing plate is also one aspect of the present invention.
  • the polarizing element is not particularly limited, and examples thereof include a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, and an ethylene-vinyl acetate copolymer saponified film that are dyed and stretched with iodine.
  • the light-transmitting substrate preferably a triacetyl cellulose film.
  • the present invention is also an image display device comprising the antireflection film or the polarizing plate.
  • the image display device may be an image display device such as an LCD, PDP, FED, ELD (organic EL, inorganic EL), CRT, touch panel, tablet PC, or electronic paper.
  • the LCD includes a transmissive display and a light source device that irradiates the transmissive display from the back.
  • the image display device of the present invention is an LCD
  • the antireflection film of the present invention or the polarizing plate of the present invention is formed on the surface of the transmissive display.
  • the present invention is a liquid crystal display device having the antireflection film
  • the light source of the light source device is irradiated from the lower side of the optical laminate.
  • a retardation plate may be inserted between the liquid crystal display element and the polarizing plate.
  • An adhesive layer may be provided between the layers of the liquid crystal display device as necessary.
  • the PDP has a front glass substrate (formed with an electrode on the surface) and a rear glass substrate (disposed with discharge gas sealed between the front glass substrate and the electrode and minute grooves formed on the surface). A red, green, and blue phosphor layer is formed in the groove).
  • the image display device of the present invention is a PDP
  • the surface of the surface glass substrate or the front plate (glass substrate or film substrate) is provided with the antireflection film described above.
  • the above image display device is a zinc sulfide or diamine substance that emits light when a voltage is applied: a light emitting material is deposited on a glass substrate, and an ELD device that performs display by controlling the voltage applied to the substrate, or converts an electrical signal into light Alternatively, it may be an image display device such as a CRT that generates an image visible to human eyes.
  • the antireflection film described above is provided on the outermost surface of each display device as described above or the surface of the front plate.
  • the image display apparatus of the present invention can be used for display display of a television, a computer, a word processor, or the like.
  • it can be suitably used for the surface of high-definition image displays such as CRT, touch panel, tablet PC, electronic paper, liquid crystal panel, PDP, ELD, and FED.
  • the antireflective film of the present invention has excellent surface hardness due to the low refractive index layer having reactive silica fine particles that are unevenly distributed in the vicinity of the surface thereof.
  • the conventional antireflection film was one of the causes of inferior scratch resistance due to the presence of minute irregularities on the surface of the low refractive index layer, but the low refractive index layer having the above structure is hollow. Since the silica fine particles are in a closely packed state, it has a very uniform surface. For this reason, the antireflection film of the present invention is extremely excellent in surface hardness.
  • the antireflective film of the present invention has a low refractive index layer mainly composed of the hollow silica fine particles and the reactive silica fine particles, so that the refractive index can be made sufficiently low and excellent antireflective properties. It can have performance.
  • the antireflection film of the present invention includes a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, a tablet PC, It can be suitably applied to electronic paper and the like.
  • Example 2 is a micrograph of a cross section of an antireflection film according to Example 1.
  • 10 is a micrograph of a cross section of an antireflection film according to Example 7.
  • 2 is a micrograph of a cross section of an antireflection film according to Comparative Example 1.
  • 4 is a micrograph of a cross section of an antireflection film according to Comparative Example 2.
  • composition for hard coat layer (1) The components shown below were mixed to prepare a hard coat layer composition (1).
  • Reactive silica fine particles Z7537, manufactured by JSR, solid content 50%, product containing reactive silica fine particles 60%
  • 10 parts by mass urethane acrylate UV1700B, manufactured by Nippon Gosei Co., Ltd., 10 functional
  • UV1700B manufactured by Nippon Gosei Co., Ltd., 10 functional
  • mass polymerization initiator Irgacure 184; manufactured by BASF
  • leveling agent in the composition for hard coat layer (1) The solid content mass ratio was 0.10%.
  • composition for hard coat layer (2) The components shown below were mixed to prepare a hard coat layer composition (2).
  • the solid content mass ratio of the leveling agent in the hard coat layer composition (2) was 0.10%. It was.
  • composition for hard coat layer (3) The components shown below were mixed to prepare a hard coat layer composition (3).
  • Reactive silica fine particles Z7537, manufactured by JSR, solid content 50%, product containing 60% reactive silica fine particles
  • UV1700B Nippon Gosei Co., Ltd., 10 functional
  • mass polymerization initiator Irgacure 184; manufactured by BASF
  • leveling agent in the composition for hard coat layer (3) The solid content mass ratio was 0.10%.
  • composition for low refractive index layer (1) The following components were mixed to prepare a composition for low refractive index layer (1).
  • Hollow silica fine particles solid content of the hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle diameter: 55 nm, average porosity: 23.3%
  • PETA pentaerythritol triacrylate
  • DPHA dipentaerythritol hexaacrylate
  • reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl Isobutyl ketone, average particle size: 12 nm
  • 0.1 parts by mass antifouling agent X-22-164E, manufactured by Shin-Etsu Chemical Co., Ltd.
  • 0.01 parts by mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition for low refractive index layer (2) The following components were mixed to prepare a low refractive index layer composition (2).
  • Hollow silica fine particles solid content of hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle size: 60 nm, average porosity: 29.6%
  • PETA pentaerythritol triacrylate
  • 0.1 part by mass reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl isobutyl ketone, average particle size: 12 nm
  • RS-74 manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • TU2225 manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ketone
  • mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition (3) for low refractive index layer The following components were mixed to prepare a composition for low refractive index layer (3).
  • Hollow silica fine particles solid content of the hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle diameter: 55 nm, average porosity: 23.3%
  • PETA pentaerythritol triacrylate
  • DPHA dipentaerythritol hexaacrylate
  • reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl Isobutyl ketone, average particle size: 12 nm
  • 0.1 parts by mass antifouling agent X-22-164E, manufactured by Shin-Etsu Chemical Co., Ltd.
  • 0.01 parts by mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition for low refractive index layer (4) The following components were mixed to prepare a composition for low refractive index layer (4).
  • Hollow silica fine particles solid content of hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle size: 60 nm, average porosity: 29.6%
  • PETA pentaerythritol triacrylate
  • reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl isobutyl ketone, average particle size: 12 nm
  • RS-74 manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • Antifouling agent TU2225, manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ketone
  • mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition (5) for low refractive index layer The following components were mixed to prepare a composition for low refractive index layer (5).
  • Hollow silica fine particles solid content of hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle size: 60 nm, average porosity: 29.6%
  • PETA pentaerythritol triacrylate
  • 0.1 part by mass reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl isobutyl ketone, average particle size: 12 nm
  • 0.02 mass Antifouling agent RS-74, manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • TU2225 manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ketone
  • mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition for low refractive index layer (6) The following components were mixed to prepare a composition for low refractive index layer (6).
  • Hollow silica fine particles solid content of the hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle diameter: 55 nm, average porosity: 23.3%
  • PETA pentaerythritol triacrylate
  • DPHA dipentaerythritol hexaacrylate
  • reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl Isobutyl ketone, average particle size: 12 nm
  • RS-74 manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • Antifouling agent TU2225, manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ket
  • composition for low refractive index layer (7) The following components were mixed to prepare a composition for low refractive index layer (7).
  • Hollow silica fine particles solid content of hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle size: 60 nm, average porosity: 29.6%
  • PETA pentaerythritol triacrylate
  • reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl isobutyl ketone, average particle size: 12 nm
  • 0.1 mass Antifouling agent RS-74, manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • TU2225 manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ketone
  • mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition for low refractive index layer (8) The following components were mixed to prepare a low refractive index layer composition (8).
  • Hollow silica fine particles solid content of hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle size: 60 nm, average porosity: 29.6%
  • PETA pentaerythritol triacrylate
  • 0.1 part by mass reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl isobutyl ketone, average particle size: 12 nm
  • Antifouling agent RS-74, manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • TU2225 manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ketone
  • mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition for low refractive index layer (9) The following components were mixed to prepare a composition for low refractive index layer (9).
  • Hollow silica fine particles solid content of hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle size: 60 nm, average porosity: 29.6%
  • PETA pentaerythritol triacrylate
  • 0.1 part by mass reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl isobutyl ketone, average particle size: 12 nm
  • RS-74 manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • TU2225 manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ketone
  • mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition for low refractive index layer (10) The following components were mixed to prepare a composition for low refractive index layer (10).
  • Hollow silica fine particles solid content of hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle size: 60 nm, average porosity: 29.6%
  • PETA pentaerythritol triacrylate
  • reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl isobutyl ketone, average particle size: 12 nm
  • Antifouling agent RS-74, manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • TU2225 manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ketone
  • mass polymerization initiator Irgacure 127; manufactured by BASF
  • composition (11) for low refractive index layer The following components were mixed to prepare a composition for low refractive index layer (11).
  • Hollow silica fine particles solid content of the hollow silica fine particles: 20% by mass solution; methyl isobutyl ketone, average particle diameter: 55 nm, average porosity: 23.3%
  • PETA pentaerythritol triacrylate
  • DPHA dipentaerythritol hexaacrylate
  • reactive silica fine particles solid content of the reactive silica fine particles: 30% by mass solution; methyl Isobutyl ketone, average particle size: 12 nm
  • RS-74 manufactured by DIC, 20% by mass solution; methyl ethyl ketone
  • TU2225 manufactured by JSR, 15% by mass solution; methyl isobutyl butyl ketone
  • Example 1 The composition for hard coat layer (1) was applied on one side of a cellulose triacetate film (thickness: 80 ⁇ m) with a wet weight of 30 g / m 2 (dry weight of 15 g / m 2 ). It dried for 30 seconds at 50 degreeC, and irradiated the ultraviolet-ray 50mJ / cm ⁇ 2 >, and formed the hard-coat layer. Next, on the formed hard coat layer, the composition (1) for the low refractive index layer is dried (25 ° C. ⁇ 30 seconds ⁇ 70 ° C. ⁇ 30 seconds) so that the film thickness becomes 0.1 ⁇ m. Applied.
  • the ultraviolet irradiation device (The fusion UV system Japan company make, light source H bulb), it irradiated with ultraviolet irradiation with the irradiation dose of 192 mJ / m ⁇ 2 >, and it was made to harden, and the antireflection film was obtained.
  • the film thickness was adjusted so that the minimum value of reflectivity was around 550 nm.
  • the blending ratio of hollow silica fine particles to (meth) acrylic resin content of hollow silica fine particles / content of (meth) acrylic resin was 1.60. It was.
  • Example 2 An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer composition (2) was used instead of the low refractive index layer composition (1).
  • the blending ratio of hollow silica fine particles to (meth) acrylic resin was 1.60. It was.
  • Example 3 The hard coat layer composition (2) was applied on one side of a cellulose triacetate film (thickness: 80 ⁇ m) to form a hard coat layer by applying a wet weight of 30 g / m 2 (dry weight of 15 g / m 2 ).
  • An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer was formed on the coating layer using the composition for low refractive index layer (2).
  • Example 4 An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer composition (3) was used instead of the low refractive index layer composition (1).
  • the mixing ratio of hollow silica fine particles to (meth) acrylic resin was 1.00. It was.
  • Example 5 An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer composition (4) was used instead of the low refractive index layer composition (1).
  • the mixing ratio of hollow silica fine particles to (meth) acrylic resin was 0.94. It was.
  • Example 6 An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer composition (5) was used instead of the low refractive index layer composition (1).
  • the blending ratio of hollow silica fine particles to (meth) acrylic resin was 1.60. It was.
  • Example 7 The hard coat layer composition (3) was applied on one side of a cellulose triacetate film (thickness: 80 ⁇ m) to form a hard coat layer by applying a wet weight of 30 g / m 2 (dry weight: 15 g / m 2 ).
  • An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer was formed on the coating layer using the composition for low refractive index layer (2).
  • Example 8 An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer composition (6) was used instead of the low refractive index layer composition (1).
  • the blending ratio of hollow silica fine particles to (meth) acrylic resin was 1.60. It was.
  • the low refractive index layer composition (11) is used in place of the low refractive index layer composition (1), and the low refractive index layer composition (11) is dried at 120 ° C. for 1 minute.
  • An antireflection film was obtained in the same manner as in Example 1 except that the rate layer was formed.
  • Example 2 A low refractive index layer composition (12) having the same composition as the low refractive index layer composition (1) except that the reactive silica fine particles are not contained is prepared, and the low refractive index layer composition (12) is prepared. An antireflection film was obtained in the same manner as in Example 1 except that was used.
  • composition for low refractive index layer (1) the composition for low refractive index layer (MEK-ST, manufactured by Nissan Chemical Industries, Ltd.) having reactive silica fine particles having no reactive functional group on the surface (1) 13) was prepared, and an antireflection film was obtained in the same manner as in Example 1 except that the composition for low refractive layer (13) was used.
  • MEK-ST the composition for low refractive index layer having reactive silica fine particles having no reactive functional group on the surface (1) 13
  • Example 3 An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer composition (9) was used instead of the low refractive index layer composition (1).
  • the blending ratio of hollow silica fine particles to (meth) acrylic resin was 1.60. It was.
  • content of the reactive silica fine particle in a low-refractive-index layer was 65 mass parts with respect to 100 mass parts of (meth) acrylic resins.
  • Example 4 An antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer composition (10) was used instead of the low refractive index layer composition (1).
  • the blending ratio of hollow silica fine particles to (meth) acrylic resin was 1.60. It was.
  • content of the reactive silica fine particle in a low-refractive-index layer was 3 mass parts with respect to 100 mass parts of (meth) acrylic resins.
  • Example 1 The antireflection films obtained in Examples and Comparative Examples were cut in the thickness direction, and the respective cross sections were observed with STEM (applied voltage: 30.0 kV, magnification: 200,000 times).
  • the result of Example 1 is shown in FIG. 1
  • the result of Example 7 is shown in FIG. 2
  • the result of Comparative Example 1 is shown in FIG. 3
  • the result of Comparative Example 2 is shown in FIG.
  • the antireflection film obtained in Comparative Example 1 formed a vapor deposition layer made of carbon having a thickness of about 150 nm during cross-sectional observation. Further, in the lower right of FIGS. 1 to 4, one scale indicates a scale of 20 nm.
  • the antireflection film according to Example 1 is confirmed to have reactive silica fine particles unevenly distributed in the vicinity of the interface opposite to the hard coat layer of the low refractive index layer. Further, the antireflection film according to Example 7 is confirmed. In the film, reactive silica fine particles unevenly distributed in the vicinity of the interface on the hard coat layer side of the low refractive index layer and in the vicinity of the interface opposite to the hard coat layer were confirmed, both of which were filled with hollow silica fine particles densely And the surface of the low refractive index layer was extremely uniform.
  • the antireflection film according to Example 3 has a state in which reactive silica fine particles unevenly distributed in the vicinity of the interface on the hard coat layer side of the low refractive index layer are confirmed, and hollow silica fine particles are also densely packed.
  • the surface of the low refractive index layer was in a very uniform state.
  • the antireflection films according to Examples 2, 4 to 6, and 8 were all confirmed to have reactive silica fine particles unevenly distributed in the vicinity of the interface opposite to the hard coat layer of the low refractive index layer, The hollow silica fine particles were also densely packed, and the surface of the low refractive index layer was extremely uniform.
  • the antireflection films according to the examples had sufficient antifouling properties, antireflection performance and scratch resistance. From the results of the examples, it was found that the scratch resistance was the best in the following cases.
  • the reactive silica fine particles are unevenly distributed on the side opposite to the hard coat layer of the low refractive index layer, and the amount of the reactive silica fine particles unevenly distributed is optimal (30 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin) Or more).
  • the hard coat layer also contains reactive silica fine particles, the hardness of the entire layer (light-transmitting substrate and hard coat layer) serving as the base of the low refractive index layer is high.
  • the antifouling property is best when the reactive silica fine particles are unevenly distributed on the hard coat layer side of the low refractive index layer. This is because the antifouling agent itself tends to come out on the surface of the low refractive index layer because there is no reactive silica fine particle on the outermost surface of the low refractive index layer, and the antifouling agent exists on the entire outermost surface of the low refractive index layer. It is presumed that.
  • the antireflection film according to Comparative Example 2 is in a state where the hollow silica fine particles are densely packed and the surface is uniform, but the reactive silica fine particles are present in the low refractive index layer. Since it was not included, the scratch resistance was poor.
  • the antireflection film according to Comparative Example 3 is in a state where the hollow silica fine particles are densely packed and the surface is uniform, but does not have a reactive functional group in the low refractive index layer. Since it contained silica fine particles, it was inferior in scratch resistance.
  • the ratio of the hollow silica fine particle with respect to the (meth) acrylic resin of the low refractive index layer was small, and the antireflection film according to Reference Example 1 was inferior in antireflection performance.
  • the antireflection films according to Reference Examples 2 and 3 have a high content of reactive silica fine particles in the low refractive index layer, and the reactive silica fine particles are insufficiently distributed and exist uniformly in the low refractive index layer. Further, the hollow silica fine particles were not in a densely packed state and were inferior in scratch resistance and antifouling property.
  • the antireflection film according to Reference Example 4 has a low content of reactive silica fine particles in the low refractive index layer, the uneven distribution of reactive silica fine particles is insufficient, and is uniformly present in the low refractive index layer,
  • the hollow silica fine particles were not in a densely packed state and were inferior in scratch resistance and antifouling properties.
  • the antireflection film of the present invention Since the antireflection film of the present invention has the low refractive index layer having the above-described configuration, it has excellent antireflection performance and surface hardness. Therefore, the antireflection film of the present invention is a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, a tablet PC, an electronic It can be suitably applied to paper or the like.
  • CTR cathode ray tube display
  • LCD liquid crystal display
  • PDP plasma display
  • ELD electroluminescence display
  • FED field emission display
  • touch panel a touch panel
  • tablet PC an electronic It can be suitably applied to paper or the like.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
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