JP2006146027A - Antiglare antireflection film, polarizing plate and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare antireflection film which is superior in film strength and surface uniformity having no irregularities, and to provide a polarizing plate and a display device that has the antiglare antireflection film. <P>SOLUTION: In the antiglare antireflection film, a hard coat layer, essentially consisting of an active energy ray curable resin, is disposed on the transparent support, the surface of the hard coat layer has a fine rugged shape for antiglare performance and a low-refractive index layer is directly or indirectly formed on the hard coat layer. Therein, the low-refractive index layer contains hollow and globular fine particles which have outer core layers and porous and hollow inner parts and the hollow and globular silica fine particles exist on a recessed part, rather than on a protrusion part in the low-refractive index layer formed along the rugged shape. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antiglare antireflection film, a polarizing plate and a display device, and particularly relates to an antiglare antireflection film excellent in film strength and uniform surface uniformity, and a polarizing plate and a display device using the antiglare antireflection film.

  In recent years, development of thin and light notebook computers has been progressing. Along with this, the demand for thinner and higher performance protective films for polarizing plates used in display devices such as liquid crystal display devices is also increasing. Computers and word processors with anti-reflection layers for improving visibility, anti-glare, and anti-glare layers with uneven surfaces to scatter reflected light to obtain display with less glare. Such liquid crystal image display devices (also referred to as liquid crystal displays) have come to be frequently used.

  Various types and performance improvements have been made to the antireflection layer and antiglare layer depending on the application, and various front plates with these functions are attached to the polarizer of a liquid crystal display, etc., to improve visibility on the display. Therefore, a method of providing an antireflection function or an antiglare function is used. These optical films used as the front plate are provided with an antireflection layer or an antiglare layer formed by coating or sputtering.

  The antiglare layer reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and reflection of the reflected image is noticeable when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It is to prevent it from becoming.

  By providing appropriate irregularities on the surface of the antiglare layer, the above properties can be provided. Conventionally, as a method for forming such unevenness, for example, a method of adding fine particles as disclosed in JP-A-59-58036 or the like to a coating solution is used. In addition, an embossing method disclosed in JP-A-6-234175, a method for transferring a mold in advance disclosed in JP-A-63-298201, and the like are known. However, in the method of adding the above-mentioned fine particles to the coating solution, the film strength may deteriorate if an attempt is made to increase the size or addition amount of the fine particles in order to provide sufficient antiglare properties. In addition, in the above-described embossing, it is difficult to form fine irregularities, and therefore, it is insufficient to prevent glare.

  The anti-glare film has an insufficient effect on the outermost surface of the liquid crystal display device, and the reflection of a fluorescent lamp becomes a problem with the clear hard coat anti-reflection film. Many techniques relating to an antiglare antireflection film having a (refractive index layer) have been proposed. Further, there is a demand from the market for a more excellent antiglare antireflection film satisfying both the reduction in reflectance and the strength of the surface film.

  An effective means for reducing the reflectance is to reduce the refractive index of the low refractive index layer. Patent application has been made for hollow spherical silica-based fine particles having an outer shell layer and having a porous or hollow interior. Documents 1 to 5 are known for use in low refractive index layers.

However, as a result of the study by the present inventors, when a low refractive index layer containing hollow spherical silica-based fine particles was formed on the antiglare hard coat layer, the film strength and performance of surface uniformity without unevenness were improved. It turned out to be insufficient.
Japanese Patent Laid-Open No. 2001-167637 JP 2001-233611 A JP 2002-79616 A JP 2002-265866 A JP 2003-292831 A

  An object of the present invention is to provide an antiglare antireflection film excellent in film strength and uniform surface uniformity, and a polarizing plate and a display device using the same.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
It has a hard coat layer mainly composed of an active energy ray-curable resin on a transparent film support, the surface of the hard coat layer has an antiglare fine uneven shape, and is directly on the hard coat layer Alternatively, in the antiglare antireflection film in which a low refractive index layer is indirectly formed, the low refractive index layer contains hollow spherical silica-based fine particles having an outer shell layer and porous or hollow inside. An antiglare antireflection film, wherein the hollow spherical silica-based fine particles are present more in the concave portion than in the convex portion in the low refractive index layer formed along the concave-convex shape.

(Claim 2)
2. The antiglare reflection according to claim 1, wherein when the number of convex portions of the silica-based fine particles per unit cross-sectional area is 100, the number of concave portions per unit cross-sectional area is 130 to 300. 3. Prevention film.

(Claim 3)
The antiglare antireflection film according to claim 1 or 2, wherein a surface treatment is performed on the surface of the hard coat layer, and then a low refractive index layer is formed.

(Claim 4)
The antiglare antireflection film according to claim 3, which is subjected to an aging treatment after the surface treatment.

(Claim 5)
The antiglare antireflection according to any one of claims 1 to 4, wherein the hard coat layer contains silica fine particles or polystyrene fine particles so that the surface has a fine uneven shape having an antiglare property. the film.

(Claim 6)
The surface of the low refractive index layer has a centerline average roughness (Ra) defined by JIS B 0601 of 0.15 to 0.50 μm, according to any one of claims 1 to 5. The antiglare antireflection film as described.

(Claim 7)
The antiglare according to any one of claims 1 to 6, further comprising a high refractive index layer or a middle refractive index layer and a high refractive index layer between the hard coat layer and the low refractive index layer. Antireflection film.

(Claim 8)
The antiglare antireflection film according to any one of claims 1 to 7, wherein the entire layer contains a fluorine-based or silicone-based surfactant.

(Claim 9)
The antiglare antireflection film according to any one of claims 1 to 8, wherein the binder component of the low refractive index layer contains an alkoxysilane compound as a main component.

(Claim 10)
A polarizing plate comprising the antiglare antireflection film according to claim 1.

(Claim 11)
A display device comprising the antiglare antireflection film according to claim 1.

  According to the present invention, it is possible to provide an antiglare antireflection film excellent in film strength and surface uniformity without unevenness, and a polarizing plate and a display device using the same.

  As a result of earnest research, the inventor has a hard coat layer mainly composed of an active energy ray-curable resin on a transparent film support, and the surface of the hard coat layer has an antiglare fine uneven shape, In the antiglare antireflection film in which the low refractive index layer is formed directly or indirectly on the hard coat layer, the low refractive index layer has an outer shell layer and the inside is porous or hollow. The hollow spherical silica-based fine particles are contained in the low refractive index layer formed along the concavo-convex shape, and the hollow spherical silica-based fine particles are present more in the concave portions than in the convex portions, so that the film strength and unevenness are reduced. It was found that an antiglare antireflection film excellent in surface uniformity was obtained.

  Hereinafter, the present invention will be described in detail.

[Hard coat layer]
The hard coat layer according to the present invention will be described.

  The hard coat layer is provided on at least one surface of the transparent film support. In the present invention, on the hard coat layer, at least a low refractive index layer, preferably a high refractive index layer or a middle refractive index layer and a high refractive index layer are provided between the hard coat layer and the low refractive index layer. The antiglare antireflection film of the invention is constituted.

  Although the hard coat layer has fine irregularities on the surface, the irregularities preferably contain particles having an average particle diameter of 0.01 to 4 μm as described below in the hard coat layer. As will be described later, the center line average roughness (Ra) defined by JIS B 0601 is adjusted to 0.15 to 0.50 μm as the surface roughness of the low refractive index layer provided on the hard coat layer. It is preferable to do.

(particle)
As particles contained in the hard coat layer, for example, inorganic or organic fine particles are used.

  Examples of the inorganic fine particles include silicon oxide (silica fine particles), titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate.

  The organic fine particles include polymethacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicon resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, and polyfluoroethylene resin fine particles.

  In the present invention, in particular, it is preferable that the surface is made into an antiglare fine uneven shape by containing silicon oxide fine particles or polystyrene fine particles.

  The inorganic or organic fine particles are preferably used in addition to a coating composition containing a resin or the like used for producing a hard coat layer. In addition, the average particle size of these fine particles is preferably 0.01 to 4 μm, more preferably 0.01 to 3 μm.

  In order to impart antiglare properties to the hard coat layer, the content of inorganic or organic fine particles is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the resin for preparing the hard coat layer. , 0.1 to 20 parts by mass. In order to provide a more preferable antiglare effect, it is preferable to use 1 to 15 parts by mass of fine particles having an average particle diameter of 0.1 to 1 μm with respect to 100 parts by mass of the resin for preparing the hard coat layer. It is also preferable to use two or more kinds of fine particles having different average particle diameters.

(Antistatic agent)
The hard coat layer preferably contains an antistatic agent, and the antistatic agent is selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W and V. A conductive material containing at least one element as a main component and having a volume resistivity of 10 ⁷ Ω · cm or less is preferable.

  Examples of the antistatic agent include metal oxides and composite oxides having the above elements.

As an example of the metal oxide, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or a composite oxide thereof is preferable. In particular, ZnO, In ₂ O ₃ , TiO ₂ and SnO ₂ are preferred. Examples of containing different atoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and addition of Sb, Nb and halogen elements to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, but more preferably in the range of 0.1 to 15 mol%.

Further, the volume resistivity of these conductive metal oxide powders is 10 ⁷ Ω · cm or less, particularly 10 ⁵ Ω · cm or less.

(Center line average roughness (Ra))
The surface of the hard coat layer according to the present invention has a fine uneven shape. As described above, the unevenness of the low refractive index layer provided on the hard coat layer is a centerline average defined by JIS B 0601. It is preferable to add and adjust the fine particles as described above so that the surface roughness Ra falls within the range of 0.15 to 0.50 μm, and more preferable Ra is 0.10 to 0.30 μm.

(Fine irregularities)
The fine unevenness | corrugation of the hard-coat layer surface based on this invention can obtain the hard-coat layer which has a more preferable unevenness | corrugation by adjusting the addition amount, particle size, film thickness, etc. of the above-mentioned fine particles. Further, the fine irregularities on the surface of the hard coat layer according to the present invention are formed as a fine structure having 5 to 20 convex portions per 100 μm ² having a height of 0.5 to ² μm with respect to the adjacent concave bottom. It is preferable.

Fine irregularities on the surface of the hard coat layer can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, the unevenness is measured two-dimensionally in the range of about 4000 μm ² (55 μm × 75 μm) using an optical interference type surface roughness measuring device, and the unevenness is color-coded as a contour line from the bottom side and displayed.

Here, the number of convex portions having a height of 0.5 to ² μm with respect to the adjacent bottom portion was counted and indicated by the number per 100 μm ² area. The measurement was carried out by measuring 10 arbitrary points per 1 m ² of the antiglare and antireflection film and obtaining the average value.

The surface of the hard coat layer preferably has a fine structure having a height of 0.2 μm or more with respect to the average level of the surface of 80 or more per 100 μm ² . In the same manner as described above, the unevenness is measured two-dimensionally in the range of about 4000 μm ² (55 μm × 75 μm) using an optical interference type surface roughness measuring machine, and the portion below the average level, the average level or higher to the height is 0.2 μm. Less than part, height is 0.2 μm or more of the area of at least three areas are displayed in color, and the number of parts that are convex at the height of 0.2 μm or more is counted, 100 μm It can be shown by the number per ² area.

(Average interval between fine peaks and valleys)
The hard coat layer according to the present invention preferably has an average crest / valley spacing of fine irregularities on the surface of 1 to 80 μm, more preferably 10 to 40 μm.

  Here, the shape of the fine concavo-convex structure can be measured by a stylus type surface roughness measuring machine or the like. For example, the fine concavo-convex structure is formed via a measuring needle having a diameter of 1 mm with a tip portion made of diamond having a conical shape with an apex angle of 55 degrees. It is possible to obtain knowledge as a surface roughness curve obtained by scanning the surface with a length of 3 mm in a certain direction, measuring the movement change in the vertical direction of the measuring needle in that case, and recording it. Alternatively, it can be measured by an optical interference type surface roughness measuring machine as described above.

  Here, the average crest-valley interval is assumed to be a reference line on which the unevenness change of the surface roughness curve can be evaluated as a protrusion based on a portion where the unevenness change in the surface roughness curve is minute (portion close to flat), Based on the intersection of the surface roughness curve passing from the bottom to the top (or from the top to the bottom) of the surface roughness curve with the average height of the convex part from the reference line as the center line, the distance between the intersections Can be defined as average.

(Refractive index)
The refractive index of the hard coat layer according to the present invention is preferably from 1.5 to 2.0, particularly from 1.6 to 1.7 from the viewpoint of optical design for obtaining a low reflective film. The refractive index of the hard coat layer can be adjusted depending on the refractive index and content of the fine particles to be added or the inorganic matrix.

(Film thickness)
From the viewpoint of imparting sufficient durability and impact resistance, the thickness of the hard coat layer is preferably 0.5 to 15 μm, and more preferably 1.0 to 7 μm.

(Haze)
In order to acquire the effect as described in this invention, it is preferable that the haze of a hard-coat layer is 5 to 40%, More preferably, it is 6 to 30%.

  The haze can be measured according to ASTM-D1003-52.

  As a means for adjusting the haze value of the hard coat layer according to the present invention to a preferable range, the organic fine particles and / or inorganic fine particles described above are preferably contained in the hard coat layer. Is preferably used because it is easily dispersed uniformly. In addition, those obtained by surface-treating fine particles such as silicon dioxide with an organic substance are also preferably used.

(Active energy ray curable resin)
The hard coat layer according to the present invention contains an active energy ray-curable resin that is cured by irradiation with active energy rays such as ultraviolet rays.

  The active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an active energy ray other than an ultraviolet ray or an electron beam may be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. .

  An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, JP-A No. 59-151112).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  UV curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.

  As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, useful epoxy-based active energy ray reactive compounds are shown.

(A) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by reaction of epichlorohydrin and bisphenol A)
(B) A compound having a glycidyl ether group by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs such as bisphenol A. (c) Glycidyl ether of 4,4'-methylenebisphenol (D) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin (e) Compound having alicyclic epoxide, for example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) ) Adipate, bis (3,4-epoxy-6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxy Rhohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3', 4'-epoxy-1 '-Methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3', 4'-epoxy-6'-methyl-1'-cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl- 5 ', 5'-spiro-3 ", 4" -epoxy) cyclohexane-meta-dioxane (f) diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, di Glycidyl hexahydrophthalate, diglycidyl Phthalate (g) Diglycidyl ether of glycol, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) di Glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (h) Glycidyl ester of polymer acid, for example, polyglycidyl ester of polyacrylic acid, polyester diglycidyl ester (i) Polyhydric alcohol Glycidyl ethers such as glycerin triglycidyl ether, trimethylolpropane triglyceride Dil ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether (j) As diglycidyl ether of 2-fluoroalkyl-1,2-diol, the low refractive index substance (K) Examples of the fluorine-containing alkane-terminated diol glycidyl ether include fluorine-containing epoxy compounds of the fluorine-containing resin of the low refractive index material, and the like. it can.

  The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.

  When the above epoxy compound is cured by active energy rays, it is effective to use a compound having a polyfunctional epoxy group (h) or (i) in order to increase the hardness.

  The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy-based active energy ray-reactive compound is a compound capable of releasing a cationic polymerization initiator by irradiation with active energy rays, and particularly preferably a cation by irradiation. It is a group of double salts of onium salts that release Lewis acids capable of initiating polymerization.

  The active energy ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is not affected by oxygen in the reaction system, and is therefore a preferred active energy ray reactive resin.

  The active energy ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or photosensitizer that releases a substance that initiates cationic polymerization upon irradiation with active energy rays. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  A typical example is a compound represented by the following general formula (a).

General formula (a)
[(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{w +} [MeX _v ] ^w-
Wherein cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg I, Br, Cl), or N = N (diazo), R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeX _v ] ^w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), tetra Examples thereof include fluoroarsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

  Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic halonium salts described in JP-A Nos. 50-151996 and 50-158680 are particularly useful. VIA group aromatic onium salts described in Kaisho 50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56-149402, Preference is given to oxosulfoxonium salts described in JP-A-57-192429, aromatic diazonium salts described in JP-B-49-17040, thiopyrilum salts described in US Pat. No. 4,139,655, and the like. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  In the case of an active energy ray-reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photosensitizer and photoinitiator used for the active energy ray-reactive compound are sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet-reactive compound. The amount is preferably 1 part by mass to 10 parts by mass. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the active energy ray-curable resin composition useful in the present invention, the polymerization initiator is generally used in an amount of 0.1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable epoxy resin (prepolymer). Is more preferable, and 1 to 10 parts by mass is more preferable.

  An epoxy resin can be used in combination with the urethane acrylate type resin, polyether acrylate type resin, or the like. In this case, it is preferable to use an active energy ray radical polymerization initiator and an active energy ray cationic polymerization initiator in combination.

  Moreover, an oxetane compound can also be used for the hard-coat layer based on this invention. The oxetane compound used is a compound having a three-membered oxetane ring containing oxygen or sulfur. Among them, a compound having an oxetane ring containing oxygen is preferable. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, or an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl -3 chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, 3,3-dimethyloxetane and the like. In the present invention, any of a monomer, an oligomer and a polymer may be used.

In the hard coat layer according to the present invention, a binder such as a known thermoplastic resin, a thermosetting resin, or a hydrophilic resin such as gelatin can be mixed with the active energy ray curable resin described above. These resins preferably have a polar group in the molecule. Examples of the polar _{group, -COOM, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OSO 3 M, -PO 3 M 2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali A metal or an ammonium group, X represents an acid forming an amine salt, R represents a hydrogen atom or an alkyl group).

(Type of active energy rays, irradiation method)
As a method of irradiating active energy rays, active energy rays may be irradiated after coating a hard coat layer, an antireflection layer (medium, high refractive index layer and low refractive index layer) on the support, It is preferable to irradiate an active energy ray when the hard coat layer is applied.

The active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, γ ray, etc., but ultraviolet ray and electron beam are preferable, especially easy handling and high energy. UV rays are preferred in that they can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated is preferably 20 mJ / cm ² or more, more preferably an 50~10000mJ / cm ^2, particularly preferably 50~2000mJ / cm ^2.

  The ultraviolet irradiation may be performed every time one layer is provided for each of a plurality of layers (medium refractive index layer, high refractive index layer, low refractive index layer) constituting the antireflection layer, or after lamination. Also good. Or you may irradiate combining these. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

  Moreover, an electron beam can be used similarly. As the electron beam, 50 to 1000 keV emitted from various electron beam accelerators such as cockroft Walton type, bandegraph type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type, preferably 100 to 100 An electron beam having an energy of 300 keV can be given.

  In order to initiate the photopolymerization or photocrosslinking reaction of the active energy ray-reactive compound used in the present invention, the active energy ray-reactive compound alone is initiated, but the polymerization induction period is long or the polymerization initiation is slow. Therefore, it is preferable to use a photosensitizer or a photoinitiator, which can accelerate the polymerization.

(Photoinitiator, photosensitizer)
When the hard coat layer according to the present invention contains an active energy ray-curable resin, a photoreaction initiator and a photosensitizer can be used during irradiation with active energy rays.

  Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. Moreover, when using a photoreactant for the synthesis | combination of an epoxy acrylate-type resin, sensitizers, such as n-butylamine, a triethylamine, a tri-n-butylphosphine, can be used. The amount of the photoreaction initiator and / or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying is preferably 1 to 10% by mass, particularly preferably 2%. .5 to 6% by mass.

  Moreover, when using ultraviolet curable resin as active energy ray curable resin, you may include the ultraviolet absorber mentioned later in the ultraviolet curable resin composition to such an extent that the photocuring of the said ultraviolet curable resin is not prevented.

(Antioxidant)
In order to increase the heat resistance of the hard coat layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  Examples of the ultraviolet curable resin include Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) ), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101 FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam's PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 )), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UC Corporation), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102 RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.), Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sun Rad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (Grace (Available from Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), or other commercially available products.

  The coating composition containing the active energy ray-curable resin preferably has a solid content concentration of 10 to 95% by mass, and an appropriate concentration is selected depending on the coating method.

(Surfactant)
The hard coat layer, the low refractive index layer and other layers according to the present invention preferably contain a surfactant. As the surfactant, a silicon-based or fluorine-based surfactant is preferable.

  As the silicon-based surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  A nonionic surfactant is a generic term for a system surfactant that does not have a group capable of dissociating into ions in an aqueous solution. In addition to a hydrophobic group, a hydrophilic group includes a hydroxyl group of a polyhydric alcohol, a polyoxyalkylene chain ( Polyoxyethylene) or the like as a hydrophilic group. The hydrophilicity becomes stronger as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant according to the present invention is characterized by having dimethylpolysiloxane as a hydrophobic group.

  When a nonionic surfactant composed of a dimethylpolysiloxane having a hydrophobic group and a polyoxyalkylene having a hydrophilic group is used, unevenness of the hard coat layer and the low refractive index layer and antifouling property of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

  Specific examples of these nonionic surfactants include, for example, Nippon Unicar Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ- 2163, FZ-2164, FZ-2166, FZ-2191 and the like.

  Moreover, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a linear block copolymer. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle at a plurality of locations so as to cover the surface of the silica fine particle by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

  Specific examples thereof include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208 and the like manufactured by Nippon Unicar Co., Ltd.

  As the fluorine-based surfactant, a surfactant having a hydrophobic group having a perfluorocarbon chain can be used. As types, fluoroalkylcarboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, sodium 3- (fluoroalkyloxy) -1-alkylsulfonate, 3- (ω-fluoroalkanoyl-N-ethylamino) -1- Sodium propanesulfonate, N- (3-perfluorooctanesulfonamido) propyl-N, N-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonic acid Salt, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethyl Ruhonirugurishin salts, phosphoric acid bis (N- perfluorooctylsulfonyl -N- ethylamino ethyl) and the like. In the present invention, nonionic surfactants are preferred.

  These fluorosurfactants are commercially available under the trade names such as Megafac, F-Top, Surflon, Footagen, Unidyne, Florard, Zonyl and the like.

  A preferred addition amount is 0.01 to 3.0%, more preferably 0.02 to 1.0%, based on the solid content contained in the hard coat layer coating solution.

  Uses other anionic, cationic or other nonionic surfactants to disperse hollow spherical silica-based fine particles that have an outer shell layer, which will be described later, and are porous or hollow inside, and have low refraction. The coating unevenness that is likely to occur when forming the rate layer is not limited to the unevenness, but greatly affects the antifouling property, the reflection performance, and the like. By using these nonionic surfactants according to the present invention, These irregularities are substantially eliminated.

  However, other surfactants may be used in combination, and as appropriate, for example, anionic surfactants such as sulfonates, sulfates, and phosphates, and polyoxyethylene chain hydrophilic groups A nonionic surfactant such as an ether type or an ether ester type may be used in combination.

(Method for producing hard coat layer)
The solvent for coating the hard coat layer according to the present invention is appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or used by mixing. it can. Preferably, a solvent containing 5% by mass or more, more preferably 5 to 80% by mass or more of propylene glycol mono (C1-C4) alkyl ether or propylene glycol mono (C1-C4) alkyl ether ester is used.

  As a coating method of the hard coat layer composition coating solution, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater or an air doctor coater can be used. The coating amount is suitably 5 to 30 μm in wet film thickness, and preferably 10 to 20 μm. The coating speed is preferably 10 to 60 m / min.

  The hard coat layer composition is preferably applied and dried, and then irradiated with an active energy ray such as an ultraviolet ray or an electron beam and cured, but the irradiation time of the active energy ray is preferably 0.5 seconds to 5 minutes. More preferably, it is 3 seconds to 2 minutes in view of the curing efficiency and work efficiency of the ultraviolet curable resin.

(Antireflection layer)
The antireflection layer according to the present invention will be described.

(Configuration of antireflection layer)
The antireflective layer according to the present invention has a low refractive index layer formed directly or indirectly on the fine uneven surface of the hard coat layer, and the low refractive index layer has an outer shell layer and is porous inside. Alternatively, it is characterized by containing hollow spherical silica-based fine particles.

  In the low refractive index layer of the present invention, an antiglare antireflection film is prepared by setting the optical film thickness of the low refractive index layer to λ / 4 with respect to light of wavelength λ. The optical film thickness is an amount defined by the product of the refractive index n and the film thickness d of the layer. The level of the refractive index is largely determined by the metal or compound contained therein, for example, Ti is high, Si is low, F-containing compounds are further low, and the refractive index is set by such a combination. The refractive index and the film thickness can be calculated and calculated by measuring the spectral reflectance.

  The antiglare antireflection film of the present invention is preferably provided with a multilayer refractive index layer. Laminated with a hard coat layer on a transparent film support, taking into account the refractive index, film thickness, number of layers, layer order, etc., so that the reflectivity is reduced by optical interference on the fine uneven surface it can. The antireflection layer is composed of a combination of a high refractive index layer having a higher refractive index than that of the support and a low refractive index layer having a lower refractive index than that of the support, and particularly preferably from three or more refractive index layers. 3 layers having different refractive indices from the support side, medium refractive index layer (layer having a higher refractive index than that of the support or hard coat layer and lower refractive index than that of the high refractive index layer). It is preferable to laminate in the order of / high refractive index layer / low refractive index layer.

  Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.

  The example of the preferable layer structure of the anti-glare antireflection film of this invention is shown below. Here, / indicates that the layers are arranged in layers.

Back coat layer / support / hard coat layer / low refractive index layer Back coat layer / support / hard coat layer / high refractive index layer / low refractive index layer Back coat layer / support / hard coat layer / medium refractive index layer / High refractive index layer / Low refractive index layer Back coat layer / Support / Antistatic layer / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Antistatic layer / Support / Hard coat layer / Medium refractive index layer / high refractive index layer / low refractive index layer back coat layer / support / hard coat layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer In order to facilitate, an antifouling layer may be further provided on the outermost low refractive index layer. As the antifouling layer, fluorine-containing organic compounds are preferably used.

As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. The antistatic layer is preferably a layer containing conductive polymer fine particles (for example, crosslinked cation fine particles) or metal oxide fine particles (for example, SnO ₂ , ITO, etc.), and can be provided by coating. Alternatively, a metal oxide layer (ZnO ₂ , SnO ₂ , ITO, or the like) can be provided by atmospheric pressure plasma treatment, plasma CVD, or the like.

(Low refractive index layer)
(surface treatment)
In the present invention, it is preferable that after the hard coat layer is formed, the surface of the hard coat layer is subjected to a surface treatment, and the low refractive index layer according to the present invention is formed on the surface of the hard coat layer subjected to the surface treatment.

  Examples of the surface treatment include cleaning methods, alkali treatment methods, flame plasma treatment methods, high frequency discharge plasma methods, electron beam methods, ion beam methods, sputtering methods, acid treatments, corona treatment methods, atmospheric pressure glow discharge plasma methods, and the like. An alkali treatment method, a flame plasma treatment method and a corona treatment method are preferred, and an alkali treatment method is particularly preferred.

  When the antiglare antireflection film of the present invention uses a cellulose ester film such as triacetyl cellulose (TAC) as a support, and the film is used for LCD applications, to obtain adhesion between TAC and a polarizing plate substrate. In addition, it is preferable to serve as an alkali treatment generally performed because the burden of the process can be reduced.

  The alkali treatment method is not particularly limited as long as it is a method in which a film coated with a hard coat layer is immersed in an alkaline aqueous solution. The alkali treatment conditions are appropriately adjusted within a range where the surface shape of the antiglare layer does not change greatly.

  As the aqueous alkali solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and an aqueous sodium hydroxide solution is particularly preferable. The alkali concentration of the aqueous alkali solution, for example, sodium hydroxide concentration is preferably 0.1 to 25% by mass, and more preferably 0.5 to 15% by mass.

  The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C.

  The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably neutralized with acidic water and then thoroughly washed with water. The film after moisture treatment is sufficiently dried.

(Aging process)
In the present invention, it is preferable to perform an aging treatment after the surface treatment. The aging treatment of the present invention means that the hard coat layer coated on the support is surface-treated and then stored under conditions of 24 hours or more at room temperature and 6 hours or more at 50 ° C.

  The aging treatment of the present invention may be performed at a high temperature, for example, at 50 ° C. for 10 hours to 10 days. Preferably, 10 to 40 ° C., 3 days or more, and more preferably 7 to 180 days.

  The storage temperature is preferably stored at a constant temperature, most preferably within a range of ± 5 ° C. of the temperature at which the low refractive index layer is coated, and aging is preferably performed while wound on a roll.

(Hollow spherical silica-based fine particles)
Next, hollow spherical silica-based fine particles that have an outer shell layer and are porous or hollow inside will be described.

  The hollow spherical fine particles are: (1) composite particles composed of porous particles and a coating layer provided on the surface of the porous particles; or (2) cavities in the interior, and the content is a solvent, gas or porous Cavity particles filled with a substance. The low refractive index layer only needs to contain either (1) composite particles or (2) hollow particles, or both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. The hollow spherical fine particles have an average particle size of 5 to 300 nm, preferably 10 to 200 nm. The hollow spherical fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and are desirably 2/3 to 1/10 of the film thickness of the formed transparent film such as a low refractive index layer. . These hollow spherical fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later. In some cases, the composite particles enter the inside of the composite particles and the internal porosity is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. .

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. In addition, components other than silica may be contained. Specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is 0.001-0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, particles having a small pore volume and a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a low refractive index. is there.

  The pore volume of such porous particles is 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used in preparing the hollow particles, the catalyst used, and the like. Examples of the porous substance include those composed of the compounds exemplified for the porous particles. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow spherical fine particles, for example, the method for preparing complex oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow spherical fine particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. Can do. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using the seed particle dispersion, the pH of the seed particle dispersion is adjusted to 10 or more, and then the aqueous solution of the compound is added to the above-described alkaline aqueous solution with stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of the silica and the inorganic compound other than silica in the first step is calculated by converting the inorganic compound to silica into an oxide (MO _X ), and the molar ratio of MO _X / SiO ₂ is 0.05 to 2.0, Preferably it is 0.2-2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, the molar ratio of MO _X / SiO ₂ is preferably 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the body, the formed coating layer becomes a particle wall to form hollow particles.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organic silicon compound used for the silica protective film formed of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, such as acrylic group An alkoxysilane represented by a hydrocarbon group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third step: Formation of silica coating layer In the third step, the porous particle dispersion prepared in the second step (in the case of hollow particles, the hollow particle precursor dispersion) contains a fluorine-substituted alkyl group-containing silane compound. By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, An alkoxysilane represented by a hydrocarbon group such as an acryl group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or silicic acid solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. The refractive index of the low refractive index layer according to the present invention is preferably 1.30 to 1.50, and more preferably 1.35 to 1.44.

In the present invention, commercially available SiO ₂ fine particles can be used. Specific examples of commercially available particles include P-4 manufactured by Catalytic Chemical Industry Co., Ltd.

  The content (mass) of the hollow spherical silica-based fine particles having an outer shell layer and porous or hollow inside in the low refractive index layer coating solution is preferably 10 to 80% by mass, more preferably 20 to 60% by mass. %.

(Distribution of hollow spherical silica-based fine particles)
The low refractive index layer according to the present invention includes hollow spherical silica-based fine particles having an outer shell layer and porous or hollow inside, and is formed directly or indirectly along the fine uneven shape of the hard coat layer. In the low refractive index layer, hollow spherical silica-based fine particles are present more in the concave portion than in the convex portion. A convex part means the part by the side of the surface (distance far from a support body) which divided | segmented the uneven | corrugated shaped low refractive index layer 23 into two by height, as shown in FIG. The concave portion refers to a portion close to the support divided into two. The degree of the size is preferably 130 to 300 per unit cross-sectional area of the concave portion when the number per unit cross-sectional area of the convex portion of the silica-based fine particles 24 is 100. The number of silica-based fine particles per unit cross-sectional area can be determined from a tomographic photograph of an electron microscope.

(Alkoxysilane compound)
Various sol-gel materials can also be used as the binder material for the low refractive index layer. As such a sol-gel material, metal alcoholates (alcolates such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. Of these, alkoxysilanes, organoalkoxysilanes and hydrolysates thereof are preferred. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency. In the present invention, it is preferable to prepare by applying a coating solution containing an alkoxysilane compound as a main component.

  When hydrolyzing the tetraalkoxysilane, it is preferable to mix the inorganic fine particles in order to increase the film strength.

  The low refractive index layer according to the present invention preferably contains the silica fine particles and the following silane coupling agent.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Specific examples of the silane coupling agent include: Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-403, KBM-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE- 503, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-802, KBM-803 and the like.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  A specific method of surface treatment with a coupling agent is shown below.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surface of the silica fine particles described above easily reacts to form a stronger film. Moreover, you may add the hydrolyzed silane coupling agent in a coating liquid previously.

  The low refractive index layer can also contain a polymer in an amount of 5 to 50% by weight. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer and performing a polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out a combination of two or all of the above (1) to (3), and to carry out a combination of (1) and (3) or (1) to (3) all of the combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment of fine particles It is preferable to carry out a surface treatment on fine particles (particularly inorganic fine particles) to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the fine particles are made of SiO _{2, the} surface treatment with the above-described silane coupling agent can be carried out particularly effectively.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Mention may be made of esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after coating the low refractive index layer, by a polymerization reaction (if necessary, a crosslinking reaction). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

  In addition, the low refractive index layer according to the present invention may be a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”).

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemicals) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). In the latter, it is possible to introduce a crosslinked structure by adding a compound having a group that reacts with a functional group in the polymer and another reactive group after copolymerization, as disclosed in JP-A-10-25388 and 10-147739 In the issue. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is crosslinked by heating by a cross-linking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the thermosetting type In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., it is an ionizing radiation curable type. .

  In addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR), etc. Can be mentioned.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  The low refractive index layer according to the present invention is applied by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (US Pat. No. 2,681,294). Can be formed. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).

  Each film thickness of the low refractive index layer according to the present invention is preferably 50 to 200 nm, and more preferably 60 to 150 nm.

[High refractive index layer and medium refractive index layer]
In the present invention, it is preferable to provide a high refractive index layer between the transparent support provided with the hard coat layer and the low refractive index layer in order to reduce the reflectance. In addition, it is more preferable to provide an intermediate refractive index layer between the transparent support and the high refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of the high refractive index layer and the middle refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The haze of the high refractive index layer and the middle refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more, with a pencil hardness of 1 kg.

  In the present invention, the high refractive index layer is formed by applying and drying a coating solution containing a monomer, oligomer or hydrolyzate of an organic titanium compound represented by the following general formula (1). A layer having a rate of 1.55 to 2.5 is preferred.

General formula (1) Ti (OR ₁ ) ₄
In the formula, R ₁ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

As monomers and oligomers of organic titanium compounds, Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (Oi-C ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ di- to 10-mer, Ti (O-i-C ₃ H ₇ ) ₄ 2 to 10 Preferred examples include a monomer, a di- to 10-mer of Ti (On-C ₄ H ₉ ) ₄ , and the like. These can be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  Among the coating solutions for the high refractive index layer used in the present invention, it is preferable to add the organic titanium compound to a solution in which water and an organic solvent described later are sequentially added. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is 0.25-3 mol with respect to 1 mol of organic titanium compounds. If the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and white turbidity. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  The organic solvent used in the present invention is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted so that the water content is less than 10% by mass relative to the total amount of the coating solution.

  The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention preferably accounts for 50.0 to 98.0% by mass in the solid content contained in the coating solution. The solid content ratio is more preferably 50 to 90% by mass, and further preferably 55 to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and medium refractive index layer used in the present invention preferably contain metal oxide particles as fine particles, and further contain a binder polymer.

  When the hydrolyzed and polymerized organotitanium compound and metal oxide particles are combined in the coating solution preparation method, the metal oxide particles and the hydrolyzed and polymerized organotitanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The mass average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The mass average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, further preferably 10 to 100 nm, and preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles can contain oxides of these metals as main components and further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent is most preferable.

  Two or more types of coupling agents may be used in combination, and other silane coupling agents may be used in addition to the silane coupling agent. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are easy to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In the present invention, the treatment may be performed by combining two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The high refractive index layer and medium refractive index layer used in the present invention preferably use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide, and melamine resin. Among these, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Moreover, it is more preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, the anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated. The linking group that binds the anionic group and the polymer chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, and more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably a carbon number. 1 to 6 alkyl groups. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by blending a monomer for generating a cross-linked polymer to prepare a coating solution for forming a high refractive index layer and a medium refractive index layer, and is generated by a polymerization reaction simultaneously with or after coating of the coating solution. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method in which a crosslinked polymer is produced by a polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of a hard-coat layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, and alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

  In addition to the above-mentioned components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the antireflection layer or its coating solution is a polymerization inhibitor, leveling agent, thickener, anti-coloring agent. An agent, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.

  In the present invention, after coating the high refractive index layer and the low refractive index layer, it is preferable to irradiate active energy rays in order to promote hydrolysis or curing of the composition containing the metal alkoxide. More preferably, the active energy ray is irradiated every time each layer is coated.

The active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, and γ ray, but ultraviolet ray and electron beam are preferable, and handling is particularly simple and high energy. Ultraviolet rays are preferred because they can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably ²⁰ to 10,000 mJ / cm ² , more preferably 100 to 2,000 mJ / cm ² , and particularly preferably 400 to 2,000 mJ / cm 2. ² .

  When ultraviolet rays are used, the multilayer antireflection layer may be irradiated one by one, or may be irradiated after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

  Moreover, an electron beam can be used similarly. As the electron beam, 50 to 1000 keV emitted from various electron beam accelerators such as cockroft Walton type, bandegraph type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type, preferably 100 to 100 An electron beam having an energy of 300 keV can be given.

(Antireflection layer thickness)
The thickness of each refractive index layer constituting the antireflection layer is preferably in the range of 1 to 200 nm, more preferably 5 to 150 nm, but each film has an appropriate thickness depending on the refractive index of each layer. It is preferable to select.

(Reflectivity of antireflection layer)
The antireflection layer according to the present invention preferably has an average reflectance at 450 to 650 nm of 1% or less, particularly preferably 0.5% or less. Further, the minimum reflectance in this range is particularly preferably from 0.00 to 0.3%.

  The refractive index and film thickness of the antireflection layer can be calculated and calculated by measuring the spectral reflectance. Moreover, the reflective optical characteristic of the produced low reflection film can measure a reflectance on the conditions of a 5-degree regular reflection using a spectrophotometer. In this measurement method, after roughening the substrate surface on which the antireflection layer is not applied, a light absorption treatment is performed using a black spray to prevent reflection of light on the back surface of the film and reflectivity. Is measured.

  In the measurement, the transmittance at a transmittance of 550 nm is measured using a spectrophotometer with reference to air.

(Center line average roughness of antireflection layer (Ra))
The outermost surface of the antireflection layer according to the present invention needs to have fine irregularities. In addition to forming fine irregularities on the surface of the hard coat layer, when the fine particles described above are added and the outermost surface is a low refractive index layer, the centerline average surface roughness Ra defined by JIS B 0601 is It is preferable to adjust to 0.15-0.50 micrometer. More preferably, it is adjusted to 0.10 to 0.30 μm. In addition, when cohesive fine particles such as silicon dioxide are used, the unevenness can be finely adjusted depending on the dispersion conditions.

(Measurement of fine irregularities in the antireflection layer)
Further, the fine irregularities of the antireflection layer according to the present invention are formed as a fine structure having 5 to 20 convex portions per 100 μm ² having a height of 0.5 to ² μm with respect to the adjacent concave bottoms. It is preferable.

  About the fine unevenness | corrugation of an antireflection layer, it can measure using the method similar to the fine unevenness | corrugation of the said hard-coat layer.

Further, the surface of the antireflection layer according to the present invention preferably has a fine structure having 80 or more protrusions per 100 μm ² having a height of 0.2 μm or more based on the average level of the surface. The structure can also be measured by a method using an optical interference type surface roughness measuring machine or the like, similarly to the measurement of the fine structure of the hard coat layer.

  The average crest / valley interval of fine irregularities on the surface of the antireflection layer according to the present invention is also defined in the same manner as in the case of the average crest / valley interval of fine irregularities on the hard coat layer surface described above, and is a commercially available stylus type surface roughness. It can be measured by a thickness measuring machine or an optical interference type surface roughness measuring machine.

  By adjusting the fine concavo-convex structure on the surface on which the antireflection layer is formed to the above range, the occurrence of glare phenomenon due to the reduction in pixel size and the increase in screen size can be prevented, and This has the effect of preventing the occurrence of visual interference due to surface reflection.

[Transparent film support]
As the transparent film support used for the antiglare antireflection film of the present invention, it is easy to manufacture, the hard coat layer or the antireflection layer is easily adhered, is optically isotropic, It is preferably optically transparent. Any of these may be used, for example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate. Polyester film, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin Film, polymethylpentene film, polyetherketone film, Polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, cycloolefin polymer films, there may be mentioned polymethyl methacrylate film or an acrylic film or the like, but are not limited to. Among these, cellulose ester films (for example, Konica Minoltak KC8UX2M, KC4UX2M, KC4UY, KC8UT, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4 (above, manufactured by Konica Minolta Opto Co., Ltd.)), polycarbonate film, polysulfone (Polysulfone) (Including ether sulfones), cycloolefin polymer films are preferred, and in the present invention, cellulose triacetate films and cellulose acetate propionate films are particularly preferred in terms of production, cost, transparency, isotropic properties, and adhesiveness. preferable.

(Cellulose ester film)
In the present invention, the cellulose ester is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A Nos. 10-45804 and 08-231761 , Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

  If the molecular weight of the cellulose ester is too small, the tear strength decreases. However, if the molecular weight is excessively increased, the viscosity of the cellulose ester solution becomes too high, resulting in a decrease in productivity. The molecular weight of the cellulose ester is preferably 70000-200000, more preferably 100,000-200000 in terms of number average molecular weight (Mn).

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate. When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy | fills 1) and (2) simultaneously.

Formula (1) 2.6 <= X + Y <= 3.0
Formula (2) 0 ≦ X ≦ 2.5
Of these, cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The portion that is not substituted with an acyl group is usually present as a hydroxyl group. These can be synthesized by known methods.

  As the cellulose ester, a cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from cotton linter (hereinafter sometimes referred to simply as linter) alone or in combination.

  The cellulose ester film used in the present invention may be one produced by a solution casting method or one produced by a melt casting method, but is preferably at least stretched in the width direction, and particularly solution casting. It is preferable that the film is stretched 1.01 to 1.5 times in the width direction when the amount of the residual dissolution in the process is 3 to 40% by mass. More preferably, it is biaxially stretched in the width direction and the lengthwise direction, and when the amount of residual dissolution is 3 to 40% by mass, it is stretched by 1.01 to 1.5 times in the width direction and the lengthwise direction, respectively. It is desirable that By carrying out like this, the anti-glare antireflection film excellent in visibility can be obtained. Furthermore, by performing biaxial stretching and knurling, it is possible to remarkably improve the deterioration of the winding shape during storage of the long low-reflection film in the form of a roll.

  The draw ratio at this time is preferably 1.01 to 1.5 times, and more preferably 1.03 to 1.45 times.

  In the present invention, it is preferable to use a long film, and specifically, a film of about 100 m to 5000 m is shown. Moreover, 1.4 m or more is preferable and, as for the width | variety of a base film, it is more preferable that it is 1.4-4m.

  In the present invention, the cellulose ester film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

In the present invention, the cellulose ester film support preferably has a thickness of 10 to 100 μm, and the moisture permeability is preferably 200 g / m ² · 24 hours or less at 25 ° C. and 90 ± 2% RH, More preferably, it is 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less. In particular, it is preferable that the film thickness is 10 to 60 μm and the moisture permeability is within the above range. Here, the moisture permeability of the support can be measured according to the method described in JIS Z 0208.

(Plasticizer)
When a cellulose ester film is used for the support used in the present invention, the following plasticizer is preferably contained. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy For trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid, and the like can be used. As glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The polyhydric alcohol ester plasticizer comprises an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid. Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl- 1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like can be raised. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable. There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid can be raised. Examples of preferable alicyclic monocarboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof. Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. Aromatic monocarboxylic acids or their derivatives can be raised. Particularly preferred is benzoic acid. Although there is no restriction | limiting in particular in the molecular weight of a polyhydric alcohol ester, It is preferable that it is the range of molecular weight 300-1500, and it is further more preferable that it is the range of 350-750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified with carboxylic acid, or a part of the OH groups may be left as they are.

  These plasticizers are preferably used alone or in combination.

  The amount of these plasticizers used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13% by mass, based on the cellulose ester, in terms of film performance, processability and the like.

(UV absorber)
The ultraviolet absorber according to the support used in the present invention will be described.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of preferably used ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like. However, it is not limited to these.

  As the benzotriazole ultraviolet absorber, a compound represented by the following general formula (A) is preferably used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

  Moreover, these groups described above may have an arbitrary substituent.

  Although the specific example of the ultraviolet absorber used for this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba Specialty Chemicals)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Specialty Chemicals)
As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (B) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  Specific examples of the benzophenone compound represented by the general formula (B) are shown below, but the present invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the above-mentioned ultraviolet absorbers preferably used in the present invention, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers that are highly transparent and excellent in preventing deterioration of polarizing plates and liquid crystals are preferable, and unnecessary coloring A benzotriazole-based ultraviolet absorber with a lower content is particularly preferably used.

  In addition, an ultraviolet absorber having a distribution coefficient of 9.2 or more described in Japanese Patent Application No. 11-295209 is excellent in surface quality of the support and excellent in coatability when used in the support. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorber (or ultraviolet ray) described in the general formula (1) or general formula (2) of JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039. Absorbable polymers) are also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

(Fine particles)
In the present invention, the cellulose ester film preferably contains fine particles. Examples of the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, and hydration. It is preferable to contain inorganic fine particles such as calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film. The average particle size of the secondary particles of the fine particles is 0.01 to 1.0 μm, and the content is preferably 0.005 to 0.3% by mass with respect to the cellulose ester. In many cases, fine particles such as silicon dioxide are surface-treated with an organic substance, but such particles are preferable because they can reduce the haze of the film. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (particularly alkoxysilanes having a methyl group), silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the mat effect, and on the contrary, the smaller the average particle size, the better the transparency. Therefore, the average particle size of the preferred primary particles is 5 to 50 nm, more preferably 7 to 16 nm. It is. These fine particles are usually present as aggregates in the cellulose ester film, and it is preferable to form irregularities of 0.01 to 1.0 μm on the surface of the cellulose ester film. Examples of the fine particles of silicon dioxide include Aerosil (Aerosil) 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600 manufactured by Aerosil Co., preferably AEROSIL (Aerosil) 200V, R972, R972V, R974, R202, and R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, AEROSIL (Aerosil) 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9 to 0.1. In the present invention, the fine particles may be dispersed together with cellulose ester, other additives, and an organic solvent at the time of preparing the dope, but in a sufficiently dispersed state like a fine particle dispersion separately from the cellulose ester solution. It is preferable to prepare the dope. In order to disperse the fine particles, it is preferably preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force. After that, it is preferable to disperse in a larger amount of organic solvent, merge with the cellulose ester solution, and mix with an in-line mixer to obtain a dope. In this case, an ultraviolet absorbent may be added to the fine particle dispersion to form an ultraviolet absorbent liquid.

  The deterioration inhibitor, the ultraviolet absorber and / or the fine particles may be added together with the cellulose ester and the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.

(Organic solvent)
The organic solvent useful for forming the dope in the present invention simultaneously dissolves cellulose ester, a compound having at least two aromatic rings, and at least two aromatic rings having a planar structure, and other additives. Anything can be used without limitation. For example, as the chlorinated organic solvent, methylene chloride, as the non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, and nitroethane. Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used. Particularly preferred is methyl acetate.

  In addition to the organic solvent, the dope according to the present invention preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the role of promoting dissolution of cellulose esters in non-chlorine organic solvent systems There is also. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability, boiling point of these inner dopes, relatively good drying, and no toxicity.

  The concentration of the cellulose ester in the dope is preferably adjusted to 15 to 40% by mass, and the dope viscosity is preferably adjusted to a range of 100 to 500 poise (P) in order to obtain good film surface quality.

〔Polarizer〕
The polarizing plate can be produced by a general method. The back side of the antiglare antireflection film of the present invention is subjected to alkali saponification treatment and bonded to at least one surface of a polarizing film prepared by immersing and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. preferable. The film may be used on the other surface, or another polarizing plate protective film may be used. Commercially available cellulose ester films (for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UY, KC4UY, KC12UR, and above, manufactured by Konica Minolta Opto Co., Ltd.) are preferably used. With respect to the antiglare antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, a phase difference of 20 to 70 nm, and Rt of 100 to 400 nm. Preferably it is. These can be produced, for example, by the methods described in JP-A-2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using it in combination with the antiglare antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the optical film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  A conventional polarizing plate using an antiglare antireflection film is inferior in flatness, and when the reflected image is seen, fine wavy irregularities are recognized, and the durability test under conditions of 60 ° C. and 90% RH shows that it is wavy. On the other hand, the polarizing plate using the antiglare antireflection film of the present invention was excellent in flatness. Further, even in the durability test under the conditions of 60 ° C. and 90% RH, the wavy unevenness did not increase.

[Display device]
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The antiglare antireflection film of the present invention is a reflection type, transmission type, transflective LCD or various drive systems such as TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), and IPS type. It is preferably used in LCDs. Further, the antiglare antireflection film of the present invention is excellent in flatness and is preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper. In particular, a large-screen display device having a screen of 30 or more types, particularly 30 to 54 types, has no white spots at the periphery of the screen, and the effect is maintained for a long period of time. In particular, the MVA liquid crystal display device has a remarkable effect. Is recognized. In addition, there was little color unevenness, glare and wavy unevenness, and the eyes were not tired even during long-time viewing.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
[Preparation of Support 1]
The following cellulose ester solution (dope) was prepared, and the support 1 was produced by a solution casting film forming method.

(Cellulose ester solution (dope))
Cellulose ester (cellulose triacetate, acetyl group substitution degree 2.9, Mn = 16000, Mw / Mn = 1.8) 100 kg
Plasticizer (trimethylolpropane tribenzoate) 5kg
Plasticizer (ethyl phthalyl ethyl glycolate) 5kg
UV absorber (Tinubin 109, manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0kg
UV absorber (Tinuvin 171 manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0kg
Fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 0.3kg
Solvent (methylene chloride) 440kg
Solvent (ethanol) 110kg
That is, the solvent was put into an airtight container, the remaining materials were put in order with stirring, and completely dissolved and mixed while heating and stirring. The fine particles were added dispersed in a part of the solvent. After the temperature was lowered to the temperature at which the solution was cast and allowed to stand overnight, a defoaming operation was performed, and then the solution was Azumi Filter Paper No. Filtration using 244 gave a cellulose ester solution.

  Next, the cellulose ester solution whose temperature was adjusted to 33 ° C. was fed to a die and uniformly cast from a die slit onto a stainless steel belt. The cast part of the stainless steel belt was heated from the back with hot water of 37 ° C. After casting, the dope film on the metal support (which is called a web after casting on the stainless steel belt) is dried by applying hot air of 44 ° C., and the residual solvent in the peeling is peeled off at 120 mass%. The web end is gripped with a tenter while the residual solvent amount is from 35% by mass to 10% by mass in the width direction. It extended | stretched so that it might become 1.1 times the draw ratio. After stretching, the width is maintained for several seconds, and after the tension in the width direction is relaxed, the width is released and further conveyed for 20 minutes in a third drying zone set at 125 ° C., and dried. The support 1 having a width of 1.5 m and a film thickness of 50 μm was produced.

[Preparation of Support 2]
In the production of the support 1, after drying, the embossing controlled at 250 ° C. was pressed while adjusting the pressing amount and the pressing pressure, and after embossing with a height of 5 μm and a width of 5 μm, the winding tension was 98.0 N. The support 2 having a width of 1.5 m and a film thickness of 50 μm was prepared by winding it on a roll with a uniform tension of / m.

[Preparation of antiglare hard coat film]
On the surface of the above support (B side; surface in contact with the support mirror surface such as a stainless steel band used in the casting film forming method; support side), the following hard coat layer coating solutions 1 to 6 having a pore diameter of 20 μm After filtering with a polypropylene filter, this was applied using a micro gravure coater, dried at 90 ° C., and then applied using an ultraviolet lamp with an irradiance of 100 mW / cm ² and an irradiation dose of 80 mJ / cm ^2. The layer was cured, an antiglare hard coat layer having a thickness of 5 μm was formed to produce an antiglare hard coat film, and then the following surface treatments 1 to 5 were performed.

(Hard coat layer coating solution 1)
The following materials were stirred and mixed to obtain hard coat layer coating solution 1.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Synthetic silica fine particles (average particle diameter: 4.5 μm) 40 parts by mass Photopolymerization initiator: Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
25 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass (hard coat layer coating solution 2)
The following materials were stirred and mixed to obtain hard coat layer coating solution 2.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Synthetic silica fine particles (average particle diameter: 4.5 μm) 40 parts by mass Photopolymerization initiator: Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
25 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass Silicone surfactant: FZ2222 (manufactured by Nippon Unicar) 10% by mass Propylene glycol monomethyl ether solution 0.2% by mass of solid content
(Hard coat layer coating solution 3)
The following materials were stirred and mixed to obtain hard coat layer coating solution 3.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Synthetic silica fine particles (average particle diameter: 4.5 μm) 40 parts by mass Photopolymerization initiator: Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
25 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass Fluorosurfactant: Megafac F manufactured by Dainippon Ink & Chemicals, Inc.
0.2% by mass of solid content
(Hard coat layer coating solution 4)
The following materials were stirred and mixed to obtain hard coat layer coating solution 4.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 226 parts by mass Cross-linked styrene beads (average particle size 3.5 μm) 40 parts by mass Photopolymerization initiator: Irgacure 184 (manufactured by Ciba Specialty Chemicals)
25 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass Silicone surfactant: FZ2207 (Nihon Unicar) 10% by mass Propylene glycol monomethyl ether solution 0.2% by mass of solid content
(Hard coat layer coating solution 5)
The following materials were stirred and mixed to obtain hard coat layer coating solution 5.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Synthetic silica fine particles (average particle size 1.8 μm) 40 parts by mass Photopolymerization initiator: Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
25 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass (hard coat layer coating solution 6)
The following materials were stirred and mixed to obtain hard coat layer coating solution 6.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Photopolymerization initiator: Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
25 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass (Surface treatment 1)
Alkali treatment: The hard coat film was immersed in a 1.5 mol / l-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then washed with a 0.5 mass% -H ₂ SO ₄ aqueous solution at room temperature for 30 minutes. It was immersed for 2 seconds to neutralize, washed with water and dried.

(Surface treatment 2)
Alkali treatment: The hard coat film was immersed in a 1.5 mol / l-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then washed with a 0.5 mass% -H ₂ SO ₄ aqueous solution at room temperature for 30 minutes. It was immersed for 2 seconds to neutralize, washed with water and dried. Then, it was left for 1 week at room temperature.

(Surface treatment 3)
Alkali treatment: The hard coat film was immersed in a 1.5 mol / l-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then washed with a 0.5 mass% -H ₂ SO ₄ aqueous solution at room temperature for 30 minutes. It was immersed for 2 seconds to neutralize, washed with water and dried. Then, it was left at 50 ° C. for 1 day.

(Surface treatment 4)
Flame plasma treatment: The hard coat layer surface of the hard coat film produced above was subjected to flame plasma (FP) treatment using the flame plasma treatment apparatus shown in FIG. The treatment conditions were such that the contact time between the flame and the film was about 0.01 seconds, the ratio of the contact area of the outer flame to the maximum area of the inner flame was 5, and the distance from the tip of the inner flame was 5 mm. The inner flame maximum area is a value obtained by multiplying the width of the center of the inner flame I in FIG. 3 by the processing width of the film, and the contact area of the outer flame is the treatment of the effective flame G (also outer flame). It is a value obtained by multiplying the width in contact with the film to be processed and the processing width of the film.

(Surface treatment 5)
Corona treatment: Using a solid state corona treatment machine 6KVA model manufactured by Pillar, the hard coat layer surface of the hard coat film was treated at room temperature at 20 m / min. From the current and voltage readings at this time, it was found that the support was processed at 0.375 kV · A · min / m ² . The treatment frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

[Preparation of antiglare antireflection film]
Next, the low refractive index layers 1 to 3 were provided on the produced antiglare hard coat film as described below to produce an antiglare antireflection film.

(Coating of low refractive index layer 1)
64.5 parts by mass of tetraethoxysilane, 30 parts by mass of the following silica-based fine particles P-2 (hollow spherical fine particles), and 378 parts by mass of ethanol are mixed, and an aqueous nitric acid solution (2% by mass) is added thereto for hydrolysis polycondensation. Then, a tetraethoxysilane hydrolyzate A was prepared.

  To this tetraethoxysilane hydrolyzate A, 5 parts by mass of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KMB503), silicone surfactant FZ2222 (manufactured by Nihon Unicar, 10 mass% propylene glycol monomethyl ether solution) 0 .5 parts by mass, and 95 parts by mass of a mixed solvent of propylene glycol monomethyl ether (PGME): isopropyl alcohol: methyl ethyl ketone (MEK) = 5: 5: 1 is mixed with 5 parts by mass of this solid content to give a low refractive index. A layer coating solution is prepared, and this coating solution is applied onto the hard coat layer that has been surface-treated with an extrusion coater (part of which is not surface-treated), followed by the following drying and solidification treatments 1 to 7, and antiglare antireflection A film was prepared.

<Preparation of silica-based fine particles P-2>
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. did. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass. (Process (a))
1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which 3000 g (concentration of 3.5% by mass) was added to form a first silica coating layer was obtained. (Process (b))
Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid that has been washed with an ultrafiltration membrane to form a first silica coating layer having a solid concentration of 13% by mass, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles was prepared (step (c)). A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) is added. The surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, a dispersion of silica-based fine particles (P-2) having a solid content concentration of 20% by mass, in which the solvent was replaced with ethanol using an ultrafiltration membrane, was prepared.

The thickness of the first silica coating layer of the hollow silica-based fine particles was 3 nm, the average particle size was 47 nm, MOx / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter was measured by a dynamic light scattering method.

(Coating of low refractive index layer 2)
35 parts by mass of tetraethoxysilane, 30 parts by mass of the above silica-based fine particles P-2 (hollow spherical fine particles), and 378 parts by mass of ethanol are mixed, and an aqueous nitric acid solution (2% by mass) is added thereto for hydrolysis polycondensation, Tetraethoxysilane hydrolyzate B was prepared.

In this tetraethoxysilane hydrolyzate B, 34.5 parts by mass of (CH ₃ O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (OCH ₃ ) ₃ , silicone surfactant FZ2222 (manufactured by Nihon Unicar) 10 parts by mass propylene glycol monomethyl ether solution) is mixed with 0.5 part by mass, and 5 parts by mass of this solid content is mixed with propylene glycol monomethyl ether (PGME): isopropyl alcohol: methyl ethyl ketone (MEK) = 5: 5: 1. A low refractive index layer coating solution is prepared by mixing 95 parts by mass of a solvent, and this coating solution is applied onto the hard coat layer that has been subjected to the above surface treatment by an extrusion coater (part of which is not surface treated), followed by drying and solidifying as described below Processing 5 was performed and the anti-glare antireflection film was produced.

(Coating of low refractive index layer 3)
69.5 parts by mass of fluorine-containing resin Opstar JM5010 (manufactured by JSR Corporation) having an actinic radiation curable group, 30 parts by mass of the silica-based fine particles P-2 (hollow spherical fine particles), and 378 parts by mass of ethanol were mixed.

To this, 34.5 parts by mass of (CH ₃ O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (OCH ₃ ) ₃ , silicone surfactant FZ2222 (manufactured by Nippon Unicar, 10 mass% propylene glycol monomethyl) 0.5 parts by mass of ether solution) was mixed, and 95 parts by mass of a mixed solvent of propylene glycol monomethyl ether (PGME): isopropyl alcohol: methyl ethyl ketone (MEK) = 5: 5: 1 was mixed with 5 parts by mass of this solid content. Then, a coating solution with a low refractive index layer is prepared, and this coating solution is applied onto the hard coat layer that has been surface-treated by an extrusion coater (part of which is not surface-treated), and then subjected to the following drying and solidification treatment 5 for antiglare property An antireflection film was produced.

(Dry solidification process 1)
Dry and solidify at 100 ° C under 3 m / sec wind speed, heat cure at 120 ° C for 5 minutes, further cure by irradiating with ultraviolet rays, and apply a low refractive index layer to a film thickness of 95 nm, antiglare An antireflection film was obtained.

(Dry solidification process 2)
After drying and solidifying at 100 ° C. under 0.1 m / sec wind speed, heat curing at 120 ° C. for 5 minutes, further curing by irradiating with ultraviolet rays, and applying a low refractive index layer to a film thickness of 95 nm, An antiglare antireflection film was obtained.

(Dry solidification process 3)
Dry and solidify at 80 ° C under no wind speed, heat cure at 120 ° C for 5 minutes, further cure by irradiating with ultraviolet rays, and apply a low refractive index layer to a film thickness of 95nm, anti-glare reflection A prevention film was obtained.

(Dry solidification treatment 4-7)
In the drying and solidification treatment 3, the drying temperature was changed to 70 ° C., 50 ° C., 40 ° C., and 20 ° C., and the drying solidification treatments 4, 5, 6, and 7 were respectively performed.

[Evaluation of antiglare antireflection film]
The antiglare antireflection film prepared above was evaluated as follows. The evaluation results are shown in Table 1.

(Number of hollow silica particles for the concave portion relative to the convex portion)
The number of hollow silica particles per unit area was determined from a tomographic photograph of an electron microscope, and the number per unit cross-sectional area of the concave portion was calculated when the number per unit cross-sectional area of the convex portion was 100.

(Center line average roughness (Ra))
Measured at a reference length of 5.0 mm and a cut-off value of 0.8 mm in accordance with the method defined in JIS-B-0601 after conditioning for 24 hours in a 25 ° C., 65% RH environment with the measurement samples not being superimposed. The centerline average roughness Ra was determined.

(Steel wool scuff resistance (SW))
The produced antiglare antireflection film was left as it was (on the same day) and at 60 ° C. and 90% RH for 500 hours, and then returned to 23 ° C. and 55% RH (HHT for 2 weeks). Next, Nippon Steel Wool Co., Ltd. with a weight of 100 g per cm ² : Bonster # 0000 steel wool was cut into 22 mmφ, the sample surface was rubbed 10 times, and the number of scratches generated was counted visually. did.

(Reflective color unevenness)
The reflected color unevenness was visually evaluated according to the following criteria.

◎: Change in color tone of reflected light is not recognized ○: Change in color tone of reflected light is recognized in a small part (less than 10% of area)
Δ: Partial change in color of reflected light is recognized (10% or more and less than 30% of area)
X: Change in color tone of reflected light is recognized as a whole

  From Table 1, it was found that the sample of the present invention was superior in steel wool scuff resistance and reflection color unevenness as compared with the comparative example.

Example 2
(Coating of medium refractive index layer and high refractive index layer)
In the antiglare antireflection film 8 produced in Example 1, the following medium refractive index layer and high refractive index layer were provided between the antiglare hard coat layer and the low refractive index layer, and the medium refractive index, high refractive index, A three-layer antiglare antireflection film with a low refractive index was produced.

  That is, the antiglare hard coat layer produced in Example 1 was subjected to the surface treatment 1, and the following medium refractive index layer coating solution was applied thereon using a bar coater, dried at 60 ° C., and then irradiated with ultraviolet rays. Irradiate to cure the coating layer, apply the medium refractive index layer, and then apply the following high refractive index layer coating solution using a bar coater, dry at 60 ° C., and then irradiate with ultraviolet rays to coat the coating layer. Were cured to form high refractive index layers, respectively.

(Preparation of titanium dioxide dispersion)
Titanium dioxide (primary particle mass average particle size: 50 nm, refractive index: 2.70) 30 parts by mass Anionic diacrylate monomer (PM21, manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts by mass Cationic methacrylate monomer (DMAEA, Manufactured by Kojin Co., Ltd.) 0.3 parts by mass 65.2 parts by mass or more of methyl ethyl ketone was dispersed by a sand grinder to prepare a titanium dioxide dispersion.

(Preparation of medium refractive index layer coating solution)
47 parts by mass of the above titanium dioxide dispersion electroconductive ITO fine particles (ELCOM V2504, ITO sol, solid content 20% by mass, manufactured by Catalytic Chemical) 3 parts by mass Dipentaerythritol hexaacrylate (matrix) 50 parts by mass Irgacure 184 (photopolymerization initiator) ) 3 parts by mass γ-methacryloxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503, silane coupling agent) 10 parts by mass Poly-n-butyl methacrylate (matrix) 5 parts by mass Propylene glycol monomethyl ether (PGME) 720 parts by mass Isopropyl Alcohol 1470 parts by weight Methyl ethyl ketone (MEK) 250 parts by weight (Preparation of coating solution for high refractive index layer)
70 parts by mass of the titanium dioxide dispersion 1.5 parts by mass of tetra (n) butoxytitanium γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503)
3 parts by mass Silicone surfactant; FZ2207 (Nihon Unicar) 10% by mass propylene glycol monomethyl ether solution 2 parts by mass Isopropyl alcohol 555 parts by mass Propylene glycol monomethyl ether (PGME) 278 parts by mass Methyl ethyl ketone (MEK) 93 parts by mass On the high refractive index layer of the film having the refractive index layer and the high refractive index layer, the low refractive index layer coating solution 1 of Example 1 is applied by an extrusion coater, and is dried and solidified 5 so as to be antiglare antireflection film. Was made.

  The produced antiglare antireflection film was evaluated in the same manner as in Example 1. As a result, this antiglare antireflection film reproduced Example 1, was excellent in abrasion resistance and uneven reflection color, and had a high reflectance. It decreased from 1.6% of Example 1 to 0.4%, and it turned out that the more superior antireflection property is shown.

Example 3
The antiglare antireflection film No. 1 prepared in Example 1 was used. 1 to 11 were used to produce a polarizing plate as described below, and the polarizing plate was incorporated into a liquid crystal display panel (image display device) to evaluate the visibility.

  According to the following method, a polarizing plate was prepared using an antiglare antireflection film and a cellulose triacetate film used as a support for the film as a polarizing plate protective film.

(A) Production of Polarizing Film A long polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. . This was washed with water and dried to obtain a polarizing film.

(B) Production of Polarizing Plate Next, according to the following steps 1 to 5, the polarizing film and the polarizing plate protective film were bonded together to produce a polarizing plate.

  Step 1: The cellulose triacetate film was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried. A surface of the antiglare antireflection film provided with the antireflection layer was previously protected with a peelable protective film (PET).

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Excess adhesive adhered to the polarizing film in Step 2 was lightly removed, and it was sandwiched between an alkali-treated cellulose triacetate film and an antireflection film and laminated.

Process 4: It bonded together at the speed | rate of about 2 m / min with the pressure of 20-30 N / cm < ² > with the two rotating rollers. At this time, care was taken to prevent bubbles from entering.

  Step 5: The sample prepared in Step 4 in a dryer at 80 ° C. was dried for 2 minutes to prepare a polarizing plate.

  The polarizing plate on the outermost surface of a commercially available liquid crystal display panel (NEC color liquid crystal display MultiSync LCD1525J: model name LA-1529HM) was carefully peeled off, and a polarizing plate having a polarization direction was attached thereto to prepare a liquid crystal display device.

(Evaluation)
Visibility in moving images was confirmed as a display device. The display device using the anti-glare antireflection film of the comparison is reflected depending on the scene, and the reflection color unevenness is worrisome, whereas the display device using the anti-glare antireflection film of the present invention is satisfactory without any problem. there were.

It is sectional drawing of an anti-glare antireflection film. It is the schematic of a flame plasma processing apparatus. It is detail drawing of a plasma processing means.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Surface treatment apparatus 2, 21 Support body 3 Conveyance means 4 Application | coating means 11 Rotating cooling drum 12 Plasma processing means 13 Electric field generation means 14 Introduction means 15 Pre-neutralization means 16 Post-neutralization means 22 Hard coat layer 23 Low refractive index layer 24 Silica system Fine particles B Burner C Shielding plate E, E 'Outer flame I Inner flame G Effective flame R Roller S Effective treatment hole (slit)

Claims (11)

It has a hard coat layer mainly composed of an active energy ray-curable resin on a transparent film support, the surface of the hard coat layer has an antiglare fine uneven shape, and is directly on the hard coat layer Alternatively, in the antiglare antireflection film in which a low refractive index layer is indirectly formed, the low refractive index layer contains hollow spherical silica-based fine particles having an outer shell layer and porous or hollow inside. An antiglare antireflection film, wherein the hollow spherical silica-based fine particles are present more in the concave portion than in the convex portion in the low refractive index layer formed along the concave-convex shape. 2. The antiglare reflection according to claim 1, wherein when the number of convex portions of the silica-based fine particles per unit cross-sectional area is 100, the number of concave portions per unit cross-sectional area is 130 to 300. 3. Prevention film. The antiglare antireflection film according to claim 1 or 2, wherein a surface treatment is performed on the surface of the hard coat layer, and then a low refractive index layer is formed. The antiglare antireflection film according to claim 3, which is subjected to an aging treatment after the surface treatment. The antiglare antireflection according to any one of claims 1 to 4, wherein the hard coat layer contains silica fine particles or polystyrene fine particles so that the surface has a fine uneven shape having an antiglare property. the film. The surface of the low refractive index layer has a centerline average roughness (Ra) defined by JIS B 0601 of 0.15 to 0.50 μm, according to any one of claims 1 to 5. The antiglare antireflection film as described. The antiglare according to any one of claims 1 to 6, further comprising a high refractive index layer or a middle refractive index layer and a high refractive index layer between the hard coat layer and the low refractive index layer. Antireflection film. The antiglare antireflection film according to any one of claims 1 to 7, wherein the entire layer contains a fluorine-based or silicone-based surfactant. The antiglare antireflection film according to any one of claims 1 to 8, wherein the binder component of the low refractive index layer contains an alkoxysilane compound as a main component. A polarizing plate comprising the antiglare antireflection film according to claim 1. A display device comprising the antiglare antireflection film according to claim 1.

Images