JP2007034281A - Anti-reflection film and image display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-cost anti-reflection film which has high antistatic characteristics and high light transmissivity, is superior in surface abrasion resistance and is neutral in color, has proper surface appearance, and to provide an image display apparatus that has the anti-reflection film incorporated therein. <P>SOLUTION: The anti-reflection film comprises at lest two layers composed of an A layer which consists essentially of an acrylic system resin and conductive metal oxide particulates, and has a film thickness ≥0.3μm and a B layer which consists essentially of a siloxane polymer homogenized with silica series particulates, on at lest one surface of a base material film so that the A layer is located nearer to the base material film than the B layer is, and the B layer is laminated on the A layer. A condensate compound, consisting of a siloxane compound (1): R<SP>1</SP><SB>2</SB>SiR<SP>2</SP><SB>2</SB>and a siloxane compound (2): R<SP>3</SP>SiR<SP>4</SP><SB>3</SB>, is contained in the A layer by 0.001 to 20 mass% of the A layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection film having high antistatic properties and light transmittance, excellent surface scratch resistance, neutral color and low cost, and an image display device using the same. More specifically, the present invention relates to an antireflection film used on the display display surface, the surface of the deflecting plate, and the like. The present invention also relates to an image display device incorporating an antireflection film.

  In display devices such as televisions and personal computer monitors, external light such as sunlight and fluorescent lamps is reflected and reflected on the surface, which makes it difficult to see the displayed image. In order to solve this problem, a method has been employed in which irregularities are provided on the surface to diffuse externally reflected light, or thin films having a high refractive index and a low refractive index are alternately laminated to prevent light reflection.

  However, the method of irregularly reflecting external light is insufficient in terms of improving the visibility of the image because the image on the display looks blurred.

  As a method for improving this, there has been proposed a method (Patent Document 1) in which a hard coat layer, a high refractive index layer, and a low refractive index layer are provided on the surface of an organic film from the lower layer side.

  However, in this method, since the conductive metal oxide fine particles contained in the high refractive index layer are many and the film thickness is thin, the haze as an antireflection film is increased to lower the clearness of the image, and the surface is uneven. As a result, there arises a problem that the surface hardness and chemical resistance are lowered, and the cost is increased due to the large number of laminated layers. In addition, if the refractive index difference between the high refractive index layer and the low refractive index layer is large, the reflectance is relatively higher in the low wavelength region of the visible light region or in the high wavelength region than near the lowest reflectance, and the reflected light is blue or red. There is a problem in terms of purity of color tone.

  In addition, a method of sequentially laminating porous silica and a polysiloxane polymer on the antiglare hard coat layer has been proposed (Patent Document 2).

  However, this method has a problem that the antiglare hard coat layer has a high haze, and the clearness of the image is impaired when used as an antireflection film for an image display device. Further, when anti-glare is realized only with the conductive oxide fine particles, it is necessary to contain a large amount of the conductive oxide fine particles in the layer, which is very expensive. Furthermore, even when anti-glare is realized with conductive oxide fine particles and other particles having a larger diameter, more conductive oxide fine particles than non-glare type are required to construct a conductive network for imparting antistatic properties. And the cost is high, and the bondability between the resin portion and the large-diameter particles may result in low hardness and may be unsuitable for practical use.

  When a clear hard coat layer is used instead of the antiglare hard coat layer, good results can be expected with respect to haze. However, when the hard coat layer is an organic resin, a hard layer is formed when a polysiloxane polymer is laminated. Adhesion at the interface between the coat layer and the polysiloxane polymer may be poor, and the surface scratch resistance may be significantly reduced. On the other hand, when the hard coat layer is an inorganic resin such as a polysiloxane polymer, it can be expected to improve the adhesion, but the time required for curing may increase and the productivity may decrease. There is concern about the high cost itself.

In addition, a method of improving the adhesion with a polysiloxane polymer by adding a known silane coupling agent or the like to the clear type hard coat layer can be considered, but in the case of a normal silane coupling agent, a polysiloxane polymer In order to obtain the effect of improving the interfacial adhesion between the hard coat layer and the hard coat layer, it is necessary to add a large amount, which may reduce the hardness of the hard coat layer itself and may hinder the formation of a conductive network. Furthermore, there is a risk that defects such as surface roughness and film thickness unevenness are likely to occur with respect to the surface appearance of the hard coat layer.
JP 2001-350001 A JP 2003-139908 A

  In view of the background art, the present invention has a high antistatic property and light transmittance, an excellent anti-scratch property on the surface, a neutral color, a good surface appearance, and a low-cost anti-reflection film, and its incorporation It is intended to provide an image display device.

  The present invention employs the following means in order to solve such problems. That is, the antireflection film of the present invention comprises an A layer having a film thickness of 0.3 μm or more and a silica-based fine particle, the main component of which is an acrylic resin and conductive metal oxide fine particles, on at least one side of the base film And at least two of the B layers mainly composed of a siloxane polymer, the A layer is closer to the base film than the B layer, and the B layer is on the A layer. In which the condensate compound composed of the following siloxane compound (1) and the following siloxane compound (2) is 0.001 to 20 mass with respect to the A layer in the A layer. % Is included.

R ¹ ₂ SiR ² ₂ (1)
(Wherein, R ¹ represents fluoroalkyl group having fluorine 3 17, a methyl group, an ethyl group, a hydroxyl group, a methoxy group, an ethoxy group, respectively, same with or may be different .R ² is a hydroxyl group Represents a methoxy group or an ethoxy group, which may be the same or different.
R ³ SiR ⁴ ₃ (2)
(However, R ³ represents a vinyl group, a (meth) acryl group and a substituted product thereof. R ⁴ represents a methyl group, an ethyl group, a hydroxyl group, a methoxy group, and an ethoxy group, which are the same or different. Is also good.)
The image display device of the present invention is characterized in that the antireflection film is adhered to the image display surface or the surface of the front plate.

  According to the present invention, an antireflection film having good antistatic properties, light transmittance, and surface scratch resistance, neutral color and good surface appearance can be provided at low cost. It is suitably used as an antireflection film applied to the front surface of a large flat screen television such as a display or the front surface of a liquid crystal television.

  The present invention has intensively studied the above-mentioned problems, that is, an antireflection film having a good antistatic property, light transmittance, and surface scratch resistance, a neutral color and a good surface appearance, and an acrylic resin and a conductive material. From the B layer, at least two layers of the A layer containing the condensate compound composed mainly of the oxide fine particles and the specific siloxane compound group and the B layer containing the siloxane polymer homogenized with the silica-based fine particles from the B layer The layer A is closer to the base film, and the layer B is laminated on the layer A. The layer A and layer B are used to form the minimum reflectance and the maximum reflection of the antireflection film. When the rate is configured to satisfy a specific condition, it has been found that this problem can be solved at once.

  The layer A of the present invention needs to contain acrylic resin and conductive metal oxide fine particles as main components in order to impart hardness, durability and antistatic properties to the antireflection film. The main component here means that the weight fraction of the acrylic resin and the conductive metal oxide fine particles in the A layer is 50% or more.

  The layer A of the present invention is required to contain an acrylic resin as a main component in the layer A in order to provide excellent curability, flexibility and productivity, and to provide hardness and durability at low cost. An actinic radiation curable acrylic resin or a thermosetting acrylic resin is preferably used. Among such acrylic resins, a (meth) acrylate resin is preferably radically polymerized by irradiation with actinic rays. It is easy to achieve the effect of improving the solvent resistance and hardness of the formed film. More preferably, a (meth) acrylate resin having a (meth) acryloyl group composed of two or more polyfunctional (meth) acrylate compounds in the molecule may improve solvent resistance. For example, as such (meth) acrylate resin, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, ethylene-modified trimethylolpropane tri (meth) acrylate, tris- ( 2-hydroxyethyl) -isocyanuric acid ester tri (meth) acrylate such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. A tetrafunctional or higher functional (meth) acrylate or the like is used. In the present invention, “... (Meta) acrylic ...” is an abbreviation of “... acrylic ... or meta acrylic ...”.

  In order to improve the dispersibility of the particles, a (meth) acrylate compound (monomer) having an acidic functional group such as a carboxyl group, a phosphate group, or a sulfonate group can be used for the acrylic resin of the A layer. . Specifically, as the acidic functional group-containing monomer, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, Phosphoric acid (meth) acrylic acid esters such as mono (2- (meth) acryloyloxyethyl) acid phosphate and diphenyl-2- (meth) acryloyloxyethyl phosphate, 2-sulfoester (meth) acrylate, and the like are used. In addition, a (meth) acrylate compound having a polar bond such as an amide bond, a urethane bond, or an ether bond can be used. Furthermore, a resin having a urethane bond, such as a urethane (meth) acrylate oligomer, is particularly preferable because of its high polarity and good particle dispersibility.

  In forming the A layer in the present invention, an initiator may be used to advance curing. As the initiator, the applied acrylic resin starts or accelerates polymerization and / or crosslinking reaction by radical reaction, anion reaction, cation reaction, etc., and various conventionally known photopolymerization initiators can be used. is there. Specific examples of such photopolymerization initiators include sulfides such as sodium methyldithiocarbamate sulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide, thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, Thioxanthone derivatives such as 2,4-diethylthioxanthone, azo compounds such as hydrazone and azobisisobutyronitrile, diazo compounds such as benzenediazonium salt, benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, dimethylaminobenzophenone Michler's ketone, benzylanthraquinone, t-butylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, Aromatic carbonyl compounds such as -chloroanthraquinone, dialkylaminobenzoic acid esters such as methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, butyl D-dimethylaminobenzoate, isopropyl p-diethylaminobenzoate, Peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, 9-phenylacridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine, benzacridine, etc. Acridine derivatives, phenazine derivatives such as 9,10-dimethylbenzphenazine, 9-methylbenzphenazine, 10-methoxybenzphenazine, and 6,4 ′, 4 ″ -trimethoxy-2,3-diphenylquinoxaline Quinoxaline derivatives, 2,4,5-triphenylimidazolyl dimer, 2-nitrofluorene, 2,4,6-triphenylpyrylium tetrafluoride boron salt, 2,4,6-tris (trichloromethyl) ) -1,3,5-triazine, 3,3′-carbonylbiscoumarin, thiomichler ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- ( 4- (1-methylvinyl) phenyl) propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, and the like can be used.

  The amount of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1.0 to 15.0 parts by mass with respect to 100 parts by mass of the acrylic resin. If it is less than 0.1 parts by mass, photopolymerization is slow, and it tends to require long-time light irradiation in order to satisfy hardness and scratch resistance, and sometimes tends to be uncured. On the other hand, when it exceeds 20 mass parts, functions, such as antistatic property of a coating film, abrasion resistance, and a weather resistance, will fall easily.

  Moreover, when forming A layer by this invention, in order to prevent the fall of the sensitivity of the said initiator by oxygen inhibition, you may coexist an amine compound with a photoinitiator. Such an amine compound is not particularly limited as long as it is a non-volatile compound such as an aliphatic amine compound or an aromatic amine compound. For example, triethanolamine, methyldiethanolamine and the like are suitable.

  The layer A of the present invention has the advantages that it is less dependent on humidity and processing conditions and has high transparency in providing antistatic properties, and therefore contains conductive metal oxide fine particles as a main component. It is necessary.

  As the conductive metal oxide fine particles, tin-containing antimony oxide particles (ATO), zinc-containing antimony oxide particles, tin-containing indium oxide particles (ITO), zinc oxide / aluminum oxide particles, antimony oxide particles, and the like are preferable, and more preferably. Tin-containing indium oxide particles (ITO) and tin-containing antimony oxide particles (ATO) are used.

  The particles constituting the conductivity preferably have an average particle size (sphere equivalent diameter (defined by JIS Z8819-1) measured by the BET method shown in JIS R1626) of 0.5 μm or less, more preferably Are preferably particles having a particle diameter of 0.001 to 0.3 μm, particularly preferably 0.005 to 0.2 μm. If the average particle diameter exceeds this range, the transparency of the coating film (A layer) is reduced. If the average particle diameter is less than this range, the particles tend to aggregate and the haze value of the generated coating film (A layer) increases. In either case, it becomes difficult to obtain a desired haze value.

  The mass ratio of the conductive metal oxide fine particles to the acrylic resin is preferably 40% by mass or less, more preferably 30% by mass or less, and various physical and chemical strengths of the obtained film are good and This is because haze can be kept low, high transparency can be maintained, and cost can be reduced.

  The layer A of the present invention contains a condensate compound composed of the siloxane compound (1) and the siloxane compound (2) represented by the following formula, and thus adheres when the B layer is laminated on the A layer. Necessary for expression, surface scratch resistance improvement, surface appearance improvement and the like.

R ¹ ₂ SiR ² ₂ (1)
(Wherein, R ¹ represents fluoroalkyl group having fluorine 3 17, a methyl group, an ethyl group, a hydroxyl group, a methoxy group, an ethoxy group, respectively, same with or may be different .R ² is a hydroxyl group Represents a methoxy group or an ethoxy group, which may be the same or different.
R ³ SiR ⁴ ₃ (2)
(However, R ³ represents a vinyl group, a (meth) acryl group and a substituted product thereof. R ⁴ represents a methyl group, an ethyl group, a hydroxyl group, a methoxy group, and an ethoxy group, which are the same or different. Is also good.)
Examples of the siloxane compound represented by the formula (1) include trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, Decafluorooctyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and their hydrolysates are preferably used. Are, but not necessarily limited to these particularly preferably a trifluoromethyl trimethoxy silane, methyl trimethoxy silane, dimethyl dimethoxy silane or hydrolyzate thereof.

  Examples of the siloxane compound represented by the formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. , 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and their hydrolysates are preferably used, particularly preferably 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane. Although it is a methoxysilane and these hydrolysates, it is not necessarily limited to these.

  In the condensate compound composed of the above formulas (1) and (2), the molar ratio of the siloxane compound (1) and the siloxane compound (2) is in the range of (1) :( 2) = 0.1: 1 to 20: 1. It is preferable because the effect of improving the adhesion per condensate compound content in the layer A is increased and the effect of improving the surface appearance is increased, more preferably 1: 1 to 15: 1, and still more preferably. Is from 2: 1 to 15: 1, particularly preferably from 3: 1 to 15: 1. In order to reduce the surface resistivity, the ratio is preferably 2: 1 to 15: 1, more preferably 3: 1 to 15: 1.

In addition, the condensate compound has a kinematic viscosity measured at 25 ° C. based on JIS K2283, preferably 40 mm ² / s or more, and the effect of improving adhesion per condensate compound content in the layer A And the surface appearance improving effect is improved.

  The content of the condensate compound in the layer A is 0.001% by mass to 20% by mass, suppressing an increase in surface resistivity, improving antistatic performance, and preventing a decrease in surface hardness. It is necessary above, and is preferably 10% by mass or less.

  The constituent components of the A layer of the present invention include the above-described acrylic resin component, conductive metal oxide fine particles, a condensate compound composed of the siloxane compound (1) and the siloxane compound (2), and a photopolymerization initiator as essential constituent components. Furthermore, if necessary, for example, various additives such as a polymerization inhibitor, a curing catalyst, an antioxidant and a dispersant may be contained.

  In the present invention, the constituents of the A layer can further contain an organic metal compound such as a conductive polymer such as polypyrrole, polyaniline and polythiophene, a metal alcoholate and a chelate compound for the purpose of imparting conductivity. In addition, for the purpose of improving the surface hardness, the component of the A layer can further contain colloidal silica, dry silica, wet silica, inorganic particles such as titanium oxide, and colloidally dispersed silica fine particles. .

  The A layer of the present invention needs to have a film thickness of 0.3 μm or more. When the thickness of the A layer is less than 0.3 μm, the antistatic property and the scratch resistance of the surface are remarkably lowered, and the difference between the maximum reflectance and the minimum reflectance in the 400 to 700 nm region becomes large, and the neutral color tone. Is difficult to obtain, and is preferably 1 μm or more, more preferably 2 μm or more. In order to suppress curling as an antireflection film, the A layer thickness is preferably 20 μm or less, and more preferably 15 μm or less.

  The layer A of the present invention has a refractive index of 1.48 or more and 1.62 or less, and suppresses the maximum reflectance to 3.5% or less and suppresses an increase in the minimum reflectance to realize a neutral color tone. Therefore, it is preferable. Further, it is preferable that the refractive index of the A layer is higher than that of the B layer because the number of antireflection layers can be reduced.

  In the present invention, the B layer is mainly composed of a silica-based fine particle and a siloxane polymer that is homogenized in order to achieve both surface scratch resistance and a low refractive index.

  Here, “homogenized” means a state where the silica component of the silica fine particles and the siloxane polymer of the matrix are reacted and homogenized. This state can be known by observing the boundary between the silica fine particles and the siloxane polymer with a transmission electron microscope (hereinafter referred to as TEM). An example of a homogeneous state is shown in FIG. 2, and examples of a non-uniform state are shown in FIGS. 2, 3 and 4 are all cross-sectional TEM photographs of layer B containing silica fine particles having cavities surrounded by an outer shell. In the B layer 11 of FIG. 2, the white circular shape is the cavity 7 inside the silica fine particles. The outer side of the white circle is a shell of silica fine particles and a siloxane compound. As shown in the figure, both are homogenized, and the boundary between the silica fine particles and the siloxane compound is not observed. In FIGS. 3 and 4, the white cavities are the cavities 7 inside the silica fine particles. Unlike FIG. 2, in FIGS. 3 and 4, a dark thin layer exists outside the white circle so as to cover it, and a light color matrix exists outside the white circle. The dark-colored thin layer is the outer shell 8 of silica fine particles, and the light-colored matrix is the siloxane compound 9. That is, since both are not homogenized, the boundary portion 10 between the silica fine particles and the siloxane compound is clearly observed as shown in the figure. That is, in the homogeneous state, as shown in FIG. 2, the boundary between the silica fine particles and the siloxane compound is not observed, whereas in the case of non-homogeneous, the silica fine particles and the siloxane are shown in FIG. 3 and FIG. The polymer boundary can be clearly observed.

  Such a homogenized state is considered to be because the silica fine particles and the siloxane polymer are bonded. Thereby, the dispersion stability of the silica fine particles in the siloxane-based paint is improved, and secondary aggregation can be suppressed. Further, when a coating is formed, the surface hardness of the coating is improved because the siloxane polymer, which is a matrix material, and the silica fine particles are firmly bonded.

  Such a siloxane-based paint can be obtained by hydrolyzing a silane compound in a solvent with an acid catalyst in the presence of silica fine particles to form a silanol compound and then subjecting the silanol compound to a condensation reaction. .

  As such a silane compound, a polyfunctional fluorine-containing silane compound is preferably used from the viewpoint of low refractive index and antifouling property. For example, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxy Trifunctional fluorine-containing silane compounds such as silane, trifluoropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane, Bifunctional fluorine-containing silane compounds such as heptadecafluorodecylmethyldimethoxysilane are preferably used. From the viewpoint of surface hardness, trifluoromethylmethoxysilane, trifluoromethyl ethoxide, etc. Shishiran, trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane, more preferably used.

  Examples of such polyfunctional fluorine-free silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methyltrimethoxysilane, and methyltriethoxy. Silane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Trifunctional silanes such as silane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxysipropyltrimethoxysilane Compound, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-amino Propylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, 3-methacryloxypropyldimethoxy Bifunctional silane compounds such as silane and octadecylmethyldimethoxysilane, tetrafunctional silane compounds such as tetramethoxysilane and tetraethoxysilane, etc. Any of these are preferably used. From the viewpoint of surface hardness, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are used. More preferable.

  Moreover, as the above-mentioned silica fine particles, silica-based fine particles having an average particle diameter of 1 nm to 200 nm are sufficiently bonded to the matrix material to obtain good hardness, and between the particles generated by introducing many particles. It is preferable because many voids are generated and low refractive index can be realized, and the average particle diameter is particularly preferably 1 nm to 70 nm. Further, among the silica-based fine particles, those having a structure having a cavity inside are particularly preferably used in order to lower the refractive index.

  Examples of the silica-based fine particles having cavities therein include silica-based fine particles having cavities surrounded by an outer shell, porous silica-based fine particles having a large number of cavities, and the like. As such an example, it can manufacture by the method currently disclosed by patent 3272111, for example. Further, the refractive index of the fine particles themselves is preferably 1.20 to 1.40, more preferably 1.20 to 1.35. Although a method of measuring the refractive index is described later, it can also be measured by a method disclosed in Japanese Patent Laid-Open No. 2001-233611. As such silica-based fine particles, for example, those disclosed in Japanese Patent Application Laid-Open No. 2001-233611 and those generally marketed such as Japanese Patent No. 3272111 can be used.

  Acid catalysts used for the hydrolysis reaction include acid catalysts such as formic acid, succinic acid, hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. It is done.

  In particular, formic acid and acetic acid are preferably used as catalysts from the viewpoint of improving the hardness of the transparent coating.

  A preferable addition amount is preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass with respect to the total silane compound content used in the synthesis of the siloxane polymer. . If the amount of the acid catalyst is less than 0.05% by mass, the hydrolysis reaction may not proceed sufficiently. Moreover, when it exceeds 10 mass%, there exists a possibility that a hydrolysis reaction may run away.

  In the hydrolysis reaction, it is preferable to perform the reaction in a solvent because the control of the reaction is easy, and the solvent used is preferably an organic solvent. For example, alcohols such as ethanol, propanol, butanol, 3-methyl-3-methoxy-1-butanol; glycols such as ethylene glycol, propylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethyl Ethers such as ether; ketones such as methyl isobutyl ketone and diisobutyl ketone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, ethyl cellosolve acetate, 3-methyl-3-methoxy-1-butanol acetate ; In addition to aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane, γ-butyrolactone, N-methyl 2-pyrrolidone, dimethyl sulfoxide can be used. The amount of the solvent is preferably added in the range of 50% by mass to 500% by mass, more preferably in the range of 80% by mass to 200% by mass with respect to the total silane compound content used in the synthesis of the siloxane polymer. It is. If it is less than 50% by mass, the reaction may run away and gel. On the other hand, if it exceeds 500 mass%, hydrolysis may not proceed.

  Moreover, as water used for a hydrolysis, ion-exchange water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of silane.

  The hydrolysis reaction is preferably performed at room temperature to 55 ° C by adding the acid catalyst and water in the solvent to the silane compound.

  As a condition for the condensation reaction for obtaining the siloxane polymer of the present invention, it is preferable to carry out the reaction solution under reflux for 1 to 100 hours after hydrolysis to obtain a silanol compound. In addition, in order to increase the degree of polymerization of the siloxane polymer, it is possible to reheat or add a base catalyst.

  In the antireflection film of the present invention, it is necessary to laminate at least two layers of the A layer and the B layer on at least one surface of the base film, and the A layer is closer to the base film than the B layer. And the B layer needs to be laminated on the A layer. If the order of lamination is different, in order to function as an antireflection film, it is necessary to further form a layer having a lower refractive index than the B layer on the B layer, resulting in high cost, antistatic properties, and surface scratch resistance. descend.

  In addition, another layer may be provided between the A layer and the base film as long as the antireflection function is not hindered. From the viewpoint of productivity including the color tone and cost of the reflective color, the base film It is preferable to provide a configuration in which an A layer is provided on top and a B layer is provided thereon. The refractive index measurement method here is as defined later.

In order to impart a desired level of antistatic properties to the antireflection film of the present invention, the surface resistivity of the antireflection film surface measured by the method shown in JIS K6911 is 1 × 10 ¹¹ Ω / □ or less. It is preferable that it is 5 × 10 ¹⁰ Ω / □ or less.

  The antireflection film of the present invention preferably has a total light transmittance of 85% or more and a haze of 1.5% or less because of excellent image clearness when used as an image display device, and more preferably a total light transmission. The rate is 87% or more, and the haze is 1.2% or less.

  The minimum reflectance and the maximum reflectance in the antireflection film of the present invention are as follows: (1) The minimum reflectance is 0.6% or more and 2.0% or less in the surface reflection spectrum at a wavelength of 400 to 700 nm, (2) It is preferable to simultaneously satisfy the three conditions that the maximum reflectance is 3.5% or less and (3) the difference between the maximum reflectance and the minimum reflectance is 2.5% or less. That is, in order to obtain an antireflection effect effective in the visible light region, it is preferable that the maximum reflectance of the surface reflection spectrum at a wavelength of 400 to 700 nm is 3.5% or less. In order to prevent the reflected color from having a specific color tone, the minimum reflectance is 0.6% or more and 2.0% or less, and the difference between the maximum reflectance and the minimum reflectance is 2.5. % Or less is preferable. More preferably, in addition to satisfying the condition (1) of the surface reflection spectrum that can be placed at a wavelength of 500 to 700 nm, (2) the maximum reflectance is 2.2% or less, and (3) the maximum reflectance and the minimum reflectance The condition is that the difference is 1.5% or less. The reflectance measuring method here is as defined later.

  As described above, the antireflection film of the present invention has a refractive index and thickness of the A layer of 1.62 or less and 0.3 μm or more, respectively. It is preferable that the wavelength is 1/4 of the wavelength of normal visible light. Accordingly, in the B layer, it is preferable that four times the product of the thickness d and the refractive index n of each layer be in the wavelength range of 400 to 700 nm. The relationship between the refractive index n and the thickness d in the B layer is The minimum reflectance of the surface reflection spectrum at a wavelength of 400 to 700 nm is 0.6% or more and 2.0% or less, that the refractive index is 1.42 or less and the thickness satisfies the following formula (1). Moreover, it is preferable for the maximum reflectance to be 3.5% or less and the difference between the maximum reflectance and the minimum reflectance to be 2.5% or less.

n · d = λ / 4 Formula (1)
(Here, λ is the wavelength range of visible light and is usually in the range of 380 nm ≦ λ ≦ 780 nm).

  As the base film in the present invention, a film that can be formed by melt film formation or solution film formation is preferably used. Specific examples thereof include films made of polyester, polyolefin, polyamide, polyphenylene sulfide, acetate, polycarbonate, acrylic resin, and the like. Among these, a film made of a thermoplastic resin excellent in transparency, mechanical strength, dimensional stability and the like is particularly preferable. In order to use it for image display device applications, it is preferable that the film has at least one selected from polyester, acetate and acrylic resin because it has high light transmittance and low haze value. In view of transparency, haze value, and mechanical properties, a film made of polyester is particularly preferably used.

  For example, the total light transmittance indicated by JIS K7361-1 of the base film is preferably 40% or more, more preferably 60% or more. The haze value of the substrate film is preferably 5% or less, more preferably 3% or less. Satisfying both of these conditions is more preferable in terms of sharpness when used as a member for an image display device. Further, the upper limit of the light transmittance is about 99.5%, and the lower limit of the haze value is about 0.1%.

  Examples of the polyester preferably used in the present invention include polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, and polypropylene naphthalate. Two or more of these may be mixed. In addition, these may be a polyester copolymerized with other dicarboxylic acid components and diol components, but the copolymerization ratio is preferably 25% or more in the degree of crystallinity in a film in which crystal orientation is completed. More preferred is 30% or more, and still more preferred is 35% or more. When the crystallinity is less than 25%, dimensional stability and mechanical strength tend to be insufficient. The crystallinity can be measured by a method described in “Practical Spectroscopy Series (3) Raman Spectroscopy” issued by IPC Corporation.

  When the above-described polyester is used, its intrinsic viscosity (measured in o-chlorophenol at 25 ° C. according to JIS K7367) is preferably 0.4 to 1.2 dl / g, more preferably 0.00. 5 to 0.8 dl / g. When the intrinsic viscosity is less than 0.4 dl / g, the mechanical strength is insufficient, which is not preferable. Further, even if the intrinsic viscosity exceeds this preferable range, not only is the quality excessive, but also the operability during film production is deteriorated, which is economically undesirable.

  Triacetyl cellulose or the like is used as the acetate, and polymethyl methacrylate or the like is used as the acrylic resin.

  The base film used in the present invention may be a composite film having a laminated structure of two or more layers. As the composite film, for example, a composite film that is substantially free of particles in the inner layer portion and provided with a layer containing particles in the surface layer portion, has coarse particles in the inner layer portion, and fine particles in the surface layer portion. And a composite film having a layer in which the inner layer portion contains fine bubbles are used. In the composite film, the polymer constituting the inner layer portion and the surface layer portion may be a chemically different polymer or the same kind of polymer.

  The base film in the present invention has sufficient thermal stability of the film, particularly dimensional stability and mechanical strength, and from the viewpoint of improving the flatness, in the state where the hard coat layer is provided, biaxial stretching is performed. A crystal-oriented film is preferred. The crystal orientation by biaxial stretching means that the thermoplastic film before unstretched, that is, before the crystal orientation is completed, is preferably stretched about 2.5 to 5 times in the longitudinal direction and the width direction, respectively, and then heat-treated. The crystal orientation is completed by the above, and it indicates a biaxial orientation pattern by wide-angle X-ray diffraction.

  The thickness of the base film used in the present invention is appropriately selected according to the use for which the hard coat film of the present invention is used. From the viewpoint of mechanical strength and handling properties, it is preferably 10 to 500 μm, more Preferably it is 20-300 micrometers.

  The base film of the present invention may contain various additives, resin compositions, cross-linking agents and the like within a range that does not impair the effects of the present invention. For example, antioxidants, heat stabilizers, UV absorbers, organic and inorganic particles, pigments, dyes, antistatic agents, nucleating agents, acrylic resins, polyester resins, urethane resins, polyolefin resins, polycarbonate resins, alkyd resins, epoxy resins , Urea resin, phenol resin, silicone resin, rubber resin, wax composition, melamine crosslinking agent, oxazoline crosslinking agent, methylolated, alkylolized urea crosslinking agent, acrylamide, polyamide, epoxy resin, isocyanate compound Aziridine compounds, various silane coupling agents, various titanate coupling agents, and the like can be used.

  Among these, when inorganic particles such as silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, barium sulfate, carbon black, zeolite, titanium oxide, metal fine powder, etc. are added, it is easy to slip. This is particularly preferable since the property and scratch resistance are improved. The average particle size of the inorganic particles is preferably 0.005 to 5 μm, more preferably about 0.05 to 1 μm. The particle diameter here is a value obtained by measurement using a laser diffraction particle size distribution measuring apparatus. The average particle size is 50% distributed particle size. The 50% distribution particle size refers to the particle size where the particle size distribution is 50%. Moreover, the addition amount of the inorganic particles is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass in 100 parts by mass of the base film.

The base film of the present invention preferably has a configuration in which an easy-adhesion layer is provided on at least one surface for the purpose of improving the adhesion, in order to improve the adhesion with a layer laminated on the easy-adhesion layer. Such an easy-adhesion layer preferably has a refractive index of 1.52 to 1.66, and moreover, (refractive index of the easy-adhesion layer) = {(refractive index of the base film) × (easy-adhesion layer) It is preferable that the refractive index of the layer laminated on the upper layer}} ^1/2 ± 0.02 is satisfied because interference fringes generated when laminated on the easy-adhesion layer can be reduced. Such an easy-adhesion layer is not particularly limited as long as it has excellent adhesion to the layer laminated on the easy-adhesion layer and has the above-mentioned refractive index, but is water-dispersible polyester resin, water-dispersibility A polyurethane resin is preferably used. Moreover, this easy-adhesion layer is applied in the middle of a film forming process, and the method of forming simultaneously with film forming is used preferably, The thickness becomes like this. Preferably it is 0.08-0.20 micrometers.

  The scratch resistance of the surface of the antireflection film defined below according to the present invention is preferably at least third grade, more preferably at least fourth grade. That is, by satisfying such scratch resistance, when the image display device is used and during the process, the film surface is less likely to be scratched or the dust adhered to the film surface is wiped off with a cloth. It is possible to make it difficult for the image to become sticky, and it is possible to maintain the sharpness of the image. Here, the grade 3 or higher means any of grade 3, grade 4, and grade 5, and the grade 4 or higher means grade 4 or grade 5.

The scratch resistance is such that the antireflection film side surface of the antireflection film is subjected to 10 reciprocal frictions at a stroke width of 10 cm and a speed of 30 mm / sec by applying a load of 250 g to # 0000 steel wool, and then the surface is visually observed. The method of scratching is evaluated in the following five stages.
5th grade: No scratches.
Fourth grade: 1 to 5 scratches.
3rd grade: 6 to 10 scratches.
Second grade: 11 or more scratches.
First grade: Countless scratches on the entire surface.

  Next, the manufacturing method of the antireflection film of this invention is demonstrated.

  FIG. 1 is a schematic cross-sectional view showing an example of a preferred embodiment of the antireflection film of the present invention. An antireflection layer 6 composed of an A layer 2 and a B layer 1 is laminated on the base film 3, and a near-infrared absorbing layer 4 and an adhesive are provided on the surface of the base film 3 opposite to the antireflection layer 6. Layer 5 is laminated.

  As a method of providing A layer 2 and B layer 1, any method such as a method of directly laminating on a base film by coating, a method of laminating a layer formed on another base material on a base film by transfer, etc. However, from the viewpoint of production stability at an appropriate film thickness and cost, it is preferable to employ a method of directly laminating on a base film by coating.

  As the coating method, various coating methods such as reverse coating method, gravure coating method, rod coating method, bar coating method, die coating method, spray coating method and the like can be used, and any of these can be suitably used. In forming the layer, a reverse coating method, particularly a reverse coating using a small-diameter gravure roll is preferable from the viewpoint of coating accuracy.

  In addition, when applying the A layer 2 and the B layer 1, it is preferable to prepare a coating solution in which the above components are dispersed in a solvent, and apply, dry and cure. Such a solvent improves coating or printing workability. For this purpose, various known organic solvents can be used as long as they dissolve the resin component. In particular, in the present invention, an organic solvent having a boiling point of 60 to 180 ° C. is preferable from the viewpoints of viscosity stability and drying property of the composition. Specific examples of such organic solvents include methanol, ethanol, isopropyl alcohol, n-butanol, tert-butanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, cyclohexanone, butyl acetate, isopropyl acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetyl acetone, acetyl acetone and the like are preferably used. These may be used alone or in combination of two or more.

  When preparing the coating solution used for forming the A layer 2, the amount of the organic solvent may be blended in an arbitrary amount so that the composition has a viscosity with good workability according to the coating means and the printing means. In general, it is appropriate that the solid content concentration of the composition is 60% by mass or less, preferably 50% by mass or less. As the preparation of the composition for forming a photocurable film of the present invention, any method can be adopted, but conductive particles are usually added to a solution in which a resin component is dissolved in an organic solvent, a paint shaker, A method of dispersing by a dispersing machine such as a ball mill, sand mill, three rolls, attritor, homomixer, etc., and then adding a photopolymerization initiator and dissolving it uniformly is suitable. Further, when an additive such as a condensate compound composed of the siloxane compound (1) and the siloxane compound (2) is added, it is preferably added immediately before coating.

  When an active ray curable acrylic resin is used as the main component of the A layer 2 in the present invention, the active ray is an acrylic ray such as ultraviolet ray, electron beam and radiation (α ray, β ray, γ ray, etc.). An electromagnetic wave for polymerizing vinyl groups is used, and practically, ultraviolet rays are simple and preferable. As the ultraviolet ray source, an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like can be used. Moreover, when irradiating actinic radiation, if it irradiates under a low oxygen concentration, it can harden | cure efficiently.

  The coating solution used for forming the B layer 1 of the present invention is preferably composed mainly of the siloxane polymer, diluted with a solvent by adding a curing agent or the like, and the content of the solvent is the total silane used during the synthesis of the siloxane polymer. It is preferable to add in the range of 1300 mass% to 9900 mass% with respect to the compound content, and particularly preferably in the range of 1500 mass% to 6000 mass%. If the amount is less than 1300% by mass and exceeds 9900% by mass, it becomes difficult to form a transparent film having a predetermined film thickness.

  As the curing agent, titanium, zirconium, aluminum and magnesium are used. Among these, for the purpose of lowering the refractive index, aluminum-based and magnesium-based curing agents having a low refractive index are preferable. These curing agents can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.

  Preferable specific examples of the metal group chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethyl acetoacetate), aluminum tris Aluminum chelate compounds such as (acetylacetonate), magnesium chelate compounds such as ethylacetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkylacetoacetate magnesium monosopropylate, magnesium bis (acetylacetonate) It is done. Of these, aluminum tris (acetylacetonate), aluminum tris (ethyl acetoacetate), magnesium bis (acetylacetonate), and magnesium bis (ethyl acetoacetate) are preferable, considering storage stability and availability. Then, aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate) are particularly preferable. The amount of the metal chelate compound to be added is preferably 0.1% by mass to 10% by mass, particularly preferably 1% by mass to 6% by mass with respect to the total silane compound content used in the synthesis of the siloxane polymer. % By mass. When the amount introduced is less than 0.1% by mass, curing becomes insufficient, and when a transparent film is formed, the hardness decreases. On the other hand, when it exceeds 10% by mass, the curing becomes sufficient and the hardness of the transparent film is improved, but the refractive index is also improved, which is not preferable.

  The near-infrared absorption layer 4 can be provided in the antireflection film of this invention on the surface opposite to the surface which has the antireflection layer 6 of a base film. The near-infrared absorbing layer can be used without any particular limitation, such as those obtained by dispersing a near-infrared absorbing dye in a polymer resin, or provided with a near-infrared absorbing dye alone.

  As the near infrared absorbing dye, for example, a diimonium salt compound, a fluorine-containing phthalocyanine compound, a thionickel complex compound, an aminium compound, a cyanine compound, an azo compound, a polymethine compound, a quinone compound, a diphenylmethane compound, A triphenylmethane compound, a mercaptonaphthol compound, or the like is used, and either a single compound system or a mixed system can be suitably used.

  When the near-infrared absorbing dye is dispersed in a polymer resin, examples of the polymer resin include polyester-based, acrylic-based, cellulose-based, polyethylene-based, polypropylene-based, polyolefin-based, polyvinyl chloride-based, polycarbonate, and phenol-based resins. Urethane resins and the like are used, and any of them can be suitably used, and it is preferable to contain an ultraviolet absorber such as benzophenone or benzotriazole in order to suppress the deterioration of light resistance of the near infrared absorbing dye. Moreover, it is preferable to disperse | distribute 1-10 mass parts near-infrared absorption pigment | dye with respect to 100 mass parts of polymeric resins.

  In the antireflection film of the present invention, an adhesive layer 5 can be provided on the opposite surface of the base film having the antireflection layer 6. The pressure-sensitive adhesive layer 5 is not particularly limited as long as two objects are bonded by their pressure-sensitive adhesive action. As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 5, rubber-based, vinyl polymerization-based, condensation polymerization-based, thermosetting resin-based, silicone-based, and the like can be used. Among these, as the rubber-based adhesive, a butadiene-styrene copolymer system (SBR), a butadiene-acrylonitrile copolymer system (NBR), a chloroprene polymer system, an isobutylene-isoprene copolymer system (butyl rubber), or the like may be used. it can. As the vinyl polymerization adhesive, acrylic resin, styrene resin, vinyl acetate-ethylene copolymer system, vinyl chloride-vinyl acetate copolymer system, and the like can be used. As the condensation polymerization pressure-sensitive adhesive, a polyester resin system can be used. As the thermosetting resin-based pressure-sensitive adhesive, an epoxy resin system, a urethane resin system, a formalin resin system, or the like can be used. These resins may be used alone or in combination of two or more.

  Furthermore, as the pressure-sensitive adhesive, either a solvent-type pressure-sensitive adhesive or a solventless pressure-sensitive adhesive can be used. The pressure-sensitive adhesive layer 5 is formed using a conventional technique such as coating using the pressure-sensitive adhesive as described above. Furthermore, you may make the adhesion layer 5 contain a coloring agent. This is easily achieved by mixing and using a colorant such as a pigment or dye in the adhesive. When it contains a colorant, it is desirable that the light transmittance at 550 nm is in the range of 40 to 80% as a laminated film.

  Since the antireflection film of the present invention has high surface hardness and scratch resistance, it can be used in a wide range of applications. For example, it can be applied to the surface of membrane switches, curved mirrors, rearview mirrors, goggles, window glass, posters, advertising towers, nameplates and instrument covers, and other various commercial displays. Especially for image display members such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescence display (ELD), cathode ray tube display (CRT), portable digital assistant (PDA), adhesive layer or adhesive layer The image display device can be attached to the surface of the image display surface and / or the front plate thereof via the.

[Characteristic measurement method and effect evaluation method]
The characteristic measurement method and effect evaluation method in the present invention are defined as follows.

(1) Scratch resistance: Steel wool hardness evaluation Scratch resistance was rubbed 10 times at a stroke width of 10 cm and a speed of 30 mm / sec by applying a load of 250 g to # 0000 steel wool on the antireflection surface of the antireflection film. Then, the surface was observed visually and how to get a damage | wound was evaluated in the following five steps.
5th grade: No scratches 4th grade: 1 to 5 scratches 3rd grade: 6 to 10 scratches 2nd grade: 11 to 11 scratches 1st grade: Countless scratches on the entire surface For image display devices If it is used as a grade 3, grade 4, grade 5, or grade 5 is acceptable.

(2) Total light transmittance and haze measurement Based on JISK7105, it measured using Nippon Denshoku Industries Co., Ltd. turbidimeter NDH2000. It is desirable that the total light transmittance is 85% or more and the haze value is 1.5% or less.

(3) Evaluation of surface resistivity (antistatic property) The antireflection film was sampled into a square of 100 mm × 100 mm, pretreated by the method shown in JIS K6911, and HIRESTA UP (MCP-HT450) manufactured by Mitsubishi Yuka Co., Ltd. : According to JIS K6911), the surface resistivity was measured.
When used for an image display device, 1 × 10 ¹¹ Ω / □ or less is a pass level to show sufficient antistatic properties.

(4) Reflectance measurement The surface opposite to the measurement surface (the surface on which the antireflection layer is provided) is uniform with 320-400 water-resistant sandpaper so that the 60 ° C. gloss (JIS Z 8741) is 10 or less. After roughening, the black paint was applied and colored so that the visible light transmittance was 5% or less. Using a spectrophotometer (UV-3150) manufactured by Shimadzu Corporation, the absolute reflection spectrum in the wavelength region of 380 nm to 800 nm was measured at an incident angle of 5 degrees from the measurement surface, and the reflectance at wavelengths of 400 nm and 700 nm The minimum reflectance in the region of 400 nm to 700 nm was determined. When the measured reflection spectrum has undulations, the respective reflectances were obtained from curves connecting intermediate points between undulation peaks (maximum points) and valleys (minimum points). The lower the minimum reflectance, the higher the antireflection function and the better, and 1.1% or less is preferable. The smaller the difference between the maximum reflectivity (usually the reflectivity at the minimum wavelength is often the maximum reflectivity) and the minimum reflectivity, the reflected color will be neutral without any specific color tone, and the better the reflection. The rate difference is preferably 1.6% or less.

(5) Refractive index measurement About the coating film formed with the spin coater on the silicon wafer, the refractive index of 633 nm was measured with the phase difference measuring apparatus (Nikon Corporation make: NPDM-1000) on 25 degreeC temperature conditions. did.

  Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these.

(Preparation of layer B paint-1)
A silica slurry comprising 144 parts by mass of porous silica particles having an outer shell with a primary particle diameter of 50 nm and 560 parts by mass of isopropyl alcohol was prepared, 219 parts by mass of methyltrimethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane 158 parts by mass, 704 parts by mass of the above silica slurry, and 713 parts by mass of polypropylene glycol monoethyl ether are mixed and mixed with 1 part by mass of phosphoric acid and 130 parts by mass of water. The polymer was decomposed and polymerized while stirring at 60 ° C. ± 5 ° C. for 60 minutes to obtain a silica particle-containing polymer.

  Next, 1200 parts by mass of this silica particle-containing polymer and 5244 parts by mass of isopropyl alcohol were stirred and mixed, then 15 parts by mass of acetoxyaluminum as a curing catalyst was added and stirred again to prepare a paint having a refractive index of 1.35. .

(Preparation of layer B paint-2)
483 parts by mass of a sol of silica-based fine particles dispersed in isopropyl alcohol having a particle diameter of 12 nm and having no voids (trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd., solid content concentration: 30% by mass) A silica particle-containing polymer is prepared in the same manner as in the preparation of the layer B paint-1, except that the silica slurry is composed of 144 parts by mass of porous silica particles having an outer shell with a diameter of 50 nm and 560 parts by mass of isopropyl alcohol. Got.

  Next, after 1200 parts by mass of this silica particle-containing polymer and 5466 parts by mass of isopropyl alcohol were mixed with stirring, 15 parts by mass of acetoxyaluminum was added as a curing catalyst and mixed again with stirring to prepare a paint having a refractive index of 1.38. .

(Preparation of Condensate Compound-1 Consisting of Siloxane Compound (1) and Siloxane Compound (2))
326.9 g of methyltrimethoxysilane as the siloxane compound (1) and 93.7 g of 3-acryloxypropyltrimethoxysilane as the siloxane compound (2) (molar ratio of siloxane compound (1) to siloxane compound (2) = 6: 1 ), 179.4 g of methanol were mixed with stirring, and a mixture of formic acid and water (3.35 g of formic acid and 100.9 g of water: blended) was added dropwise over 15 minutes at 0 ° C. ± 5 ° C., and further at 0 ° C. ± 30 minutes. After hydrolysis by stirring at 5 ° C., the temperature of the heating medium was raised to 90 ° C. ± 5 ° C. (solvent reflux state), and polymerization was carried out with stirring for 180 minutes. Further, after cooling to 40 ° C., the solvent / water was distilled off at 40 ° C. under reduced pressure (3 hours) to increase the degree of polymerization to obtain a condensate compound having a kinematic viscosity of 150 mm ² / s (25 ° C.).

(Preparation of condensate compound-2 comprising siloxane compound (1) and siloxane compound (2))
Except for using 456.5 g of trifluoromethyltrimethoxysilane as the siloxane compound (1) (the molar ratio of the siloxane compound (1) to the siloxane compound (2) = 6: 1), the above (siloxane compound (1) and Preparation of condensate compound-1 comprising siloxane compound (2)) was performed in the same manner as above to obtain a condensate compound having a kinematic viscosity of 110 mm ² / s (25 ° C.).

(Preparation of condensate compound-3 comprising siloxane compound (1) and siloxane compound (2))
Except for using 163.5 g of methyltrimethoxysilane and 144.3 g of dimethyldimethoxysilane as the siloxane compound (1) (molar ratio of siloxane compound (1) to siloxane compound (2) = 6: 1), the above (siloxane Preparation of condensate compound-1 comprising compound (1) and siloxane compound (2)) was carried out in the same manner as above to obtain a condensate compound having a kinematic viscosity of 120 mm ² / s (25 ° C.).

(Preparation of Condensate Compound-4 Consisting of Siloxane Compound (1) and Siloxane Compound (2))
Except for using 99.4 g of 3-methacryloxypropyltrimethoxysilane as the siloxane compound (2) (molar ratio of siloxane compound (1) to siloxane compound (2) = 6: 1), the above (siloxane compound ( 1) and a condensate compound having a kinematic viscosity of 145 mm ² / s (25 ° C.) was synthesized in the same manner as in Preparation of condensate compound-1 comprising siloxane compound (2).

(Preparation of Condensate Compound-5 Consisting of Siloxane Compound (1) and Siloxane Compound (2))
163.5 g of methyltrimethoxysilane as siloxane compound (1), 93.7 g of 3-acryloxypropyltrimethoxysilane as siloxane compound (2) (molar ratio of siloxane compound (1) to siloxane compound (2) = 3: 1 ), Synthesized in the same manner as (Preparation of condensate compound-1 consisting of siloxane compound (1) and siloxane compound (2)) except that 102.5 g of methanol, 1.91 g of formic acid and 57.7 g of water were used. Thus, a condensate compound having a kinematic viscosity of 135 m ² / s (25 ° C.) was obtained.

(Preparation of Condensate Compound-6 Composed of Siloxane Compound (1) and Siloxane Compound (2))
653.9 g of methyltrimethoxysilane as siloxane compound (1), 93.7 g of 3-acryloxypropyltrimethoxysilane as siloxane compound (2) (molar ratio of siloxane compound (1) and siloxane compound (2) = 12: 1 ), Methanol (333.2 g), formic acid (6.22 g) and water (187.4 g), except that synthesis is carried out in the same manner as above (preparation of condensate compound-1 consisting of siloxane compound (1) and siloxane compound (2)) and a kinematic viscosity was obtained condensate compound of ^{160m 2 / s (25 ℃)} .

(Preparation of Condensate Compound-7 Consisting of Siloxane Compound (1) and Siloxane Compound (2))
326.9 g of methyltrimethoxysilane as the siloxane compound (1) and 93.7 g of 3-acryloxypropyltrimethoxysilane as the siloxane compound (2) (molar ratio of siloxane compound (1) to siloxane compound (2) = 6: 1 ), 168.3 g of isopropanol were mixed with stirring, and a mixture of formic acid and water (3.35 g of formic acid and 100.9 g of water: blended) was added dropwise over 15 minutes at 0 ° C. ± 5 ° C., and further at 0 ° C. ± 30 minutes. After hydrolysis by stirring at 5 ° C., the temperature of the heating medium was raised to 100 ° C. ± 5 ° C. (solvent reflux state), and polymerization was performed with stirring for 90 minutes. After further cooling to 30 ° C., the solvent and water were distilled off at 30 ° C. under reduced pressure (20 minutes). A condensate compound having a kinematic viscosity of 35 mm ² / s (25 ° C.) was obtained.

(Preparation of Condensate Compound-8 Consisting of Siloxane Compound (1) and Siloxane Compound (2))
54.5 g of methyltrimethoxysilane as the siloxane compound (1) and 93.7 g of 3-acryloxypropyltrimethoxysilane as the siloxane compound (2) (molar ratio of siloxane compound (1) to siloxane compound (2) = 1: 1) ), Methanol 51.3 g, formic acid 0.96 g, and water 28.8 g were used and synthesized in the same manner as described above (Preparation of condensate compound-1 consisting of siloxane compound (1) and siloxane compound (2)). Thus, a condensate compound having a kinematic viscosity of 45 m ² / s (25 ° C.) was obtained.

(Preparation of Condensate Compound-9 Composed of Siloxane Compound (1) and Siloxane Compound (2))
54.5 g of methyltrimethoxysilane as the siloxane compound (1) and 93.7 g of 3-acryloxypropyltrimethoxysilane as the siloxane compound (2) (molar ratio of siloxane compound (1) to siloxane compound (2) = 1: 1) ), Methanol (51.3 g), formic acid (0.96 g), and water (28.8 g), except that the stirring time at a heating medium temperature of 90 ° C. ± 5 ° C. (solvent reflux state) is 300 minutes. 1) and a condensate compound having a kinematic viscosity of 110 m ² / s (25 ° C.) was synthesized in the same manner as in Preparation of condensate compound-1 comprising siloxane compound (2).

(Preparation of Condensate Compound-10 Consisting of Siloxane Compound (1) and Siloxane Compound (2))
27.2 g of methyltrimethoxysilane as the siloxane compound (1) and 93.7 g of 3-acryloxypropyltrimethoxysilane as the siloxane compound (2) (molar ratio of siloxane compound (1) to siloxane compound (2) = 0.5 1), the same method as the above (preparation of condensate compound-1 comprising siloxane compound (1) and siloxane compound (2)) except that 51.3 g of methanol, 0.96 g of formic acid and 28.8 g of water are used. And a condensate compound having a kinematic viscosity of 40 m ² / s (25 ° C.) was obtained.

(Preparation of Condensate Compound-1 Consisting of Other Siloxane Compound)
94.5 g of 3-glycidoxypropyltrimethoxysilane which is another siloxane compound instead of the siloxane compound (2) (molar ratio of siloxane compound (1) and 3-glycidoxypropyltrimethoxysilane = 6: 1) Is synthesized in the same manner as in the above (Preparation of condensate compound-1 comprising siloxane compound (1) and siloxane compound (2)), and the kinematic viscosity is 140 m ² / s (25 ° C.). Body compound was obtained.

(Preparation of condensate compound-2 comprising other siloxane compounds)
Other than using siloxane compound (1) without using siloxane compound (2), 656.1 g of 3-acryloxypropyltrimethoxysilane, 179.4 g of methanol, 3.35 g of formic acid, and 100.9 g of water ( Preparation of condensate compound-1 comprising siloxane compound (1) and siloxane compound (2)) was carried out in the same manner as above to obtain a condensate compound having a kinematic viscosity of 90 mm ² / s (25 ° C.).

Example 1
A paint containing 25% by mass of antimony-containing tin oxide fine particles having an average particle diameter of about 10 nm and a polyfunctional acrylate on the easy-adhesion surface of a commercially available optically-adhesive polyester film (Lumirror (registered trademark) QT63, manufactured by Toray Industries, Inc., 100 μm thick) (large Seika Beam PET-HC15NS (AS-41) manufactured by Nissei Kasei Co., Ltd .: Condensate compound-1 consisting of a refractive index of 1.53 and a solid content concentration of 30% by mass and the above (siloxane compound (1) and siloxane compound (2)) The condensate compound obtained in (Preparation) was mixed at a mass ratio of 163.4: 1 (condensate compound consisting of siloxane compound (1) and siloxane compound (2) contained in layer A was 2% by mass) and stirred. and coating the coating liquid in a small-diameter gravure coater was, after drying at 90 ° C., and then cured by irradiation with ultraviolet rays 400 mJ / cm ^2, provided the a layer having a thickness of about 3μm . Next, on this A layer, the paint prepared in the above (adjustment of B layer paint-1) is applied with a small-diameter gravure coater, dried and cured at 130 ° C., and a B layer having a thickness of about 0.1 μm. An antireflection film was produced. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the surface resistivity, scratch resistance, haze, minimum reflectance at a wavelength of 400 to 700 nm, reflectance difference, and total light transmittance are very good values, and interference unevenness is also very high. The surface appearance was very good with little, and the color of the reflected color was neutral.

(Example 2)
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-2 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the surface resistivity, haze, minimum reflectance at a wavelength of 400 to 700 nm, difference in reflectance, and total light transmittance all showed very good values, and the scratch resistance also reached a pass level. The color of the reflected color was neutral, and the surface appearance was very good with very little interference unevenness.

(Example 3)
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-3 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the surface resistivity, haze, minimum reflectance at a wavelength of 400 to 700 nm, difference in reflectance, and total light transmittance all showed very good values, and the scratch resistance also reached a pass level. The color of the reflected color was neutral, and the surface appearance was very good with very little interference unevenness.

Example 4
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-4 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the surface resistivity, haze, minimum reflectance at a wavelength of 400 to 700 nm, difference in reflectance, and total light transmittance all showed very good values, and the scratch resistance also reached a pass level. The color of the reflected color was neutral, and the surface appearance was very good with very little interference unevenness.

(Example 5)
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-5 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, haze, minimum reflectance at a wavelength of 400 to 700 nm, difference in reflectance, and total light transmittance are very good values, the surface resistivity reaches a fairly good level, and scratch resistance Also reached a passing level. The reflected color was neutral, and there was little interference unevenness and the surface appearance was good.

(Example 6)
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-6 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the surface resistivity, haze, minimum reflectance at a wavelength of 400 to 700 nm, difference in reflectance, and total light transmittance all showed very good values, and the scratch resistance also reached a pass level. The color of the reflected color was neutral, and the surface appearance was very good with very little interference unevenness.

(Example 7)
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-7 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the surface resistivity, haze, minimum reflectance at a wavelength of 400 to 700 nm, difference in reflectance, and total light transmittance all showed very good values, and the scratch resistance also reached a pass level. The reflected color was neutral, and there was little interference unevenness and the surface appearance was good.

(Example 8)
For layer A, paint containing 25% by mass of antimony-containing tin oxide fine particles having an average particle diameter of about 10 nm and polyfunctional acrylate (Seika Beam PET-HC15NS (AS-41) manufactured by Dainichi Seika Co., Ltd.): refractive index 1.53, solid (Concentration of 30% by mass) and the condensate compound obtained in the above (preparation of condensate compound-1 consisting of siloxane compound (1) and siloxane compound (2)) at a mass ratio of 30: 1 (included in layer A) An antireflection film was produced in the same manner as in Example 1 except that the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) was used in an amount of 10% by mass). The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the scratch resistance, haze, minimum reflectance at a wavelength of 400 to 700 nm, difference in reflectance, and total light transmittance all showed very good values, and the surface resistivity also reached an acceptable level. The color of the reflected color was neutral, and the surface appearance was very good with very little interference unevenness.

Example 9
Regarding layer A, paint containing 50% by mass of antimony-containing tin oxide fine particles having an average particle diameter of about 10 nm and polyfunctional acrylate (Seika Beam PET-HC15NS (AS-21) manufactured by Dainichi Seika Co., Ltd.): refractive index 1.59, solid (Concentration concentration 30 mass%) and the condensate compound obtained in the above (preparation of condensate compound-1 comprising siloxane compound (1) and siloxane compound (2)) at a mass ratio of 163.4: 1 (layer A) An antireflection film was produced in the same manner as in Example 1 except that the condensate compound consisting of the siloxane compound (1) and the siloxane compound (2) contained in 2% by mass was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the scratch resistance was very good and the surface resistivity was extremely good. The haze and total light transmittance have reached a level where there is no problem in practical use. The minimum reflectance at a wavelength of 400 to 700 nm is very good, and the difference in reflectance is within an allowable range. The color of the reflected color was slightly bluish, but there was no problem in actual use, the interference unevenness was very small, and the surface appearance was very good.

(Example 10)
Regarding the B layer, an antireflection film was produced in the same manner as in Example 1 except that the paint prepared in (Preparation of B layer paint-2) was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the surface resistivity, scratch resistance, haze, reflectance difference at a wavelength of 400 to 700 nm, and total light transmittance showed very good values. The minimum reflectance is also a good level. There was very little interference unevenness, the surface appearance was very good, and the color of the reflected color was neutral.

(Example 11)
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-8 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is clear from Table 2, the haze, the minimum reflectance at a wavelength of 400 to 700 nm, the reflectance difference, and the total light transmittance showed very good values. Surface resistivity and scratch resistance are also acceptable levels. Interference unevenness is within an allowable range, and the surface appearance is at a level that causes no problem in actual use. The neutral color of the reflected color was obtained.

(Example 12)
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-9 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, haze, minimum reflectance at a wavelength of 400 to 700 nm, difference in reflectance, and total light transmittance are very good values, the surface resistivity reaches a fairly good level, and scratch resistance Also reached a passing level. The reflected color was neutral, and there was little interference unevenness and the surface appearance was good.

(Example 13)
Regarding the A layer, the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in the A layer is (preparation of condensate compound-10 composed of the siloxane compound (1) and the siloxane compound (2)). An antireflection film was produced in the same manner as in Example 1 except that the product obtained in 1 was used. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is clear from Table 2, the haze, the minimum reflectance at a wavelength of 400 to 700 nm, the reflectance difference, and the total light transmittance showed very good values. Scratch resistance is also acceptable. The surface resistivity is at a level that can be used. Interference unevenness is within an allowable range, and the surface appearance is at a level that causes no problem in actual use. The neutral color of the reflected color was obtained.

(Comparative Example 1)
With respect to the A layer, Example 1 except that the condensate compound composed of the siloxane compound contained in the A layer was obtained from (Preparation of condensate compound-1 composed of another siloxane compound). An antireflection film was produced in the same manner. The evaluation results of the obtained antireflection film are shown in Table 2.

  As can be seen from Table 2, it has reached acceptable levels such as scratch resistance and has some other characteristics that show good values, but its surface resistivity is extremely poor and antistatic performance cannot be expected at all. It became unsuitable for. As for the surface appearance, defects such as repelling are often found to be defective.

(Comparative Example 2)
With respect to the A layer, Example 1 except that the condensate compound composed of the siloxane compound contained in the A layer was obtained from (Preparation of condensate compound-2 composed of another siloxane compound). An antireflection film was produced in the same manner. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the optical properties were generally good, but the scratch resistance and surface resistivity did not reach acceptable levels, and there were problems in use.

(Comparative Example 3)
For layer A, paint containing 25% by mass of antimony-containing tin oxide fine particles having an average particle diameter of about 10 nm and polyfunctional acrylate (Seika Beam PET-HC15NS (AS-41) manufactured by Dainichi Seika Co., Ltd.): refractive index 1.53, solid (Concentration concentration 30 mass%) and the condensate compound obtained in the above (preparation of condensate compound-1 consisting of siloxane compound (1) and siloxane compound (2)) at a mass ratio of 7.75: 1 (layer A) An antireflective film was produced in the same manner as in Example 1 except that the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) contained in was used in an amount of 30% by mass. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, the scratch resistance did not reach an acceptable level, and the surface resistivity was extremely poor and antistatic performance could not be expected at all. The minimum reflectivity is slightly higher.

(Comparative Example 4)
Regarding layer A, an antireflection film was produced in the same manner as in Example 1 except that the condensate compound composed of siloxane compound (1) and siloxane compound (2) was not added. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, although it has reached a good level except for the scratch resistance, the scratch resistance is at a level that is not practical at all, and is not suitable for use.

(Comparative Example 5)
Regarding the A layer, a paint containing no conductive metal oxide fine particles (a paint containing a polyfunctional acrylate, Desolite Z7528 manufactured by JSR Corporation: refractive index 1.50, solid content concentration 50% by mass) and the above (siloxane compound (1 ) And siloxane compound (2) to prepare condensate compound-1) in a mass ratio of 98: 1 (from siloxane compound (1) and siloxane compound (2) contained in layer A) An antireflection film was produced in the same manner as in Example 1 except that the condensate compound to be used was 2% by mass). The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, although there are very good characteristics such as scratch resistance, the surface resistivity is very poor and antistatic performance cannot be expected at all, so that it is not suitable for use. The minimum reflectivity is slightly higher.

(Comparative Example 6)
For layer B, a paint containing a fluorine-containing copolymer (fluoroolefin / vinyl ether copolymer) (manufactured by JSR Corporation, JN-7215: refractive index 1.42) is used and dried and cured at 150 ° C. Except for this, an antireflection film was produced in the same manner as in Example 1. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, although some of the properties exhibiting good values are present, the scratch resistance is at a level where it is not practical and the minimum reflectance is high, making it unsuitable for use.

(Comparative Example 7)
Regarding the A layer, an antireflection film was produced in the same manner as in Example 1, except that the film thickness was 0.1 μm. The evaluation results of the obtained antireflection film are shown in Table 2.

  As is apparent from Table 2, although some characteristics exhibiting very good values are present, the scratch resistance and surface resistivity are at levels that are not practical at all, and are not suitable for use.

(Example 14)
On the surface of the antireflection film obtained in Example 1, on which the antireflection layer 6 is not provided, two kinds of near infrared absorbing dyes (diimonium salt type: IRG-022 manufactured by Nippon Kayaku Co., Ltd., phthalocyanine type: ( EEX Color 810K manufactured by Nippon Shokubai Co., Ltd.) 1.9 mass% and 1.0 mass%, respectively, and acrylic resin (Mitsubishi Rayon Co., Ltd. Dianar BR-80) 97.1 mass% mixed were used. And provided a near-infrared absorbing layer. Furthermore, on this near-infrared absorbing layer, a dye having an absorption maximum at a wavelength of 595 nm and a dye for correcting the chromaticity of white light are mixed with an adhesive AGR-100 (manufactured by Nippon Kayaku Co., Ltd.) to form an adhesive layer. After being provided and bonded to glass, it was cured with an ultraviolet irradiation amount of 1000 mJ / cm ² to obtain a front protective plate for plasma display.

(Example 15)
The front protective plate for the plasma display panel of Example 12 was set on the front surface of the plasma display panel. A plasma display with less reflection and neutral reflection color was obtained.

  According to the present invention, since the antireflection film of the present invention has a low surface reflectance and a neutral color, it is applied to, for example, the front surface of a large flat screen television such as a plasma display, the front surface of a liquid crystal television, and the like. It is suitable as an antireflection film.

It is sectional drawing which represented typically the cross section which shows an example of the antireflection film of this invention. It is the TEM photograph which expanded B layer of the antireflection film of the present invention at a magnification of 200,000 times. It is the TEM photograph which expanded the B layer which has a silica type fine particle and the siloxane polymer which is not homogenized as a main component by 200,000 times magnification. It is the TEM photograph expanded to 200,000 times which shows another example of B layer which has a silica type microparticle and the siloxane polymer which is not homogenized as a main component.

Explanation of symbols

1: B layer 2: A layer 3: Base film 4: Near-infrared absorbing layer 5: Adhesive layer 6: Antireflection layer 7: Internal cavity of silica-based fine particles 8: Outer shell of silica-based fine particles 9: Siloxane polymer 10 : Boundary 11: B layer

Claims (14)

At least one side of the base film is composed mainly of an acrylic resin and conductive metal oxide fine particles, a layer A having a film thickness of 0.3 μm or more, and a siloxane polymer homogenized with silica fine particles. At least two of the B layers are antireflection films in which the A layer is closer to the base film than the B layer, and the B layer is laminated on the A layer. An antireflection film in which a condensate compound composed of the following siloxane compound (1) and the following siloxane compound (2) is contained in the A layer in an amount of 0.001 to 20% by mass with respect to the A layer.
R ¹ ₂ SiR ² ₂ (1)
(However, R ¹ represents a fluoroalkyl group having 3 to 17 fluorine atoms, a methyl group, an ethyl group, a hydroxyl group, a methoxy group, or an ethoxy group, and may be the same or different. R ² represents a hydroxyl group. Represents a methoxy group or an ethoxy group, which may be the same or different.
R ³ SiR ⁴ ₃ (2)
(However, R ³ represents a vinyl group, a (meth) acryl group and a substituted product thereof. R ⁴ represents a methyl group, an ethyl group, a hydroxyl group, a methoxy group, and an ethoxy group, which are the same or different. Is also good.)   2. The antireflection film according to claim 1, wherein a molar ratio of the siloxane compound (1) to the siloxane compound (2) (siloxane compound (1): siloxane compound (2)) is 0.1: 1 to 20: 1. . The antireflection film according to claim 1 or 2, wherein the condensate compound composed of the siloxane compound (1) and the siloxane compound (2) has a kinematic viscosity of 40 mm ² / s (25 ° C) or more.   The antireflection film according to claim 1, wherein the silica-based fine particles have a cavity inside.   The antireflection film according to claim 1, wherein the siloxane polymer contains a polyfunctional fluorine-containing silane compound.   The antireflective film according to claim 1, wherein the refractive index of the A layer is 1.48 or more and 1.62 or less.   7. The antireflection film according to claim 1, wherein a content of the conductive metal oxide fine particles is 40% by mass or less with respect to the A layer. The antireflection film according to claim 1, which has a surface resistivity of 1 × 10 ¹¹ Ω / □ or less.   The antireflection film according to any one of claims 1 to 8, wherein the scratch resistance of the surface defined in the text is grade 3 or higher.   Haze is 1.5% or less, The antireflection film in any one of Claims 1-9. The antireflection film according to any one of claims 1 to 10, wherein a surface reflection spectrum at a wavelength of 400 to 700 nm defined in the text satisfies all of the following three conditions.
(1) The minimum reflectance is 0.6% or more and 2.0% or less,
(2) The maximum reflectance is 3.5% or less,
(3) The difference between the maximum reflectance and the minimum reflectance is 2.5% or less.   The antireflection film according to claim 1, wherein the total light transmittance is 85% or more.   The antireflection film according to claim 1, wherein the base film is made of at least one selected from the group consisting of a polyester resin, an acetate resin, and an acrylic resin.   An image display device comprising the antireflection film according to claim 1 attached to an image display surface or a surface of a front plate.