JP2007185824A - Antireflection laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To inexpensively provide an antireflection laminated film which is used appropriately for the display screen surfaces of various displays including a liquid crystal display, CRT display, projection display, plasma display, and EL display, has high antistatic and antireflection properties in particular, and is excellent in transparency, surface hardness, scratch resistance, and antifouling properties. <P>SOLUTION: In the antireflection laminated film, a hard coat layer with a refractive index of at least 1.50 and an antistatic, low-refractive index layer which contains a binder and an organic antistatic agent and has a refractive index of 1.49 or below are laminated on a substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a display (liquid crystal display, CRT display, projection display, plasma, having productivity, high antistatic properties and antireflection properties, and excellent in high transparency, surface hardness, scratch resistance, and antifouling properties. The present invention relates to an antireflection laminated film applied to the display screen surface of a display, an EL display, or the like.

  Many displays are used in an environment where external light or the like enters regardless of whether indoors or outdoors. Incident light such as external light is specularly reflected on the display surface or the like, and the reflected image is mixed with display light to lower the display quality and make the display image difficult to see. For this reason, in order to provide an antireflection function, a multilayer film in which transparent thin films of metal oxide are laminated has been conventionally used. The transparent thin film of metal oxide is formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, and in particular, is formed by a vacuum vapor deposition method which is a physical vapor deposition method. The antireflection film thus formed exhibits excellent optical characteristics, but the formation method by vapor deposition has a problem that productivity is low and it is not suitable for mass production.

  Furthermore, since the surface of a polymer material such as plastic or film is relatively flexible, a technique of polymerizing an acrylic polyfunctional compound on the surface of the article and providing a hard coat layer is used to obtain surface hardness. . The hard coat layer thus obtained has high surface hardness, glossiness, transparency, and scratch resistance, which are properties unique to acrylic resins. On the other hand, it is easy to be charged because of its excellent insulating properties, and it can cause troubles due to contamination due to dust adhering to the surface of the product provided with a hard coat layer and charging when used in precision machinery. I had a problem to do.

  In order to solve these problems, a conductive layer is very thin enough not to drop the surface hardness between the base material and the hard coat layer or between the hard coat layer and the low refractive index layer. There is a method of providing Moreover, the coating method is used as the formation method, and the improvement of productivity is attempted.

Examples of the conductive agent used include metal oxide fine particles, conductive polymers, various activators, hydrophilic compounds, and ionic conductive compounds. In the technique using electron conductive fine particles, a hard coat kneading method and a method of providing a conductive layer between layers are used. In the kneading method (see, for example, Patent Document 1), the refractive index of the fine particles is usually high, and the amount of fine particles is determined because it is electronically conductive, thereby reducing light interference with the substrate. It becomes difficult to achieve both conductivity. If the blending amount is too small, conductivity will not be exhibited, and if it is too large, there will be a problem that the light transmittance will decrease, and if the film thickness is reduced to increase the transmittance, the function of protecting the substrate will decrease. There is a problem. In addition, since the antireflection layer is formed on the hard coat layer, there is a problem that the antistatic performance is lowered. Conductive polymers have similar problems. In the method of providing a conductive layer between the base material and the hard coat layer (for example, see Patent Document 2), it is necessary to perform a special treatment on the upper layer in consideration of conductivity by laminating it on the upper layer of the conductive layer. In addition, the multi-layer structure causes a problem that the number of processes increases and the productivity decreases. Similarly, in the method of providing a conductive layer between the hard coat layer and the antireflection layer (see, for example, Patent Document 3), a multi-layer structure causes a problem that the number of processes is increased and productivity is lowered.
JP-A-11-92750 JP-A-11-326602 JP 2001-330702 A

  The present invention has been made to solve the above-described problems, and has particularly high antistatic properties and antireflection properties, and is excellent in high transparency, surface hardness, scratch resistance, and antifouling properties. An object is to provide an antireflection laminated film at a low cost.

  In order to achieve the above object, that is, the invention described in claim 1 includes a hard coat layer having a refractive index of 1.50 or more, a binder, and an organic antistatic agent on a substrate. 1. An antireflection laminate film comprising an antistatic low refractive index layer having a refractive index of 1.49 or less.

  The invention described in claim 2 is the antireflection laminated film according to claim 1, wherein the binder is thermosetting.

  The invention according to claim 3 is the antireflection laminated film according to claim 1 or 2, wherein the antistatic low refractive index layer contains a fluorine atom-containing substance.

The invention according to claim 4 is characterized in that the antistatic low refractive index layer is
nd = λ / 4
(Where n represents the refractive index of the layer, d represents the layer thickness, λ represents the wavelength of light, and is an integer satisfying 450 ≦ λ ≦ 650)
It is satisfy | filling. It is an antireflection laminated film of any one of Claims 1-3 characterized by the above-mentioned.

  The invention according to claim 5 is characterized in that the hard coat layer is made of a polymer mainly composed of a polyfunctional monomer having a (meth) acryloyloxy group. It is an antireflection laminated film of description.

  The invention according to claim 6 is the antireflection laminated film according to any one of claims 1 to 5, wherein the hard coat layer further contains a filler having an average particle diameter of 10 nm to 10 μm. is there.

  According to the present invention, it is possible to provide a low-cost antireflection laminate film having particularly high antistatic properties and antireflection properties, and excellent in high transparency, surface hardness, scratch resistance and antifouling properties. The antireflection laminated film of the present invention is suitably used for the display screen surface of various displays such as a liquid crystal display, a CRT display, a projection display, a plasma display, and an EL display.

  Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of an antireflection laminated film according to an embodiment of the present invention.

  As shown in FIG. 1, an antireflection laminated film 1 as an example of the present invention includes a hard coat layer 3 having a refractive index of 1.50 or more, a binder, and an organic antistatic agent on a base material 2. 1. An antireflection laminated film obtained by laminating an antistatic low refractive index layer 4 of 1.49 or less.

As the substrate 2 in the present invention, a plastic film serving as a transparent support is used, and films or sheets made of various organic polymers can be used. In general, a base material used for an optical member such as a display is a polyolefin-based material in consideration of optical properties such as transparency and refractive index of light, as well as various physical properties such as impact resistance, heat resistance and durability. Polyethylene, polypropylene, etc.), polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene nallate, etc.), celluloses (triacetylcellulose, diacetylcellulose, cellophane, etc.), polamides (nylon-6, nylon-66, etc.), acrylic Organic polymers such as system (polymethyl methacrylate, etc.), polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, ethylene vinyl alcohol, etc. are used. In particular, polyethylene terephthalate, triacetyl cellulose, polycarbonate, and polymethyl methacrylate are preferable. Furthermore, known additives such as ultraviolet absorbers, infrared absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants, etc. are added to these organic polymers to add functions. it can. In addition, the base material may be a single substance or a laminate or mixture of a plurality of substances. Moreover, the thickness of a base material can be suitably selected according to the use which uses a surface protection film, and 25-300 micrometers is preferable. However, the present invention is not limited to this. In addition, surface treatment can be performed for the purpose of improving the adhesion to the surface protective layer provided on the substrate. As this surface treatment method, for example, surface roughening treatment such as sandblasting or solvent treatment, or surface oxidation treatment such as corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, etc. Can be mentioned.

  The hard coat layer 3 in the present invention is laminated on the plastic film, and the hard coat layer is composed of an ultraviolet ray and an electron beam curable resin alone, or an organic silicon alkoxide and a hydrolyzate thereof in the cured product. The filler is included.

  Ultraviolet and electron beam curable resin compounds used in hard coat layers for the purpose of surface modification of base materials, scratch resistance by steel wool rubbing test, surface hardness by pencil scratch test, adhesion by cello tape (registered trademark) peel test The resin can be selected and used so as to satisfy the specifications required for various properties such as the properties and cracking properties by the minimum bending test. This compound contains a photopolymerizable prepolymer, a photopolymerizable monomer, a photopolymerization initiator, and the like.

  Examples of the photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, polyol acrylate, and the like. These photopolymerizable prepolymers may be used alone or in combination of two or more.

  Examples of the photopolymerizable monomer include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. Moreover, although these refractive indexes are around 1.5, monomers having a high refractive index include those having a cyclic group and / or those containing halogen atoms other than fluorine atoms and atoms such as S, N and P. Can be mentioned. The cyclic group includes an aromatic group, a heterocyclic group and an aliphatic ring group. Examples thereof include bis (4-methacryloylthiophenoxy) sulfide, bisphenoxyethanol full orange acrylate, and tetrabromobisphenol A diepoxy acrylate. In particular, in the present invention, it is preferable to use urethane acrylate as a prepolymer and dipentaerythritol hexa (meth) acrylate, bisphenoxyethanol full orange acrylate, or the like as a monomer.

  Furthermore, examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like.

Moreover, n-butylamine, triethylamine, poly-n-butylphosphine, etc. can be mixed and used as a photosensitizer. ...
The hard coat layer in the present invention can further contain an organosilicon alkoxide and a hydrolyzate thereof. The organosilicon alkoxide satisfies the following general formula. _{R 'y Si (OR) 4} -y ··· formula (B)
(However, in the formula, R represents an alkyl group, and R ′ represents an unreactive functional group such as an alkyl group or a fluorinated alkyl group at the terminal, a vinyl group, an amino group, an epoxy group, an aryl group, a (meth) acryloyl group, etc. And y is an integer satisfying 1 ≦ y ≦ 3.) For example, octyltrimethoxysilane, octadecyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 1H, 1H 2H, 2H-purple chlorohexyltrimethoxysilane, 1H, 1H, 2H, 2H-purple olodecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopro Biltrimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, 3-g Risidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane.

  The hard coat layer in the present invention can further add a function to the antireflection film by further adding a filler having an average particle diameter of 10 nm or more and 10 μm or less. By adding a filler, high hardness and refractive index can be adjusted.

  When particles having a large particle size (0.1 μm or more) are used, antiglare properties can be imparted to the film.

  If the particle size is 10 μm or more, the particle diameter is too large compared to the thickness of the hard coat layer, so that it is difficult to laminate the upper antistatic low refractive index layer. As the filler, inorganic fillers such as silica, alumina, zirconia and the like, two or more kinds of composite oxide fillers, organic fillers such as acrylic, styrene, urethane, melamine, and benzoanamine, and two or more kinds of copolymer fillers can be used. . The filler may be used alone or in combination of two or more. In order to improve the strength of the hard coat layer, colloidal particles having an average particle diameter of 0.5 μm or less can be added. The colloidal particle diameter is preferably 0.1 μm or less from the viewpoint of transparency. Examples of the colloidal particles include silica, alumina, and zirconia. These may be used alone, or two or more kinds of complex oxides or a mixture of two or more kinds.

  The hardness of the hard coat layer is preferably H or higher in pencil hardness, and can have scratch resistance necessary for the antireflection laminated film.

  In preparing the hard coat agent for forming the hard coat layer, there is no particular limitation on the blending order of the components, and ultraviolet rays, electron beam curable resin compounds, and the like are added and mixed in various solvents.

Solvents include, but are not limited to, ketones such as methyl ethyl ketone, acetone, and methyl isoptyl ketone, esters such as methyl acetate, ethyl acetate, and butyl acetate, aromatic compounds such as toluene and xylene, diethyl ether And ethers such as tetrahydrofuran and alcohols such as methanol, ethanol and isopropanol. Moreover, well-known additives, such as an antifoamer and a leveling agent, can be mix | blended with this hard-coat agent if desired. There is no restriction | limiting in particular about solid content concentration of a hard-coat agent, The range of 10 to 70 weight% is preferable from surfaces, such as coating property, drying property, economical efficiency, and the range of 30 to 50 weight% is especially suitable.

  There are no particular restrictions on the method of applying the hard coating agent to the substrate, and a bar coating method, a micro gravure method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or the like can be used.

  The thickness of the hard coat layer can be controlled by calculating the required amount of hard coat agent applied from the solid content concentration of the hard coat agent and the density of the hard coat layer after curing. A thickness of 2 μm to 20 μm is preferable, and a thickness of 3 μm to 10 μm is particularly preferable.

  Alternatively, the coating layer after drying may be cured by irradiation with ultraviolet rays and electron beams in an atmosphere purged with nitrogen to form a hard coat layer with less surface damage and high surface hardness.

  There is no restriction | limiting in particular about the ultraviolet irradiation apparatus used for hardening, For example, the well-known ultraviolet irradiation apparatus using a high pressure mercury lamp, a xenon lamp, a metal halide lamp etc. can be used. The amount of ultraviolet irradiation is usually about 100 to 800 mJ / cm2. There is no restriction | limiting in particular about an electron beam irradiation apparatus, and an acceleration voltage is 50-300 kV normally.

  The hard coat layer thus obtained is excellent in adhesion to the substrate, surface hardness, flexibility, scratch resistance, transparency or antiglare property on the surface of the article.

  The antistatic low refractive index layer 4 in the present invention is provided on the hard coat layer, and an antistatic property can be exhibited by adding an organic antistatic agent to a binder to form a coating film. What are organic antistatic agents? These organic antistatic agents can be used alone, in a mixture of two or more kinds, and in two or more kinds of composite fine particles.

  The addition amount of the organic antistatic agent is not particularly limited. However, if the addition amount is large, it may bleed and impair transparency, so the range of 1 to 30% by weight of the solid content is preferable, particularly 5 to 20% by weight. A range is preferred.

Examples of the organic antistatic agent include a quaternary ammonium base-containing polymer, a quaternary ammonium base-containing silane coupling agent, or a hydrolysis-condensation product thereof. Specific examples of such a quaternary ammonium base-containing polymer are shown below. (A) N, N-dialkylaminoalkyl (meth) acrylic ester / quaternary ammonium salt of other (meth) acrylic ester copolymer, (b) N, N-dialkylaminoalkyl (meth) acrylamide / Quaternary ammonium salts of copolymers with other (meth) acrylic acid esters, (c) N, N-dialkylaminoalkyl (meth) acrylic acid esters / other (meth) acrylic acid esters (/ styrenes ) / Hydroxyalkyl (meth) acrylic ester copolymer and adduct of (meth) acryloyl group-containing isocyanate compound, quaternary ammonium salt, (d) N, N-dialkylaminoalkyl (meth) acrylic acid Esters / other (meth) acrylic acid esters (/ styrenes) / hydroxyalkyl (meth) acrylic acid esters / Quaternary ammonium salt of (meth) acryloyl-terminated polydimethylsiloxane copolymer and adduct of (meth) acryloyl group-containing isocyanate compound, (e) N, N-dialkylaminoalkyl (meth) acrylic acid ester / Other (meth) acrylic acid esters / (/ styrenes) / Hydroxyalkyl (meth) acrylic acid esters / (meth) acryloyl-terminated polydimethylsiloxane copolymers and addition of (meth) acryloyl group-containing isocyanate compounds (F) N, N-dialkylaminoalkyl (meth) acrylic acid ester / (meth) acrylic acid ester (/ styrenes) / Hydroxyalkyl (meth) acrylate / me A quaternary ammonium salt of a copolymer of capto-terminated polydimethylsiloxane and an adduct of a (meth) acryloyl group-containing isocyanate compound, (g) N, N-dialkylaminoalkyl (meth) acrylamide / (meth) acrylic acid Examples include esters (/ styrenes) / hydroxyalkyl (meth) acrylic esters / mercapto-terminated polydimethylsiloxane copolymers and adducts of (meth) acryloyl group-containing isocyanate compounds, quaternary ammonium salts, and the like. be able to.

  Quaternizing agents for modifying amino groups to quaternary ammonium salts include alkyl halides (such as methyl chloride), alkenyl halides (such as allyl chloride), aralkyl halides (such as benzyl chloride), dimethyl sulfate, diethyl Alkyl sulfates such as sulfuric acid, sulfonate esters such as methyl p-toluenesulfonate, α-haloaliphatic carboxylic acid derivatives such as methyl chloroacetate, α-haloketones such as chloroacetone, α-haloalkyl such as chloroacetonitrile A nitrile etc. can be illustrated. Among these, in order to obtain excellent antistatic properties, it is preferable to use an alkyl halide having 4 or less carbon atoms, an alkenyl halide, an α-haloaliphatic carboxylic acid derivative, or the like as a quaternizing agent. In addition, N, N-dialkylaminoalkyl (meth) acrylic acid ester as in the above (f), other (meth) acrylic acid ester and / or styrenes, hydroxyalkyl (meth) acrylic acid ester, mercapto A quaternary ammonium base-containing polymer obtained by modifying an adduct of a terminal polydimethylsiloxane copolymer and a (meth) acryloyl group-containing isocyanate compound with a quaternizing agent such as methyl chloride, allyl chloride, or methyl chloroacetate preferable.

  Although some quaternary ammonium base-containing silane coupling agents are commercially available, their functions as antistatic agents are generally low. This is because the molecular weight is low, so that it is easily adsorbed on the surface of the inorganic oxide particles, and the concentration of the quaternary ammonium group is lowered. As shown below, N, N-dialkylaminoalcohol and a silane coupling agent having an NCO group are connected by a urethane bond and then quaternized with an appropriate quaternizing agent, and a silane having a molecular weight of 400 or more. Molecular weight obtained by quaternizing the coupling agent and / or the hydrolysis condensate thereof, or an adduct of a N, N-dialkylaminoalkyl (meth) acrylate ester and a silane coupling agent having an SH group with a thioether bond Is preferably a silane coupling agent having a molecular weight of 400 or more, a hydrolysis condensate of such a silane coupling agent alone, a hydrolysis cocondensation product with another silane coupling agent, or the like.

  Specific examples of such quaternary ammonium base-containing silane coupling agents include N, N-dialkylamino aliphatic alcohols (N, N-dimethylaminoethanol, N, N-dimethylaminopropanol, etc.) and NCO groups. Quaternary ammonium salts, N, N-dialkylaminoalkyl (meth) acrylic acid esters (N, N-dimethylamino methacrylate, etc.) and mercapto groups of reaction products of trialkoxysilane (γ-trimethoxysilylpropyl isocyanate etc.) contained A quaternary ammonium salt of a reaction product with a trialkoxysilane (γ-mercaptopropyltrimethoxysilane or the like) having a silane, a single hydrolysis condensate of these, a cohydrolysis condensate of these with another silane coupling agent, etc. Can be mentioned. As other silane coupling agents, silane coupling agents having an alkylene oxide chain exemplified above and silane coupling agents capable of radical polymerization are particularly preferred.

Examples of other antistatic agents include quaternary phosphonium base compounds having an alkyl group. Some typical examples of such compounds are shown below. Radical polymerization of tetraalkylphosphonium halides such as dodecyltrimethylphosphonium chloride, aralkyltrialkylphosphonium halides such as benzyltrimethylphosphonium chloride, methacryloxyethyltrimethylphosphonium chloride, etc. Examples thereof include quaternary phosphonium salts having various functional groups.

  Examples of other antistatic agents include polyhydric alcohols having an ethylene oxide chain or derivatives thereof. Some typical examples of such compounds are: polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polyhydric alcohols (glycerin, trimethylolpropane, pentaerythritol, dipenta And an alkylene oxide adduct of erythritol and the like, and (meth) acrylic acid esters thereof.

  Examples of other antistatic agents include phosphates. Some representative examples of such substances include tertiary amine salts of bis (β-methacryloxyethyl) phosphate, sodium polyphosphate, and the like.

  Examples of other antistatic agents include conductive polymers. Some typical examples of such substances include polyaniline, polyacetylene, polypyrrole, polythiophene, and polyvinylcarbazole.

  As other antistatic agents, ionic liquids can be exemplified. Examples of the cation constituting the ionic liquid include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation. As anions constituting the ionic liquid, halogen (fluorine, chlorine, bromine, etc.) ions, alkyl (carbon number 1-12) benzenesulfonic acid (p-toluenesulfonic acid, etc.) ions and poly (n = 1-25) fluoro Alkane sulfonic acid (undecafluoropentane sulfonic acid etc.) ion etc. are mentioned.

  As the binder for the antistatic low refractive index layer, various ionizing radiation curable and thermosetting organic and inorganic binders can be used. A thermosetting resin is preferable because a resin having a low refractive index can be easily selected.

  As the thermosetting binder, a thermosetting resin or silicon alkoxide (refractive index of about 1.45) can be preferably used.

  The silicon alkoxide contained in the antistatic low refractive index layer satisfies the following general formula (A).

R _x Si (OR) _4-x ... General formula (A)
(In the formula, R represents an alkyl group, and x is an integer satisfying 0 ≦ x ≦ 4.) For example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetrabutoxy Examples thereof include silane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane.

  The organosilicon alkoxide contained in the antistatic low refractive index layer satisfies the general formula (B).

_{R 'y Si (OR) 4} -y ··· formula (B)
(However, in the formula, R represents an alkyl group, and R ′ represents an unreactive functional group such as an alkyl group or a fluorinated alkyl group at the terminal, a vinyl group, an amino group, an epoxy group, an aryl group, a (meth) acryloyl group, etc. And y is an integer satisfying 1 ≦ y ≦ 3.) For example, the organosilicon alkoxide is mentioned.

  In the preparation of the coating solution for forming the antistatic low refractive index layer, there is no particular limitation on the blending order of each component, and silicon alkoxide, its hydrolyzate, porous conductive fine particles, and organic in various above-mentioned solvents. Silicon alkoxide and its hydrolyzate are added and mixed.

  As a method for forming the antistatic low refractive index layer, coating is performed by the above-described various coating methods so as to satisfy the general formula (C) nd = λ / 4 (range of 450 ≦ λ ≦ 650), followed by drying treatment. After performing the above, ultraviolet and electron beam irradiation is performed as necessary. By controlling the layer thickness d in the range of 450 ≦ λ ≦ 650, an antireflection laminated film having a low luminous reflectance can be obtained.

  By performing surface treatment on the base material and hard coat layer that are transparent supports, the surface tension of each surface can be changed, thus improving the adhesion between the hard coat layer and the antistatic low refractive index layer. be able to. As the surface treatment method, alkali treatment, plasma treatment, laser treatment, or corona treatment can be performed. By improving the adhesion between the layers and performing various surface treatments, foreign substances on the surface can be reduced. Thereby, an antireflection laminated film having no defect in appearance can be provided.

  As described above, by forming a hard coat layer and an antistatic low refractive index layer on a substrate that is a transparent support, multiple functions can be realized with a small number of layers, and the number of steps can be reduced. And cost can be reduced. Since the antistatic low refractive index layer is on the surface of the antireflection laminated film, the antistatic performance tends to be stable. Anti-static, anti-reflective, surface hardness, scratch resistance, antifouling properties due to surface hardness, flexibility, scratch resistance, transparency or anti-glare property due to hard coat layer, and anti-static low refractive index layer Thus, it is possible to provide a low-cost antireflection film that can provide the above-mentioned multiple functions and that also has adhesion between layers.

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

  The performance of the antireflection laminated film obtained in the following examples was evaluated based on the following method.

<Measurement method of reflectance>
Using an automatic spectrophotometer (U-4000, manufactured by Hitachi, Ltd.), the luminous reflectance was measured from the spectral reflectance. At the time of measurement, the surface opposite to the coated surface was matted and black paint was applied, and antireflection treatment from the back side was performed.

<Measurement method of surface resistance value>
The measurement was performed according to JIS K6911.

<Anti-fouling evaluation method>
Fingerprints, magic and tissue scraps were attached to the surface, and the possibility of wiping was judged. (○: Can be wiped off, ×: Cannot be wiped off)

<Adhesion evaluation method>
After the film surface was cut at 100 points of 1 mm square, a peel test was performed using an adhesive cellophane tape [24 mm wide cello tape (registered trademark) manufactured by Nichiban Co., Ltd.], and the remaining rate of the 100-point cut part was evaluated.

Adeka optomer KRX-559-37 (manufactured by Asahi Denka Co., Ltd., solid content: 70%) was diluted with methyl isobutyl ketone to a solid content of 40%, and applied to the A4100 easy-bonding surface of Toyobo by the bar coating method. After drying in an oven for 1 minute, it was cured with 400 mJ / cm ² ultraviolet rays to obtain a coating film having a thickness of 2.5 μm (cured film refractive index 1.62). Next, 0.2 g of KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed with 100 g of the ion conductive antistatic agent Colcoat N-103X (manufactured by Colcoat), and applied onto the coating film by a bar coating method. The film was cured in minutes to obtain a coating film having a thickness of about 0.1 μm (cured film refractive index: about 1.45). The minimum reflectivity of the film having this layer structure was 1.8%, and the surface resistance value was 2.53 + E9 (500 V applied).

Adeka optomer KRX-559-37 (manufactured by Asahi Denka Co., Ltd., solid content: 70%) was diluted with methyl isobutyl ketone to a solid content of 40%, and applied to the A4100 easy-bonding surface of Toyobo by the bar coating method. After drying in an oven for 1 minute, it was cured with 400 mJ / cm ² ultraviolet rays to obtain a coating film having a thickness of 2.5 μm (cured film refractive index 1.62). 1g of tetraethoxysilane (manufactured by Kanto Chemical) 0.675g of 1N HCl, 24g of IPA, 0.1g of quaternary ammonium salt Nikkataibo (manufactured by Nippon Kasei), KBM-5103 (manufactured by Shin-Etsu Chemical) After mixing 0.1 g, it was applied onto the coating film by a bar coating method to obtain a 0.1 μm coating film (cured film refractive index: about 1.65). The minimum reflectance of the film having this layer constitution was 3.7% (cured film refractive index 1.48), and the surface resistance value was 9.0 + E11 (500 V applied).

(Comparative example)
Adeka optomer KRX-559-37 (manufactured by Asahi Denka Co., Ltd., solid content: 70%) was diluted with methyl isobutyl ketone to a solid content of 40%, and applied to the A4100 easy-bonding surface of Toyobo by the bar coating method. After drying in an oven for 1 minute, it was cured with 400 mJ / cm ² ultraviolet rays to obtain a coating film having a thickness of 2.5 μm (cured film refractive index 1.62). The ITO conductive coating agent EI-3 (manufactured by Dainippon Paint) was applied onto this coating film by the bar coating method, dried at 80 ° C. for 1 minute, and then cured by irradiating with 400 mJ / cm ² of ultraviolet light. A coating film of about 0.1 μm was obtained (cured film refractive index: about 1.65). The minimum reflectivity of the film having this layer structure was 5.8%, and the surface resistance value was 5.0 + E6 (10 V applied).

(Comparative example)
Adeka optomer KRX-559-37 (manufactured by Asahi Denka Co., Ltd., solid content: 70%) was diluted with methyl isobutyl ketone to a solid content of 40%, and applied to the A4100 easy-bonding surface of Toyobo by the bar coating method. After drying in an oven for 1 minute, it was cured with 400 mJ / cm ² ultraviolet rays to obtain a coating film having a thickness of 2.5 μm (cured film refractive index 1.62). Next, 1 g of tetraethoxysilane, 0.675 g of 1N HCl and 24 g of IPA were mixed, and then applied onto the coating film by a bar coating method to obtain a 0.1 μm coating film (cured film refraction). The rate is about 1.65). The minimum reflectance of the film having this layer structure was 3.7% (cured film refractive index: 1.48), and the surface resistance value was OVER (500 V applied).

From Table 1, the antireflection laminated film of the present invention obtained in Examples 1 and 2 was compared with the antireflection laminated film obtained in Examples 3 and 4 as comparative examples of the present invention. Excellent surface resistance and antifouling properties. As described above, the antireflection laminate film of the present invention has a particularly high antistatic property and antireflection property, and is a low-cost antireflection laminate having excellent transparency, surface hardness, scratch resistance, and antifouling property. A film can be provided and is suitably used for the display screen surface of various displays such as a liquid crystal display, a CRT display, a projection display, a plasma display, and an EL display.

It is sectional drawing which shows the reflection preventing laminated film concerning one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Antireflection laminated film 2 ... Base material (transparent support)
3 ... Hard coat layer 4 ... Antistatic low refractive index layer

Claims (6)

  A laminate comprising a hard coat layer having a refractive index of 1.50 or more and an antistatic low refractive index layer having a refractive index of 1.49 or less containing a binder and an organic antistatic agent on a substrate. Anti-reflection laminated film.   2. The antireflection laminated film according to claim 1, wherein the binder is thermosetting.   3. The antireflection laminated film according to claim 1, wherein the antistatic low refractive index layer contains a fluorine atom-containing substance. The antistatic low refractive index layer is
nd = λ / 4
(Where n represents the refractive index of the layer, d represents the layer thickness, λ represents the wavelength of light, and is an integer satisfying 450 ≦ λ ≦ 650)
The antireflection laminated film according to claim 1, wherein the antireflection laminated film is satisfied.   5. The antireflection laminated film according to claim 1, wherein the hard coat layer is made of a polymer mainly composed of a polyfunctional monomer having a (meth) acryloyloxy group.   The antireflection multilayer film according to any one of claims 1 to 5, wherein the hard coat layer further contains a filler having an average particle diameter of 10 nm or more and 10 µm or less.

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