JP2008241882A - Coating agent and anti-reflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-reflection film in which layers constituting it have a high adhesion property, high scratch resistance, and low minimum reflectance, and a coating agent. <P>SOLUTION: The anti-reflection film 19 includes a transparent substrate layer (a) 13, a hard coat layer (b) 15, and a low refractive index layer (c) 17, the anti-reflection film 19 is characterized in that a layer structure from (a) 13 to (c) 17 is (a) 13/(b) 15/(c) 17, and the (b) 15 comprises an acrylate and a bi- or tri-functional methacrylate as main components, and the compounding ratio of the bi- or tri-functional methacrylate with respect to 100 pts.wt. of the acrylate is in the range of 0.5-50 pts.wt. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antireflection film to be mounted on the surface of a display screen in televisions, PCs, various mobile devices, and the like, and a coating agent used in the production thereof.

  In recent years, in televisions and PCs, plasma displays (PDPs) and liquid crystal displays (LCDs) have been increasing in size and thickness in place of conventional cathode ray tubes. Since these displays have high image quality, the reflection of light and objects on the screen has a great influence on the appearance of the image, and it is necessary to provide antireflection performance.

  In addition, because it is used outdoors in display materials for mobile devices such as mobile phones, personal digital assistants (PDAs), and electronic paper that use display methods such as liquid crystal and organic EL, images of light and objects are reflected. Therefore, it is necessary to provide antireflection performance.

  As one method of preventing reflection, attaching an antireflection film to the surface of a display screen has been performed. As this antireflection film, on one side of a transparent substrate, a hard coat layer having a high hardness such as an acrylic resin and a high refractive index, and a low refractive index layer having a low refractive index such as a silicone resin or a fluorine resin Are sequentially laminated.

However, in the conventional antireflection film as described above, the adhesion between the hard coat layer and the low refractive index layer cannot be said to be excellent, and problems such as delamination occur when used over a long period of time. As a result, the antireflection performance may deteriorate. In order to solve this problem, Patent Document 1 discloses a method in which a hard coat layer is half cured by ultraviolet irradiation, a low refractive index layer is applied, and then cured. In this method, the adhesion between the layers is increased by irradiating the hard coat layer with ultraviolet rays in two stages.
JP 2003-311911 A

  However, the method described in Patent Document 1 has a problem of raising the minimum reflectance, which is one of important performances of the antireflection film. Further, the conventional antireflection film has a problem that the scratch resistance is insufficient.

  The present invention has been made in view of the above points, and an object thereof is to provide an antireflection film and a coating agent having high adhesion of layers constituting the antireflection film, high scratch resistance, and low minimum reflectance. And

(1) The invention of claim 1
A coating agent used for forming a hard coat layer of an antireflection film, comprising an acrylate and a 2-3 trifunctional methacrylate as main components, and a blending ratio of the 2-3 trifunctional methacrylate with respect to 100 parts by weight of the acrylate, The gist of the coating agent is in the range of 0.5 to 50 parts by weight.

  When a methacrylate having 2 to 3 functional groups (particularly 3) is mixed with acrylate and cured, the methacrylate acts as a curing retarder for the acrylate, and the outermost surface of the cured film can be locally made semi-cured. By making it a semi-cured state, the recoatability of the resin is improved, and the adhesion with the overcoated resin is excellent.

  The blending ratio of methacrylate to 100 parts by weight of acrylate is in the range of 0.5 to 50 parts by weight, more preferably 5 to 30 parts by weight. When it is 0.5 parts by weight or more, a sufficient curing delay effect can be obtained, and when it is 50 parts by weight or less, tack remains after curing and roll-to-roll production cannot be performed. Absent.

The “main component” means that when the total composition of the (b) hard coat layer is 100 parts by weight, it occupies more than 50 parts by weight.
The coating agent mainly contains an acrylate, a bi- or trifunctional methacrylate, a photopolymerization initiator, and a solvent.

  Examples of the acrylate include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, and dicyclopentanyl diacrylate. , Caprolactone-modified dicyclopentenyl diacrylate, ethylene oxide-modified phosphate diacrylate, allylated cyclohexyl diacrylate, isocyanurate diacrylate, trimethylolpropane triacrylate, dipentaerythritol triacrylate, propionic acid-modified dipentaerythritol triacrylate, pentaerythritol Triacrylate, propylene oxide modified trimethylolpropane triacryl , Tris (acryloxyethyl) isocyanurate, dipentaerythritol pentaacrylate, propionic acid modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, and commercially available urethane acrylate and melamine An acrylate etc. are mentioned, An acrylate with many functional groups has high surface hardness, and is preferable. You may use these individually or in mixture of 2 or more types.

  Examples of the bifunctional methacrylate include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1.6-hexanediol dimethacrylate, 1.9-nonane. Examples include diol dimethacrylate, 1.10-decanediol dimethacrylate, glycerin dimethacrylate, dimethylol-tricyclodecane dimethacrylate, and the like. Examples of the trifunctional methacrylate include trimethylolpropane trimethacrylate and ethoxylated trimethylolpropane trimethacrylate, and these may be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, benzyl, benzoin, benzoin methyl ether, and benzoin ethyl ether. , Carbonyl compounds such as benzoin isopropyl ether, sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, tetramethylthiuram disulfide, etc., and commercially available products such as Irgacure 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur 1116, 1173 (above, Ciba Specialty Chemicals Ltd.) Co., Ltd., trade name); LucirinLR8728 (BASF Co., Ltd., trade name); Ubecryl P36 (UCB Co., Ltd., trade name), and the like. Moreover, you may add a photopolymerization sensitizer and a photopolymerization accelerator as needed.

  Examples of the solvent include organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as acetone and cyclohexane, aromatic solvents such as xylene, ester solvents such as ethyl acetate and butyl acetate, ethylene glycol ethyl ether acetate, propylene Glycol ether ester solvents such as glycol methyl ether acetate and ethyl-3-ethoxypropionate, ether solvents such as tetrahydrofuran and dioxane, amide solvents such as dimethylformamide and dimethylacetamide, methyl alcohol, ethyl alcohol, isopropyl alcohol, Alcohol solvents such as butyl alcohol can be used.

  The viscosity of the coating agent of the present invention is preferably in the range of 1 to 50000 mPa · s / 20 ° C. from the viewpoints of coating properties, leveling properties and ease of coating. In addition, the viscosity of the coating agent can be adjusted by appropriately adding a solvent or various additives that do not inhibit the polymerization reaction.

  Depending on the required performance, acrylic resin, urethane resin, styrene resin, phenol resin, melamine resin, barium hydroxide, magnesium hydroxide, aluminum hydroxide, silicon oxide, titanium oxide, antimony trioxide, In addition to inorganic fillers such as antimony pentoxide, calcium sulfate, barium sulfate, calcium carbonate, basic zinc carbonate, basic lead carbonate, silica sand, clay, talc, silica compound, titanium dioxide, cups such as silanes and titanates Formulation of ring agents, bactericides, preservatives, plasticizers, flow regulators, thickeners, pH adjusters, surfactants, leveling regulators, antifoaming agents, colored pigments, near infrared absorbers, rust preventive pigments, etc. Materials may be added. Moreover, you may add antioxidant and a ultraviolet absorber for the purpose of light resistance improvement.

  In addition, as other compounding materials, for example, an antistatic agent, an ionic liquid, a conductive polymer, conductive fine particles, and the like can be added to impart an antistatic function. Moreover, a metal oxide can also be utilized as a refractive index adjusting agent.

  Examples of the antistatic agent include nonionic polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, and polyoxyethylene fatty acid sorbitan ester. , Fatty acid glycerin ester, alkyl polyethyleneimine and the like. Examples of the cationic antistatic agent include alkylamine salts, alkyl quaternary ammonium salts, and alkyl imidazoline derivatives. Moreover, an acrylate compound having ethylene oxide as a skeleton or an ion conduction type antistatic agent in which metal ions such as lithium ions are mixed can also be used.

Examples of the ionic liquid include aromatic compounds such as imidazolium salts and pyridium salts based on the cation component side, aliphatic quaternary ammonium salt systems, BF ₄ ⁻ , PF ₆ ^{− and the} like on the anion component side. The inorganic ion system can be freely selected from combinations of fluorine-containing organic anion systems such as CF ₃ SO ₂ ⁻ and (CF ₃ SO ₂ ) ₂ N ⁻ .

Examples of the conductive polymer that can be used include polyaniline, polypyrrole, polythiophene, poly-3,4-ethylenedioxythiophene, and derivatives thereof.
Examples of the conductive fine particles include antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide, and antimony suboxide.

The metal oxide is, for _{example, SiO 2, TiO 2, ZrO} 2, HfO 2, ZnO, Sb 2 O 5 and the like. By adding metal oxide fine powder particles or a slurry in which the metal oxide fine particles are dispersed, the refractive index of the resin can be adjusted, and adhesion between layers and scratch resistance can be further increased. The addition amount is preferably in the range of 0.01 to 70 parts by weight, more preferably in the range of 10 to 50 parts by weight, based on 100 parts by weight of the coating agent for antireflection film.
(2) The invention of claim 2
(A) a transparent substrate layer, (b) a hard coat layer, and (c) a low refractive index layer, wherein the layer structures (a) to (c) are (a) / (b) / ( In addition to c), the above (b) is formed by applying and curing the coating agent according to claim 1.

  The coating agent according to claim 1 contains bifunctional or trifunctional methacrylate, and (b) a hard coat layer formed by using the coating agent and a layer adjacent thereto (for example, (c) low refractive index) The layer) has high adhesion and hardly peels between layers.

  In the present invention, the coating agent according to claim 1 can be applied onto (a) the transparent substrate layer, for example. In that case, (a) the transparent substrate layer and (b) the hard coat layer are adjacent layers.

  The (a) transparent base material layer used in the present invention is not particularly limited, and is appropriately selected from known transparent plastic films having a total light transmittance of 90% or more and a thickness of 10 μm to 5 mm, for example. Can be used. Examples of such transparent base material layers include saturated polyester resins, polycarbonate resins, polyacrylate resins, polyolefin resins, polystyrene resins, polyvinyl chloride resins, polyvinyl acetate resins, and polyimide resins. What processed resin, such as resin, in the shape of a film or a sheet can be used. More specifically, polyester film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film , Polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluorine resin film, nylon film, acrylic film, etc. .

  (B) The method for forming the hard coat layer is not particularly limited, and (b) a known spray coat, roll coat, die coat, air knife using the coating agent according to claim 1 containing a component that becomes the hard coat layer. It can be formed by coating methods such as coating, blade coating, spin coating, reverse coating, gravure coating, and wire bar, or printing methods such as gravure printing, screen printing, offset printing, and ink jet printing.

Further, (c) the method of forming the low refractive index layer is not particularly limited, and can be formed by the various coating methods and printing methods described above.
(B) The thickness of the hard coat layer is preferably in the range of 1 μm to 10 μm. (B) When the thickness of the hard coat layer is 1 μm or more, sufficient hard coat performance is obtained, and when it is 10 μm or less, problems of warpage and cracks are less likely to occur. The refractive index of the (b) hard coat layer is preferably in the range of 1.50 to 1.80. Since the antireflection performance can be increased as the refractive index is higher, the material may be selected according to the required performance.

  The coating agent for forming each layer constituting the antireflection film of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and as an ultraviolet irradiation device, a known device such as a high-pressure mercury lamp or a metal halide lamp is used. Can be used.

  (C) The thickness of the low refractive index layer is such that (c) the phase of the reflected light reflected by the surface of the low refractive index layer in the visible light incident on the antireflection film, (b) the hard coat layer, and (c) It is desirable to set the phase of the reflected light reflected at the boundary with the low refractive index layer to be opposite. Thereby, (c) the reflected light reflected on the surface of the low refractive index layer and (b) the reflected light reflected at the boundary between the hard coat layer and (c) the low refractive index layer cancel each other, and reflection is performed. It can prevent efficiently. (C) The specific thickness of the low refractive index layer is preferably 50 to 150 nm, for example. The refractive index of the (c) low refractive index layer is particularly preferably in the range of 1.35 to 1.45. Since the antireflection performance can be enhanced as the refractive index is lower, the material may be selected in accordance with the required performance.

  When the resin constituting the (c) low refractive index layer is a resin that is susceptible to oxygen inhibition, the (c) low refractive index layer may be cured in a nitrogen atmosphere. If necessary, (c) the low refractive index layer may be cured and then the (b) hard coat layer may be completely cured using an ultraviolet irradiator.

  Moreover, the antireflection film of the present invention may further include an adhesive layer on the back surface thereof. The pressure-sensitive adhesive layer only needs to be made of a pressure-sensitive adhesive or an adhesive capable of bringing the anti-reflection film and the surface of the display into close contact with each other while maintaining the transparency of the anti-reflection film. Resins, epoxy resins, polyester resin-based adhesives, thermoplastic, thermosetting, and UV-curable adhesives can be used. In particular, an acrylic resin system is preferable from the viewpoint of optical properties, from light resistance, weather resistance, heat resistance, and transparency. Examples of the monomer constituting the acrylic resin include ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, benzyl acrylate, alkyl acrylates, methacrylic acid, and the like. Contains methacrylic acid alkyl esters such as butyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, ethyl methacrylate, and vinyl groups such as vinyl acetate, vinyl propionate, vinyl ether, styrene, acrylonitrile, methacrylonitrile, etc. A compound may be copolymerized. Furthermore, in order to improve the adhesion durability performance of the adhesive layer and suppress the generation of outgas, the main component of the adhesive is an acrylic resin, the weight average molecular weight is 500,000 or more, and the polydispersity is 5 or less. Good.

  For the adhesive layer, if necessary, crosslinking agent, catalyst, antioxidant, color pigment, glass beads, filler, flame retardant, antibacterial agent, light stabilizer, colorant, fluidity improver, lubricant, antiblocking agent Further, an antistatic agent, a crosslinking aid and the like can be blended. These may be used alone or in combination of two or more. Any crosslinking agent can be used without particular limitation as long as it does not interfere with the required properties. For example, polyisocyanate, chelate resin, epoxy resin, melamine resin, amide resin and the like can be mentioned. In addition, an infrared absorber, a UV absorber, or the like may be added to the adhesive layer to incorporate a mechanism for cutting off harmful light that is thought to adversely affect the human body.

  The method for forming the adhesive layer is not particularly limited, but may be Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, spin coater, nozzle coater, dip coater. Examples of the coating method include bar coating and blade coating. There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. The drying condition may be about 60 to 180 ° C., although it depends on the cured form of the adhesive layer, the film thickness and the selected solvent. Although the film thickness of an adhesion layer is not specifically limited, 0.1 micrometers-50 micrometers are preferable, and 10 micrometers-50 micrometers are especially preferable.

A release film for protecting the adhesive layer may be further adhered on the adhesive layer. The release film can be polyethylene terephthalate, polyethylene, polyvinyl chloride, polycarbonate, polymethyl acrylate, paper, cloth, glass, ceramic, metal plate, acrylic plate, olefin resin, PPS resin, TAC film, acrylic resin film, or What gave mold release processing etc. can be used. The thickness of the release film is not particularly limited, but is preferably less than 500 μm, particularly preferably 25 μm to 75 μm.
(3) The invention of claim 3
3. The antireflection film according to claim 2, wherein the low refractive index layer (c) is made of a fluorine-modified silicone resin, and has a contact angle with water of 90 degrees or more and a contact angle with oleic acid of 50 degrees or more. Is the gist.

  In the antireflection film of the present invention, (c) the low refractive index layer is made of a fluorine-modified silicone resin and has a contact angle with water of 90 ° or more and a contact angle with oleic acid of 50 ° or more. When it is attached to a display panel, dirt such as fingerprints is not accumulated, and excellent antifouling properties can be achieved.

Although it does not specifically limit as said fluorine-modified silicone resin, For example, what mainly has perfluoroalkyl alkoxysilane is mentioned. Specifically, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane Etc. In addition, a silicone resin (for example, a silicone resin having a siloxane-based condensate as a main skeleton), a fluorine-based resin, inorganic particles such as porous silica and magnesium fluoride may be added to the fluorine-modified silicone resin.
(4) The invention of claim 4
A coating agent used for forming a hard coat layer and a low refractive index layer of an antireflection film, wherein 100 parts by weight (solid content) of resin constituting the hard coat layer and fluorine constituting the low refractive index layer The gist is a coating agent containing 1 to 30 parts by weight of low refractive index fine particles mainly composed of a system (meth) acrylate.

  In the coating agent of the present invention, the addition amount of the low refractive index fine particles is 1 to 30 parts by weight with respect to 100 parts by weight of the solid content of the resin component that is the material of the (b) hard coat layer. When it is 1 part by weight or more, sufficient antireflection performance is obtained, and when it is 30 parts by weight or less, the miscibility between the low refractive index fine particles and the resin is deteriorated, and the haze is increased. There is nothing.

  Examples of the fluorine-based (meth) acrylate that is a main raw material of the low refractive index fine particles include 2,2,2-trifluoroethyl acrylate, 2,2,2, -trifluoroethyl methacrylate, 2,2,3, Examples include 3-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, and perfluorooctylethyl methacrylate. These may be used alone or in admixture of two or more.

  The shape of the low refractive index fine particles is preferably spherical or beaded, but is not particularly limited thereto. The average primary particle diameter is the diameter of a single particle that has not been agglomerated. For spherical particles, the diameter is indicated, and for particles other than the spherical shape, the arithmetic average value of the major axis diameter and the minor axis diameter is indicated. The value measured by an electron microscope.

  The average primary particle diameter of the low refractive index fine particles is desirably in the range of 80 to 500 nm. When it is 80 nm or more, sufficient antireflection performance can be imparted, and when it is 500 nm or less, it is difficult for haze to increase and visibility to decrease.

  The refractive index of the low refractive index fine particles is preferably in the range of 1.40 to 1.49. When the refractive index is 1.40 or more, the synthesis of the low refractive index fine particles is easy, and when it is 1.49 or less, sufficient antireflection performance is obtained.

The low refractive index fine particles can be synthesized, for example, by an emulsion polymerization method. In this case, 1 part by weight or more of 100 parts by weight of the monomer used in the emulsion polymerization method is preferably a bifunctional or higher functional (meth) acrylate monomer. If the emulsion polymerization method is used, the variation in the primary particle diameter of the synthesized low refractive index fine particles can be reduced. As a result, the (c) low refractive index layer composed of the low refractive index fine particles can be uniformly oriented, and the antireflection effect can be made more uniform in the screen.
(5) The invention of claim 5
(A) a transparent substrate layer, (b) a hard coat layer, and (c) a low refractive index layer, wherein the layer structures (a) to (c) are (a) / (b) / ( (c) and (b) and (c) are formed by phase separation after the coating agent according to claim 4 is applied and cured. And

  In the antireflection film of the present invention, (b) the hard coat layer and (c) the low refractive index layer can be formed simultaneously. That is, as shown in FIG. 1, (b) a low refractive index fine particle mainly composed of a resin component 1 (for example, acrylate or acrylate and methacrylate) as a material of the hard coat layer and a fluorine-based (meth) acrylate. When a coating agent 5 containing 3 is applied onto (a) the transparent substrate layer 7, as shown in FIG. 2, the low refractive index fine particles 3 are separated into surface layers, and (c) a low refractive index layer 9 is formed. In the coating agent 5, the resin component excluding the low refractive index fine particles 3 forms the (b) hard coat layer 11. At this time, the low refractive index fine particles are uniformly oriented on the surface of the (b) hard coat layer, thereby forming the (c) low refractive index layer. Furthermore, (c) the refractive index of the low refractive index layer can be lowered by using low refractive index fine particles mainly composed of fluorine-based (meth) acrylate for the formation of the low refractive index layer, The compatibility between the low refractive index fine particles and (b) the resin component as the material of the hard coat layer can be lowered, and the separation between the low refractive index fine particles and (b) the hard coat layer can be promoted.

As described above, the antireflection film of the present invention can form, for example, (b) a hard coat layer and (c) a low refractive index layer in one step on (a) a transparent substrate layer. The productivity of the anti-reflection film is greatly improved, and (b) the adhesion between the hard coat layer and the low refractive index fine particles (c) the low refractive index layer improves the surface hardness, resulting in delamination between layers. Is less likely to occur.
(6) The invention of claim 6
Further, (d) a near-infrared absorbing layer is provided, and the layer structure of (a) to (d) is (d) / (a) / (b) / (c). The gist is the antireflection film according to any one of 3, 5 and 5.

  When the target to which the anti-reflection film is applied is a large plasma display, unnecessary near infrared rays are radiated when plasma discharge is generated, causing a malfunction of remote controls such as TVs and air conditioners. However, the antireflection film of the present invention comprises (d) a near-infrared absorption layer, so that it can absorb near-infrared rays and prevent malfunctions of remote controls such as televisions and air conditioners. In addition, since it is not necessary to separately attach a near-infrared absorbing film to a front plate such as a plasma display panel, the manufacturing cost of the plasma display panel or the like can be reduced.

The (d) near-infrared absorbing layer is prepared by, for example, using the above-described various coating methods and printing methods using a transparent resin such as a polyester resin with a near-infrared absorbing dye added thereto and stirring. It can be formed on the back side of the layer. (D) As for the thickness of a near-infrared absorption layer, 5-20 micrometers is preferable.
(7) The invention of claim 7
7. The antireflection film according to claim 6, wherein (d) contains a near-infrared absorbing pigment, and the antireflection film has a transmittance of 20% or less in a wavelength region of 850 to 1100 nm. And

Since the antireflection film of the present invention contains a near-infrared absorbing dye, the effect of preventing unnecessary near-infrared emission and preventing malfunction of a remote control or the like is further remarkable.
Further, since the transmittance of the antireflection film in the entire wavelength range from 850 nm to 1100 nm is 20% or less, the effect of preventing unnecessary near-infrared emission and preventing malfunction of the remote controller or the like is further remarkable.

The near-infrared absorbing dye is not particularly limited as long as it is a material that absorbs near-infrared light and has translucency. Such dyes include diimonium, phthalocyanine, cyanine, aminium, azo, azine, anthraquinone, indigoid, oxazine, quinophthalonine, squalium, stilbene, triphenylmethane, naphthoquinone Polymethine series and the like can be used. These have absorption wavelengths peculiar to materials, and can also provide absorption performance in a wide wavelength range by using them alone or in combination of two or more.
(8) The invention of claim 8
The (d) contains a neon cut dye having a maximum absorption wavelength in a wavelength range of 550 to 650 nm, and the antireflection film has a transmittance of 50% or less at the maximum absorption wavelength portion. Item 7 is the antireflection film according to item 7.

  The antireflection film of the present invention comprises (d) a near-infrared absorption layer containing a neon-cut dye having a maximum absorption wavelength at a wavelength of 550 nm to 650 nm, thereby producing an orange color peculiar to neon gas generated by a plasma display panel or the like. It can be cut and the red color can be vividly developed.

  Moreover, since it is not necessary to affix the near-infrared absorption film which gave the neon cut function which cuts the said orange separately on front plates, such as a plasma display panel, the manufacturing cost of a plasma display panel etc. can be reduced.

  Examples of the neon-cut dye having the maximum absorption wavelength at the wavelength of 550 nm to 650 nm include, for example, cyanine, azulenium, squalium, diphenylmethane, triphenylmethane, oxazine, azine, thiopylium, viologen, azo Type, azo metal complex type, azaporphyrin type, bisazo type, anthraquinone type, phthalocyanine type. These dyes can be used alone or in admixture of two or more.

Hereinafter, description will be given based on examples.

(1) Preparation of fluorine-modified silicone solution for forming low refractive index layer A fluorine-modified silicone resin solution was prepared by the following procedure. In a sealed container, 12 parts by weight of trifluoropropyltriethoxysilane (trade name KBM7103 manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts by weight of tetraethoxysilane (trade name KBE04 manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed and cooled to 20 ° C. Then, after adding 2 parts by weight of 0.25N acetic acid, it was hydrolyzed by aging at 20-30 ° C. overnight. To this solution, 35 parts by weight of isopropyl alcohol (IPA) and 100 parts by weight of methyl ethyl ketone (MEK) were added to prepare a fluorine-modified silicone resin solution having a solid content of 10%.
(2) Preparation of coating agent 100 parts by weight of hexafunctional acrylate dipentaerythritol hexaacrylate (trade name A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.) in a sealed container, ethylene glycol dimethacrylate (Shin-Nakamura) Chemical Industry Co., Ltd. product name 1G) 20 parts by weight and MEK 165 parts by weight were mixed and stirred. Furthermore, 5 parts by weight of 1-hydroxy-cyclohexyl luphenyl ketone (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals) was added as an initiator to obtain a coating agent.
(3) Production of Antireflection Film Next, as shown in FIG. 3, the film thickness after curing is 3 μm on a polyethylene terephthalate film (hereinafter referred to as PET film) 13 having a thickness of 100 μm (trade name Lumirror U34 manufactured by Toray Industries, Inc.). As described above, the coating agent prepared in the above (2) was applied, and an ultraviolet treatment with an irradiation intensity of 1500 mW / cm ^{2 and} an amount of work of 300 mJ / cm ² was performed using an ultraviolet irradiator to obtain a hard coat layer 15. It was. Next, the low refractive index layer-forming silicone resin solution prepared in the above (1) is applied so that the film thickness after curing is 0.1 μm, cured at 100 ° C., and the low refractive index layer 17 is formed. The antireflection film 19 was obtained.

  In Example 1, 10 parts by weight of trifunctional methacrylate trimethylolpropane trimethacrylate (trade name TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of 20 parts by weight of ethylene glycol dimethacrylate when preparing the coating agent. An antireflection film was obtained in the same manner except that it was.

  In Example 2, when preparing the coating agent, trifunctional methacrylate ethoxylated trimethylolpropane trimethacrylate (trade name TMPT-9EO manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of trimethylolpropane trimethacrylate. In the same manner as above, an antireflection film was obtained.

  In Example 2, when preparing the coating agent, instead of 100 parts by weight of A-DPH, 100 parts by weight of acrylic urethane monomer (trade name UN-3320HA manufactured by Negami Kogyo Co., Ltd.) was used in the same manner. An antireflection film was obtained.

  In Example 2, when preparing the coating agent, instead of 100 parts by weight of A-DPH, 100 parts by weight of acrylic melamine monomer (trade name Oresta XRA-1165 manufactured by Mitsui Chemicals) was used in the same manner. An antireflection film was obtained.

  In Example 2, when preparing the coating agent, pentaerythritol triacrylate of trifunctional methacrylate (trade name A-TMM-3, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of 100 parts by weight of A-DPH. In the same manner as above, an antireflection film was obtained.

  In Example 2, an antireflection film was obtained in the same manner except that 133 parts by weight of zirconia slurry (15% solid content manufactured by C-I Kasei Co., Ltd.) was further added during the preparation of the coating agent.

  In Example 2, when preparing the coating agent, an antireflection film was obtained in the same manner except that 100 parts by weight of ATO slurry (trade name SNS-10M, solid content 30%, manufactured by Ishihara Sangyo Co., Ltd.) was further added. It was.

  In Example 3, the anti-reflection film was prepared in the same manner except that 33 parts by weight of colloidal silica slurry (trade name MEK-ST, solid content 30%, manufactured by Nissan Chemical Co., Ltd.) was further added during the preparation of the coating agent. Obtained.

(1) Preparation of coating agent for near-infrared absorbing layer For 100 parts by weight of a polyester resin (trade name Byron RV200, manufactured by Toyobo Co., Ltd.), a near-infrared absorbing dye (trade name: EEX Color IR-14, manufactured by Nippon Shokubai Co., Ltd.) 7 parts by weight, 5 parts by weight of near-infrared absorbing dye (trade name EEX Color IR-12, manufactured by Nippon Shokubai Co., Ltd.), 3 parts by weight of near-infrared absorbing dye (trade name TX-EX-910B, manufactured by Nippon Shokubai Co., Ltd.) 3 parts by weight of infrared absorbing dye (Hayashibara Biochemical Laboratories Co., Ltd., trade name NK-3508), 3 parts by weight of neon cut dye (trade name Adeka Arcles TY-102 manufactured by Asahi Denka Kogyo Co., Ltd.) and 100 parts by weight of MEK Thus, a coating agent for forming a near-infrared absorbing layer was obtained.
(2) Manufacture of antireflection film Next, as shown in FIG. 3, the PET film 13 (Lumirror U34) having a thickness of 100 μm is subjected to (2) of Example 1 so that the film thickness after curing becomes 3 μm. The hard coating layer 15 was obtained by applying the coating agent prepared in (1) above and performing ultraviolet treatment with an irradiation intensity of 1500 mW / cm ² and a work amount of 300 mJ / cm ² using an ultraviolet irradiator.

  Next, the low refractive index layer-forming silicone resin solution prepared in (1) of Example 1 was applied so that the film thickness after curing was 0.1 μm and cured at 100 ° C. The rate layer 17 was formed. Further, as shown in FIG. 4, the coating agent for forming a near infrared absorption layer prepared in (1) of Example 10 was applied to the back surface of the PET film 13 so that the film thickness after curing was 7 μm. The near-infrared absorption layer 21 was formed by curing at 100 ° C., and the antireflection film 19 was obtained.

  An antireflection film was obtained in the same manner as in Example 10, except that the coating agent used to form the hard coat layer 15 was the coating agent prepared in Example 2.

  An antireflection film was obtained in the same manner as in Example 10 except that the blending amount of ethylene glycol dimethacrylate in the hard coat layer 15 was 5 parts by weight.

  An antireflection film was obtained in the same manner as in Example 10, except that the amount of ethylene glycol dimethacrylate in the hard coat layer 15 was 45 parts by weight.

  An antireflection film was obtained in the same manner as in Example 11 except that the blending amount of TMPT in the hard coat layer 15 was 5 parts by weight.

  An antireflection film was obtained in the same manner as in Example 11 except that the blending amount of TMPT in the hard coat layer 15 was 45 parts by weight.

(1) Preparation of Low Refractive Index Fine Particle Slurry (1-1) Preparation of Low Refractive Index Fine Particle Slurry A-3 In a polymerization vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 120 weight of deionized water Parts, 0.3 parts by weight of sodium dialkylsulfosuccinate and 0.1 parts by weight of sodium bicarbonate as a pH buffering agent were charged and heated to 60 ° C. with stirring, and then purged with nitrogen. To this, 2 parts by weight of methyl methacrylate was added, and after 10 minutes, 0.1 part of sodium persulfate dissolved in 0.98 parts by weight of deionized water was added to perform seed polymerization. 60 minutes after the start of heat generation, 0.1 part by weight of sodium persulfate dissolved in 4.9 parts of deionized water was added, and after another 10 minutes, 70 parts by weight of 2,2,2-trifluoroethyl methacrylate, methyl An emulsified monomer liquid consisting of 25 parts by weight of methacrylate, 5.0 parts by weight of ethylene glycol dimethacrylate, 60 parts by weight of deionized water, 0.8 parts by weight of sodium dialkylsulfosuccinate, and 0.3 parts by weight of sodium bicarbonate is stirred. The solution was added dropwise over 3 hours while maintaining the temperature at 80 ° C., and the polymerization was terminated by maintaining 85 ° C. for 2 hours after the completion of the addition to obtain an aqueous latex (A-1). The aqueous latex (A-1) contains 33.9% of low refractive index fine particles in solid content, the average particle diameter of the low refractive index fine particles is 490 nm, and the refractive index of the low refractive index fine particle solid is 1.43. there were.

  An ion exchange resin (trade name Amberlite MB-2, manufactured by Rohm and Haas) for the purpose of removing ionic impurities that hinder phase inversion to an organic solvent to the aqueous latex (A-1) synthesized above. 15 parts by weight was added and stirred. After stirring for 24 hours, the ion exchange resin was removed by filtration to obtain an aqueous latex (A-2).

To this purified aqueous latex (A-2), 570 parts by weight of ethyl acetate was added and stirred, and phase inversion of the low refractive index fine particles present in the aqueous latex to the organic layer was performed. Thereafter, the mixture was allowed to stand to separate a transparent aqueous phase and a cloudy organic phase, thereby obtaining a low refractive index fine particle slurry (A-3) as a non-aqueous fine particle dispersion. The solid content of the low refractive index fine particle slurry (A-3) was 15.0%.
(1-2) Preparation of Low Refractive Index Fine Particle Slurry B-3 In a polymerization vessel equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet, 120 parts by weight of deionized water and sodium dialkylsulfosuccinate 0.8 After adding 0.4 parts by weight of sodium bicarbonate as a part by weight and a pH buffering agent, the mixture was heated to 60 ° C. with stirring and then purged with nitrogen. To this, 2 parts by weight of methyl methacrylate was added, and after 10 minutes, 0.1 part by weight of sodium persulfate dissolved in 0.98 part by weight of deionized water was added to perform seed polymerization. 60 minutes after the start of exotherm, 0.1 part by weight of sodium persulfate dissolved in 4.9 parts by weight of deionized water was added, and after another 10 minutes, 70 parts by weight of 2,2,2-trifluoroethyl methacrylate, An emulsified monomer solution consisting of 25 parts by weight of methyl methacrylate, 5 parts by weight of ethylene glycol dimethacrylate, 60 parts by weight of deionized water, 1.2 parts by weight of sodium dialkylsulfosuccinate, and 0.5 parts by weight of sodium bicarbonate was stirred. While maintaining the temperature at 80 ° C., the solution was added dropwise over 3 hours, and after completion of the addition, the temperature was maintained at 85 ° C. for 2 hours to complete the polymerization to obtain an aqueous latex (B-1). The aqueous latex (B-1) contains 34.1% of low refractive index fine particles in solid content, the average particle diameter of the low refractive index fine particles is 100 nm, and the refractive index of the low refractive index fine particle solid is 1.43. there were.

  To the aqueous latex (B-1) synthesized above, 25 parts by weight of ion exchange resin MB-2 was added and stirred for the purpose of removing ionic impurities that hindered phase inversion to an organic solvent. After stirring for 24 hours, the ion exchange resin was removed by filtration to obtain an aqueous latex (B-2).

To the purified aqueous latex (B-2), 570 parts by weight of ethyl acetate was added and stirred, and the phase of the low refractive index fine particles present in the aqueous latex was changed to the organic layer. Thereafter, the mixture was allowed to stand, and the transparent aqueous phase and the cloudy organic phase were separated to obtain a low refractive index fine particle slurry (B-3) which is a non-aqueous fine particle dispersion. The solid content of the low refractive index fine particle slurry (B-3) was 15.0%.
(1-3) Preparation of Low Refractive Index Fine Particle Slurry C-3 In a polymerization vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 120 parts by weight of deionized water, sodium dialkylsulfosuccinate 0.8 After adding 0.4 parts by weight of sodium bicarbonate as a part by weight and a pH buffering agent, the mixture was heated to 60 ° C. with stirring and then purged with nitrogen. To this was added 2 parts by weight of methyl methacrylate, and 10 minutes later, 0.1 part by weight of sodium persulfate dissolved in 0.98 parts by weight of deionized water was added to perform seed polymerization. 60 minutes after the start of exotherm, 0.1 part by weight of sodium persulfate dissolved in 4.9 parts by weight of deionized water was added. After another 10 minutes, 95 parts by weight of methyl methacrylate, 5 parts by weight of ethylene glycol dimethacrylate, An emulsified monomer liquid consisting of 60 parts by weight of deionized water, 1.2 parts by weight of sodium dialkylsulfosuccinate and 0.5 parts by weight of sodium bicarbonate was added dropwise over 3 hours while maintaining the temperature at 80 ° C. with stirring. After completion of dropping, the temperature was maintained at 85 ° C. for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (C-1). The aqueous latex (C-1) contains 34.1% of low refractive index fine particles in solid content, the average particle diameter of the low refractive index fine particles is 100 nm, and the refractive index of the low refractive index fine particle solid is 1.49. there were.

  To the aqueous latex (C-1) synthesized above, 25 parts by weight of ion exchange resin MB-2 was added and stirred for the purpose of removing ionic impurities that hindered phase inversion to an organic solvent. After stirring for 24 hours, the ion exchange resin was removed by filtration to obtain an aqueous latex (C-2).

To this purified aqueous latex (C-2), 570 parts by weight of ethyl acetate was added and stirred, and phase inversion of the low refractive index fine particles present in the aqueous latex to the organic layer was performed. Thereafter, the mixture was allowed to stand, and the transparent aqueous phase and the cloudy organic phase were separated to obtain a low refractive index fine particle slurry (C-3) which is a non-aqueous fine particle dispersion. The solid content of the low refractive index fine particle slurry (C-3) was 15.0%.
(2) Preparation of coating agent 33.3 parts by weight of low refractive index fine particle slurry B-3 (solid content 15%) prepared in the above (1-3) and zirconia slurry (Ci Kasei) with respect to 100 parts by weight of A-DPH 156.7% solid content) 66.7 parts by weight, 65.0 parts by weight MEK, 5 parts by weight Irgacure 184 as an initiator, SN leveler S-906 as a leveling agent (50% solids by San Nopco) Was added in an amount of 0.5 parts by weight to obtain a coating agent a.
(3) Production of anti-reflection film Next, the coating agent a was applied to a PET film (Lumirror U34) having a thickness of 100 μm by a bar coating method so that the cured film thickness was 3 μm, and then heated at 100 ° C. with a hot air dryer. Dried for 2 minutes. Thereafter, an ultraviolet ray treatment with an irradiation intensity of 1500 mW / cm ^{2 and} an amount of work of 300 mJ / cm ² was performed and cured using an ultraviolet ray irradiation device to obtain an antireflection film.

  33.3 parts by weight of the low refractive index fine particle slurry A-3 (solid content 15%) prepared in (1-1) of Example 16 with respect to 100 parts by weight of A-DPH, zirconia slurry (solid content 15%) 33.3 parts by weight, 5 parts by weight of Irgacure 184 as an initiator, and 0.5 parts by weight of SN leveler S-906 as a leveling agent were added to obtain a coating agent b.

Next, the coating agent b was applied to a PET film (Lumirror U34) having a thickness of 100 μm by a bar coating method so as to have a cured film thickness of 3 μm, and dried with a hot air dryer at 100 ° C. for 2 minutes. . Thereafter, an ultraviolet ray treatment with an irradiation intensity of 1500 mW / cm ² and a work amount of 300 mJ / cm ² was performed by using an ultraviolet ray irradiation device and cured to obtain an antireflection film.

  6.7 parts by weight of the low refractive index fine particle slurry B-3 (solid content 15%) prepared in (1-2) of Example 16 with respect to 100 parts by weight of A-DPH, zirconia slurry (solid content 15%) Was 333.3 parts by weight, 5 parts by weight of Irgacure 184 was used as an initiator, and 0.5 part by weight of SN leveler S-906 was added as a leveling agent to obtain a coating agent c.

Next, the coating agent c was applied to a PET film (Lumirror U34) having a thickness of 100 μm by a bar coating method so that the cured film thickness was 3 μm, and dried with a hot air dryer at 100 ° C. for 2 minutes. . Thereafter, an ultraviolet ray treatment with an irradiation intensity of 1500 mW / cm ² and a work amount of 300 mJ / cm ² was performed by using an ultraviolet ray irradiation device and cured to obtain an antireflection film.

  166.7 parts by weight of low refractive index fine particle slurry B-3 (solid content 15%) prepared in (1-2) of Example 16 with respect to 100 parts by weight of A-DPH, zirconia slurry (solid content 15%) 333.3 parts by weight, 5 parts by weight of Irgacure 184 as an initiator, and 0.5 parts by weight of SN leveler S-906 as a leveling agent were added to obtain a coating agent d.

Next, the coating agent d was applied to a 100 μm thick PET film (Lumirror U34) by a bar coating method so as to have a cured film thickness of 3 μm, and dried with a hot air drier at 100 ° C. for 2 minutes. Thereafter, an ultraviolet ray treatment with an irradiation intensity of 1500 mW / cm ² and a work amount of 300 mJ / cm ² was performed by using an ultraviolet ray irradiation device and cured to obtain an antireflection film.

  33.3 parts by weight of low refractive index fine particle slurry B-3 (solid content 15%) prepared in (1-2) of Example 16 and 5 parts by weight of Irgacure 184 as an initiator with respect to 100 parts by weight of A-DPH As a leveling agent, 0.5 part by weight of SN leveler S-906 was added to obtain a coating agent e.

Next, the coating agent e was coated on a 100 μm thick PET film (Lumirror U34) by a bar coating method so as to have a cured film thickness of 3 μm, and dried with a hot air dryer at 100 ° C. for 2 minutes. . Thereafter, an ultraviolet ray treatment with an irradiation intensity of 1500 mW / cm ² and a work amount of 300 mJ / cm ² was performed by using an ultraviolet ray irradiation device and cured to obtain an antireflection film.

  First, in the same manner as in Example 16, the coating agent a was applied to one side of a PET film, dried and subjected to ultraviolet treatment. Thereafter, the near-infrared absorbing layer forming coating agent prepared in (1) of Example 10 was applied to the opposite surface of the PET film so that the film thickness after curing was 7 μm, and at 100 ° C. It was cured to form a near-infrared absorbing layer to obtain an antireflection film.

First, in the same manner as in Example 17, the coating agent b was applied to one side of a PET film, followed by drying and ultraviolet treatment. Thereafter, the near-infrared absorbing layer forming coating agent prepared in (1) of Example 10 was applied to the opposite surface of the PET film so that the film thickness after curing was 7 μm, and at 100 ° C. It was cured to form a near-infrared absorbing layer to obtain an antireflection film.
[Comparative Example 1]
In the previous Example 1, when preparing the coating agent, an antireflection film was obtained in the same manner except that 30 parts by weight of methyl methacrylate, which is a monofunctional methacrylate, was used instead of 20 parts by weight of ethylene glycol dimethacrylate. .
[Comparative Example 2]
In Comparative Example 1, an antireflection film was obtained in the same manner except that methyl methacrylate was not added when the coating agent was prepared.
[Comparative Example 3]
In Example 5, an antireflection film was obtained in the same manner except that trimethylolpropane trimethacrylate was not added during the preparation of the coating agent.
[Comparative Example 4]
In Example 7, an antireflection film was obtained in the same manner except that trimethylolpropane trimethacrylate was not added during the preparation of the coating agent.
[Comparative Example 5]
In Example 6, an antireflection film was obtained in the same manner except that trimethylolpropane trimethacrylate was not added during the preparation of the coating agent.
[Comparative Example 6]
In Example 1, an antireflection film was obtained in the same manner except that 20 parts by weight of polyethylene glycol diacrylate was used instead of methacrylate when preparing the coating agent.
[Comparative Example 7]
In Comparative Example 2, when the coating agent was cured, instead of performing an ultraviolet treatment with an irradiation intensity of 1500 mW / cm ² and a work amount of 300 mJ / cm ² using an ultraviolet irradiator, 700 mW / An antireflection film was obtained in the same manner except that the ultraviolet ray treatment was performed with an irradiation intensity of cm ² and a work amount of 150 mJ / cm ² to perform half cure.
[Comparative Example 8]
(1) In the case of forming the low refractive index layer in Example 1, except that the silicone resin solution prepared by the procedure shown in the following (2) was used instead of the fluorine-modified silicone resin solution, An antireflection film was obtained.
(2) Preparation of silicone resin solution for forming low refractive index layer 4 parts by weight of hydroxypropyltrimethoxysilane (50% methanol solution manufactured by Toray Dow Corning Co., Ltd.), methyltriethoxysilane (Toray Dow Corning) in a sealed solution 10 parts by weight) were mixed and cooled to 20 ° C. Next, 4 parts by weight of 1N hydrochloric acid was gradually added over 1 hour, followed by aging at 20-30 ° C. overnight for hydrolysis. 7 parts by weight of acetic acid, 25 parts by weight of isopropyl alcohol (IPA), and 70 parts by weight of methyl ethyl ketone (MEK) were added to this solution to prepare a silicone resin solution for forming a low refractive index layer having a solid content of 10%.
[Comparative Example 9]
An antireflection film was obtained in the same manner as in Example 10, except that the amount of 1G (ethylene glycol dimethacrylate, which is a bifunctional methacrylate) in the hard coat layer 15 was 0.3 parts by weight.
[Comparative Example 10]
An antireflection film was obtained in the same manner as in Example 10, except that the amount of 1G in the hard coat layer 15 was 55 parts by weight.
[Comparative Example 11]
An antireflection film was obtained in the same manner as in Example 10 except that 10 parts by weight of methyl methacrylate was used as a component of the hard coat layer 15 instead of 20 parts by weight of 1G.
[Comparative Example 12]
33.3 parts by weight of the low refractive index fine particle slurry C-3 (solid content 15%) prepared in (1-3) of Example 16 and 66.7 parts by weight of zirconia slurry with respect to 100 parts by weight of A-DPH. Then, 65.0 parts by weight of MEK, 5 parts by weight of Irgacure 184 as an initiator, and 0.5 parts by weight of SN leveler S-906 as a leveling agent were added to obtain a coating agent f.

Next, the coating agent f was applied to a PET film (Lumirror U34) having a thickness of 100 μm by a bar coating method so as to have a cured film thickness of 3 μm, and dried with a hot air dryer at 100 ° C. for 2 minutes. . Thereafter, an ultraviolet ray treatment with an irradiation intensity of 1500 mW / cm ^{2 and} an amount of work of 300 mJ / cm ² was performed using an ultraviolet ray irradiation device to obtain an antireflection film.
[Comparative Example 13]
0.7 parts by weight of low refractive index fine particle slurry B-3 (solid content 15%) prepared in (1-2) of Example 10 and 333.3 parts by weight of zirconia slurry with respect to 100 parts by weight of A-DPH. Then, 5 parts by weight of Irgacure 184 as an initiator and 0.5 parts by weight of SN leveler S-906 as a leveling agent were added to obtain a coating agent g.

Next, the coating agent g was applied to a PET film (Lumirror U34) having a thickness of 100 μm by a bar coating method so as to have a cured film thickness of 3 μm, and dried by a hot air dryer at 100 ° C. for 2 minutes. . Thereafter, an ultraviolet ray treatment with an irradiation intensity of 1500 mW / cm ^{2 and} an amount of work of 300 mJ / cm ² was performed using an ultraviolet ray irradiation device to obtain an antireflection film.
[Reference Example 1]
200 parts by weight of low refractive index fine particle slurry B-3 (solid content 15%) prepared in (1-2) of Example 1 and 333 zirconia slurry (solid content 15%) with respect to 100 parts by weight of A-DPH. .3 parts by weight, 5 parts by weight of Irgacure 184 as an initiator, and 0.5 parts by weight of SN leveler S-906 as a leveling agent were added to obtain a coating agent h.

Next, the coating agent h was applied to a PET film (Lumirror U34) having a thickness of 100 μm by a bar coating method so as to have a cured film thickness of 3 μm, and dried with a hot air dryer at 100 ° C. for 2 minutes. . Thereafter, an ultraviolet ray treatment with an irradiation intensity of 1500 mW / cm ^{2 and} an amount of work of 300 mJ / cm ² was performed using an ultraviolet ray irradiation device to obtain an antireflection film.

  Tables 1 to 4 show the blending components of the coating agent used for forming the hard coat layer in Examples 1 to 15 and Comparative Examples 1 to 11. In addition, the addition amount in Examples 1-15 and Comparative Examples 1-11 is a weight part (solid content) when the addition amount of an acrylate is 100 weight part.

  Moreover, the compounding component of the coating agent used in order to form an anti-reflective film in the present Examples 16-22, the comparative examples 12 and 13, and the reference example 1 in Table 5 and Table 6 is shown. Here, the “addition amount of the low refractive index fine particles” is the addition amount (parts by weight) of the low refractive index fine particles with respect to 100 parts by weight of the resin (solid content). Tables 5 and 6 show the refractive index after curing of the resin, the refractive index after curing of the low refractive index fine particles, and the dry film thickness formed by applying the coating agent.

The antireflection films manufactured in Examples 1 to 22 and Comparative Examples 1 to 13 and Reference Example 1 were tested for confirming their effects.
(A) Test / Evaluation Method (i) Measurement of Total Light Transmittance (Tt) Measured according to JIS K 7361-1 (2000 version) 3.2. As a measuring device, Hazeguard II manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
(Ii) Measurement of haze value (Hz) The haze value (Hz) was measured according to JIS K 7136 (2000 version). Specifically, among the incident parallel light, the percentage of the transmitted light deviated by 0.44 rad (2.5 °) or more from the incident light by forward scattering was measured. As a measuring device, Hazeguard II manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
(Iii) Measurement of pencil hardness It was performed based on the provisions of JIS K 5600-5-4 (1999 edition). (Iv) Measurement of abrasion resistance using a pencil scratch coating film hardness tester (Type P) manufactured by Toyo Seiki Seisakusho Co., Ltd. as a measuring device. A 200 g load was applied to the surface of the antireflection film. The degree of scratches was visually evaluated by rubbing with steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. When the number of scratches was 3 or less, ◎, 4-8 were evaluated as ◯, 9-15 were evaluated as △, and more than ×.
(V) Measurement of minimum reflectance The back surface of the prepared antireflection film was uniformly polished with sandpaper, and a sample was painted with black marker, and the 5 °, -5 ° spectral reflection spectrum from 350 to 780 nm was measured in Japan. It measured using the ultraviolet visible spectrophotometer (V-550) by a spectrum company, and read the minimum reflectance from the reflectance spectrum. If there is an amplitude in the reflection spectrum, the center is defined as the minimum reflectance. If the minimum reflectance was 2.5% or less, it had antireflection performance and was considered good.
(Vi) Measurement of near-infrared transmittance Using the spectrophotometer, the transmittance of the maximum absorption wavelength portion in the near-infrared region of 850 nm to 1100 nm was recorded.
(Viii) Measurement of contact angle Ion exchange water and oleic acid primary reagent are dropped on the surface of the antireflection film, and the contact angle is measured. As a measuring device, a contact angle meter CA-X type manufactured by Kyowa Interface Science Co., Ltd. was used.
(B) Test / Evaluation Results The test / evaluation results are shown in Tables 1 to 6 above. As is clear from these tables, the antireflection films of Examples 1 to 22 are excellent in adhesion and wear resistance and have a low minimum reflectance even without a plurality of curing steps by ultraviolet irradiation. The contact angle for oleic acid was high. Furthermore, in the antireflection films of Examples 10 to 15 and 21 to 22, the transmittance of the maximum absorption wavelength portion in the near infrared region was low.

It is explanatory drawing showing the manufacturing method of an antireflection film. It is sectional drawing showing the structure of an antireflection film. It is sectional drawing showing the structure of an antireflection film. It is sectional drawing showing the structure of an antireflection film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Resin component 3 ... Low-refractive-index fine particle 5 ... Coating agent 7, 13 ... Transparent base material layer 9, 17 ... Low-refractive-index layer 11, 15 ... Hard-coat layer 19 ... Antireflection film 21 ... Near-infrared absorbing layer

Claims (8)

A coating agent used for forming a hard coat layer of an antireflection film,
A coating agent comprising an acrylate and a 2-3 functional methacrylate as main components, wherein the blending ratio of the 2-3 functional methacrylate with respect to 100 parts by weight of the acrylate is in the range of 0.5 to 50 parts by weight. . (A) a transparent substrate layer;
(B) a hard coat layer;
(C) a low refractive index layer,
The layer structures (a) to (c) are (a) / (b) / (c),
Said (b) is formed by apply | coating and hardening | curing the coating agent of Claim 1, The antireflection film characterized by the above-mentioned.   The antireflection film according to claim 2, wherein (c) comprises a fluorine-modified silicone resin, and has a contact angle with water of 90 ° or more and a contact angle with oleic acid of 50 ° or more. A coating agent used for forming a hard coat layer and a low refractive index layer of an antireflection film,
100 parts by weight (solid content) of resin constituting the hard coat layer;
A coating agent comprising 1 to 30 parts by weight of low refractive index fine particles mainly comprising fluorine-based (meth) acrylate constituting the low refractive index layer. (A) a transparent substrate layer;
(B) a hard coat layer;
(C) a low refractive index layer,
The layer structures (a) to (c) are (a) / (b) / (c),
Said (b) and said (c) are formed by phase separation after apply | coating and hardening | curing the coating agent of Claim 4, The antireflection film characterized by the above-mentioned. And (d) a near-infrared absorbing layer.
6. The antireflection according to claim 2, wherein the layer structures (a) to (d) are (d) / (a) / (b) / (c). the film. (D) contains a near-infrared absorbing dye,
The antireflection film according to claim 6, wherein the antireflection film has a transmittance of 20% or less in a wavelength region of 850 to 1100 nm. (D) contains a neon cut dye having a maximum absorption wavelength in the wavelength range of 550 to 650 nm,
The antireflection film according to claim 7, wherein the antireflection film has a transmittance at a maximum absorption wavelength portion of 50% or less.

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