JP4556664B2 - Anti-reflection laminate - Google Patents

Description

  The present invention relates to an antireflection laminate in which a hard coat layer and a low refractive index layer are laminated on a transparent resin substrate, a polarizing plate with an antireflection function obtained by laminating this antireflection laminate, and the polarizing plate with an antireflection function. The present invention relates to a liquid crystal display device comprising:

The principle of optical interference in image display devices such as cathode ray tube display devices (CRT), plasma display devices (PDP), and liquid crystal display devices (LCD) in order to prevent contrast degradation and image reflection due to reflection of external light A film-like antireflective laminate that reduces the reflectivity using is generally placed on the outermost surface of the display.
The antireflection laminate is generally formed by laminating optical functional layers such as an antistatic layer, a hard coat layer, a high refractive index layer, and a low refractive index layer on a transparent resin substrate.

  Various types of antireflection films are known. For example, in Patent Document 1, in a plastic laminate in which a hard coat layer is provided on at least one surface of a plastic substrate and an antireflection layer is provided thereon, the surface hardness of the hard coat layer is 2H or more, surface A plastic laminate having a scraping index of 1.0 to 15.0 and a center line average roughness (Ra) of the hard coat layer surface of 0.001 to 0.02 μm is disclosed. Specifically, this hard coat layer is a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in one molecule, particles, and a high molecular weight having an unsaturated double bond copolymerizable at the terminal. A resin comprising a molecular weight monomer and / or an acrylic polymer is contained, the particles are powdered silica or colloidal silica, and the surfaces of the particles are treated and bonded with an organic compound via a silyloxy group. The antireflection layer is a multilayer laminate of inorganic oxides. Patent Document 1 states that such a configuration can reduce the reflectance to 0.6%. However, the reflectance cannot fall below 0.6%.

  Patent Document 2 has a low refractive index layer having a lower refractive index than the transparent support on the transparent support, and an adhesion layer in the lower layer adjacent to the low refractive index layer, and the surface of the adhesion layer is 0. An antireflective film having a centerline average roughness (Ra) of 0.001 to 0.030 μm is disclosed. This adhesion layer is composed of inorganic particles and an organic binder, and interparticle voids are formed in the adhesion layer. Further, the adhesion layer is an adhesion layer / high refractive index layer having a higher refractive index than that of the transparent support, and a hard coat layer having a thickness of 1 μm or more between the adhesion layer / high refractive index layer and the transparent support. Is provided. It is disclosed that the refractive index of the hard coat layer is 1.57 to 2.00, and the hard coat layer has matting agent particles having an average particle size of 0.3 to 20 μm and has antiglare properties. ing. Patent Document 2 discloses that the reflectance can be reduced to 0.4% by such a configuration, but the reflectance is 1.0% in order to obtain an antiglare property to the extent that the outline of the fluorescent lamp is not known. The haze is as high as 12%. Moreover, since the layer structure becomes complicated with four or more layers including the base material, the productivity is low. In addition, in the order of the low refractive index layer, the adhesion layer under the layer, and the base material in the order of maintaining the adhesion, the haze is as low as 0.2%, but the reflectance is as high as 1.7% or more, and the reflection Both the prevention performance and transparency were not satisfactory.

  Patent Document 3 discloses an antireflection article in which a conductive hard coat film and a low refractive index film are provided on a substrate. It is disclosed that the conductive hard coat film preferably has a refractive index of 1.62 or more. It is shown that the reflectance can be reduced to 0.7% by this configuration. However, the adhesion between the hard coat layer and the low refractive index film was not sufficient.

JP 2004-287308 A Japanese Patent Laid-Open No. 2002-311204 JP 11-211901 A

  Conventional antireflection laminates have high reflectivity when trying to improve the adhesion between the hard coat layer and the low refractive index layer, and the balance between reflectivity, adhesion, haze and scratch resistance is insufficient. . Accordingly, an object of the present invention is to provide an antireflection laminate having high adhesion between the hard coat layer and the low refractive index layer and having an excellent balance of low haze, low reflectance, and scratch resistance, and laminating the antireflection laminate. It is to provide a polarizing plate with an antireflection function and a liquid crystal display device including the polarizing plate with an antireflection function.

  The inventor has a hard coat layer and a low refractive index layer laminated in this order on a transparent resin substrate, the total light transmittance is not less than a specific value, and the haze value is less than the specific value. An antireflection laminate comprising a coating layer containing an active energy ray-curable resin and inorganic oxide particles, wherein the hard coat layer has an average surface roughness (Ra) of a specific value or less and a high refractive index of the hard coat layer. However, it has been found that the adhesion between the hard coat layer and the low refractive layer is high and the balance between low haze and low reflectance is excellent, and the present invention has been completed based on this finding.

That is, the present invention is (1) a hard coat layer and a low refractive index layer are laminated in this order on a transparent resin substrate, the total light transmittance is 94% or more, and the haze value is less than 1%. And the rate of change of the total light transmittance before and after the scratch resistance test is 3% or less,
The hard coat layer contains 100 parts by weight of active energy ray-curable resin and 400 to 1200 parts by weight of inorganic oxide particles, the hard coat layer has an average surface roughness (Ra) of 35 nm or less, and the hard coat layer. Is an antireflection laminate having a refractive index of 1.55 or more.

Moreover, the aspect of the suitable antireflection laminated body of this invention is:
(2) The hard coat layer further contains 0.2 to 4 parts by weight of a fluorinated alkyl group-containing oligomer with respect to 100 parts by weight of the active energy ray-curable resin.
(3) The transparent resin substrate is made of at least one resin selected from the group consisting of an alicyclic structure-containing polymer resin, a cellulose polymer resin, and a polyester polymer resin.
(4) The metal oxide particles are antimony pentoxide or tin oxide doped with phosphorus.
(5) The low refractive index layer is made of aerogel and has a refractive index of 1.37 or less.
Another aspect of the present invention is (6) a polarizing plate with an antireflection function formed by laminating the antireflection laminate and a polarizer, and (7) a liquid crystal display device comprising the polarizing plate with an antireflection function.

When 400 to 800 parts by weight of inorganic oxide particles are contained with respect to 100 parts by weight of the active energy ray-curable resin constituting the hard coat layer, a hard coat layer having a large average surface roughness is obtained, and a low refractive index layer And the total light transmittance of the laminate is lowered, and the haze is increased. However, when the inorganic oxide particles are dispersed with a fluorinated alkyl group-containing oligomer or the like and the average surface roughness (Ra) is 30 nm or less, the anchor effect works effectively and the adhesion between the hard coat layer and the low refractive index layer is achieved. When the refractive index of the hard coat layer is 1.55 or more, the balance between low haze and low reflectance is improved.
When a polarizing plate with an antireflection function is obtained by laminating such an antireflection laminate with a polarizer, and this polarizing plate is provided in a liquid crystal display device, the visibility and contrast of the display screen are improved even in places with strong external light. It is good.

In the antireflection laminate of the present invention, a hard coat layer and a low refractive index layer are laminated in this order on a transparent resin substrate.
The transparent resin substrate is made of a transparent resin. The shape is not particularly limited, but is usually a film or a sheet.
The transparent resin can be used without particular limitation as long as it has a total light transmittance of 80% or more, preferably 90% or more when formed into a 1 mm-thick molded body.
Specific examples of the transparent resin include a polymer resin having an alicyclic structure, a chain olefin polymer such as polyethylene and polypropylene, a cellulose polymer resin, a polycarbonate polymer, a polyester polymer, and a polysulfone polymer. , Polyethersulfone polymers, polystyrene polymers, polyvinyl alcohol polymers, polymethacrylate polymers, and the like.
Among these, alicyclic structure-containing polymer resins such as norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof; Cellulose polymer resins such as cellulose diacetate, cellulose triacetate, and cellulose acetate butyrate; polyester polymer resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; are preferred, transparency, low moisture absorption, and dimensional stability From the viewpoints of lightness and the like, norbornene polymers, triacetylcellulose and polyethylene terephthalate are more preferable, and norbornene polymers are particularly preferable. These can be used alone or in combination. Examples of norbornene polymers include, for example, ring-opening polymers of norbornene monomers, ring-opening polymers of norbornene monomers and other monomers, and hydrogenated products of these ring-opening polymers; norbornene-based polymers Examples thereof include addition polymers of monomers, addition polymers of norbornene monomers and other monomers, and hydrogenated products of these addition polymers. Among these, a hydrogenated product of a ring-opening polymer of a norbornene monomer is particularly preferable because it is excellent in transparency.

The transparent resin has a polystyrene-reduced weight average molecular weight of usually 10,000 to 300,000, preferably 15,000 to 250,000, as measured by gel permeation chromatography using cyclohexane (toluene if the polymer resin does not dissolve) as a solvent. More preferably, it is the range of 20000-200000. A transparent resin having a weight average molecular weight within this range is suitable because it highly balances the mechanical strength and moldability of the substrate.
The transparent resin is not particularly limited by its molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)), but is usually 1 to 10, preferably 1 to 6, more preferably 1.1 to 4. is there. By adjusting the molecular weight distribution in such a range, the mechanical strength and molding processability of the substrate are well balanced.

  Moreover, various compounding agents can be added to the transparent resin as desired. The compounding agent is not particularly limited as long as it is usually used in thermoplastic resin materials. For example, antioxidants such as phenolic antioxidants, phosphoric acid antioxidants, sulfur antioxidants; UV absorbers such as triazole UV absorbers, benzoate UV absorbers, benzophenone UV absorbers, acrylate UV absorbers, metal complex UV absorbers; light stabilizers such as hindered amine light stabilizers; dyes and pigments Colorants such as aliphatic alcohol esters, polyhydric alcohol esters, fatty acid amides, inorganic particles, etc. lubricants; triester plasticizers, phthalate ester plasticizers, fatty acid-basic ester plasticizers, oxyacids And plasticizers such as ester plasticizers; antistatic agents such as fatty acid esters of polyhydric alcohols; and the like.

The transparent resin substrate used in the present invention can be obtained by forming the transparent resin into a film or a sheet by a known molding method.
As the molding method, a melt extrusion molding method is preferable because the content of volatile components in the film and uneven thickness can be reduced. Examples of the melt extrusion method include a method using a die such as a T die, an inflation method, and the like, but a method using a T die is preferable in terms of excellent productivity and thickness accuracy.

Moreover, as a transparent resin base material used for this invention, what gave the surface modification process to the single side | surface or both surfaces can be used. By performing the surface modification treatment, the adhesion with the hard coat layer and the polarizer can be improved. Examples of the surface modification treatment include energy beam irradiation treatment and chemical treatment.
Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, and ultraviolet ray irradiation treatment. From the viewpoint of processing efficiency, corona discharge treatment and plasma treatment are preferred, and corona discharge treatment is particularly preferred. Examples of the chemical treatment include a method of immersing in an oxidizing agent aqueous solution such as potassium dichromate solution or concentrated sulfuric acid and then washing with water.

  The thickness of the transparent resin substrate is usually 5 to 300 μm, more preferably 40 to 200 μm. More preferably, it is 50-100 micrometers. When the thickness of the substrate is in the above range, a polarizing plate excellent in durability, mechanical strength, scratch resistance and optical performance can be obtained.

The hard coat layer constituting the antireflection laminate of the present invention is a layer having a high surface hardness. Specifically, it is a layer having a hardness of “HB” or more, preferably “H” or more, in a pencil hardness test (500 g load) defined in JIS K5400.
The hard coat layer has a refractive index of 1.55 or more, preferably 1.6 to 2.3. By setting the refractive index to 1.55 or more, reflection of external light or the like can be prevented, and a polarizing plate or the like having excellent scratch resistance and antifouling properties can be obtained. The refractive index can be measured and determined using, for example, a known spectroscopic ellipsometer.
The hard coat layer has an average surface roughness (Ra) of 30 nm or less, preferably 5 to 25 nm, particularly preferably 10 to 20 nm. When the average surface roughness is within this range, the adhesion between the hard coat layer and the low refractive index layer is increased due to the anchor effect, etc., the total light transmittance is a specific value or more, and the haze value is less than the specific value. The balance between high transparency, low haze and low reflectivity is improved. Moreover, although the average thickness of a hard-coat layer is not specifically limited, Usually, 0.5-30 micrometers, Preferably it is 3-15 micrometers. The average surface roughness (Ra) can be measured by using a non-contact type three-dimensional structural analysis microscope (zygo NewView 5032: manufactured by Zygo Corporation) to scan the uneven surface of the film and observe interference fringes.

The hard coat layer contains an active energy ray-curable resin and inorganic oxide particles, and more preferably contains a fluorinated alkyl group-containing oligomer.
The active energy ray-curable resin is a resin obtained by curing a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule by irradiation with active energy rays. An active energy ray refers to an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking molecules. Usually, ultraviolet rays or electron beams are used.

  Examples of prepolymers and oligomers having a polymerizable unsaturated bond or epoxy group in the molecule include unsaturated polyesters such as a condensation product of unsaturated dicarboxylic acid and polyhydric alcohol; polyester methacrylate, polyether methacrylate, polyol methacrylate And methacrylates such as melamine methacrylate, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, acrylates such as melamine acrylates, and cationic polymerization type epoxy compounds.

  Examples of the monomer having a polymerizable unsaturated bond or epoxy group in the molecule include styrene monomers such as styrene and α-methylstyrene; methyl acrylate, ethyl acrylate, -2-ethylhexyl acrylate, methoxy acrylate Acrylic esters such as ethyl, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, methacrylic acid Methacrylic acid esters such as phenyl and lauryl methacrylate; acrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N-dimethylamino) ethyl, acrylic acid-2- (N, N -Dibenzylamino) methyl, acrylic -2-(N, N-diethylamino) substituted amino alcohol esters of unsaturated substituted and propyl; acrylamide, unsaturated carboxylic acid amides such as methacrylamide;

  Ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate 2-hydroxy acrylate, 2-hexyl acrylate, phenoxyethyl acrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate Multifunctional Acrela such as REIT Polythiols having two or more thiol groups in the molecule such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycolate; glycidyl acrylate, glycidyl methacrylate, glycidyl Phenyl ether, glycidyl ethyl ether, epichlorohydrin, allyl glycidyl ether, ethylene oxide, propylene oxide, neopentyl glycol diglycidyl ether, trimethylolpropane diglycidyl ether, glycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tri Glycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ester Ether, tris (2-hydroxyethyl) diglycidyl ethers of isocyanurates, phenol novolak polyglycidyl ether, epoxy compounds such as cresol novolac polyglycidyl ether; and the like. In the present invention, these prepolymers, oligomers and / or monomers can be used singly or in combination of two or more.

  In order to polymerize and cure these prepolymers, oligomers and / or monomers, a photopolymerization initiator and a photopolymerization accelerator are blended. As photopolymerization initiators, radical polymerization initiators such as acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether; aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metathelone compounds, benzoin sulfonic acids Cationic polymerizable initiators such as esters; These can be used individually by 1 type or in combination of 2 or more types. The amount of the photopolymerization initiator is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the prepolymer, oligomer and / or monomer.

The inorganic oxide particles used in the present invention are particles that can adjust the conductivity, refractive index, and the like of the hard coat layer.
The inorganic oxide particles for increasing the refractive index are preferably inorganic oxide particles having a refractive index of 1.6 or more, particularly 1.6 to 2.3.
Examples of the inorganic oxide particles having a high refractive index include titania (titanium oxide), zirconia (zirconium oxide), zinc oxide, tin oxide, cerium oxide, antimony pentoxide, titanium dioxide, tin-doped indium oxide (ITO). Antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO), fluorine-doped tin oxide (FTO) Etc. Among these, tin oxide doped with antimony pentoxide or phosphorus is particularly suitable as a component for adjusting the refractive index because it has a high refractive index and an excellent balance between conductivity and transparency. These may be used alone or in combination.

The inorganic oxide particles preferably have a primary particle diameter of 1 nm to 100 nm, preferably 1 nm to 50 nm, in order not to lower the transparency of the hard coat layer.
The primary particle diameter of the inorganic oxide particles may be visually measured from a secondary electron emission image photograph obtained by a scanning electron microscope (SEM) or the like, or a dynamic light scattering method or a static light scattering method may be used. Mechanical measurement may be performed by a particle size distribution meter to be used.

  It is preferable that at least a part of the surface of the inorganic oxide particles is coated with an organic compound or an organometallic compound having an anionic polar group. The coating method is not particularly limited. For example, an organic compound and / or an organic metal compound having an anionic polar group described below is dissolved in an organic solvent, and inorganic oxide particles are dispersed in this solution. A method of completely evaporating and removing the organic solvent can be mentioned.

  As the organic compound having an anionic polar group, those having an anionic polar group such as a carboxyl group, a phosphate group, or a hydroxyl group can be used. For example, stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, ethylene oxide, modified phosphoric acid triacrylate, epichlorohydrin modified glycerol triacrylate, and the like can be given.

  Examples of the organometallic compound having an anionic polar group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Silane coupling agents such as vinyltris (2-methoxyethoxy) silane and 3-methacryloxypropyltrimethoxysilane; KR-TTS, KR-46B, KR-55, KR-41B, KR-38S, KR-138S, KR -238S, 338X, KR-44, KR-9S , KR-ET (above, titanate coupling agent manufactured by Ajinomoto Fine Techno Co., Ltd.), tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra n-propoxy titanium, tetra n-butoxy titanium, tetra sec-butoxy And titanate coupling agents such as titanium and tetra-tert-butoxytitanium;

  Two or more inorganic oxide particles may be used in combination. By combining the inorganic oxide particles, a hard coat layer having a plurality of functions in a well-balanced manner can be formed. For example, combining a rutile-type titanium oxide particle with a very high refractive index but a low conductivity with a conductive inorganic oxide having a very high conductivity but a refractive index lower than that of a rutile-type titanium oxide, a predetermined refractive index and good A hard coat layer having excellent antistatic performance can be formed. The amount of the inorganic oxide particles is 300 to 800 parts by weight, preferably 350 to 700 parts by weight, and more preferably 400 to 600 parts by weight with respect to 100 parts by weight of the active energy ray curable resin.

  In order to uniformly disperse the inorganic oxide particles in the hard coat layer, it is preferable to contain a fluorinated alkyl group-containing oligomer in the hard coat layer.

The fluorinated alkyl group-containing oligomer is a kind of fluorosurfactant, and preferably nonionic.
The fluorinated alkyl group-containing oligomer is obtained by introducing a fluorinated alkyl group into the oligomer, and the introduction method is not particularly limited. For example, a method of plasma-treating a non-fluorinated polymer, a method of reacting a non-fluorinated polymer having a reactive functional group with a fluorinated alkyl group-containing compound having a reactive functional group, a fluorinated alkyl group-containing ethylenic compound Examples include a method of polymerizing an unsaturated monomer, a method of using a compound containing a fluorinated alkyl group as an initiator and / or a chain transfer agent when a polymer is synthesized, or a method combining such methods. However, a method of polymerizing a fluorinated alkyl group-containing ethylenically unsaturated monomer is preferred.

The fluorinated alkyl group-containing ethylenically unsaturated monomer (A) is a compound having an ethylenically unsaturated group and a fluorinated alkyl group in the molecule. From the viewpoint of availability of raw materials, compatibility with active energy curable resins, ease of controlling such compatibility, or polymerization reactivity, those containing an acrylic ester group and its related groups are suitable. Specifically, a fluorinated (meth) acrylate represented by the following general formula (1) is preferable. (Meth) acrylate is a generic term for methacrylate, acrylate, fluoroacrylate, and chlorinated acrylate.

[Wherein R _f is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group, linear, branched, or having an oxygen atom intervening in the main chain, such as-( OCF ₂ CF ₂ ) ₂ CF (CF ₃ ) ₂ or the like may be used, R ₁ is H, CH ₃ , Cl, or F, and X is a divalent linking group.

The fluorinated alkyl group-containing oligomer used in the present invention may be one obtained by copolymerizing other monomers in addition to the fluorinated alkyl group-containing ethylenically unsaturated monomer (A).
It is preferable to contain a silicone chain-containing ethylenically unsaturated monomer (B) as a monomer to be copolymerized.

  The silicone chain-containing ethylenically unsaturated monomer (B) is not particularly limited as long as it is a compound having a silicone chain and an ethylenically unsaturated group in one molecule, and specifically, represented by the general formula (2). It is a compound.

[Wherein R ₁ represents H, Cl, F, or CH ₃ , and R ₂ and R ₃ represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a functional group represented by the general formula (3). ,

(Wherein R ₇ , R ₈ and R ₉ represent an alkyl group or phenyl group having 1 to 20 carbon atoms), R ₄ , R ₅ and R ₆ represent an alkyl group or phenyl group having 1 to 20 carbon atoms. , X is _{-CH 2 CH (OH) CH 2} OCO -, - (CH 2) n NHCH 2 CH (OH) CH 2 0CO -, - (CH 2) n OCO -, - (CH 2) n -O- _{(CH 2) m OCO -,} - OCH 2 CH (OH) CH 2 OCO -, - (CH 2) n C (CF 3) represents a divalent linking group selected from ₂ OCO-, q is 0 to 3 , M and n are integers of 2 to 6, and p is 0 or 1. ]

  Further, as a copolymerizable monomer, a polyoxyalkylene group-containing unsaturated monomer (C) and / or an ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule. It can be included.

The polyoxyalkylene group-containing unsaturated monomer (C) is not particularly limited as long as it is a compound having a polyoxyalkylene group and an ethylenically unsaturated group in one molecule. Is appropriately selected.
The oxyalkylene group is preferably an ethylene oxide group and / or a propylene oxide group. The degree of polymerization of the oxyalkylene group is 1 to 50, preferably 5 to 30.
The ethylenically unsaturated group contains a (meth) acrylic ester group and related groups from the viewpoints of availability of raw materials, compatibility, ease of controlling such compatibility, polymerization reactivity, and the like. Things are suitable.

  Specific examples of the compound include polyethylene glycol, polypropylene glycol, and poly (alkylene glycol) mono (meth) acrylate such as a copolymer of ethylene oxide and propylene oxide (hereinafter referred to as “poly (ethylene glycol)”). This expression shall generically refer to both alkyl acrylates and alkyl methacrylates.), Or polyethylene glycol having a degree of polymerization of 1-100 capped with an alkyl group having 1-6 carbon atoms, Examples thereof include polypropylene glycol and mono (meth) acrylate of polyalkylene glycol such as a copolymer of ethylene oxide and propylene oxide. Only one type of polyoxyalkylene group-containing unsaturated monomer (C) may be used, or two or more types may be used in combination.

  The ethylenically unsaturated monomer (D) is not particularly limited as long as it has two or more unsaturated bonds in one molecule, but the ethylenically unsaturated group is an acrylic ester from the viewpoint of polymerization reactivity. Those containing groups and their analogous groups are suitable. Specifically, di (meth) acrylic acid ester of polyalkylene glycol such as polyethylene glycol, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide having a polymerization degree of 1 to 100, or terminal Of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide with a degree of polymerization of 1-100 capped by an alkyl group having 1 to 6 carbon atoms (Meth) acrylic acid ester, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane tri (meth) acrylate and its EO-modified product, tetramethylolpropane tri (meth) acrylate and its EO-modified product, tetramethylo Methane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate and the like. As the ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule, only one type may be used or two or more types may be used in combination.

  The proportions of the monomers (A), (B), (C), and (D) can be appropriately selected according to the type of active energy curable resin and inorganic oxide particles, and also depending on the coating method and the like. Is usually preferably in the range of (A) / (B) / (C) / (D) = 5 to 50/0 to 40/0 to 90/0 to 30, more preferably on a weight basis. Is (A) / (B) / (C) / (D) = 10-40 / 5-30 / 30-70 / 1-10, with a particularly preferred range being (A) / (B) / (C ) / (D) = 10-25 / 5-5 / 20 / 50-70 / 2-7.

The fluorinated alkyl group-containing oligomer used in the present invention introduces an ethylenically unsaturated monomer (E) other than the monomers (A), (B), (C), and (D) as a copolymerization component. be able to. Examples of the ethylenically unsaturated monomer (E) include styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, vinyl acetate and other fatty acid vinyls, and α, β -Ethylenically unsaturated carboxylic acids, ie mono- or divalent carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and derivatives of α, β-ethylenically unsaturated carboxylic acids (Meth) acrylic acid alkyl ester having 1 to 18 carbon atoms, hydroxyalkyl ester having 1 to 18 carbon atoms of (meth) acrylic acid, aminoalkyl ester having 1 to 18 carbon atoms of (meth) acrylic acid, ( Di-cyclopentanyl ether of an oxygen ester containing 3 to 18 carbon atoms of (meth) acrylic acid Shiruechiru (meth) acrylate, bridging bond-containing monomers such as isobornyl oxyl ethyl (meth) acrylate, alkyl vinyl ethers of alkyl carbon atoms 1 to 18, (meth) glycidyl esters of acrylic acid, various macro monomer. Furthermore, a silane coupling group-containing monomer, a monomer containing a polar group, particularly an anionic group or a hydroxyl group in the molecule, and the like can be mentioned. Only one type of ethylenically unsaturated monomer (E) may be used, or two or more types may be used in combination.
The ratio of the monomer (E) is [(A) + (B) + (C) + on a weight basis with respect to the total amount of the monomers (A), (B), (C) and (D). (D)] / (E) = 20/80 to 100/0 is preferable, and a more preferable range is [(A) + (B) + (C) + (D)] / (E ) = 50/50 to 97/3, and a particularly preferable range is [(A) + (B) + (C) + (D)] / (E) = 70/30 to 95/5.

The fluorinated alkyl group-containing oligomer used in the present invention is not limited by its production method, and is based on a known method, that is, based on a polymerization mechanism such as a radical polymerization method, a cation polymerization method, or an anion polymerization method, a solution polymerization method, a bulk polymerization method. Further, it can be obtained by an emulsion polymerization method or the like.
The fluorinated alkyl group-containing oligomer used in the present invention has a polystyrene-equivalent number average molecular weight of usually 800 to 200,000, preferably 1,000 to 100,000, particularly preferably 2,000 to 20,000. When an oligomer having a molecular weight within the above range is used, the dispersibility of the inorganic oxide particles is improved, and a low surface roughness hard coat layer constituting the antireflection laminate of the present invention can be easily obtained.
A commercially available fluorinated alkyl group-containing oligomer can also be used. Commercially available products include Megafac F470, F471, F472, F472SF, F474, F475, F476-20, F477, F478, F479, F172D, F178K, F-178RM, ESM-1, R, manufactured by Dainippon Ink and Chemicals, Inc. -08, R-30, R-60PM-20, BL-20, MCF-350SF, MCF-350-5 and the like.

  The amount of the fluorinated alkyl group-containing oligomer is 0.2 to 4 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the active energy curable resin. When the amount of the fluorinated alkyl group-containing oligomer is small, the dispersibility of the inorganic oxide particles is reduced, and the low surface roughness hard coat layer constituting the antireflection laminate of the present invention is easily obtained. Sometimes. If the amount of the fluorinated alkyl group-containing oligomer is too large, the hardness of the hard coat layer may be lowered or the transparency may be lowered.

  The hard coat layer constituting the present invention may further contain an organic reactive silicon compound. Examples of organic reactive silicon compounds include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyl Trimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldi Formulas such as ethoxysilane, hexyltrimethoxysilane, etc .: RmSi (OR ′) n (wherein R and R ′ each independently represent an alkyl group having 1 to 10 carbon atoms, and m and n are each independently To, organic silicon compounds represented by a positive integer satisfying the relationship of m + n = 4).;

  3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane 3-methacryloxypropylmethoxysilane, N-3- (N-vinylbenzylaminoethyl) -3-aminopropylmethoxysilane hydrochloride, 3-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltri Acetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (3-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, Le trichlorosilane, silane coupling agents such as dimethyldichlorosilane;

  One-end vinyl group-substituted polysilane, both-end vinyl group-substituted polysilane, one-end vinyl group-substituted polysiloxane, both-end vinyl group-substituted polysiloxane, vinyl group-substituted polysilane obtained by reacting these compounds, or vinyl group-substituted poly Active energy ray-curable silicon compounds such as siloxane; other organosilicon compounds such as 3- (meth) acryloxypropyltrimethoxysilane and (meth) acryloxysilane compounds such as 3- (meth) acryloxypropylmethyldimethoxysilane And the like.

The hard coat layer is usually formed by applying a solution in which an active energy ray-curable resin, inorganic oxide particles, and a fluorinated alkyl group-containing oligomer blended as necessary are dissolved or dispersed on the substrate. It can be obtained by drying to obtain a coating film, followed by irradiation with active energy rays and curing. Examples of the coating method include a wire bar coating method, a dip method, a spray method, a spin coating method, a roll coating method, and a gravure coating method.
The irradiation intensity and irradiation time of the active energy ray are not particularly limited, and irradiation conditions such as irradiation intensity and irradiation time can be appropriately set according to the active energy ray curable resin to be used.
Examples of the solvent for dissolving or dispersing the active energy ray-curable resin include alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, Glycols such as diethylene glycol, diethylene glycol monobutyl ether, diacetone glycol; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate; methyl ethyl ketone And ketones such as methyl isobutyl ketone; oximes such as methyl ethyl ketoxime; and combinations of two or more thereof.

  The low refractive index layer constituting the antireflection laminate of the present invention is a layer having a refractive index lower than that of the hard coat layer. The refractive index of the low refractive index layer is preferably 1.37 or less, more preferably 1.25 to 1.35, and particularly preferably 1.30 to 1.34. By being the said preferable conditions, the polarizing plate etc. which were excellent in the balance of visibility, abrasion resistance, and intensity | strength can be obtained.

The material forming the low refractive index layer is preferably a material constituting a layer having a refractive index of 1.37 or less. In particular, an airgel is preferable in terms of easy control of the refractive index and excellent water resistance.
An airgel is a transparent porous body in which minute pores are dispersed in a matrix. Most of the size of the pores is 200 nm or less, and the occupation ratio of the pores is usually 10% by volume or more and 60% by volume or less, preferably 20% by volume or more and 40% by volume or less.
Specific examples of the airgel in which minute pores are dispersed include silica aerogel and a porous body in which hollow particles are dispersed in a matrix.

  Silica airgel is a wet state composed of a silica skeleton obtained by hydrolysis polymerization reaction of alkoxysilane as disclosed in US Pat. No. 4,402,927, US Pat. No. 4,432,956, US Pat. No. 4,610,863 and the like. These gel compounds can be produced by supercritical drying. In this supercritical drying, for example, a drying liquid such as carbon dioxide or alcohol is replaced with all or part of the solvent of the gel compound, the drying liquid is changed to a supercritical state, and then changed from the supercritical state to the gas phase. This can be done by discharging the liquid (gas). Silica airgel may be produced in the same manner as described above using sodium silicate as a raw material as disclosed in US Pat. No. 5,137,279, US Pat. No. 5,124,364, and the like.

  Here, as disclosed in JP-A-5-279011 and JP-A-7-138375, it is preferable to impart hydrophobicity to the silica airgel by hydrophobizing the gel compound. . This hydrophobic silica airgel can prevent moisture, water and the like from entering, and prevent the performance of the silica airgel such as refractive index and light transmittance from deteriorating.

  This hydrophobizing treatment can be performed before or during supercritical drying of the gel compound. The hydrophobizing treatment is performed by reacting the hydroxyl group of the silanol group present on the surface of the gel compound with the functional group of the hydrophobizing agent and replacing it with the hydrophobic group of the hydrophobizing agent. As a method for performing the hydrophobizing treatment, there is a method in which the hydrophobizing agent is infiltrated into the gel-like compound by immersing and mixing the gel-like compound in the hydrophobizing agent solution, followed by heating as necessary. can give.

The refractive index of silica airgel can be freely changed by the raw material compounding ratio of silica airgel.
The formation method of the low refractive index layer made of silica aerogel is not particularly limited. For example, the gel compound is coated on the hard coat layer by a known coating method, and the supercritical drying is performed. The method of forming is mentioned. Further, the hydrophobization treatment may be performed before or during supercritical drying.

As a porous body in which hollow particles are dispersed in a matrix, which is another aspect of the airgel, as disclosed in JP-A-2001-233611 and JP-A-2003-149642, the inside of the particles is used. Examples thereof include a porous body in which hollow particles having voids are dispersed in a binder resin.
The binder resin can be selected and used from resins that meet conditions such as dispersibility of hollow particles, transparency of the porous body, and strength of the porous body. For example, conventionally used polyester resins and acrylic resins Resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluorine resin, silicone resin, butyral resin, phenol resin, vinyl acetate resin, etc .; UV curable resin, electron beam curable resin, emulsion resin, water-soluble resin, hydrophilic Examples thereof include resins, mixtures of these resins, and coating resins such as copolymers and modified products of these resins; hydrolyzable organosilicon compounds such as alkoxysilanes, and hydrolysates thereof.
Among these, hydrolyzable organosilicon compounds such as acrylic resins, epoxy resins, urethane resins, silicone resins, alkoxysilanes and hydrolysates thereof are preferred from the viewpoint of particle dispersibility and the strength of the porous body.

The hydrolyzable organosilicon compound such as alkoxysilane and the hydrolyzate thereof are formed from one or more compounds selected from the group consisting of the following (a) to (c), and in the molecule: -(O-Si) _m -O- (wherein _m represents a natural number) has a bond.
(A) the general formula (4): a compound represented by SiX _4.
(B) At least one partial hydrolysis product of the compound represented by the general formula (4).
(C) At least one complete hydrolysis product of the compound represented by the general formula (4).

  However, in General formula (4), X is halogen atoms, such as a chlorine atom and a bromine atom; Monovalent hydrocarbon group which may have a substituent; Oxygen atom; Organic acid radicals, such as an acetate radical and a nitrate radical; A 3-diketonate group such as acetylacetonate; an inorganic acid group such as nitrate or sulfate; an alkoxy group such as methoxy, ethoxy, n-propoxy or n-butoxy; or a hydroxyl group.

Examples of the monovalent hydrocarbon group which may have a substituent include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; a cyclopentyl group, A cycloalkyl group such as a cyclohexyl group; an aryl group optionally having a substituent such as a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, and a 2-naphthyl group; an alkenyl group such as a vinyl group and an allyl group; Aralkyl groups such as benzyl group, phenethyl group and 3-phenylpropyl group; haloalkyl groups such as chloromethyl group and 3-chloropropyl group; 3,3,3-trifluoropropyl group, methyl-3,3,3-tri Perfluoroalkyl groups such as a fluoropropyl group, a heptadecafluorodecyl group, a trifluoropropyl group, a tridecafluorooctyl group; Alkenylcarbonyloxyalkyl groups such as -methacryloxypropyl groups; alkyl groups having epoxy groups such as 3-glycidoxypropyl groups and 3,4-epoxycyclohexylethyl groups; alkyls having mercapto groups such as 3-mercaptopropyl groups A group; an alkyl group having an amino group such as a 3-aminopropyl group; and the like. Among these, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group, and a phenyl group are preferable because of easy synthesis, easy availability, and low reflection characteristics.
Among these compounds (a), general formula (5): RaSiY _4-a [wherein R represents a monovalent hydrocarbon group which may have a substituent, and a is an integer of 0 to 2] And when a is 2, R may be the same or different. Y represents a hydrolyzable group, and Y may be the same or different. ] The silicon compound represented by this is preferable.

In the formula (5), Y represents a hydrolyzable group. Here, the hydrolyzable group refers to a group that is hydrolyzed in the presence of an acid or a base catalyst as desired to form a — (O—Si) _m —O— bond.
Specific examples of the hydrolyzable group include alkoxy groups such as methoxy group, ethoxy group and propoxy group; acyloxy groups such as acetoxy group and propionyloxy group; oxime group (—O—N═C—R ′ (R ″) )), Enoxy group (—O—C (R ′) ═C (R ″) R ′ ″), amino group, aminoxy group (—O—N (R ′) R ″), amide group (— N (R ′) — C (═O) —R ″) and the like. In these groups, R ′, R ″, and R ′ ″ each independently represent a hydrogen atom or a monovalent hydrocarbon group. Among these, Y is preferably an alkoxy group from the viewpoint of availability.

The silicon compound represented by the formula (5) is preferably a silicon compound in which a is an integer of 0 to 2 in the formula (5). Specific examples thereof include alkoxysilanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are more preferable because of their availability.

  In the formula (5), examples of the tetraalkoxysilane in which a is 0 include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane in which a is 1 include methyltrimethoxysilane and methyltriethoxy. Examples include silane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. Examples of the diorganodialkoxysilane in which a is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

  The molecular weight of the compound represented by the formula (4) is not particularly limited, but is preferably 40 to 300, and more preferably 100 to 200.

At least one partial hydrolysis product (hereinafter referred to as “compound (3)”) of the compound represented by formula (4) in (b), and represented by formula (4) in (c). At least one complete hydrolysis product of the compound (hereinafter referred to as “compound (4)”) is obtained by completely or partially hydrolyzing one or more of the compounds represented by the formula (4). Can be obtained by condensation.

Compound (3) and compound (4) are, for example, a metal tetraalkoxide represented by Si (Or) ₄ (r represents a monovalent hydrocarbon group) and a molar ratio [H ₂ O] / [Or ] Can be obtained by hydrolysis in the presence of water in an amount of 1 or more, 1 to 5, preferably 1 to 3. Hydrolysis can be performed by stirring the whole volume at a temperature of 5 to 100 ° C. for 2 to 100 hours.

When hydrolyzing the compound represented by the formula (4), a catalyst may be used as necessary. The catalyst to be used is not particularly limited, but the obtained partial hydrolyzate and / or complete hydrolyzate is likely to have a two-dimensional cross-linked structure, and the condensed compound is easily made porous. From the viewpoint of shortening the time required for this, an acid catalyst is preferred. Examples of the acid catalyst to be used include organic acids such as acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid. And inorganic acids such as hydrochloric acid, nitric acid, and halogenated silane; acidic sol fillers such as acidic colloidal silica and oxidized titania sol; These acid catalysts can be used alone or in combination of two or more.
Instead of the acid catalyst, a base catalyst such as an aqueous solution of an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide or calcium hydroxide, an aqueous ammonia or an aqueous solution of amines may be used.

  The molecular weights of the compound (3) and the compound (4) are not particularly limited, but usually the weight average molecular weight is in the range of 200 to 5,000.

The hollow particles are not particularly limited as long as they are inorganic compound particles, but inorganic hollow particles in which pores are formed in the outer shell are preferred, and the use of silica-based hollow particles is particularly preferred.
As the inorganic compound, an inorganic oxide is common. As the inorganic _{oxide, SiO 2, Al 2 O 3} , B 2 O 3, TiO 2, ZrO 2, SnO 2, Ce 2 O 3, P 2 O 5, Sb 2 O 3, MoO 3, ZnO 2, WO One or two or more of ₃ or the like can be mentioned. Examples of the two or more inorganic oxides include TiO ₂ —Al ₂ O ₃ , TiO ₂ —ZrO ₂ , In ₂ O ₃ —SnO ₂ , and Sb ₂ O ₃ —SnO ₂ . These can be used alone or in combination of two or more.

  As the inorganic hollow particles, (a) a single layer of an inorganic oxide, (b) a single layer of a composite oxide composed of different kinds of inorganic oxides, and (c) a double layer of the above (a) and (b) What is included can be used.

  The outer shell may be porous with pores, or the pores may be closed and the pores sealed against the outside of the outer shell. The outer shell is preferably a plurality of inorganic oxide coating layers comprising an inner first inorganic oxide coating layer and an outer second inorganic oxide coating layer. By providing the second inorganic oxide coating layer on the outer side, it is possible to obtain fine inorganic hollow particles in which the outer shell is closed by closing the pores of the outer shell and the inner pores are sealed. In particular, when a fluorine-containing organic silicon compound is used for forming the second inorganic oxide coating layer, the refractive index is lowered, dispersibility in an organic solvent is improved, and antifouling properties are further imparted. Such fluorine-containing organic silicon compounds include 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecyl. Examples include trichlorosilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane.

  The thickness of the outer shell is preferably in the range of 1 to 50 nm, particularly 5 to 20 nm. If the thickness of the outer shell is less than 1 nm, the inorganic hollow particles may not be able to maintain a predetermined particle shape. On the other hand, when the thickness of the outer shell exceeds 50 nm, the pores in the inorganic hollow particles are small, and as a result, the ratio of the pores is decreased, and the refractive index may not be sufficiently lowered.

When the first inorganic oxide coating layer and the second inorganic oxide coating layer are provided as outer shells as described above, the total thickness of these layers may be in the range of 1 to 50 nm. In particular, in the case of a densified outer shell, the thickness of the second inorganic oxide coating layer is preferably in the range of 20 to 40 nm.
Further, the pores may contain the solvent used when preparing the inorganic hollow particles and / or the gas that enters during drying.

  The average particle size of the inorganic hollow particles is not particularly limited, but is preferably 5 to 2000 nm, and more preferably 20 to 100 nm. If it is smaller than 5 nm, the effect of lowering the refractive index tends to be small. Conversely, if it is larger than 2000 nm, the transparency is deteriorated and the contribution due to diffuse reflection tends to be large. Here, the average particle diameter is a number average particle diameter by observation with a transmission electron microscope.

  The inorganic hollow particles that can be used in the present invention can be produced, for example, based on the method described in detail in JP-A No. 2001-233611, and commercially available inorganic hollow particles can also be used.

  The blending amount of the inorganic hollow particles is not particularly limited, but is preferably 10 to 30% by weight with respect to the entire low refractive index layer. When the blending amount of the inorganic hollow particles is within this range, a polarizing plate protective film excellent in visibility and scratch resistance can be obtained.

  When the low refractive index layer is a porous body in which hollow particles are dispersed in a matrix, the formation method is not particularly limited. For example, a coating comprising hollow particles and a binder resin on a hard coat layer. Examples include a method in which the working liquid is applied by a known coating method and, if necessary, is subjected to drying and heat treatment. Examples of the coating method include a wire bar coating method, a dip method, a spray method, a spin coating method, a roll coating method, and a gravure coating method. The temperature of the heating performed as necessary is usually 50 to 200 ° C, preferably 80 to 150 ° C.

  In the present invention, the average thickness of the low refractive index layer is 10 to 1000 nm, preferably 20 to 500 nm, more preferably 30 to 300 nm, and most preferably 50 to 150 nm. By setting the average thickness within this range, a polarizing plate having an excellent balance of antireflection effect, transparency, and scratch resistance can be obtained in a wide wavelength band.

In the antireflection laminate of the present invention, an antifouling layer may be further formed on the low refractive index layer in order to enhance the antifouling property of the low refractive index layer.
The material for forming the antifouling layer is not particularly limited as long as the function of the low refractive index layer is not inhibited and the required performance as the antifouling layer is satisfied. Usually, a compound having a hydrophobic group can be preferably used.
As specific examples, a perfluoroalkylsilane compound, a perfluoropolyethersilane compound, or a fluorine-containing silicone compound can be used. As the method for forming the antifouling layer, for example, a physical vapor deposition method such as vapor deposition or sputtering; a chemical vapor deposition method such as CVD; a wet coating method; The thickness of the antifouling layer is not particularly limited, but is usually preferably 20 nm or less, and more preferably 1 to 10 nm.

The antireflection laminate of the present invention has a total light transmittance of 94% or more, preferably 95% or more. The preferred antireflective laminate of the present invention has a reduction in total light transmittance of 3% or less before and after rubbing the laminate surface 10 times in a state where a load of 0.025 MPa is applied to steel wool # 0000. , Preferably within 2%, more preferably. Within 1%. The total light transmittance is measured according to JIS K7361-1 (1997) by using “turbidimeter NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd. The same measurement is performed five times at five different locations in the plane, and the arithmetic average value is calculated as the total light transmittance value. The decrease in total light transmittance is obtained from the following equation.
ΔR = (Rc−Rd) / Rc × 100 (%)
Rc represents the total light transmittance before rubbing with steel wool, and Rd represents the total light transmittance after rubbing with steel wool.

  The antireflection laminate of the present invention has a haze value of less than 1%, preferably less than 0.8%, more preferably less than 0.6%. By setting the haze value to less than 1%, when incorporated in a liquid crystal display device, the light transmittance is improved and the image becomes clear. The haze value is measured using “turbidimeter NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7136 (2000). The measurement is performed five times at five different locations in the plane, and the arithmetic average value is defined as the haze value.

  In the antireflection laminate of the present invention, the reflectance of light having an incident angle of 5 ° and a wavelength of 550 nm is preferably 0.7% or less, and particularly preferably 0.6% or less. When the reflectance is in the above range, the polarizing plate is excellent in visibility without reflection of external light and glare. The reflectance was determined by using a spectrophotometer (UV-visible near-infrared spectrophotometer V-570, manufactured by JASCO Corporation), the reflectance at a wavelength of 550 nm at an incident angle of 5 °, and the maximum reflectance at 430 to 700 nm. .

  The antireflection laminate of the present invention is, for example, a mobile phone, a digital information terminal, a pager (registered trademark), navigation, an in-vehicle liquid crystal display, a liquid crystal monitor, a light control panel, a display for OA equipment, a display for AV equipment, etc. It is useful as a protective film for polarizing plates used in various liquid crystal display elements, electroluminescence display elements, touch panels and the like.

  The polarizing plate with an antireflection function of the present invention is characterized in that a polarizer is laminated on the substrate side of the antireflection laminate.

  The polarizer is not particularly limited as long as it has a polarization function. For example, a polyvinyl alcohol (PVA) type or polyene type polarizer can be used. A polarizer is not specifically limited by the manufacturing method. As a method for producing a PVA polarizer, a method of stretching uniaxially after adsorbing iodine ions on a PVA film, a method of adsorbing iodine ions after stretching a uniaxially stretched PVA film, A method of simultaneously performing iodine ion adsorption and uniaxial stretching, a method of stretching a uniaxial film after dyeing a PVA film with a dichroic dye, a method of stretching a uniaxial film and then adsorbing with a dichroic dye, a PVA system The method of performing simultaneously dyeing | staining with a dichroic dye and uniaxial stretching to a film is mentioned. In addition, as a method for producing a polyene-based polarizing plate, a method of heating and dehydrating in the presence of a dehydration catalyst after stretching a PVA-based film uniaxially, and in the presence of a dehydrochlorination catalyst after stretching a polyvinyl chloride-based film uniaxially. And publicly known methods such as heating and dehydrating.

  A primer layer can be formed between the substrate and the polarizer. The primer layer increases the adhesion strength between the antireflection laminate and the polarizer. Examples of the material constituting the primer layer include polyester urethane resins, polyether urethane resins, polyisocyanate resins, polyolefin resins, resins having a hydrocarbon skeleton in the main chain, polyamide resins, acrylic resins, and polyester resins. Examples thereof include resins, vinyl chloride / vinyl acetate copolymers, chlorinated rubber, cyclized rubber, and modified products obtained by introducing polar groups into these polymers. Among these, a modified product of a resin having a hydrocarbon skeleton in the main chain and a modified product of a cyclized rubber can be suitably used.

Examples of the resin having a hydrocarbon skeleton in the main chain include a polybutadiene skeleton or a resin having a polybutadiene skeleton hydrogenated to at least a part thereof, specifically, a polybutadiene resin, a hydrogenated polybutadiene resin, a styrene / butadiene / styrene. Examples thereof include a block copolymer (SBS copolymer), a hydrogenated product thereof (SEBS copolymer), and the like. Among these, a modified product of a hydrogenated product of a styrene / butadiene / styrene block copolymer can be suitably used.

  As a compound for introducing a polar group used for obtaining a modified product of a polymer, a carboxylic acid or a derivative thereof is preferable. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; halides, amides, imides, anhydrides and esters of unsaturated carboxylic acids such as maleyl chloride, maleimide, maleic anhydride and citraconic anhydride And the like; and the like. Among these, a modified product with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is excellent in adhesion, and thus can be suitably used. Among the unsaturated carboxylic acids or anhydrides thereof, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are more preferable, and maleic acid and maleic anhydride are particularly preferable. These unsaturated carboxylic acids and the like can be modified by mixing two or more kinds.

  The method for forming the primer layer is not particularly limited, and examples thereof include a method in which a primer layer forming coating solution in which the resin is dissolved is applied onto a substrate by a known coating method. The thickness of the primer layer is not particularly limited, but is usually 0.01 to 5 μm, preferably 0.1 to 2 μm.

In the polarizing plate with an antireflection function of the present invention, the protective film (2) may be laminated via a primer layer on the surface of the polarizer on which the antireflection laminate of the present invention is not laminated.
Examples of the protective film (2) include those made of a resin such as a cellulose ester such as triacetyl cellulose and an alicyclic structure-containing polymer. However, the protective film (2) is an oil that is excellent in transparency, birefringence, dimensional stability, and the like. What consists of a cyclic structure containing polymer is preferable. Examples of the alicyclic structure-containing polymer are the same as those described in the explanation part of the substrate. The protective film (2) can be obtained by forming into a film by a solution casting method, a melt extrusion method, preferably a melt extrusion method, and stretching and orientation as necessary.

  The liquid crystal display device of the present invention comprises the polarizing plate with an antireflection function of the present invention. The liquid crystal display device usually has at least a liquid crystal cell and a polarizing plate sandwiching the liquid crystal cell. In the liquid crystal display device of the present invention, the polarizing plate with an antireflection function of the present invention is placed on the side far from the liquid crystal cell as the polarizing plate located on the viewing side of the two polarizing plates. Has been placed. The polarizing plate with antireflection function and the liquid crystal cell may be bonded together via a primer layer.

  The liquid crystal cell is not particularly limited depending on the liquid crystal mode. Liquid crystal modes include TN (Twisted Nematic), STN (Super Twisted Nematic), HAN (Hybrid Alignment Nematic), VA (Vertical Alignment), MVA (Multiple Alignment). OCB (Optical Compensated Bend) type, reflective type, transflective type, and the like.

  Next, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. The test and evaluation in an Example and a comparative example were performed with the following method.

(1) Refractive index Using a high-speed spectroscopic ellipsometry (model number: M-2000U, manufactured by JA Woollam), the measurement wavelength is 400-1000 nm, and the incident angles are measured at 55, 60, and 65 degrees, respectively. Calculated from measured values.
(2) Surface roughness Using a non-contact type three-dimensional structural analysis microscope (zygo NewView 5032: manufactured by Zygo Corporation), the surface roughness can be measured by scanning the uneven surface of the film and observing the interference fringes.
(3) Scratch resistance The surface state after rubbing the surface 10 times in a state where a load of 0.025 MPa was applied to steel wool # 0000 was visually observed.
○: Scratches are not recognized.
Δ: Slight scratches are observed.
X: Scratches are observed.

(4) Cross cut test Adhesiveness was calculated | required with the test method according to description of JIS-K5400-8.5.1. Specifically, 100 grid-like cuts reaching the substrate were made using a cutter guide with a gap interval of 1 mm. Next, a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., cello tape CT-18) is attached to the cut surface of the grid, and after rubbing with an eraser, it is peeled off vertically to visually determine adhesion from the following formula. It was.
Adhesion (%) = (1-peeling area / evaluation area) × 100

(5) Reflectance Using a spectrophotometer (UV-visible near-infrared spectrophotometer V-570, manufactured by JASCO Corporation), the wavelength spectrum is measured at an incident angle of 5 °, and the maximum rate at a wavelength of 430 to 700 nm is obtained. The reflectance at 550 nm was measured. The above measurement was performed five times at five different locations in the plane, and the arithmetic average value thereof was used as the reflectance value.

(6) Total light transmittance and reduction rate The total light transmittance is measured in accordance with JIS K7136 (2000) using “Durbidity Meter NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd. The same measurement is performed five times at five different places in the plane, and the arithmetic average value is calculated as a representative value of the total light transmittance.
The rate of decrease is obtained by the following equation. Td represents (3) the total light transmittance after the scratch resistance test, and Tc represents the total light transmittance before the scratch resistance test.
ΔT (%) = (Tc−Td) / Tc × 100

(7) Haze In accordance with JIS K7136 (2000), measurement is performed using “turbidimeter NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd. The average value is the haze value.

(8) Visibility Remove the liquid crystal display panel from the commercially available liquid crystal television (MVA mode, IPS mode 20V type liquid crystal television), peel off the polarizing plate installed on the viewing side of the liquid crystal cell, and change it. The polarizing plates obtained in the examples or comparative examples were bonded to the liquid crystal cell, the liquid crystal display panel was reassembled, and the original liquid crystal television was installed. The liquid crystal display element was displayed outdoors on a clear day, and the substrate was visually observed from the front side, and evaluated in the following three stages. Glare refers to discomfort or difficulty in seeing when a point or surface with excessively high brightness is visible in the field of view.
○: No glare or image blur.
Δ: There is a slight glare and blurring of the image, which is worrisome.
X: Glare and image blurring are conspicuous.

Preparation of hard coating agent 1 Antimony pentoxide modified alcohol sol (solid content 40%: manufactured by Catalytic Chemical Industry Co., Ltd.) 100 parts by weight, UV curable urethane acrylate (purple UV7640B: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 10 parts by weight And 0.4 part by weight of a photopolymerization initiator (Irgacure-184: manufactured by Ciba Geigy) and 0.1 part by weight of a fluorinated alkyl group-containing oligomer (Megafac F470: manufactured by Dainippon Ink & Chemicals, Inc.) are mixed and UV cured. A mold hard coat agent 1 was obtained.

Preparation of Hard Coat Agent 2 Phosphorus-doped stannic oxide (PTO) methyl ethyl ketone sol (solid content concentration 30%: manufactured by Catalyst Kasei Co., Ltd.) with 135 parts by weight of UV curable urethane acrylate (purple UV7640B: Nippon Synthetic Chemical Industry) 10 parts by weight) and a photopolymerization initiator (Irgacure-184: manufactured by Ciba Geigy) 0.4 parts by weight, fluorinated alkyl group-containing oligomer (Megafac F470: manufactured by Dainippon Ink & Chemicals, Inc.) 0.1 weight Partial mixing was performed to obtain a UV curable hard coat agent 2.

Preparation of hard coating agent 3 Antimony pentoxide modified alcohol sol (solid content concentration 40%: manufactured by Catalyst Kasei Kogyo Co., Ltd.), UV curable urethane acrylate (purple UV7640B: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 5 parts by weight And 0.5 parts by weight of a photopolymerization initiator (Irgacure-184: manufactured by Ciba Geigy) and 0.1 part by weight of a fluorinated alkyl group-containing oligomer (Megafac F470: manufactured by Dainippon Ink & Chemicals, Inc.) are mixed and UV cured. A mold hard coat agent 3 was obtained.

Preparation of Hard Coat Agent 4 Hard Coat Agent 4 was prepared in the same formulation as Hard Coat Agent 1 except that the fluorinated alkyl group-containing oligomer was not added.

Preparation of hard coating agent 5 Preparation of hard coating agent 1 was the same as hard coating agent 1 except that dimethyl silicone (TSF451-500: manufactured by GE Toshiba Silicone) was used instead of the fluorinated alkyl group-containing oligomer. Thus, hard coat agent 5 was obtained.

Preparation of hard coating agent 6 Hard coating agent 1 was prepared by using alkyl polyether (PO / EO) modified silicone oil (TSF4450: manufactured by GE Toshiba Silicone) instead of fluorinated alkyl group-containing oligomer. With the same formulation as coating agent 1, hard coating agent 6 was obtained.

Preparation of hard coating agent 7 Antimony pentoxide modified alcohol sol (solid content concentration 40%: manufactured by Catalyst Kasei Kogyo Co., Ltd.) 250 parts by weight, UV curable urethane acrylate (purple UV7640B: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 10 parts by weight And 0.5 parts by weight of a photopolymerization initiator (Irgacure-184: manufactured by Ciba Geigy) and 0.5 parts by weight of a fluorinated alkyl group-containing oligomer (Megafac F470: manufactured by Dainippon Ink & Chemicals, Inc.) are mixed and UV cured. A mold hard coat agent 7 was obtained.

Preparation of coating solution 1 for forming a low refractive index layer Tetramethoxysilane oligomer ("Methyl silicate 511" manufactured by Colcoat Co., Ltd.), methanol, water, and 0.01N hydrochloric acid aqueous solution were used in a weight ratio of 22: 36: 2. 2 and mixed in a high-temperature bath at 25 ° C. for 2 hours to obtain a silicone resin having a weight average molecular weight of 870.
Next, hollow silica isopropanol dispersion sol (solid content 25%, average primary particle diameter of about 30 nm, outer shell thickness of about 7 nm) is added to the silicone resin as hollow silica particles, and the hollow silica particles / silicone resin (condensation compound equivalent) is solid. The mixture was blended so that the weight ratio was 8: 2 on a minute basis, and then diluted with methanol so that the total solid content was 1% to prepare a coating solution 1 for forming a low refractive index layer.

Preparation of Coating Solution 2 for Forming Low Refractive Index Layer A tetramethoxysilane oligomer (“Methyl silicate 511” manufactured by Colcoat Co.) and methanol were mixed at a weight ratio of 47:79 to obtain solution A. Next, water, ammonia water (ammonia 28% by weight) and methanol were mixed at a weight ratio of 60: 1.2: 97.2 to obtain a liquid B. A liquid and B liquid were mixed by weight ratio 16:17, and the coating liquid 2 for low refractive index layer formation was obtained.

Preparation of coating solution 3 for forming low refractive index layer For forming low refractive index layer, except that the weight ratio of tetramethoxysilane oligomer to methanol was 47:72 in the preparation of coating solution 2 for low refractive index layer. A coating liquid 3 for a low refractive index layer was obtained with the same formulation of the coating liquid 2.

(Preparation of polarizer G)
A 85 μm thick PVA film (Kurarayvinilon # 7500) was attached to the chuck and immersed in an aqueous solution of 0.2 g / l iodine and 60 g / l potassium iodide at 30 ° C. for 240 seconds, and then boric acid 70 g / l. Then, the sample was immersed in an aqueous solution having a composition of 30 g / l potassium iodide and simultaneously subjected to boric acid treatment for 5 minutes while being uniaxially stretched 6.0 times. Finally, it was dried at room temperature for 24 hours to obtain a polarizer G. The degree of polarization was 99.993%.

Example 1
Using a norbornene polymer film having a thickness of 100 μm (Zeonor film ZF14-100, manufactured by Optes Co., Ltd., hereinafter referred to as “base material 1A”), both sides were used using a high-frequency transmitter (manufactured by Kasuga Electric Co., Ltd.) Corona discharge treatment was performed so that the surface tension was 0.072 N / m.
The hard coat agent 1 was applied to one side of this film using a die coater. Next, the substrate was dried at 80 ° C. for 5 minutes, irradiated with ultraviolet rays (accumulated light amount 300 mJ / cm ² ) to cure the hard coat agent 1 and obtain a substrate 1B on which a hard coat layer having a thickness of 5 μm was laminated. The coating liquid 1 for forming a low refractive index layer is applied to the surface of the substrate 1B having a hard coat layer by a micro gravure coater, and the coating is heat-treated at 120 ° C. for 5 minutes to form a low refractive index layer having a thickness of 100 nm. Was formed to obtain an antireflection film 1C.
An acrylic adhesive solution was applied to the surface of the antireflection film 1C on the base 1A side, and a polarizer G was bonded thereto. Next, another base material 1A was bonded to the polarizer G bonded to the antireflection film 1C to obtain a polarizing plate 1.

Example 2
The same procedure as in Example 1 was conducted except that a triacetyl cellulose (TAC) film (KC8UX2M: manufactured by Konica Minolta Co., Ltd.) having a thickness of 80 μm was used instead of the substrate 1A and the hard coating agent 2 was used instead of the hard coating agent 1. Thus, an antireflection film 2C and a polarizing plate 2 were obtained.

Example 3
Reflection was carried out in the same manner as in Example 1 except that a polyethylene terephthalate (PET) film (A4300: manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm was used instead of the substrate 1A and the hard coating agent 3 was used instead of the hard coating agent 1. The prevention film 3C and the polarizing plate 3 were obtained.

Comparative Example 1
An antireflection film 4C and a polarizing plate 4 were obtained in the same manner as in Example 1 except that the hard coating agent 4 was used instead of the hard coating agent 1.

Comparative Example 2
An antireflection film 5C and a polarizing plate 5 were obtained in the same manner as in Example 1 except that the hard coat agent 5 was used instead of the hard coat agent 1.

Comparative Example 3
An antireflection film 6C and a polarizing plate 6 were obtained in the same manner as in Example 1 except that the hard coating agent 6 was used instead of the hard coating agent 1.

Comparative Example 4
An antireflection film 7C and a polarizing plate 7 were obtained in the same manner as in Example 1 except that the hard coat agent 7 was used instead of the hard coat agent 1.

Comparative Example 5
An antireflection film 8C and a polarizing plate 8 were obtained in the same manner as in Example 1 except that the low refractive index layer forming coating solution 2 was used instead of the low refractive index layer forming coating solution 1 in Example 1. It was.

Comparative Example 6
An antireflection film 9C and a polarizing plate 9 were obtained in the same manner as in Example 1 except that the low refractive index layer forming coating solution 3 was used instead of the low refractive index layer forming coating solution 1 in Example 1. It was.

  The evaluation results of the antireflection films (that is, the antireflection laminates) 1C to 9C obtained in Examples 1 to 3 and Comparative Examples 1 to 6 are shown in Tables 1 and 2.

  From Table 1 and Table 2, it has a hard coat layer having an average surface roughness of 30 nm or less and a refractive index of 1.55 or more, a total light transmittance of 94% or more, a haze value of less than 1%, and resistance. The antireflection laminates of Examples 1 to 3 in which the decrease rate of the total light transmittance before and after the scratch test is 3% or less are free from unevenness and repellency of the low refractive index layer, and the hard coat layer and the low refractive index layer It can be seen that the adhesiveness is excellent, the balance of reflectance, haze, adhesiveness and scratch resistance is excellent, and the visibility is also excellent.

Claims (5)

A hard coat layer and a low refractive index layer are laminated in this order on a transparent resin substrate, the total light transmittance is 94% or more, the haze value is less than 1%, and the total light before and after the scratch resistance test. The rate of decrease in transmittance is 3% or less,
The hard coat layer contains 100 parts by weight of an active energy ray-curable resin, 300 to 800 parts by weight of inorganic oxide particles , and 0.5 to 2 parts by weight of a fluorinated alkyl group-containing oligomer . the average surface roughness (Ra) Ri der refractive index of 1.55 or more and a hard coat layer at 30nm or less,
The low refractive index layer comprises an airgel, the refractive index is 1.25 to 1.37 der Ru antireflection stack.   The antireflection laminate according to claim 1, wherein the transparent resin substrate comprises at least one resin selected from the group consisting of an alicyclic structure-containing polymer resin, a cellulose polymer resin, and a polyester polymer resin.   The antireflection laminate according to claim 1 or 2, wherein the metal oxide particles are antimony pentoxide or tin oxide doped with phosphorus.   A polarizing plate with an antireflection function, wherein a polarizer is laminated on the base material side of the antireflection laminate according to claim 1.   A liquid crystal display device comprising the polarizing plate with an antireflection function according to claim 4.