Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/02—Diffusing elements; Afocal elements
  • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
  • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
  • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
  • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
  • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/416—Reflective
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2551/00—Optical elements

Definitions

• the present invention relates to an optical film suitably used as a protective film for a polyvinyl alcohol polarizing film constituting a polarizing plate, an antiglare film having an antiglare layer formed on the optical film, and the optical film or antiglare film. Relates to a polarizing plate laminated on a polarizing film.
• the polarizing plate is widely used mainly for components of liquid crystal display devices.
• a polarizing plate usually circulates in a state where a protective film is laminated on at least one surface of a polarizing film made of a polyvinyl alcohol-based resin, and is incorporated into a liquid crystal display device or the like.
• a triacetyl cellulose film has been used as a protective film for a polyvinyl alcohol polarizing film constituting such a polarizing plate.
• triacetyl cellulose does not have sufficient moisture and heat resistance, and a polarizing plate using a triacetyl cellulose film as a protective film may deteriorate in performance such as degree of polarization and hue under high temperature and high humidity conditions. It was.
• the use of an acrylic resin excellent in transparency and moisture and heat resistance as a protective film in place of triacetylcellulose is being studied.
• the thickness of the acrylic resin layer is set to 40 ⁇ m or less, a thermoplastic resin layer that can be peeled off is formed on both surfaces, and the thermoplastic resin layers on both sides are peeled off before use. It is disclosed to use a protective film for a plate.
• a protective film having a three-layer structure of acrylic resin film / polyethyleneimine layer / polyvinyl alcohol resin layer is bonded to a polyvinyl alcohol polarizing film on the polyvinyl alcohol resin layer side, A polarizing plate is disclosed.
• JP2007-52404-A an adhesive layer / metal salt layer / protective film is provided in this order on one surface of a polyvinyl alcohol-based polarizing film to form a polarizing plate, and the protective film is composed of an acrylic resin. It is disclosed.
• JP2009-25762-A 0.1 to 1.5 parts by weight of a lubricant composed of a metal salt is blended with 100 parts by weight of a resin component mainly composed of an acrylic resin to form a protective film for a polarizing plate. Is disclosed.
• an antiglare film made of an acrylic resin film having a hard coat layer is laminated on one surface of a polyvinyl alcohol-based polarizing film and disposed on the viewing side of the liquid crystal display device.
• the acrylic resin constituting the antiglare film preferably contains acrylic rubber particles from the viewpoint of impact resistance and film-forming property of the film. is there.
• an acrylic resin is used as an optical film including a protective film for a polyvinyl alcohol polarizing film
• a phenomenon called squeezing is observed in which a dent or the like is observed on the outermost surface of the roll film. When such tightening occurs, the indentation or the like becomes a defect, and it is virtually impossible to apply to the optical film.
• the lubricant is specified as a metal salt, and then the lubricant composed of the metal salt is added to 100 parts by weight of the resin component. Contains ⁇ 1.5 parts by weight.
• the film surface can be made slippery by blending in a proportion of 0.0 parts by weight, preferably 0.1 to 0.8 parts by weight, to form a film.
• JP2004-151573-A is to form irregularities on the film surface with inorganic fine particles and to further increase the slipperiness with a lubricant, and is also disclosed in this document for acrylic resins. It is conceivable to improve the slipperiness of the film surface by blending such inorganic fine particles and a lubricant.
• One of the objects of the present invention is to improve the impact resistance and film-forming property of the film by blending rubber elastic particles into the acrylic resin as the main component, and to make it tight when rolled.
• An object of the present invention is to provide an optical film that does not easily occur.
• Another object of the present invention is to provide an optical film that is also used as a protective film for a polarizing film by imparting ultraviolet absorbing ability to the optical film.
• Still another object of the present invention is to provide an antiglare film in which an antiglare layer is formed on these optical films.
• another object of the present invention is to provide a polarizing plate in which these optical films or antiglare films are bonded to a polarizing film as a protective film, and are less likely to be wound when rolled. There is to do.
• the inventors of the present invention improve the slipperiness when a film is formed by blending a small amount of a lubricant with an acrylic resin composition mainly composed of an acrylic resin and containing a predetermined amount of rubber elastic particles. Thus, it has been found that winding tightening is less likely to occur, and bleeding out of the lubricant can be suppressed, and the present invention has been completed.
• the present invention includes the following.
• An optical film composed of a resin lubricant composition comprising 100 parts by weight of an acrylic resin composition and 0.01 to 0.09 part by weight of a lubricant, the acrylic resin composition comprising a transparent acrylic resin And elastic rubber particles having an average particle diameter of 10 to 300 nm, and the content of the elastic rubber particles is 25 to 45% by weight in the acrylic resin composition.
• the antiglare layer comprises 100 parts by weight of a transparent resin and 3 to 30 parts by weight of fine particles having an average particle size of 0.5 to 5 ⁇ m and a refractive index difference of 0.02 to 0.2 from the transparent resin.
• a polarizing plate comprising a polarizing film made of a polyvinyl alcohol-based resin and the optical film according to any one of [1] to [3] bonded to the polarizing film.
• a polarizing film comprising a polyvinyl alcohol-based resin, and an antiglare polarizing film comprising the antiglare film according to [4] or [5] bonded to the polarizing film on the side opposite to the antiglare layer Board.
• a predetermined amount of rubber elastic particles having a predetermined average particle diameter is blended with a transparent acrylic resin, and a small amount of lubricant is blended to improve the slip property of the film surface. For this reason, when the film is rolled, it is difficult for winding to occur and the productivity is excellent.
• a transparent acrylic resin is blended with a rubber elastic particle and a lubricant together with a UV absorber to impart UV absorbing ability, it becomes more suitable as a protective film for a polarizing film.
• These optical films or antiglare films having an antiglare layer formed on the surface thereof are useful as protective films for polyvinyl alcohol polarizing films, and these optical films or antiglare films are bonded to the polarizing films. Similarly, the polarizing plate is less likely to be tightened and has excellent productivity.
• the optical film of the present invention is composed of a resin lubricant composition containing 100 parts by weight of an acrylic resin composition and 0.01 to 0.09 parts by weight of a lubricant, and the acrylic resin composition is a transparent acrylic resin. And rubber elastic particles having an average particle diameter of 10 to 300 nm, and the content of the rubber elastic particles is 25 to 45% by weight in the acrylic resin composition.
• the acrylic resin is usually a polymer mainly composed of alkyl methacrylate. Specifically, a homopolymer of alkyl methacrylate or a copolymer using two or more kinds of alkyl methacrylate may be used, or 50 wt% or more of alkyl methacrylate and 50 wt% of monomers other than alkyl methacrylate. % Or less copolymer.
• alkyl methacrylate those having 1 to 4 carbon atoms in the alkyl group are usually used, and methyl methacrylate is preferably used.
• the monomer other than alkyl methacrylate may be a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule, or two or more polymerizable carbons in the molecule.
• -A polyfunctional monomer having a carbon double bond may be used, but a monofunctional monomer is particularly preferably used.
• alkyl acrylates such as methyl acrylate and ethyl acrylate
• styrene monomers such as styrene and alkyl styrene
• unsaturated nitriles such as acrylonitrile and methacrylonitrile.
• alkyl acrylate When alkyl acrylate is used as a copolymerization component, the alkyl group usually has about 1 to 8 carbon atoms.
• the monomer composition of the acrylic resin is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more based on the amount of the whole monomer. Further, it is preferably 99% by weight or less.
• This acrylic resin preferably does not have a glutarimide derivative, a glutaric anhydride derivative, a lactone ring structure, or the like.
• An acrylic resin having a cyclic structure such as a glutarimide derivative, a glutaric anhydride derivative, or a lactone ring structure tends to make it difficult to obtain sufficient mechanical strength and wet heat resistance as an optical film.
• the acrylic resin is a polymer in which the monomer is substantially composed only of alkyl methacrylate, or the alkyl methacrylate is, for example, 70% by weight or more, preferably 90% by weight of the monomer composition. It is preferable that the copolymer is composed of only the monomer selected from alkyl acrylate, styrene monomer and unsaturated nitrile.
• the rubber elastic body particles blended in the acrylic resin and constituting the acrylic resin composition are particles including a layer exhibiting rubber elasticity.
• the rubber elastic particles may be particles composed only of a layer exhibiting rubber elasticity, or may be particles having a multilayer structure having other layers together with a layer exhibiting rubber elasticity.
• Examples of the rubber elastic body include an olefin elastic polymer, a diene elastic polymer, a styrene-diene elastic copolymer, an acrylic elastic polymer, and the like. Of these, acrylic elastic polymers are preferably used from the viewpoints of surface hardness, light resistance, and transparency of the optical film.
• the acrylic elastic polymer can be composed of a polymer mainly composed of alkyl acrylate. This may be a homopolymer of alkyl acrylate or a copolymer of 50% by weight or more of alkyl acrylate and 50% by weight or less of other monomers.
• alkyl acrylate an alkyl acrylate having 4 to 8 carbon atoms is usually used.
• Examples of copolymerization of monomers other than alkyl acrylate include alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, styrene monomers such as styrene and alkylstyrene, acrylonitrile and methacrylo Monofunctional monomers such as unsaturated nitriles such as nitriles, alkenyl esters of unsaturated carboxylic acids such as allyl (meth) acrylate and methallyl (meth) acrylate, and dibasic acids such as diallyl maleate And polyfunctional monomers such as unsaturated carboxylic acid diesters of glycols such as alkylene glycol di (meth) acrylate.
• alkyl methacrylates such as methyl methacrylate and ethyl methacrylate
• styrene monomers such as styrene and alkylstyrene
• the rubber elastic particles containing the acrylic elastic polymer are preferably multi-layered particles having an acrylic elastic polymer layer.
• the thing of the 3 layer structure which has a polymer layer is mentioned.
• An example of the monomer composition in the polymer mainly composed of alkyl methacrylate constituting the hard polymer layer formed on the outside or inside of the acrylic elastic body is the methacrylic acid mentioned above as an example of the acrylic resin.
• acrylic rubber elastic particles having a multilayer structure can be produced, for example, by the method described in JPS55-27576-B.
• rubber elastic particles having an average particle diameter of the rubber elastic layer contained therein of 10 to 300 nm are used. Thereby, when it bonds to a polarizing film using an adhesive agent, the protective film which cannot peel easily from an adhesive bond layer can be obtained.
• the average particle size of the rubber elastic particles is preferably 50 nm or more, and preferably 250 nm or less.
• the average particle diameter of rubber elastic particles containing an acrylic elastic polymer is measured as follows. That is, when such rubber elastic particles are mixed with an acrylic resin to form a film and the cross section thereof is dyed with an aqueous solution of ruthenium oxide, only the rubber elastic layer is colored and observed in a substantially circular shape. Acrylic resin is not dyed. Therefore, from the cross section of the film dyed in this way, a thin piece is prepared using a microtome or the like, and this is observed with an electron microscope. And after extracting 100 dye
• the outermost layer is a hard polymer mainly composed of methyl methacrylate and rubber elastic particles in which an acrylic elastic polymer is encapsulated are used, when it is mixed with the base acrylic resin, The outermost layer of rubber elastic particles is mixed with the base acrylic resin. Therefore, when the cross section is dyed with ruthenium oxide and observed with an electron microscope, the rubber elastic particles are observed as particles excluding the outermost layer. Specifically, when rubber elastic particles having a two-layer structure in which the inner layer is an acrylic elastic polymer and the outer layer is a hard polymer mainly composed of methyl methacrylate, the acrylic elastic of the inner layer is used.
• the polymer part is dyed and observed as particles of a single layer structure, the innermost layer is a hard polymer mainly composed of methyl methacrylate, the intermediate layer is an acrylic elastic polymer, and the outermost layer is methacrylic.
• the innermost particle center portion is not dyed, and only the acrylic elastic polymer portion of the intermediate layer is dyed. It will be observed as particles having a two-layer structure.
• Such rubber elastic particles are blended in a proportion of 25 to 45% by weight based on the above-mentioned acrylic resin composition (total amount of transparent acrylic resin and rubber elastic particles).
• total amount of transparent acrylic resin and rubber elastic particles By blending rubber elastic particles at this ratio, the film-forming property is improved, the impact resistance of the resulting optical film is increased, and even a slight unevenness is formed on the film surface, so that slip properties are improved. Increases the effect.
• a resin lubricant composition is produced by blending a small amount of a lubricant with an acrylic resin composition in which a predetermined amount of rubber elastic particles are blended with the acrylic resin described above, and then formed into an optical film.
• the lubricant used for this purpose only needs to have a function of improving the slipperiness of the acrylic resin film surface.
• compounds having such functions include stearic acid compounds, acrylic compounds, ester compounds, and the like. Among these, in the present invention, stearic acid compounds are preferably used as lubricants.
• stearic acid compounds used as lubricants include stearic acid itself, as well as stearic acid esters such as methyl stearate, ethyl stearate, and monoglyceride stearate; stearic acid amides; sodium stearate, calcium stearate, stearic acid Metal stearates such as zinc, lithium stearate, magnesium stearate; 12-hydroxystearic acid, sodium 12-hydroxystearate, zinc 12-hydroxystearate, calcium 12-hydroxystearate, lithium 12-hydroxystearate Examples thereof include 12-hydroxystearic acid such as magnesium 12-hydroxystearate and a metal salt thereof. Of these, stearic acid is preferably used in the present invention.
• the blending amount of the lubricant is in the range of 0.01 to 0.09 parts by weight with respect to 100 parts by weight of the acrylic resin composition (the total of acrylic resin and rubber elastic particles).
• a more preferable blending amount of the lubricant is 0.03 parts by weight or more and 0.07 parts by weight or less with respect to 100 parts by weight of the acrylic resin composition. If the blending amount of the lubricant with respect to 100 parts by weight of the acrylic resin composition is less than 0.01 parts by weight, sufficient slipping of the film surface cannot be obtained, and winding tightening tends to occur. On the other hand, if the blending amount exceeds 0.09 parts by weight, the lubricant may bleed out from the film or the transparency of the film may be reduced.
• the resin lubricant composition in which the elastic rubber particles and the lubricant are blended with the acrylic resin may be any composition as long as it finally has the composition described above.
• an elastic resin containing rubber elastic particles is produced by first producing rubber elastic particles, polymerizing a monomer as a raw material of the acrylic resin in the presence thereof, and generating a base acrylic resin.
• a composition, a method of adding a predetermined amount of a lubricant to this, a rubber elastic body particle and an acrylic resin are mixed to obtain an acrylic resin composition of a predetermined composition, a predetermined amount of the lubricant is added thereto, and melt kneading, etc.
• the method of mixing etc. is mentioned.
• the resin lubricant composition in which a lubricant is blended with an acrylic resin composition used in the present invention further contains an ultraviolet absorber and has an ultraviolet absorbing ability when used as a film.
• an ultraviolet absorber and has an ultraviolet absorbing ability when used as a film.
• the liquid crystal display device intended as the main application of the polarizing plate of the present invention has a liquid crystal panel in which polarizing plates are bonded to both sides of the liquid crystal cell as a main component, and is enclosed in the liquid crystal cell.
• Liquid crystal materials are often deteriorated by ultraviolet rays.
• the liquid crystal panel's viewing side is exposed to sunlight and other external light, and the back side is exposed to light from the backlight, both of which contain ultraviolet rays. This is effective in preventing the deterioration of the liquid crystal substance in the liquid crystal cell.
• the ultraviolet absorber is a compound that absorbs ultraviolet rays having a wavelength of 400 nm or less.
• the optical film of the present invention is used as a protective film for a polyvinyl alcohol polarizing film
• the effect of improving the durability of the polarizing plate in which the protective film is bonded to the polarizing film is obtained by blending an ultraviolet absorber.
• the effect of protecting the liquid crystal substance in the liquid crystal cell in which the polarizing plate is disposed can also be obtained.
• the ultraviolet absorber known ones such as a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and an acrylonitrile ultraviolet absorber can be used.
• benzotriazole-based ultraviolet absorbers are preferable, for example, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl ) Phenol] is one of the preferred UV absorbers.
• the blending amount of the ultraviolet absorber can be selected in such a range that the transmittance of the optical film at a wavelength of 370 nm or less is preferably 10% or less, more preferably 5% or less, and further preferably 2% or less. Moreover, it is also preferable to mix
• the above-mentioned acrylic resin composition (acrylic resin and rubber elastic particles)
• the blending amount of the ultraviolet absorber is determined so as to satisfy the above-described transmittance from the range of about 0.1 to 2.5 parts by weight, particularly about 0.5 to 2 parts by weight with respect to 100 parts by weight. It is preferable to do.
• the ultraviolet absorber is premixed in an acrylic resin and pelletized, and this is formed into a film by melt extrusion or the like. Any method can be used.
• a resin lubricant composition in which rubber elastic particles and a lubricant are blended with an acrylic resin, or a composition in which a UV absorber is further blended is used as necessary.
• An infrared absorber is a compound that absorbs infrared rays having a wavelength of 800 nm or more.
• infrared absorbers are preferably selected so that they can absorb the entire infrared ray (light having a wavelength in the range of about 800 to 1100 nm), and two or more types may be used in combination.
• the compounding quantity of an infrared absorber can be suitably adjusted, for example so that the light transmittance in wavelength 800nm or more of an optical film may be 10% or less.
• the acrylic resin composition constituting the optical film of the present invention preferably has a glass transition temperature Tg in the range of 80 to 120 ° C. Further, this composition has high surface hardness when formed into a film.
• Tg glass transition temperature
• this composition preferably has a flexural modulus of not more than 1500 MPa, measured according to JIS K 7171: 2008 “Plastics—How to Obtain Bending Properties”, from the viewpoint of the flexibility of the optical film.
• the flexural modulus is more preferably 1300 MPa or less, and still more preferably 1200 MPa or less.
• This flexural modulus varies depending on the type and amount of acrylic resin and rubber elastic particles in the acrylic resin composition. For example, as the content of rubber elastic particles increases, the flexural modulus generally decreases. .
• the use of a copolymer of an alkyl methacrylate and an alkyl acrylate as an acrylic resin generally has a lower flexural modulus than using an alkyl methacrylate homopolymer.
• the bending elastic modulus is generally smaller when using the above-mentioned two-layered acrylic elastic polymer particles than using the above-mentioned three-layered acrylic elastic polymer particles.
• the use of acrylic elastic polymer particles having a single layer structure has a lower bending elastic modulus.
• the type and amount of acrylic resin and rubber elastic particles may be adjusted within the predetermined range so that the flexural modulus is 1500 MPa or less.
• the optical film of the present invention is formed from a resin lubricant composition in which a predetermined amount of rubber elastic particles are blended in an acrylic resin and a small amount of a lubricant is blended, and preferably a UV absorber is further blended.
• a resin lubricant composition in which a predetermined amount of rubber elastic particles are blended in an acrylic resin and a small amount of a lubricant is blended, and preferably a UV absorber is further blended.
• the layer that can exist other than the layer formed from the resin lubricant composition described above is not particularly limited in its composition, for example, an acrylic resin containing no rubber elastic particles or It may be a layer of the composition, or may be a layer formed from a composition of rubber elastic particles and acrylic resin whose content and average particle diameter are outside the ranges specified in the present invention. .
• it has a two-layer or three-layer structure, for example, a two-layer structure comprising a layer of a resin lubricant composition as defined in the present invention / a layer of an acrylic resin that does not contain rubber elastic particles or a composition thereof.
• the resin lubricant composition layer defined in the present invention / the acrylic resin not containing the rubber elastic particles or the composition layer / the resin lubricant composition layer defined in the present invention has a three-layer structure. .
• a layer formed from the resin lubricant composition defined in the present invention may be used as a bonding surface to the polarizing film.
• the contents of the rubber elastic particles and the above-described additives in each layer may be different from each other.
• a configuration in which layers containing no ultraviolet absorber and no infrared absorber are stacked with a layer containing an ultraviolet absorber and / or an infrared absorber interposed therebetween may be employed.
• the content of the ultraviolet absorber in the layer composed of the resin lubricant composition defined in the present invention is more than the content of the ultraviolet absorber in the layer composed of an acrylic resin not containing rubber elastic particles or the composition thereof, It may be made higher, and this makes it possible to efficiently block ultraviolet rays without deteriorating the color tone of the polarizing plate, and to prevent a decrease in the degree of polarization during long-term use.
• the optical film of the present invention is a resin lubricant composition in which a predetermined amount of rubber elastic particles are blended with the acrylic resin described above and a small amount of lubricant is blended, or a resin lubricant composition in which an ultraviolet absorber is blended. It can manufacture by forming into a film.
• this optical film is used as a protective film for a polyvinyl alcohol polarizing film, its thickness can be arbitrarily selected from the range of usually about 5 to 200 ⁇ m. The thickness is preferably 10 ⁇ m or more, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less.
• the resin lubricant composition described so far is melt-extruded and sandwiched between two metal rolls.
• the metal roll is preferably a mirror roll, whereby an optical film having excellent surface smoothness can be obtained.
• the resin lubricant composition defined in the present invention may be multilayer-extruded together with another acrylic resin or a composition thereof to form a film.
• the optical film can be subjected to a hard coat treatment from the viewpoint of preventing surface scratches in the assembly process of the liquid crystal module.
• surface treatment such as antistatic treatment can be performed.
• the antistatic function can be imparted by subjecting the optical film to a surface treatment, an adhesive layer, etc. It can also be applied to other parts of the polarizing plate in which this optical film is incorporated.
• Other examples of the surface treatment for the optical film include antireflection treatment and antifouling treatment.
• an antiglare treatment can be performed from the viewpoints of improving visibility, preventing reflection of external light, and reducing moire due to interference between the prism sheet and the color filter.
• a term will be explained anew and here, other functional layers are explained in order.
• the hard coat layer has a function of increasing the surface hardness of the optical film and is provided for the purpose of preventing scratches on the surface.
• the hard coat layer is a pencil hardness test defined in JIS K 5600-5-4: 1999 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 4: Scratch Hardness (Pencil Method)” It is preferable that the optical film on which the hard coat layer is formed is placed on a glass plate and measured) to show a value of 2H or harder.
• the material for forming such a hard coat layer is generally cured by heat or light.
• organic hard coat materials such as organic silicone, melamine, epoxy, acrylic, and urethane acrylate, and inorganic hard coat materials such as silicon dioxide can be used.
• urethane acrylate-based and polyfunctional acrylate-based hard coat materials are preferable because the adhesive strength of the base material to the acrylic resin film is good and the productivity is excellent.
• the hard coat layer contains various fillers for the purpose of adjusting the refractive index, improving the flexural modulus, stabilizing the volume shrinkage, and improving heat resistance, antistatic properties, antiglare properties, etc., if desired. can do.
• the hard coat layer can also contain additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a leveling agent, and an antifoaming agent.
• the antistatic layer is provided for the purpose of imparting conductivity to the surface of the film and suppressing the influence of static electricity.
• a method of applying a resin composition containing a conductive substance (antistatic agent) can be employed.
• an antistatic hard coat layer can be formed by allowing an antistatic agent to coexist in the hard coat material used for forming the hard coat layer described above.
• the antireflection layer is a layer for preventing reflection of external light, and is provided directly on the surface (surface exposed to the outside) of the optical film or via another layer such as a hard coat layer.
• the optical film provided with the antireflection layer preferably has a reflectance of 2% or less at an incident angle of 5 ° with respect to light having a wavelength of 430 to 700 nm, and in particular, the reflectance at the same incident angle with respect to light having a wavelength of 550 nm. Is preferably 1% or less.
• the thickness of the antireflection layer can be about 0.01 to 1 ⁇ m, and more preferably 0.02 to 0.5 ⁇ m.
• the antireflection layer is composed of a low refractive index layer having a refractive index smaller than the refractive index of the layer on which it is provided (such as an optical film or a hard coat layer), specifically, a refractive index of 1.30 to 1.45. Or a thin film made of an inorganic compound and a thin film made of an inorganic compound and a plurality of high refractive index layers laminated alternately.
• the material for forming the low refractive index layer is not particularly limited as long as it has a low refractive index.
• examples thereof include a resin material such as an ultraviolet curable acrylic resin, a hybrid material in which inorganic fine particles such as colloidal silica are dispersed in the resin, and a sol-gel material containing alkoxysilane.
• a resin material such as an ultraviolet curable acrylic resin
• Such a low refractive index layer may be formed by applying a polymer that has been polymerized, or may be formed by applying in the state of a monomer or oligomer that becomes a precursor, and then polymerizing and curing.
• each material contains the compound which has a fluorine atom in a molecule
• a material having a fluorine atom in the molecule is preferably used as the sol-gel material for forming the low refractive index layer.
• a typical example of a sol-gel material having a fluorine atom in the molecule is polyfluoroalkylalkoxysilane.
• Polyfluoroalkylalkoxysilanes can be represented, for example, by the formula: CF 3 (CF 2 ) n CH 2 CH 2 Si (OR) 3 Wherein R represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 12. Among these, compounds in which n in the above formula is 2 to 6 are preferable.
• polyfluoroalkylalkoxysilane include the following compounds. 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltrimethoxysilane, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyltrimethoxysilane, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyltriethoxysilane and the like.
• the low refractive index layer may be composed of a cured product of a thermosetting fluorine-containing compound or an ionizing radiation-curable fluorine-containing compound.
• This cured product preferably has a dynamic friction coefficient in the range of 0.03 to 0.15, and preferably has a contact angle with water in the range of 90 to 120 °.
• the curable fluorine-containing compound include polyfluoroalkyl group-containing silane compounds (for example, the above 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, In addition to 10,10-heptadecafluorodecyltriethoxysilane, etc.), fluorine-containing polymers having a crosslinkable functional group can be mentioned.
• the fluorine-containing polymer having a crosslinkable functional group is obtained by copolymerizing a fluorine-containing monomer and a monomer having a crosslinkable functional group, or by copolymerizing a fluorine-containing monomer and a monomer having a functional group, and then polymer. It can be produced by a method of adding a compound having a crosslinkable functional group to the functional group therein.
• fluorine-containing monomer used here examples include fluoroolefins such as fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, and others ( Examples thereof include partially or fully fluorinated alkyl ester derivatives of (meth) acrylic acid and completely or partially fluorinated vinyl ethers.
• Monomers having a crosslinkable functional group or compounds having a crosslinkable functional group include monomers having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate; monomers having a carboxyl group such as acrylic acid and methacrylic acid; Examples thereof include monomers having a hydroxyl group such as hydroxyalkyl methacrylate; monomers having an alkenyl group such as allyl acrylate and allyl methacrylate; monomers having an amino group; monomers having a sulfonic acid group.
• the material for forming the low refractive index layer includes a sol in which fine particles of inorganic compounds such as silica, alumina, titania, zirconia, and magnesium fluoride are dispersed in an alcohol solvent in that the scratch resistance can be improved.
• the inorganic compound fine particles used for this purpose are preferably those having a smaller refractive index from the viewpoint of antireflection properties.
• Such inorganic compound fine particles may have voids, and silica hollow fine particles are particularly preferable.
• the average particle diameter of the hollow fine particles is preferably in the range of 5 to 2000 nm, more preferably in the range of 20 to 100 nm.
• the average particle diameter here is a number average particle diameter obtained by observation with a transmission electron microscope.
• the antifouling layer is provided for imparting water repellency, oil repellency, sweat resistance, antifouling properties and the like.
• a suitable material for forming the antifouling layer is a fluorine-containing organic compound. Examples of the fluorine-containing organic compound include fluorocarbon, perfluorosilane, and high molecular compounds thereof.
• a method for forming the antifouling layer a physical vapor deposition method, a chemical vapor deposition method, a wet coating method, or the like typified by vapor deposition or sputtering can be used depending on the material to be formed.
• the average thickness of the antifouling layer is usually about 1 to 50 nm, preferably 3 to 35 nm.
• the optical film of the present invention formed from a resin lubricant composition in which a predetermined amount of rubber elastic particles are blended in an acrylic resin and a small amount of lubricant is blended, or from a resin lubricant composition in which a UV absorber is further blended. Further, an antiglare layer can be formed on the surface thereof to obtain an antiglare film. That is, the antiglare film is composed of an optical film and an antiglare layer having a fine surface irregularity formed on the surface thereof.
• the antiglare layer is a layer having a fine uneven shape on the surface, and is preferably formed from the hard coat material described above.
• the antiglare layer having a fine uneven shape on the surface includes a method of forming a coating film containing organic fine particles or inorganic fine particles on the surface of the optical film and providing unevenness based on the fine particles, or contains organic fine particles or inorganic fine particles.
• a coating film that does not contain it can be formed by a method (also called an embossing method) of transferring the uneven shape by pressing against a roll having an uneven shape on the surface.
• the method for forming the coating film include a method in which a coating liquid composed of a composition in which organic or inorganic fine particles are blended in a curable transparent resin is applied to the optical film surface.
• the fine particles When blending fine particles to form an antiglare layer, the fine particles should have an average particle size of 0.5 to 5 ⁇ m and a refractive index difference with the transparent resin of 0.02 to 0.2. Is preferred. By using fine particles whose average particle diameter and refractive index difference from the transparent resin are in this range, haze can be effectively expressed.
• the average particle diameter of the fine particles can be obtained by a dynamic light scattering method or the like. In this specification, the value obtained from the manufacturer was used as it is for the average particle size of the fine particles. This average particle size is the weight average particle size.
• silica, colloidal silica, alumina, alumina sol, aluminosilicate, alumina-silica composite oxide, kaolin, talc, mica, calcium carbonate, calcium phosphate and the like can be used.
• resin particles are generally used. For example, crosslinked polyacrylic acid particles, methyl methacrylate / styrene copolymer resin particles, crosslinked polystyrene particles, crosslinked polymethyl methacrylate particles, silicone resin particles, polyimide particles, etc. Is mentioned.
• the transparent resin for dispersing inorganic fine particles or organic fine particles is preferably selected from materials having high hardness (hard coat).
• a transparent resin a photocurable resin, a thermosetting resin, an electron beam curable resin, and the like can be used. From the viewpoint of productivity and the hardness of the obtained film, a photocurable resin is preferably used.
• a polyfunctional acrylate is used as the photocurable resin.
• polyfunctional acrylates can be used alone or in combination of two or more as required.
• a mixture of polyfunctional urethane acrylate, polyol (meth) acrylate, and (meth) acrylic polymer having an alkyl group containing two or more hydroxyl groups can be used as a photocurable resin.
• the polyfunctional urethane acrylate constituting the photocurable resin is produced using, for example, (meth) acrylic acid and / or (meth) acrylic acid ester, polyol, and diisocyanate. Specifically, by preparing hydroxy (meth) acrylate having at least one hydroxyl group in the molecule from (meth) acrylic acid and / or (meth) acrylic acid ester and polyol, and reacting it with diisocyanate, A polyfunctional urethane acrylate can be produced.
• the polyfunctional urethane acrylate produced in this way is also the photocurable resin itself listed above.
• (meth) acrylic acid and / or (meth) acrylic acid ester may be used singly or in combination of two or more, respectively, and polyol and diisocyanate are similarly used. One type may be used, or two or more types may be used in combination.
• (Meth) acrylic acid ester which is one raw material of polyfunctional urethane acrylate can be a linear or cyclic alkyl ester of (meth) acrylic acid. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, alkyl (meth) acrylate such as butyl (meth) acrylate, and cyclohexyl (meth). Examples include cycloalkyl (meth) acrylates such as acrylates.
• Polyol which is another raw material for polyfunctional urethane acrylate, is a compound having at least two hydroxyl groups in the molecule.
• Diisocyanate which is still another raw material of polyfunctional urethane acrylate, is a compound having two isocyanato groups (—NCO) in the molecule, and various aromatic, aliphatic, or alicyclic diisocyanates can be used. . Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4 '.
• the polyol (meth) acrylate constituting the above-mentioned photocurable resin together with the polyfunctional urethane acrylate is a (meth) acrylate of a compound having at least two hydroxyl groups in the molecule (that is, polyol).
• a (meth) acrylate of a compound having at least two hydroxyl groups in the molecule that is, polyol.
• Specific examples thereof include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
• polyol (meth) acrylates may be used alone or in combination.
• the polyol (meth) acrylate preferably comprises pentaerythritol triacrylate and / or pentaerythritol tetraacrylate.
• the (meth) acrylic polymer having an alkyl group containing two or more hydroxyl groups constituting the photocurable resin has two hydroxyl groups in one constituent unit. It has an alkyl group as described above.
• a polymer containing 2,3-dihydroxypropyl (meth) acrylate as a constituent unit, a polymer containing 2-hydroxyethyl (meth) acrylate as a constituent unit together with 2,3-dihydroxypropyl (meth) acrylate, and the like can be mentioned. .
• the adhesion with the optical film is improved, the mechanical strength is improved, and the surface is effectively prevented from being scratched. Can be obtained.
• Photopolymerization initiator Such a photocurable resin is combined with a photopolymerization initiator to form a photocurable resin composition.
• photopolymerization initiators such as acetophenone, benzophenone, benzoin ether, amine, and phosphine oxide.
• examples of compounds classified as acetophenone photopolymerization initiators include 2,2-dimethoxy-2-phenylacetophenone (also known as benzyldimethyl ketal), 2,2-diethoxyacetophenone, 1- (4-isopropylphenyl).
• 2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and the like.
• Examples of compounds classified as benzophenone-based photopolymerization initiators include benzophenone, 4-chlorobenzophenone, and 4,4′-dimethoxybenzophenone.
• Examples of compounds classified as benzoin ether photopolymerization initiators include benzoin methyl ether and benzoin propyl ether.
• Examples of compounds classified as amine photopolymerization initiators include N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (also known as Michler's ketone).
• Examples of the phosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• xanthone compounds and thioxant compounds are also known as photopolymerization initiators.
• photopolymerization initiators are commercially available. Examples of typical commercial products are “Irgacure 907” and “Irgacure 184" sold by Swiss Ciba, and "Lucirin TPO” sold by BASF Germany. is there.
• a solvent is added to the photocurable resin composition as necessary.
• any organic solvent that can dissolve each component constituting the composition such as ethyl acetate and butyl acetate, can be used.
• a mixture of two or more organic solvents can also be used.
• the photocurable resin composition may contain a leveling agent, and examples thereof include a fluorine-based or silicone-based leveling agent.
• silicone leveling agents include reactive silicone, polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane.
• the silicone leveling agents preferred are reactive silicone and siloxane leveling agents. When a leveling agent made of reactive silicone is used, the surface of the hard coat layer is provided with slipperiness, and excellent scratch resistance can be maintained for a long period of time. Further, if a siloxane leveling agent is used, film formability can be improved.
• the resin composition is optically used.
• a hard coat layer (antiglare layer) in which fine particles are dispersed in a transparent resin can be formed by coating on a film and irradiating light.
• the mold shape is transferred to a resin layer formed on an optical film using a mold having a fine irregularity shape. do it.
• the resin layer to which the uneven shape is transferred may or may not contain inorganic or organic fine particles.
• the uneven shape transfer by the embossing method is preferably a UV embossing method using an ultraviolet curable resin.
• an ultraviolet curable resin layer is formed on the surface of the optical film and cured while pressing the ultraviolet curable resin layer against the uneven surface of the mold, so that the uneven surface of the mold becomes an ultraviolet curable resin layer.
• an ultraviolet curable resin is applied onto the optical film, and the ultraviolet curable resin is irradiated with ultraviolet rays from the optical film side while the applied ultraviolet curable resin is in close contact with the uneven surface of the mold.
• the resin is cured, and then the shape of the mold is transferred to the ultraviolet curable resin by peeling the optical film on which the cured ultraviolet curable resin layer is formed from the mold.
• the kind in particular of ultraviolet curable resin is not restrict
• a visible light curable resin that can be cured with visible light having a wavelength longer than that of ultraviolet light by appropriately selecting a photopolymerization initiator may be used.
• the thickness of the antiglare layer is not particularly limited, but is generally 2 ⁇ m or more and 30 ⁇ m or less, preferably 3 ⁇ m or more, and preferably 20 ⁇ m or less.
• the thickness of the antiglare layer is less than 2 ⁇ m, sufficient hardness cannot be obtained and the surface tends to be easily damaged.
• the thickness is more than 30 ⁇ m, the antiglare layer is easily broken and is prevented by curing shrinkage of the antiglare layer. There is a tendency that the dazzling film curls and the productivity decreases.
• the antiglare film is given haze by the antiglare layer.
• the haze value of the antiglare film is preferably in the range of 5 to 50%. When the haze value is less than 5%, sufficient antiglare performance cannot be obtained, and external light tends to be reflected on the screen. On the other hand, in the area where the haze value exceeds 50%, the reflection of external light can be reduced, but the black display screen is reduced.
• the haze value is a ratio of diffuse transmittance to total light transmittance, and is measured according to JIS K 7136: 2000 “How to determine haze of plastic-transparent material”.
• the optical film formed from the resin lubricant composition described above or the antiglare film provided with an antiglare layer on the surface thereof can be bonded to a polarizing film as a protective film to form a polarizing plate.
• a polarizing film When bonding an anti-glare film to a polarizing film, it is bonded to a polarizing film on the surface opposite to the anti-glare layer.
• the optical film or the antiglare film of the present invention can be bonded to one surface of the polarizing film, and a protective film made of another resin can be bonded to the other surface of the polarizing film.
• the term “optical film” includes an antiglare film.
• the polarizing film can be a film obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film to obtain predetermined polarizing characteristics.
• the dichroic dye iodine or a dichroic organic dye is used.
• Such polarizing films include an iodine polarizing film in which iodine is adsorbed and oriented on a polyvinyl alcohol resin film, and a dye polarizing film in which a dichroic organic dye is adsorbed and oriented on a polyvinyl alcohol resin film.
• the polyvinyl alcohol resin constituting the polarizing film can be obtained by saponifying a polyvinyl acetate resin.
• the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and a copolymer of vinyl acetate and another monomer copolymerizable therewith.
• examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, and vinyl ethers.
• the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like can be used.
• the polarizing plate is usually a humidity adjusting step for adjusting the moisture of the polyvinyl alcohol-based resin film, a step for uniaxially stretching the polyvinyl alcohol-based resin film, and the dichroic pigment by dyeing the polyvinyl alcohol-based resin film with a dichroic pigment.
• Uniaxial stretching may be performed before dyeing, may be performed during dyeing, or may be performed during boric acid treatment after dyeing. You may uniaxially stretch in these several steps. Uniaxial stretching may be performed between rolls having different peripheral speeds, or may be performed using a hot roll. Moreover, the dry-type extending
• the thickness of the stretched and dyed polyvinyl alcohol polarizing film can be, for example, about 1 to 50 ⁇ m, preferably about 10 to 35 ⁇ m.
• An adhesive is generally used for laminating the polarizing film and the optical film.
• an adhesive having epoxy resin, urethane resin, cyanoacrylate resin, acrylamide resin, or the like as an adhesive component can be used.
• One of the adhesives preferably used is a solventless adhesive. Solventless adhesives do not contain a significant amount of solvent, and are curable compounds (monomers or oligomers) that are reactively cured by heating or irradiation with active energy rays (for example, ultraviolet rays, visible light, electron beams, X-rays, etc.).
• the adhesive layer is formed by curing of the curable compound, and typically includes a curable compound that is reactively cured by heating or irradiation of active energy rays, and a polymerization initiator.
• a curable compound that is reactively cured by heating or irradiation of active energy rays and a polymerization initiator.
• solventless adhesives those that are cured by cationic polymerization are preferable from the viewpoint of reactivity.
• solventless epoxy adhesives that use epoxy compounds as curable compounds include polarizing films, acrylic Since it is excellent in adhesiveness with the optical film which consists of resin or another resin film, it is used preferably.
• the epoxy compound which is a curable compound contained in the solvent-free epoxy adhesive, is preferably cured by cationic polymerization, and particularly contains no aromatic ring from the viewpoint of weather resistance, refractive index, and the like. It is more preferable to use an epoxy compound. Examples of such epoxy compounds that do not contain an aromatic ring in the molecule include hydrides of aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds. In addition, the epoxy compound that is a curable compound usually has two or more epoxy groups in the molecule.
• the hydride of an aromatic epoxy compound is a nuclear water obtained by selectively subjecting an aromatic polyhydroxy compound, which is a raw material of an aromatic epoxy compound, to an aromatic ring in the presence of a catalyst and under pressure.
• the additive polyhydroxy compound can be obtained by a method of glycidyl etherification.
• aromatic epoxy compounds include bisphenol-type epoxy compounds such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S; phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde Examples include novolak-type epoxy resins such as phenol novolac epoxy resins; glycidyl ethers of tetrahydroxyphenylmethane, glycidyl ethers of tetrahydroxybenzophenone, and polyfunctional epoxy resins such as epoxidized polyvinylphenol.
• Aromatic polyhydroxy compounds typified by these raw materials, bisphenols, are hydrogenated as described above, and epichlorohydrin is reacted with the hydroxyl groups to obtain hydrides of aromatic epoxy compounds. .
• hydrogenated glycidyl ether of bisphenol A is preferred as the hydride of the aromatic epoxy compound.
• the alicyclic epoxy compound means an epoxy compound having at least one epoxy group bonded to the alicyclic ring in the molecule, and “has at least one epoxy group bonded to the alicyclic ring in the molecule”.
• the alicyclic epoxy compound is a compound having at least one structure represented by the above formula in the molecule and a total of two or more epoxy groups in the molecule including the structure. More specifically, a compound in which a group in a form in which one or a plurality of hydrogen atoms in (CH 2 ) m in the above formula are removed is bonded to another chemical structure can be an alicyclic epoxy compound. One or more hydrogen atoms in (CH 2 ) m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group.
• a suitable alicyclic epoxy compound is illustrated concretely.
• the aliphatic epoxy compound can be a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof. More specifically, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, propylene Polyethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as glycol diglycidyl ether, ethylene glycol, propylene glycol, and glycerin Examples thereof include glycidyl ether.
• the epoxy compounds described above may be used alone or in combination of two or more.
• the epoxy equivalent of the epoxy compound contained in the solventless epoxy adhesive is usually in the range of 30 to 3000 g / equivalent, preferably 50 to 1500 g / equivalent.
• the epoxy equivalent is less than 30 g / equivalent, the flexibility of the optical film after the adhesive layer is cured may be reduced, or the adhesive strength may be reduced.
• the epoxy equivalent exceeds 3000 g / equivalent, the compatibility with other components contained in the epoxy adhesive may be lowered.
• the solventless epoxy adhesive usually contains a cationic polymerization initiator in order to cationically polymerize the epoxy compound.
• the cationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, electron beams, or heating, and initiates an epoxy group polymerization reaction. Any of these types of cationic polymerization initiators may be used, but it is preferable from the viewpoint of workability that the potential is imparted.
• a cationic polymerization initiator that generates a cationic species or a Lewis acid upon irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams and initiates a polymerization reaction of an epoxy group is a photocationic polymerization initiator. Also called.
• the adhesive component can be cured at room temperature, reducing the need to take into account the heat resistance of the polarizing film or distortion due to expansion. Can be formed.
• a cationic photopolymerization initiator when used, it acts catalytically by light, so that it is excellent in storage stability and workability even when mixed with an epoxy adhesive.
• photocationic polymerization initiator for example, aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; iron-allene complexes can be used.
• aromatic sulfonium salts are particularly preferable because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and thus can provide a cured product having excellent curability and good mechanical strength and adhesive strength. Used.
• photocationic polymerization initiators can be easily obtained as commercial products, for example, “Kayarad PCI-220” sold by Nippon Kayaku Co., Ltd., and “Kayarad PCI-620”, “UVI-6990” sold by Union Carbide, “Adekaoptomer SP-150” and “Adekaoptomer SP-170” sold by ADEKA Corporation, Nippon Soda ( “CI-5102”, “CIT-1370", “CIT-1682”, “CIP-1866S”, “CIP-2048S” and “CIP-2064S” sold by Midori Chemical Co., Ltd.
• the amount of the cationic photopolymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 part by weight or more, and preferably 15 parts by weight or less with respect to 100 parts by weight of the epoxy compound.
• the solventless epoxy adhesive can contain a photosensitizer as required in addition to the photocationic polymerization initiator.
• a photosensitizer By using a photosensitizer, the reactivity is improved and the mechanical strength and adhesive strength of the cured product can be improved.
• the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.
• the amount is about 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy compound.
• thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heating and initiates a polymerization reaction of an epoxy group
• a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heating and initiates a polymerization reaction of an epoxy group
• thermal cationic polymerization initiators can also be easily obtained as commercial products.
• “ADEKA OPTON CP77” and “ADEKA OPTON CP66” sold by ADEKA Co., Ltd.
• thermal cationic polymerization initiators may be used alone or in combination of two or more.
• a photocationic polymerization initiator and a thermal cationic polymerization initiator can be used in combination.
• the solventless epoxy adhesive may further contain a compound that promotes cationic polymerization, such as oxetanes and polyols.
• the polarizing film and the optical film can be bonded by applying the adhesive to the adhesive surface of the optical film and / or the polarizing film and bonding them together.
• the method of applying the solventless epoxy adhesive to the polarizing film and / or the optical film For example, various coatings such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater. A scheme is available.
• each coating method has an optimum viscosity range, the viscosity may be adjusted using a small amount of solvent.
• the solvent used for this is not particularly limited as long as it can dissolve the epoxy adhesive well without deteriorating the optical performance of the polarizing film.
• hydrocarbons typified by toluene, typified by ethyl acetate, and the like.
• Organic solvents such as esters can be used.
• the adhesive layer is cured by irradiating active energy rays or heating, and optical The film is fixed on the polarizing film.
• ultraviolet rays are preferably used.
• the ultraviolet light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a black light lamp, and a metal halide lamp.
• the irradiation intensity and irradiation amount of active energy rays such as ultraviolet rays are appropriately selected so as to sufficiently activate the cationic polymerization initiator and not adversely affect the cured adhesive layer, polarizing film, and optical film.
• the temperature and time at that time can sufficiently activate the cationic polymerization initiator, and the cured adhesive layer or It is appropriately selected so as not to adversely affect the polarizing film and the optical film.
• the thickness of the adhesive layer made of the epoxy adhesive after curing obtained as described above can usually be in the range of about 0.1 to 50 ⁇ m, preferably 1 ⁇ m or more. More preferably, it is in the range of 1 to 20 ⁇ m, more preferably 2 to 10 ⁇ m.
• the solvent-free epoxy adhesive described above is bonded between an optical film made of an acrylic resin and a polarizing film, or bonded between an optical film made of a resin film other than an acrylic resin and a polarizing film, or these It can use preferably for pasting of both.
• an aqueous adhesive that is, an adhesive component dissolved in water, or a dispersion of this in water.
• a water-based adhesive When a water-based adhesive is used, the thickness of the adhesive layer can be further reduced.
• water-based adhesives include those containing water-soluble crosslinkable epoxy resins or hydrophilic urethane resins as adhesive components.
• a water-soluble crosslinkable epoxy resin for example, a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine and a polyamide polyamine obtained by a reaction of a dicarboxylic acid such as adipic acid are reacted with epichlorohydrin. Mention may be made of the polyamide epoxy resin obtained.
• Commercially available products of such polyamide epoxy resins include “Smileys Resin 650” and “Smileys Resin 675” sold by Sumika Chemtex Co., Ltd. under the trade name.
• a water-soluble crosslinkable epoxy resin is used as the adhesive component
• it is preferable to mix other water-soluble resins such as a polyvinyl alcohol resin in order to further improve the coatability and adhesiveness.
• Polyvinyl alcohol resins are modified such as partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, as well as carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino group-modified polyvinyl alcohol.
• Polyvinyl alcohol resin may be used.
• a saponified product of a copolymer of vinyl acetate and unsaturated carboxylic acid or a salt thereof, that is, carboxyl group-modified polyvinyl alcohol is preferably used.
• carboxyl group-modified polyvinyl alcohol is preferably used.
• the “carboxyl group” is a concept including —COOH and a salt thereof.
• Examples of suitable commercially available carboxyl group-modified polyvinyl alcohols are “Kuraraypoval KL-506”, “Kuraraypoval KL-318” and “Kuraray” sold by Kuraray Co., Ltd. under the trade names.
• AF-17”, “AT-17”, and “AP-17” and the like which are sold by Vintner Poval Co., Ltd.
• An adhesive containing a water-soluble crosslinkable epoxy resin can be prepared as an aqueous adhesive solution by dissolving the above epoxy resin and other water-soluble resin such as a polyvinyl alcohol resin added as necessary in water.
• the water-soluble crosslinkable epoxy resin preferably has a concentration in the range of about 0.2 to 2 parts by weight with respect to 100 parts by weight of water.
• the amount is preferably about 1 to 10 parts by weight, more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of water.
• suitable urethane resins include ionomer type urethane resins, especially polyester type ionomer type urethane resins.
• the ionomer type is obtained by introducing a small amount of an ionic component (that is, a hydrophilic component) into a urethane resin constituting the skeleton.
• the polyester ionomer type urethane resin is a urethane resin having a polyester skeleton, into which a small amount of an ionic component (hydrophilic component) is introduced.
• Such an ionomer-type urethane resin is suitable as a water-based adhesive because it is emulsified directly in water without using an emulsifier to form an emulsion.
• polyester ionomer-type urethane resins include “Hydran AP-20” and “Hydran APX-101H” sold by DIC Corporation, both of which are in the form of emulsions. Available.
• the isocyanate-based crosslinking agent is a compound having at least two isocyanato groups (—NCO) in the molecule.
• Examples thereof include 2,4-tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,
• polyisocyanate monomers such as 6-hexamethylene diisocyanate and isophorone diisocyanate
• isocyanurate forms in which isocyanurate rings are formed at the part, and polyisocyanate modified forms such as burettes formed by hydration and decarboxylation of the three diisocyanate molecules at the respective one-end isocyanato groups.
• polyisocyanate modified forms such as burettes formed by hydration and decarboxylation of the three diisocyanate molecules at the respective one-end isocyanato groups.
• isocyanate crosslinking agents that can be suitably used include those sold by DIC Corporation under the trade name “Hydran Assist C-1.”
• the concentration of the urethane resin is about 10 to 70% by weight, further 20% by weight or more, and 50% by weight or less from the viewpoint of viscosity and adhesiveness. Thus, those dissolved or dispersed in water are preferred.
• the isocyanate crosslinking agent is blended, the blending amount is appropriately selected so that the isocyanate crosslinking agent is about 5 to 100 parts by weight with respect to 100 parts by weight of the urethane resin.
• the polarizing film and the optical film can be adhered by applying the adhesive to the adhesive surface of the optical film and / or the polarizing film and bonding them together. More specifically, a water-based adhesive is uniformly applied to a polarizing film and / or an optical film by, for example, a coating method such as a doctor blade, a wire bar, a die coater, a comma coater, or a gravure coater. The other film is stacked and bonded with a roll or the like and dried. Drying can be performed at a temperature of about 60 to 100 ° C., for example. In order to further improve the adhesiveness, it is preferable to cure for about 1 to 10 days after drying at a temperature slightly higher than room temperature, for example, a temperature of about 30 to 50 ° C.
• water-based adhesives are bonded to an optical film made of an acrylic resin and a polarizing film, or polarized with an optical film made of a resin other than an acrylic resin, like the solventless epoxy adhesive described above. It can use preferably for pasting with a film, or pasting of both of these.
• an optical film made of an acrylic resin is laminated on both surfaces of a polarizing film, an optical film made of an acrylic resin is laminated on one surface of the polarizing film, and an optical film made of a resin other than an acrylic resin is laminated on the other surface
• the same adhesive is used for adhering films laminated on both sides of the polarizing film.
• different adhesives may be used, but it is preferable to use the same adhesive in order to simplify the manufacturing process and reduce the number of constituent members of the polarizing plate.
• the corona discharge treatment is a treatment for activating the resin film disposed between the electrodes by discharging by applying a high voltage between the electrodes.
• the effect of corona discharge treatment varies depending on the type of electrode, electrode interval, voltage, humidity, type of resin film used, etc., but for example, the electrode interval is set to 1 to 5 mm and the moving speed is set to about 3 to 20 m / min. It is preferable to do this.
• a polarizing film is bonded to the treated surface via the adhesive as described above.
• Example 1 (Acrylic resin and acrylic elastic polymer particles) A copolymer having a weight ratio of methyl methacrylate / methyl acrylate of 96/4 was used as an acrylic resin.
• the innermost layer is a hard polymer polymerized with methyl methacrylate using a small amount of allyl methacrylate, and the intermediate layer is polymerized with butyl acrylate as the main component, and further using styrene and a small amount of allyl methacrylate.
• the outermost layer is a three-layered elastic particle made of a hard polymer obtained by polymerizing methyl methacrylate with a small amount of ethyl acrylate, up to an elastic body that is an intermediate layer Acrylic elastic polymer particles having an average particle size of 240 nm were used.
• Example 2 An acrylic resin film was produced in the same manner as in Example 1 except that the amount of stearic acid added was changed from 0.05 part to 0.03 part, and was wound around a 6-inch diameter core. When the film was stored for 3 months in the state of being wound on the core in this way, even after 3 months of storage, no tightening was observed, and no lubricant bleed-out was observed.
• Example 3 An acrylic resin film was produced in the same manner as in Example 1 except that the amount of stearic acid added was changed from 0.05 part to 0.07 part, and was wound around a 6-inch diameter core. When the film was stored for 3 months in the state of being wound on the core in this way, even after 3 months of storage, no tightening was observed, and no lubricant bleed-out was observed.
• Example 4 In Example 1, together with stearic acid as a lubricant, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole) as a benzotriazole-based ultraviolet absorber 2-yl) phenol] is added in an amount of 0.5 part with respect to a total of 100 parts by weight of the acrylic resin and acrylic elastic polymer particles, and the rest of the resin lubricant composition pellets are added in the same manner as in Example 1. Then, an acrylic resin film was produced from the pellets by the same melt extrusion method as in Example 1, and wound around a core having a diameter of 6 inches. This film exhibited a transmittance of 23% at a wavelength of 380 nm. When the film was stored for 3 months in the state of being wound on the core in this way, even after 3 months of storage, no tightening was observed, and no lubricant bleed-out was observed.
• Example 5 In Example 4, the blending amount of the benzotriazole-based UV absorber with respect to a total of 100 parts by weight of the acrylic resin and the acrylic elastic polymer particles was changed to 1.9 parts.
• a system resin film was prepared and wound around a 6-inch diameter core. This film showed a transmittance of 0.9% at a wavelength of 380 nm. When the film was stored for 3 months in the state of being wound on the core in this way, even after 3 months of storage, no tightening was observed, and no lubricant bleed-out was observed.
• Comparative Example 1 An acrylic resin film was produced in the same manner as in Example 1 except that stearic acid was not added, and was wound around a 6-inch diameter core. When the film was stored for 3 months in the state of being wound on the core in this way, tightening was observed after storage for 3 months.
• the tightening is a phenomenon in which the film is tightened in a rolled state, and a dent or the like is generated on the outermost surface of the rolled film.
• Comparative Example 2 An acrylic resin film was produced in the same manner as in Example 1 except that the amount of stearic acid added was changed from 0.05 part to 0.10 part, and wound around a 6-inch diameter core. When the film is stored for 3 months in the state of being wound on the core in this way, although squeezing does not occur, bleed out of stearic acid occurs.
• Example 6 (Preparation of coating solution for antiglare layer formation) It contains pentaerythritol triacrylate and polyfunctional urethanized acrylate (reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate), the former / latter weight ratio is 60/40, and the total concentration of both is 60%.
• a photocurable resin composition dissolved in ethyl acetate and further containing a leveling agent was prepared.
• the pentaerythritol triacrylate and polyfunctional urethanized acrylate constituting the photocurable resin composition are collectively referred to as “curable acrylate”.
• the photo-curing resin composition used here was formed into a film by adding the above-mentioned photopolymerization initiator, and the refractive index of the resin cured by UV irradiation was 1.53, whereas the above-mentioned methyl methacrylate / The refractive index of the styrene copolymer resin particles was 1.49. Therefore, the refractive index difference between them was 0.04.
• Example 7 Preparation of polarizing plate
• a triacetyl cellulose film, a norbornene-based resin film, or a polypropylene-based resin film (each of which a phase difference may be imparted) are bonded via an adhesive, respectively, to be used suitably for a liquid crystal display device.
• a dazzling polarizing plate is obtained.

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• Physics & Mathematics (AREA)
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