JP2011123168A - Polarizing plate - Google Patents

Abstract

Disclosed is a polarizing plate in which an acrylic resin film is laminated on both surfaces of a polarizing film made of polyvinyl alcohol resin via an adhesive layer, and has excellent adhesion between the polarizing film and the film. To provide.
The present invention provides a polarizing plate in which an acrylic resin film is laminated on at least one surface of a polarizing film made of a polyvinyl alcohol resin via an adhesive layer, the acrylic resin film comprising: A copolymer of methyl methacrylate and methyl acrylate having a copolymerization ratio of methyl acrylate of 5% by weight or more and rubber elastic particles, and having an in-plane retardation of 10 nm or less, The polarizing plate is characterized in that the agent layer is a layer formed by curing an active energy ray-curable composition containing an oxetane compound and a cationic polymerization initiator.
[Selection figure] None

Description

  The present invention relates to a polarizing plate in which a protective film is laminated on at least one surface of a polarizing film.

  In recent years, low-power consumption, low-voltage, lightweight, and thin liquid crystal display devices have been widely used for information display devices such as mobile phones, portable information terminals, computer monitors, and televisions. Such an information display device is required to have reliability in a harsh environment depending on the application. For example, a liquid crystal display device for a car navigation system may have a very high temperature and humidity in the car in which it is placed, and the required temperature and humidity conditions compared to a normal television or personal computer monitor. Is severe. For such applications, a polarizing plate constituting a liquid crystal display device is also required to have high durability.

  The polarizing plate usually has a structure in which a transparent protective film is laminated on both sides or one side of a polarizing film made of a polyvinyl alcohol-based resin having a dichroic dye adsorbed and oriented. In general, a film made of triacetyl cellulose is used as the protective film, and the protective film is bonded to the polarizing film via an adhesive made of an aqueous solution of a polyvinyl alcohol resin. However, a polarizing plate made by laminating a protective film made of triacetylcellulose has a high moisture permeability of triacetylcellulose, so that when used for a long time in a high-humidity heat environment, the polarizing performance is deteriorated or protected. The film and the polarizer may peel off.

  Thus, it has been known so far to use an acrylic resin film as a protective film for a polarizing plate having a lower moisture permeability than a triacetyl cellulose film (Patent Documents 1 and 2). It has also been proposed to use a curable composition containing an epoxy resin as a main component for adhesion between the acrylic resin film and the polarizing film (Patent Document 3). Any means is expected to improve the moisture resistance of the polarizing plate by using an acrylic resin film having a low moisture permeability as a protective film for the polarizing plate, and in addition to an adhesive made of a polyvinyl alcohol aqueous solution, an epoxy type It is expected that the heat resistance of the polarizing plate is improved by using the resin composition as an adhesive.

  However, a polarizing plate using an acrylic resin film as a protective film has a weak adhesive force between the acrylic resin film and the polarizing film, and the interface may open during processing such as cutting of the polarizing plate. In addition, even when the epoxy resin composition is used as an adhesive, in a severe environment such as high temperature and high humidity, the polarizing film bonded to the liquid crystal cell may be damaged or discolored or protected. The film sometimes peeled off from the polarizing film.

JP 2009-122645 A JP 2009-163216 A JP 2009-210592 A

  An object of the present invention is a polarizing plate in which an acrylic resin film is laminated on at least one surface of a polarizing film made of a polyvinyl alcohol resin via an adhesive layer, the polarizing film and the acrylic resin film, It is in providing the polarizing plate excellent in adhesiveness.

  According to the present invention, there is provided a polarizing plate in which an acrylic resin film is laminated on at least one surface of a polarizing film made of a polyvinyl alcohol resin via an adhesive layer, and the acrylic resin film is an acrylic film. A copolymer of methyl methacrylate and methyl acrylate having a copolymerization ratio of methyl acrylate of 5% by weight or more and rubber elastic particles, and having an in-plane retardation of 10 nm or less, and the adhesive layer Is a layer formed by curing an active energy ray-curable composition containing an oxetane compound and a cationic polymerization initiator.

  In this polarizing plate, an olefin resin film is preferably laminated on the surface of the polarizing film opposite to the surface on which the acrylic resin film is laminated.

  Since the polarizing plate of the present invention uses an acrylic resin film as a protective film and the in-plane retardation is controlled to 10 nm or less, the liquid crystal display device to which it is applied conventionally uses a triacetyl cellulose film. In addition to having a display quality comparable to that of an acrylic resin film, the copolymerization ratio of methyl acrylate in the acrylic copolymer constituting the acrylic resin film is set to a specific value or more, and the oxetane compound is laminated on the polarizing film. And a cured layer of an active energy ray-curable composition containing a cationic polymerization initiator, the laminated surface has a stronger adhesive force than before, and a liquid crystal display device using the laminated surface is in a harsh environment It will be excellent in reliability.

  Hereinafter, the present invention will be described in detail. The polarizing plate of the present invention is obtained by laminating an acrylic resin film via an adhesive layer on at least one surface of a polarizing film made of a polyvinyl alcohol resin.

[Polarized film]
The polarizing film used in the present invention is usually a step of uniaxially stretching a polyvinyl alcohol resin film by a known method, a step of adsorbing a dichroic dye by dyeing the polyvinyl alcohol resin film with a dichroic dye. The polyvinyl alcohol-based resin film on which the dichroic dye is adsorbed is manufactured through a step of treating with a boric acid aqueous solution and a step of washing with water after the treatment with the boric acid aqueous solution.

  As the polyvinyl alcohol resin, a saponified polyvinyl acetate resin can be used. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers with other monomers copolymerizable with vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

  The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. This polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, and preferably about 1,500 to 5,000.

  What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of a polarizing film. The method for forming the polyvinyl alcohol-based resin into a film is not particularly limited, and a known method is employed. The film thickness of the polyvinyl alcohol-based raw film is not particularly limited, but is, for example, about 10 μm to 150 μm.

  Uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing the dichroic dye. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before boric acid treatment or during boric acid treatment. Moreover, you may uniaxially stretch in these several steps.

  In uniaxial stretching, it may be uniaxially stretched between rolls having different peripheral speeds, or may be uniaxially stretched using a hot roll. Further, this uniaxial stretching may be dry stretching in which stretching is performed in the air, or wet stretching in which a polyvinyl alcohol-based resin film is stretched using a solvent such as water or an organic solvent. May be. The draw ratio is usually about 3 to 8 times.

  As a method of dyeing the polyvinyl alcohol resin film with the dichroic dye, for example, a method of immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichroic dye is employed. As the dichroic dye, iodine or a dichroic dye is used. In addition, it is preferable that the polyvinyl alcohol-type resin film performs the immersion process to water before a dyeing process.

  When iodine is used as the dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is usually employed. The content of iodine in this aqueous solution is usually about 0.01 to 1 part by weight per 100 parts by weight of water. The content of potassium iodide is usually about 0.5 to 20 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C. Moreover, the immersion time (dyeing time) in this aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic dye is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed. The content of the dichroic dye in this aqueous solution is usually about 1 × 10 ⁻⁴ to 10 parts by weight and preferably about 1 × 10 ⁻³ to 1 part by weight per 100 parts by weight of water. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the aqueous dichroic dye solution used for dyeing is usually about 20 to 80 ° C. Moreover, the immersion time (dyeing time) in this aqueous solution is usually about 10 to 1,800 seconds.

  The boric acid treatment after dyeing with a dichroic dye can usually be performed by immersing the dyed polyvinyl alcohol-based resin film in a boric acid-containing aqueous solution. The amount of boric acid in the boric acid-containing aqueous solution is usually about 2 to 15 parts by weight per 100 parts by weight of water, and preferably 5 to 12 parts by weight. When iodine is used as the dichroic dye, the boric acid-containing aqueous solution preferably contains potassium iodide. The amount of potassium iodide in the boric acid-containing aqueous solution is usually about 0.1 to 15 parts by weight and preferably about 5 to 12 parts by weight per 100 parts by weight of water. The immersion time in the boric acid-containing aqueous solution is usually about 60 to 1,200 seconds, preferably about 150 to 600 seconds, and more preferably about 200 to 400 seconds. The temperature of the boric acid-containing aqueous solution is usually 50 ° C or higher, preferably 50 to 85 ° C, and more preferably 60 to 80 ° C.

  The polyvinyl alcohol resin film after the boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by immersing a boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the water washing treatment is usually about 5 to 40 ° C. Further, the immersion time is usually about 1 to 120 seconds.

  After washing with water, a drying process is performed to obtain a polarizing film. The drying process can be performed using a hot air dryer or a far infrared heater. The temperature of the drying treatment is usually about 30 to 100 ° C, and preferably 50 to 80 ° C. The time for the drying treatment is usually about 60 to 600 seconds, and preferably 120 to 600 seconds.

  By the drying treatment, the moisture content of the polarizing film is reduced to a practical level. The water content is usually 5 to 20% by weight, preferably 8 to 15% by weight. When the moisture content is less than 5% by weight, the flexibility of the polarizing film is lost, and the polarizing film may be damaged or broken after drying. Moreover, when a moisture content exceeds 20 weight%, it may be inferior to the thermal stability of a polarizing film.

  The thickness of the polarizing film on which the dichroic dye thus obtained is adsorbed and oriented can usually be about 5 to 40 μm.

[Acrylic resin film]
The acrylic resin film used in the present invention comprises a copolymer of methyl methacrylate and methyl acrylate having a copolymerization ratio of methyl acrylate of 5% by weight or more, and rubber elastic particles. Usually, it is obtained by forming a film of an acrylic resin composition containing the copolymer and rubber elastic particles.

[Copolymer of methyl methacrylate and methyl acrylate]
The copolymer of methyl methacrylate and methyl acrylate used in the present invention is an acrylic copolymer containing 5% by weight or more of methyl acrylate units, with the total of methyl methacrylate units and methyl acrylate units being 100% by weight. It is. This copolymer can be usually obtained by polymerizing a monofunctional monomer containing methyl methacrylate and methyl acrylate in the presence of a radical polymerization initiator and a chain transfer agent.

  By making the copolymerization ratio of methyl acrylate 5% by weight or more and using an active energy ray-curable compound described later as an adhesive with a polarizing film, the polarizing plate has excellent durability.

  The copolymerization ratio of methyl acrylate is 5% by weight or more, and the upper limit thereof is not particularly limited as long as the effect of the present invention is not impaired, but is generally 40% by weight or less, and preferably 20% by weight or less.

  In addition, a third monofunctional monomer can be copolymerized with the acrylic copolymer as long as the effects of the present invention are not impaired. If desired, a small amount of a polyfunctional monomer can be copolymerized.

  Examples of the third monofunctional monomer that can be copolymerized with methyl methacrylate and methyl acrylate include, for example, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate. , And methacrylates other than methyl methacrylate, such as 2-hydroxyethyl methacrylate; ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and acrylic acid 2 Acrylic esters such as hydroxyethyl; methyl 2- (hydroxymethyl) acrylate, methyl 2- (1-hydroxyethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, and 2- Hydroxyalkyl acrylates such as (hydroxymethyl) butyl acrylate; Unsaturated acids such as methacrylic acid and acrylic acid; Halogenated styrenes such as chlorostyrene and bromostyrene; Substituted styrenes such as vinyltoluene and α-methylstyrene And unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated acid anhydrides such as maleic anhydride and citraconic anhydride; unsaturated imides such as phenylmaleimide and cyclohexylmaleimide. Each of these may be used alone, or a plurality of different types may be used in combination.

  When copolymerizing polyfunctional monomers, examples of polyfunctional monomers that can be copolymerized with methyl methacrylate and methyl acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene. Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, etc. Esterified with methacrylic acid; Propylene glycol or its oligomers hydroxylated at both terminal hydroxyl groups with acrylic acid or methacrylic acid; Neopentyl glycol di (meth) acrylate, One obtained by esterifying a hydroxyl group of a dihydric alcohol such as xanthdiol di (meth) acrylate and butanediol di (meth) acrylate with acrylic acid or methacrylic acid; bisphenol A, alkylene oxide adduct of bisphenol A, or halogens thereof Those obtained by esterifying hydroxyl groups at both ends of the substituent with acrylic acid or methacrylic acid; those obtained by esterifying polyhydric alcohols such as trimethylolpropane and pentaerythritol with acrylic acid or methacrylic acid, and glycidyl acrylate or glycidyl at these terminal hydroxyl groups Ring-opening addition of an epoxy group of methacrylate; dibasic acids such as succinic acid, adipic acid, terephthalic acid, phthalic acid, and halogen-substituted products thereof, and alkylene oxy Id adducts as epoxy group of glycidyl acrylate or glycidyl methacrylate was ring-opening addition to the like; aryl (meth) acrylate; and aromatic divinyl compounds such as divinylbenzene. Among these, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neopentyl glycol dimethacrylate are preferably used.

  The acrylic copolymer having such a composition may be further modified by a reaction between functional groups of the copolymer. As the reaction, for example, demethanol condensation reaction in a polymer chain between a methyl ester group of methyl acrylate and a hydroxyl group of methyl 2- (hydroxymethyl) acrylate, a carboxyl group of acrylic acid and 2- (hydroxymethyl) acrylic Examples thereof include a dehydration condensation reaction in a polymer chain with a hydroxyl group of methyl acid.

  The glass transition temperature of the acrylic copolymer is preferably in the range of 80 to 120 ° C. In order to adjust the glass transition temperature of the acrylic copolymer to the above range, the polymerization ratio of the methacrylic acid ester monomer to the acrylic acid ester monomer, the carbon chain length of each ester group and the amount thereof are usually A method of appropriately selecting the type of functional group and the polymerization ratio of the polyfunctional acrylic monomer to the whole monomer; by intramolecular reaction as described above, a lactone ring structure, an acid anhydride ring structure, an imide ring structure, etc. For example, a method of introducing a rigid structural unit into a copolymer molecule is employed.

  The acrylic copolymer used in the present invention can be easily obtained as a commercial product. For example, under the trade name, Sumipex (manufactured by Sumitomo Chemical Co., Ltd.), Acripet (manufactured by Mitsubishi Rayon Co., Ltd.), Delpet (manufactured by Asahi Kasei Co., Ltd.), parapet (manufactured by Kuraray Co., Ltd.), acryl viewer (manufactured by Nippon Shokubai Co., Ltd.), etc.

[Rubber elastic particles]
The rubber elastic particles contained in the acrylic resin film used in the present invention may be particles composed of only one kind of rubber elastic body, or a multilayer structure or rubber having two or more layers of rubber elastic bodies. It may be a multi-layered particle having a hard layer in addition to the elastic layer. Examples of the rubber elastic body include olefin-based elastic polymers, diene-based elastic polymers, styrene-diene-based elastic copolymers, and acrylic-based elastic polymers. Among these, an acrylic elastic polymer is preferably used from the viewpoint of the surface hardness, light resistance, and transparency of the polarizer protective film.

  The acrylic elastic polymer may be a polymer mainly composed of alkyl acrylate, may be a homopolymer of alkyl acrylate, or may be a single polymer other than alkyl acrylate of 50% by weight or more and alkyl acrylate. A copolymer with 50% by weight or less of the monomer may be used. As the alkyl acrylate, those having 4 to 8 carbon atoms in the alkyl group are usually used. Examples of monomers other than alkyl acrylate include alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, styrene monomers such as styrene and alkyl styrene, and unsaturated nitriles such as acrylonitrile and methacrylonitrile. Monofunctional monomers such as alkenyl esters of unsaturated carboxylic acids such as allyl (meth) acrylate and methallyl (meth) acrylate, dialkenyl esters of dibasic acids such as diallyl maleate, alkylene glycol di (meth) ) Polyfunctional monomers such as unsaturated carboxylic acid diesters of glycols such as acrylates.

  The rubber elastic particles containing the acrylic elastic polymer are preferably multi-layered particles having an acrylic elastic polymer layer, and a polymer layer mainly composed of alkyl methacrylate is provided outside the acrylic rubber elastic body. It may be a two-layer structure or a three-layer structure having a polymer layer mainly composed of alkyl methacrylate inside the acrylic rubber elastic body. An example of the monomer composition of the polymer mainly composed of alkyl methacrylate constituting the layer formed on the outside or inside of the acrylic rubber elastic body is the alkyl methacrylate mentioned above as an example of the acrylic resin. It is the same as that of the example of the monomer composition of the polymer which has as a main component. Such acrylic rubber elastic particles having a multilayer structure can be produced, for example, by the method described in Japanese Patent Publication No. 55-27576.

  The number average particle diameter of the rubber elastic particles is preferably in the range of 10 to 300 nm, and more preferably in the range of 50 to 250 nm. Rubber elastic particles having a number average particle size of less than 10 nm are generally difficult to produce and may have poor handling properties when blended. Further, when the number average particle diameter of the rubber elastic particles exceeds 300 nm, whitening may occur during the production or processing of the acrylic resin film.

  Here, the number average particle diameter of the rubber elastic particles is the diameter of the portion that is dyed and observed in a substantially circular shape when the cross section of the acrylic resin film is stained with ruthenium oxide and observed with an electron microscope. Number average value.

[Acrylic resin composition]
The ratio of methyl methacrylate and methyl acrylate copolymer and rubber elastic particles in the acrylic resin composition constituting the acrylic resin film is such that the total is 100 parts by weight, and the copolymer is 55 to 85 weights. The rubber elastic particles are preferably in the range of 15 to 45 parts by weight, more preferably the copolymer is in the range of 60 to 80 parts by weight, and the rubber elastic body particles are in the range of 20 to 40 parts by weight.

  When the blending amount of the rubber elastic particles is less than 15 parts by weight, the acrylic resin film lacks flexibility and its handling property may be lowered. On the other hand, if the amount of the elastic rubber particles exceeds 45 parts by weight, the surface hardness of the polarizer protective film may be lowered.

  As a method for producing the acrylic resin composition, for example, after obtaining rubber elastic particles, a method of polymerizing monomers in the presence thereof, after obtaining the copolymer and rubber elastic particles, For example, a method of forming a pellet having a diameter or length of about 2 to 10 mm by melting and kneading with an extruder is used.

  Moreover, if necessary, prepare rubber pellets containing the rubber elastic particles in the copolymer in an amount of about 2 to 20 times the required amount, and mix with pellets that do not contain rubber elastic particles during film formation to be described later. Thus, a method of obtaining a film in which rubber elastic particles are adjusted to a required amount is also preferably employed.

  In the acrylic resin composition thus obtained, if necessary, coloring agents including pigments and dyes, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers, infrared absorbers, ultraviolet absorbers, You may contain additives, such as an antistatic agent, antioxidant, and a lubrication agent.

  The flexural modulus of the acrylic resin composition is preferably 3000 MPa or less, more preferably 2800 MPa or less, and further preferably 2500 MPa or less from the viewpoint of flexibility. This flexural modulus is a value measured according to JIS K7171.

  This flexural modulus is adjusted by the blending amount, composition ratio and structure of the rubber elastic particles in the acrylic resin composition, and the blending amount, composition ratio and structure of the copolymer of methyl methacrylate and methyl acrylate. can do. For example, the flexural modulus can generally be reduced by increasing the copolymerization ratio of the alkyl acrylate of the acrylic copolymer and by making the alkyl ester structural unit a flexible long-chain hydrocarbon group. On the other hand, as the content of the rubber elastic particles is increased and the average particle size thereof is decreased, generally, the flexural modulus can be decreased. As the rubber elastic particles, the acrylic elastic weight of the three-layer structure is used. Rather than using coalesced particles, it is generally possible to reduce the flexural modulus by using the acrylic elastic polymer particles having the two-layer structure, and it is more preferable to use acrylic elastic polymer particles having a single-layer structure. In general, the flexural modulus can be reduced.

[Deposition of acrylic resin composition]
The acrylic resin composition thus obtained can be formed into an acrylic resin film. A method for forming the acrylic resin composition is not particularly limited, but a melt extrusion film forming method is preferably employed.

  The melt-extrusion film-forming method is usually a method in which a thermoplastic resin is introduced into an extruder and melted, and a film-like molten resin is extruded from a T-die and taken on a cooling roll as it is to be cooled and solidified to continuously form a long film. The method of obtaining. Here, the thickness of the film can be determined by appropriately controlling the lip interval of the T die. The acrylic resin film has a thickness of usually 100 μm or less, preferably 40 to 80 μm.

  The acrylic resin film can be a single layer film or a multilayer film having two or more layers. In order to obtain a multilayer film, a method is generally adopted in which a plurality of extruders are installed in the melt extrusion film forming method described above, and the molten resin that has passed through each extruder is extruded so as to be multilayered in a T-die. The In addition, as other methods, a plurality of extruders and a T-die are continuously arranged, and the extruded film-like molten resin is stacked. A film-like molten resin is formed on a single-layer film once formed. And a method of forming a multilayer by pressing a plurality of deposited films.

  When the acrylic resin film has a multilayer structure, there is no particular limitation on the composition other than the acrylic resin composition layer. For example, a suitable thermoplastic resin containing no rubber elastic particles or a layer of the composition But you can.

  Moreover, when making an acrylic resin film into a multilayer structure, it is good also as rubber | gum elastic body particle | grains and the said additive for different content in each layer. For example, a layer containing an ultraviolet absorber and a layer not containing an ultraviolet absorber may be laminated. By including an ultraviolet absorber in the acrylic resin film in this way, it is possible to efficiently block ultraviolet rays without deteriorating the color tone of the polarizing plate, and polarization during long-term use of the polarizing plate using the film as a protective film. Degradation can be suppressed.

  The in-plane retardation value of the acrylic resin film used in the present invention is 10 nm or less, preferably 7 nm or less, and more preferably 5 nm or less. By setting the in-plane retardation to 10 nm or less, the display quality when the polarizing plate of the present invention is applied to a liquid crystal display device is a polarizing plate using a conventionally used triacetyl cellulose film as a protective film. It will not be inferior to the case.

  In order to set the in-plane retardation value to 10 nm or less, for example, a method of setting a film forming condition that does not cause orientation birefringence during film formation of an acrylic resin film, a positive value depending on the stretching of the acrylic resin composition A method of blending an appropriate amount of a compound that exhibits birefringence, a method of blending an appropriate amount of a polymer that exhibits positive birefringence in an acrylic resin composition, and the like are employed. Among them, a method that does not cause orientation birefringence depending on the film forming conditions is simple and preferably employed.

  In order to prevent the copolymer of the acrylic resin composition from being oriented (does not cause orientation birefringence), it is heated to a temperature at which the copolymer is sufficiently melted, and the melt viscosity is adjusted relatively low. And a method of arranging the lip (discharge groove) portion of the T die and the resin contact portion of the cooling roll as short as possible, or a method of precisely matching the extrusion speed of the molten resin and the take-up speed of the cooling roll is preferable. Adopted. By such a method, film formation may be performed so that excessive tensile or compressive stress and shearing force are not applied to the discharged molten resin, and distortion due to it, that is, the orientation of the copolymer does not remain.

  The center line average roughness of at least one surface of the acrylic resin film thus obtained is preferably 1/3 or less of the number average particle diameter of the rubber elastic particles, and preferably 0.01 to 0.05 μm, Values that apply to both are more preferred. Moreover, it is preferable to use the surface adjusted in this way for the surface laminated | stacked with a polarizing film. Here, the center line average roughness is a value measured by a method defined in JIS B0601.

  When the center line average roughness of the surface of the acrylic resin film is less than 0.01 μm, the films are likely to be blocked when the film itself is wound, and the films are damaged by adhesion between the films when pulled out. In some cases, the handling property is inferior. Also, if the center line average roughness of the surface of the acrylic resin film exceeds one third of the number average particle diameter of the rubber elastic particles or exceeds 0.05 μm, it is laminated on the polarizing film using an adhesive. In such a case, sufficient adhesive force may not be obtained, and the scattering of reflected light due to the roughness of the film surface increases, and in a liquid crystal display device using a polarizing plate composed thereof, the screen is whitened, In some cases, the display quality is deteriorated such that the contrast is lowered.

  The method of adjusting the center line surface roughness of the acrylic resin film to the above range is not particularly limited. For example, in the melt extrusion film forming method, the surface of the cooling roll is transferred to the film surface in contact therewith, A method using a cooling roll having a surface roughness in a desired range is employed.

  The acrylic resin film preferably has a residual solvent content of 0.01% by weight or less. Here, the residual solvent content can be determined from a weight loss value when the acrylic resin film is heated at 200 ° C. for 30 minutes, or a value obtained by quantifying the gas generated by the heating by gas chromatography. When the residual solvent amount is in the above range, for example, it is possible to prevent the protective film from being deformed in a high temperature / high humidity environment and to prevent the optical performance from being deteriorated.

  The method for obtaining the acrylic resin film having the residual solvent amount as described above is not particularly limited. For example, an extruder used for obtaining the acrylic resin composition or an appropriate part of the extruder used for film formation is vented. A method is adopted in which holes are provided and the inside of the extruder is depressurized from the holes.

  Moreover, it is preferable that anti-glare property (haze) is provided to the acrylic resin film. The method for imparting antiglare properties is not particularly limited, but a method of coating a coating liquid obtained by mixing inorganic fine particles or organic fine particles with a curable resin binder on one side of the film and curing the resin binder, or processing into a film A method of dispersing a light diffusing agent in advance in the acrylic resin composition and then heating and kneading as it is, a multilayer film, when mixing one side of the two-layer film with inorganic fine particles or organic fine particles Examples of the method include a diffusion layer, or a method in which the center of a three-layer film is the same diffusion layer as described above.

  The light diffusing agent to be blended is not particularly limited as long as it can impart the desired antiglare performance to the film. For example, an inorganic or organic material having a refractive index different from that of the methyl methacrylate resin. System transparent particles are used. Examples of such transparent particles include inorganic particles such as calcium carbonate, barium sulfate, titanium oxide, aluminum hydroxide, silica, glass, talc, mica, white carbon, magnesium oxide, and zinc oxide, and fatty acids in these inorganic particles. And the like, and resin particles such as crosslinked or high molecular weight styrene resin particles, crosslinked or high molecular weight acrylic resin particles, and silicone resin particles.

  The particle size of the light diffusing agent is usually 1 to 20 μm, preferably 2 to 15 μm. If the particle size is less than 1 μm, the light diffusion effect may not be sufficiently exhibited. On the other hand, when the particle diameter exceeds 20 μm, the surface smoothness of the blended acrylic resin film is lowered, and the appearance of the surface may be impaired.

  A functional layer such as a conductive layer, a hard coat layer, and a low reflection layer can be further laminated on the antiglare film thus obtained or the antiglare layer thereof. Moreover, the resin composition which has either of these functions can also be selected as a resin composition which comprises an anti-glare layer.

  The surface hardness of the film is preferably 3H or more in terms of pencil hardness. Here, the pencil hardness is a value measured with a load of 500 g in accordance with JIS K5600-5-4. In order to set the surface hardness of the film to the above value or more, usually, a method of adjusting the elastic modulus of the particles to be blended within a range that does not impair the effects of the present invention, and adjusting the blending amount to be small, the elasticity of the acrylic copolymer A method of adjusting the rate high by the same method as the adjustment of the glass transition temperature, a method of providing a high hardness resin on the surface in the case of a multilayer film, a method of laminating the hard coat layer on the surface of an acrylic resin film, etc. Is adopted.

  The acrylic resin film used in the present invention can have a two- to three-layer structure in which the layer containing the rubber particles and the layer having antiglare property are coextruded by the method for producing the multilayer film. However, in this case, the multilayer film is formed so that the layer made of the acrylic resin composition is exposed on one side or both sides because the layer is adhered to the polarizing film.

  Moreover, when forming a film, the acrylic resin composition put into the extruder may contain an additive as necessary. Examples of the additive include a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, an ultraviolet absorber, and a light resistance agent. The addition amount is preferably kept in a range that does not adversely affect the optical properties.

[Adhesive layer]
The adhesive layer used in the present invention is formed by curing an active energy ray-curable composition containing an oxetane compound and a cationic polymerization initiator.

The oxetane compound contained in the active energy ray-curable composition has an oxetane ring composed of one oxygen atom and three carbon atoms in the molecule. Such an oxetane compound is, for example, a method in which one-side hydroxyl group of a 1,3-diol derivative compound is halogenated or tosylated and then subjected to a cyclization reaction accompanied by elimination under basic conditions, or a 1,3-diol derivative compound and an alkyl A method of carrying out a cyclization reaction involving removal of CO ₂ from a carbonate through a carbonate, a method of carrying out a cyclization reaction by photodimerization of a compound having a carbonyl group and a vinyl compound, a methylene chain on an epoxy ring using an ylide compound It can be manufactured by a method of inserting. Among them, a method of performing a cyclization reaction accompanied by de-CO ₂ through a cyclic carbonate from trimethylolpropane or a derivative thereof and an alkyl carbonate is preferably employed.

  Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, 3-ethyl-3- (2-ethyl). Hexyloxymethyl) oxetane, bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, phenol novolac oxetane, 1, And 3-bis [(3-ethyloxetane-3-yl) methoxy] benzene. Each of these may be used alone, or a plurality of different types may be used in combination.

  The oxetane compound can be easily obtained as a commercial product. For example, “Aron Oxetane” (manufactured by Toagosei Co., Ltd.), “ETERRNACOLL” (manufactured by Ube Industries, Ltd.), and the like are listed. .

  The active energy ray-curable composition can also contain a cationically polymerizable compound other than the oxetane compound. An example of such a compound is an epoxy compound.

  Examples of the epoxy compound include a glycidyl etherified product of an aromatic compound or a chain compound having a hydroxyl group, a glycidyl aminated product of a compound having an amino group, an epoxidized product of a chain compound having a C—C double bond, and a saturated carbocyclic ring. And an alicyclic epoxy compound in which a glycidyloxy group or an epoxyethyl group is bonded directly or via an alkylene, or an epoxy group is bonded directly to a saturated carbocyclic ring. Among these, alicyclic epoxy compounds are preferably used because of their excellent cationic polymerizability. Moreover, these epoxy compounds may be used independently and multiple different types may be used together.

  A glycidyl etherified product of an aromatic compound or a chain compound having a hydroxyl group can be obtained, for example, by a method of addition condensation of epichlorohydrin to a hydroxyl group of the aromatic compound or chain compound under basic conditions. Examples thereof include bisphenol type epoxy resins, polyaromatic ring type epoxy resins, alkylene glycol type epoxy resins and the like.

  Examples of the bisphenol-type epoxy resin include glycidyl etherified products of bisphenol A and oligomers thereof, glycidyl etherified products of bisphenol F and oligomers thereof, and 3,3 ′, 5,5′-tetramethyl-4,4′- Examples thereof include glycidyl etherified products of biphenol and oligomers thereof.

  Examples of polyaromatic epoxy resins include glycidyl etherified products of phenol novolac resins, glycidyl etherified products of cresol novolac resins, glycidyl etherified products of phenol aralkyl resins, glycidyl etherified products of naphthol aralkyl resins, and glycidyl phenolic dicyclopentadiene resins. And etherified products. Furthermore, glycidyl etherified products of trisphenols and oligomers thereof also belong to the polyaromatic ring type epoxy resin.

  Examples of the alkylene glycol type epoxy resin include glycidyl etherification product of ethylene glycol, glycidyl etherification product of diethylene glycol, glycidyl etherification product of 1,4-butanediol, glycidyl etherification product of 1,6-hexanediol, and the like.

  A glycidyl aminated product of a compound having an amino group can be obtained, for example, by a method of addition condensation of epichlorohydrin to the amino group of the compound under basic conditions. The compound having an amino group may have a hydroxyl group at the same time. For example, glycidyl amination product of 1,3-phenylenediamine and oligomer thereof, glycidyl amination product and oligomer of 1,4-phenylenediamine, glycidyl amination and glycidyl etherification product of 3-aminophenol and oligomer thereof Glycidylamination and glycidyletherification of 4-aminophenol, oligomers thereof and the like.

  An epoxidized product of a chain compound having a C—C double bond can be obtained, for example, by a method of epoxidizing a C—C double bond of the chain compound under basic conditions using a peroxide. Can do. Examples of the chain compound having a C—C double bond include butadiene, polybutadiene, isoprene, pentadiene, hexadiene and the like. Terpenes having a double bond can also be used as a raw material for epoxidation, and examples of acyclic monoterpenes include linalool. Examples of the peroxide used for epoxidation include hydrogen peroxide, peracetic acid, tert-butyl hydroperoxide, and the like.

  An alicyclic epoxy compound in which a glycidyloxy group or an epoxyethyl group is bonded to a saturated carbocycle directly or via alkylene is an aromatic ring of an aromatic compound having a hydroxyl group, typically a bisphenol as mentioned above. Examples thereof include a glycidyl etherified product of a hydrogenated cyclic polyhydroxy compound obtained by hydrogenation, a glycidyl etherified product of a saturated cyclic compound having a hydroxyl group, and an epoxidized product of a saturated cyclic compound having a vinyl group.

  The epoxy compounds as described above can be easily obtained from commercial products. For example, “Epicoat” (manufactured by Japan Epoxy Resin Co., Ltd.) and “Epicron” (manufactured by DIC Corporation) are available under the trade names. "Epototo" (manufactured by Toto Kasei Co., Ltd.), "Adeka Resin" (manufactured by ADEKA Corporation), "Denacol" (manufactured by Nagase ChemteX Corporation), "Dow Epoxy" (manufactured by Dow Chemical Company), "Tepic" (Nissan Chemical) Kogyo Co., Ltd.).

  On the other hand, an alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocycle, for example, peroxidizes a CC double bond of a non-aromatic cyclic compound having a CC double bond in the ring. Can be obtained by a method of epoxidizing the product under basic conditions. Examples of the non-aromatic cyclic compound having a C—C double bond in the ring include, for example, a compound having a cyclopentene ring, a compound having a cyclohexene ring, a cyclopentene ring or a cyclohexene ring and at least two carbon atoms bonded thereto. Examples include polycyclic compounds forming an additional ring. This non-aromatic cyclic compound having a C—C double bond in the ring may have another C—C double bond outside the ring. As an example of such a compound, 4- Examples include vinylcyclohexene, monocyclic monoterpenes limonene and α-pinene.

  An alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocyclic ring has an alicyclic structure having an epoxy group directly bonded to the ring as described above in the molecule through an appropriate linking group. It may be a compound in which at least two are formed. Examples of the linking group herein include a group having an ester bond, an ether bond, or alkylene.

  Examples of the alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocycle include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 1 , 2-epoxy-4-epoxyethylcyclohexane, 1,2-epoxy-1-methyl-4- (1-methylepoxyethyl) cyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate, bis (3,4- Epoxycyclohexylmethyl) adipate, adduct of 2,2-bis (hydroxymethyl) -1-butanol and 4-epoxyethyl-1,2-epoxycyclohexane, ethylene bis (3,4-epoxycyclohexanecarboxylate), oxy Diethylene bis (3,4-ethylene Carboxymethyl cyclohexane carboxylate), 1,4-cyclohexane dimethyl bis (3,4-epoxycyclohexane carboxylate), 3- (such as 3,4-epoxycyclohexyl-methoxycarbonyl) propyl 3,4-epoxycyclohexane carboxylate.

  An alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocyclic ring can also be easily obtained as a commercial product. For example, “Celoxide” and “Cyclomer” (hereinafter, Daicel Chemical Industries, Ltd.), “Syracure” (manufactured by Dow Chemical Company), etc.

  As the oxetane compound and the epoxy compound to be blended in the active energy ray-curable composition, it is preferable to use those which are not diluted with an organic solvent or the like. In addition, with respect to a small amount of components such as a cationic polymerization initiator and a sensitizer constituting the active energy ray-curable composition described later, the compound alone in which the organic solvent is removed and dried rather than the one dissolved in the organic solvent. It is preferable to use a powder or a liquid.

  Moreover, the amount ratio of the oxetane compound and the epoxy compound blended in the active energy ray-curable composition is such that the blending amount of the oxetane compound is 20 parts by weight or more when the total of the oxetane compound and the epoxy compound is 100 parts by weight. It is preferably 30 parts by weight or more.

  When the blending amount of the oxetane compound is less than 20 parts by weight, the adhesive force between the acrylic resin film and the polarizing film is not sufficiently improved, and the durability of the polarizing plate and the reliability of the liquid crystal display device using the same are conventional. It may not be expressed well enough. Further, the blending amount of the oxetane compound may be 100 parts by weight as long as the effects of the present invention are not impaired, but it is usually 80 parts by weight or less, and preferably 20 parts by weight or more of the epoxy compound is blended.

  The cationic polymerization initiator compounded in the active energy ray-curable composition generates an active energy ray, particularly a cationic species upon irradiation with ultraviolet rays, and the adhesive strength required for this active energy ray-curable composition. And any curing agent that can give the curing rate to the adhesive composition. Examples thereof include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes. .

  Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

  Examples of the aromatic iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.

  Examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 4,4′-bis [Di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate, 7- [di (p-toluyl) sulfoni ] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide hexa Fluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) Sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like.

  Examples of iron-allene complexes include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) -tris. And (trifluoromethylsulfonyl) methanide.

  Among them, aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and therefore can provide a cured layer having excellent curability and good mechanical strength and adhesive strength. . Moreover, these cationic polymerization initiators may be used independently and multiple different types may be used together.

  Such cationic polymerization initiators can be easily obtained from commercial products, for example, “Kayarad” (manufactured by Nippon Kayaku Co., Ltd.) and “Syracure” (manufactured by Union Carbide), respectively, under the trade names. , Photoacid generator “CPI” (manufactured by Sun Apro Co., Ltd.), photoacid generators “TAZ”, “BBI” and “DTS” (manufactured by Midori Chemical Co., Ltd.), “Adekaoptomer” (manufactured by ADEKA Corporation) ), “RHODORSIL” (manufactured by Rhodia) and the like.

  The compounding quantity of a cationic polymerization initiator is 0.5-20 weight part normally with respect to a total of 100 weight part of an adhesive composition, and 1-15 weight part is preferable. If the amount is less than 0.5 parts by weight, curing may be insufficient, and the mechanical strength and adhesive strength of the cured product layer may be reduced. On the other hand, when the amount exceeds 20 parts by weight, the ionic substance in the cured product layer is increased, so that the hygroscopic property of the cured product layer is increased, and the durability performance of the obtained polarizing plate may be lowered.

  The active energy ray-curable composition can contain a photosensitizer as necessary. By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product layer can be further improved. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.

  Examples of the carbonyl compound include benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, and α, α-dimethoxy-α-phenylacetophenone; anthracene compounds such as 9,10-dibutoxyanthracene; benzophenone and 2,4-dichloro Benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, and 4,4′-bis (diethylamino) benzophenone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone Acridone derivatives such as N-methylacridone and N-butylacridone; acetophenone derivatives such as α, α-diethoxyacetophenone; xanthone derivatives Fluorenone derivatives and the like.

  Examples of the organic sulfur compound include thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone. In addition, benzyl compounds and uranyl compounds can also serve as photosensitizers.

  As for the compounding quantity of a photosensitizer, 0.1-20 weight part is preferable with respect to a total of 100 weight part of an active energy ray curable composition. This photosensitizer may be used alone or a plurality of different types may be used in combination.

  Moreover, various additives can be mix | blended with an active energy ray curable composition, unless the effect of this invention is impaired. Examples of the additive include an ion trap agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a plasticizer, and an antifoaming agent. Furthermore, the active energy ray-curable composition may be blended with a cured resin composition that is cured by a reaction mechanism different from that of the cationic polymerization as long as the effects of the present invention are not impaired.

  The active energy ray-curable composition only needs to have a viscosity that can be applied to the film by an appropriate method, but preferably exhibits a viscosity in the range of 10 to 30,000 mPa · s at 25 ° C. The range of 6,000 mPa · s is more preferable. If the viscosity of the active energy ray-curable composition is less than 10 mPa · s, the apparatus that can be applied is limited, and even if it can be applied, a uniform coating without unevenness may not be obtained. On the other hand, if it exceeds 30,000 mPa · s, it is difficult to flow, so that the apparatus that can be applied in the same way is limited, and a uniform coating film without unevenness may not be obtained. The viscosity of the active energy ray-curable composition is a value measured at 60 rpm after adjusting the composition to 25 ° C. using a B-type viscometer.

  The active energy ray-curable composition described above is applied to an acrylic resin film or a polarizing film, and after both are bonded through the coating layer, the active energy ray-curable composition is cured by irradiation with active energy rays. It becomes the adhesive bond layer which comprises the polarizing plate of invention.

  Examples of the active energy ray used for curing the active energy ray-curable composition include X-rays having a wavelength of 1 pm to 10 nm, ultraviolet rays having a wavelength of 10 to 400 nm, and visible rays having a wavelength of 400 to 800 nm. Among these, ultraviolet rays are preferably used in terms of ease of use, ease of preparation of the active energy ray-curable composition, stability, and curing performance.

  Examples of the light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp having a light emission distribution at a wavelength of 400 nm or less.

The irradiation intensity is determined by the composition of the adhesive and the irradiation time, and is not particularly limited. For example, a range of 0.1 to 300 mW / cm ² is preferable in a wavelength region effective for activation of the initiator, A range of 1 to 200 mW / cm ² is more preferable. When the light irradiation intensity to the active energy ray-curable composition is less than 0.1 mW / cm ² , the curing reaction time becomes long, that is, it does not cure unless a long irradiation time is applied, which is disadvantageous for productivity. There is. Moreover, when it exceeds 300 mW / cm ² , yellowing of the active energy ray-curable composition or deterioration of the polarizing film occurs due to heat radiated from the lamp and heat generation during polymerization of the active energy ray-curable resin composition. There is a case.

The irradiation time is determined by the composition of the active energy ray-curable composition and the irradiation intensity, and is not particularly limited. For example, the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is 10 to 5, it is preferable to set to be 000mJ / cm ^2, further is more preferably set such that the 50~1,000mJ / cm ^2. When the integrated light amount to the active energy ray-curable composition is less than 10 mJ / cm ² , the generation of active species derived from the initiator is not sufficient, and the resulting adhesive layer may be insufficiently cured. On the other hand, when it exceeds 5,000 mJ / cm ² , the irradiation time becomes very long, which may be disadvantageous for productivity.

  The thickness of the adhesive layer thus cured is usually about 1 to 50 μm, but is preferably in the range of 1 to 10 μm.

[Polarizer]
As described above, after coating the active energy ray-curable composition on the adhesive surface of either the acrylic resin film or the polarizing film, the two are bonded together, and the active energy ray is irradiated to curable composition. The polarizing plate of the present invention is obtained by curing the product.

  Here, the same acrylic resin film may be laminated on the surface of the polarizing film opposite to the surface on which the acrylic resin film is laminated, or another transparent resin film may be laminated as a protective film. May be. Moreover, a retardation film can also be laminated as a protective film.

  The acrylic resin film, the polarizing film, and the transparent resin film laminated on the opposite surface thereof are subjected to corona discharge treatment, plasma irradiation treatment, electron on the laminated surface before application of the active energy ray-curable composition. It is preferable to perform a beam irradiation treatment or other surface activation treatment.

  When laminating a film similar to the acrylic resin film used in the present invention on the opposite surface, the active energy ray-curable composition is preferably used for the adhesive. Moreover, when laminating | stacking another transparent resin film, the thing of the kind which fully expresses the adhesive force of a polarizing film and the transparent resin film can be arbitrarily selected and used for the adhesive agent. Even in this case, it is preferable from the viewpoint of productivity to select from an active energy ray-curable adhesive.

  As such an active energy ray-curable adhesive, in addition to the active energy ray-curable composition used in the present invention, an adhesive compound containing a polyfunctional acrylic compound and a photo radical polymerization initiator, an epoxy compound And those containing a photocationic polymerization initiator, and mixtures thereof.

  The other transparent resin film is not particularly limited as long as it functions as a protective film for a polarizing plate or a retardation film, and examples thereof include a triacetyl cellulose film, a polycarbonate film, a polyethylene terephthalate film, and an olefin resin film. It is done. Among these, an olefin resin film is preferably used.

  In this case, the acrylic resin film side in the polarizing plate of the present invention is preferably disposed on the opposite side of the liquid crystal cell with the polarizing film interposed therebetween. The polarizing plate is more preferably disposed on the viewing side of the liquid crystal cell.

[Olefin resin]
The olefin resin is, for example, a resin obtained by polymerizing a chain olefin monomer such as ethylene and propylene, or a cyclic olefin monomer such as norbornene and other cyclopentadiene derivatives using a polymerization catalyst.

  Examples of the olefin resin made of a chain olefin monomer include polyethylene or polypropylene resin. Among these, a polypropylene resin made of a homopolymer of propylene is preferable. Also preferred is a polypropylene copolymer resin in which a comonomer mainly composed of propylene and copolymerized therewith is usually copolymerized at a ratio of 1 to 20% by weight, preferably 3 to 10% by weight.

  The comonomer copolymerizable with propylene is preferably ethylene, 1-butene, or 1-hexene. Among them, a copolymer obtained by copolymerizing ethylene at a ratio of 1 to 20% by weight, particularly 3 to 10% by weight is preferable because of relatively excellent transparency and stretch processability. By making the copolymerization ratio of ethylene 1% by weight or more, an effect of improving transparency and stretch processability appears. On the other hand, if the ratio exceeds 20% by weight, the melting point of the resin is lowered, and the heat resistance required for the optical compensation film may be impaired.

  Such polypropylene resins can be easily obtained as commercial products. For example, “Prime Polypro” (manufactured by Prime Polymer Co., Ltd.), “Novatech” and “Wintech” , Nippon Polypro Co., Ltd.), “Sumitomo Noblen” (manufactured by Sumitomo Chemical Co., Ltd.), “Sun Aroma” (manufactured by Sun Aroma Co., Ltd.), and the like.

  An olefin resin obtained by polymerizing a cyclic olefin monomer is generally referred to as a cyclic olefin resin, an alicyclic olefin resin, or a norbornene resin. Here, it is called a cyclic olefin resin.

  Examples of the cyclic olefin-based resin include a resin obtained by performing ring-opening metathesis polymerization from cyclopentadiene and olefins by a Diels-Alder reaction or a derivative thereof as a monomer, followed by hydrogenation; Resins obtained by performing ring-opening metathesis polymerization from olefins or methacrylates with Diels-Alder reaction obtained by Diels-Alder reaction as monomers, followed by hydrogenation; norbornene, tetracyclododecene, them A resin obtained by carrying out ring-opening metathesis copolymerization in the same manner using two or more of the above-mentioned derivatives or other cyclic olefin monomers, followed by hydrogenation; norbornene, tetracyclodode And down and at least one cyclic olefin selected from derivatives thereof, and the like aliphatic or aromatic compound and the addition copolymer are allowed to obtain a resin having a vinyl group.

  Such a cyclic olefin-based resin can be easily obtained as a commercial product. For example, under the trade name, “Topus” (Topas Advanced Polymers GmbH), “Arton” (manufactured by JSR Corporation), “Zeonoa” and “Zeonex” (manufactured by ZEON CORPORATION), “Apel” (manufactured by Mitsui Chemicals, Inc.), and the like.

[Olefin resin film]
Although the method for forming the chain olefin resin or the cyclic olefin resin into a film is not particularly limited, a melt extrusion film formation method similar to the film formation of the acrylic resin film is usually employed.

  Olefin-based resin films can be easily obtained as commercial products. For example, polypropylene-based resin films have the trade names “FILMAX CPP film” (manufactured by FILMAX), “Santox” (Sun. Manufactured by Tox Co., Ltd., “Tosero” (manufactured by Tosero Co., Ltd.), “Toyobo Pyrene Film” (manufactured by Toyobo Co., Ltd.), “Trephan” (manufactured by Toray Film Processing Co., Ltd.), “Nihon Polyace” (Nihon Polyace) Co., Ltd.), “Dazai FC” (Futamura Chemical Co., Ltd.) and the like. In the case of cyclic olefin-based resin films, “ZEONOR FILM” (manufactured by ZEON CORPORATION), “ARTON FILM” (manufactured by JSR Corporation), and the like are listed under the trade names.

  The olefin-based resin film can be further laminated with an optical functional film or coated with an optical functional layer. Examples of the optical functional film and the optical functional layer include an easy adhesion layer, a conductive layer, and a hard coat layer.

[Phase difference film]
A retardation film can be obtained by stretching the olefin-based resin film described above and imparting refractive index anisotropy to the film. The stretching method is selected according to the required refractive index anisotropy and is not particularly limited. Usually, longitudinal uniaxial stretching, transverse uniaxial stretching, or longitudinal and transverse sequential biaxial stretching is employed.

  Since the olefin resin has a positive refractive index anisotropy and has the highest refractive index in the direction in which stress is applied, a film in which the olefin resin is longitudinally uniaxially stretched usually has a refractive index of nx> ny≈nz. Gives anisotropy. Here, nx is the refractive index in the in-plane slow axis direction of the film (the direction in which the refractive index is maximum in the plane, and the stretching direction in the case of a resin having positive refractive index anisotropy), and ny Is the refractive index in the in-plane fast axis direction of the film (the direction perpendicular to the fast axis in the plane), and nz is the refractive index in the normal direction of the film. A film obtained by sequentially biaxially stretching an olefin resin usually gives refractive index anisotropy of nx> ny> nz.

  Moreover, in order to provide a desired refractive index characteristic, a heat-shrinkable film is bonded to a target film, and the film is contracted instead of or along with the stretching process. Usually, this operation is performed to obtain a retardation film having a refractive index anisotropy of nx> nz> ny or nz> nx ≧ ny.

  A phase difference film made of an olefin resin can be easily obtained as a commercial product. For example, as an optical compensation film made of a cyclic olefin resin, “ZEONOR FILM” (Nippon Zeon Corporation) And “Arton Film” (manufactured by JSR Corporation), “Essina Retardation Film” (manufactured by Sekisui Chemical Co., Ltd.), and the like.

  In addition to the retardation film, an optical functional film can be laminated on the surface or an optical functional layer can be coated in the same manner as the olefin resin film.

[Adhesive layer]
The polarizing plate of the present invention can be a polarizing plate with an adhesive layer by forming an adhesive layer on one or both sides. Examples of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer include a pressure-sensitive adhesive having an acrylic polymer, a silicone-based polymer, polyester, polyurethane, polyether, or the like as a base polymer. Among them, acrylic pressure-sensitive adhesives based on acrylic polymers are excellent in optical transparency, maintain appropriate wettability and cohesion, and have excellent adhesion to protective films or retardation films. It is preferably used because it has high weather resistance, heat resistance, and the like, and hardly causes peeling problems such as floating and peeling under heating and humidification conditions.

  Examples of the acrylic base polymer contained in the acrylic pressure-sensitive adhesive include alkyl esters of acrylic acid in which the alkyl group in the ester portion is an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, and a butyl group, ) An acrylic copolymer with a functional group-containing (meth) acrylic monomer such as acrylic acid or hydroxyethyl (meth) acrylate is preferably used. The pressure-sensitive adhesive layer made of such an acrylic pressure-sensitive adhesive is excellent in adhesiveness with a protective film or retardation film constituting the surface of the polarizing plate, and after being bonded to a glass substrate, The glass substrate can be peeled relatively easily without causing adhesive residue or the like. The glass transition temperature of this acrylic copolymer is preferably 25 ° C. or lower, and more preferably 0 ° C. or lower. Further, the weight average molecular weight of the acrylic copolymer is preferably 100,000 or more.

  A diffusion adhesive in which a light diffusing agent is dispersed can also be used as the adhesive that forms the adhesive layer. The light diffusing agent is for imparting light diffusibility to the pressure-sensitive adhesive layer, and may be fine particles having a refractive index different from that of the base polymer constituting the pressure-sensitive adhesive layer. Fine particles made of (polymer) can be used. Since the base polymer constituting the pressure-sensitive adhesive layer including the acrylic base polymer as described above often has a refractive index of around 1.4, the refractive index of the light diffusing agent is about 1-2. What is necessary is just to select suitably from the thing. The refractive index difference between the base polymer constituting the pressure-sensitive adhesive layer and the light diffusing agent is usually 0.01 or more, and from the viewpoint of the brightness and visibility of the liquid crystal display device, 0.01 to 0.5. Is preferred. The fine particles used as the light diffusing agent are preferably spherical and those close to monodisperse. For example, fine particles having an average particle diameter in the range of about 2 to 6 μm are preferably used.

  Examples of the fine particles made of an inorganic compound include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45).

  Examples of the fine particles made of an organic compound (polymer) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate / styrene copolymer resin beads (refractive index). 1.50), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46) ), Silicone resin beads (refractive index 1.46), and the like.

  The amount of the light diffusing agent is appropriately determined in consideration of the haze value required for the pressure-sensitive adhesive layer in which it is dispersed and the brightness of the liquid crystal display device to which it is applied. It is about 3-30 weight part with respect to 100 weight part of resin which comprises a layer.

  The haze value of the pressure-sensitive adhesive layer in which the light diffusing agent is dispersed is 20 from the viewpoint of ensuring the brightness of the liquid crystal display device to which the pressure-sensitive adhesive layer-attached polarizing plate is applied and making the display image less likely to bleed or blur. A range of ˜80% is preferred. The haze value is a value represented by (diffuse transmittance / total light transmittance) × 100 (%), and is measured according to JIS K 7105.

  Each of the components constituting the transparent adhesive or diffusion adhesive is applied on an appropriate substrate in a state dissolved in an appropriate solvent such as ethyl acetate and dried to form an adhesive layer.

  As a method for forming the pressure-sensitive adhesive layer on the protective film or the retardation film, for example, a release film is used as the base material, the pressure-sensitive adhesive composition is applied to form a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive obtained A method of laminating a layer on the surface of a protective film or a retardation film, a method of applying a pressure-sensitive adhesive composition on the surface of a protective film or a retardation film, forming a pressure-sensitive adhesive layer, and attaching a release film to the pressure-sensitive adhesive surface Adopted.

  Moreover, after forming an adhesive layer on a peeling film, another peeling film is bonded on an adhesive layer, and the double-sided peeling film which cannot be supported by an optical film (for example, a polarizing plate or its protective film) A mold pressure-sensitive adhesive sheet can also be obtained. Such a double-sided release film-type pressure-sensitive adhesive sheet is used for bonding to a polarizing plate by peeling off a release film on one side at a necessary time.

  Commercially available products of the double-sided release film type adhesive sheet include, for example, “LUCIACS” (manufactured by Nitto Denko Corporation), “Non-Carrier” (manufactured by Lintec Corporation), “double-sided adhesive for optical substrates”, for example. Tape MHM-F25 "(manufactured by Niei Engineering Co., Ltd.)," optical adhesive sheet FS800 "(manufactured by Toyo Ink Co., Ltd.)," optical double-sided tape SK "(manufactured by Soken Chemical Co., Ltd.), and the like.

  The pressure-sensitive adhesive layer formed on the polarizing plate is usually aged for about 3 to 20 days at a temperature of 23 ° C. and a relative humidity of about 65%, and after the reaction of the cross-linking agent has been sufficiently advanced, Used for pasting.

  The thickness of the pressure-sensitive adhesive layer is determined according to its adhesive strength and is not particularly limited, but is usually about 1 to 40 μm. In order to obtain a thin polarizing plate without impairing properties such as workability and durability, the thickness of the pressure-sensitive adhesive layer is preferably about 3 to 25 μm. In addition, by setting the thickness of the pressure-sensitive adhesive layer to about 3 to 25 μm, it is possible to maintain brightness when the liquid crystal display device is viewed from the front or from an oblique direction, and to prevent blurring or blurring of the display image. it can.

[Laminated optical member]
In the polarizing plate of the present invention, an optical functional layer other than the polarizing function can be laminated on the surface opposite to the acrylic resin film via an adhesive layer. Examples of the optical functional layer laminated on the polarizing plate include a reflective layer, a transflective reflective layer, a light diffusing layer, a retardation film, a condensing sheet, and a brightness enhancement film.

[Liquid Crystal Display]
The polarizing plate of the present invention can be bonded to a liquid crystal cell via an adhesive layer to form a liquid crystal panel. Examples of the liquid crystal cell include TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertical Alignment), IPS (In-Plane Switching), OCB (Optically Compensated B, etc.). In the mode.

  A liquid crystal panel in which a polarizing plate is bonded to a liquid crystal cell is a liquid crystal display device in which a drive circuit, a backlight unit, and the like are incorporated. This liquid crystal display device is excellent in reliability by using the polarizing plate of the present invention.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In the examples, “%” and “part” representing the content or amount used are based on weight unless otherwise specified. Moreover, the evaluation methods in the following examples are as follows.

[Adhesion test between acrylic resin film and polarizing film]
The cutting edge of a cutter knife was inserted between the polarizing film of the sample polarizing plate and the protective film (acrylic resin film), and both sides with cuts were held by hand and peeled. The result was determined as follows.

A: It is difficult to insert the blade edge and to peel off.
B: Insertion of the blade edge is possible, but peeling is difficult.

C: The cutting edge can be easily inserted and peeled off easily.
[Cool thermal shock test]
The sample polarizing plate was cut into a long side of 345 mm and a short side of 277 mm using a super cutter (manufactured by Hadano Seiki Co., Ltd.), subjected to corona treatment on the phase difference film side made of a cyclic olefin resin, and passed through an adhesive sheet. And bonded to non-alkali glass to obtain a test sample. The test sample was placed upright in a thermal shock test machine, and a durability test was performed between 150 to 600 cycles, with 1 cycle being placed at −35 ° C. for 1 hour and then 70 ° C. for 1 hour. The test results were judged according to the following criteria.

  A: Even after 600 cycles of the test, defects such as peeling of the polarizing plate or its interlayer and damage to the polarizing film are not recognized.

  B: After the 450-cycle test, peeling of the polarizing plate or its interlayer and damage to the polarizing film are not observed, but a defect is observed in the 600-cycle test.

  C: After the 300-cycle test, peeling of the polarizing plate or its interlayer and damage to the polarizing film are not observed, but a defect is observed in the 450-cycle test.

  D: After the 150-cycle test, no peeling of the polarizing plate or its interlayer or damage to the polarizing film is observed, but a defect is observed in the 300-cycle test.

  E: After 150 cycles of the test, defects such as peeling of the polarizing plate or its interlayer and damage to the polarizing film are observed.

[Rubber elastic particles]
In the following examples, the following rubber elastic particles were used.

  Acrylic rubber elastic particles: manufactured according to Example 3 of JP-B-55-27576, the innermost layer is a crosslinked polymer obtained by polymerizing methyl methacrylate with a small amount of allyl methacrylate, and the intermediate layer is , Soft rubber elastic body mainly composed of butyl acrylate, polymerized with styrene and a small amount of allyl methacrylate, outermost layer is a hard polymer polymerized with a small amount of ethyl acrylate on methyl methacrylate A polymer having an average particle size of about 240 nm when kneaded with an acrylic resin.

[Production Example 1: Production of acrylic resin film]
80 parts of a copolymer having a methyl methacrylate / methyl acrylate weight ratio of 95/5 and 20 parts of the acrylic rubber elastic particles shown above were mixed with a Henschel mixer and then melt-kneaded with an extruder. did. Subsequently, melt extrusion was performed at a resin temperature of 260 ° C., and the resin extruded from the die was solidified while being drawn with a cooling roll set at 80 ° C., thereby producing an acrylic resin film having a thickness of 80 μm. The in-plane retardation value of the acrylic resin film was measured by a retardation measuring device “KOBRA-WR” (trade name, manufactured by Oji Scientific Instruments Co., Ltd.) and found to be 0.8 nm. This is referred to as an acrylic resin film A.

  The copolymer was changed to a methyl methacrylate / methyl acrylate weight ratio of 96/4, and an acrylic resin film having a thickness of 80 μm was prepared in the same manner as above. The in-plane retardation value of this acrylic resin film was 1.8 nm. This is referred to as an acrylic resin film B.

  Further, the copolymer was changed to one having a methyl methacrylate / methyl acrylate weight ratio of 98/2, and an acrylic resin film having a thickness of 80 μm was prepared in the same manner as above. The in-plane retardation value of this acrylic resin film was 1.3 nm. This is referred to as an acrylic resin film C.

The configuration of the extruder used in the following examples is as follows.
Extruder: Screw diameter 65mm, single screw, with vent (Toshiba Machine Co., Ltd.)
Die: T die, lip width 1,400 mm, lip interval 1 mm (manufactured by Hitachi Zosen Corporation).

[Production Example 2: Preparation of active energy ray-curable composition]
The following components were mixed and degassed to prepare an active energy ray-curable composition A.

Diglycidyl ether of hydrogenated bisphenol A 70 parts Bis (3-ethyl-3-oxetanylmethyl) ether 30 parts Diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate 4.0 parts Benzoin methyl ether 1.0 part

Similarly, the following components were mixed and defoamed to prepare an active energy ray-curable composition B.
Bis (3,4-epoxycyclohexylmethyl) adipate 100 parts Diglycidyl ether of nuclear hydrogenated bisphenol A 25 parts 4,4'-bis (diphenylsulfonio) phenyl sulfide bis (hexafluorophosphate) 2.2 parts

[Example 1]
Acrylic resin film A is applied to one side of a polarizing film having a thickness of about 28 μm in which iodine is adsorbed and oriented on polyvinyl alcohol, and a cyclic olefin resin film “ZEONOR film” (Zeon Nippon Co., Ltd., thickness 65 μm, in-plane retardation value 63 nm, thickness direction retardation value 220 nm) are bonded via the active energy ray-curable composition A prepared in Production Example 2, respectively, and cyclic olefin type Ultraviolet rays were irradiated from the resin film surface with an integrated light amount of 300 mJ / cm ² to prepare a polarizing plate having a protective film made of an acrylic resin film on one side and a retardation film made of a cyclic olefin resin on the other side. Using this polarizing plate as a sample, an adhesion test between the acrylic resin film and the polarizing film was performed by the above-described method.

  Further, the release film on one side of the double-sided release film type pressure-sensitive adhesive sheet (thickness 25 μm) was peeled off and bonded to the retardation film side of this polarizing plate to prepare a polarizing plate with an adhesive layer. Using this pressure-sensitive adhesive layer-attached polarizing plate as a sample, a thermal shock test was conducted by the above-described method. Each test result is shown in Table 1.

[Comparative Example 1]
A polarizing plate was produced in the same manner as in Example 1 except that the active energy ray-curable composition was changed to the composition B, and an adhesion test between the acrylic resin film and the polarizing film was performed. Also, with this polarizing plate, Example 1. Each test result is shown in Table 1.

[Comparative Example 2]
The protective film bonded to one surface of the polarizing film is changed to the acrylic resin film B, and the others are produced in the same manner as in Comparative Example 1, and the adhesion test between the acrylic resin film and the polarizing film is performed. It was. Moreover, using this polarizing plate, a polarizing plate with an adhesive layer was prepared in the same manner as in Example 1, and a thermal shock test was performed. Each test result is shown in Table 1.

[Comparative Example 3]
The protective film bonded to one surface of the polarizing film is changed to the acrylic resin film C, and the others are produced in the same manner as in Comparative Example 1, and the adhesion test between the acrylic resin film and the polarizing film is performed. It was. Moreover, using this polarizing plate, a polarizing plate with an adhesive layer was produced in the same manner as in Example 1, and a thermal shock test was conducted. The results are shown in Table 1.

Claims (2)

A polarizing plate in which an acrylic resin film is laminated on at least one surface of a polarizing film made of polyvinyl alcohol resin via an adhesive layer,
The acrylic resin film comprises a copolymer of methyl methacrylate and methyl acrylate having a copolymerization ratio of methyl acrylate of 5% by weight or more and rubber elastic particles, and has an in-plane retardation of 10 nm. And
The polarizing plate, wherein the adhesive layer is a layer formed by curing an active energy ray-curable composition containing an oxetane compound and a cationic polymerization initiator.   The polarizing plate according to claim 1, wherein an olefin resin film is laminated on a surface opposite to a surface on which the acrylic resin film of the polarizing film is laminated.