WO2006019086A1

WO2006019086A1 - Polarization plate and liquid crystal display device

Info

Publication number: WO2006019086A1
Application number: PCT/JP2005/014931
Authority: WO
Inventors: Tetsuya Toyoshima; Masanori Yoshihara; Kouhei Arakawa
Original assignee: Zeon Corporation
Priority date: 2004-08-17
Filing date: 2005-08-16
Publication date: 2006-02-23
Also published as: JPWO2006019086A1

Abstract

A polarization plate that by the use of a specified transparent protective layer for polarizer, excels in transparency, mechanical strength and adhesion, exhibiting a little change of birefringence versus external stress, and that can exert satisfactory polarization potency even in high temperature high humidity conditions; and a relevant liquid crystal display device. The polarization plate comprises resin film (A) of alicyclic-structure-having resin superimposed on one major surface of polarizer, hard coat layer (B) superimposed on the surface of resin film (A), antireflection layer (C) superimposed on the surface of hard coat layer (B) and resin film (D) superimposed on the other major surface of the polarizer. The resin film (A) has a thickness of 5 to 200 μm, a water vapor permeability of 0.3 to 40 g/m2·24 hr, a photoelastic coefficient of ≤ 12.0×10-12/Pa, a die line maximum depth or maximum height of ≤ 50 nm and a die line minimum width of ≥ 500 nm. The resin film (D) has a thickness of 5 to 200 μm and a water vapor permeability of 50 to 1500 g/m2·24 hr.

Description

ing.

[0007] However, since TAC has high hygroscopicity, it tends to generate unevenness due to stress distortion, which has a large dimensional change due to temperature. The birefringence generated by this stress strain is a cause of deterioration in display quality such as color unevenness and contrast reduction (light leakage) at the edge of the screen. In particular, light leakage tends to become more pronounced as the LCD becomes larger. As LCDs become thinner, larger, and higher in definition, the durability of polarizing plates has been demanded more than ever. The protective film with the above TAC force is durable enough to satisfy it. There was a problem!

Therefore, recently, instead of TAC, it has been proposed to use thermoplastic saturated norbornene resin as a protective film for a polarizer as a film with low moisture permeability! (Patent Documents 1 to 4) ).

However, the PVA polarizer, which is a general polarizer, is hydrophilic and has a high hygroscopic property. Therefore, the above-described low moisture permeability film is used for the PVA polarizer. When used on both sides, the protective film may be bonded and dried, preventing water from being emitted from the PVA polarizer cover, resulting in poor adhesion. Furthermore, when such a polarizing plate is used in a high temperature environment, the inside of the polarizing plate itself is in a high temperature and high humidity state, and as a result, the amount of change in light transmittance, degree of polarization, etc. becomes large, resulting in polarization. In some cases, the reliability of the plate was insufficient.

[0010] Patent Document 1: JP 2001-272534 A

Patent Document 2: Japanese Patent Laid-Open No. 2003-207637

Patent Document 3: Japanese Patent Application Laid-Open No. 2003-232930

Patent Document 4: Japanese Patent Laid-Open No. 2003-097031

Disclosure of the invention

Problems to be solved by the invention

The object of the present invention has been made in view of the circumstances of such prior art, and is excellent in transparency, mechanical strength, and adhesiveness, and has a small change in birefringence with respect to external stress. It is an object of the present invention to provide a polarizing plate and a liquid crystal display device that can exhibit a sufficient polarizing function even in a high temperature and high humidity state. Means for solving the problem

As a result of diligent research to solve the above problems, the present inventors have used a specific polarizing plate protective film, and a polarizing film in which a hard coat layer and an antireflection layer are sequentially laminated on one protective film. Based on this finding, the present inventors have found that a plate can achieve the above object, and have completed the present invention.

[0013] Forcibly, means for solving the above-mentioned problem is:

(1) A resin film (A) made of an alicyclic structure-containing resin laminated on one surface of a polarizer, and a no coat layer (B) laminated on the surface of the resin film (A), An antireflection layer (C) laminated on the surface of the hard coat layer (B), and a resin film (D) laminated on the other surface of the polarizer, the resin film (A) , thickness 5 to 200 mu m, moisture permeability ^{0. 3~ 40g / m 2 - 24hr} , photoelastic coefficient 12. OX 10- ¹² ZPa less, and the maximum depth and the maximum height of the die line is at 50nm or less minimum width is not less 500nm or more, the榭脂film (D), the thickness force S5~200 μ m, permeability, moisture mosquito 50-1500 _8/1 1 ² '24111: Dearu polarizers.

(2) The antireflection layer (C) is a polarizing plate of (1) having a refractive index of 1.37 or less,

(3) The antireflection layer (C) is the polarizing plate of (1) comprising an air mouth gel,

(4) A resin film (D) force A polarizing plate of (1) mainly comprising cellulose ester,

(5) Resin film (D) force It is a polarizing plate of (1), which is a film showing letter decision,

(6) The resin film (A) is a polarizing plate according to (1) having an in-plane letter pattern (Re) of 4 nm or less,

(7) The resin film (A) is a polarizing plate of (1) having a thickness direction letter-thickness (Rth) force of not more than nm, and (8) a light source, an incident-side polarizing plate, a liquid crystal cell, The output side polarizing plate is the polarizing plate according to claim 1, and the antireflection layer (C) side of the output side polarizing plate faces the viewing side. It is a liquid crystal display device.

The invention's effect

[0014] According to the present invention, the transparency, mechanical strength, and adhesiveness are excellent, and a sufficient polarization function can be exhibited even in a high-temperature and high-humidity state with little change in birefringence with respect to external stress. A polarizing plate can be provided. Further, by using such a polarizing plate, a liquid crystal display device excellent in display performance can be provided. Brief Description of Drawings

FIG. 1 is a diagram for explaining a polarizing plate of the present invention.

FIG. 2 is a diagram for explaining a die line.

FIG. 3 is a diagram for explaining a die line.

[0018] FIG. 4 is a diagram showing measurement points of the degree of polarization and transmittance performed in the present example and the comparative example.

Explanation of symbols

[0019] 1 Polarizing plate

2 Resin film (D)

3 Polarizer

4 Resin film (A)

5 Hard coat layer (B)

6 Antireflection layer (C)

BEST MODE FOR CARRYING OUT THE INVENTION

[0020] The polarizing plate of the present invention includes a resin film (A) comprising an alicyclic structure-containing resin laminated on one surface of a polarizer, and a hard film laminated on the surface of the resin film (A). A coating layer (B); an antireflection layer (C) laminated on the surface of the hard coating layer ( _B) ; and a resin film (D) laminated on the other surface of the polarizer. fat film (a) has a thickness of 5 to 200 mu m, moisture permeability 0. 3~40gZm ² '24hr, photoelastic coefficient 12. 0 X 10- ¹² / Pa or less, the maximum depth of the force one die line and The maximum height is 50 nm or less and the minimum width is 500 nm or more. The above-mentioned resin film (D) has a thickness of 5 to 200 μm and a moisture permeability of 50 to 1500 ₈ 1! 1 ² '24111: It is characterized by.

[0021] Hereinafter, the polarizing plate of the present invention will be briefly described with reference to FIG. As shown in FIG. 1, the polarizing plate 1 includes a polarizer 3, a resin film (A) 4 bonded to one surface of the polarizer 3 with an adhesive, and a resin film (A) 4. The adhesive layer (B) 5 laminated on the surface, the antireflection layer (C) 6 laminated on the surface of the hard coat layer (B), and the other surface of the polarizer 3 are adhered with an adhesive. The prepared resin film (D) 2 is provided.

[0022] The polarizer that can be used in the present invention has any function as a polarizer. There is no particular limitation. For example, (1) PVA 'iodine polarizer with iodine adsorbed on butyl alcohol polymer (PVA) film, (2) PVA' dye polarizer with dichroic dye adsorbed on PVA film, (3) Polyethylene polarizer in which dehydration reaction is induced from PVA film or polyene is formed by dehydrochlorination reaction of polyvinyl chloride film, (4) Surface of PVA film made of modified PVA containing cationic group in the molecule and Z Or the polarizer etc. which have dichroic dye inside are mentioned. From the viewpoint of the initial polarization performance of the polarizer, (1) PVA 'iodine polarizer is preferred for the heat resistance viewpoint power that PVA' iodine polarizer is preferred.

[0023] The polarizer that can be used in the present invention is not particularly limited by its production method. For example, 1) A method of adsorbing iodine ions after stretching PVA film, 2) A method of stretching PVA film after dyeing with dichroic dye, 3) A method of stretching PVA film and then dyeing with dichroic dye Methods, 4) a method of stretching a dichroic dye after printing on a PVA film, and 5) a method of printing a dichroic dye after stretching a PVA film.

[0024] For example, in the method of 1), more specifically, iodine is dissolved in a potassium iodide solution to form iodine ion, this ion is adsorbed on a PVA film and stretched, and then 1 to 4% boron. A polarizer is produced by dipping in an acid water solution at a bath temperature of 30 to 40 ° C. More specifically, in the method of 2), the PVA film is immersed in a boric acid aqueous solution in the same manner as in 1), and then stretched about 3 to 7 times in the uniaxial direction, and the dichroism of 0.05 to 5%. A polarizer is produced by immersing the dye in an aqueous dye solution at a bath temperature of 30-40 ° C to adsorb the dye, drying at 80-100 ° C, and heat setting. The polarization degree of the polarizer is preferably 99.5% or more.

[0025] The average thickness of the resin film (A) comprising the alicyclic structure-containing resin used in the present invention is 5 to 200 μm, preferably 30 to LOO μm.

[0026] When the thickness is less than the above range, the mechanical strength as a protective film is lowered, and warpage or the like tends to occur when the polarizing plate is placed in a high-temperature and high-humidity environment. When the thickness exceeds the above range, the light transmittance of the protective film is lowered, and further, the adhesive is not sufficiently dried when the respective films are bonded, and the durability of the polarizer is lowered. Therefore, when the thickness of the resin film (A) is in the above range, a laminate having excellent mechanical strength and durability can be obtained. [0027] The moisture permeability of the resin film (A) is 0.3 to 40 gZm ² '24 hr, preferably 0.6 to 20 gZm ² ' 24 hr. If the moisture permeability is too low, drying of the adhesive will be insufficient, and if it is too high, the moisture absorption of the polarizer will increase in the usage environment, and the durability of the polarizer will decrease even in the case of V or deviation. When the moisture permeability is in the above range, the durability of the polarizer is improved. The moisture permeability is a value measured at a temperature of 40 ° C and a humidity of 90% using the cup method according to JI S Z0280.

[0028] photoelastic coefficient榭脂film (A) used in the present invention, 12.0 X 10- ¹² ZPa less, favored properly, or less 9.0 X 10- ¹² / Pa. If the photoelastic coefficient is too higher than the above value, light leakage is likely to occur if the color refraction rate changes greatly when stressed by heat or the like is applied. That is, when a polarizing plate using the resin film (A) having a photoelastic coefficient equal to or lower than the above value is incorporated in a liquid crystal display device, uneven color and light leakage can be prevented.

[0029] The photoelastic coefficient is also referred to as a piezo optical coefficient, and is a material constant that describes the magnitude of the piezo optical effect (photoelastic effect), and can be measured using an ellipsometer. The photoelastic coefficient is a value indicating the degree of optical distortion with respect to external stress. The smaller the value, the better the optically protective film for the polarizing plate.

[0030] The resin film (A) used in the present invention comprises an alicyclic structure-containing resin.

An alicyclic structure-containing coffin has an alicyclic structure in the main chain and Z or side chain, and from the viewpoint of mechanical strength, heat resistance, etc., it preferably has an alicyclic structure in the main chain. .

[0031] Examples of the alicyclic structure-containing resin include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength, heat resistance, and the like. Of these, a cycloalkane structure is most preferable, and a cycloalkene structure is most preferable.

[0032] The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15. Within such a range, the mechanical strength, heat resistance, and film formability are highly balanced, which is preferable. The ratio of the repeating unit containing the alicyclic structure in the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is preferably 30% by weight or less. Furthermore, it is more preferably 50% by weight or more, particularly preferably 70% by weight or more, and most preferably 90% by weight or more. Repeating unit having alicyclic structure in alicyclic structure If the ratio is within this range, the transparency and heat resistance of the film are also preferable.

[0033] The alicyclic structure-containing coconut resin specifically includes (1) norbornene polymer, (2) monocyclic cyclic olefin polymer, (3) cyclic conjugated diene polymer, (4) vinyl alicyclic ring And a hydrocarbon polymer thereof, and hydrogenated products thereof. Of these, norbornene polymers are more preferred from the viewpoint of transparency and moldability! /.

[0034] Specific examples of norbornene polymers include ring-opening polymers of norbornene monomers, ring-opening copolymers of norbornene monomers and other monomers capable of ring-opening copolymerization, and hydrogenated products thereof. And addition polymers of norbornene monomers and addition copolymers with other monomers copolymerizable with norbornene monomers. Among these, a ring-opening (co) polymer hydrogenated product of norbornene monomer is most preferable from the viewpoint of transparency.

[0035] Examples of the polymer resin having the alicyclic structure include known polymers disclosed in JP-A-2002-321302.

[0036] Among norbornene polymers suitably used for the resin film (A), as a repeating unit, a bicyclo [3.3.0] octane-2,4-diyl-ethylene structure (abbreviated as X structure). And tricyclo [4. 3. 0. 1 ² ' ⁵ ] decane-7,9-diyl-ethylene structure (abbreviated as Y structure), and the content power of these repeating units is repeated in the polymer. Thermoplastic that is 90% by weight or more with respect to the whole unit, and the ratio of the content ratio of the X structure and the content ratio of the Y structure is 100: 0 to 40:60 in terms of the weight ratio of the X structure: Y structure Norbornene rosin is preferred! By using such a resin, it is possible to obtain a resin film excellent in stability of optical characteristics that does not undergo dimensional change over a long period of time.

[0037] Examples of the monomer that can be polymerized to give a repeating unit of the X structure include a norbornene monomer having a structure in which a 5-membered ring is condensed to a norbornene ring. More specifically, tricyclo [4. . I ^2, ^5] dec - 3,7-Jen (common name: dicyclopentadiene) and its derivatives, 7, 8-benzo tricyclo [4. 3. 0. 1 ° ^'5] dec - 3- E (Common name: methanotetrahydrofluorene) and derivatives thereof.

[0038] Further, as a monomer that is polymerized to give a repeating unit of Y structure, tetracyclo [4.4.

0. I ² ' ^5. 1 ⁷ ' ^1G ] Deca-3,7-gen (common name: tetracyclododecene) and its derivatives Can be mentioned.

Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Norbornene monomers can be used alone or in combination of two or more.

[0040] As means for obtaining such a norbornene polymer, specifically, a) a monomer that is polymerized to give the repeating unit of the X structure, and a monomer that is polymerized to give the repeating unit of the Y structure A method in which the polymerization ratio is controlled and hydrogenated unsaturated bonds in the polymer as necessary, and b) a polymer having the X structure as a repeating unit, and the Y structure having a repeating unit. The method of controlling by the blend ratio with the polymer is mentioned.

[0041] The molecular weight of the alicyclic structure-containing resin used in the present invention was measured by gel “permeation” chromatography (hereinafter abbreviated as “GPC”) using cyclohexane as a solvent. However, when toluene is used as a solvent, the weight average molecular weight (Mw) in terms of polystyrene) is usually 8,000 to 100,000, preferably <is 10,000 to 80,000, more preferably 15, 000-50, 000. When the weight average molecular weight is in such a range, the mechanical strength and moldability of the film are highly balanced, which is preferable.

[0042] The molecular weight distribution (weight average molecular weight (Mw) Z number average molecular weight (Mn)) of the alicyclic structure-containing resin used in the present invention is not particularly limited, but is usually 1.0 to 10.0, preferably 1. It is in the range of 0 to 4.0, more preferably 1.2 to 3.5.

[0043] The alicyclic structure-containing rosin that can be used in the present invention includes a compounding agent! /, Or may /!

The compounding agent is not particularly limited, but is a layered crystal compound; inorganic fine particles; antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, ultraviolet absorbers, near infrared absorbers, and other stabilizers; lubricants, plastics Examples thereof include a resin modifier such as an agent; a colorant such as a dye or a pigment; and an antistatic agent. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not impairing the object of the present invention.

[0044] The thickness variation of the resin film (A) in the present invention can be determined as follows. That is, first, contact type web thickness gauge (RC-101 rotary carrier made by Meisho Co., Ltd.) ), Move the thickness gauge to the side, and measure it at 0.48mm intervals in the width direction of the resin film. The arithmetic average value (average thickness), maximum thickness, and minimum thickness of the measured values were obtained. Compare the difference between the maximum thickness and the average thickness, and the difference between the minimum thickness and the average thickness. If the difference is larger, the percentage of the average thickness is calculated, and this is the thickness variation.

In the present invention, the thickness variation of the resin film (A) is preferably within 3.0% of the average thickness, more preferably within 2.5%. When the thickness of the resin film (A) is within the above range, color unevenness when the resin film (A) of the present invention is incorporated in a liquid crystal display device can be reduced.

[0046] In the resin film (A) used in the present invention, the content of volatile components in the resin film is preferably 0.1% by weight or less, more preferably 0.05% by weight or less. When the content of volatile components is within the above range, the dimensional change due to the use environment can be reduced, and even if it is used in a liquid crystal display for a long time, display unevenness of the display does not occur. Excellent stability.

[0047] The volatile component is a relatively low-boiling substance having a molecular weight of 200 or less contained in a trace amount in the resin film, and examples thereof include residual monomers and solvents. The content of the volatile component is the total of substances having a molecular weight of 200 or less contained in a small amount in the alicyclic structure-containing resin, and can be quantified by analyzing by gas chromatography.

[0048] The die line of the resin film (A) used in the present invention has a maximum depth and maximum height of a die line formed in the longitudinal direction of the resin film of 50 nm or less, and a minimum width of the die line of 500 ηm or more. .

[0049] The depth, height, and width of the die line can be determined by using a three-dimensional structural analysis microscope (manufactured by Saigo Co., Ltd.) and scanning the uneven surface of the film at a constant speed on the lower force to observe interference fringes. It can be decided.

[0050] When the die line force is in the above range, even when incorporated in a liquid crystal display unit having a backlight unit having a high luminance, a good display state can be obtained with no bright spots.

[0051] In the present invention, it is preferable that the maximum value of the in-plane letter distortion (Re) (hereinafter referred to as "Re") of the resin film (A) is 4 nm or less. Because Re is 4nm or less Color unevenness when incorporated in a liquid crystal display unit can be suppressed.

[0052] Re can be obtained by Re = (nx—ny) X d where nx and ny are the main refractive indices in the film plane and d is the thickness of the film (where nx and ny are Refractive index in two directions perpendicular to the thickness direction and perpendicular to each other, where nx> ny).

[0053] In addition, in the thickness direction of the resin film (Rth) (hereinafter referred to as "Rth"), the main refractive index in the film plane is nx, ny, and the refractive index in the film thickness direction is If nz and the film thickness is d (nm), then Rth = {(nx + ny) Z2—nz} Xd. It is preferable that the Rth of the greave film (A) is 4nm or less!

[0054] Re and Rth in the film plane can be measured using a commercially available automatic birefringence meter ("KOBRA-21ADHJ" manufactured by Oji Scientific Instruments).

[0055] The resin film used in the present invention can be obtained by a solution casting method, a melt extrusion method, or preferably a melt extrusion method.

In the present invention, the hard coat layer (B) is provided on the surface of the resin film (A). The hard coat layer (B) preferably has a high refractive index. By using a high refractive index, reflection such as reflection of external light is prevented, and a polarizing plate having excellent scratch resistance and antifouling properties can be obtained. When the hard coat layer (B) itself is not a high refractive index, a high refractive index layer may be provided separately from the hard coat layer (B).

Here, the high refractive index means a refractive index larger than the refractive index of the antireflection layer (C) to be laminated later, preferably 1.55 or more.

[0058] The refractive index can be measured, for example, using a known spectroscopic ellipsometer.

[0059] The material for forming the hard coat layer is not particularly limited as long as it shows a hardness of "HB" or higher in the pencil hardness test specified in JIS K5600-5-4. Examples thereof include organic hard coat materials such as organic silicones, melamines, epoxies, acrylics, and urethane acrylates; and inorganic hard coat materials such as diacids. Among these, from the viewpoint of good adhesion and excellent productivity, it is preferable to use a hard coat material such as urethane acrylate or polyfunctional acrylate.

[0060] The method for forming the hard coat layer (B) is not particularly limited. For example, an active energy ray-curable resin coating solution is applied onto the resin film (A) by a known coating method. , UV etc. And a method of forming the film by irradiating and curing the energy beam. The average thickness of the hard coat layer is 0.5 to 30 μm, preferably 3 to 15 μm.

[0061] By containing the active energy ray-curable resin, a high refractive index hard coat layer having sufficient strength, durability, adhesion, and transparency can be obtained.

Active energy ray-curable resin is a resin cured by irradiation with prepolymers, oligomers, and Z or monomer force active energy rays having a polymerizable unsaturated bond or epoxy group in the molecule. An active energy ray refers to an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking a molecule, and usually an ultraviolet ray or an electron beam is used.

[0062] Examples of prepolymers and oligomers having a polymerizable unsaturated bond or an epoxy group in the molecule include unsaturated polyester compounds such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol; polyester metatalylate, Methacrylate compounds such as polyether methacrylate, polyol methacrylate, melamine methacrylate, polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, melamine acrylate And cation polymerization type epoxy compounds.

[0063] Examples of the monomer having a polymerizable unsaturated bond or an epoxy group in the molecule include styrene monomers such as styrene and a-methylstyrene; methyl acrylate, ethyl acrylate, -2-ethyl acrylate Hexyl, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, acrylic acid phenol and other acrylate esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, Methacrylic acid ester compounds such as ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate; acrylic acid-2- (N, N-jetylamino) ethyl, acrylic acid-2- (N, N-dimethylamino) ethyl, acrylic acid -2- (N, N-Diben ziramino) methyl, acrylic - 2- (N, N- Jechiruamino) substituted § amino alcohol ester compounds of unsaturated substituted and propyl; acrylamide, unsaturated force carboxylic acid amide compounds such as methacrylamide;

Ethylene glycol ditalylate, propylene glycol ditalylate, neopent Diglycol ditalarilate, 1,6-hexanediol ditalylate, triethylene glycol ditalylate, dipropylene glycol ditalylate, ethylene glycol ditalariate, propylene glycol dimetatalylate, diethyleneglycolose methacrylate, 2-Hydroxy Atalylate, 2-Hexyl Atylate, Phenoxetyl Atylate, Ethylene Glycol Ditalylate, 1,6-Hexanediol Ditalylate, Trimethylol Oral Pantriathalylate, Pentaerythritol Multi-functional ataretoy compounds such as triatalylate, pentaerythritol tetra acrylate, dipentaerythritol hexaacrylate;

And polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithioglycolate, pentaerythritol tetrathioglycolate, and the like.

In the present invention, these prepolymers, oligomers, and Z or monomers can be used singly or in combination of two or more.

[0064] The content of the prepolymer, oligomer, and Z or monomer in the active energy ray-curable resin used is preferably 5% by weight to 95% by weight from the viewpoint of obtaining excellent coating suitability.

[0065] The hard coat layer (B) preferably further contains inorganic oxide particles. By adding inorganic oxide particles, a hard coat layer having excellent scratch resistance and a refractive index of 1.55 or more can be easily formed.

[0066] The inorganic oxide particles that can be used in the hard coat layer (B) preferably have a high refractive index. Specifically, inorganic oxide fine particles having a refractive index of 1.7 or more, particularly 1.7 to 2.3 are preferable.

[0067] Examples of such inorganic oxides having a high refractive index include titanium (titanium oxide), zirconium oxide (zirconium oxide), zinc oxide, tin oxide, cerium oxide, antimony pentoxide, Sud-doped indium oxide (ITO), antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO), and fluorine-doped Examples include tin oxide (FTO).

[0068] Among these, antimony pentaoxide is a balance between conductivity and high transparency that have a high refractive index. Therefore, it is suitable as a component for adjusting the refractive index.

[0069] These inorganic oxide particles may be used alone, or may be used in combination of two or more.

[0070] The inorganic oxide particles have a so-called ultrafine particle size, more specifically, a primary particle size of 1 nm to 100 nm, preferably 1 nm to 50 nm so as not to lower the transparency of the hard coat layer. I prefer to use it!

[0071] The primary particle diameter of the inorganic oxide particles may be visually measured from a secondary electron emission image photograph obtained by a scanning electron microscope (SEM) or the like. Mechanical measurement may be performed by a particle size distribution analyzer using a scattering method or the like.

[0072] As long as the primary particle diameter of the inorganic oxide particles is within the above range, the particle shape may be spherical, needle-like, or any other shape used in the present invention. be able to . In the case of a needle shape, the length is viewed as the particle diameter.

[0073] Further, as the inorganic oxide particles that can be used in the present invention, in order to improve dispersibility in an organic solvent, at least a part of the surface of the inorganic oxide particles has an ionic polar group. Preferably, it is coated with a compound or an organometallic compound.

[0074] As the organic compound having a terionic polar group, those having an anionic polar group such as a carboxyl group, a phosphoric acid group, or a hydroxyl group can be used. For example, stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, pentaerythritol triatalylate, dipentaerythritol pentaatalylate, ethylene oxide, modified triatalylate phosphate, epichlorohydrin modified glycerol And triatrate.

[0075] In addition, examples of organometallic compounds having a ionic polar group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexane. Xylyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyljetoxysilane, 3-mercaptopropyltrimethoxy Silane coupling agents such as silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane; KR-TTS, KR-46B, KR-55, KR-41B, KR -38S, KR-138S, KR-238S, 338X, KR-44, KR-9SA, KR-ET (Titanate coupling agent manufactured by Ajinomoto Fine Techno Co., Ltd.), tetramethoxy titanium, tetraethoxy titanium, And titanate coupling agents such as tetraisopropoxy titanium, tetra n-propoxy titanium, tetra n-butoxy titanium, tetra sec-butoxy titanium, tetra tert-butoxy titanium, and the like.

[0076] Further, the surface of the inorganic oxide particles is coated with an organic compound and Z or an organometallic compound to impart hydrophobicity. Obtained by dissolving the organic compound having anionic polar groups and Z or organometallic compound in an organic solvent, dispersing the inorganic oxide in the solution, and completely evaporating and removing the organic solvent. Can do. Through this process, the dispersibility of the inorganic oxide particles can be improved and re-aggregation can be prevented.

[0077] The inorganic oxide particles may be used in combination of two or more. In this case, a transparent thin film having a plurality of functions in a well-balanced manner can be formed by combining inorganic oxide particles having different main functions. For example, a small rutile acid-titanium fine particle having a very high refractive index but low conductivity, and a very high conductivity but a refractive index smaller than that of rutile acid-titanium, the conductive inorganic acid described above. It is possible to form a hard coat layer having a predetermined refractive index and a good antistatic performance by combining the above-mentioned materials.

[0078] The blending amount of the inorganic oxide fine particles is not particularly limited, but is active from the viewpoint of easily obtaining a hard coat layer having excellent scratch resistance and a refractive index of 1.55 or more. The energy is preferably 40 to 90 parts by weight with respect to 100 parts by weight of the whole-line curable resin.

[0079] When the active energy ray-curable resin is cured by ultraviolet irradiation, a photopolymerization initiator or a photopolymerization accelerator is added. Examples of photopolymerization initiators include radical polymerizable initiators such as acetophenone compounds, benzophenone compounds, thixanthone compounds, benzoin, and benzoin methyl ether; And cation-polymerizable initiators such as benzoin sulfonates. These can be used singly or in combination of two or more. The addition amount of the photopolymerization initiator is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin.

Moreover, an organic reactive silicon compound may be added to the active energy ray-curable resin. The organic reactive silicon compounds that can be used include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra- tert-Butoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane, Methyltripropoxysilane, Methyltributoxysilane, Dimethylenoresimethoxysilane, Dimethinolegoxysilane, Dimethinoreethoxysilane, Dimethylmethoxysilane, Dimethylenopropoxysilane, Dimethinolevoxysilane, methinoresimethoxysilane, methyljetoxysilane, hexyltrimethoxysilane, etc., formula: R Si (OR ')

m

(In the formula, R and R ′ each independently represent an alkyl group having 1 to 10 carbon atoms, and m and n are each independently a positive integer satisfying the relationship of m + n = 4. ) Organic key compound represented by

3- (2-aminoethinole) aminopropyltrimethoxysilane, 3- (2-aminoethinole) aminoprone, 3-aminopropyltriethoxysilane, 3-methacryloxypropylmethoxysilane, N-3- (N-Bulbe Nylaminoethyl) -3-Aminopropylmethoxysilane hydrochloride, 3-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltri Silane coupling agents such as methoxysilane, hexamethyldisilazane, buturris (3-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane, dimethyldichlorosilane;

One-end bull group-substituted polysilane, both-end vinyl group-substituted polysilane, one-end vinyl group-substituted polysiloxane, both-end bull group-substituted polysiloxane, or vinyl group-substituted polysilane obtained by reacting these compounds, or vinyl group-substituted Active energy ray-curable key compounds such as polysiloxane; other organic key compounds such as 3- (meth) aryloxypropyltrimethoxysila compound; and the like. [0081] The active energy ray-curable resin that can be used includes prepolymers, oligomers, and Z or monomers having a polymerizable unsaturated bond or an epoxy group in the molecule, and optionally inorganic acid oxide particles. It can be prepared by dissolving or dispersing in an appropriate organic solvent.

[0082] Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol, Glycols such as diethylene glycol monobutyl ether and diacetone glycol; Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons such as n-hexane and n-heptane; Esters such as ethyl acetate and butyl acetate; Ketones such as tilketone and methylisobutylketone; oximes such as methylethylketoxime; and combinations of two or more of these;

[0083] The method for coating the active energy ray-curable resin on the resin film (A) is not particularly limited, and a known coating method can be employed. Examples of the coating method include a wire bar coating method, a dip method, a spray method, a spin coating method, and a roll coating method.

[0084] After obtaining the active energy ray-curable resin coating, it can be dried and cured by irradiation with active energy rays to form a hard coat layer (B).

[0085] Irradiation intensity and irradiation time of the active energy ray are not particularly limited, and irradiation conditions such as irradiation intensity and irradiation time can be appropriately set according to the active energy line curable resin used.

[0086] The antireflection layer (C) used in the present invention refers to a layer having a refractive index lower than that of the hard coat layer (B). The refractive index of the antireflective layer (C) should satisfy the above conditions, but 1. 1. 37 or less is preferable 1. 35-1. 25 is more preferable 1. 34-1 30 is particularly preferred. When the refractive index of the antireflection layer (C) is in the above range, an antireflection layer excellent in the balance between antireflection performance, scratch resistance and strength is formed.

[0087] The material used for the antireflection layer (C) is not particularly limited as long as it is a material constituting a layer having a refractive index of 1.37 or less! However, it is easy to control the refractive index and has water resistance. From the viewpoint of excellent properties, air mouth gel is preferable. [0088] The air mouth gel is a transparent porous body in which minute bubbles are dispersed in a matrix. The size of the bubble is mostly 200 nm or less, and the bubble content is usually 10% by volume or more and 60% by volume or less, preferably 20% by volume or more and 40% by volume or less.

[0089] Specific examples of the air mouth gel in which minute bubbles are dispersed include silica air mouth gel and a porous body in which hollow particles are dispersed in a matrix.

[0090] Silica Aerogenole is disclosed in US Patent No. 4402927 and US Patent No. 4432956.

As disclosed in U.S. Pat. No. 4,610,863, etc., a wet gel-like compound having a silica skeleton obtained by hydrolysis polymerization reaction of alkoxysilane is obtained by using alcohol or diacid-carbon. In the presence of a solvent such as (dispersion medium) in the supercritical state above the critical point of the solvent. In supercritical drying, for example, a gel compound is immersed in liquefied carbon dioxide, and all or part of the solvent contained in the gel compound is replaced with liquid carboxylic acid carbon having a lower critical point than this solvent. Thereafter, the drying can be carried out by drying under supercritical conditions of a single system of diacid-carbon or a mixed system of diacid-carbon and a solvent. Further, the silica air-mouthed gel may be produced in the same manner as described above using sodium silicate as a raw material as disclosed in US Pat. No. 5,137,279, US Pat. No. 5,124,364, and the like.

Here, as disclosed in JP-A-5-279011 and JP-A-7-138375 (US Pat. No. 5496527), hydrolysis and polymerization of alkoxysilane as described above. It is preferable to impart hydrophobicity to the silica gel by hydrophobizing the gel-like compound obtained by the reaction. Hydrophobic silica air gel with hydrophobicity in this way can prevent moisture, water, etc. from entering, and can prevent the performance of silica air gel, such as refractive index and light transmittance, from deteriorating. is there.

[0092] This hydrophobization treatment step can be performed before or during supercritical drying of the gel compound. Hydrophobic treatment is performed by making the hydroxyl group of the silanol group present on the surface of the gel-like compound react with the functional group of the hydrophobizing agent and replacing it with the hydrophobic group of the hydrophobizing agent. Is what you do. As a method for performing the hydrophobization treatment, the gel is immersed in a hydrophobization treatment solution in which the hydrophobization treatment agent is dissolved in a solvent, and mixed, for example, so that the hydrophobization treatment agent is infiltrated into the gel. Depending on heating, hydrophobization reaction is performed. A way to let it go.

[0093] Examples of the solvent used for the hydrophobization treatment include methanol, ethanol, isopropanol, xylene, toluene, benzene, N, N-dimethylformamide, hexamethyldisioxane, etc. It is not limited to these as long as it dissolves in the solvent and can be replaced with the solvent contained in the gel before the hydrophobic treatment. In addition, when supercritical drying is performed in a later step, a medium that can be easily supercritically dried, such as methanol, ethanol, isopropanol, liquid phosphonic acid, carbon, or the like that can be replaced with the same is preferable. . Examples of the hydrophobizing agent include hexamethyldisilazane, hexamethyldisiloxane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, etyltrimethoxysilane, trimethylethoxysilane, dimethyljetoxysilane, and methyltrimethylsilane. And ethoxysilane.

[0094] The refractive index of the silica air mouth gel can be freely changed depending on the raw material blending ratio of the silica air mouth gel.

[0095] The method for forming the antireflection layer (C) comprising silica gel is not particularly limited. For example, the gel compound is applied on the hard coat layer (B) by a known coating method. And a method of forming by performing the above-mentioned supercritical drying.

[0096] Examples of the porous body in which hollow fine particles are dispersed in a matrix include hollow fine particles having voids inside the fine particles as disclosed in JP-A-2001-233611 and JP-A-2003-149642. And a porous body in which is dispersed in a binder resin.

[0097] As the binder resin, it is possible to select and use a resin equivalent force that meets the conditions such as the dispersibility of the hollow fine particles, the transparency of the porous material, and the strength of the porous material. Polyester resin, acrylic resin, urethane resin, chlor resin, epoxy resin, melamine resin, fluorine resin, silicone resin, petital resin, phenol resin, butyl acetate resin, UV curable resins, electron beam curable resins, emulsion resins, water-soluble resins, hydrophilic resins, mixtures of these resins, and coating resins such as copolymers and modified products of these resins, Or hydrolysable organosilicon compounds such as alkoxysilanes and hydrolysates thereof.

[0098] Among these, the dispersibility of fine particles, the strength of the porous material, acrylic resin, epoxy resin Hydrolyzable organosilicon compounds such as urethane resin, silicone resin, alkoxysilane, and hydrolysates thereof are preferred.

[0099] The hydrolyzable organosilicon compound such as alkoxysilane and the hydrolyzate thereof are formed with one or more compound forces in which the following (a) to (c) group forces are also selected, It has a "(O-Si)-0- (where m represents a natural number) bond.

(a) Formula (1): A compound represented by SIX.

Four

(b) At least one partial hydrolysis product of the compound represented by the formula (1).

(c) At least one complete water decomposition product of the compound represented by the formula (1).

[0100] However, in the formula (1), X is a halogen atom such as a chlorine atom or a bromine atom; has a substituent !, may! /, A monovalent hydrocarbon group; an oxygen atom; an acetate radical, Organic acid radical such as nitrate radical; 3-diketonate group such as acetylacetonate; inorganic acid radical such as nitrate radical and sulfate radical; alkoxy group such as methoxy group, ethoxy group, n-propoxy group, n-butoxy group; or hydroxyl group .

[0101] The monovalent hydrocarbon group may have a substituent! / Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group Alkyl groups such as: Cycloalkyl groups such as cyclopentyl and cyclohexyl groups; even if they have substituents such as a phenyl group, a 4-methylphenol group, a 1-naphthyl group, and a 2-naphthyl group Good aryl group; alkenyl group such as bur group and aryl group; aralkyl group such as benzyl group, phenethyl group and 3-phenylpropyl group; haloalkyl group such as chloromethyl group and 3-chloropropyl group 3, 3, 3-trifluoropropyl group, methyl-3,3,3-trifluoropropyl group, heptadecafluorodecyl group, trifluoropropyl group, tridecafluorooctyl group, etc. Perfluoroalkyl group; 3-methacrylic Alkylcarboxylalkyl group such as xylpropyl group; alkyl group having epoxy group such as 3-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group; mercapto group such as 3-mercaptopropyl group An alkyl group having an amino group such as 3-aminopropyl group; and the like. Among these, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group, and a phenyl group are preferable because of easy synthesis, availability, and low reflection characteristics. [0102] Among these compounds (a), formula (2): R SiY [wherein R may have a substituent a 4 to a

Represents a monovalent hydrocarbon group, a represents an integer of 0 to 2, and when a is 2, R may be the same or different. Y represents a hydrolyzable group, and Y may be the same or different. A key compound represented by the formula is preferred.

[0103] In the above formula (2), Y represents a hydrolyzable group. Here, the hydrolyzable group refers to a group that can be hydrolyzed in the presence of an acid or a base catalyst to form a-(O-Si) -0- bond as desired.

Specific examples of the hydrolyzable group include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group; an acyloxy group such as an acetoxy group and a propio-loxy group; an oxime group (—0-N = CR ′ ( ')), Enoxy group (-0-di () = di (') "), amino group, aminoxy group (-0- N (R ') R"), amide group (-N (R')-C (= 0)-R "), etc. In these groups, R ', R", R' "each independently represents a hydrogen atom or a monovalent hydrocarbon group. Y is preferably an alkoxy group because of its availability.

[0105] The key compound represented by the formula (2) is preferably a key compound in which a is an integer of 0 to 2 in the formula (2). Specific examples thereof include alkoxysilanes, acetoxysilanes, talented oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Of these, alkoxysilanes are more preferred because of their availability.

[0106] In the formula (2), examples of the tetraalkoxysilane in which a is 0 include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane in which _a is 1 include methyltrimethoxysilane. And methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. Examples of the diorganodialkoxysilane in which a is 2 include dimethylenoresimethoxysilane, dimethylenoresetoxysilane, dipheninoresimethoxysilane, diphenyljetoxysilane, and methylphenoldimethoxysilane.

[0107] The molecular weight of the compound represented by formula (1) is not particularly limited, but is preferably 40 to 300, more preferably 100 to 200.

[0108] At least one partial hydrolysis product of the compound represented by the formula (1) in the above (b) , "I compound (3)". And at least one complete hydrolysis product (hereinafter referred to as “compound (4)”) of the compound represented by formula (1) in (c) is a compound represented by formula (1). One or more of these can be obtained by complete or partial hydrolysis and condensation.

Compound (3) and compound (4) are, for example, Si (Or) (r represents a monovalent hydrocarbon group.)

Four

The metal tetraalkoxide represented by the molar ratio [H 0

2] Z [Or] is 1 · 0 or more, 1 · 0 ～ 5 · 0

It can be obtained by hydrolysis in the presence of water in an amount of preferably 1.0 to 3.0. The hydrolysis can be carried out by stirring the whole volume at a temperature of 5 to: L00 ° C. for 2 to: L00 hours.

[0110] When the compound represented by the formula (1) is hydrolyzed, a catalyst may be used as necessary. The catalyst to be used is not particularly limited, but the resulting partially hydrolyzed product and Z or fully hydrolyzed product have a two-dimensional cross-linked structure, and the condensed product is immediately porous. From the viewpoint of shortening the time required for hydrolysis, an acid catalyst is preferred.

[0111] The acid catalyst to be used is not particularly limited, and examples thereof include acetic acid, acetic acid acetic acid, and quenoic acid.

, Benzoic acid, dimethylmalonic acid, formic acid, propionic acid, dartaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, oxalic acid and other organic acids; hydrochloric acid, nitric acid, halogenated silanes and other inorganic acids; acidic Examples thereof include acidic sol-type fillers such as colloidal silica and acid titasol. These acid catalysts can be used alone or in combination of two or more.

[0112] Further, instead of the acid catalyst, an aqueous solution of an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide or calcium hydroxide, an aqueous solution of ammonia water or an amine, etc. Use a base catalyst.

[0113] The molecular weight of the compound (3) and the compound (4) is not particularly limited, but the weight average molecular weight is usually in the range of 200 to 5,000.

[0114] The hollow fine particles are not particularly limited as long as they are fine particles of an inorganic compound, but it is particularly preferable to use silica-based hollow fine particles, which are preferable to inorganic hollow fine particles in which cavities are formed inside the outer shell. [0115] As an inorganic compound, an inorganic oxide is generally used. Inorganic oxides include SiO, A1

2

O, B O, TiO, ZrO, SnO, Ce O, P 2 O, Sb 2 O, MoO, ZnO, WO, etc.

2 3 2 3 2 2 2 2 3 2 5 2 3 3 2 3

1 type or 2 types or more can be mentioned. TiO -A1 O as two or more inorganic oxides

2 2 3

, TiO 2 —ZrO, In 2 O 3 —SnO, and Sb 2 O 3 —SnO. These are one single

2 2 2 3 2 2 3 2

You can use a combination of two or more.

[0116] The inorganic hollow fine particles include (a) a single layer of an inorganic oxide, (b) a single layer of a composite oxide comprising different types of inorganic oxides, and (c) the above (a) and It is possible to use one including a double layer with (b).

[0117] The outer shell may be a porous one having pores or may be one in which the pores are closed outside and the cavity is sealed. The outer shell is preferably a plurality of inorganic oxide coating layers including an inner first inorganic oxide coating layer and an outer second inorganic oxide coating layer. By providing the second inorganic oxide coating layer on the outside, the outer shell pores are closed and the outer shell is densified. Can do.

In particular, when a fluorine-containing organic silicon compound is used for forming the second inorganic oxide coating layer, since the coating layer containing fluorine atoms is formed, the resulting particles have a lower refractive index and an organic solvent. In addition to its dispersibility, it is also effective for imparting antifouling properties to the low refractive index layer. Such fluorine-containing organosilicon compounds include 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecaflurane. Examples include chlorodecyltrichlorosilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and the like.

[0118] The thickness of the outer shell is preferably in the range of 1 to 50 nm, particularly 5 to 20 nm. If the thickness of the outer shell is less than the above range, the inorganic hollow fine particles may not maintain a predetermined particle shape.

On the other hand, if the thickness of the outer shell exceeds the above range, the cavities in the inorganic hollow fine particles are small. As a result, the ratio of the cavities may be reduced, and the refractive index may not be sufficiently lowered.

[0119] As described above, the first inorganic oxide coating layer and the second inorganic oxide coating layer are provided as outer shells. In this case, the total force of the thicknesses of these layers is preferably in the range of 1 to 50 nm. Particularly in the case of a densified outer shell, the thickness of the second inorganic oxide coating layer is preferably in the range of 20 to 40 nm.

The cavity may contain the solvent used when preparing the inorganic hollow fine particles and Z or a gas that enters during drying.

[0120] The average particle size of the inorganic hollow fine particles is not particularly limited, but 5 to 2000 nm is preferable, and 20 to 100 nm is more preferable. If the value is smaller than the above value, the effect of lowering the refractive index tends to be small. Conversely, if the value is larger than the above value, the transparency is deteriorated and the contribution due to diffuse reflection tends to be large. Here, the average particle diameter is a number average particle diameter by observation with a transmission electron microscope.

[0121] The inorganic hollow fine particles that can be used in the present invention can be produced, for example, based on the method described in detail in Japanese Patent Application Laid-Open No. 200-233611, and the commercially available inorganic hollow fine particles are used. You can also

[0122] The blending amount of the inorganic hollow fine particles is not particularly limited, but is preferably 10 to 30% by weight based on the entire composition forming the antireflection layer (C). When the amount of the inorganic hollow fine particles is within this range, a laminated film having both antireflection properties and scratch resistance can be obtained.

[0123] When the antireflection layer (C) is a porous body in which hollow particles are dispersed in a matrix, the formation method is not particularly limited, and for example, hollow fine particles and hard particles on the hard coat layer (B). Examples thereof include a method in which a coating solution containing Noinda rosin is applied by a known coating method and, if necessary, dried and heat-treated. The temperature of heating performed as needed is usually 50-200. C, preferably 80-150. . It is.

In the present invention, the average thickness of the antireflection layer (C) is from 10 to: LOOOnm, preferably from 30 to

500.

In the polarizing plate of the present invention, an antifouling layer can be further formed on the antireflection layer (C) in order to enhance the antifouling performance of the antireflection layer (C).

[0126] The antifouling layer forming material is not particularly limited as long as the function of the antireflection layer (C) is not inhibited and the required performance as the antifouling layer is satisfied. Usually, a compound having a hydrophobic group can be preferably used. Specific examples include perfluoroalkylsilane compounds and perfluoro Fluoropolyethersilane compounds and fluorine-containing silicone compounds can be used

. The method for forming the antifouling layer may be, for example, a physical vapor deposition method such as vapor deposition or sputtering; a chemical vapor deposition method such as CVD; a wet coating method; it can. The thickness of the antifouling layer is not particularly limited, but it is usually 1 to 1 Onm, preferably 20 nm or less! /.

The thickness of the resin film (D) that can be used in the present invention is 5 to 200 / ζ πι, preferably 20 to 100 μm.

[0128] When the thickness of the resin film (D) is less than the above range, the durability, mechanical strength, and scratch resistance of the polarizing plate are deteriorated. Warpage is likely to occur, and the light transmittance also decreases. Therefore, when the thickness of the resin film (D) is in the above range, a polarizing plate excellent in durability, mechanical strength, scratch resistance and optical performance can be obtained.

[0129] The material constituting the resin film (D) may be any resin film in which the moisture permeability when the film thickness is within the above range is within the above range. For example, a copolymer of ethylene-but alcohol, Examples include polycarbonate, polyester, polymetatalylate, polysulfone, and cellulose. Among them, acetylated cellulose ester is preferred.

[0130] Examples of the acetylated cellulose ester include diacetyl cellulose and triacetyl cellulose. In particular, triacetyl cellulose is most preferred from the viewpoint of transparency, mechanical strength, and the like.

[0131] The moisture permeability of the resin film (D) used in the present invention is 50 to 1500 gZm ² .24 hr, preferably 100 to 800 gZm ² '24 hr. If the moisture permeability is too lower than the above range, drying of the adhesive becomes insufficient when the resin film (D) is bonded to the polarizer using the adhesive. Moreover, when the water vapor transmission rate is too higher than the above range, the polarizer absorbs moisture in the use environment. For this reason, in any case, the durability of the polarizer decreases. If the moisture permeability is in the above range, the moisture-proof balance is good, so that moisture can be prevented from entering from the front and back of the polarizer, and even when a water-based primer is used for adhesion to the polarizer. , Separation hardly occurs between the resin film (D) and the polarizer. Therefore, the reliability as a polarizing plate is improved. [0132] Further, when the polarizing plate of the present invention is incorporated in a liquid crystal display device, the polarizing plate has a low moisture permeability, 0.3 to 40 gZm ² '24 hr of the resin film (A) on the viewer side, A 50 to 1500gZm ² '24hr resin film (D) with high moisture permeability is installed on the opposite side (liquid crystal panel side).

That is, the resin film (D) is not exposed to the outer surface. For this reason, the resin film

By preventing moisture absorption in (D), deformation of the polarizing plate due to moisture absorption can be prevented, and uneven color and light leakage due to stress generation can be prevented.

[0134] The resin film (D) preferably has a letter decision! /.

[0135] The in-plane letter retardation (Re) of the resin film (D) used in the present invention is 2

The force can be 200 nm, and the letter thickness (Rth) in the film thickness direction can be 70 to 400 nm.

[0136] As a method of imparting letter retardation to the resin film (D), a method of stretching a film containing a polymer that develops birefringence by stretching, a method of applying a liquid crystalline compound to the surface, or a method thereof. Examples include a method in which the methods are used in combination.

[0137] The liquid crystalline compound used in the resin film (D) of the present invention is particularly preferably a discotic compound (discotic liquid crystal).

[0138] Examples of discotic liquid crystals include benzene derivatives described in a research report by C. Destrade et al., Mol. Cryst. 71, p. 111 (1981), a research report by C. Destrade et al., Mol Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990), a research report of B. Kohne et al., Angew. Chem. 96, 70 (1984) and cyclohexane derivatives described in JM Lehn et al., J. Chem. Commun., 1794 (1985), J. Zhang et al., J. Am. Chem. Soc. 116 頁, 2655 (1994) [These are described here! Aza-crown type and ferro-acetylene type macrocycle. A discotic liquid crystal generally has a structure in which these are used as a mother nucleus at the center of a molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain, and exhibits liquid crystallinity. . However, the molecule itself is not limited to the above description as long as it has negative uniaxiality and can give a certain orientation. [0139] The letter retardation in the resin film (D) used in the present invention is preferably formed by forming a layer having negative birefringence composed of a compound having a discotic structure, and the surface of the discotic structure. The angle between the surface of the resin film (D) and the surface of the discotic structure and the surface of the resin film (D) is changed in the thickness direction of the resin film, It is preferable.

[0140] The surface angle (tilt angle) of the discotic liquid crystal structure generally increases with increasing thickness of the discotic liquid crystal phase as the surface force of the resin film increases in the thickness direction of the resin film. Increase or decrease.

[0141] It is preferable that the tilt angle increases as the thickness of the discotic liquid crystal phase increases. In addition, examples of changes in the inclination angle include continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, and intermittent change including increase and decrease. Can do.

[0142] The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction. It is preferable that the inclination angle increases or decreases as a whole even if it includes a region where it does not change. Furthermore, it is preferable that the inclination angle increases as a whole, and it is particularly preferable that the inclination angle changes continuously.

[0143] The resin film (D) having the above-mentioned letter decision is generally prepared by applying a solution obtained by dissolving a discotic compound and other compounds in a solvent onto the resin film (D), drying, and then applying V. It is obtained by heating to the discotic nematic phase formation temperature and then cooling while maintaining the orientation state (discotic nematic phase).

[0144] Alternatively, the resin film (D) having the above-mentioned letter decision is prepared by dissolving a solution in which a discotic compound and other compounds (for example, a polymerizable monomer and a photopolymerization initiator) are dissolved in a solvent. It is obtained by coating on a film, drying, heating to a discotic nematic phase formation temperature, polymerization (by irradiation with UV light, etc.), and further cooling.

[0145] The tilt angle of the discotic phase structure of the discotic liquid crystal, which is a constituent element of the resin film (D) having a letter decision, is generally determined by the discotic compound or the type of alignment film described later or the rubbing of the alignment film surface. Adjust by selecting processing conditions can do. In addition, the inclination angle of the discotic structure on the air surface side is generally determined by selecting a discotic compound or another compound (eg, plasticizer, surfactant, polymerizable monomer and polymer) to be used with the discotic compound. You can also adjust it. Furthermore, the degree of change in the tilt angle can be adjusted by the above selection.

[0146] The plasticizer, surfactant, and polymerizable monomer are compatible with the discotic compound, as long as they do not impair the ability to change the tilt angle of the liquid crystalline discotic compound, or the alignment. Any compound can be used. Among these, a polymerizable monomer (eg, a compound having a vinyl group, a buroxy group, an taliloyl group and a methacryloyl group) is preferable. The above compound is generally used in an amount of 1 to 50% by mass (preferably 5 to 30% by mass) based on the discotic compound.

[0147] As the polymer used together with the discotic compound, any polymer can be used as long as it is compatible with the discotic squeeze compound and can change the tilt angle of the liquid crystalline discotic compound. can do. The polymer is generally 0.1 to 10% by mass (preferably 0.1 to 8% by mass, particularly preferably 0.1 to the discotic compound) so as not to inhibit the alignment of the liquid crystalline discotic compound. Used in an amount of ~ 5% by mass).

[0148] A resin film having a lettering which also has liquid crystalline properties used in the present invention

(D) can be formed of a cellulose acetate film and a film having a lettering formed by disposing a discotic compound provided thereon.

[0149] An alignment film is preferably formed on the surface of the resin film (D) prior to the application of the compound. By providing the alignment film, the arrangement of the discotic compounds can be made regular.

[0150] As a method of forming the alignment film, for example, after applying an alignment polymer such as modified polyvinyl alcohol to the surface of the resin film (D), the surface of the alignment polymer is measured in a certain direction with paper or cloth. A method of turning around is mentioned. Preferable examples of the alignment polymer used in the present invention include alignment polymers described in JP-A-9-152509.

[0151] For the purpose of adjusting letter determination, an aromatic compound having at least two aromatic rings is used as a letter determination increasing agent in a cellulose acetate film. A little.

[0152] The number of aromatic rings of the aromatic compound is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8. 6 is most preferred. The bond relationship between two aromatic rings can be classified into (a) when forming a condensed ring, (b) when directly connecting with a single bond, and (c) when connecting via a linking group (the aromatic ring Therefore, spiro bonds cannot be formed). The bonding relationship may be any of (a) to (c). The aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). Aromatic heterocycles are generally unsaturated heterocycles. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. The heteroatom is particularly preferably a nitrogen atom, preferably a nitrogen atom, an oxygen atom or a sulfur atom.

[0153] Examples of the aromatic heterocycle include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, and triazole. Ring, pyran ring, pyridine ring, pyridazine ring, pyrimidin ring, pyrazine ring and 1,3,5-triazine ring. Preferred aromatic rings are benzene, furan, thiophene, pyrrole, oxazole, thiazole, imidazole, triazole, pyridine, pyrimidine, pyrazine and 1,3,5-triazine. More preferred are benzene rings and 1,3,5-triazine rings.

[0154] The aromatic compound particularly preferably has at least one 1, 3, 5-triazine ring. Such a letter raising agent is in the range of 0.01 to 20 parts by mass, preferably in the range of 0.05 to 15 parts by mass, and more preferably in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of cellulose acetate. : Used in the range of L0 parts by mass. Two or more letter raising agents may be used in combination. Specific examples of the letter decision-increasing agent include compounds described in JP-A Nos. 2000-111914, 2000-275434, and PCTZJP00Z02619.

[0155] In the polarizing plate of the present invention, a primer layer may be provided between the polarizer and the resin film (A) and between the polarizer and the resin film (D). By providing a primer layer, Adhesion with the photon is improved, and mechanical strength, durability of the polarizer, and optical characteristics are improved.

[0156] The primer layer may be a vinyl alcohol polymer layer, a silicone-based layer, a urethane-based layer, an acrylic-based layer, a conjugation-based polymer having a cyclized structure therein, or a hydrogenated product thereof. And the like, and the like. From the viewpoints of reliability, mechanical strength, optical properties, etc., a layer containing a butyl alcohol polymer or a primer containing a conjugated gen-based polymer having a cyclized structure inside or a hydrogenated product thereof, or vinyl alcohol polymerization I like the physical strength.

[0157] The bull alcohol polymer is a conventionally known polymer that is generally known. In this PVA, for example, a vinyl monomer mainly composed of a vinyl ester monomer is polymerized by a conventionally known method to produce a vinyl ester polymer (that is, a single polymer of vinyl ester monomers, two or more types). A copolymer of a vinyl ester monomer and a copolymer of a vinyl ester monomer and another ethylenically unsaturated monomer), and then saponifying the bull ester polymer by a conventional method. Easy to obtain. In the present invention, the saponification degree of PVA used in the present invention is preferably 70 to 99%, and the polymerization degree is 200 to 3000. The PVA used in the present invention may be one in which, for example, acrylic acid, crotonic acid, itaconic acid and the like are copolymerized to a few mol% within a range that does not impair the object of the present invention. It may be modified by graft addition of a compound having an alkyl group, an epoxy group, a carbonyl group, a silanol group, or a thiol group.

[0158] Examples of the primer include a curing agent; a coupling agent such as a silane coupling agent and a titanium coupling agent; a terpene resin, a phenol resin, a terpene-phenol resin, and the like. Tackifiers such as rosin rosin and xylene rosin; inorganic fillers such as calcium carbonate, clay, titanium oxide and carbon black; thixotropic agents such as air mouth gill and disse baron; UV absorbers and antioxidants In addition, stabilizers such as heat stabilizers and hydrolysis stabilizers may be contained.

[0159] The average thickness of the primer layer is preferably 0.01 to 20 μm. 0.05 to: LO μm is more preferable. If the thickness is less than 0.01 μm, it will be difficult to control the thickness, and if it exceeds 20 μm, the durability of the polarizer will decrease.

[0160] The method for forming the primer layer is not particularly limited. For example, the primer layer-forming coating solution Can be formed by coating on a resin film by a known coating method.

[0161] The polarizing plate of the present invention is not particularly limited depending on the production method thereof, but a hard coat layer (B) and an antireflection layer (C) are laminated on one surface of the resin film (A) in advance, and then The other side of the resin film (A) is overlapped with the polarizer through the aforementioned primer layer and Z or adhesive, and the other side of the polarizer is similarly passed through the primer layer and Z or adhesive. The method of laminating the resin film (D) is preferred.

[0162] As the adhesive, known ones can be used, and examples thereof include acrylic-based, polyvinyl alcohol-based, silicon-based, polyester-based, polyurethane-based, polyether-based, and rubber-based adhesives. Among these, it is preferable to use an acrylic adhesive for the resin film (A), and it is preferable to use a polyvinyl alcohol adhesive for the resin film (D).

[0163] In the lamination method using a primer, a solution containing a primer component is applied, and a hard coat layer (B) and an antireflection layer (C) are laminated on both sides of the polarizer before the coating film is dried. The above-mentioned resin film (A) and the above-mentioned resin film (D) are bonded together, and then the solvent is removed and bonded (hereinafter “wet lamination”).

And the solution containing the primer component was applied, and then the solvent was removed and the coating film was dried. Then, the hard coat layer (B) and the antireflection layer (C) were laminated on both sides of the polarizer. Examples thereof include a method in which the resin film (A) and the resin film (D) are bonded together and bonded together by pressurization and Z or heating (hereinafter referred to as “dry lamination”).

[0164] In the case of wet lamination, the solution is applied or dropped onto a polarizer and Z or film with a Meyer bar, gravure coater, microgravure coater, etc., and the laminate is laminated with, for example, two rolls while using a solvent Is removed by heating or the like.

[0165] In the case of dry lamination, the solution is applied to the polarizer and Z or film with a bar coater, roll coater, gravure coater, etc., and the solvent in the coating film is removed using a means such as passing through a drying furnace. Remove.

[0166] In the above, the kind of the intervening primer and the method of pasting the resin film on the polarizer are the above-mentioned resins in which the polarizer, the hard coat layer (B) and the antireflection layer (C) are laminated. Between the film (A) and between the polarizing plate and the resin film (D). It may be different.

[0167] In the present invention, when the resin film (A) and the resin film (D) in which the hard coat layer (B) and the antireflection layer (C) are laminated are bonded to a polarizer, It is preferable to produce a laminate by wet lamination using a solution of a vinyl alcohol polymer. In that case, the viscosity of the vinyl alcohol polymer solution used is preferably in the range of 10 to 20000 cP (centipoise), more preferably 100 to 12000 cP. When the viscosity is less than the above range, the solution flows out of the laminate excessively by pressurization during lamination, and the primer thickness is reduced. On the other hand, when the viscosity exceeds the above range, the coating property is lowered. .

[0168] In wet lamination, it is preferable to use water as the solvent because the adhesive strength between the layers of the laminate is excellent.

[0169] In both wet lamination and dry lamination, lamination of each film and polarizer may be performed by any known means. Is also preferable. -As the roll, a rubber roll and a metal roll, or a rubber roll and a rubber roll can be combined. The pressure at the time of lamination is usually from 1 to: LOOkgf / cm, preferably 3 to 30 kgf / cm.

[0170] By curing, the polarizing plate obtained by the above method can improve the adhesive strength between the polarizer and each film and the durability of the polarizer, and can reduce the warpage of the polarizing plate in a high-temperature and high-humidity environment. . The curing conditions are a temperature of preferably 2 to 150 ° C, more preferably 20 to 80 ° C, a holding time of 0.5 to 200 hours, preferably 48 to: LOO time. When the curing temperature and holding time are in the above ranges, a polarizing film excellent in durability, optical performance and the like can be obtained.

In addition, it is preferable to control the thickness of the primer by applying a pressure to each film and a polarizer after pasting them together via a primer.

[0171] In the polarizing plate of the present invention, the reflectance of the surface on which the resin film (A), the hard coat layer (B), and the antireflection layer (C) are sequentially laminated is usually 0.7% or less, preferably Is less than 0.5%. For example, the reflectance can be obtained as a reflectance at a wavelength of 550 nm by measuring a reflection spectrum at a predetermined incident angle using a known spectrophotometer.

The surface on the antireflection layer (C) side of the polarizing plate of the present invention is excellent in scratch resistance. For example, steel Even after a test (steel wool test) in which the surface of the antireflection layer (C) side of the polarizing plate is rubbed 10 times with a load of 0.025 MPa applied to the wool, the film is visually observed. No scratches are observed on the surface.

Example

[0172] The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified. Evaluation in this example is performed by the following method.

[0173] (1) Depth, height and width of die line

The resin film (A) as a protective layer is irradiated with light, the transmitted light is projected on the screen, and the part with bright or dark stripes of light appearing on the screen. Cut out a 30mm square. The surface of the cut out film of the protective layer is observed with a three-dimensional surface structure analysis microscope (viewing area 5mm x 7mm), converted into a three-dimensional image (Fig. 2), and the cross-sectional profile ( Figure 3) was obtained. The cross-sectional profile was obtained at lmm intervals in the visual field region.

[0174] An average line 11 is drawn on the cross-sectional profile 12, and the length from the average line 11 to the bottom of the concave portion is the depth of the concave portion, or the length from the average line 11 to the top of the convex portion is the convex portion height. Become. The distance between the intersection of the average line 1 1 and the profile 12 is the width.

[0175] The measured force values of the concave portion depth and the convex portion height were respectively determined maximum values, and the widths of the concave portions or convex portions showing the maximum values were respectively determined. The above-mentioned maximum values of the obtained recess depth and convex height, the width of the concave portion showing the maximum value, and the narrower width of the convex portion are the maximum height of the die line and the maximum depth of the die line. And the minimum width of the die line.

[0176] (2) Film thickness Installed a contact web thickness meter (RC-101 rotary caliper meter, manufactured by Meisho Co., Ltd.) on a 1350 mm wide resin film and moved the thickness meter to the side. Measure in the width direction of the resin film at intervals of 0.48 mm. The arithmetic average value (average thickness), maximum thickness, and minimum thickness of the measured values were obtained.

[0177] (3) Moisture permeability

Each film was prepared, and measured by a method according to the cup method described in J IS Z 0208 under the test conditions of leaving for 24 hours in an environment of 40 ° C. and 92% RH. The unit of moisture permeability is gZm ² '2 4h.

[0178] (4) In-plane letter decision (Re), thickness direction letter decision (Rth)

The value was measured using an automatic birefringence meter (manufactured by Oji Scientific Instruments Co., Ltd., KOBRA-21ADH).

[0179] (5) Refractive index of antireflection layer

High-speed spectroscopic ellipsometry (manufactured by J.A. Woollam, M-2000U), temperature 20 ° C ± 2

Under the conditions of ° C and humidity of 60 ± 5%, the antireflection layer (C) of the polarizing plate is irradiated with light in the entire wavelength region at incident angles of 55, 60, and 65 degrees. Wavelength range after measuring

Using the measurement results from 400 to 1000 nm, the refractive index was calculated from these measurement results by fitting.

[0180] (6) Polarizing pencil hardness

According to Japanese Industrial Standard JIS K5600-5-4, the surface of the antireflection layer (C) of the polarizing plate was measured with a load of 500 g.

[0181] (7) Reflectance (%)

A black vinyl tape No. 21 (manufactured by Nitto Denko Corporation) is attached to the surface of the resin film (A) constituting the laminated film C1, and a spectrophotometer (manufactured by JASCO Corporation: “UV-Visible Near-Infrared Spectrophotometer”).

V-570 ”) was used to measure a reflection spectrum at an incident angle of 5 ° on the surface of the antireflection layer (C) constituting the laminated film C1 to obtain a reflectance (%) at a wavelength of 550 nm.

[0182] (8) Scratch resistance test

The antireflection layer surface of the polarizing plate was rubbed 10 times with a load of 0.025 MPa applied to steel wool # 0000, followed by microscopic observation, and scratch resistance was evaluated using the following indices.

○: No scratch

△: Slight scratch

X: Many conspicuous scratches

[0183] (9) Durability test

A polarizing plate (a square with a side of 10 cm) was placed in a constant temperature bath at a temperature of 60 ° C and a humidity of 90%, allowed to stand for 1000 hours, and then returned to room temperature to observe the change of the force polarizing plate.

○: No change. Δ: Sled at both ends.

X: Deformation, shrinkage, or winding occurs at both ends.

[0184] (10) Photoelastic coefficient

The measurement was carried out using a photoelastic constant measuring apparatus (PHEL-20A manufactured by Uniobuto) under the conditions of a temperature of 20 ° C ± 2 ° C and a humidity of 60 ± 5%.

[0185] (11) Evaluation of display performance

The prepared liquid crystal display device is left in a constant temperature bath at 60 ° C and 90% humidity for 500 hours, then removed, and the background is displayed in black with white characters, and the line of sight is moved up, down, left and right from the front. The angle at which white characters cannot be read is measured. The angle of the viewing angle was evaluated based on the following criteria to evaluate the quality of the viewing angle characteristics.

○: 60 degrees or more

X: Less than 60 degrees

[0186] (12) Light leakage evaluation

The polarizing plate was cut into a size of 10 inches square, and bonded to one side of the glass plate with a pressure-sensitive adhesive so that the resin film D was on the glass plate side, to prepare a test polarizing plate. Two test polarizing plates were prepared and left for 500 hours in a constant temperature bath at a temperature of 60 ° C and a humidity of 90%. The two test polarizing plates after standing are arranged in a crossed Nicol orientation with the resin film D facing each other, and the light transmittance for the nine-point JIS Z8701 twice field of view (C light source) shown in Fig. 4 Were measured, and the measured values were substituted into the following formula to calculate the light leakage.

[0187] Light leakage = ((T2 + T4 + T6 + T8) / 4) / ((Tl + T3 + T5 + T7 + T9) / 5) Tx is the light transmittance at the measurement point (X) (1), (2), (3), (4), (5), (6), (7), and (8) were measured at a position 10 mm from the end. 5 was measured at the intersection of diagonal lines of the test polarizing plate.

○: Light leakage is 2 or less

X: Light leakage is over 2

[0188] (13) Color unevenness

Place the prepared polarizing plate on a backlight with an illuminance of 33,000 lux, and observe the uneven color within the polarizing plate surface. Y: No color unevenness

X: Color irregularity

[0189] (14) Heat resistance test

Place the polarizing plate (a square with a side of 10 cm) in a thermostat at 90 ° C, leave it for 1000 hours, and leave it at room temperature before and after the test (position (5) in Fig. 4). Change (ΔT) was investigated. The heat test results were evaluated according to the following evaluation criteria.

○: ΔΤ is 1.0% or less

□: ΔΤ exceeds 1.0% and less than 3.0%

X: ΔΤ is 3.0% or more

[0190] (15) Moisture resistance test

A polarizing plate (a square with a side of 10 cm) is placed in a thermostatic chamber at 60 ° C and 90% humidity, left for 1000 hours, and then left at room temperature before and after the test ((5) in Fig. 4). Change (ΔΤ). The moisture resistance test results were evaluated according to the following evaluation criteria.

○: ΔΤ is 2.0% or less

□: ΔΤ exceeds 2.0% and less than 5.0%

Χ: ΔΤ is 5.0% or more

[0191] (Production Example 1) Preparation of resin film A1

A pellet of norbornene polymer (hydrogenated product of ring-opening polymer of norbornene monomer, ΖΕΟΝΟ R 1420, manufactured by Nippon Zeon Co., Ltd .; glass transition temperature Tg: 136 ° C) was used with a hot air dryer in which air was circulated. Dry at 100 ° C. for 4 hours. The pellets were then processed into a 650 mm-wide vertical type with a 50 mm single-screw extruder with a leaf disk-shaped polymer filter (filtration accuracy 30 μm) and a chrome plating with a surface roughness of Ra = 0.23 μm on the inner surface. Extrude at 260 ° C using a die and pass the extruded sheet-like amorphous thermoplastic resin through three cooling drums (diameter 250mm, drum temperature 120 ° C, take-off speed 0.35mZs) After cooling, a resin film A1 which is an optical film having a thickness of 40 / ζ πι and a width of 600 mm was obtained. In the above-described extrusion cooling process, all the cooling drums (three) for the T-type die force are placed in a pressure vessel maintained at 30 kPa.

[0192] (Production Example 2) Keny treatment of resin film On both sides of triacetylcellulose (TAC) film (Co-Force Minolta, KC 4UX2M: photoelastic coefficient 32 X 10 " ¹² / Pa, moisture permeability 300gZm ² '24hr) with an average thickness of 40 μm Apply 25 mL Zm 2 of a 1.5 molar ZL isopropyl alcohol solution of potassium hydroxide and dry for 5 seconds at 25 ° C, then wash with running water for 10 seconds, and finally spray the air at 25 ° C. The surface was dried to obtain a resin film D1 in which both sides of the triacetyl cellulose film were subjected to a ken treatment.

[Production Example 3] Formation of alignment film

One side of the resin film D1 obtained in Production Example 2 comprises 10 parts of polybulal alcohol represented by the following chemical formula 1, 371 parts of water, 119 parts of methanol, and 0.5 part of glutaraldehyde (crosslinking agent). The alignment film coating solution is applied using a # 16 wire bar coater and dried with 60 ° C hot air for 60 seconds and then with 90 ° C hot air for 150 seconds to form a film with an alignment film laminated. Got. Subsequently, the alignment film formed on the film D1 was rubbed in a direction parallel to the direction of the slow axis of the resin film.

[0194] [Chemical 1]

[0195] (Production Example 4) Preparation of resin film D4

The alignment film subjected to a rubbing treatment, the discotic liquid crystal I匕合object 32 shown below of 2.6 wt ^_0/0, cellulose acetate butyrate 0.7 wt ^_0/0, modified trimethyl Chiroru Represented by Formula 3 tri Atari rate 3.2 weight ^_0/0, a sensitizer 0.4 wt ^_0/0 Represented by Formula 4, photoinitiator shown below hear 5 1.1 wt%, and methyl E chill ketone 62 A curable composition containing 0% by weight was applied by spin coating, the solvent was removed, and then ultraviolet rays were irradiated at an intensity of 20 mjZcm ² (adjusted to an average irradiation time of 3 seconds) to produce liquid crystal. The alignment state of the functional compound was fixed to obtain a resin film D4 in which a liquid crystal layer was formed. Obtained fat Irum D4 Re was 50nm, Rth was 20nm

[0196] [Chemical 2]

[0197] [Chemical 3]

C H 2 (O C ^ l-ί) i — O— C O C H = C H 2

2 H g--'― I i 2 (2 H 4) _ra ― ― ^ ― 1 Ιΐ s

1 3. 5

[0198] [Chemical 4] ο

:(,)) — c _{2 H i}

2 ⁱ 5

[0199] [Chemical 5]

H 3 C S

(Production Example 5) Preparation of resin film D5

4- n-heptylbenzoic acid 10 mmol, terephthalic acid 95 mmol, methylhydroquinone case Polymerization was carried out at 270 ° C. for 12 hours in a nitrogen atmosphere using 50 mmole of tate, 50 mmole of cateconoresin acetate, and 10 mg of sodium acetate to obtain a reaction product. Next, the obtained reaction product was dissolved in tetrachloroethane and then reprecipitated with methanol for purification to obtain 22 g of liquid crystalline polyester.

[0201] This liquid crystalline polyester had a logarithmic viscosity of 0.15, a nematic phase as a liquid crystal phase, an isotropic-liquid crystal phase transition temperature of 240 ° C, and a glass transition temperature of 75 ° C.

[0202] Next, an 8 wt% tetrachloroethane solution of the above-mentioned liquid crystalline polyester was applied onto the alignment film obtained in Production Example 3, the solvent was removed, and then heat-treated at 190 ° C for 20 minutes and air-cooled. The orientation state of the property compound was fixed to obtain a resin film D5. The obtained resin film D5 had a Re of 50 nm and an Rth of 130 nm.

[0203] (Production Example 6) Preparation of resin film A2

A resin film A2 was obtained in the same manner as in Production Example 1 except that in the extrusion process using three cooling drums, these cooling drums were not put in the pressure vessel.

[0204] (Production Example 7) Preparation of hard coat layer forming composition H

30 parts of hexafunctional urethane acrylate oligomer, 40 parts of butinorea acrylate, 30 parts of isopropanol acrylate and 10 parts of 2,2 diphenol 1-one were mixed with a homogenizer to produce antimony pentaoxide fine particles (average particle size 20 nm, a hydroxyl group is bonded to the antimony atom appearing on the surface of the pyrochlore structure at a ratio of 1).) A 40% methyl isobutyl ketone solution of A hard coat layer forming composition H was prepared by mixing at a ratio of 50% by weight of the total solid content.

[0205] (Production Example 8) Preparation of composition L for forming an antireflection layer

Silicone having a weight average molecular weight of 850, 21 parts of tetramethoxysilane, 36 parts of methanol, 2 parts of water, and 2 parts of 0.1N aqueous hydrochloric acid were mixed and stirred in a high-temperature bath at 25 ° C for 2 hours. A resin was obtained. Next, hollow silica fine particle Z silicone resin (condensation compound equivalent) is prepared by carving hollow silica fine particle isopropanol dispersion sol (solid content 20%, average primary particle size approx. 35 nm, outer shell thickness approx. 8 nm) on the silicone resin. ) Was 8: 2 by weight ratio based on solid content. Finally, dilute with methanol so that the total solid content is 1%. An antireflection layer forming composition L was prepared.

[Production Example 9] Production of polarizer P

A 75-m-thick polybulal alcohol film is uniaxially stretched 2.5 times and iodine 0.2 g

Immerse in an aqueous solution containing ZL and potassium iodide 60gZL at 30 ° C for 240 seconds, then immerse in an aqueous solution containing 70gZL hydrofluoric acid and 30gZL potassium iodide, and simultaneously uniaxially stretch 6.0 times for 5 minutes Retained. Finally, it was dried at room temperature for 24 hours, and a polarizer P with an average thickness of 30 m and a degree of polarization of 99.95% was obtained.

[Production Example 10] Fabrication of backlight (light source) side polarizing plate PB

Through the polyvinyl alcohol adhesive so that the saponified surface of the resin film D1 obtained in Production Example 2 is on the polarizer P side on both sides of the polarizer P obtained in Production Example 9. The knock light side polarizing plate PB was obtained by pasting.

(Example 1)

Corona discharge treatment was performed on both surfaces of the resin film A1 obtained in Production Example 1 using a high-frequency oscillator [Kasuga Electric Co., Ltd., high-frequency power supply AGI-024, output 0.8 KW], and the surface tension was 0 072 NZm of a resin film was obtained.

[0208] Next, the hard coat layer forming composition H obtained in Production Example 7 was applied to the resin film using a die coater, dried at 80 ° C for 5 minutes, and then irradiated with ultraviolet rays (integrated). The hard coat layer forming composition H was cured by irradiating a light amount of 300 mj / cm ² ) to form a hard coat layer having a thickness of 5 μm to obtain a laminated film B1.

[0209] Further, the antireflection layer-forming composition L obtained in Production Example 8 was coated on the hard coat layer side of the laminated film B1, and the film was heat-treated at 120 ° C for 10 minutes in an oxygen atmosphere. A laminated film C 1 having an antireflection layer having a thickness of 1 OO nm was obtained.

[0210] A polarizer P was bonded to the resin film A1 side of the laminated film C1 via an acrylic adhesive (manufactured by Sumitomo 3EM, "D P-8005 Clear"), and then obtained in Production Example 2. The obtained Ken-treated resin film D1 was bonded to the other surface of the polarizer P via a polybular alcohol-based adhesive to obtain a polarizing plate 1. Table 1 shows the evaluation results.

[0211] (Example 2)

50 μm thick polycarbonate film PC (Sumitomo Beta) A polarizing plate 2 was obtained in the same manner as in Example 1 except that Sumilite FS-1650H manufactured by Wright Co. was used.

[0212] (Example 3)

A polarizing plate 3 was obtained in the same manner as in Example 1 except that a 25-um thick polyethylene terephthalate film PET (Ester film E5101, manufactured by Toyobo Co., Ltd.) was used instead of the resin film D1.

[0213] (Comparative Example 1)

A polarizing plate 4 was obtained in the same manner as in Example 1 except that the resin film A2 obtained in Production Example 6 was used instead of the resin film A1. Table 1 shows the evaluation results.

[0214] (Comparative Example 2)

A polarizing plate 5 was obtained in the same manner as in Example 1 except that the resin film D1 treated in both sides obtained in Production Example 2 instead of the resin film A1 was used as the resin film A3. .

[0215] The evaluation results are shown in Table 1.

[0216] (Example 4)

Next, a liquid crystal display device was produced. Here, instead of the resin film D1, the resin film D4 obtained in Production Example 4 was used, and the surface on which the liquid crystal layer was not formed was aligned with the slow axis of the resin film D4 relative to the absorption axis of the polarizer. A polarizing plate 6 was obtained in the same manner as in Example 1 except that it was bonded to a polarizer so as to be vertical. The polarizing plate 6 was used as an observer side polarizing plate (outgoing side polarizing plate). Further, the polarizing plate PB obtained in Production Example 10 was used as the backlight side polarizing plate (incident side polarizing plate). In the IPS mode liquid crystal cell (thickness 2.74 m, positive dielectric anisotropy, birefringence index An = 0.09884 with a wavelength of 550 nm, pretilt angle 0 degree), the polarizing plate 6 is slow when no voltage is applied to the liquid crystal cell. The liquid crystal layer of the polarizing plate 6 was attached so that the phase axis and the slow axis of the resin film D4 were parallel to each other and the liquid crystal layer of the polarizing plate 6 was on the liquid crystal cell side. Then, the backlight side polarizing plate PB was attached to the other surface of the liquid crystal cell in a crossed Nicol arrangement to produce a liquid crystal display device 1. Table 2 shows the evaluation results.

[Example 5]

Instead of the resin film D1, the resin film D5 obtained in Production Example 5 is used as the resin film D. A polarizing plate 7 was obtained in the same manner as in Example 1 except that bonding was performed so that the slow axis of 5 was the absorption axis of the polarizer P. Here, the polarizing plate 7 was used as the observer-side polarizing plate. In addition, in the VA mode liquid crystal cell (thickness 2.74 ^ m, dielectric anisotropy is positive, birefringence An = 0.99884 with a wavelength of 550 nm, pretilt angle 90 degrees), the above polarizing plate 7 has no liquid crystal cell. The film was pasted so that the slow axis at the time of voltage application and the slow axis of the resin film D5 were parallel, and the liquid crystal layer of the polarizing plate 7 was on the liquid crystal cell side. Subsequently, the liquid crystal display device 2 was produced so that the knock light side polarizing plate PB was placed in a crossed Nicols arrangement. Table 2 shows the evaluation results.

[0218] (Comparative Example 3)

A polarizing plate 8 was obtained in the same manner as in Example 1 except that the resin film D1 obtained in Production Example 2 was used as the resin film A3 instead of the resin film A1. A liquid crystal display device 3 was obtained in the same manner as in Example 4 except that the polarizing plate 8 was used instead of the polarizing plate 6. Table 2 shows the evaluation results.

[0219] [Table 1]

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Polarizing plate 1 2 3 4 5 Antireflection layer (c)

Refractive index 1.36 1.36 1.36 1.36 1.36 Hard coat layer (B) HHHHH Refractive index 1.62 1.62 1.62 1.62 1.62 Resin film (A) A1 A1 A1 A2 A3 (D1) Thickness (m) 40 40 40 40 40 Moisture permeability (gm ² '24hr ) 2.8 2.8 2.8 3.5 300 photoelastic coefficient ^{(X10- 12 ZPa) 6.5 6.5 6.5} 7.5 32 die lines maximum depth and a maximum

Nm) 28 28 28 75 40 Die line minimum width (nm) 1300 1300 1300 350 700 Polarizer PPPPP resin film (D) D1 PC PET D1 D1 Thickness 40 50 25 40 40 Moisture permeability 300 65 75 300 300 Reflectivity 0.6 0.6 0.6 0.6 0.6 Pencil hardness HHHHH Scratch resistance test ○ ○ ○ ○ ○ Durability test ○ ○ ○ ○ X

Heat resistance test / 0) ○ Δ Δ Δ Δ Humidity test / 0) ○ Δ Δ ○ X

Light leakage ○ ○ ○ ○ X

Color unevenness ○ ○ ○ X X

[0220] [Table 2]

[0221] From the results of Tables 1 and 2, the following can be seen.

[0222] As shown in Example 1, the polarizing plate of the present invention uses a resin film (A) having a predetermined photoelastic coefficient and moisture permeability, and a resin film having substantially no die line (D ), Especially TAC It can be seen that by using the film, a polarizing plate having excellent mechanical strength, antireflection performance, scratch resistance, heat resistance, and moisture resistance with no color unevenness can be formed. Furthermore, in the durability test

It is clear that the polarizing plate has no light leakage. Although Examples 2 and 3 are slightly inferior to Example 1 in heat resistance and moisture resistance, the other effects can be substantially the same as Example 1.

[0223] On the other hand, in Comparative Example 1, it can be seen that the depth and height of the die line are larger than the predetermined values, and therefore the color unevenness is inferior. Moreover, in Comparative Example 2, it can be seen that the resin film (A) has poor mechanical strength and display performance because the photoelastic coefficient and moisture permeability are large.

[0224] As shown in Table 2, when the liquid crystal display devices shown in Examples 4 and 5 were prepared and the viewing angle characteristics were evaluated according to various liquid crystal modes, the liquid crystal display using the polarizing plate of the present invention was evaluated. It can be seen that the device has good viewing angle characteristics even after the durability test. On the other hand, in Comparative Example 3, it was confirmed that the viewing angle characteristics deteriorated after the durability test.

Claims

The scope of the claims

[1] A resin film (A) made of an alicyclic structure-containing resin laminated on one surface of a polarizer, and a hard coat layer (B) laminated on the surface of the resin film (A),

An antireflection layer (C) laminated on the surface of the hard coat layer ( _B) ;

A resin film (D) laminated on the other surface of the polarizer,

The榭脂film (A) has a thickness of 5 to 200 mu m, moisture permeability 0. 3~40gZm ² '24hr, photoelastic coefficient 12. 0 X 10- ¹² ZPa less, and a maximum depth of die line and The maximum height is 5 Onm or less and the minimum width of the die line is 500 nm or more. The resin film (D) has a thickness of 5 to 200 μm and a moisture permeability of 50 to 1500 ₈ 1! 1 ² '24111: A polarizing plate.

[2] The polarizing plate according to [1], wherein the antireflection layer (C) has a refractive index of 1.37 or less.

[3] The polarizing plate according to [1], wherein the antireflection layer (C) comprises an air mouth gel.

[4] The resin film according to claim 1, wherein the resin film (D) has a cellulose ester as a main component.

[5] The polarizing plate according to claim 1, which is a film showing a resin film (D) force letter decision.

[6] The polarizing plate according to claim 1, wherein the resin film (A) has an in-plane letter pattern (Re) of 4 nm or less.

[7] The polarizing plate according to [1], wherein the resin film (A) has a thickness direction letter-thickness (Rth) of 4 nm or less.

[8] Having a light source, an incident side polarizing plate, a liquid crystal cell, and an outgoing side polarizing plate in this order,

The exit-side polarizing plate is a polarizing plate according to claim 1,

A liquid crystal display device in which the antireflection layer (C) side of the output-side polarizing plate faces the viewing side.