JP2006071875A - Polarizing plate, its manufacture method and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polarizing plate suitable for the backlight side of a liquid crystal display device, which is free from dimensional deviation in a width direction when a retardation film, a polarizing film and a backlight side polarizing film protection film are stuck, is inexpensive and is excellent in mass productivity, and to provide its manufacture method and the liquid crystal display device. <P>SOLUTION: The polarizing plate is used for the backlight side of the liquid crystal cell of the liquid crystal display device, and has protection films on both sides of the polarizing film. The polarizing film is a polyvinyl alcohol based polarizing film, a liquid crystal cell side polarizing film protection film is the retardation film produced by stretching cellulose ester film and set so that retardation Ro is 20 to 300 nm and retardation Rt is 70 to 400 nm under a condition of 23°C and 55%RH, and the backlight side polarizing film protection film is the cellulose ester film whose rate of dimensional change after saponification treatment is 0.01 to 0.10% of that before the saponification treatment. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polarizing plate, a manufacturing method thereof, and a liquid crystal display device.

  In recent years, development of thin and light notebook computers has been progressing. Along with this, the demand for thinner and higher performance protective films for polarizing plates used in display devices such as liquid crystal display devices has become stronger. Required.

  A polarizing plate used in a liquid crystal display device or the like is generally configured by attaching protective films made of a polymer film on both surfaces of a polarizing film.

  The polarizing film includes, for example, a polyvinyl alcohol film, an ethylene vinyl alcohol film, a cellulose film, a polycarbonate film, etc., but a stretched polyvinyl alcohol film dyed with iodine for reasons of workability or the like, or polyvinyl In general, an alcohol film is stretched and then dyed with iodine.

  As a protective film, it has low optical anisotropy, excellent transparency, and adhesion to the polarizing film, as well as UV absorption and moisture barrier functions to prevent dimensional stability and polarizing film deterioration. It is important to excel. The polarizing film and the protective film use an adhesive or pressure sensitive adhesive mainly composed of natural rubber, synthetic rubber, acrylic resin, butyral resin, epoxy resin, polyester resin, polyamide resin, polyvinyl alcohol resin, etc. Glued together.

  Retardation films used in liquid crystal display devices, etc. are used in combination with polarizing plates to solve problems such as color compensation and viewing angle expansion. Thus, it has a function of converting linearly polarized light into circularly polarized light or conversely converting circularly polarized light into linearly polarized light. In order to obtain the above effect with a single retardation film, the retardation is preferably λ / 4 at the wavelength (λ) incident on the retardation film. Moreover, it is possible to reduce the coloring of reflected light by using it as an antireflection film in a front plate of a plasma display or a display using an organic EL element. When the retardation film is used in combination with a polarizing plate, the effects as described above can be obtained. Until now, in a liquid crystal display device, a polarizing plate and a retardation film have been configured as separate optical elements.

  Examples of the material for the retardation film include norbornene, polycarbonate, polysulfone, polyethersulfone, and amorphous polyolefin. Since these polymer retardation films are used in combination with a polarizing plate, they are generally used by being bonded together, and there are disadvantages that the number of laminated films is large and the cost is high. Moreover, in addition to the complexity of the manufacturing process, there is a problem in that defective products are generated when bubbles or foreign substances enter or wrinkles enter during bonding.

  On the other hand, the retardation film mainly composed of cellulose ester film can shorten the manufacturing process of the liquid crystal display device by bonding the retardation film to the polarizing film instead of the protective film of the polarizing plate. It is known that the occurrence of defects can be reduced (see, for example, Patent Documents 1 to 5).

  The polarizing plate is composed of a cellulose ester-based retardation film, a polarizing film using polyvinyl alcohol and iodine, and a cellulose ester-based polarizing plate protective film having substantially no retardation value.

  When using a polarizing plate in a liquid crystal display device, the polarizing plate on the viewing side is provided with an antireflection layer, an antiglare layer, and an antiglare antireflection layer on a cellulose ester-based polarizing plate protective film. A scratch-preventing protective film is applied for the purpose of protecting the antireflection layer, the antiglare layer, and the antiglare and antireflection layer (to prevent scratches on the outermost surface during handling). For this reason, the scratch-protecting protective film is stuck during the saponification treatment for improving the adhesion with the polarizing film.

  On the other hand, it is known that the polarizing plate used on the backlight side of the liquid crystal cell is used after saponifying the cellulose ester polarizing plate protective film as it is. And, when trying to process the cellulose ester-based polarizing plate protective film in a roll state to improve production efficiency, there is no problem of dimensional difference in the polarizing plate manufacturing on the viewing side, but in the manufacturing of the polarizing plate on the backlight side, saponification is performed. Because the dimensions in the width direction are different between the cellulose ester phase-difference film after treatment and the cellulose ester-type polarizing plate protective film after saponification treatment, the end part is in a single state at the time of bonding, and liquid crystal including meandering It has been found that there is a problem that the usable range is narrowed for safety for size cutting for display devices.

  In addition, the cellulose ester-based retardation film on the viewing side has a scratch-preventing protective film, so the analysis shows that there is almost no dimensional variation, and the cellulose-ester polarizing plate protective film on the backlight side is also visible. Although the said problem can be solved by sticking a flaw prevention protective film similarly to the side, the number of processes increases and a problem arises in terms of cost.

Moreover, in patent document 6, the active ray hardening resin layer is provided on the surface of the cellulose-ester film of the both sides of the polarizing film used for a polarizing plate, the polarizing plate which provided the single-sided antireflection layer was produced, and the upper and lower sides of a liquid crystal cell However, the present invention is not suggested.
JP 2002-71957 A JP 2002-62430 A JP 2001-249223 A JP 2002-82226 A JP 2002-98732 A JP 2003-29036 A

  The object of the present invention is that there is no deviation in the width direction when laminating a retardation film, a polarizing film, and a backlight side polarizing film protective film, and it is on the backlight side of a liquid crystal display device that is low in cost and excellent in mass productivity. An object is to provide a suitable polarizing plate, a method for producing the same, and a liquid crystal display device.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A polarizing plate used on a backlight side of a liquid crystal cell of a liquid crystal display device, wherein the polarizing film has a protective film on both sides of the polarizing film, the polarizing film is a polyvinyl alcohol polarizing film, and the liquid crystal cell side polarizing film protection The film is produced by stretching a cellulose ester film, and is a retardation film having a retardation Ro defined by the following formula of 20 to 300 nm and a retardation Rt of 70 to 400 nm under the conditions of 23 ° C. and 55% RH. The polarizing plate, wherein the right-side polarizing film protective film is a cellulose ester film having a dimensional change rate of 0.01 to 0.10% after the saponification treatment with respect to that before the saponification treatment.

Ro = (Nx−Ny) × d
Rt = ((Nx + Ny) / 2−Nz) × d
(In the formula, Nx represents the maximum refractive index in the film plane, Ny represents the refractive index in the direction perpendicular to Nx in the film plane, Nz represents the refractive index in the thickness direction, and d represents the thickness (nm) of the film.)
(Claim 2)
The backlight side polarizing film protective film has an actinic radiation curable resin layer on the backlight side, and the retardation Ro defined by the above formula is 0 to 20 nm and the retardation Rt is 0 under the conditions of 23 ° C. and 55% RH. The polarizing plate according to claim 1, wherein the polarizing plate is ˜70 nm.

(Claim 3)
The polarizing plate according to claim 1, wherein the retardation film contains a retardation increasing agent.

(Claim 4)
The polarizing plate according to claim 3, wherein the retardation increasing agent is a rod-shaped compound.

(Claim 5)
The backlight side polarizing film protective film is cellulose triacetate, the active ray curable resin used for the active ray curable resin layer is an acrylic or acrylurethane UV curable resin, and the active ray curable resin layer film Thickness is 1-20 micrometers, The polarizing plate of any one of Claims 1-4 characterized by the above-mentioned.

(Claim 6)
A method for producing a polarizing plate used on a backlight side of a liquid crystal cell of a liquid crystal display device, wherein the polarizing film has a protective film on both sides of the polarizing film, the polarizing film being a roll-shaped polyvinyl alcohol polarizing film The liquid crystal cell-side polarizing film protective film is produced by stretching a cellulose ester film, and under the conditions of 23 ° C. and 55% RH, the retardation Ro defined by the following formula is 20 to 300 nm, and the retardation Rt is 70 to It is a roll-like retardation film of 400 nm, and the backlight side polarizing film protective film has a dimensional change rate after saponification treatment of 0.01 to 0.10% with respect to that before saponification treatment except for the front and rear ends. The saponified retardation film, the polyvinyl alcohol polarizing film, the saponified backlight side polarizing film protective film Method for producing a polarizing plate, characterized in that bonded to the continuous state.

Ro = (Nx−Ny) × d
Rt = ((Nx + Ny) / 2−Nz) × d
(In the formula, Nx represents the maximum refractive index in the film plane, Ny represents the refractive index in the direction perpendicular to Nx in the film plane, Nz represents the refractive index in the thickness direction, and d represents the thickness (nm) of the film.)
(Claim 7)
The method for producing a polarizing plate according to claim 6, wherein the average value of the dimensional change rate in the width direction after the saponification treatment of the backlight side polarizing film protective film is 0.04% or less.

(Claim 8)
Between the step of continuously laminating the saponified retardation film, the polyvinyl alcohol polarizing film, the saponified backlight-side polarizing film protective film in a roll state and the winding step, the retardation film The method for producing a polarizing plate according to claim 6 or 7, further comprising a step of providing an adhesive layer and a peeling protective layer on an adhesive surface to the liquid crystal cell.

(Claim 9)
A polarizing plate used on a backlight side of a liquid crystal cell of a liquid crystal display device, wherein the polarizing film has a protective film on both sides of the polarizing film, the polarizing film is a polyvinyl alcohol polarizing film, and the liquid crystal cell side polarizing film protection The film is prepared by stretching a cellulose ester film, and contains a retardation increasing agent having a retardation Ro defined by the following formula of 20 to 300 nm and a retardation Rt of 70 to 400 nm under the conditions of 23 ° C. and 55% RH. It is a phase difference film, and the backlight side polarizing film protective film is a cellulose ester film having a retardation Ro defined by the following formula of 0 to 20 nm and a retardation Rt of 0 to 70 nm under the conditions of 23 ° C. and 55% RH. An active ray curable resin layer having a film thickness of 1 to 20 μm on the backlight side surface; A polarizing plate, wherein the active ray curable resin used to line the cured resin layer is an acrylic, acrylic urethane UV curing resin.

Ro = (Nx−Ny) × d
Rt = ((Nx + Ny) / 2−Nz) × d
(In the formula, Nx represents the maximum refractive index in the film plane, Ny represents the refractive index in the direction perpendicular to Nx in the film plane, Nz represents the refractive index in the thickness direction, and d represents the thickness (nm) of the film.)
(Claim 10)
The polarizing plate according to any one of claims 1 to 5 and 9, or the polarizing plate obtained by the method for producing a polarizing plate according to any one of claims 6 to 8 is used. Liquid crystal display device.

  According to the present invention, there is no dimensional deviation in the width direction when laminating the retardation film, the polarizing film and the backlight side polarizing film protective film, and it is suitable for the backlight side of a liquid crystal display device which is low in cost and excellent in mass productivity. A polarizing plate, a manufacturing method thereof, and a liquid crystal display device can be provided.

  The present inventor, when producing a polarizing plate by continuously laminating a saponified retardation film, a polarizing film and a saponified backlight-side polarizing film protective film in a roll shape, We analyzed and analyzed the phenomenon of misalignment. As a result, the retardation film after the saponification treatment is slightly larger in dimensions than before the saponification treatment, whereas the backlight side polarizing film protective film is expanded due to the saponification treatment, and the amount of elongation is larger. I found out.

  As a result of earnest research combined with these analysis studies, the present inventor is a polarizing plate used on the backlight side of the liquid crystal cell of the liquid crystal display device, and having a protective film on both sides of the polarizing film, The polarizing film is a polyvinyl alcohol polarizing film, the liquid crystal cell side polarizing film protective film is produced by stretching a cellulose ester film, and the retardation Ro defined by the above formula is 20 under the conditions of 23 ° C. and 55% RH. Cellulose ester having a retardation film having a retardation Rt of 70 to 400 nm and a polarizing film protective film on the backlight side of 0.01 to 0.10% after saponification, With the polarizing plate that is a film, the width direction of the retardation film, polarizing film, and backlight side polarizing film protective film is bonded. No displacement law, found that a polarizing plate which is suitable for a backlight side of a liquid crystal display device with excellent mass productivity can be obtained at low cost. Particularly, the dimensional change rate of the backlight side polarizing film protective film is 0.01 to 0.10%, which is a low value close to the dimensional change rate of the retardation film.

  Further, a polarizing plate used on the backlight side of a liquid crystal cell of a liquid crystal display device, and having a protective film on both sides of the polarizing film, the polarizing film is a polyvinyl alcohol polarizing film, The film protective film is prepared by stretching a cellulose ester film, and contains a retardation increasing agent having a retardation Ro defined by the following formula of 20 to 300 nm and a retardation Rt of 70 to 400 nm under the conditions of 23 ° C. and 55% RH. The backlight side polarizing film protective film is a cellulose ester film having a retardation Ro defined by the following formula of 0 to 20 nm and a retardation Rt of 0 to 70 nm under the conditions of 23 ° C. and 55% RH. Yes, it has an actinic radiation curable resin layer with a film thickness of 1-20 μm on the backlight side surface Active ray curable resin is acrylic used for the active ray curable resin layer, the polarizing plate is a UV curable resin acrylic urethane, it found that similar effect is obtained. In the present invention, the retardation film contains a retardation increasing agent, and the retardation of the retardation film is high, whereby the dimensional change rate of the backlight side polarizing film protective film exceeds 0.10%. The same effect can be obtained.

  Further, a method for producing a polarizing plate used on the backlight side of a liquid crystal cell of a liquid crystal display device, wherein the polarizing film has a roll-shaped polyvinyl alcohol system. It is a polarizing film, and the liquid crystal cell-side polarizing film protective film is produced by stretching a cellulose ester film. Under the conditions of 23 ° C. and 55% RH, the retardation Ro defined by the following formula is 20 to 300 nm, and the retardation Rt is It is a roll-shaped retardation film of 70 to 400 nm, and the backlight side polarizing film protective film has a dimensional change rate after saponification treatment of 0.01 to 0.10% with respect to that before saponification treatment except for the front and rear ends. The retardation film subjected to saponification treatment, the polyvinyl alcohol polarizing film, and the backlight side polarizing film protective film subjected to saponification treatment Due to the manufacturing method of the polarizing plate that is continuously bonded in a roll state, there is no deviation in the width direction when laminating the retardation film, polarizing film and backlight side polarizing film protective film, and low cost and mass productivity It has been found that a method for producing a polarizing plate suitable for the backlight side of an excellent liquid crystal display device can be obtained.

  Hereinafter, the present invention will be described in detail.

(Cellulose ester film)
In the present invention, a cellulose ester film having a low low birefringence / wavelength dispersion property is used as a preferable organic material for the liquid crystal cell side polarizing film protective film (retardation film) and the backlight side polarizing film protective film.

  Examples of cellulose ester films include triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, and cellulose nitrate. Although cellulose ester is mentioned, Preferably it is cellulose ester.

  The cellulose used as a raw material for the cellulose ester film is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. In addition, the cellulose ester films obtained from these can be used alone or in an arbitrary ratio, but it is preferable to use 50% by mass or more of cotton linter.

  If the molecular weight of the cellulose ester film is large, the modulus of elasticity increases. However, if the molecular weight is increased too much, the viscosity of the cellulose ester solution becomes too high, resulting in a decrease in productivity. The molecular weight of the cellulose ester is preferably 80000 to 200000 in terms of number average molecular weight (Mn), more preferably 100000 to 200000. The cellulose ester used in the present invention preferably has an Mw / Mn ratio of 1.4 to 3.0, more preferably 1.4 to 2.3.

  Since the average molecular weight and molecular weight distribution of the cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the mass average molecular weight (Mw) can be calculated using this, and the ratio can be calculated.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 1,000,000 to 500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

  The total acyl group substitution degree of the cellulose ester is 2.0 to 2.95 (unsubstituted hydroxyl group 0.05 to 1.0), and 2.6 to 2.9 (unsubstituted hydroxyl group 0.1 to 0). .4) is preferably used. The total acyl group substitution degree can be measured according to ASTM-D817-96.

  Another preferred cellulose ester has an acyl group having 2 to 22 carbon atoms as a substituent, the substitution degree of the acetyl group is X, and the substitution degree of the acyl group of 3 to 22 carbon atoms is Y. Sometimes, it is a cellulose ester that simultaneously satisfies the following formulas (I) and (II).

Formula (I) 2.6 ≦ X + Y ≦ 2.9
Formula (II) 0 ≦ X ≦ 2.5
Among them, cellulose acetate propionate (total acyl group substitution degree = X + Y) satisfying 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 1.0 is preferable. The portion not substituted with an acyl group usually exists as a hydroxyl group. These cellulose esters can be synthesized by a known method.

<solvent>
The cellulose ester film is dissolved in a solvent to form a dope, which is cast on a substrate to form a film. At this time, since it is necessary to evaporate the solvent after extrusion or casting, it is preferable to use a volatile solvent. Furthermore, it does not react with a reactive metal compound or a catalyst, and does not dissolve the casting base material. Two or more solvents may be mixed and used.

  Here, an organic solvent having good solubility with respect to the cellulose ester film is referred to as a good solvent, and exhibits a main effect on dissolution, and an organic solvent used in a large amount among them is a main (organic) solvent or a main ( Organic) solvent.

  Examples of good solvents include ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethers such as tetrahydrofuran (THF), 1,4-dioxane, 1,3-dioxolane, 1,2-dimethoxyethane, and formic acid. In addition to esters such as methyl, ethyl formate, methyl acetate, ethyl acetate, amyl acetate, and γ-butyrolactone, methyl cellosolve, dimethylimidazolinone, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, sulfolane, nitroethane, chloride Examples include methylene and methyl acetoacetate, and 1,3-dioxolane, THF, methyl ethyl ketone, acetone, methyl acetate and methylene chloride are preferred.

  The dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. After casting the dope on the metal support, the solvent starts to evaporate and the ratio of alcohol increases so that the web (referred to as the dope film after casting the dope of the cellulose ester film on the support). Is used as a gelling solvent that makes the web strong and makes it easy to peel from the metal support, or when these ratios are small, dissolve the cellulose ester film of non-chlorine organic solvent There is also a role to promote gelation, and also has a role to suppress gelation, precipitation, and viscosity increase of the reactive metal compound.

  Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, and propylene glycol monomethyl ether. Of these, ethanol is preferred because it has excellent dope stability, has a relatively low boiling point, good drying properties, and no toxicity. These organic solvents alone are not soluble in cellulose esters and are referred to as poor solvents.

  The most preferable solvent that satisfies such conditions and dissolves cellulose ester, which is a preferred polymer compound, at a high concentration is a mixed solvent having a ratio of methylene chloride: ethyl alcohol of 95: 5 to 80:20. Alternatively, a mixed solvent of methyl acetate: ethyl alcohol 60:40 to 95: 5 is also preferably used.

  Moreover, it is also a preferable aspect that the cellulose ester used in the present invention is a cellulose ester cast by hot melt casting without using an organic solvent disclosed in JP-A No. 2000-352620. In this case, various additives described later can be preferably used in the same manner as in the solution casting method. The stretching in this case is performed in the cooling step after the hot melt casting.

(Additive)
The retardation film in the present invention includes a plasticizer that imparts processability, flexibility, and moisture resistance to the film, an ultraviolet absorber that imparts an ultraviolet absorption function, an antioxidant that prevents deterioration of the film, and a slipperiness to the film. Fine particles to be imparted (mat agent) may be contained. Moreover, it is preferable to contain the retardation raising agent etc. which raise the retardation of a film.

<Plasticizer>
The plasticizer used is not particularly limited, but a cellulose ester film or a reactive metal compound polycondensate capable of hydrolytic polycondensation so as not to generate haze or bleed out or volatilize from the film. It preferably has a functional group capable of interacting by hydrogen bonding or the like.

  Examples of such functional groups include hydroxyl groups, ether groups, carbonyl groups, ester groups, carboxylic acid residues, amino groups, imino groups, amide groups, imide groups, cyano groups, nitro groups, sulfonyl groups, sulfonic acid residues, Examples thereof include a phosphonyl group and a phosphonic acid residue, and a carbonyl group, an ester group and a phosphonyl group are preferred.

  Examples of such plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic ester plasticizers, pyromellitic acid plasticizers, polyhydric alcohol plasticizers, glycolate plasticizers. Citric acid ester plasticizers, fatty acid ester plasticizers, carboxylic acid ester plasticizers, polyester plasticizers and the like can be preferably used. Particularly preferred are polyhydric alcohol plasticizers and glycolate plasticizers. is there.

  The polyhydric alcohol ester is composed of an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.

  The polyhydric alcohol used in the present invention is represented by the following formula.

R _1- (OH) _n
(However, R ₁ represents an n-valent organic group, and n represents a positive integer of 2 or more.)
Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane- Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.

  Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

  As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, the compatibility with the cellulose ester film is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.

  Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid , Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, Examples thereof include unsaturated fatty acids such as oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid.

  Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.

  Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. Examples thereof include aromatic monocarboxylic acids and derivatives thereof, and benzoic acid is particularly preferable.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferable because it is less likely to volatilize, and a lower molecular weight is preferable in terms of moisture permeability and compatibility with the cellulose ester film.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.

  The glycolate plasticizer is not particularly limited, but a glycolate plasticizer having an aromatic ring or a cycloalkyl ring in the molecule can be preferably used. As preferred glycolate plasticizers, for example, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate and the like can be used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dicyclohexyl phthalate and the like can be used.

  These plasticizers can be used alone or in combination of two or more. If the amount of the plasticizer used is less than 1% by mass relative to the cellulose ester film, it is not preferable because the effect of reducing the moisture permeability of the film is small. If it exceeds 20% by mass, the plasticizer bleeds out from the film, and the physical properties of the film 1 to 20% by mass is preferable. 6-16 mass% is further more preferable, Most preferably, it is 8-13 mass%.

<Ultraviolet absorber>
The ultraviolet absorbing function is preferably imparted to various optical films such as a polarizing plate protective film, a retardation film, and an optical compensation film from the viewpoint of preventing deterioration of the liquid crystal. For such an ultraviolet absorbing function, a material that absorbs ultraviolet rays may be included in the cellulose ester film, or a layer having an ultraviolet absorbing function may be provided on a film made of the cellulose ester film.

  As such an ultraviolet absorber having an ultraviolet absorbing function, those having an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more are preferably used. Specific examples of preferably used ultraviolet absorbers include triazine compounds, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these. Moreover, the polymeric ultraviolet absorber described in JP-A-6-148430 is also preferably used.

  Specific examples of ultraviolet absorbers useful in the present invention include 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl). -Phenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl) -Phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methyl-phenyl) benzotriazole, 2 , 2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2′-hydroxy -3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methyl-phenol << TINUVIN 171 >>, 2-octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3 -[3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate mixture << TINUVIN 109 >>, 2- (2H-benzotriazole -2yl) -4,6-bis (1-methyl-1-phenylethyl) phenol << Tinuvin 234 >> 2- (3-t- butyl-5-methyl-2-hydroxyphenyl) -5-chloro - can be exemplified benzotriazole << Tinuvin 326 >>, and the like. In addition, any of the above-mentioned tinuvins such as tinuvin 109, tinuvin 171 and tinuvin 326 are commercially available products manufactured by Ciba Specialty Chemicals and can be preferably used.

  Specific examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy- 5-benzoylphenylmethane) and the like, but is not limited thereto.

  Moreover, since the ultraviolet absorber which can be used for a phase difference film is excellent also in the applicability | paintability of various coating layers, it contains the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2000-187825 is 9.2 or more. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Moreover, the polymeric ultraviolet absorber (or ultraviolet absorbing polymer) described in JP-A-6-148430 and JP-A-2002-47357 can be preferably used. The polymer ultraviolet absorbers described in general formula (1), general formula (2) of JP-A-6-148430, or general formulas (3), (6) and (7) of JP-A-2002-47357 are particularly preferably used. It is done.

  In addition, a compound having a 1,3,5-triazine ring can be preferably used as the ultraviolet absorber of the retardation film of the present invention. The compound can also be used as a retardation adjusting agent.

  The addition amount of these compounds is preferably 0.1 to 5.0% by mass ratio, and more preferably 0.5 to 1.5% with respect to the cellulose ester film.

<Antioxidant>
Antioxidants are also referred to as deterioration inhibitors. When a liquid crystal image display device or the like is placed in a high humidity and high temperature state, the retardation film may be deteriorated. The antioxidant has a role of delaying or preventing the retardation film from being decomposed by, for example, the residual solvent amount of halogen in the retardation film or phosphoric acid of the phosphoric acid plasticizer. It is preferable to make it contain in a film.

  Antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, and amine compounds are preferred as the antioxidants and deterioration inhibitors, and JP-A-3-199201 and 5- Nos. 1907073, 5-194789, 5-271471, and 6-107854. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA). Further, as such an antioxidant, a hindered phenol compound is preferably used. For example, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino ) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Ttadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxy Benzyl) -isocyanurate and the like. In particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.

  The amount of these compounds added is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose ester film.

<Matting agent>
Fine particles such as a matting agent can be added to the cellulose ester film in order to impart slipperiness. Examples of the fine particles include fine particles of an inorganic compound or fine particles of an organic compound.

The amount of fine particles added is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.5 g, and still more preferably 0.08 to 0.3 g per 1 m ^{2 of the} retardation film. Thereby, it is preferable that a 0.1-1 micrometer convex part is formed in the phase difference film surface, and slipperiness is provided to a film.

  Examples of the fine particles added to the retardation film include inorganic compounds such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, and hydrated silica. Mention may be made of calcium acid, aluminum silicate, magnesium silicate and calcium phosphate. Among them, those containing silicon are preferable because the turbidity is low and the haze of the film can be reduced, and silicon dioxide is particularly preferable.

  In many cases, fine particles such as silicon dioxide are surface-treated with an organic material, but such particles are preferable because they can reduce the haze of the film. Preferred organic materials for the surface treatment include halosilanes, alkoxysilanes, silazanes, siloxanes, and the like.

  The silicon dioxide fine particles can be obtained, for example, by burning vaporized silicon tetrachloride and hydrogen mixed at 1000 to 1200 ° C. in the air.

  The fine particles of silicon dioxide preferably have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / L or more. The average diameter of the primary particles is more preferably 5 to 16 nm, and further preferably 5 to 12 nm. These fine particles form a secondary agglomerate in the film and form unevenness on the film surface to impart slipperiness. A smaller primary particle average diameter is preferred because haze is low. The apparent specific gravity is more preferably 90 to 200 g / L or more, and further preferably 100 to 200 g / L or more. Higher apparent specific gravity makes it possible to produce a high-concentration fine particle dispersion, and less haze and large aggregates are generated. In the present invention, the liter is represented by L.

  As preferable fine particles of silicon dioxide, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.) manufactured by Nippon Aerosil Co., Ltd. A commercially available one can be mentioned, and Aerosil 200V, R972, R972V, R974, R202, R812 can be preferably used. The fine particles of zirconium oxide are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.), and any of them can be used.

  Among these, Aerosil 200V, Aerosil R972V, and Aerosil TT600 are particularly preferable because they have a large effect of lowering the turbidity and lowering the friction coefficient of the retardation film of the present invention.

  Examples of the fine particles of the organic compound include silicone resin, fluorine resin, and acrylic resin. Of these, silicone resins are preferred, and those having a three-dimensional network structure are particularly preferred. For example, Tospearl 103, 105, 108, 120, 145, 3120 and 240 (manufactured by Toshiba Silicone Co., Ltd.) Can be mentioned.

  In the measurement of the primary average particle diameter of the fine particles, the particles are observed with a transmission electron microscope (magnification of 500,000 to 2,000,000 times), 100 particles are observed, and the average value is used as the primary average particle diameter. can do.

  Further, the apparent specific gravity described above can be calculated by the following equation by taking a certain amount of silicon dioxide fine particles in a graduated cylinder and measuring the weight at this time.

Apparent specific gravity (g / L) = silicon dioxide mass (g) / volume of silicon dioxide (L)
The inorganic fine particles added here can impart slipperiness to the film surface, but the retardation fluctuation suppressing effect obtained by adding the polycondensate of the reactive metal compound used in the present invention cannot be obtained. In addition, the addition of a large amount of inorganic fine particles is different in that it involves an increase in aggregates and a significant increase in haze.
As a compound to be added for increasing the retardation, an aromatic compound having two or more aromatic rings as described in EP 911,656 A2 can be used.

  Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring. An aromatic heterocyclic ring is particularly preferred, and the aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. Of these, a 1,3,5-triazine ring is particularly preferred.

  The number of aromatic rings contained in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 8, and most preferably 3 to 6. The bonding 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 (for aromatic rings). , Spiro bonds cannot be formed). The connection relationship may be any of (a) to (c).

  Examples of the condensed ring of (a) (condensed ring of two or more aromatic rings) include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a naphthacene ring, a pyrene ring, Indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline ring, quinolidine Ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, pteridine ring, carbazole ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring and thianthrene ring It is. Among these, naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferable.

  The single bond (b) is preferably a bond between carbon atoms of two aromatic rings. Two aromatic rings may be bonded with two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.

  The linking group in (c) is also preferably bonded to carbon atoms of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, —CO—, —O—, —NH—, —S—, or a combination thereof. Examples of linking groups composed of combinations are shown below. In addition, the relationship between the left and right in the following examples of the linking group may be reversed.

  -CO-O-, -CO-NH-, -alkylene-O-, -NH-CO-NH-, -NH-CO-O-, -O-CO-O-, -O-alkylene-O-, -CO-alkenylene-, -CO-alkenylene-NH-, -CO-alkenylene-O-, -alkylene-CO-O-alkylene-O-CO-alkylene-, -O-alkylene-CO-O-alkylene-O -CO-alkylene-O-, -O-CO-alkylene-CO-O-, -NH-CO-alkenylene-, -O-CO-alkenylene-.

  The aromatic ring and the linking group may have a substituent. Examples of the substituent include halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, aliphatic acyl group , Aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic Substituted sulfamoyl groups, aliphatic substituted ureido groups and non-aromatic heterocyclic groups are included.

  It is preferable that the alkyl group has 1 to 8 carbon atoms. A chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable. The alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group). Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethylaminoethyl. The alkenyl group preferably has 2 to 8 carbon atoms. A chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable. The alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl. The alkynyl group preferably has 2 to 8 carbon atoms. A chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable. The alkynyl group may further have a substituent. Examples of alkynyl groups include ethynyl, 1-butynyl and 1-hexynyl.

  The aliphatic acyl group preferably has 1 to 10 carbon atoms. Examples of the aliphatic acyl group include acetyl, propanoyl and butanoyl. The number of carbon atoms in the aliphatic acyloxy group is preferably 1-10. Examples of the aliphatic acyloxy group include acetoxy. The alkoxy group preferably has 1 to 8 carbon atoms. The alkoxy group may further have a substituent (eg, alkoxy group). Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy and methoxyethoxy. The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl. The number of carbon atoms of the alkoxycarbonylamino group is preferably 2-10. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.

  The alkylthio group preferably has 1 to 12 carbon atoms. Examples of the alkylthio group include methylthio, ethylthio and octylthio. The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl. The number of carbon atoms in the aliphatic amide group is preferably 1-10. Examples of the aliphatic amide group include acetamide. The number of carbon atoms of the aliphatic sulfonamide group is preferably 1-8. Examples of the aliphatic sulfonamido group include methanesulfonamido, butanesulfonamido and n-octanesulfonamido. The number of carbon atoms of the aliphatic substituted amino group is preferably 1-10. Examples of the aliphatic substituted amino group include dimethylamino, diethylamino and 2-carboxyethylamino. The aliphatic substituted carbamoyl group preferably has 2 to 10 carbon atoms. Examples of the aliphatic substituted carbamoyl group include methylcarbamoyl and diethylcarbamoyl. The number of carbon atoms in the aliphatic substituted sulfamoyl group is preferably 1-8. Examples of the aliphatic substituted sulfamoyl group include methylsulfamoyl and diethylsulfamoyl. The number of carbon atoms in the aliphatic substituted ureido group is preferably 2-10. Examples of the aliphatic substituted ureido group include methylureido. Examples of non-aromatic heterocyclic groups include piperidino and morpholino.

  The molecular weight of the retardation increasing agent is preferably 300 to 800. This can arbitrarily select the polarity of the molecular structure from the viewpoint of suppressing the outflow at the time of use and processing of the polarizing plate.

  Among them, the compound having a 1,3,5-triazine ring is preferably a compound represented by the following general formula (I).

In the general formula (I), X ¹ is a single bond, —NR ₄ —, —O— or —S—; X ² is a single bond, —NR ₅ —, —O— or —S—; X ³ is a single bond, —NR ₆ —, —O— or —S—; R ¹ , R ² and R ³ are an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. The compound represented by the general formula (I) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (I), X ¹ , X ² and X ³ are —NR ₄ —, —NR ₅ — and —NR ₆ —, respectively, or X ¹ , X ² and X 3 ³ is a single bond, and R ¹ , R ² and R ³ are heterocyclic groups having a free valence on the nitrogen atom. ^{-X 1 -R 1, -X 2 -R} 2 and -X ³ -R ³ are preferably the same substituents. R ¹ , R ² and R ³ are particularly preferably aryl groups. R ₄ , R ₅ and R ₆ are particularly preferably a hydrogen atom.

  The alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group. A linear alkyl group is preferred to a branched alkyl group.

  The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, still more preferably 1-8, 6 is most preferred. The alkyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy). The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. A linear alkenyl group is preferable to a branched chain alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, 6 is most preferred. The alkenyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) or an acyloxy group (for example, each group such as acryloyloxy and methacryloyloxy).

  The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

  Specific examples of the substituent include, for example, a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxy Carbonyl group, aryloxycarbonyl group, sulfamoyl, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamido group, carbamoyl, alkyl-substituted carmoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio Groups, alkenylthio groups, arylthio groups and acyl groups are included. The said alkyl group is synonymous with the alkyl group mentioned above.

  The alkyl group of the alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl-substituted sulfamoyl group, sulfonamido group, alkyl-substituted carbamoyl group, amide group, alkylthio group and acyl group is also synonymous with the alkyl group described above.

  The said alkenyl group is synonymous with the alkenyl group mentioned above.

  The alkenyl part of the alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl-substituted sulfamoyl group, sulfonamide group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group is also synonymous with the alkenyl group described above.

  Specific examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl, and 4-dodecyloxyphenyl. Can be mentioned.

  Examples of the aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamido group, aryl-substituted carbamoyl group, amide group, arylthio group, and acyl group are the same as the above aryl group.

When X ¹ , X ² or X ³ is —NR—, —O— or —S—, the heterocyclic group preferably has aromaticity.

  The heterocyclic ring in the heterocyclic group having aromaticity is generally an unsaturated heterocyclic ring, preferably a heterocyclic ring having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring.

  The hetero atom in the heterocyclic ring is preferably each atom such as N, S or O, and particularly preferably an N atom.

  As the heterocyclic ring having aromaticity, a pyridine ring (as the heterocyclic group, for example, each group such as 2-pyridyl or 4-pyridyl) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.

When X ¹ , X ² or X ³ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms.

  Moreover, the hetero atom in a heterocyclic group may have hetero atoms other than a nitrogen atom (for example, O atom, S atom). The heterocyclic group may have a substituent. Specific examples of the substituent of the heterocyclic group are the same as the specific examples of the substituent of the aryl moiety.

  Specific examples of the heterocyclic group having a free valence on the nitrogen atom are shown below.

  Specific examples of the compound having a 1,3,5-triazine ring are shown below.

  In addition, several R shown below represents the same group.

(1) Butyl (2) 2-Methoxy-2-ethoxyethyl (3) 5-Undecenyl (4) Phenyl (5) 4-Ethoxycarbonylphenyl (6) 4-Butoxyphenyl (7) p-Biphenylyl (8) 4 -Pyridyl (9) 2-naphthyl (10) 2-methylphenyl (11) 3,4-dimethoxyphenyl (12) 2-furyl

(14) phenyl (15) 3-ethoxycarbonylphenyl (16) 3-butoxyphenyl (17) m-biphenylyl (18) 3-phenylthiophenyl (19) 3-chlorophenyl (20) 3-benzoylphenyl (21) 3 -Acetoxyphenyl (22) 3-benzoyloxyphenyl (23) 3-phenoxycarbonylphenyl (24) 3-methoxyphenyl (25) 3-anilinophenyl (26) 3-isobutyrylaminophenyl (27) 3-phenoxy Carbonylaminophenyl (28) 3- (3-ethylureido) phenyl (29) 3- (3,3-diethylureido) phenyl (30) 3-methylphenyl (31) 3-phenoxyphenyl (32) 3-hydroxyphenyl (33) 4-Ethoxycarbonylphenyl (34) 4-butoxyphenyl (35) p-biphenylyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl (38) 4-benzoylphenyl (39) 4-acetoxyphenyl (40) 4-benzoyloxyphenyl ( 41) 4-phenoxycarbonylphenyl (42) 4-methoxyphenyl (43) 4-anilinophenyl (44) 4-isobutyrylaminophenyl (45) 4-phenoxycarbonylaminophenyl (46) 4- (3-ethyl (Ureido) phenyl (47) 4- (3,3-diethylureido) phenyl (48) 4-methylphenyl (49) 4-phenoxyphenyl (50) 4-hydroxyphenyl (51) 3,4-diethoxycarbonylphenyl ( 52) 3,4-dibutoxyphenyl (53) 3 -Diphenylphenyl (54) 3,4-diphenylthiophenyl (55) 3,4-dichlorophenyl (56) 3,4-dibenzoylphenyl (57) 3,4-diacetoxyphenyl (58) 3,4-dibenzoyl Oxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxyphenyl (61) 3,4-dianilinophenyl (62) 3,4-dimethylphenyl (63) 3,4-diphenoxy Phenyl (64) 3,4-dihydroxyphenyl (65) 2-naphthyl (66) 3,4,5-triethoxycarbonylphenyl (67) 3,4,5-tributoxyphenyl (68) 3,4,5- Triphenylphenyl (69) 3,4,5-triphenylthiophenyl (70) 3,4,5-trichlorophenyl (71) 3,4,5-tribenzoylphenyl (72) 3,4,5-triacetoxyphenyl (73) 3,4,5-tribenzoyloxyphenyl (74) 3,4,5-triphenoxycarbonylphenyl (75) 3,4,5-trimethoxyphenyl (76) 3,4,5-trianilinophenyl (77) 3,4,5-trimethylphenyl (78) 3,4,5-triphenoxyphenyl (79 ) 3,4,5-trihydroxyphenyl

(80) phenyl (81) 3-ethoxycarbonylphenyl (82) 3-butoxyphenyl (83) m-biphenylyl (84) 3-phenylthiophenyl (85) 3-chlorophenyl (86) 3-benzoylphenyl (87) 3 -Acetoxyphenyl (88) 3-benzoyloxyphenyl (89) 3-phenoxycarbonylphenyl (90) 3-methoxyphenyl (91) 3-anilinophenyl (92) 3-isobutyrylaminophenyl (93) 3-phenoxy Carbonylaminophenyl (94) 3- (3-ethylureido) phenyl (95) 3- (3,3-diethylureido) phenyl (96) 3-methylphenyl (97) 3-phenoxyphenyl (98) 3-hydroxyphenyl (99) 4-Ethoxycarbonylphenyl (100) 4-butoxyphenyl (101) p-biphenylyl (102) 4-phenylthiophenyl (103) 4-chlorophenyl (104) 4-benzoylphenyl (105) 4-acetoxyphenyl (106) 4-benzoyloxyphenyl ( 107) 4-phenoxycarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-isobutyrylaminophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4- (3-ethyl (Ureido) phenyl (113) 4- (3,3-diethylureido) phenyl (114) 4-methylphenyl (115) 4-phenoxyphenyl (116) 4-hydroxyphenyl (117) 3,4-diethoxycarbonylphenyl ( 118) 3 , 4-dibutoxyphenyl (119) 3,4-diphenylphenyl (120) 3,4-diphenylthiophenyl (121) 3,4-dichlorophenyl (122) 3,4-dibenzoylphenyl (123) 3,4- Diacetoxyphenyl (124) 3,4-dibenzoyloxyphenyl (125) 3,4-diphenoxycarbonylphenyl (126) 3,4-dimethoxyphenyl (127) 3,4-dianilinophenyl (128) 3,4 -Dimethylphenyl (129) 3,4-diphenoxyphenyl (130) 3,4-dihydroxyphenyl (131) 2-naphthyl (132) 3,4,5-triethoxycarbonylphenyl (133) 3,4,5- Tributoxyphenyl (134) 3,4,5-triphenylphenyl (135) 3 4,5-triphenylthiophenyl (136) 3,4,5-trichlorophenyl (137) 3,4,5-tribenzoylphenyl (138) 3,4,5-triacetoxyphenyl (139) 3,4 5-tribenzoyloxyphenyl (140) 3,4,5-triphenoxycarbonylphenyl (141) 3,4,5-trimethoxyphenyl (142) 3,4,5-trianilinophenyl (143) 3,4 , 5-trimethylphenyl (144) 3,4,5-triphenoxyphenyl (145) 3,4,5-trihydroxyphenyl

(146) phenyl (147) 4-ethoxycarbonylphenyl (148) 4-butoxyphenyl (149) p-biphenylyl (150) 4-phenylthiophenyl (151) 4-chlorophenyl (152) 4-benzoylphenyl (153) 4 -Acetoxyphenyl (154) 4-benzoyloxyphenyl (155) 4-phenoxycarbonylphenyl (156) 4-methoxyphenyl (157) 4-anilinophenyl (158) 4-isobutyrylaminophenyl (159) 4-phenoxy Carbonylaminophenyl (160) 4- (3-ethylureido) phenyl (161) 4- (3,3-diethylureido) phenyl (162) 4-methylphenyl (163) 4-phenoxyphenyl (164) 4-hydroxyphenyl

(165) phenyl (166) 4-ethoxycarbonylphenyl (167) 4-butoxyphenyl (168) p-biphenylyl (169) 4-phenylthiophenyl (170) 4-chlorophenyl (171) 4-benzoylphenyl (172) 4 -Acetoxyphenyl (173) 4-benzoyloxyphenyl (174) 4-phenoxycarbonylphenyl (175) 4-methoxyphenyl (176) 4-anilinophenyl (177) 4-isobutyrylaminophenyl (178) 4-phenoxy Carbonylaminophenyl (179) 4- (3-ethylureido) phenyl (180) 4- (3,3-diethylureido) phenyl (181) 4-methylphenyl (182) 4-phenoxyphenyl (183) 4-hydroxyphenyl

(184) phenyl (185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenylyl (188) 4-phenylthiophenyl (189) 4-chlorophenyl (190) 4-benzoylphenyl (191) 4 -Acetoxyphenyl (192) 4-benzoyloxyphenyl (193) 4-phenoxycarbonylphenyl (194) 4-methoxyphenyl (195) 4-anilinophenyl (196) 4-isobutyrylaminophenyl (197) 4-phenoxy Carbonylaminophenyl (198) 4- (3-ethylureido) phenyl (199) 4- (3,3-diethylureido) phenyl (200) 4-methylphenyl (201) 4-phenoxyphenyl (202) 4-hydroxyphenyl

(203) phenyl (204) 4-ethoxycarbonylphenyl (205) 4-butoxyphenyl (206) p-biphenylyl (207) 4-phenylthiophenyl (208) 4-chlorophenyl (209) 4-benzoylphenyl (210) 4 -Acetoxyphenyl (211) 4-benzoyloxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutyrylaminophenyl (216) 4-phenoxy Carbonylaminophenyl (217) 4- (3-ethylureido) phenyl (218) 4- (3,3-diethylureido) phenyl (219) 4-methylphenyl (220) 4-phenoxyphenyl (221) 4-hydroxyphenyl

(222) phenyl (223) 4-butylphenyl (224) 4- (2-methoxy-2-ethoxyethyl) phenyl (225) 4- (5-nonenyl) phenyl (226) p-biphenylyl (227) 4-ethoxy Carbonylphenyl (228) 4-butoxyphenyl (229) 4-methylphenyl (230) 4-chlorophenyl (231) 4-phenylthiophenyl (232) 4-benzoylphenyl (233) 4-acetoxyphenyl (234) 4-benzoyl Oxyphenyl (235) 4-phenoxycarbonylphenyl (236) 4-methoxyphenyl (237) 4-anilinophenyl (238) 4-isobutyrylaminophenyl (239) 4-phenoxycarbonylaminophenyl (240) 4- ( 3-ethylureido Phenyl (241) 4- (3,3-diethylureido) phenyl (242) 4-phenoxyphenyl (243) 4-hydroxyphenyl (244) 3-butylphenyl (245) 3- (2-methoxy-2-ethoxyethyl) ) Phenyl (246) 3- (5-nonenyl) phenyl (247) m-biphenylyl (248) 3-ethoxycarbonylphenyl (249) 3-butoxyphenyl (250) 3-methylphenyl (251) 3-chlorophenyl (252) 3-phenylthiophenyl (253) 3-benzoylphenyl (254) 3-acetoxyphenyl (255) 3-benzoyloxyphenyl (256) 3-phenoxycarbonylphenyl (257) 3-methoxyphenyl (258) 3-anilinophenyl (259) 3-I Butyrylaminophenyl (260) 3-phenoxycarbonylaminophenyl (261) 3- (3-ethylureido) phenyl (262) 3- (3,3-diethylureido) phenyl (263) 3-phenoxyphenyl (264) 3 -Hydroxyphenyl (265) 2-butylphenyl (266) 2- (2-methoxy-2-ethoxyethyl) phenyl (267) 2- (5-nonenyl) phenyl (268) o-biphenylyl (269) 2-ethoxycarbonyl Phenyl (270) 2-Butoxyphenyl (271) 2-Methylphenyl (272) 2-Chlorophenyl (273) 2-Phenylthiophenyl (274) 2-Benzoylphenyl (275) 2-Acetoxyphenyl (276) 2-Benzoyloxy Phenyl (277) 2 Phenoxycarbonylphenyl (278) 2-methoxyphenyl (279) 2-anilinophenyl (280) 2-isobutyrylaminophenyl (281) 2-phenoxycarbonylaminophenyl (282) 2- (3-ethylureido) phenyl ( 283) 2- (3,3-diethylureido) phenyl (284) 2-phenoxyphenyl (285) 2-hydroxyphenyl (286) 3,4-dibutylphenyl (287) 3,4-di (2-methoxy-2) -Ethoxyethyl) phenyl (288) 3,4-diphenylphenyl (289) 3,4-diethoxycarbonylphenyl (290) 3,4-didodecyloxyphenyl (291) 3,4-dimethylphenyl (292) 3, 4-dichlorophenyl (293) 3,4-dibenzoyl Enyl (294) 3,4-diacetoxyphenyl (295) 3,4-dimethoxyphenyl (296) 3,4-di-N-methylaminophenyl (297) 3,4-diisobutyrylaminophenyl (298) 3 , 4-diphenoxyphenyl (299) 3,4-dihydroxyphenyl (300) 3,5-dibutylphenyl (301) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl (302) 3,5- Diphenylphenyl (303) 3,5-diethoxycarbonylphenyl (304) 3,5-didodecyloxyphenyl (305) 3,5-dimethylphenyl (306) 3,5-dichlorophenyl (307) 3,5-dibenzoyl Phenyl (308) 3,5-diacetoxyphenyl (309) 3,5-dimethoxyphenyl (3 0) 3,5-di-N-methylaminophenyl (311) 3,5-diisobutyrylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3,5-dihydroxyphenyl (314) 2,4 -Dibutylphenyl (315) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl (316) 2,4-diphenylphenyl (317) 2,4-diethoxycarbonylphenyl (318) 2,4-di Dodecyloxyphenyl (319) 2,4-dimethylphenyl (320) 2,4-dichlorophenyl (321) 2,4-dibenzoylphenyl (322) 2,4-diacetoxyphenyl (323) 2,4-dimethoxyphenyl ( 324) 2,4-di-N-methylaminophenyl (325) 2,4-diisobutyrylaminopheny (326) 2,4-diphenoxyphenyl (327) 2,4-dihydroxyphenyl (328) 2,3-dibutylphenyl (329) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl (330) 2,3-diphenylphenyl (331) 2,3-diethoxycarbonylphenyl (332) 2,3-didodecyloxyphenyl (333) 2,3-dimethylphenyl (334) 2,3-dichlorophenyl (335) 2, 3-dibenzoylphenyl (336) 2,3-diacetoxyphenyl (337) 2,3-dimethoxyphenyl (338) 2,3-di-N-methylaminophenyl (339) 2,3-diisobutyrylaminophenyl (340) 2,3-diphenoxyphenyl (341) 2,3-dihydroxyphenyl (342 2,6-dibutylphenyl (343) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl (344) 2,6-diphenylphenyl (345) 2,6-diethoxycarbonylphenyl (346) 2, 6-didodecyloxyphenyl (347) 2,6-dimethylphenyl (348) 2,6-dichlorophenyl (349) 2,6-dibenzoylphenyl (350) 2,6-diacetoxyphenyl (351) 2,6- Dimethoxyphenyl (352) 2,6-di-N-methylaminophenyl (353) 2,6-diisobutyrylaminophenyl (354) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl (356) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2-ethoxy) Til) phenyl (358) 3,4,5-triphenylphenyl (359) 3,4,5-triethoxycarbonylphenyl (360) 3,4,5-tridodecyloxyphenyl (361) 3,4,5- Trimethylphenyl (362) 3,4,5-trichlorophenyl (363) 3,4,5-tribenzoylphenyl (364) 3,4,5-triacetoxyphenyl (365) 3,4,5-trimethoxyphenyl ( 366) 3,4,5-tri-N-methylaminophenyl (367) 3,4,5-triisobutyrylaminophenyl (368) 3,4,5-triphenoxyphenyl (369) 3,4,5 -Trihydroxyphenyl (370) 2,4,6-tributylphenyl (371) 2,4,6-tri (2-methoxy-2-ethoxyethyl) ) Phenyl (372) 2,4,6-triphenylphenyl (373) 2,4,6-triethoxycarbonylphenyl (374) 2,4,6-tridodecyloxyphenyl (375) 2,4,6-trimethyl Phenyl (376) 2,4,6-trichlorophenyl (377) 2,4,6-tribenzoylphenyl (378) 2,4,6-triacetoxyphenyl (379) 2,4,6-trimethoxyphenyl (380 ) 2,4,6-tri-N-methylaminophenyl (381) 2,4,6-triisobutyrylaminophenyl (382) 2,4,6-triphenoxyphenyl (383) 2,4,6- Trihydroxyphenyl (384) Pentafluorophenyl (385) Pentachlorophenyl (386) Pentamethoxyphenyl (38 ) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl (388) 5-N-methylsulfamoyl-2-naphthyl (389) 6-N-phenylsulfamoyl-2-naphthyl (390) 5-Ethoxy-7-N-methylsulfamoyl-2-naphthyl (391) 3-methoxy-2-naphthyl (392) 1-ethoxy-2-naphthyl (393) 6-N-phenylsulfamoyl-8- Methoxy-2-naphthyl (394) 5-methoxy-7-N-phenylsulfamoyl-2-naphthyl (395) 1- (4-methylphenyl) -2-naphthyl (396) 6,8-di-N- Methylsulfamoyl-2-naphthyl (397) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2-naphthyl (398) 5-acetoxy-7- N-phenylsulfamoyl-2-naphthyl (399) 3-benzoyloxy-2-naphthyl (400) 5-acetylamino-1-naphthyl (401) 2-methoxy-1-naphthyl (402) 4-phenoxy-1 -Naphtyl (403) 5-N-methylsulfamoyl-1-naphthyl (404) 3-N-methylcarbamoyl-4-hydroxy-1-naphthyl (405) 5-methoxy-6-N-ethylsulfamoyl- 1-naphthyl (406) 7-tetradecyloxy-1-naphthyl (407) 4- (4-methylphenoxy) -1-naphthyl (408) 6-N-methylsulfamoyl-1-naphthyl (409) 3- N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl (410) 5-methoxy-6-N-benzylsulfamoyl 1-naphthyl (411) 3,6-di-N-phenylsulfamoyl-1-naphthyl (412) methyl (413) ethyl (414) butyl (415) octyl (416) dodecyl (417) 2-butoxy-2 -Ethoxyethyl (418) benzyl (419) 4-methoxybenzyl

(424) Methyl (425) Phenyl (426) Butyl

(430) methyl (431) ethyl (432) butyl (433) octyl (434) dodecyl (435) 2-butoxy-2-ethoxyethyl (436) benzyl (437) 4-methoxybenzyl

  In the present invention, a melamine polymer may be used as the compound having a 1,3,5-triazine ring. The melamine polymer is preferably synthesized by a polymerization reaction between a melamine compound represented by the following general formula (II) and a carbonyl compound.

In the above synthetic reaction scheme, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

  The alkyl group, alkenyl group, aryl group, heterocyclic group, and substituents thereof have the same meanings as the groups and substituents described in the general formula (I).

  The polymerization reaction between the melamine compound and the carbonyl compound is the same as the method for synthesizing a normal melamine resin (for example, melamine formaldehyde resin). Moreover, you may use a commercially available melamine polymer (melamine resin).

  The molecular weight of the melamine polymer is preferably 2,000 to 400,000. Specific examples of the repeating unit of the melamine polymer are shown below.

MP-1: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
^{MP-2: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-3: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-4: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-5: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-6: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-7: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-8: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-9: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-10: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-11: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-12: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-13: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-14: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-15: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-16: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-17: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-18: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-19: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-20: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
MP-21: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH _{2 On} -C ₄ H ₉
^{MP-22: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-23: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-24: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-25: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-26: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-27: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-28: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-29: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-30: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-31: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-32: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-33: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-34: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-35: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-36: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-37: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-38: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-39: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-40: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-41: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-42: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-43: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-44: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-45: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-46: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-47: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-48: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-49: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-50: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-51: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-52: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-53: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-54: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-55: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-56: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-57: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-58: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-59: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-60: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-61: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-62: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-63: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-64: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-65: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-66: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-67: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-68: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-69: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-70: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-71: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-72: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-73: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-74: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-75: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-76: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-77: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-78: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-79: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-80: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-81: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-82: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-83: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-84: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-85: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-86: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-87: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-88: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-89: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-90: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-91: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-92: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-93: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-94: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-95: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-96: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-97: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-98: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-99: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-100: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-101: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-102: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-103: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-104: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-105: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-106: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-107: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-108: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-109: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-110: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-111: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-112: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-113: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-114: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-115: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-116: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-117: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-118: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-119: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-120: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-121: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-122: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-123: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-124: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-125: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-126: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-127: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-128: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-129: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-130: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-131: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-132: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-133: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-134: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-135: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-136: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-137: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-138: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-139: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-140: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-141: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-142: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-143: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-144: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-145: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-146: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-147: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-148: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-149: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-150: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-151: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-152: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-153: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-154: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-155: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-156: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-157: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-158: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-159: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-160: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-161: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-162: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-163: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-164: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-165: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-166: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-167: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-168: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-169: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-170: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-171: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-172: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-173: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-174: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-175: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
MP-176: R ¹³ , R ¹⁴ , R ¹⁶ : CH _{2 On} -C ₄ H ₉ ; R ¹⁵ : CH ₂ OH
^{MP-177: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-178: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-179: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-180: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-181: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-182: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-183: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-184: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-185: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-186: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-187: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-188: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-189: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-190: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-191: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-192: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-193: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-194: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-195: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-196: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-197: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-198: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-199: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-200: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
In the present invention, a copolymer obtained by combining two or more of the above repeating units may be used. Two or more homopolymers or copolymers may be used in combination.

  Moreover, you may use together the compound which has a 2 or more types of 1,3,5- triazine ring. Two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton) may be used in combination.

  As another type of retardation increasing agent preferably used in the present invention, a retardation controlling agent (elevating agent) described in JP-A Nos. 2002-267847, 2002-363343, 2003-35821, 2004-4550, etc. ). A rod-like compound having a maximum absorption wavelength (λmax) shorter than 250 nm in the ultraviolet absorption spectrum of the solution is used as a retardation control agent. From the viewpoint of the function of the retardation control agent, the rod-like compound preferably has at least one aromatic ring, and more preferably has at least two aromatic rings. The rod-like compound preferably has a linear molecular structure. The linear molecular structure means that the molecular structure of the rod-like compound is linear in the most thermodynamically stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculation can be performed using molecular orbital calculation software (eg, WinMOPAC2000, manufactured by Fujitsu Limited) to obtain a molecular structure that minimizes the heat of formation of a compound. The molecular structure being linear means that the angle of the molecular structure is 140 degrees or more in the thermodynamically most stable structure obtained by calculation as described above.

  As the rod-like compound, a compound represented by the following formula (I) is preferable.

(I) Ar ¹ -L ¹ -Ar ²
In the formula (I), Ar ¹ and Ar ² are each independently an aromatic group. The aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group. An aryl group and a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The heterocycle of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocycle is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring. Aromatic heterocycles generally have the most double bonds. As a hetero atom, a nitrogen atom, an oxygen atom or a sulfur atom is preferable, and a nitrogen atom or a sulfur atom is more preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine Rings, pyridazine rings, pyrimidine rings, pyrazine rings, and 1,3,5-triazine rings are included. As the aromatic ring of the aromatic group, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring and a pyrazine ring are preferable, and a benzene ring is particularly preferable. .

  Examples of substituents for substituted aryl groups and substituted aromatic heterocyclic groups include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, alkylamino groups (eg, methylamino, ethylamino) , Butylamino, dimethylamino), nitro, sulfo, carbamoyl, alkylcarbamoyl groups (eg, N-methylcarbamoyl, N-ethylcarbamoyl, N, N-dimethylcarbamoyl), sulfamoyl, alkylsulfamoyl groups (eg, N- Methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), ureido, alkylureido groups (eg, N-methylureido, N, N-dimethylureido, N, N, N′-trimethyl) Ureido), alkyl groups (eg, methyl, ethyl, propyl, butyl, pentyl, Butyl, octyl, isopropyl, s-butyl, t-amyl, cyclohexyl, cyclopentyl), alkenyl groups (eg, vinyl, allyl, hexenyl), alkynyl groups (eg, ethynyl, butynyl), acyl groups (eg, formyl, acetyl, Butyryl, hexanoyl, lauryl), acyloxy groups (eg, acetoxy, butyryloxy, hexanoyloxy, lauryloxy), alkoxy groups (eg, methoxy, ethoxy, propoxy, butoxy, pentyloxy, heptyloxy, octyloxy), aryloxy groups (Eg, phenoxy), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, heptyloxycarbonyl), aryloxycarbo Group (eg, phenoxycarbonyl), alkoxycarbonylamino group (eg, butoxycarbonylamino, hexyloxycarbonylamino), alkylthio group (eg, methylthio, ethylthio, propylthio, butylthio, pentylthio, heptylthio, octylthio), arylthio group (eg, , Phenylthio), alkylsulfonyl groups (eg, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, heptylsulfonyl, octylsulfonyl), amide groups (eg, acetamide, butylamide group, hexylamide, laurylamide) and non- Aromatic heterocyclic groups (eg, morpholyl, pyrazinyl) are included.

  Substituents for substituted aryl groups and substituted aromatic heterocyclic groups include halogen atoms, cyano, carboxyl, hydroxyl, amino, alkyl-substituted amino groups, acyl groups, acyloxy groups, amide groups, alkoxycarbonyl groups, alkoxy groups, alkylthios. And groups and alkyl groups are preferred. The alkyl moiety of the alkylamino group, alkoxycarbonyl group, alkoxy group, and alkylthio group and the alkyl group may further have a substituent. Examples of alkyl moieties and substituents of alkyl groups include halogen atoms, hydroxyl, carboxyl, cyano, amino, alkylamino groups, nitro, sulfo, carbamoyl, alkylcarbamoyl groups, sulfamoyl, alkylsulfamoyl groups, ureido, alkylureido Group, alkenyl group, alkynyl group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkylsulfonyl group, amide group and non-aromatic An aromatic heterocyclic group is included. As the substituent for the alkyl moiety and the alkyl group, a halogen atom, hydroxyl, amino, alkylamino group, acyl group, acyloxy group, acylamino group, alkoxycarbonyl group and alkoxy group are preferable.

In the formula (I), L ¹ is a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, —O—, —CO—, and combinations thereof. The alkylene group may have a cyclic structure. As the cyclic alkylene group, cyclohexylene is preferable, and 1,4-cyclohexylene is particularly preferable. As the chain alkylene group, a linear alkylene group is more preferable than a branched alkylene group. The number of carbon atoms of the alkylene group is preferably 1-20, more preferably 1-15, still more preferably 1-10, still more preferably 1-8, 6 is most preferred.

  The alkenylene group and the alkynylene group preferably have a chain structure rather than a cyclic structure, and more preferably have a linear structure rather than a branched chain structure. The number of carbon atoms of the alkenylene group and the alkynylene group is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, and still more preferably 2 to 4. Most preferred is 2 (vinylene or ethynylene).

  The example of the bivalent coupling group which consists of a combination is shown.

L-1: —O—CO-alkylene group —CO—O—
L-2: -CO-O-alkylene group -O-CO-
L-3: —O—CO—alkenylene group —CO—O—
L-4: -CO-O-alkenylene group -O-CO-
L-5: -O-CO-alkynylene group -CO-O-
L-6: -CO-O-alkynylene group -O-CO-
In the molecular structure of the formula (I), the angle formed by Ar ¹ and Ar ² across L ¹ is preferably 140 degrees or more. As the rod-like compound, a compound represented by the following formula (II) is more preferable.

(II) Ar ¹ -L ² -XL ³ -Ar ²
In the formula (II), Ar ¹ and Ar ² are each independently an aromatic group. The definition and examples of the aromatic group are the same as those for Ar ¹ and Ar ^{2 in} the formula (I).

In the formula (II), L ² and L ³ are each independently a divalent linking group selected from the group consisting of an alkylene group, —O—, —CO—, and combinations thereof. The alkylene group preferably has a chain structure rather than a cyclic structure, and more preferably has a linear structure rather than a branched chain structure. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, still more preferably 1 to 4, and 1 or Most preferred is 2 (methylene or ethylene). L ² and L ³ are particularly preferably —O—CO— or —CO—O—.

  In the formula (II), X is 1,4-cyclohexylene, vinylene or ethynylene.

  Specific examples of the compound represented by formula (I) are shown below.

  These rod-shaped compounds can be synthesized with reference to methods described in the literature. As literature, Mol. Cryst. Liq. Cryst. 53, 229 (1979), 89, 93 (1982), 145, 111 (1987), 170, 43 (1989); Am. Chem. Soc. 113, p. 1349 (1991), p. 118, p. 5346 (1996), p. 92, p. 1582 (1970). Org. Chem. 40, 420 (1975), Tetrahedron, 48, 16, 3437 (1992).

<Film formation>
Hereinafter, the preferable film forming method of the retardation film and the backlight side polarizing film protective film used in the present invention will be described.

1) Dissolution process In a dissolution vessel, the cellulose ester and additives are dissolved in an organic solvent mainly containing a good solvent for the cellulose ester while stirring to form a dope, or the additive solution is mixed with the cellulose ester solution. And forming a dope.

  For dissolving the cellulose ester, a method performed at normal pressure, a method performed at a temperature lower than the boiling point of the main solvent, a method performed at a pressure higher than the boiling point of the main solvent, JP-A-9-95544, JP-A-9-95557, or Various dissolution methods such as a method using a cooling dissolution method as described in Kaihei 9-95538 and a method using a high pressure as described in Japanese Patent Application Laid-Open No. 11-21379 can be used. A method in which pressure is applied is preferable.

  The concentration of the cellulose ester in the dope is preferably 10 to 35% by mass. An additive is added to the dope during or after dissolution to dissolve and disperse, then filtered through a filter medium, defoamed, and sent to the next step with a liquid feed pump.

  All or part of additives such as plasticizers and UV absorbers may be added to these dopes. After all the materials are dissolved, they are filtered with a filter medium, defoamed, and sent to the next process with a liquid feed pump.

2) Casting process An endless metal belt, such as a stainless steel belt or a rotating metal drum, which feeds the dope through a liquid feed pump (for example, a pressurized metering gear pump) to a pressure die and transfers it indefinitely. This is a step of casting the dope from the pressure die slit to the upper casting position.

  A pressure die that can adjust the slit shape of the die base portion and can easily make the film thickness uniform is preferable. The pressure die includes a coat hanger die and a T die, and any of them is preferably used. The surface of the metal support is a mirror surface. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously.

3) Solvent evaporation step In this step, the web is heated on the metal support, and the solvent is evaporated until the web becomes peelable from the metal support.

  In order to evaporate the solvent, there are a method of blowing air from the web side and / or a method of transferring heat from the back side of the metal support by a liquid, a method of transferring heat from the front and back by radiant heat, and the like. However, the drying efficiency is preferable. A method of combining them is also preferable. In the case of backside liquid heat transfer, it is preferable to heat at or below the boiling point of the main solvent of the organic solvent used in the dope or the organic solvent having the lowest boiling point.

4) Peeling process It is the process of peeling the web which the solvent evaporated on the metal support body in a peeling position. The peeled web is sent to the next process. It should be noted that if the residual solvent amount of the web at the time of peeling (the following formula) is too large, it is difficult to peel, or conversely, if it is peeled off after being sufficiently dried on the metal support, a part of the web is partway through It may come off.

  Here, there is a gel casting method (gel casting) as a method for increasing the film forming speed (the film forming speed can be increased by peeling while the residual solvent amount is as large as possible). For example, there are a method in which a poor solvent for the cellulose ester film is added to the dope and the gel is formed after casting the dope, a method in which the temperature of the metal support is lowered and the gel is formed. By gelling on the metal support and increasing the strength of the film at the time of peeling, the speed of film formation can be increased by speeding up the peeling.

  The amount of residual solvent during peeling of the web on the metal support is preferably within a range of 5 to 150% by mass depending on the strength of drying conditions, the length of the metal support, etc., but the amount of residual solvent is larger. In the case of peeling at a point in time, if the web is too soft, flatness at the time of peeling is impaired, or slippage or vertical stripes due to peeling tension are likely to occur. Therefore, the residual solvent amount at the time of peeling is determined in consideration of economic speed and quality. In the present invention, the temperature at the peeling position on the metal support is preferably -50 to 40 ° C, more preferably 10 to 40 ° C, and most preferably 15 to 30 ° C.

  Further, the residual solvent amount of the web at the peeling position is preferably 10 to 150% by mass, and more preferably 10 to 120% by mass.

  The amount of residual solvent can be represented by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of the web at an arbitrary point in time, and N is the mass when the mass M is dried at 110 ° C. for 3 hours.

5) Drying and stretching step After peeling, the web is transferred using a drying device that alternately passes the web through a roll arranged in the drying device and / or a tenter device that clips and transports both ends of the web with clips. To dry.

  As a method of stretching 1.0 to 2.0 times with respect to the width direction between the clips, it is preferable to stretch using a tenter device. The stretching amount is preferably 1.05 to 1.5 for the liquid crystal cell side polarizing protective film and 1.01 to 1.15 for the backlight side polarizing protective film.

  More preferably, it is biaxially stretched in the longitudinal and transverse directions. In the biaxial stretching, a desired retardation value can also be obtained by relaxing by 0.8 to 1.0 times in the longitudinal direction. The draw ratio is set according to the target optical characteristics (Ro, Rt). Moreover, when manufacturing the cellulose ester film which concerns on this invention, it can also be uniaxially stretched in the elongate direction. In the present invention, under conditions of 23 ° C. and 55% RH, the liquid crystal cell side polarizing protective film (retardation film) has a retardation Ro defined by the following formula of 20 to 300 nm and a retardation Rt of 40 to 400 nm. It is necessary to be a film, and the backlight side polarizing protective film preferably has a retardation Ro of 0 to 20 nm and a retardation Rt of 0 to 70 nm.

Ro = (Nx−Ny) × d
Rt = ((Nx + Ny) / 2−Nz) × d
(In the formula, Nx represents the maximum refractive index in the film plane, Ny represents the refractive index in the direction perpendicular to Nx in the film plane, Nz represents the refractive index in the thickness direction, and d represents the thickness (nm) of the film.)
The temperature during stretching is 80 to 180 ° C., preferably 90 to 160 ° C., and the amount of residual solvent during stretching is 5 to 40% by mass, preferably 10 to 30% by mass.

  Thereby, the retardation film excellent in durability with little fluctuation | variation of Ro and Rt can be provided even on the conditions which humidity changes.

  As a drying means, hot air is generally blown on both sides of the web, but there is also a means for heating by applying a microwave instead of the wind. Too rapid drying tends to impair the flatness of the finished film. Throughout, the drying temperature is usually in the range of 40 to 250 ° C. The drying temperature, the amount of drying air, and the drying time differ depending on the solvent used, and the drying conditions may be appropriately selected according to the type and combination of the solvents used.

  Although the thickness of a film is not specifically limited, For example, a film of arbitrary thickness, such as a thing of about 10 micrometers-1 mm, can be produced. Preferably, the film thickness after drying, stretching and the like is preferably 10 to 500 μm, particularly preferably 30 to 120 μm.

(Actinic radiation curable resin layer)
The backlight side polarizing film protective film according to the present invention preferably has an actinic radiation curable resin layer on the backlight side.

  In the present invention, the actinic radiation curable resin layer uses actinic radiation curable resin as a main component. The actinic radiation curable resin layer refers to a layer mainly composed of a resin that cures through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams.

  As the actinic radiation curable resin used for the actinic radiation curable resin layer, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an actinic energy ray such as an ultraviolet ray or an electron beam. An actinic radiation curable resin layer is formed. Examples of the active energy ray-curable acrylate resin include acrylic urethane resins, polyester acrylate resins, epoxy acrylate resins, polyol acrylate resins, and the like. In the present invention, the actinic radiation curable resin layer is preferably mainly composed of an acrylic or acrylic urethane UV curable resin as a binder.

  Acrylic urethane-based resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates including methacrylates) to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added to the oligomer, and a reaction. Those described in US Pat. No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Examples of the resin monomer include common monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Among these, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolethane (meth) acrylate as the main component of the binder , An acrylic selected from dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate A system active ray curable resin is preferred.

  Examples of commercially available ultraviolet curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), etc. Can be selected as appropriate.

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  After the active energy ray-curable resin composition is applied and dried, it is cured by irradiating active energy rays, for example, ultraviolet rays.

  It is preferable to add inorganic or organic fine particles to the cured film layer thus obtained in order to prevent blocking and to improve scratch resistance and the like. Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like, and examples of the organic fine particles include polymethacrylic acid. Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder , Polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, and the like, which can be added to the ultraviolet curable resin composition. The average particle size of these fine particle powders is preferably 0.005 to 1 μm, and particularly preferably 0.01 to 0.1 μm.

  As for the ratio of actinic ray curable resin composition and fine particle powder, it is desirable to mix | blend so that it may be 0.1-10 mass parts with respect to 100 mass parts of resin compositions.

  The layer obtained by curing the actinic radiation curable resin thus formed is a clear actinic radiation curable resin layer having a centerline average roughness Ra of 1 to 50 nm as defined in JIS B 0601, even if Ra is 0. An antiglare layer of about 1 to 1 μm may be used.

  The refractive index of the actinic radiation curable resin layer is preferably within ± 0.005 with respect to the refractive index of the cellulose ester film in order to prevent interference unevenness, and more preferably within ± 0.002.

  An adhesion layer and an adhesive layer may be provided between the cellulose ester film and the actinic radiation curable resin layer. In this case, the film thickness should be 0.1 μm or less so as not to obstruct the effect of the present invention. . Flame treatment, corona discharge, and plasma processing may be performed as pretreatment for applying the active ray curable resin layer on the cellulose ester film. These actinic radiation curable resin layer layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active energy rays is usually 5 to 500 mJ / cm ² , preferably 5 to 100 mJ / cm ² , and particularly preferably 20 to 80 mJ / cm ² .

  Moreover, when irradiating an active energy ray, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roll, or the tension may be applied in the width direction or the biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  The ultraviolet curable resin layer composition coating solution may contain a solvent, or may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), It can be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  In addition, it is particularly preferable to add a silicon compound to the ultraviolet curable resin layer composition coating solution. For example, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the coating film is dried. On the contrary, when the number average molecular weight exceeds 100,000, it tends to be difficult to bleed out on the surface of the coating film.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Over's, FZ series (FZ-2203, FZ-2206, FZ-2207) and the like, are preferably used.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

  As a method for applying the ultraviolet curable resin composition coating solution, the above-described methods can be used. The coating amount is suitably 1 to 40 μm as a wet film thickness, and preferably 3 to 20 μm. The dry film thickness is 1 to 20 μm, preferably 1.5 to 10 μm. When the film thickness is 1 to 20 μm, there is also an effect of preventing fine scratches due to contact with the transport roller when handling the polarizing plate in a roll shape.

The ultraviolet curable resin composition is preferably irradiated with ultraviolet rays during or after coating and drying, and the irradiation time for obtaining the necessary dose of active energy rays is preferably about 0.1 second to 1 minute. From the viewpoint of curing efficiency or work efficiency of the curable resin, 0.1 to 10 seconds is more preferable. Moreover, it is preferable that the illumination intensity of these active energy ray irradiation parts is 50-150 mW / m < ² >. When two actinic radiation curable resin layers are applied in layers, it is preferable to irradiate with ultraviolet rays in the state of being overlapped.

  The nanoindentation hardness (H) of the active ray curable resin layer of the backlight side polarizing film protective film is preferably 0.8 to 2.0 GPa, and the nanoindentation elastic modulus (Er) is preferably 6 to 15 GPa. .

  The nanoindentation hardness (H) and elastic modulus (Er) of the outermost surface layer are defined as follows depending on whether the film thickness of the outermost surface layer is 10 nm or less and exceeds 10 nm, respectively.

(1) When the film thickness of the outermost surface layer exceeds 10 nm When the film thickness of the outermost surface layer exceeds 10 nm, the nanoindentation hardness (H) and elastic modulus (Er) of the outermost surface layer itself are measured by the measurement method described later. ) Is required.

(2) When the film thickness of the outermost surface layer is 10 nm or less When the film thickness of the outermost surface layer is 10 nm or less, in the measurement method described later, the nanoindentation hardness (H), elastic modulus ( In such a case, in the present invention, measurement is performed in an embodiment including the outermost surface layer and the lower layer of the outermost surface layer. Indentation hardness (H) and elastic modulus (Er) are defined respectively.

  For example, when the outermost surface layer is a protective layer having a thickness of 10 nm or less and the lower layer of the protective layer is a polarizing film protective film, the nanoindentation hardness (H) and elastic modulus (Er) of the outermost surface layer Is measured as data over two layers of protective layer + polarizing film protective film.

  When the nanoindentation hardness (H) is smaller than 0.8 GPa or the elastic modulus (Er) is smaller than 6 GPa, the scratch resistance is deteriorated. Further, when the hardness (H) is greater than 2 GPa or the elastic modulus (Er) is greater than 15 GPa, there is a problem that cracks are likely to occur under heating conditions.

  The nanoindentation hardness (H) and elastic modulus (Er) of the actinic radiation curable resin layer according to the present invention are measured by an indentation amount of 15 ± 3% or an indentation amount of 250 nm of the thickness of the actinic radiation curable resin layer. However, in the present invention, when the value of 15 ± 3% of the thickness of the actinic radiation curable resin layer is 250 nm or more, the indentation amount is set to 250 nm and the measurement is performed.

  From the viewpoint of imparting sufficient scratch resistance to the actinic radiation curable resin layer according to the present invention and preventing the occurrence of cracks under heating conditions, the nanoindentation hardness (H) is in the range of 0.8 to 2.0 GPa. And the elastic modulus (Er) is preferably adjusted in the range of 6 to 15 GPa.

  The measurement of the nanoindentation hardness (H) and the nanoindentation elastic modulus (Er) of the active ray curable resin layer, which is the outermost surface layer of the backlight side polarizing film protective film according to the present invention, is performed by using Triboscope manufactured by Hystron Corp. with Digital Instruments. The measurement was carried out on a Nanoscope III manufactured by the company.

  For the measurement, a triangular pyramid type diamond indenter called a Belkovic indenter (tip ridge angle 142.3 °) was used as an indenter.

  A triangular pyramid-shaped diamond indenter was applied to the sample surface at a right angle, a load was gradually applied, and the load was gradually returned to 0 after reaching the maximum load. A value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion was calculated as nanoindentation hardness (H). The nanoindentation elastic modulus (Er) was calculated using the following formula, assuming the slope S of the unloading curve.

(formula)
Er = (S × √π) / (2√A) (π is the circumference)
In addition, the apparatus was calibrated and measured in advance so that the hardness obtained as a result of pressing the attached fused silica as a standard sample was 9.5 ± 1.5 GPa.

  Details of the principle are described in Handbook of Micro / Nano Tribology (CRC edited by Bharat Bhushan).

  A drop of adhesive Aron Alpha manufactured by Toagosei Co., Ltd. was dropped on a slide glass, and then a sample was placed on a 1 cm square film and allowed to stand for 24 hours to be cured.

For the measurement of the outermost surface, the maximum load P was set in advance so that the maximum depth was 15 nm. Loading and unloading were performed in 5 seconds [Manufacture of polarizing plates and liquid crystal display devices]
The polarizing plate is composed of a polarizing film and two transparent protective films (a liquid crystal cell side polarizing film protective film and a backlight side polarizing film protective film) disposed on both sides thereof. Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. In this invention, it manufactures using the polyvinyl-alcohol-type film (polyvinyl-alcohol-type polarizing film) of an iodine type polarizing film and a dye-type polarizing film.

  The polarizing plate of the present invention can be produced by a general method. For example, after subjecting the liquid crystal cell-side polarizing film protective film according to the present invention to an alkali saponification treatment, the backlight-side polarizing film protective film is subjected to an alkali saponification treatment on one side of a polarizing film prepared by immersion and stretching in an iodine solution, There is a method of bonding using a completely saponified polyvinyl alcohol aqueous solution. The alkali saponification treatment is a treatment in which the cellulose ester film is immersed in a strong alkaline solution at high temperature in order to improve the wetness of the aqueous adhesive and improve the adhesion.

  As the polarizer used in the polarizing plate of the present invention, a polyvinyl alcohol film is treated with a dichroic dye such as iodine and stretched, or a plastic film such as vinyl chloride is treated and oriented (polyvinyl alcohol). System polarizing film). The polarizer thus obtained is bonded to a cellulose ester film.

  When adhering the polarizing film and the polarizing film protective film in the present invention, for example, an adhesive made of a vinyl alcohol polymer, or a water-soluble vinyl alcohol polymer such as boric acid, borax, glutaraldehyde, melamine, or oxalic acid. It can be carried out via an adhesive composed of a functional crosslinking agent. In particular, it is preferable to use a polyvinyl alcohol-based adhesive because it has the best adhesiveness to the polyvinyl alcohol-based film. Such an adhesive layer can be formed as a coating / drying layer or the like of an aqueous solution, but other additives and catalysts such as acids can be blended as necessary when preparing the aqueous solution.

  As a method for producing a polarizing plate, the polarizing film is a roll-shaped polyvinyl alcohol polarizing film, and the liquid crystal cell-side polarizing film protective film is produced by stretching a cellulose ester film, under the conditions of 23 ° C. and 55% RH. The retardation Ro defined by the above formula is a roll-shaped retardation film having a retardation Rt of 20 to 300 nm and a retardation Rt of 70 to 400 nm, and the backlight side polarizing film protective film is the same as before the saponification treatment except for the front and rear ends. The dimensional change after saponification is 0.01 to 0.10%, and the saponified retardation film, the polyvinyl alcohol-based polarizing film, and the saponified backlight-side polarizing film protective film are in a roll state. It is preferable to stick them together continuously.

  Moreover, it is preferable that the average value of the dimensional change rate in the width direction after the saponification treatment of the backlight side polarizing film protective film is 0.04% or less.

  Further, between the step of continuously laminating the saponified retardation film, the polyvinyl alcohol polarizing film, and the saponified backlight-side polarizing film protective film in a roll state and the winding step, It is preferable to have a step of providing an adhesive layer and a release protective layer described later on the adhesive surface of the retardation film to the liquid crystal cell.

  In the present invention, the method for laminating the polarizing plate on the liquid crystal cell is not particularly limited, but conventionally known adhesives and pressure-sensitive adhesives can be used and can be determined as appropriate. The pressure-sensitive adhesive is preferably a transparent pressure-sensitive adhesive having excellent stress relaxation properties such as an acrylic polymer, silicone polymer, polyester, polyurethane, polyether, polyvinyl alcohol polymer, and synthetic rubber polymer material. The adhesive or pressure-sensitive adhesive is preferably applied to the surface of the polarizing plate on the liquid crystal cell side to provide an adhesive layer or a pressure-sensitive adhesive layer and bonded to the glass surface of the liquid crystal cell. The thickness of the adhesive layer or the pressure-sensitive adhesive layer is not particularly limited and can be appropriately determined. For example, it is generally 1 to 500 μm, preferably 2 to 200 μm, particularly preferably 5 to 5 μm from the viewpoints of adhesive strength and thinning. 100 μm. In addition, the adhesive layer or the pressure-sensitive adhesive layer, if necessary, a tackifier such as petroleum resin, rosin resin, terpene resin, coumarone indene resin, phenol resin, xylene resin, alkyd resin, Conventionally known additives such as softeners such as phthalic acid esters, phosphoric acid esters, chlorinated paraffins, polybutenes, polyisobutylenes, and other various fillers and anti-aging agents may be appropriately blended.

  In addition, the adhesive layer or adhesive layer prevents foaming and peeling due to moisture absorption, reduces optical characteristics due to differences in thermal expansion, prevents warping of the liquid crystal cell, and forms an image display device with high quality and excellent durability. The adhesive layer or the pressure-sensitive adhesive layer has a low moisture absorption rate and excellent heat resistance. Alternatively, the adhesive layer or the pressure-sensitive adhesive layer may contain fine particles to form an adhesive layer or a pressure-sensitive adhesive layer exhibiting light diffusibility.

  In the present invention, the adhesive layer or the pressure-sensitive adhesive layer formed on the surface of the polarizing plate is preferably covered with a release protective layer (liner). By covering in this way, it is possible to prevent contamination of the adhesive layer or the pressure-sensitive adhesive layer and improve handleability until it is mounted on a liquid crystal cell or the like. The liner can be formed by, for example, a method of providing a release coat with a release agent such as silicone, long chain alkyl, fluorine, or molybdenum sulfide on an appropriate film such as the transparent protective film.

  At this time, the retardation film according to the present invention may be used as the backlight-side polarizing film protective film, or another cellulose ester film that is not a retardation film can be used. For the backlight side polarizing film protective film, a commercially available cellulose ester film (KC8UX2M, KC4UX2M, KC5UN, KC4UY, KC8UY (manufactured by Konica Minolta Opto Co., Ltd.)) is provided with an active ray curable resin layer and used as a polarizing film protective film. Can do.

  It is preferable from the object of the present invention that the curling of the polarizing plate is small. Numerically, when it is cut into a 50 cm square and left on a horizontal flat plate under the conditions of 23 ° C. and 55% RH, the distance that the end is lifted from the plane is 50 mm or less, particularly preferably 20 mm or less. is there. Curling can be adjusted by the material composition, manufacturing method, film thickness, etc. of the polarizing protective film. Curling can also be adjusted by adjusting the saponification conditions.

  The polarizing plate of the present invention obtained as described above is bonded to the backlight side of the liquid crystal cell, and on the viewing side of the liquid crystal cell, from the surface side, an antireflection layer, an antiglare layer, an antireflection antiglare layer. A viewing-side polarizing film protective film coated with any surface layer, a polyvinyl alcohol polarizing film, a liquid crystal-side polarizing film protective film, and an adhesive layer (a liquid crystal-side polarizing film protective film and a liquid crystal cell are attached) are laminated in this order. Thus, the liquid crystal display device of the present invention can be manufactured.

  For the polarizing plate protective film used on the viewing side of the liquid crystal cell, it is possible to use a viewing-side polarizing film protective film coated with any surface layer of an antireflection layer, an antiglare layer, or an antireflection antiglare layer. It is more preferable than mass production, cost, and performance (because of the same behavior as the backlight side and less likely to cause problems). The specific coating layer configuration is preferably provided with a clear active ray curable resin layer, an antiglare active ray curable resin layer, an antireflection layer, an antistatic layer, and an antifouling layer, coating, sputtering, CVD, atmospheric pressure It can preferably be provided by a method such as plasma CVD or vacuum deposition.

  Moreover, at the time of producing the polarizing plate, it is preferable to bond the retardation film according to the present invention so that the in-plane slow axis of the retardation film and the transmission axis of the polarizer are substantially parallel. In this case, it is particularly preferable for production to use a long film to bond by roll-to-roll. As a result, light leakage at the time of black display is remarkably improved, and even a large-screen liquid crystal display device of 15 type or more, preferably 19 type or more has no white spots at the periphery of the screen, and the effect thereof. Even under an environment where the humidity fluctuation is large, a stable viewing angle characteristic is maintained for a long time, and a remarkable effect is recognized particularly in an MVA (multi-domain vertical alignment) type liquid crystal display device. Further, the viewing angle characteristics of the liquid crystal display device adopting various driving methods such as TN, VA, OCB, and HAN can be optimized, and the effect is exhibited particularly in the VA type.

  In particular, the liquid crystal display device using the polarizing plate of the present invention has a size of 15 inches or more, and the present invention is effective for a thin liquid crystal display device having a large influence of heat with a short distance between the light source and the polarizing plate. A planar white LED is a light source preferably used in the liquid crystal display device of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
<< Production of cellulose ester film >>
A cellulose ester film was produced according to the method described below.

[Preparation of dope]
(Preparation of silicon oxide dispersion)
Aerosil 200V (Nippon Aerosil Co., Ltd.) 1kg
Ethanol 9kg
The above material was stirred and mixed with a dissolver for 30 minutes, and then dispersed using a Manton Gorin type high-pressure dispersion device.

(Preparation of additive solution A)
Cellulose acetate (acetyl substitution degree: 60.3%) 4kg
76 kg of methylene chloride
Tinuvin 326 (Ciba Specialty Chemicals) 3kg
Tinuvin 109 (Ciba Specialty Chemicals) 4kg
Tinuvin 171 (Ciba Specialty Chemicals) 4kg
The above material was put into a sealed container and completely dissolved and filtered while heating and stirring. To this, 9 kg of the above silicon oxide dispersion was added with stirring, and the mixture was further stirred for 30 minutes, followed by filtration to prepare additive solution A.

[Preparation of Dope A]
Triphenyl phosphate 15kg
Ethyl phthalyl ethyl glycolate 5kg
Retardation raising agent A 7.7 kg
640 kg of methylene chloride
120 kg of ethanol
Cellulose acetate (acetyl substitution degree: 60.3%) 220 kg
The above materials were sequentially put into a sealed container with stirring, and completely dissolved and mixed while heating and stirring. The dope was lowered to the temperature at which the dope was cast and allowed to stand overnight, and after defoaming operation, the solution was added to Azumi Filter Paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. Filtered using 244. Further, 2 kg of the additive solution A was added per 100 kg of the solution, sufficiently mixed with an in-line mixer (Toray static in-pipe mixer Hi-Mixer SWJ), and then filtered to prepare a dope A.

[Preparation of dope B]
In the preparation of the dope A, a dope B was prepared in the same manner except that the retardation increasing agent A was changed to the retardation increasing agent B.

[Preparation of dope C]
In the preparation of the dope A, cellulose acetate (acetyl substitution degree: 60.3%) was changed to cellulose acetate propionate (acyl substitution degree: 60.3%), and the retardation increasing agent A was removed in the same manner. Dope C was prepared.

(Measurement of substitution degree of cellulose ester)
The degree of substitution of the cellulose ester used for the preparation of each of the above-mentioned dopes A to C was measured according to the method prescribed in ASTM-D817-96.

[Production of retardation film (liquid crystal cell side polarizing film protective film)]
Retardation films 1 to 3 were prepared using the prepared dopes A to C as follows.

  After the dopes A to C were filtered, they were uniformly cast on a stainless band support having a dope temperature of 35 ° C. and a temperature of 30 ° C. using a belt casting apparatus. Then, after drying to the peelable range, the web was peeled from the stainless steel band support body. At this time, the residual solvent amount of the web was 80%.

  After peeling from the stainless steel band support, it was dried while being conveyed in a roll at 85 ° C., and when the residual solvent amount was less than 35% by mass, it was biaxial so that Ro was 45 and Rt was 130. After stretching in 90 ° C while stretching in the TD direction (width direction) and MD direction (film-forming direction) with a stretching tenter, release the width gripping and finish drying in the 125 ° C drying zone while further transporting rolls. Then, a knurling process having a width of 10 mm and a height of 8 μm was applied to both ends of the film to prepare retardation films 1 to 3. The stretching ratios of the retardation films 1 to 3 in the TD direction were 1.31, 1.32, and 1.30, respectively, and the film thicknesses were 82, 81, and 80 μm, respectively. The film widths of the retardation films 1 to 3 were 1300 mm, and the winding length was 2000 m. The residual solvent amount at the time of winding was less than 0.1% by mass.

(Measurement of retardation Rt)
Using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments), a three-dimensional refractive index measurement is performed at a wavelength of 590 nm in an environment of 23 ° C. and 55% RH, and refractive indexes nx, ny , Nz was determined. According to the above, retardation Rt was calculated.

(Measurement of retardation Ro)
Refractive indexes nx and ny were determined by the same method as described above. According to the above formula, the retardation Ro) in the plane direction was calculated.

[Preparation of protective film for backlight-side polarizing film]
<Preparation of cellulose ester film 11>
(Preparation of dope D)
Cellulose ester (cellulose triacetate synthesized from linter cotton)
100 parts by weight Triphenyl phosphate 9.5 parts by weight Ethylphthalyl ethyl glycolate 2.2 parts by weight Methylene chloride 440 parts by weight Ethanol 40 parts by weight or more is put into a sealed container, heated and stirred, and completely dissolved Azumi Filter Paper No. manufactured by Azumi Filter Paper Co., Ltd. 24 was used to prepare a dope D. The dope D was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the film production line. (A part of the dope D was also used for preparing the following inline additive solution D.)
(Silicon dioxide dispersion D)
Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd., average particle size of primary particles 12 nm, apparent specific gravity 100 g / liter) 2 parts by mass Ethanol 18 parts by mass or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. The liquid turbidity after dispersion was 100 ppm. 18 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution D.

(Preparation of inline additive solution D)
Methylene chloride 100 parts by weight Dope D 34 parts by weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 5 parts by weight Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 5 parts by weight Tinuvin 326 (manufactured by Ciba Specialty Chemicals) 3 More than part by mass was put into a sealed container, heated, stirred and completely dissolved and filtered. To this was added 20 parts by mass of silicon dioxide dispersion diluted solution D while stirring, and the mixture was further stirred for 60 minutes, followed by filtration with Advantech Toyo Co., Ltd. polypropylene wind cartridge filter TCW-PPS-1N. Was prepared.

  In-line additive solution D was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the in-line additive solution line. Add 2.5 parts by mass of the filtered inline additive D to 100 parts by mass of the filtered dope solution D, and mix well with an inline mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ). Using a casting apparatus, casting was uniformly performed on a stainless steel band support at a temperature of 35 ° C. and a width of 1800 mm. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and then peeled off from the stainless steel band support. The peeled cellulose ester web was evaporated at 35 ° C., slit to 1650 mm width, and then stretched 1.1 times in the TD direction (direction perpendicular to the film transport direction) with a tenter, Dried at the drying temperature. At this time, the residual solvent amount when starting stretching with a tenter was 20%. Thereafter, drying is completed while transporting the drying zone at 120 ° C. and 110 ° C. with a number of rolls, slitting to a width of 1400 mm, a knurling process with a width of 15 mm and an average height of 10 μm is applied to both ends of the film, and an initial winding tension of 220 N The cellulose ester film 11 was obtained by winding it around a 6-inch inner diameter core at a final tension of 110 N / m. The residual solvent amount of the cellulose ester film 11 was 0.2%, the average film thickness was 80 μm, the number of turns was 4000 m, Ro was 1 nm, and Rt was 54 nm.

<Preparation of cellulose ester film 12>
(Preparation of dope E)
Cellulose ester (cellulose acetate propionate, acetyl group substitution degree 1.9, propionyl group substitution degree 0.8, Mn = 70000, Mw / Mn = 2.14)
100 parts by weight Triphenyl phosphate 8 parts by weight Ethyl phthalyl ethyl glycolate 2 parts by weight Methylene chloride 300 parts by weight Ethanol 60 parts by weight or more is put into a closed container, heated and stirred, completely dissolved, and Azumi filter paper Azumi filter paper No. 24 was used to prepare a dope E. The dope E was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the film production line.

(Silicon dioxide dispersion E)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd., average particle size 16 nm, apparent specific gravity 90 g / liter) 10 parts by mass Ethanol 75 parts by mass or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. The liquid turbidity after dispersion was 200 ppm. 75 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed with a dissolver for 30 minutes to prepare a silicon dioxide dispersion dilution E.

(Preparation of inline additive solution E)
Methylene chloride 100 parts by weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 4 parts by weight Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 4 parts by weight Tinuvin 326 (manufactured by Ciba Specialty Chemicals) Seal 2 parts by weight or more The solution was put into a container, heated, dissolved completely with stirring and filtered. To this was added 20 parts by mass of silicon dioxide dispersion diluent E with stirring, and the mixture was further stirred for 30 minutes, and then cellulose ester (cellulose acetate propionate, acetyl group substitution degree 1.9, propionyl group substitution degree 0.8). , Mn = 70000, Mw / Mn = 2.14) Add 5 parts by mass and stir for another 60 minutes, then filter with Advantech Toyo's polypropylene wind cartridge filter TCW-PPS-1N. Additive liquid E was prepared.

  In-line additive solution E was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the in-line additive solution line. 4 parts by mass of the filtered in-line additive liquid E is added to 100 parts by mass of the filtered dope E, and sufficiently mixed with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ). Was cast uniformly on a stainless steel band support at a temperature of 35 ° C. and a width of 1800 mm. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and then peeled off from the stainless steel band support. The peeled cellulose ester web was evaporated at 55 ° C. and slit to 1650 mm width. Thereafter, drying is completed while transporting the drying zone of 120 ° C. and 110 ° C. with a number of rolls, slitting to a width of 1400 mm, a knurling process having a width of 15 mm and an average height of 10 μm is applied to both ends of the film, and an initial winding tension of 220 N / M and a final tension of 110 N / m were wound around a 6-inch inner diameter core to obtain a cellulose ester film 12. The residual solvent amount of the cellulose ester film 12 was 0.1%, the average film thickness was 80 μm, the number of turns was 4000 m, Ro was 0.2 nm, and Rt was 50 nm.

[Preparation of protective film for polarizing film with active ray curable resin layer]
The following actinic radiation curable resin layer coating compositions 16 to 19 were extrusion coated on the cellulose ester films 11 and 12 produced above, and then dried in a drying section set at 80 ° C., and then 118 mJ / cm ^2. UV-irradiated, provided with an active ray curable resin layer 16-19 having a dry film thickness of 1 to 25 μm (described in Table 1) and a center line average surface roughness (Ra) of 8 nm, and a polarizing film protective film with an active ray curable resin layer Was made.

<Actinic radiation curable resin layer coating composition 16>
Dipentaerythritol hexaacrylate monomer 60 parts by weight Dipentaerythritol hexaacrylate dimer 20 parts by weight Dipentaerythritol hexaacrylate trimer or higher component 20 parts by weight Dimethoxybenzophenone photoinitiator 4 parts by weight Methyl ethyl ketone 75 parts by weight Propylene Glycol monomethyl ether 75 parts by mass <Actinic radiation curable resin layer coating composition 17>
Polyurethane polyacrylate 100 parts by weight Dimethoxybenzophenone photoinitiator 4 parts by weight Methyl ethyl ketone 75 parts by weight Propylene glycol monomethyl ether 75 parts by weight <Actinic radiation curable resin layer coating composition 18>
Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Components greater than dipentaerythritol hexaacrylate trimer 20 parts by mass Cross-linked polystyrene particles (SX350H, manufactured by Soken Kagaku, particle size 3.5 μm) ) 20 parts by mass Silicon oxide fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 10 parts by mass Dimethoxybenzophenone photoreaction initiator 4 parts by mass Methyl ethyl ketone 75 parts by mass Propylene glycol monomethyl ether 75 parts by mass <Actinic radiation curable resin layer coating composition 19>
Epoxy acrylate 60 parts by mass Epoxy acrylate dimer 20 parts by mass Components of epoxy acrylate trimer or more 20 parts by mass Dimethoxybenzophenone photoinitiator 4 parts by mass Methyl ethyl ketone 75 parts by mass Propylene glycol monomethyl ether 75 parts by mass Next, the above-described method The nanoindentation hardness (H) and nanoindentation elastic modulus (Er) of the actinic radiation curable resin layer prepared above were measured. Furthermore, the dimensional change rate after saponification processing of the polarizing film protective film with an active ray curable resin layer was measured by the following method.

<Measurement of dimensional change rate>
About the polarizing film protective film, it is cut into a size of 150 mm in the longitudinal direction and 1300 mm in the width direction. Humidity is adjusted for 24 hours or more, and the distance L1 between the marks is measured with a microscope at each of 10 positions about 100 mm to the left, 100 mm to the right, and the center. Next, the sample was treated with a 1 mol / L KOH aqueous solution at 44 to 46 ° C. for 2 minutes to saponify the surface, washed with water for 20 seconds, dried at 95 to 100 ° C. for 30 seconds, and again the sample was treated with 23 Humidity is adjusted for 24 hours in an environment of 55 ° C and RH, and the distance L2 between the marks after saponification treatment is measured with a microscope. The dimensional change rate before and after this processing is obtained by the following equation.

Dimensional change rate (%) = (L1-L2) / L1 × 100
L1: Distance between marks before saponification treatment L2: Distance between marks after saponification treatment Table 2 shows the dimensional change rates of the retardation films 1 to 3 together with retardation.

<< Preparation of polarizing plate for liquid crystal cell's backlight >>
In the combinations shown in Table 1, iodine-doped stretching with retardation films 1 to 3 and a backlight side polarizing film protective film whose surfaces were saponified by treatment with 1 mol / L KOH aqueous solution at 44 to 46 ° C. for 2 minutes The roll-shaped polarizing plates 1-16 of the structure which pinched | interposed the polarizing film which consists of polyvinyl alcohol were produced.

<Evaluation of polarizing plate on the backlight side of the liquid crystal cell>
The adhesion state of the edge part of the produced polarizing plate was evaluated in four stages according to the following criteria.

◎: Adhesive component does not protrude from the edge, no difference in level, very good ○: Adhesive component does not protrude from the edge, but film step is observed △: Adhesive component protrudes from the edge Although it is recognized, there is no substantial problem. X: Table 1 shows the result of the level evaluation and the dimensional change rate which are problematic because the adhesive component protrudes from the end.

  The sample of the present invention having a smaller dimensional change rate than Table 1 has better adhesion at the end of the polarizing plate than the comparative product.

Example 2
<< Preparation of polarizing plate for liquid crystal cell's backlight >>
In the same manner as in Example 1, 16 types of backlight-side polarizing plates of liquid crystal cells were produced. However, a roll-like retardation film and a polarizing film protective film were used, and the saponification was performed under the following conditions. The pressure-sensitive adhesive layer and the release protective layer were provided as follows on the adhesion surface of the retardation film to the liquid crystal cell, and a polarizing plate was produced by continuous treatment.

(Saponification conditions)
The surface is saponified by treatment with a 1 mol / L KOH aqueous solution at 44 to 46 ° C. for 2 minutes, washed with water for 20 seconds, and dried at 95 to 100 ° C. for 30 seconds. The conveyance tension is 75 to 85N.

(Formation of adhesive layer and release protective layer)
The following acrylic pressure-sensitive adhesive is coated on a release paper so that the film thickness after drying is 10 μm, dried to prepare an adhesive layer, and then the adhesive layer and the release protective layer are bonded to the retardation film surface of the polarizing plate. .

<Production of acrylic adhesive>
Add 92.9 parts of n-butyl acrylate, 7 parts of N-cyclohexylmaleimide, 0.1 part of 2-hydroxyethyl acrylate, 0.3 part of 2,2'-azobisisobutyronitrile, and in ethyl acetate. A copolymerization reaction was performed at 60 ° C. for 5 hours and further at 70 ° C. for 1.5 hours in a nitrogen gas atmosphere to obtain a copolymer solution having a solid content concentration of 30% by mass. To this solution, 2 parts of trimethylolpropane tolylene diisocyanate per 100 parts of the copolymer was mixed and subjected to intermolecular crosslinking to prepare an acrylic pressure-sensitive adhesive.

<< Production of polarizing plate on the viewing side of liquid crystal cell >>
<< Preparation of antireflection film >>
[Production of cellulose ester film]
A cellulose ester solution (dope) was prepared using the following cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent, and a cellulose ester film was prepared by a solution casting film forming method.

Cellulose ester (cellulose triacetate, acetyl group substitution degree 2.9, Mn = 16000, Mw / Mn = 1.8) 100 kg
Plasticizer (trimethylolpropane tribenzoate) 5kg
Plasticizer (ethyl phthalyl ethyl glycolate) 5kg
UV absorber (Tinubin 109, manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0kg
UV absorber (Tinuvin 171 manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0kg
Fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 0.3kg
Solvent (methyl acetate) 440kg
Solvent (ethanol) 110kg
A cellulose ester solution (dope) was prepared using the above cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent.

  That is, the solvent was put into an airtight container, the remaining materials were put in order with stirring, and completely dissolved and mixed while heating and stirring. The fine particles were added dispersed in a part of the solvent. After the temperature was lowered to the temperature at which the solution was cast and allowed to stand overnight, a defoaming operation was performed, and then the solution was Azumi Filter Paper No. Filtration using 244 gave a cellulose ester solution.

  Next, the cellulose ester solution whose temperature was adjusted to 33 ° C. was fed to a die and uniformly cast from a die slit onto a stainless steel belt. The cast part of the stainless steel belt was heated from the back with hot water of 37 ° C. After casting, the dope film on the metal support (referred to as a web after casting on a stainless steel belt) is dried by applying hot air of 44 ° C., and the residual solvent in the peeling is peeled off at 120% by mass. Then, the web was stretched so that the longitudinal stretching ratio was 1.1 times, and then the web edge was gripped with a tenter while the residual solvent amount was from 35% by mass to 10% by mass. It extended | stretched so that it might become 1.1 times the draw ratio. After stretching, the width is maintained for several seconds, and after the tension in the width direction is relaxed, the width is released and further conveyed for 20 minutes in a third drying zone set at 125 ° C., and dried. A cellulose ester film having a width of 1.5 m and a film thickness of 50 μm was produced.

[Production of hard coat film]
On the surface of the cellulose ester film (the B side; the surface in contact with the support mirror surface such as a stainless steel band used in the casting film forming method; the support side), the following actinic radiation curable resin layer coating solution was applied with a pore size of 0. An actinic radiation curable resin layer coating solution is prepared by filtration through a 4 μm polypropylene filter, which is applied using a micro gravure coater, dried at 90 ° C., and then the illuminance of the irradiated part is 100 mW / cm using an ultraviolet lamp. ² , the irradiation amount was 80 mJ / cm ² , the coating layer was cured, and an actinic radiation curable resin layer having a thickness of 5 μm was formed to produce a hard coat film.

(Active ray curable resin layer coating solution)
The following materials were stirred and mixed to obtain an actinic radiation curable resin layer coating solution.

Dipentaerythritol hexaacrylate monomer 60 mass parts Dipentaerythritol hexaacrylate dimer 20 mass parts Dipentaerythritol hexaacrylate trimer or higher component 20 mass parts Polymerization initiator: Irgacure 184 (manufactured by Ciba Specialty Chemicals) )
4 parts by mass Propylene glycol monomethyl ether 75 parts by mass Methyl ethyl ketone 75 parts by mass Ultrafine particle silica Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd.) 0.002 parts by mass or more was used to prepare a hard coat film.

[Preparation of antireflection film]
After performing the following surface treatment on the hard coat film, the following medium refractive index layer, high refractive index layer and low refractive index layer were coated in this order as shown in Table 1 to prepare an antireflection film.

(surface treatment)
The hard coat film is immersed in a 1.5 mol / l-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then immersed in a 0.5 mass% -H ₂ SO ₄ aqueous solution at room temperature for 30 seconds. Neutralized, washed with water and dried.

(Preparation of medium refractive index layer)
The following medium refractive index layer coating solution is applied onto the actinic radiation curable resin layer of the hard coat film prepared above using a bar coater, dried at 60 ° C., and then irradiated with ultraviolet rays to cure the coating layer and have a medium refractive index. A layer was formed.

Medium refractive index layer thickness: 100 nm
Refractive index of medium refractive index layer: 1.64
(Medium refractive index layer composition)
Titanium oxide fine particle dispersion (RTSPNB, manufactured by CI Kasei Kogyo Co., Ltd., solid content 15%)
270 parts by mass Dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.) 55 parts by mass FZ-2207 (silicon compound, manufactured by Nippon Unicar Co., Ltd.) 1 part by mass Irgacure 907 (Ciba Geigy) 3 parts by mass propylene glycol Monomethyl ether 1470 parts by weight Isopropyl alcohol 2720 parts by weight Methyl ethyl ketone 490 parts by weight [Preparation of high refractive index layer]
The following high-refractive-index layer coating solution was applied onto the produced medium-refractive-index layer using a bar coater, dried at 60 ° C., and then irradiated with ultraviolet rays to cure the applied layer to form a high-refractive-index layer.

High refractive index layer thickness: 50 nm
Refractive index of high refractive index layer: 1.80
(High refractive index layer composition)
RTSPNB (Cai Kasei Kogyo Co., Ltd., titanium oxide fine particle dispersion, solid content 15%) 60 parts by weight KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight Tetrabutoxy titanium 5 parts by weight FZ-2207 (Silicon compound, manufactured by Nippon Unicar Co., Ltd.) 0.2 parts by mass Irgacure 907 (manufactured by Ciba Geigy) 2 parts by mass Isopropyl alcohol 560 parts by mass Methyl ethyl ketone 90 parts by mass Propylene glycol monomethyl ether 280 parts by mass [Production of low refractive index layer]
The following low refractive index layer coating solution was coated on the high refractive index layer produced above using a bar coater, dried at 60 ° C., and then irradiated with ultraviolet rays to cure the coated layer to form a low refractive index layer.

Low refractive index layer thickness: 90 nm
Refractive index of the low refractive index layer: 1.38
(Low refractive index layer composition)
<Preparation of alkoxysilicon hydrolyzate 1>
A hydrolyzate liquid 1 was prepared by mixing 289 g of tetraethoxysilane and 553 g of ethanol, adding 157 g of a 0.15% aqueous acetic acid solution thereto, and stirring in a water bath at 25 ° C. for 30 hours.

Alkoxysilicon hydrolyzate liquid 1 100 parts by weight KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight FZ-2207 (silicon compound, manufactured by Nippon Unicar Co., Ltd.) 1 part by weight Propylene glycol monomethyl ether 380 parts by weight Part Isopropyl alcohol 380 parts by mass Using the produced antireflection film, a viewing side polarizing plate of a liquid crystal cell with an antireflection layer used on the viewing side of a liquid crystal display panel (image display device) was produced.

(A) Production of Polarizing Film A long polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. . This was washed with water and dried to obtain a long polarizing film.

(B) Production of Polarizing Plate Next, according to the following steps 1 to 5, the polarizing film and the polarizing plate protective film were bonded together to produce a polarizing plate.

  Step 1: The cellulose triacetate film and the antireflection film were immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried. A surface of the antireflection film provided with the antireflection layer was previously protected with a peelable protective film (PET).

  Similarly, the cellulose triacetate film was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried.

  Process 2: The above-mentioned polarizing film was immersed for 1 to 2 seconds in the polyvinyl alcohol adhesive tank of 2 mass% of solid content.

  Step 3: Excess adhesive adhered to the polarizing film in Step 2 was lightly removed, and it was sandwiched between the cellulose triacetate film and the antireflective film that had been subjected to alkali treatment in Step 1, and laminated.

Process 4: It bonded together at the speed | rate of about 2 m / min with the pressure of 20-30 N / cm < ² > with the two rotating rollers. At this time, care was taken to prevent bubbles from entering.

  Step 5: The sample prepared in Step 4 in a dryer at 80 ° C. was dried for 2 minutes to prepare the polarizing plate of the present invention.

<Production of liquid crystal display device>
The backlight side polarizing plate and the viewing side polarizing plate of the liquid crystal cell of the Aquos liquid crystal display device manufactured by Sharp Corporation are peeled off, and the backlight side polarizing plate and the viewing side polarizing plate (having an antireflection film) of the prepared liquid crystal cell are liquid crystal. A 30-inch liquid crystal display device was produced by pasting on the cell. This device is a direct backlight light source in which several fluorescent lamps are arranged in parallel.

<Evaluation of liquid crystal display device>
It was found that when a roll-shaped polarizing plate having a problem in Example 1 was used, the protruding component adhered to other parts by roller transfer and had a problem as a display device in mass production. The display device using the polarizing plate of the present invention was good. Further, a polarizing plate having no resin layer (active ray curable resin layer) on the polarizing plate protective film has scratches on the backlight surface (does not affect the observation from the viewing side of the liquid crystal display itself). In the coated present invention, there was no scratch and the appearance was good.

  Moreover, the liquid crystal display device of the present invention was excellent in visibility performed by the following method, and was excellent in mass productivity at low cost.

(Visibility evaluation method)
The liquid crystal display device obtained as described above was placed on a desk 80 cm high from the floor, and a daylight direct fluorescent lamp (FLR40S • D / MX Matsushita Electric) was placed on the ceiling 3 m high from the floor. 10 sets are arranged at intervals of 1.5 m, with 40W × 2 pieces (produced by Sangyo Co., Ltd.) as one set. At this time, when the evaluator is in front of the liquid crystal display device, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling portion from the evaluator's overhead to the rear. The liquid crystal display device was tilted by 25 ° from the vertical direction with respect to the desk, and a fluorescent lamp was reflected so that the visibility of the screen (visibility) was evaluated as follows.

A: You don't have to worry about the movement of the nearest fluorescent lamp, and you can clearly read characters with a font size of 8 or less. Can manage to read characters with a font size of 8 or less C: It is difficult to read characters with a font size of 8 or less. The part of the reflection is not able to read characters having a font size of 8 or less. As a result of the evaluation, the liquid crystal display device of the present invention was B or more, which was better than the comparative liquid crystal display device.

Claims (10)

A polarizing plate used on a backlight side of a liquid crystal cell of a liquid crystal display device, wherein the polarizing film has a protective film on both sides of the polarizing film, the polarizing film is a polyvinyl alcohol polarizing film, and the liquid crystal cell side polarizing film protection The film is produced by stretching a cellulose ester film, and is a retardation film having a retardation Ro defined by the following formula of 20 to 300 nm and a retardation Rt of 70 to 400 nm under the conditions of 23 ° C. and 55% RH. The polarizing plate, wherein the right-side polarizing film protective film is a cellulose ester film having a dimensional change rate of 0.01 to 0.10% after the saponification treatment with respect to that before the saponification treatment.
Ro = (Nx−Ny) × d
Rt = ((Nx + Ny) / 2−Nz) × d
(In the formula, Nx represents the maximum refractive index in the film plane, Ny represents the refractive index in the direction perpendicular to Nx in the film plane, Nz represents the refractive index in the thickness direction, and d represents the thickness (nm) of the film.) The backlight side polarizing film protective film has an actinic radiation curable resin layer on the backlight side, and the retardation Ro defined by the above formula is 0 to 20 nm and the retardation Rt is 0 under the conditions of 23 ° C. and 55% RH. The polarizing plate according to claim 1, wherein the polarizing plate is ˜70 nm. The polarizing plate according to claim 1, wherein the retardation film contains a retardation increasing agent. The polarizing plate according to claim 3, wherein the retardation increasing agent is a rod-shaped compound. The backlight side polarizing film protective film is cellulose triacetate, the active ray curable resin used for the active ray curable resin layer is an acrylic or acrylurethane UV curable resin, and the active ray curable resin layer film Thickness is 1-20 micrometers, The polarizing plate of any one of Claims 1-4 characterized by the above-mentioned. A method for producing a polarizing plate used on a backlight side of a liquid crystal cell of a liquid crystal display device, wherein the polarizing film has a protective film on both sides of the polarizing film, the polarizing film being a roll-shaped polyvinyl alcohol polarizing film The liquid crystal cell-side polarizing film protective film is produced by stretching a cellulose ester film, and under the conditions of 23 ° C. and 55% RH, the retardation Ro defined by the following formula is 20 to 300 nm, and the retardation Rt is 70 to It is a roll-like retardation film of 400 nm, and the backlight side polarizing film protective film has a dimensional change rate after saponification treatment of 0.01 to 0.10% with respect to that before saponification treatment except for the front and rear ends. The saponified retardation film, the polyvinyl alcohol polarizing film, the saponified backlight side polarizing film protective film Method for producing a polarizing plate, characterized in that bonded to the continuous state.
Ro = (Nx−Ny) × d
Rt = ((Nx + Ny) / 2−Nz) × d
(In the formula, Nx represents the maximum refractive index in the film plane, Ny represents the refractive index in the direction perpendicular to Nx in the film plane, Nz represents the refractive index in the thickness direction, and d represents the thickness (nm) of the film.) The method for producing a polarizing plate according to claim 6, wherein an average value of a dimensional change rate in the width direction after the saponification treatment of the backlight side polarizing film protective film is 0.04% or less. Between the step of continuously laminating the saponified retardation film, the polyvinyl alcohol polarizing film, the saponified backlight-side polarizing film protective film in a roll state and the winding step, the retardation film The method for producing a polarizing plate according to claim 6 or 7, further comprising a step of providing an adhesive layer and a peeling protective layer on an adhesive surface to the liquid crystal cell. A polarizing plate used on a backlight side of a liquid crystal cell of a liquid crystal display device, wherein the polarizing film has a protective film on both sides of the polarizing film, the polarizing film is a polyvinyl alcohol polarizing film, and the liquid crystal cell side polarizing film protection The film is prepared by stretching a cellulose ester film, and contains a retardation increasing agent having a retardation Ro defined by the following formula of 20 to 300 nm and a retardation Rt of 70 to 400 nm under the conditions of 23 ° C. and 55% RH. It is a phase difference film, and the backlight side polarizing film protective film is a cellulose ester film having a retardation Ro defined by the following formula of 0 to 20 nm and a retardation Rt of 0 to 70 nm under the conditions of 23 ° C. and 55% RH. An active ray curable resin layer having a film thickness of 1 to 20 μm on the backlight side surface; A polarizing plate, wherein the active ray curable resin used to line the cured resin layer is an acrylic, acrylic urethane UV curing resin.
Ro = (Nx−Ny) × d
Rt = ((Nx + Ny) / 2−Nz) × d
(In the formula, Nx represents the maximum refractive index in the film plane, Ny represents the refractive index in the direction perpendicular to Nx in the film plane, Nz represents the refractive index in the thickness direction, and d represents the thickness (nm) of the film.) It uses the polarizing plate of any one of Claims 1-5, 9 or the polarizing plate obtained by the manufacturing method of the polarizing plate of any one of Claims 6-8. Liquid crystal display device.