JP5521832B2 - λ / 4 plate and stereoscopic image display device - Google Patents

Description

The present invention relates to a lambda / 4 Ita及 beauty stereoscopic image display device. More specifically, it consists of cellulose acetate film, a small lambda / 4 plate variation of the in-plane retardation value Ro to environmental change relates及 Beauty stereoscopic image display device.

  In recent years, stereoscopic image display devices such as televisions capable of displaying stereoscopic images have been proposed. As one of the methods for displaying the stereoscopic image, there is a method for allowing the observer to recognize the two-dimensional image as a stereoscopic image by wearing dedicated stereoscopic image viewing glasses by the observer. What is currently regarded as promising in this method is that the right-eye image and the left-eye image, which are parallax images, are alternately displayed in time series on a display that displays the image, and the observer as shown in FIG. This is a method of wearing a pair of glasses for viewing a stereoscopic image (G) and viewing an image on a liquid crystal display (see, for example, Patent Document 1).

  As shown in FIG. 1, the stereoscopic image viewing glasses (G) are provided with liquid crystal shutters (S1) and (S2) for the left and right eyes, and a control circuit for controlling these liquid crystal shutters (S1) and (S2). C is connected.

  As in the stereoscopic image display device shown in FIG. 2, as an image displayed on a liquid crystal display (LCD), a left-eye image (LI) and a right-eye image (RI) are assigned to two fields, respectively. These are displayed alternately in a time series at high speed. The light emitted from the liquid crystal display (LCD) is linearly polarized light. Further, the switching between opening and closing of the left and right liquid crystal shutters (S1) and (S2) of the stereoscopic image viewing glasses G is performed in synchronization with the switching between the left eye image (LI) and the right eye image (RI).

  As shown in FIG. 3, the liquid crystal shutters (S1) and (S2) have polarizing plates (P1) and (P2) and a liquid crystal layer (LC), and are incident on the liquid crystal shutters (S1) and (S2). The transmittance of the light emitted from the liquid crystal shutters (S1) and (S2) is controlled by controlling the rotation angle of the linearly polarized light (L) to be transmitted using the liquid crystal layer (LC). By controlling the liquid crystal display (LCD) and the stereoscopic image viewing glasses (G) in this way, as shown in FIG. 2, when the left eye image (LI) is displayed on the liquid crystal display (LCD), The right-eye liquid crystal shutter (S1) is closed and the left-eye liquid crystal shutter (S2) is opened. Conversely, when the right-eye image (RI) is displayed, the right-eye liquid crystal shutter (S1) is opened. Thus, the liquid crystal shutter (S2) for the left eye is closed.

  In addition to liquid crystal displays (LCDs) and organic EL displays that use circularly polarizing plates to prevent reflections, in addition to displays that emit linearly polarized light, displays that emit light that is not linearly polarized, such as plasma displays In addition, a self-luminous display such as an organic EL display that does not use a circularly polarizing plate can be used to prevent reflection.

  The stereoscopic image display apparatus including the liquid crystal display and the glasses for visually recognizing stereoscopic images has a problem of a decrease in luminance and a change in color when the head is tilted. In order to suppress a decrease in luminance and a change in color tone when the head is tilted, it is effective to use λ / 4 on the surface on the viewing side of the liquid crystal display and the surface on the side far from the eyes of the stereoscopic image viewing glasses. .

  Patent Document 2 discloses a stereoscopic image display device using glasses that use only one polarizing plate in order to suppress flicker of external light and improve the brightness of glasses. This document discloses that crosstalk when the head is tilted can be suppressed by using a circular polarizing plate on the front surface of the display and the configuration of the glasses as λ / 4 plate / liquid crystal cell / linear polarizing plate.

  As described above, in the method using the liquid crystal shutter, the method using two glasses for the polarizing plate, the method using one glasses for the polarizing plate, and the display when the head is tilted in both methods. A λ / 4 plate is required to improve performance. In particular, it is more important in a system in which a polarizing plate uses a pair of glasses.

  Moreover, since the effect is so large that a three-dimensional image display apparatus is large, the request | requirement of enlargement is very strong. Therefore, there is a demand for a large λ / 4 plate that can be used for a large display.

  The λ / 4 plate has many uses related to antireflection films and liquid crystal display devices, and has already been used in practice.

  As the λ / 4 plate, a stretched polycarbonate film and a stretched norbornene-based polymer film are known.

  However, when a λ / 4 plate made of a stretched polycarbonate film is used on the viewing side of the liquid crystal display of the stereoscopic image display device, there is a serious problem that unevenness of Ro due to the large photoelastic coefficient of the polycarbonate film occurs.

  In addition, when a stretched norbornene-based polymer film is used on the viewing side of the liquid crystal display of a stereoscopic image display device, there is a serious problem that cracking or dissolution occurs when sebum or detergent touches the norbornene-based film. there were.

  On the other hand, stretched cellulose acetate films and stretched cellulose acetate propionate films are known as λ / 4 plates that can be used for large displays and have excellent durability.

  Since the stretched cellulose acetate film and the stretched cellulose acetate propionate film have a small photoelastic coefficient, Ro unevenness is hardly generated, and even when touched with sebum or detergent, cracks are not generated or dissolved.

  However, this cellulose triacetate film is not suitable for a retardation film because it is originally isotropic and has a weak birefringence. Therefore, by adding a so-called retardation increasing agent to the cellulose triacetate resin, among the cellulose ester resins, λ / 4 using a mixed fatty acid ester of cellulose such as cellulose acetate propionate having higher birefringence than the cellulose triacetate resin. Plates have been studied (see, for example, Patent Documents 3 and 4).

  However, in the retardation film to which the above-described retardation increasing agent is added, in order to further reduce the thickness of the retardation film, it is necessary to increase the amount of addition of the retardation increasing agent per film thickness. In some cases, a problem called bleed out occurs.

  In addition, a retardation film using a mixed fatty acid ester film of cellulose has higher birefringence than that of cellulose triacetate, but the degree of synthesis of the mixed fatty acid ester resin of cellulose itself is high and the cost of the polarizing plate is reduced. There was a problem.

  Then, the present inventors examined using the cellulose acetate whose degree of acetyl group substitution with high birefringence expressiveness is 2.0-2.6 to make a lambda / 4 board by expressing phase contrast.

Several λ / 4 plates made of a cellulose acetate film having an acetyl group substitution degree of 2.0 to 2.6 are known (see, for example, Patent Documents 5 to 7).
When these films are used in stereoscopic image display devices, the effect of improving display performance when tilting the neck when the temperature and humidity of the environment changes or when it is used continuously is reduced, and the durability of the polarizing plate It turns out that there is a problem that is low.

Japanese Patent Laid-Open No. 8-201942 JP 2002-82307 A International Publication No. 2000/65384 JP 2008-83307 A JP 2000-137116 A JP 2002-127244 A JP 2008-83307 A

  The present invention has been made in view of the above problems and situations, and its solution is to impart an appropriate function as a retardation film to a cellulose acetate film having a low retardation and high retardation. It is another object of the present invention to provide a λ / 4 plate that has a small fluctuation of the in-plane retardation value Ro with respect to environmental fluctuations and can be made thinner with an inexpensive material.

  In addition, it can reduce crosstalk or brightness reduction and color change when tilting the head when viewing stereoscopic (3D) images, and can maintain excellent visibility against changes in the usage environment. It is another object of the present invention to provide a stereoscopic image display device with higher durability.

  The above-mentioned problem according to the present invention is solved by the following means.

1. Cellulose acetate having an acetyl group average substitution degree in the range of 2.0 to 2.6 and a total average substitution degree represented by the following general formula A (1) are in the range of 5.0 to 6.9. A λ / 4 plate comprising a compound and having a hard coat layer on the surface.

(Wherein R _{1 to} R ₈ each independently represents a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ may be the same as each other) , May be different.)
2. 2. The λ / 4 plate according to item 1, wherein the hard coat layer is a clear hard coat layer or an antiglare hard coat layer.

  3. The λ / 4 plate according to the first or second item, wherein an antireflection layer having at least a low refractive index layer is provided on the surface of the hard coat layer.

  4). The λ / 4 plate according to any one of items 1 to 3, further comprising an ultraviolet absorber.

5). Any of the items 1 to 4 above, wherein an angle formed by the width direction of the λ / 4 plate and the slow axis in the plane of the λ / 4 plate is in the range of 40 to 50 °. The λ / 4 plate according to claim 1.

（式中、Ｒ_１〜Ｒ_８は、各々独立に、置換又は無置換のアルキルカルボニル基、若しくは、置換又は無置換のアリールカルボニル基を表し、Ｒ_１〜Ｒ_８は相互に同じであっても、異なっていてもよい。）
（１）下記式（Ｉ）により定義される面内リターデーション値Ｒｏ（５９０）が２０〜１５０ｎｍの範囲内であり、かつ下記式（II）により定義される厚さ方向のリターデーション値Ｒｔ（５９０）が７０〜４００ｎｍの範囲内である。
（２）下記式（Ｉ）により定義される面内リターデーション値Ｒｏ（５９０）が０〜２ｎｍの範囲内であり、かつ下記式（II）により定義される厚さ方向のリターデーション値Ｒｔ（５９０）が−１５〜１５ｎｍの範囲内である。
式（Ｉ）：Ｒｏ（５９０）＝（ｎｘ−ｎｙ）×ｄ（ｎｍ）
式（II）：Ｒｔ（５９０）＝｛（ｎｘ＋ｎｙ）／２−ｎｚ｝×ｄ（ｎｍ）
〔上式中、Ｒｏ（５９０）は測定波長５９０ｎｍにおけるフィルム内の面内リターデーション値を表し、Ｒｔ（５９０）は測定波長５９０ｎｍにおけるフィルム内の厚さ方向のリターデーション値を表す。また、ｄは光学フィルムの厚さ（ｎｍ）を表し、ｎｘは測定波長５９０ｎｍにおけるフィルムの面内の最大の屈折率を表す。ｎｙは測定波長５９０ｎｍにおけるフィルム面内で遅相軸に直角な方向の屈折率を表し、ｎｚは測定波長５９０ｎｍにおける厚さ方向におけるフィルムの屈折率を表す。〕 6). A stereoscopic image display device comprising a polarizing plate provided on the viewing side with respect to the liquid crystal cell, a liquid crystal display device having the liquid crystal cell, and liquid crystal shutter glasses,
The polarizing plate has a total average substitution degree of 4.5 to 7.5 represented by cellulose acetate having an acetyl group average substitution degree in the range of 2.0 to 2.6 and the following general formula A (1). A polarizing plate in which a λ / 4 plate having a hard coat layer on the surface, a polarizer, and an optical film satisfying the following requirement (1) or (2) are provided in this order: ,
In the liquid crystal shutter glasses, (1) a λ / 4 plate, a liquid crystal cell, and a polarizer are provided in this order, or (2) a λ / 4 plate, a polarizer, a liquid crystal cell, and a polarizer are provided in this order. A three-dimensional image display device, characterized in that it is liquid crystal shutter glasses.

(Wherein R _{1 to} R ₈ each independently represents a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ may be the same as each other) , May be different.)
(1) The in-plane retardation value Ro (590) defined by the following formula (I) is in the range of 20 to 150 nm, and the retardation value Rt in the thickness direction defined by the following formula (II) ( 590) is in the range of 70-400 nm .
(2) The in-plane retardation value Ro (590) defined by the following formula (I) is in the range of 0 to 2 nm, and the retardation value Rt in the thickness direction defined by the following formula (II) ( 590) is within the range of -15-15 nm.
Formula (I): Ro (590) = (nx−ny) × d (nm)
Formula (II): Rt (590) = {(nx + ny) / 2−nz} × d (nm)
[In the above formula, Ro (590) represents the in-plane retardation value in the film at the measurement wavelength of 590 nm, and Rt (590) represents the retardation value in the thickness direction in the film at the measurement wavelength of 590 nm. D represents the thickness (nm) of the optical film, and nx represents the maximum in-plane refractive index at the measurement wavelength of 590 nm. ny represents the refractive index in the direction perpendicular to the slow axis in the film plane at the measurement wavelength of 590 nm, and nz represents the refractive index of the film in the thickness direction at the measurement wavelength of 590 nm. ]

  By the above means of the present invention, an appropriate function as a retardation film is imparted to a cellulose acetate film having a high retardation (retardation) and a low degree of substitution, and the fluctuation of the in-plane retardation value Ro with respect to environmental fluctuation is small. Further, it is possible to provide a λ / 4 plate that can be made thinner with an inexpensive material.

  In addition, it can reduce crosstalk or brightness reduction and color change when tilting the head when viewing stereoscopic (3D) images, and can maintain excellent visibility against changes in the usage environment. Therefore, it is possible to provide a stereoscopic image display device with higher durability.

Schematic diagram of conventional stereoscopic image viewing glasses G Schematic diagram of a conventional stereoscopic image display device Schematic diagram of conventional liquid crystal shutters S1 and S2. The figure which shows an example of the rail arrangement | positioning of the tenter for extending | stretching used for manufacture of (lambda) / 4 board Schematic diagram of polarizing plate according to the present invention Schematic diagram of a 3D image display device (system with one polarizing plate for glasses) Schematic diagram of liquid 3D image display device (system with two polarizing plates for glasses)

The λ / 4 plate of the present invention has a cellulose acetate having an acetyl group average substitution degree in the range of 2.0 to 2.6, and a total average substitution degree represented by the general formula (1) of 5.0 to It is characterized by containing a compound having the general formula A (1) within the range of 6.9 and having a hard coat layer on the surface. This feature is a technical feature common to the inventions according to claims 1 to 6 .

  As an embodiment of the present invention, it is preferable that the hard coat layer is a clear hard coat layer or an antiglare hard coat layer from the viewpoint of manifesting the effects of the present invention. Moreover, it is preferable that an antireflection layer having at least a low refractive index layer is provided on the surface of the hard coat layer. Furthermore, the λ / 4 plate of the present invention preferably contains an ultraviolet absorber.

  Moreover, it is preferable that the angle formed by the width direction of the λ / 4 plate and the slow axis in the plane of the λ / 4 plate is in the range of 40 to 50 °.

  The λ / 4 plate of the present invention is a polarizing plate in which a λ / 4 plate, a polarizer, and an optical film are provided in this order, and the optical film satisfies the requirement (1) or (2). It can use suitably for a polarizing plate. Moreover, the said polarizing plate can be used suitably for the liquid crystal display device of the aspect currently provided by the visual recognition side with respect to the liquid crystal cell.

  Further, the liquid crystal display device is a stereoscopic image display device including the liquid crystal display device and liquid crystal shutter glasses, wherein the liquid crystal shutter glasses are (1) a λ / 4 plate, a liquid crystal cell, and a polarizer in this order. It can be suitably used for a stereoscopic image display device that is provided or (2) liquid crystal shutter glasses in which a λ / 4 plate, a polarizer, a liquid crystal cell, and a polarizer are provided in this order.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail.

(Λ / 4 plate)
The λ / 4 plate of the present invention has a cellulose acetate having an acetyl group average substitution degree in the range of 2.0 to 2.6, and a total average substitution degree represented by the general formula A (1) of 5.0. And a compound having a hard coat layer on the surface.

  The “λ / 4 plate” of the present invention means a plate having a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). The λ / 4 plate has an in-plane retardation value Ro of about ¼ for a predetermined wavelength of light (usually in the visible light region).

  In the λ / 4 plate of the present invention, Ro (550) measured at a wavelength of 550 nm is preferably in the range of 110 to 170 nm, Ro (550) is preferably 120 to 160 nm, and Ro (550) is 130 to 150 nm. More preferably it is.

  The λ / 4 plate of the present invention is a retardation plate (film) having a retardation of approximately ¼ of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range. Preferably there is.

  The term “retardation of approximately ¼ in the wavelength range of visible light” means a retardation value represented by the following formula (i) measured at a wavelength of 450 nm, with a larger retardation at a wavelength of 400 to 700 nm. The difference Ro (550) −Ro (450) between a certain Ro (450) and the retardation value Ro (550) measured at a wavelength of 550 nm is preferably 2 to 34 nm, and more preferably 4 to 32 nm. 8 to 28 nm is particularly preferable.

Formula (i): Ro = (nx−ny) × d
Formula (ii): Rt = {(nx + ny) / 2−nz} × d
In the formula, nx and ny are refractive indexes nx (maximum in-plane refractive index of film, refractive index in slow axis direction) at 23 ° C./55% RH, 450 nm, 550 nm or 590 nm, ny (film). (Refractive index in a direction perpendicular to the slow axis in the plane), and d is the thickness (nm) of the film.

  Ro and Rt can be measured using an automatic birefringence meter. Using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments), Ro is calculated by birefringence measurement at each wavelength in an environment of 23 ° C. and 55% RH.

  A circularly polarizing plate is obtained by laminating so that the angle between the slow axis of the λ / 4 plate and the transmission axis of the polarizer described later is substantially 45 °. “Substantially 45 °” means 40 to 50 °. The angle between the slow axis in the plane of the λ / 4 plate and the transmission axis of the polarizer is preferably 41 to 49 °, more preferably 42 to 48 °, and 43 to 47 °. Is more preferable, and it is most preferable that it is 44-46 degrees.

(Cellulose acetate)
The λ / 4 plate of the present invention is characterized by containing cellulose acetate having an acetyl group average substitution degree in the range of 2.0 to 2.6.

  The cellulose acetate according to the present invention has an average degree of acetyl group substitution in the range of 2.0 to 2.6, and more preferably in the range of 2.2 to 2.5. The average degree of acetyl group substitution here is the average value of the number of hydroxyl groups (hydroxyl groups) that are esterified (acetylated) among the three hydroxyl groups (hydroxyl groups) of each anhydroglucose constituting cellulose. The value in the range of 0-3 is shown.

  When the average acetyl group substitution degree of cellulose acetate is less than 2.0, deterioration of film surface quality due to an increase in dope viscosity, haze-up due to an increase in stretching tension, and the like may occur. Moreover, when the total acyl substitution degree is larger than 2.6, a necessary phase difference cannot be obtained.

  In the present invention, a portion not substituted with an acetyl group is usually present as a hydroxyl group (hydroxyl group). These can be synthesized by known methods.

  In addition, the substitution degree of an acetyl group is calculated | required by the method prescribed | regulated to ASTM-D817-96 (test methods, such as a cellulose acetate).

  The number average molecular weight (Mn) of the cellulose acetate according to the present invention is preferably in the range of 30,000 to 300,000 because the mechanical strength of the resulting film is strong. Furthermore, the thing of 50,000-200,000 is used preferably.

  The value of the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose acetate is preferably 1.4 to 3.0.

  The weight average molecular weight Mw and number average molecular weight Mn of cellulose acetate were measured using gel permeation chromatography (GPC).

  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 Corporation) Mw = 100000 to 500 calibration curves with 13 samples were used. Thirteen samples are used at approximately equal intervals.

  Although there is no limitation in particular as a cellulose of the raw material of the cellulose acetate which concerns on this invention, Cotton linter, wood pulp, kenaf etc. can be mentioned. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.

  The cellulose acetate according to the present invention can be produced by a known method. In general, cellulose is mixed with raw material cellulose, a predetermined organic acid (such as acetic acid), acid anhydride (such as acetic anhydride), and a catalyst (such as sulfuric acid) to esterify (acetylate) cellulose, The reaction proceeds until the ester (acetylation) is formed. In the triester (acetylation), the three hydroxyl groups (hydroxyl groups) of the glucose unit are substituted with acetyl groups of organic acids. Next, cellulose acetate having a desired degree of acetyl group substitution is synthesized by hydrolyzing the cellulose triester. Thereafter, cellulose acetate is completed through steps such as filtration, precipitation, washing with water, dehydration, and drying.

  Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.

  The λ / 4 plate according to the present invention may contain calcium and magnesium. In that case, it is preferable that the total amount of calcium and magnesium and the amount of acetic acid satisfy the following relational expression (a).

Relational expression (a): 1 ≦ (acetic acid amount) / (total amount of calcium and magnesium) ≦ 30
Calcium and magnesium are contained in the cellulose ester that is the raw material for the λ / 4 plate. However, in order to neutralize and stabilize the acid catalyst (especially sulfuric acid) added to the cellulose ester production process, Or metal salt (inorganic acid salt, organic acid salt). Moreover, you may add as a metal oxide, a metal hydroxide, and a metal salt (inorganic acid salt, organic acid salt) at the time of optical film forming.

  Cellulose acetate uses acetic anhydride or acetic acid as a reaction solvent or esterifying agent in the production process. Unreacted acetic anhydride is hydrolyzed by a reaction stopper (water, alcohol, acetic acid, etc.) to produce acetic acid. The amount of acetic acid contained in the λ / 4 plate refers to the total amount of residual acetic acid and free acetic acid.

  In the above relational expression (a), when the amount of acetic acid / (total amount of calcium and magnesium) is less than 1, light scattering due to calcium and magnesium metal salts occurs, which is not preferable. On the other hand, when the ratio is larger than 30, the deterioration of the polarizer is accelerated by acetic acid after the λ / 4 plate is bonded to the polarizer.

  The total amount of calcium and magnesium contained in the λ / 4 plate is preferably 5 to 130 ppm, more preferably 5 to 80 ppm, and even more preferably 5 to 50 ppm.

  A known method can be used to determine calcium and magnesium contained in the λ / 4 plate. For example, after the dried cellulose ester is completely burned, the ash is dissolved in hydrochloric acid and pretreated. The above can be measured by atomic absorption. The measured value is obtained in units of ppm as the calcium and magnesium contents in 1 g of the completely dry cellulose ester.

  The amount of acetic acid contained in the optical film is preferably 20 to 500 ppm, more preferably 25 to 250 ppm, and still more preferably 30 to 150 ppm.

  A known method can be used for quantification of acetic acid contained in the λ / 4 plate. For example, the following method can be used. The λ / 4 plate is dissolved in methylene chloride, and methanol is added to perform reprecipitation. The amount of acetic acid can be obtained by filtering the supernatant and measuring the supernatant with gas chromatography.

  In the present invention, the melting point of the λ / 4 plate of the present invention is preferably in the range of 200 to 290 ° C. Methods for adjusting the melting point within the above range include controlling the degree of substitution of cellulose acetate or adding a plasticizer.

  In addition, as long as the effect of this invention is not impaired, thermoplastic resins other than the said cellulose acetate can also be used together for (lambda) / 4 board of this invention.

  Here, the “thermoplastic resin” refers to a resin that becomes soft when heated to the glass transition temperature or melting point and can be molded into a desired shape.

  General thermoplastic resins include polyethylene (PE), high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS). Polyvinyl acetate (PVAc), Teflon (registered trademark) (polytetrafluoroethylene, PTFE), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), and the like can be used.

  When strength and resistance to breakage are particularly required, polyamide (PA), nylon, polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE, PPO), polybutylene terephthalate (PBT) ), Polyethylene terephthalate (PET), glass fiber reinforced polyethylene terephthalate (GF-PET), cyclic polyolefin (COP), and the like.

  Furthermore, when high heat distortion temperature and long-term use characteristics are required, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polysulfone, polyethersulfone, amorphous polyarylate, liquid crystal polymer, polyether Ether ketone, thermoplastic polyimide (PI), polyamideimide (PAI), or the like can be used.

  In addition, it is possible to perform the kind of resin and the combination of molecular weight according to the use of this invention.

  In addition, industrially, cellulose resin is synthesized using sulfuric acid as a catalyst, but this sulfuric acid is not completely removed, and the residual sulfuric acid causes various decomposition reactions during melt film formation, and the resulting cellulose resin. In order to affect the quality of the film, the content of residual sulfuric acid in the cellulose resin used in the present invention is preferably in the range of 0.1 to 40 ppm in terms of elemental sulfur. These are considered to be contained in the form of salts. If the residual sulfuric acid content exceeds 40 ppm, the deposit on the die lip during heat melting increases, such being undesirable. Moreover, since it becomes easy to fracture | rupture at the time of slitting at the time of hot drawing or after hot drawing, it is not preferable. A smaller amount is preferable, but if it is less than 0.1, it is not preferable because the burden of the washing step of the cellulose resin becomes too large. This is not well understood, although an increase in the number of washings may affect the resin. Furthermore, the range of 0.1-30 ppm is preferable. The residual sulfuric acid content can be similarly measured by ASTM-D817-96.

  Further, the total residual acid amount including other (such as acetic acid) residual acids is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less.

  For washing of cellulose resin, in addition to water, a poor solvent such as methanol or ethanol, or, as a result, a mixed solvent of a poor solvent and a good solvent can be used as long as it is a poor solvent. Organic impurities can be removed.

  In order to improve the heat resistance, mechanical properties, optical properties, etc. of the cellulose resin, it can be dissolved in a good solvent of the cellulose resin and then reprecipitated in the poor solvent to remove low molecular weight components and other impurities of the cellulose resin. it can. Furthermore, another polymer or low molecular weight compound may be added after the reprecipitation treatment of the cellulose resin.

  Moreover, it is preferable that the cellulose resin used by this invention is a thing with few bright spot foreign materials when it is set as a film. A bright spot foreign material is an arrangement of two polarizing plates orthogonally (crossed Nicols), a cellulose resin film placed between them, and the light from the light source applied from one side, and the cellulose resin film from the other side. This is the point where the light from the light source appears to leak when observed. At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used. The cause of bright spot foreign matter is considered to be one of the causes of unacetylated or low acetylated cellulose contained in the cellulose resin. Use a cellulose resin with few bright spot foreign substances and filter the molten cellulose resin or cellulose resin solution. In at least one of the latter process of synthesizing the cellulose resin and the process of obtaining the precipitate, it is possible to remove the bright spot foreign matters through the filtration process in the same manner once in the solution state. Since the molten resin has a high viscosity, the latter method is more efficient.

As the film thickness decreases, the number of bright spot foreign matter per unit area decreases, and as the cellulose resin content in the film decreases, the bright spot foreign matter tends to decrease. 0.01 mm or more is preferably 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, further preferably 50 pieces / cm ² or less, and 30 pieces / cm ² or less. The number is preferably 10 pieces / cm ² or less, but most preferably none. Moreover, it is preferable that it is 200 pieces / cm < ² > or less also about a bright spot of 0.005-0.01 mm or less, Furthermore, it is preferable that it is 100 pieces / cm < ² > or less, and it is 50 pieces / cm < ² > or less. The number is preferably 30 pieces / cm ² or less, more preferably 10 pieces / cm ² or less, and most preferably none.

When removing bright spot foreign matter by filtration, filtering a cellulose resin composition (also referred to as a dope) to which a plasticizer, an ultraviolet absorber, an antioxidant, a stabilizer and the like are added and mixed rather than filtering the cellulose resin alone. However, it is preferable because the removal efficiency of bright spot foreign matter is high. Of course, the cellulose resin may be dissolved in a solvent during the synthesis and reduced by filtration. Filtration is preferably performed with the viscosity of the melt containing the cellulose resin being 10,000 P or less, more preferably 5000 P or less, still more preferably 1000 P or less, and even more preferably 500 P or less. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluorine resins such as tetrafluoroethylene resin are preferably used, and ceramics and metals are particularly preferably used. The absolute filtration accuracy is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 10 μm or less, and even more preferably 5 μm or less. These can be used in combination as appropriate. The filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.

  The λ / 4 plate of the present invention may be obtained by appropriately mixing polymer components other than cellulose resin. The polymer component to be mixed is preferably one having excellent compatibility with the cellulose resin, and the transmittance when formed into a film is 80% or more, more preferably 90% or more, and further preferably 92% or more.

(Organic solvent)
Organic solvents that dissolve cellulose esters and are useful for forming cellulose ester solutions or dopes include chlorinated organic solvents and non-chlorinated organic solvents. Methylene chloride (methylene chloride) can be mentioned as a chlorinated organic solvent, and it is suitable for dissolving cellulose esters, particularly cellulose triacetate. Due to recent environmental problems, the use of non-chlorine organic solvents has been studied. Examples of the non-chlorine organic solvent include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1, Examples include 1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, and the like. When these organic solvents are used for cellulose triacetate, a dissolution method at room temperature can be used, but an insoluble material can be obtained by using a dissolution method such as a high-temperature dissolution method, a cooling dissolution method, or a high-pressure dissolution method. Can be reduced, which is preferable. Methylene chloride can be used for cellulose esters other than cellulose triacetate, but methyl acetate, ethyl acetate, and acetone are preferably used. Particularly preferred is methyl acetate. In the present invention, an organic solvent having good solubility with respect to the cellulose ester is referred to as a good solvent, and has 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.

  The dope used in the present invention preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. These are gelling solvents that make dope film (web) gel when the dope is cast on a metal support and the solvent starts to evaporate and the ratio of alcohol increases, making the web strong and easy to peel off from the metal support. When these ratios are small, there is also a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Of these, ethanol is preferred because it has excellent dope stability, has a relatively low boiling point, and has good drying properties. These organic solvents are called poor solvents because they are not soluble in cellulose esters alone.

  It is preferable that the concentration of the cellulose ester in the dope is adjusted to 15 to 30% by mass and the dope viscosity is adjusted to a range of 100 to 500 Pa · s in order to obtain good film surface quality.

  Additives added to the dope include plasticizers, ultraviolet absorbers, retardation adjusters, antioxidants, deterioration inhibitors, peeling aids, surfactants, dyes, fine particles, and the like. In the present invention, additives other than fine particles may be added during the preparation of the cellulose ester solution, or may be added during the preparation of the fine particle dispersion. It is preferable to add a plasticizer, an antioxidant, an ultraviolet absorber, or the like that imparts heat and moisture resistance to the polarizing plate used in the liquid crystal image display device. The additive will be described below.

(Compound represented by Formula A (1))
The compound represented by the general formula A (1) and the reference compound according to the present invention are described below, but the present invention is not limited thereto.

In General Formula A (1), R _{1 to} R ₈ each independently represent a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ are the same as each other. Or different. In addition, R described in the following table represents any one of R _{1 to} R ₈ . As the substituent for the alkylcarbonyl group and the arylcarbonyl group, substituents such as a phenyl group and an alkoxy group included in the alkylcarbonyl group and the arylcarbonyl group shown in the following table are preferable.

  (Synthesis Example: Synthesis of Compound According to the Present Invention)

A four-headed colben equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube was mixed with 34.2 g (0.1 mol) of sucrose, 180.8 g (0.8 mol) of benzoic anhydride, 379. 7 g (4.8 mol) was charged, the temperature was raised while bubbling nitrogen gas from a nitrogen gas introduction tube with stirring, and an esterification reaction was carried out at 70 ° C. for 5 hours. Next, the inside of the Kolben was depressurized to 4 × 10 ² Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 × 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off. Then, 1 L of toluene and 300 g of a 0.5% by mass aqueous sodium carbonate solution were added, and the mixture was stirred at 50 ° C. for 30 minutes and then allowed to stand to separate a toluene layer. Finally, 100 g of water is added to the collected toluene layer, and after washing with water at room temperature for 30 minutes, the toluene layer is separated, and toluene is distilled off at 60 ° C. under reduced pressure (4 × 10 ² Pa or less). A mixture of A-1, A-2, A-3, A-4 and A-5 was obtained. When the obtained mixture was analyzed by HPLC and LC-MASS, A-1 was 7% by mass, A-2 was 58% by mass, A-3 was 23% by mass, A-4 was 9% by mass, A-5. Was 3% by mass. A part of the obtained mixture was purified by column chromatography using silica gel to obtain A-1, A-2, A-3, A-4 and A-5 having a purity of 100%, respectively. .

The total average substitution degree of the compound represented by the general formula A (1) added to the cellulose acetate film in the present invention is in the range of 5.0 to 6.9, and the range of the substitution degree is 4. It is preferably 0 to 8.0. The substitution degree distribution may be adjusted to the desired substitution degree by adjusting the esterification reaction time or mixing compounds having different substitution degrees.

(Plasticizer)
To the λ / 4 plate according to the present invention, a compound known as a so-called plasticizer is added for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor permeability, adjusting retardation, etc. For example, phosphoric acid esters and carboxylic acid esters are preferably used.

  The plasticizer is preferably contained in the λ / 4 plate in an amount of 1 to 40% by mass, particularly 1 to 30% by mass.

  Examples of phosphate esters include triphenyl phosphate, tricresyl phosphate, phenyl diphenyl phosphate, and the like.

  Examples of the carboxylic acid ester include phthalic acid ester and citric acid ester. Examples of the phthalic acid ester include dimethyl phthalate, diethyl phosphate, dioctyl phthalate, and diethyl hexyl phthalate. Examples of the citrate ester include acetyl triethyl citrate and acetyl citrate. Mention may be made of tributyl. Other examples include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and triacetin. Alkylphthalylalkyl glycolates are also preferably used for this purpose. The alkyl in the alkylphthalylalkyl glycolate is an alkyl group having 1 to 8 carbon atoms. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl glycolate, Ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, propyl phthalyl ethyl glycolate, methyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl Phthalyl ethyl glycolate, propyl phthalyl butyl glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl Collate, octyl phthalyl methyl glycolate, octyl phthalyl ethyl glycolate and the like can be mentioned, such as methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, Octyl phthalyl octyl glycolate is preferably used. These alkyl phthalyl alkyl glycolates may be used in combination of two or more.

  Moreover, it is also preferable to use the citrate plasticizer represented by the following general formulas (1) to (3) described in Japanese Patent No. 3793184 as a plasticizer.

  Polyhydric alcohol esters are also preferably used.

  The polyhydric alcohol used in the λ / 4 plate of the present invention is represented by the following general formula (4).

Formula _{(4): R 1 - (} OH) n
However, R ₁ represents an n-valent organic group, n represents a positive integer of 2 or more, and an OH group represents an alcoholic and / or phenolic hydroxyl group (hydroxyl group).

  The polyhydric alcohol ester plasticizer is a plasticizer comprising 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. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

  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, xylitol and the like. 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 a 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 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-hexanoic 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, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as 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. The aromatic monocarboxylic acid which has, or those derivatives can be mentioned. 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 preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.

  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.

  Although the specific compound of the polyhydric alcohol ester plasticizer used for this invention is shown below, this invention is not limited to this.

  It is preferable that these compounds are contained so that it may become 1-30 mass% with respect to a cellulose ester, Preferably it is 1-20 mass%. In order to suppress bleeding out during stretching and drying, a compound having a vapor pressure at 200 ° C. of 1400 Pa or less is preferable.

  These compounds may be added together with the cellulose ester or the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.

  Furthermore, in this invention, it is preferable to use the aromatic terminal ester plasticizer represented by following General formula (5).

General formula (5): B- (GA) n-GB
(In the formula, B is a benzene monocarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
In the general formula (5), a benzene monocarboxylic acid residue represented by B and an alkylene glycol residue, oxyalkylene glycol residue or aryl glycol residue represented by G, an alkylene dicarboxylic acid residue or aryl dicarboxylic group represented by A It is composed of an acid residue and can be obtained by a reaction similar to that of a normal polyester plasticizer.

  Examples of the benzene monocarboxylic acid component of the aromatic terminal ester plasticizer used in the present invention include, for example, benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, There are normal propyl benzoic acid, aminobenzoic acid, acetoxybenzoic acid and the like, and these can be used as one kind or a mixture of two or more kinds, respectively.

  Examples of the alkylene glycol component having 2 to 12 carbon atoms of the aromatic terminal ester plasticizer used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, , 3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2, 2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1 , 5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3 There are hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, etc., and these glycols are used as one kind or a mixture of two or more kinds. used.

  Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal ester include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like. It can be used as a mixture of two or more.

  Examples of the aryl glycol component having 6 to 12 carbon atoms of the aromatic terminal ester include hydroquinone, resorcin, bisphenol A, bisphenol F, and bisphenol, and these glycols are used as one kind or a mixture of two or more kinds. it can.

  Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are used as one kind or a mixture of two or more kinds. Examples of the aryl dicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, 1,5 naphthalene dicarboxylic acid, and 1,4 naphthalene dicarboxylic acid.

  The aromatic terminal ester plasticizer has a number average molecular weight of preferably 300 to 2000, more preferably 500 to 1500. The acid value is 0.5 mgKOH / g or less, the hydroxyl (hydroxyl) value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl (hydroxyl) value is 15 mgKOH / g or less. Is preferred.

<Acid value of hydroxyl terminal ester, hydroxyl value>
The acid value means the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxyl group present at the molecular end) contained in 1 g of the sample. The acid value and hydroxyl (hydroxyl group) value are measured according to JIS K0070 (1992).

  Hereinafter, the synthesis example of the aromatic terminal ester plasticizer used for this invention is shown.

<Sample No. 1 (Aromatic terminal ester sample)>
Into a reaction vessel, 820 parts (5 moles) of phthalic acid, 608 parts (8 moles) of 1,2-propylene glycol, 610 parts (5 moles) of benzoic acid and 0.30 parts of tetraisopropyl titanate as a catalyst are charged all at once. While stirring in an air stream, a reflux condenser was attached to reflux excess monohydric alcohol, and heating was continued at 130 to 250 ° C. until the acid value became 2 or less, and water produced was continuously removed. Next, the distillate is removed under reduced pressure of 6.65 × 10 ³ Pa to 4 × 10 ² Pa or less at 200 to 230 ° C., followed by filtration to obtain an aromatic terminal ester having the following properties. It was.

Viscosity (25 ° C., mPa · s); 19815
Acid value: 0.4
<Sample No. 2 (Aromatic terminal ester sample)>
A sample was used except that 500 parts (3.5 moles) of adipic acid, 305 parts (2.5 moles) of benzoic acid, 583 parts (5.5 moles) of diethylene glycol and 0.45 parts of tetraisopropyl titanate as a catalyst were used in the reaction vessel. No. In the same manner as in No. 1, an aromatic terminal ester having the following properties was obtained.

Viscosity (25 ° C., mPa · s); 90
Acid value: 0.05
<Sample No. 3 (Aromatic terminal ester sample)>
Sample No. except that 410 parts (2.5 moles) of phthalic acid, 610 parts (5 moles) of benzoic acid, 737 parts (5.5 moles) of dipropylene glycol and 0.40 parts of tetraisopropyl titanate as the catalyst were used in the reaction vessel. . In the same manner as in No. 1, an aromatic terminal ester plasticizer having the following properties was obtained.

Viscosity (25 ° C., mPa · s); 43400
Acid value: 0.2
Although the specific compound of the aromatic terminal ester plasticizer used for this invention below is shown, this invention is not limited to this.

  The content of the aromatic terminal ester plasticizer used in the present invention is preferably 1 to 20% by mass, and particularly preferably 3 to 11% by mass in the cellulose ester film.

(Polyester polyol)
The polyester polyol used in the present invention is a polymer having a hydroxyl group (hydroxyl group) at the end that can be obtained by a condensation reaction between a dibasic acid or an ester-forming derivative thereof and glycol. The ester-forming derivatives referred to here are esterified products of dibasic acids, dibasic acid chlorides, and anhydrides of dibasic acids.

  The polyester polyol is obtained by dehydration condensation reaction of aromatic dibasic acid and glycol, addition of glycol to aromatic anhydride dibasic acid and dehydration condensation reaction, or by alcohol removal of esterified product of aromatic dibasic acid and glycol. It can be obtained by a condensation reaction.

  As the aromatic dibasic acid or an ester-forming derivative thereof, an aromatic dicarboxylic acid having 10 to 16 carbon atoms or an ester-forming derivative thereof can be used. For example, a benzene ring structure, a naphthalene ring structure, Dicarboxylic acids having an aromatic ring structure such as anthracene ring structure and ester-forming derivatives thereof can be used. For example, orthophthalic acid having a substituent, isophthalic acid having a substituent, terephthalic acid having a substituent, substituted Group-containing phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6 -Anthracene dicarboxylic acid and the like, esterified products thereof, acid chlorides, 1,8-naphtha Etc. can be mentioned acid anhydrides Njikarubon acid, they may have a substituent on the aromatic ring, can be used in combination use of two or more of these alone. 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid and esterified products thereof, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and esterified products thereof are preferable, and 2,6-naphthalenedicarboxylic acid and esterified products thereof are particularly preferable.

  The average of the carbon number of the dibasic acid of the polyester polyol means the carbon number of the dibasic acid when the polyester polyol is polymerized using a single dibasic acid. When the polyester polyol is polymerized using, it means the sum of the products of the carbon number of each dibasic acid and the molar fraction of the dibasic acid.

  In the present invention, it is important that the average number of carbon atoms of the dibasic acid used as a raw material for the polyester polyol is in the range of 10 to 16. If the average carbon number of the dibasic acid is 10 or more, the retardation is excellent. If the average carbon number is 16 or less, the compatibility with the cellulose ester is remarkably excellent. As a dibasic acid, Preferably the average of carbon number is 10-14, More preferably, the average of carbon number is 10-12.

  If the average carbon number is 10 to 16, the aromatic dibasic acid having 10 to 16 carbon atoms and the other dibasic acid can be used in combination.

  The dibasic acid that can be used in combination is preferably a dicarboxylic acid having 4 to 9 carbon atoms or an ester-forming derivative thereof. For example, succinic acid, glutaric acid, adipic acid, maleic acid, succinic anhydride, maleic anhydride, orthophthalic acid Examples thereof include acids, isophthalic acid, terephthalic acid, phthalic anhydride and the like, esterified products, and acid chlorides thereof.

  Examples of the glycol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol Can be used alone or in combination of two or more, among which ethylene glycol, diethylene glycol, 1,2-propylene glycol, 2-methyl 1,3-propanediol are preferred, more preferably ethylene glycol, diethylene glycol, 1,2- Russia is propylene glycol.

  The polyester polyol according to the present invention comprises the dibasic acid or an ester-forming derivative thereof and a glycol, if necessary, in the presence of an esterification catalyst, for example, within a temperature range of 180 to 250 ° C., for 10 to 25 hours. It can be produced by an esterification reaction by a well-known and usual method.

  In conducting the esterification reaction, a solvent such as toluene or xylene may be used, but a method using no solvent or glycol used as a raw material as a solvent is preferable.

  As the esterification catalyst, for example, tetraisopropyl titanate, tetrabutyl titanate, p-toluenesulfonic acid, dibutyltin oxide and the like can be used. The esterification catalyst is preferably used in an amount of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of dibasic acids or their ester-forming derivatives.

  The molar ratio in reacting the dibasic acid or their ester-forming derivative with glycol must be such that the terminal group of the polyester becomes a hydroxyl group (hydroxyl group), and therefore the dibasic acid or their ester formation. The glycol is 1.1 to 10 moles per mole of the functional derivative. Preferably, glycol is 1.5 to 7 moles with respect to 1 mole of dibasic acid or an ester-forming derivative thereof, and more preferably with respect to 1 mole of dibasic acid or an ester-forming derivative thereof. 2-5 moles of glycol.

  On the other hand, the carboxyl group terminal in the polyester polyol lowers the humidity stability, so the content is preferably low. Specifically, the acid value is preferably 5.0 or less, more preferably 1.0 or less, and particularly preferably 0.5 or less.

  The acid value as used herein refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid (carboxyl group present in the sample) contained in 1 g of the sample. The acid value is measured according to JIS K0070.

  The polyester polyol preferably has a hydroxyl (hydroxyl) value (OHV) in the range of 35 mg / g to 220 mg / g. The hydroxyl (hydroxyl group) value as used herein refers to the number of milligrams of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group (hydroxyl group) when OH groups contained in 1 g of a sample are acetylated. . Acetic anhydride is used to acetylate OH groups in the sample, and unused acetic acid is titrated with a potassium hydroxide solution, and obtained from the difference from the initial titration value of acetic anhydride.

  The polyester polyol preferably has a hydroxyl group (hydroxyl group) content of 70% or more. When the hydroxyl group (hydroxyl group) content is low, the compatibility between the polyester polyol and the cellulose ester is lowered. For this reason, the hydroxyl group (hydroxyl group) content is preferably 70% or more, more preferably 90% or more, and most preferably 99% or more.

  In the present invention, a compound having a hydroxyl group content of 50% or less is not included in the hydroxyl group (hydroxyl group) polyester polyol because one of the end groups is substituted with a group other than a hydroxyl group.

The hydroxyl group (hydroxyl group) content can be determined by the following formula (A).
Formula (A): Y / X × 100 = hydroxyl group (hydroxyl group) content (%)
X: hydroxyl value (OHV) of the polyester polyol
Y: 1 / (number average molecular weight (Mn)) × 56 × 2 × 1000
The polyester polyol preferably has a number average molecular weight within a range of 300 to 3,000, and more preferably has a number average molecular weight of 350 to 2,000.

  Moreover, it is preferable that the dispersion degree of the molecular weight of the polyester polyol based on this invention is 1.0-3.0, and it is still more preferable that it is 1.0-2.0. If the degree of dispersion is within the above range, a polyester polyol having excellent compatibility with the cellulose ester can be obtained. The polyester polyol preferably contains 50% or more of a component having a molecular weight of 300 to 1800. By setting the number average molecular weight within the above range, the compatibility can be greatly improved.

  As a method for controlling the number average molecular weight, the degree of dispersion, and the component content within the above preferred range, 2 to 5 mol of glycol is used per 1 mol of dibasic acid or ester-forming derivative thereof, and unreacted glycol is used. A method of distilling off under reduced pressure is preferred. The temperature at which the solvent is distilled off under reduced pressure is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and particularly preferably 130 to 170 ° C. The degree of reduced pressure when the solvent is distilled off under reduced pressure is preferably 0.1 to 500 Torr, more preferably 0.5 to 200 Torr, and most preferably 1 to 100 Torr.

  The polyester polyol number average molecular weight (Mn) and dispersity can be measured using gel permeation chromatography (GPC).

  An example of measurement conditions is as follows, but is not limited to this, and an equivalent measurement method can be used.

Solvent: Tetrahydrofuran (THF)
Column: TSKgel G2000HXL (Tosoh Co., Ltd., two connected and used)
Column temperature: 40 ° C
Sample concentration: 0.1% by mass
Apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Flow rate: 1.0ml / min
Calibration curve: A calibration curve by PStQuick F (manufactured by Tosoh Corporation) is used.

  In obtaining the effects of the present invention, the polyester polyol is preferably contained in the film in an amount of 5 to 30% by mass. More preferably, it is 5-20 mass%.

  Specific examples of dibasic acids having 10 to 16 carbon atoms are shown below, but the present invention is not limited thereto.

(1) 2,6-naphthalenedicarboxylic acid (2) 2,3-naphthalenedicarboxylic acid (3) 2,6-anthracenedicarboxylic acid (4) 2,6-naphthalenedicarboxylic acid: succinic acid (75: 25-99: 1 molar ratio) (5) 2,6-naphthalenedicarboxylic acid: terephthalic acid (50:50 to 99: 1 molar ratio)
(6) 2,3-naphthalenedicarboxylic acid: succinic acid (75:25 to 99: 1 molar ratio) (7) 2,3-naphthalenedicarboxylic acid: terephthalic acid (50:50 to 99: 1 molar ratio)
(8) 2,6-anthracene dicarboxylic acid: succinic acid (50:50 to 99: 1 molar ratio)
(9) 2,6-anthracene dicarboxylic acid: terephthalic acid (25:75 to 99: 1 molar ratio)
(10) 2,6-naphthalenedicarboxylic acid: adipic acid (67:33 to 99: 1 molar ratio)
(11) 2,3-naphthalenedicarboxylic acid: adipic acid (67:33 to 99: 1 molar ratio)
(12) 2,6-anthracene dicarboxylic acid: adipic acid (40:60 to 99: 1 molar ratio)
(UV absorber)
The λ / 4 plate and the optical film according to the present invention can contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. A benzotriazole-based compound with little coloring is preferable. Further, ultraviolet absorbers described in JP-A-10-182621, JP-A-8-337574, JP-A-2001-72782, JP-A-6-148430, JP-A-2002-31715, JP-A-2002-169020, 2002-2002. Polymer ultraviolet absorbers described in 47357, 2002-363420, and 2003-113317 are also preferably used. As an ultraviolet absorber, from the viewpoint of preventing the deterioration of polarizers and liquid crystals, it is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of liquid crystal display properties, the absorption of visible light having a wavelength of 400 nm or more is small. Is preferred.

  Specific examples of UV absorbers useful in the present invention include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis ( 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'- ert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, 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 and the like can be mentioned, but not limited thereto. Moreover, as a commercial item, TINUVIN 109, TINUVIN 171 and TINUVIN 326 (all manufactured by Ciba Japan) can be preferably used. An example of the polymeric ultraviolet absorber is a reactive ultraviolet absorber RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

  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.

  The ultraviolet absorber described above preferably used in the present invention is preferably a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber, which has high transparency and is excellent in the effect of preventing the deterioration of the polarizing plate and the liquid crystal element, and unnecessary coloring. A benzotriazole-based ultraviolet absorber with a lower content is particularly preferably used.

  The ultraviolet absorber can be added to the dope without limitation as long as it dissolves the ultraviolet absorber in the dope. In the present invention, the ultraviolet absorber is cellulose such as methylene chloride, methyl acetate, dioxolane and the like. Dope by dissolving in a good solvent for the ester, or a mixed solvent of a good solvent and a poor solvent such as a lower aliphatic alcohol (methanol, ethanol, propanol, butanol, etc.) and adding it to the cellulose ester solution as an ultraviolet absorber solution Is preferred. In this case, it is preferable to make the dope solvent composition and the solvent composition of the ultraviolet absorber solution the same or as close as possible. The content of the ultraviolet absorber is 0.01 to 5% by mass, particularly 0.5 to 3% by mass.

(Antioxidant)
As the antioxidant, hindered phenol compounds are 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-tert-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-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-tert-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-hydroxybenzyl) -isocyanate Examples include nurate. 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-t A phosphorus-based processing stabilizer such as -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.

  Moreover, it is also preferable to use the compound represented by the following general formula (L).

[Wherein, R _{2 to} R ₅ each independently represent a hydrogen atom or a substituent, R ₆ represents a hydrogen atom or a substituent, and n represents 1 or 2. When n is 1, R ₁ represents a substituent, and when n is 2, R ₁ represents a divalent linking group. ]
In the general formula (L), R _{2 to} R ₅ each independently represent a hydrogen atom or a substituent. The substituent represented by R _{2 to} R ₅ is not particularly limited, and examples thereof include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group). Group, dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino) Group), alkylthio group (for example, methylthio group, ethylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkenyl group (for example, vinyl group, 2-propenyl group, 3-butenyl group, 1- Methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl , Cyclohexenyl group etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group) , Imidazolyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl group (eg, methylsulfinyl group, etc.), An arylsulfinyl group (for example, phenylsulfinyl group), a phosphono group, an acyl group (for example, acetyl group, pivaloyl group, benzoyl group, etc.), a carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, Butyl Minocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group) , Cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc., sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, etc.) ), Cyano group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.) , Heterocyclic oxy group, siloxy group, acyloxy group (for example, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, Dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group) Group), imide group, ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc. ) Coxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.) ), Heterocyclic thio groups, thioureido groups, carboxyl groups, carboxylic acid salts, hydroxyl groups, mercapto groups, nitro groups, and the like. These substituents may be further substituted with the same substituent.

In the general formula (L), R _{2 to} R ₅ are preferably a hydrogen atom or an alkyl group.

In the general formula (L), R ₆ represents a hydrogen atom or a substituent, and examples of the substituent represented by R ₆ include the same groups as the substituents represented by R _{2 to} R ₅ .

In the general formula (L), R ₆ is preferably a hydrogen atom.

  In the general formula (L), n represents 1 or 2.

In the general formula (L), when n is 1, R ₁ represents a substituent, and when n is 2, R ₁ represents a divalent linking group. When R ₁ represents a substituent, examples of the substituent include the same groups as the substituents represented by R _{2 to} R ₅ . When R ₁ represents a divalent linking group, examples of the divalent linking group include an alkylene group that may have a substituent, an arylene group that may have a substituent, an oxygen atom, a nitrogen atom, and a sulfur atom. Or a combination of these linking groups.

In the general formula (L), n is preferably 1, and R ₁ at that time is preferably a substituted or unsubstituted phenyl group, and more preferably a phenyl group substituted with an alkyl group.

  Next, although the specific example of a compound represented by the said general formula (L) in this invention is shown, this invention is not limited by the following specific examples.

  These compounds can be used singly or in combination of two or more, and the blending amount is appropriately selected within a range not impairing the object of the present invention, but is usually 0.001 per 100 parts by mass of the cellulose ester. -10.0 mass parts, Preferably it is 0.01-5.0 mass parts, More preferably, it is 0.1-3.0 mass parts.

(Retardation adjuster)
As a compound to be added for adjusting the retardation, an aromatic compound having two or more aromatic rings as described in EP 911,656A2 can be used.

  Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. Particularly preferred is an aromatic heterocycle, and the aromatic heterocycle is generally an unsaturated heterocycle. 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, still more 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. Naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferred.

  The single bond (b) is preferably a bond between carbon atoms of two aromatic rings. Two aromatic rings may be bonded by 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, an 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 adjusting agent is preferably 300 or more and 800 or less. 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 (R).

In the general formula (R), 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 alkyl groups, alkenyl groups, aryl groups or heterocyclic groups; 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 (R) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (R), 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 hydrogen atoms.

  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 of 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 carbamoyl 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, sulfonamido 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.

The heterocyclic group in the case where X ¹ , X ² or X ³ is —NR—, —O— or —S— 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 an 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 (M) 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 (R).

  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 O-n-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 On} -C ₄ H ₉
MP-122: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH _{2 On} -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 On} -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 On} -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.

  In this invention, it is preferable to use at least 1 type of a benzoic acid phenylester compound as a retardation regulator, and it is preferable to add the benzoic acid phenylester compound shown by following General formula (6) to a cellulose resin especially.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent, and R ¹ , R ² , At least one of R ³ , R ⁴ and R ⁵ represents an electron donating group, R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 2 to 2 carbon atoms. 6 alkynyl groups, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 6 to 12 carbon atoms, alkoxycarbonyl groups having 2 to 12 carbon atoms, acylamino having 2 to 12 carbon atoms Represents a group, a cyano group or a halogen atom.)
In the general formula (6), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, Substituent T described later can be applied as the substituent.

At least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents an electron donating group. Preferably, one of R ¹ , R ³ or R ⁵ is an electron donating group, and R ³ is more preferably an electron donating group.

  The electron donating group is one having Hammet's σp value of O or less, Chem. Rev. , 91, 165 (1991), and those having Hammet's σp value of O or less are preferably applicable, and those having −0.85 to 0 are more preferably used. Examples thereof include an alkyl group, an alkoxy group, an amino group, and a hydroxyl group (hydroxyl group).

  The electron donating group is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 6 carbon atoms). Having 1 to 4 carbon atoms).

R ¹ is preferably a hydrogen atom or an electron donating group, more preferably an alkyl group, an alkoxy group, an amino group, or a hydroxyl group (hydroxyl group), still more preferably an alkyl group having 1 to 4 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, particularly preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to carbon atoms). 4), and most preferably a methoxy group.

R ² is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group (hydroxyl group), more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group. (Preferably 1 to 4 carbon atoms, more preferably a methyl group), an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably Is carbon number 1-4. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

R ³ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group (hydroxyl group), still more preferably an alkyl group or an alkoxy group. And particularly preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred are n-propoxy group, ethoxy group and methoxy group.

R ⁴ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group (hydroxyl group), still more preferably a hydrogen atom or a carbon number of 1 Alkyl group having 1 to 4 carbon atoms and alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Particularly preferred are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and most preferred are a hydrogen atom, a methyl group and a methoxy group.

R ⁵ is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group (hydroxyl group), more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group. (Preferably 1 to 4 carbon atoms, more preferably methyl group), alkoxy groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom). ~ 4). Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, and more preferably a hydrogen atom or a halogen atom. And more preferably a hydrogen atom.

R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl having 6 to 12 carbon atoms. Represents an oxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group or a halogen atom, and if possible, may have a substituent. Substituent T can be applied. Further, the substituent may be further substituted.

R ⁸ is preferably an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkoxycarbonyl having 2 to 12 carbon atoms. A cyano group, more preferably an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, and a cyano group, and more preferably 1 carbon atom. An alkoxy group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and a cyano group, particularly preferably an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and p-cyanophenyl. Group, a p-methoxyphenyl group, an alkoxycarbonyl group having 2 to 4 carbon atoms, and a cyano group.

  Among the compounds represented by the general formula (6), a more preferable compound is a compound represented by the following general formula (6-A).

In general formula (6-A), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as those in general formula (6), The preferred range is also the same.

R ¹¹ represents an alkyl group having 1 to 12 carbon atoms. The alkyl group represented by R ¹¹ may be linear or branched, and may further have a substituent, but is preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. An alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso group). -Butyl group, tert-butyl group and the like).

  Among the compounds represented by the general formula (6), a more preferable compound is a compound represented by the following general formula (6-B).

In general formula (6-B), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ have the same meanings as those in general formula (6), and preferred ranges are also the same. It is.

R ¹¹ has the same meaning as that in formula (6-A), and the preferred range is also the same.

  X is an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, carbon An alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom is represented.

When R ¹ , R ² , R ⁴ and R ⁵ are all hydrogen atoms, X is preferably an alkyl group, alkynyl group, aryl group, alkoxy group or aryloxy group, more preferably an aryl group or alkoxy group. Group, aryloxy group, more preferably alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms). And particularly preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group or an n-butoxy group.

When at least one of R ¹ , R ² , R ⁴ , and R ⁵ is a substituent, X is preferably an alkynyl group, an aryl group, an alkoxycarbonyl group, or a cyano group, more preferably an aryl group (preferably Is a cyano group or an alkoxycarbonyl group (preferably a carbon number of 2 to 12), more preferably an aryl group (preferably an aryl group of 6 to 12 carbon atoms, more preferably a phenyl group). , P-cyanophenyl group and p-methoxyphenyl), an alkoxycarbonyl group (preferably having 2 to 12, more preferably 2 to 6, more preferably 2 to 4 carbon atoms, particularly preferably methoxycarbonyl, Ethoxycarbonyl, n-propoxycarbonyl), cyano group, particularly preferably phenyl group, methoxy group A carbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and a cyano group.

  Among the compounds represented by the general formula (6), a more preferable compound is a compound represented by the following general formula (6-C).

In general formula (6-C), R ¹ , R ² , R ⁴ , R ⁵ , R ¹¹ and X are synonymous with those in general formula (6-B), and preferred ranges are also the same.

  Among the compounds represented by the general formula (6), a particularly preferable compound is a compound represented by the following general formula (6-D).

In general formula (6-D), R ² , R ⁴ and R ⁵ have the same meanings as those in general formula (6-C), and the preferred ranges are also the same. R ²¹ and R ²² each independently represents an alkyl group having 1 to 4 carbon atoms. X1 represents an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group.

R ²¹ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an ethyl group or a methyl group.

R ²² represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

X ¹ is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group, preferably an aryl group having 6 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a cyano group. More preferably a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl group, a methoxycarbonyl, an ethoxycarbonyl, an n-propoxycarbonyl, a cyano group, and still more preferably a phenyl group, a methoxycarbonyl group, an ethoxycarbonyl group. , N-propoxycarbonyl group, cyano group.

  Among the compounds represented by the general formula (6), the most preferable compound is a compound represented by the following general formula (6-E).

In general formula (6-E), R ² , R ⁴ and R ⁵ have the same meanings as those in general formula (6-D), and the preferred ranges are also the same. However, any one is a group represented by —OR ¹³ . Here, R ¹³ is an alkyl group having 1 to 4 carbon atoms. R ²¹ , R ²² and X ¹ have the same meanings as those in formula (6-D), and preferred ranges are also the same.

Preferably, at least one of R ⁴ and R ⁵ is a group represented by —OR ¹³ , and more preferably, R ⁴ is a group represented by —OR ¹³ .

R ¹³ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

  Hereinafter, the aforementioned substituent T will be described.

  Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert- Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably C2-8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably C2-20, more preferably C2-12, particularly preferably Has 2 to 8 carbon atoms, for example, propargyl, 3-pentynyl and the like, and an aryl group (preferably having 6 carbon atoms). 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc.), a substituted or unsubstituted amino group (preferably having a carbon number) 0 to 20, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), alkoxy groups (preferably C1-C20, More preferably, it is C1-C12, Most preferably, it is C1-C8, for example, a methoxy, an ethoxy, butoxy etc. are mentioned, and an aryloxy group (preferably C6-C20). More preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 2-naphthyloxy, etc. And an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl A group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms such as phenyloxycarbonyl), an acyloxy group (preferably having 2 to 2 carbon atoms). 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms. And benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), alkoxycarbonylamino group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group (preferably having carbon number) 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and the like, and sulfonylamino groups (preferably 1 to 20 carbon atoms, more preferably Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. And sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl and methylsulfamoyl). , Dimethylsulfamoyl, phenylsulfamoyl, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl). , Methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, Ethylthio etc.), arylthio group (preferably Has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably Has 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms) More preferably, it is C1-C16, Most preferably, it is C1-C12, for example, diethyl phosphoric acid amide, phenylphosphoric acid amide etc. are mentioned. ), Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl , Morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms). For example, trimethylsilyl, triphenylsilyl, etc.) . These substituents may be further substituted.

  Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

  Hereinafter, the compound represented by the general formula (6) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

  The compound represented by the general formula (6) used in the present invention can be synthesized by a general ester reaction of a substituted benzoic acid and a phenol derivative, and any reaction may be used as long as it is an ester bond forming reaction. Examples thereof include a method of converting a substituted benzoic acid into an acid halide and then condensing with phenol, a method of dehydrating condensation of a substituted benzoic acid and a phenol derivative using a condensing agent or a catalyst, and the like.

  In view of the production process and the like, a method in which the substituted benzoic acid is functionally converted to an acid halide and then condensed with phenol is preferable.

  Examples of the reaction solvent include hydrocarbon solvents (preferably toluene and xylene), ether solvents (preferably dimethyl ether, tetrahydrofuran, dioxane and the like), ketone solvents, ester solvents, acetonitrile and dimethyl. Formamide, dimethylacetamide and the like can be used. These solvents may be used alone or in admixture of several kinds, and preferred reaction solvents are toluene, acetonitrile, dimethylformamide and dimethylacetamide.

  The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.

  In this reaction, it is preferable not to use a base. When a base is used, either an organic base or an inorganic base may be used, preferably an organic base such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiisopropyl). Pyramine and the like).

  Furthermore, the λ / 4 plate of the present invention preferably contains a rod-like compound having a maximum absorption wavelength (λmax) in the ultraviolet absorption spectrum of the solution shorter than 250 nm as a retardation adjusting agent.

  From the viewpoint of the function of the retardation adjusting 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. The rod-shaped compound preferably exhibits liquid crystallinity. More preferably, the rod-like compound exhibits liquid crystallinity upon heating (has thermotropic liquid crystallinity). The liquid crystal phase is preferably a nematic phase or a smectic phase.

  The rod-like compound is preferably a trans-1,4-cyclohexanedicarboxylic acid ester compound represented by the following general formula (7).

Formula ^{(7): Ar 1 -L 1} -Ar 2
In Formula (7), Ar ¹ and Ar ² are each independently an aromatic group. In the present specification, 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-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. 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 Formula (7), L ¹ is a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, a divalent saturated heterocyclic group, —O—, —CO—, and combinations thereof. is there. 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 in 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. 2 (vinylene or ethynylene) is most preferred. The divalent saturated heterocyclic group preferably has a 3- to 9-membered heterocyclic ring. The hetero atom of the hetero ring is preferably an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a silicon atom, a phosphorus atom or a germanium atom. Examples of saturated heterocycles include piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, imidazolidine ring, tetrahydrofuran ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, tetrahydrothiophene ring, 1 , 3-thiazolidine ring, 1,3-oxazolidine ring, 1,3-dioxolane ring, 1,3-dithiolane ring and 1,3,2-dioxaborolane. Particularly preferred divalent saturated heterocyclic groups are piperazine-1,4-diylene, 1,3-dioxane-2,5-diylene and 1,3,2-dioxaborolane-2,5-diylene.

  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-
L-7: -O-CO-divalent saturated heterocyclic group -CO-O-
L-8: -CO-O-divalent saturated heterocyclic group -O-CO-
In the molecular structure of the general formula (7), 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 general formula (8) is more preferable.

Formula ^{(8): Ar 1 -L 2} -X-L 3 -Ar 2
In Formula (8), Ar ¹ and Ar ² are each independently an aromatic group. The definition and examples of the aromatic group are the same as Ar ¹ and Ar ^{2 in} the formula (7).

In Formula (8), 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 (8), X is 1,4-cyclohexylene, vinylene or ethynylene. Specific examples of the compound represented by formula (7) are shown below.

  Specific examples (1) to (34), (41), (42), (46), (47), (52), (53) are two asymmetric carbons at the 1st and 4th positions of the cyclohexane ring. Has atoms. However, the specific examples (1), (4) to (34), (41), (42), (46), (47), (52), (53) have a symmetric meso type molecular structure. Therefore, there is no optical isomer (optical activity) and only geometric isomers (trans and cis forms) exist. The trans type (1-trans) and cis type (1-cis) of specific example (1) are shown below.

  As described above, the rod-like compound preferably has a linear molecular structure. Therefore, the trans type is preferable to the cis type. Specific examples (2) and (3) have optical isomers (a total of four isomers) in addition to geometric isomers. As for geometric isomers, the trans type is similarly preferable to the cis type. The optical isomer is not particularly superior or inferior, and may be D, L, or a racemate. In specific examples (43) to (45), the central vinylene bond includes a trans type and a cis type. For the same reason as above, the trans type is preferable to the cis type.

  Two or more rod-shaped compounds having a maximum absorption wavelength (λmax) shorter than 250 nm in the ultraviolet absorption spectrum of the solution may be used in combination. The rod-like compound can be synthesized with reference to methods described in 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).

(Matting agent)
In the present invention, fine particles can be contained in the λ / 4 plate as a matting agent, whereby when the λ / 4 plate is a long film, it can be easily conveyed and wound.

  The particle size of the matting agent is preferably primary particles or secondary particles of 10 nm to 0.1 μm. A substantially spherical matting agent having a primary particle acicular ratio of 1.1 or less is preferably used.

  As the fine particles, those containing silicon are preferable, and silicon dioxide is particularly preferable. Preferred fine particles of silicon dioxide for the present invention include, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (Nippon Aerosil Co., Ltd.) manufactured by Nippon Aerosil Co., Ltd. What is marketed by a brand name can be mentioned, Aerosil 200V, R972, R972V, R974, R202, R812 can be used preferably. Examples of polymer fine particles include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. Examples include Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.). Can do.

  The fine particles of silicon dioxide preferably have a primary average particle size 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, further preferably 5 to 12 nm. A smaller primary particle average diameter is preferred because haze is low. The apparent specific gravity is preferably 90 to 200 g / L or more, and more preferably 100 to 200 g / L or more. Higher apparent specific gravity makes it possible to produce a high-concentration fine particle dispersion, which is preferable because no haze or aggregates are generated.

The addition amount of the matting agent in the present invention is preferably from 0.01 to 1.0 g, more preferably from 0.03 to 0.3 g, still more preferably from 0.08 to 0.16 g per 1 m ^{2 of} λ / 4 plate.

(Other additives)
In addition, thermal stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and alumina, and alkaline earth metal salts such as calcium and magnesium may be added. Further, a surfactant, a peeling accelerator, an antistatic agent, a flame retardant, a lubricant, an oil agent and the like may be added.

(Manufacture of λ / 4 plate)
The λ / 4 plate of the present invention may be produced by either a solution casting method or a melt casting method, but is preferably produced by a solution casting method.

  The production of the λ / 4 plate of the present invention is a step of preparing a dope by dissolving an additive such as cellulose acetate and the plasticizer in a solvent, and a step of casting the dope on a belt-shaped or drum-shaped metal support. , A process of drying the cast dope as a web, a process of peeling from the metal support, a process of stretching, a process of further drying, a process of further heat treating the obtained film if necessary, and a process of winding after cooling. Is called. The λ / 4 plate of the present invention preferably contains 60 to 95% by mass of cellulose acetate in the solid content.

  The process for preparing the dope will be described. The concentration of cellulose acetate in the dope is preferably higher because the drying load after casting on a metal support can be reduced. However, if the concentration of cellulose acetate is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used in the dope according to the present invention may be used alone or in combination of two or more, but it is preferable in terms of production efficiency to use a good solvent and a poor solvent of cellulose acetate, A larger amount of good solvent is preferred from the viewpoint of solubility of cellulose acetate. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose acetate to be used independently is defined as a good solvent, and what does not swell or dissolve independently is defined as a poor solvent. Therefore, depending on the degree of acetyl group substitution of cellulose acetate, the good solvent and the poor solvent change. For example, when acetone is used as a solvent, the cellulose ester acetate (acetyl group substitution degree 2.4) becomes a good solvent. Acetic acid ester (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  As a method for dissolving cellulose acetate when preparing the dope described above, a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. Further, a method in which cellulose acetate is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature with the addition of a solvent is preferably higher from the viewpoint of the solubility of cellulose acetate, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby cellulose acetate can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose acetate solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose acetate by filtration.

A bright spot foreign material is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate. The preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose acetate film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%. 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.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  In the drying step of the cellulose acetate film, the web is peeled off from the metal support, further dried, and dried until the residual solvent amount is 0.5% by mass or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  When peeling from the metal support, the web is stretched in the longitudinal direction due to the peeling tension and the subsequent conveying tension. Therefore, in the present invention, when peeling the web from the casting support, the peeling and conveying tensions are reduced as much as possible. It is preferable to carry out in the state. Specifically, for example, it is effective to set it to 50 to 170 N / m or less. At that time, it is preferable to apply a cold air of 20 ° C. or less to fix the web rapidly.

  The cellulose acetate film is further adjusted by adjusting the refractive index (the refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the in-plane slow axis and the refractive index nz in the thickness direction). be able to. In the λ / 4 plate of the present invention, Ro (550) measured at a wavelength of 550 nm is preferably in the range of 110 to 170 nm, Ro (550) is preferably 120 to 160 nm, and Ro (550) is 130 to 150 nm. More preferably it is.

  The λ / 4 plate of the present invention is a retardation plate (film) having a retardation of approximately ¼ of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range. Preferably there is.

  The term “retardation of approximately ¼ in the wavelength range of visible light” means a retardation value represented by the following formula (i) measured at a wavelength of 450 nm, with a larger retardation at a wavelength of 400 to 700 nm. The difference Ro (550) −Ro (450) between a certain Ro (450) and the retardation value Ro (550) measured at a wavelength of 550 nm is preferably 2 to 34 nm, and more preferably 4 to 32 nm. 8 to 28 nm is particularly preferable. In order to achieve the above-mentioned Ro (550), the λ / 4 plate of the present invention may be adjusted by adjusting the refractive index by controlling the stretching ratio of uniaxial stretching or by implementing unbalanced biaxial stretching. Specifically, uniaxial stretching or unbalanced biaxial stretching is performed so that the maximum stretching ratio SA and the stretching ratio SB in the direction perpendicular to the stretching direction satisfy the relationship 1 <SA / SB ≦ 3. Just do it. The draw ratio is a relative value when the length before drawing is 1. SB may be a value less than 1 (in other words, contracts). If the relationship of the above equation is satisfied, SB may be a value less than 1. Furthermore, the draw ratio is adjusted so that the retardation value is λ / 4. The biaxial stretching treatment may be performed simultaneously in two directions or sequentially.

  Incidentally, although the retardation value Rt in the film thickness direction represented by the formula (ii) described later of the λ / 4 plate of the present invention is affected by the draw ratio, it is preferably in the range of 0 to 400 nm. .

  Stretching is performed in the transport direction using the peripheral speed difference of the film transport roll, or by a tenter method in which both ends of the web are gripped with clips or the like in the direction orthogonal to the transport direction (also referred to as the width direction or the TD direction). It is also preferable to use a tenter that can independently control the gripping length of the web (distance from the start of gripping to the end of gripping) by the left and right gripping means.

  Moreover, in this invention, it is also preferable to extend | stretch either a (lambda) / 4 board or a polarizer in a 45 degree direction with respect to a film conveyance direction at an extending | stretching process.

  This is because when the angle between the longitudinal direction of the λ / 4 plate made of a roll-shaped polymer film and the in-plane slow axis is substantially 45 °, the longitudinal direction and the transmission axis are substantially parallel. A roll-shaped circularly polarizing plate can be produced simply by laminating a roll-shaped polarizer and a λ / 4 plate with a roll-to-roll. Similarly, when the angle between the longitudinal direction and the absorption axis of a polarizer made of a roll-shaped polymer film is substantially 45 °, a roll-shaped λ / 4 in which the longitudinal direction and the transmission axis are substantially parallel. A roll-shaped circularly polarizing plate can be produced simply by laminating a plate with a roll-to-roll.

  For example, a λ / 4 plate in which the angle between the longitudinal direction and the in-plane slow axis is substantially 45 ° is a roll-like cellulose ester film stretched in a direction substantially 45 ° with respect to the longitudinal direction. It can be manufactured by processing.

  Hereinafter, a method of stretching in the 45 ° direction will be described.

  In order to obliquely stretch the cellulose acetate film in a direction substantially 45 ° with respect to the longitudinal direction, it is preferable to use a tenter shown in FIG. FIG. 4 is a schematic diagram showing oblique stretching by a tenter.

  The stretched film according to the present invention is produced using a tenter. This tenter is a device that widens a film fed from a film roll (feeding roll) in an oblique direction with respect to its traveling direction (moving direction of the middle point in the film width direction) in a heating environment by an oven. The tenter includes an oven, a pair of rails on the left and right on which a gripping tool for transporting the film travels, and a number of gripping tools that travel on the rails. Both ends of the film fed out from the film roll and sequentially supplied to the entrance portion of the tenter are gripped by a gripping tool, the film is guided into the oven, and the film is released from the gripping tool at the exit portion of the tenter. The film released from the gripping tool is wound around the core. Each of the pair of rails has an endless continuous track, and the gripping tool which has released the grip of the film at the exit portion of the tenter travels outside and is sequentially returned to the entrance portion.

  The rail shape of the tenter is asymmetrical on the left and right according to the orientation angle, stretch ratio, etc. given to the stretched film to be manufactured, and can be finely adjusted manually or automatically. In the present invention, a long thermoplastic resin film is stretched, and the orientation angle θ can be set to any angle within the range of 40 ° to 80 ° with respect to the winding direction after stretching. Yes. In the present invention, the gripping tool of the tenter is configured to travel at a constant speed with a certain distance from the front and rear gripping tools.

  FIG. 4 shows a rail track (rail pattern) of a tenter used in the manufacturing method according to the present invention. The feeding direction D1 of the thermoplastic resin film is different from the winding direction (MD direction) D2 of the stretched film, thereby obtaining a wide and uniform optical characteristic even in a stretched film having a relatively large orientation angle. It is possible. The feeding angle θi is an angle formed by the feeding direction D1 of the film before stretching and the winding direction D2 of the film after stretching. In the present invention, in order to produce a film having an orientation angle of 40 ° to 80 ° as described above, the feeding angle θi is set to 10 ° <θi <60 °, preferably 15 ° <θi <50 °. The By setting the feeding angle θi in the above range, the variation in the optical characteristics in the width direction of the obtained film becomes good (becomes small).

  The thermoplastic resin film fed out from the film roll (feeding roll) is gripped at both ends (both sides) by the left and right gripping tools at the tenter inlet (position a), and travels as the gripping tool travels. The The left and right grips CL, CR, which are opposed to the direction of the film travel direction (feeding direction D1) at the tenter entrance (position a), run on the left-right asymmetric rail, and are in the preheating zone. Through an oven having a stretching zone and a heat setting zone. Here, “substantially perpendicular” indicates that the angle formed by the straight line connecting the aforementioned gripping tools CL and CR and the film feeding direction D1 is within 90 ± 1 °.

  The preheating zone refers to a section in which the vehicle travels while maintaining a constant interval between the gripping tools gripping both ends at the oven entrance. The stretching zone refers to an interval until the gap between the gripping tools gripping both ends starts to become constant again. In addition, the cooling zone refers to a section in which the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg ° C. of the thermoplastic resin constituting the film during a period in which the interval between the gripping tools after the stretching zone becomes constant again. .

  The temperature of each zone is set to Tg + 5 to Tg + 20 ° C., the temperature of the stretching zone is set to Tg to Tg + 20 ° C., and the temperature of the cooling zone is set to Tg−30 to Tg ° C. with respect to the glass transition temperature Tg of the thermoplastic resin. It is preferable to do.

  The draw ratio R (W / Wo) in the drawing step according to the present invention is preferably 1.3 to 3.0, more preferably 1.5 to 2.8. When the draw ratio is within this range, thickness unevenness in the width direction is reduced, which is preferable. In the stretching zone of the tenter stretching machine, if the stretching temperature is differentiated in the width direction, the thickness unevenness in the width direction can be further improved. In addition, Wo represents the width of the film before stretching, and W represents the width of the film after stretching.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the drying process of the web is preferably an effective heat treatment for the glass transition point of the film of −5 ° C. or lower and 100 ° C. or higher and 10 minutes or longer and 60 minutes or shorter. Drying is performed at a drying temperature of 100 to 200 ° C, more preferably 110 to 160 ° C.

  After the predetermined heat treatment, it is preferable to provide a slitter and cut off the end portion before winding to obtain a good winding shape. Furthermore, it is preferable to knurling both ends of the width.

  The knurling process can be formed by pressing a heated embossing roll. Fine embossing is formed on the embossing roll, and the embossing roll can be pressed to form asperity on the film and make the end bulky.

  The height of the knurling at both ends of the λ / 4 plate of the present invention is preferably 4 to 20 μm and a width of 5 to 20 mm.

  In the present invention, the knurling process is preferably provided after the drying in the film forming process and before winding.

  A λ / 4 plate having a multilayer structure by a co-casting method can also be preferably used. Even when the λ / 4 plate has a multilayer structure, it has a layer containing a plasticizer, which may be a core layer, a skin layer, or both.

  The center line average roughness (Ra) of the surface of the λ / 4 plate according to the present invention is preferably 0.001 to 1 μm.

  The λ / 4 plate according to the present invention preferably has a thickness in the range of 20 to 200 μm, more preferably 20 to 100 μm, and particularly preferably 30 to 80 μm. In general, the larger the film thickness of the λ / 4 plate, the easier it is to increase the phase difference. However, in the present invention, since the λ / 4 plate has the function of a polarizing plate protective film, the thickness of the entire polarizing plate is reduced. Also, the above range is preferable.

Moisture permeability, JIS Z 0208 (25 ℃, RH 90%) as a value measured according to is preferably not more than 200g ^{/ m} 2 · 24 hours, more preferably, 10~180g ^{/ m} 2 · 24 hours Or less, particularly preferably 160 g / m ² · 24 hours or less. In particular, it is preferable that the film thickness is 30 to 80 μm and the moisture permeability is within the above range.

  The long λ / 4 plate of the present invention specifically has a length of about 100 to 10,000 m, and is usually in the form of a roll. Further, the width of the λ / 4 plate of the present invention is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 4 m.

(Hard coat layer)
A hard coat layer is provided on the λ / 4 plate of the present invention, and the hard coat layer is preferably either a clear hard coat layer or an antiglare hard coat layer.

  The hard coat layer used in the present invention is provided on at least one surface of the λ / 4 plate. In the present invention, an antireflection layer including at least a low refractive index layer is preferably provided on the hard coat layer. In particular, in the case of in-vehicle car navigation, in order to further improve the visibility, it is preferable to provide an antireflection layer on the antiglare hard coat layer.

  When the hard coat layer used in the present invention is anti-glare, the surface has a fine uneven shape, and the fine uneven shape is formed by containing fine particles in the hard coat layer, and It can be formed by containing fine particles having an average particle size of 0.01 μm to 4 μm in the hard coat layer. Further, as will be described later, as the surface roughness of the outermost surface of the antireflection layer provided on the antiglare hard coat layer, the center line average roughness (Ra) defined by JIS B 0601 is 0.08 μm. It is preferable to adjust to a range of ˜0.5 μm.

  In the case of the clear hard coat layer, it is a clear hard coat layer having a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 μm, and Ra is 0.002 to 0.05 μm. It is preferable. The center line average roughness (Ra) is preferably measured by an optical interference type surface roughness measuring instrument, and can be measured, for example, using a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.

  As particles contained in the antiglare hard coat layer used in the present invention, for example, inorganic or organic fine particles are used.

  Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate.

  The organic fine particles include polymethyl methacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicone resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, and polyfluoroethylene resin fine particles.

  In the present invention, silicon oxide fine particles or polystyrene resin fine particles are particularly preferable.

  The inorganic or organic fine particles described above are preferably used in addition to a coating composition containing a resin or the like used for producing an antiglare hard coat layer.

  In order to impart anti-glare properties to the anti-glare hard coat layer used in the present invention, the content of the inorganic or organic fine particles is set to 0. 1 mass part-30 mass parts are preferable, More preferably, it is mix | blending so that it may become 0.1 mass part-20 mass parts. In order to give a more preferable antiglare effect, it is preferable to use 1 part by mass to 15 parts by mass of fine particles having an average particle size of 0.1 μm to 1 μm with respect to 100 parts by mass of the resin for preparing the antiglare hard coat layer. . It is also preferable to use two or more kinds of fine particles having different average particle diameters.

The antiglare hard coat layer used in the present invention preferably contains an antistatic agent, and examples of the antistatic agent include Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, and W. And a conductive material containing at least one element selected from the group consisting of V and V as a main component and having a volume resistivity of 10 ⁷ Ω · cm or less.

  Examples of the antistatic agent include metal oxides and composite oxides having the above elements.

Examples of metal oxides are preferably ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or a composite oxide thereof. In particular, ZnO, In ₂ O ₃ , TiO ₂ and SnO ₂ are preferred. Examples of containing different atoms include, for example, addition of Al, In, etc. to ZnO, addition of Nb, Ta, etc. to TiO ₂ , and addition of Sb, Nb, halogen elements, etc. to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

In addition, the volume resistivity of these metal oxide powders having conductivity is 10 ⁷ Ω · cm or less, particularly 10 ⁵ Ω · cm or less.

  From the viewpoint of imparting sufficient durability and impact resistance, the film thickness of the clear hard coat layer or the antiglare hard coat layer is preferably in the range of 0.5 μm to 15 μm, more preferably 1.0 μm to 7 μm. .

(Active energy ray curable resin)
The hard coat layer used in the present invention preferably contains an active energy ray-curable resin that is cured by irradiation with active energy rays such as ultraviolet rays.

  The active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an active energy ray other than an ultraviolet ray or an electron beam may be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in products obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group (hydroxyl group) such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts of Unidic 17-806 (manufactured by Dainippon Ink Chemical Co., Ltd.) and 1 part of Coronate L (manufactured by Nippon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferable. Used.

  The UV curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate or acrylic acid with a hydroxyl group (hydroxyl group) or a carboxyl group at the end of the polyester (for example, JP, 59-151112, A).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group (hydroxyl group) of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.

  As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, useful epoxy-based active energy ray reactive compounds are shown.

(A) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by reaction of epichlorohydrin and bisphenol A)
(B) a compound having a glycidyl ether group by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs such as bisphenol A (c) glycidyl ether of 4,4'-methylenebisphenol (D) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin (e) Compound having alicyclic epoxide, for example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) ) Adipate, bis (3,4-epoxy-6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo Xanthcarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3', 4'-epoxy-1 ' -Methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3 ', 4'-epoxy-6'-methyl-1'-cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5 ', 5'-spiro-3 ", 4" -epoxy) cyclohexane-meta-dioxane (f) diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, diglycidyl Hexahydrophthalate, diglycidylf (G) Diglycidyl ether of glycol, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) di Glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (h) Glycidyl ester of polymer acid, for example, polyglycidyl ester of polyacrylic acid, polyester diglycidyl ester (i) Polyhydric alcohol Glycidyl ethers such as glycerin triglycidyl ether, trimethylolpropane triglycidyl Ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether (j) As the diglycidyl ether of 2-fluoroalkyl-1,2-diol, Similar to the compound examples given for the fluorine-containing epoxy compound of the fluorine-containing resin (k) As the fluorine-containing alkane-terminated diol glycidyl ether, the fluorine-containing epoxy compound of the fluorine-containing resin of the low refractive index substance can be exemplified. .

  The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.

  In the case where the above epoxy compound is cured with active energy rays, it is effective to use a compound having a polyfunctional epoxy group (h) or (i) in order to increase the hardness.

  The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy-based active energy ray-reactive compound is a compound capable of releasing a cationic polymerization initiator by irradiation with active energy rays, and particularly preferably a cation by irradiation. It is a group of double salts of onium salts that release Lewis acids capable of initiating polymerization.

  The active energy ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is not affected by oxygen in the reaction system, and is therefore a preferred active energy ray reactive resin.

  The active energy ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or a photosensitizer that releases a substance that initiates cationic polymerization upon irradiation with active energy rays. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  A typical example is a compound represented by the following general formula (a).

General formula (a): [(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{w +} [MeX _v ] ^w−
Wherein cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeX _v ] ^w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), tetra Examples thereof include fluoroarsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

  Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic halonium salts described in JP-A Nos. 50-151996 and 50-158680 are particularly useful. VIA group aromatic onium salts described in Kaisho 50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56-149402, Preference is given to oxosulfoxonium salts described in 57-192429 and the like, aromatic diazonium salts described in JP-B-49-17040, thiopyridium salts described in US Pat. No. 4,139,655 and the like. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  In the case of an active energy ray-reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photosensitizer and photoinitiator used for the active energy ray-reactive compound are sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet-reactive compound. The amount is preferably 1 part by mass to 10 parts by mass. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the active energy ray-curable resin composition useful in the present invention, the polymerization initiator is generally 0.1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable epoxy resin (prepolymer). Is more preferable, and addition of 1 mass part-10 mass parts is more preferable.

  An epoxy resin can be used in combination with the urethane acrylate type resin, polyether acrylate type resin, or the like. In this case, it is preferable to use an active energy ray radical polymerization initiator and an active energy ray cationic polymerization initiator in combination.

  Moreover, an oxetane compound can also be used for the hard-coat layer used for this invention. The oxetane compound used is a compound having a three-membered oxetane ring containing oxygen or sulfur. Among them, a compound having an oxetane ring containing oxygen is preferable. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, or an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl -3 chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, 3,3-dimethyloxetane and the like. In the present invention, any of a monomer, an oligomer and a polymer may be used.

In the hard coat layer used in the present invention, a binder such as a known thermoplastic resin, thermosetting resin, or hydrophilic resin such as gelatin can be mixed with the active energy ray curable resin described above. These resins preferably have a polar group in the molecule. Examples of the polar _{group, -COOM, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OSO 3 M, -PO 3 M 2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali A metal or an ammonium group, X represents an acid that forms an amine salt, R represents a hydrogen atom or an alkyl group).

  When the hard coat layer used in the present invention contains an active energy ray-curable resin, the active energy ray irradiation method includes an antiglare hard coat layer and an antireflection layer (medium to high refractive index layer) on a support. In addition, the active energy ray may be irradiated after the coating of the low refractive index layer or the like, but the active energy ray is preferably irradiated when the hard coat layer is coated.

The active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, γ ray, etc., but ultraviolet ray and electron beam are preferable, especially easy handling and high energy. UV rays are preferred in that they can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. 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. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the irradiation light quantity is preferably 20 mJ / cm ² or more, more preferably 50 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is.

  The ultraviolet irradiation may be performed every time one layer is provided for each of a plurality of layers (medium refractive index layer, high refractive index layer, low refractive index layer) constituting the hard coat layer and the antireflection layer described later. The film may be irradiated after lamination. Or you may irradiate combining these. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

  In order to initiate the photopolymerization or photocrosslinking reaction of the active energy ray-reactive compound used in the present invention, the active energy ray-reactive compound alone is initiated, but the polymerization induction period is long or the polymerization start is slow. Therefore, it is preferable to use a photosensitizer or a photoinitiator, which can accelerate the polymerization.

  When the hard coat layer used in the present invention contains an active energy ray-curable resin, a photoreaction initiator and a photosensitizer can be used during irradiation with active energy rays.

  Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. Moreover, when using a photoreactant for the synthesis | combination of an epoxy acrylate-type resin, sensitizers, such as n-butylamine, a triethylamine, a tri-n-butylphosphine, can be used. The amount of the photoreaction initiator and / or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying is preferably 1% by mass to 10% by mass, particularly preferably. Is 2.5% by mass to 6% by mass.

  Moreover, when using ultraviolet curable resin as active energy ray curable resin, you may include the ultraviolet absorber mentioned later in the ultraviolet curable resin composition to such an extent that the photocuring of the said ultraviolet curable resin is not prevented.

  In order to increase the heat resistance of the hard coat layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  Examples of the ultraviolet curable resin include Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo 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 Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 )), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UC Corporation), 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.), Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sun Rad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), or other commercially available products can be used as appropriate.

  The coating composition containing the active energy ray-curable resin preferably has a solid content concentration of 10% by mass to 95% by mass, and an appropriate concentration is selected depending on the coating method.

  The hard coat layer and antireflection layer used in the present invention also preferably contain a surfactant, and the surfactant is preferably a silicone-based or fluorine-based surfactant.

  As the silicone-based surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  A nonionic surfactant is a generic term for a system surfactant that does not have a group capable of dissociating into ions in an aqueous solution. In addition to a hydrophobic group, a hydroxyl group (hydroxyl group) of a polyhydric alcohol is used as a hydrophilic group. It has an oxyalkylene chain (polyoxyethylene) or the like as a hydrophilic group. The hydrophilicity increases as the number of alcoholic hydroxyl groups (hydroxyl groups) increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant according to the present invention is characterized by having dimethylpolysiloxane as a hydrophobic group.

  When a nonionic surfactant composed of a dimethylpolysiloxane having a hydrophobic group and a polyoxyalkylene having a hydrophilic group is used, unevenness of the antiglare hard coat layer and the low refractive index layer and antifouling property of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

  Specific examples of these nonionic surfactants include, for example, Nippon Unicar Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ- 2163, FZ-2164, FZ-2166, FZ-2191 and the like.

  Moreover, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a linear block copolymer. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle at a plurality of locations so as to cover the surface of the silica fine particle by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

  Specific examples thereof include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208 and the like manufactured by Nippon Unicar Co., Ltd.

  As the fluorine-based surfactant, a surfactant having a hydrophobic group having a perfluorocarbon chain can be used. As types, fluoroalkylcarboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, sodium 3- (fluoroalkyloxy) -1-alkylsulfonate, 3- (ω-fluoroalkanoyl-N-ethylamino) -1- Sodium propanesulfonate, N- (3-perfluorooctanesulfonamido) propyl-N, N-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonic acid Salt, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethyl Ruhonirugurishin salts, phosphoric acid bis (N- perfluorooctylsulfonyl -N- ethylamino ethyl) and the like. In the present invention, nonionic surfactants are preferred.

  These fluorosurfactants are commercially available under the trade names such as Megafac, F-Top, Surflon, Footagen, Unidyne, Florard, Zonyl and the like.

  A preferable addition amount is 0.01 to 3.0%, more preferably 0.02 to 1.0% per solid content contained in the coating liquid of the hard coat layer and the antireflection layer.

  Other surfactants can be used in combination. For example, anionic surfactants such as sulfonates, sulfates, phosphates, etc., and ethers having polyoxyethylene chain hydrophilic groups Type, ether ester type nonionic surfactants and the like may be used in combination.

  The solvent for coating the hard coat layer in the present invention can be appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or can be used by mixing. . Preferably, a solvent containing 5% by mass or more, more preferably 5% by mass to 80% by mass or more of propylene glycol mono (C1-C4) alkyl ether or propylene glycol mono (C1-C4) alkyl ether ester is used.

  As a coating method of the hard coat layer composition coating solution, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, an air doctor coater, a spray coat, an ink jet method can be used. . The coating amount is appropriately 5 μm to 30 μm, preferably 10 μm to 20 μm in terms of wet film thickness. The coating speed is preferably 10 m / min to 200 m / min.

  The antiglare hard coat layer composition is preferably applied and dried and then irradiated with an active energy ray such as an ultraviolet ray or an electron beam to be cured, but the irradiation time of the active energy ray is 0.5 seconds to 5 seconds. Minutes are preferable, and more preferably 3 seconds to 2 minutes from the viewpoint of curing efficiency and work efficiency of the ultraviolet curable resin.

(Antireflection layer)
The antireflection layer used in the present invention may have a single-layer structure consisting of only a low refractive index layer, but it is also preferable to provide a multilayer refractive index layer. A λ / 4 plate has a hard coat layer, and can be laminated on the surface in consideration of the refractive index, film thickness, number of layers, layer order, etc. so that the reflectivity is reduced by optical interference. The antireflection layer is composed of a combination of a high refractive index layer having a higher refractive index than that of the support and a low refractive index layer having a lower refractive index than that of the support, and particularly preferably from three or more refractive index layers. An anti-reflection layer comprising three layers having different refractive indexes from the support side, a medium refractive index layer (having a higher refractive index than the support or anti-glare hard coat layer, and having a higher refractive index than the high refractive index layer). It is preferable that the layers are laminated in the order of (low layer) / high refractive index layer / low refractive index layer.

  Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.

  Examples of preferred layer structures of the antireflection layer according to the present invention are shown below. Here, / indicates that the layers are arranged in layers.

(Λ / 4 plate) / Clear hard coat layer / Low refractive index layer (λ / 4 plate) / Clear hard coat layer / High refractive index layer / Low refractive index layer (λ / 4 plate) / Clear hard coat layer / Medium Refractive index layer / High refractive index layer / Low refractive index layer (λ / 4 plate) / Anti-glare hard coat layer / Low refractive index layer (λ / 4 plate) / Anti-glare hard coat layer / High refractive index layer / Low refractive index layer (λ / 4 plate) / Anti-glare hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Low refractive index on the outermost surface so that dirt and fingerprints can be easily wiped off An antifouling layer can also be provided on the layer. As the antifouling layer, fluorine-containing organic compounds are preferably used.

As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. In the above layer structure, an intermediate layer may be provided as appropriate. For example, an antistatic layer containing conductive polymer fine particles (for example, crosslinked cation fine particles) or metal oxide fine particles (for example, SnO ₂ , ITO) is preferable.

<Low refractive index layer>
In the low refractive index layer used in the present invention, the following hollow spherical silica-based fine particles are preferably used.

(Hollow spherical silica-based fine particles)
The hollow spherical fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having a cavity inside, and the content is a solvent, gas or porous Cavity particles filled with a substance. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle diameter of such hollow spherical fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow spherical fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and are in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. Is desirable. These hollow spherical fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later. The inside of the composite particles may enter and the internal porosity may decrease, and the low refractive index effect may not be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. Moreover, components other than silica may be contained, and specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O _3. , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ and WO _3. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, a pore volume is small and particles having a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a material having a lower refractive index. is there.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Examples of the porous substance include those composed of the compounds exemplified for the porous particles. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow spherical fine particles, for example, the method for preparing complex oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow spherical fine particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound, or the like to a silicate solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. Can do. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using a seed particle dispersion, the pH of the seed particle dispersion is adjusted to 10 or higher, and then an aqueous solution of the compound is added to the above-mentioned alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and an inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to an oxide (MO _X ), and the molar ratio of MO _X / SiO ₂ is 0.05 to 2.0, Preferably it is in the range of 0.2-2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing the hollow particles, the molar ratio of MO _X / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  Further, when preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organic silicon compound used for the silica protective film formed of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, such as acrylic group An alkoxysilane represented by a hydrocarbon group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or the ratio of water to the organic solvent is high, it is possible to form a silica protective film using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third step: Formation of silica coating layer In the third step, the porous particle dispersion prepared in the second step (in the case of hollow particles, the hollow particle precursor dispersion) contains a fluorine-substituted alkyl group-containing silane compound. By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, An alkoxysilane represented by a hydrocarbon group such as an acryl group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilanes, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particles (cavity particle precursor in the case of hollow particles) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the silica coating layer finally obtained has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of the hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. The refractive index of the low refractive index layer used in the present invention is preferably 1.30 to 1.50, and more preferably 1.35 to 1.44.

In the present invention, the commercially available SiO ₂ fine particles can be used. Specific examples of commercially available particles include P-4 manufactured by Catalytic Chemical Industry Co., Ltd.

  The content (mass) of the hollow spherical silica-based fine particles A having an outer shell layer and having a porous or hollow interior in the low refractive index layer coating solution is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass. % By mass.

(Tetraalkoxysilane compound or hydrolyzate thereof)
The low refractive index layer used in the present invention preferably contains a tetraalkoxysilane compound or a hydrolyzate thereof as a sol-gel material.

  As a material for the low refractive index layer used in the present invention, it is also preferable to use a silicon oxide having an organic group in addition to the inorganic silicon oxide. These are generally called sol-gel materials, but metal alcoholates, organoalkoxy metal compounds and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. Tetraalkoxysilane and its hydrolyzate are particularly preferable.

  In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  When hydrolyzing the tetraalkoxysilane, it is preferable to mix the inorganic fine particles in order to increase the film strength.

  The low refractive index layer used in the present invention preferably contains the silicon oxide and the following silane coupling agent.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Specific examples of the silane coupling agent include: Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-403, KBM-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE- 503, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-802, KBM-803 and the like.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  A specific method of surface treatment with a coupling agent is shown below.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the above-described silicon oxide particles and the surface of the silicon oxide having an organic group easily react, and a stronger film is formed. Moreover, you may add the hydrolyzed silane coupling agent in a coating liquid previously.

  The low refractive index layer can also contain a polymer in an amount of 5 to 50% by weight. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treating agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and by polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out by combining two or all of the above (1) to (3), and to carry out by combining (1) and (3) or (1) to (3) all combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out by chemical surface treatment alone or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the fine particles are made of SiO _{2, the} surface treatment with the above-described silane coupling agent can be carried out particularly effectively.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Examples include fluorinated vinyl ethers and esters of fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. In place of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

  Further, the low refractive index layer used in the present invention may be a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”). .

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical), M-2020 (manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). In the latter, it is possible to introduce a crosslinked structure by adding a compound having a group that reacts with a functional group in the polymer and one or more reactive groups after copolymerization, as disclosed in JP-A-10-25388 and 10-147739. In the issue. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is crosslinked by heating with a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, it is a thermosetting type. In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, the ionizing radiation curable type is used.

  In addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR), etc. Can be mentioned.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  The low refractive index layer used in the present invention is applied by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (US Pat. No. 2,681,294). Can be formed. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).

  The film thickness of the low refractive index layer used in the present invention is preferably 50 to 200 nm, and more preferably 60 to 150 nm.

<High refractive index layer and medium refractive index layer>
In the present invention, it is preferable to provide a high refractive index layer between the hard coat layer and the low refractive index layer in order to reduce the reflectance. Alternatively, it is more preferable to provide a middle refractive index layer between the docoat layer and the high refractive index layer. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of the high refractive index layer and the middle refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 100 nm. The haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  The refractive index formed by applying and drying a coating solution containing a monomer, oligomer or hydrolyzate of an organotitanium compound represented by the following general formula (9) in the high refractive index layer used in the present invention. A layer having a rate of 1.55 to 2.5 is preferred.

General formula (9): Ti (OR ₁ ) ₄
In the formula, R ₁ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , and Ti (Oi−). C ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ dimer to 10-mer, Ti (Oi-C ₃ H ₇ ) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These can be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ 2-10 mer, 2-10 mer _{Ti (O-n-C 4} H 9) 4 are particularly preferred.

  Among the coating solutions for the high refractive index layer used in the present invention, it is preferable to add the organic titanium compound to a solution in which water and an organic solvent described later are sequentially added. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds. When the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 mol, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and cloudiness, which is not preferable. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  The organic solvent used in the present invention is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The organic titanium compound monomer, oligomer or hydrolyzate thereof used in the present invention preferably occupies 50.0 mass% to 98.0 mass% of the solid content contained in the coating solution. The solid content ratio is more preferably 50% by mass to 90% by mass, and further preferably 55% by mass to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and medium refractive index layer used in the present invention preferably contain metal oxide particles as fine particles, and further contain a binder polymer.

  When the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The weight average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent is most preferable.

  Two or more types of coupling agents may be used in combination, and in addition to the silane coupling agent, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are easy to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In this invention, you may process by combining 2 or more types of surface treatment. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The high refractive index layer and medium refractive index layer used in the present invention preferably use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide, and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Further, it is further preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, the anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated. The linking group that binds the anionic group and the polymer chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the ratio of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or the quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, and more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably a carbon number. 1 to 6 alkyl groups. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by a polymerization reaction at the same time as or after application of the coating solution by preparing a coating solution for forming a high refractive index layer and a medium refractive index layer by blending a monomer for generating a crosslinked polymer. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method of forming a crosslinked polymer by polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of an anti-glare hard-coat layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, and alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

  In addition to the above-described components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the antireflection layer or coating liquid thereof includes a polymerization inhibitor, a leveling agent, a thickener, and an anti-coloring agent. An agent, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.

  In order to promote hydrolysis or hardening of the composition containing the metal alkoxide after the application of the middle to high refractive index layer and the low refractive index layer according to the present invention, it is preferable to irradiate active energy rays. More preferably, the active energy ray is irradiated every time each layer is coated.

The active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, and γ ray, but ultraviolet ray and electron beam are preferable, and handling is particularly simple and high energy. Ultraviolet rays are preferred because they can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. 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. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated is preferably ^{20mJ / cm 2 ~10,000mJ / cm 2} , more ^preferably from ^{100mJ / cm 2 ~2,000mJ / cm 2} , particularly preferably 400 mJ / Cm ^{2 to} 2,000 mJ / cm ² .

  When ultraviolet rays are used, the multilayer antireflection layer may be irradiated one by one, or may be irradiated after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

(Antireflection layer thickness)
The thickness of each refractive index layer constituting the antireflection layer is preferably in the range of 1 nm to 200 nm, more preferably 5 nm to 150 nm, but each film has an appropriate thickness depending on the refractive index of each layer. It is preferable to select.

(Reflectivity of antireflection layer)
The antireflection layer used in the present invention preferably has an average reflectance at 450 nm to 650 nm of 1% or less, particularly preferably 0.5% or less. Further, the minimum reflectance in this range is particularly preferably from 0.00 to 0.3%.

  The refractive index and film thickness of the antireflection layer can be calculated and calculated by measuring the spectral reflectance. Moreover, the reflective optical characteristic of the produced low reflection film can measure a reflectance on the conditions of a 5-degree regular reflection using a spectrophotometer. In this measurement method, after roughening the substrate surface on which the antireflection layer is not applied, a light absorption treatment is performed using a black spray to prevent reflection of light on the back surface of the film and reflectivity. Is measured.

  In the measurement, the transmittance at a transmittance of 550 nm is measured using a spectrophotometer with reference to air.

(Polarizer)
The polarizing plate using the λ / 4 plate of the present invention is a polarizing plate in which the λ / 4 plate, a polarizer, and an optical film are provided in this order, and the optical film has the following requirements (1) or ( 2) is satisfied (see FIG. 5).
(1) The in-plane retardation value Ro (590) defined by the following formula (I) is in the range of 20 to 150 nm, and the retardation value Rt in the thickness direction defined by the following formula (II) ( 590) is in the range of 70-400 nm .
(2) The in-plane retardation value Ro (590) defined by the following formula (I) is in the range of 0 to 2 nm, and the retardation value Rt in the thickness direction defined by the following formula (II) ( 590) is within the range of -15-15 nm.
Formula (I): Ro (590) = (nx−ny) × d (nm)
Formula (II): Rt (590) = {(nx + ny) / 2−nz} × d (nm)
[In the above formula, Ro (590) represents the in-plane retardation value in the film at the measurement wavelength of 590 nm, and Rt (590) represents the retardation value in the thickness direction in the film at the measurement wavelength of 590 nm. D represents the thickness (nm) of the optical film, nx represents the maximum in-plane refractive index at the measurement wavelength of 590 nm, and is also referred to as the refractive index in the slow axis direction. ny represents the refractive index in the direction perpendicular to the slow axis in the film plane at the measurement wavelength of 590 nm, and nz represents the refractive index of the film in the thickness direction at the measurement wavelength of 590 nm. The measurement is performed in a 23 ° C./55% RH environment. ]
The polarizing plate according to the present invention is manufactured by using a stretched polyvinyl alcohol doped with iodine or a dichroic dye as a polarizer, and laminating with a configuration of λ / 4 plate / polarizer / optical film. be able to. The λ / 4 plate of the present invention is bonded to the viewing side.

<Optical film for polarizing plate>
The optical film used in the present invention is composed of cellulose acetate, plasticizer, ultraviolet absorber, antioxidant, retardation adjusting agent, matting agent, deterioration inhibitor, peeling aid, and surface activity used in the above-mentioned λ / 4 plate. An agent or the like can be preferably used.

  Retardation values Ro and Rt defined by the following formula are 20 to 150 nm and 70 to 400 nm, respectively, for the optical film bonded to the surface opposite to the surface on which the λ / 4 plate is bonded to the polarizer. Or an optical film satisfying 0 nm ≦ Ro ≦ 2 nm and −15 nm ≦ Rt ≦ 15 nm is preferably bonded.

Formula (i) Ro = (nx−ny) × d
Formula (ii) Rt = ((nx + ny) / 2−nz) × d
In the formula, nx, ny, and nz are the refractive index nx at 23 ° C./55% RH and 590 nm (also referred to as the maximum refractive index in the plane of the film and the refractive index in the slow axis direction), ny (in the plane of the film). And nz (the refractive index of the film in the thickness direction), and d is the thickness (nm) of the film.

  The optical film has retardation values Ro and Rt in the ranges of 20 to 150 nm and 70 to 400 nm, respectively. Particularly, when the optical film is used as an optical compensation film of a VA liquid crystal display device having a VA mode liquid crystal cell, the Ro value is set. 30 to 100 nm, Rt value is 70 to 250 nm when two optical compensation films are used for the VA liquid crystal display device, and Rt value is 150 when one optical film is used for the VA liquid crystal display device. It is preferable that it is -400 nm.

  As the optical film, for example, a method of supporting a discotic liquid crystalline compound, which is a compound having negative uniaxiality, on a support (see, for example, JP-A-7-325221), positive optical anisotropy. A method in which a nematic polymer liquid crystalline compound having a hybrid orientation in which the pretilt angle of liquid crystal molecules changes in the depth direction is supported on a support (see, for example, JP-A-10-186356), positive By forming a nematic liquid crystal compound having optical anisotropy of 2 layers on a support and setting the orientation direction of each layer to approximately 90 °, pseudo-uniaxially similar optical characteristics are imparted. Instead of a conventional TAC film or an optical film having an optically anisotropic layer provided on a support by a method (for example, see JP-A-8-15681). An optical film having the function of a retardation film by developing a retardation of the rosin derivative film by saponification and laminating a PVA polarizer (see, for example, JP-A-2003-270442), Examples include, but are not limited to, optical compensation films obtained by adding a retardation adjusting agent to a cellulose ester film to obtain a retardation film (see, for example, JP-A Nos. 2000-275434 and 2003-344655). Is not to be done.

  These optical films are preferably polymer films, and are preferably easy to produce, optically uniform, and optically transparent. Any of these may be used, for example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate. Polyester film such as polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin Film, polymethylpentene film, polyetherketone film, Polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, a cycloolefin polymer film, a polyvinyl acetal resin film, there may be mentioned polymethyl methacrylate film, or an acrylic film or the like, but are not limited to. As these films, films formed by a solution casting method or a melting method are preferably used. Of these, cellulose ester film, polycarbonate film, polysulfone (including polyethersulfone) and cycloolefin polymer film are preferred. In the present invention, cellulose ester film and cycloolefin polymer film are particularly advantageous in terms of production, cost and transparency. From the viewpoints of uniformity, adhesion and the like. For example, commercially available cellulose ester films include Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC16UR, KC4UE, KC8UE, KC4UE, KC4F Etc.) are preferably used.

  The most preferred optical film is a cellulose ester film stretched in the film width direction by a tenter device or the like.

  The optical film used in the present invention can also be used as a polarizing plate protective film used in a transverse electric field switching mode type (also referred to as IPS mode type) liquid crystal display device, in which case the retardation value is 0 nm ≦ An optical film satisfying Ro ≦ 2 nm and −15 nm ≦ Rt ≦ 15 nm is preferable. The optical film preferably contains an acrylic polymer containing a cellulose ester and having a weight average molecular weight of 500 or more and 30000 or less, and among them, an ethylenically unsaturated monomer Xa and a molecule having no aromatic ring and no hydrophilic group in the molecule. Polymer X having a weight average molecular weight of 5,000 to 30,000 obtained by copolymerization with ethylenically unsaturated monomer Xb having no aromatic ring and having a hydrophilic group, more preferably an aromatic ring and a hydrophilic group in the molecule Polymer having a weight average molecular weight of 5,000 to 30,000 obtained by copolymerizing an ethylenically unsaturated monomer Xa having no functional group and an ethylenically unsaturated monomer Xb having no hydrophilic ring in the molecule and having a hydrophilic group A weight average molecular weight of 500 or more and 3000 or less obtained by polymerizing X and an ethylenically unsaturated monomer Ya having no aromatic ring Preferably contains a polymer Y.

<Polymer X, Polymer Y>
The polymer X used in the present invention comprises an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule and an ethylenically unsaturated monomer Xb having no aromatic ring and having a hydrophilic group in the molecule. It is a polymer having a weight average molecular weight of 5,000 to 30,000 obtained by copolymerization.

  Preferably, Xa is an acrylic or methacrylic monomer that does not have an aromatic ring and a hydrophilic group in the molecule, and Xb is an acrylic or methacrylic monomer that does not have an aromatic ring in the molecule and has a hydrophilic group.

  The polymer X used in the present invention is represented by the following general formula (X).

General formula (X):-(Xa) m- (Xb) n- (Xc) p-
More preferably, it is a polymer represented by the following general formula (X-1).

Formula _{(X-1): - [} CH 2 -C (-R 1) (- CO 2 R 2)] m- [CH 2 -C (-R 3) (- CO 2 R 4 -OH) -] n- [Xc] p-
(Wherein R ₁ and R ₃ represent H or CH _3. R ₂ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. R ₄ represents —CH ₂ — or —C ₂ H ₄ —. Or -C ₃ H _6- , Xc represents a monomer unit polymerizable to Xa and Xb, and m, n and p represent molar composition ratios, where m ≠ 0, n ≠ 0, k ≠ 0. M + n + p = 100.)
Although the monomer as a monomer unit which comprises the polymer X used for this invention is mentioned below, it is not limited to this.

  In X, the hydrophilic group means a hydroxyl group (hydroxyl group) or a group having an ethylene oxide chain.

  Examples of the ethylenically unsaturated monomer Xa having no aromatic ring and no hydrophilic group in the molecule include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), and butyl acrylate (n-, i- , S-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n- I-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl) ), Acrylic acid (2-ethoxyethyl), or the like, or those obtained by replacing the acrylic ester with a methacrylic ester. Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate (i-, n-) are preferable.

  The ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydrophilic group is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxyl group (hydroxyl group). For example, acrylic acid (2- Hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), or these acrylic acids replaced with methacrylic acid Among them, acrylic acid (2-hydroxyethyl) and methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), and acrylic acid (3-hydroxypropyl) are preferable.

  Xc is not particularly limited as long as it is an ethylenically unsaturated monomer other than Xa and Xb and copolymerizable, but preferably has no aromatic ring.

  The molar composition ratio m: n of Xa, Xb and Xc is preferably in the range of 99: 1 to 65:35, more preferably in the range of 95: 5 to 75:25. P of Xc is 0-10. Xc may be a plurality of monomer units.

  When the molar composition ratio of Xa is large, the compatibility with the cellulose ester is improved, but the retardation value Rt in the film thickness direction is increased. When the molar composition ratio of Xb is large, the compatibility is deteriorated, but the effect of reducing Rt is high. Further, if the molar composition ratio of Xb exceeds the above range, haze tends to occur during film formation, and it is preferable to optimize these and determine the molar composition ratio of Xa and Xb.

  As for the molecular weight of the polymer X, the weight average molecular weight is from 5,000 to 30,000, more preferably from 8,000 to 25,000.

  By setting the weight average molecular weight to 5,000 or more, it is preferable because the cellulose ester film has advantages such as less dimensional change under high temperature and high humidity and less curling as a polarizing plate protective film. When the weight average molecular weight is within 30000, the compatibility with the cellulose ester is further improved, and bleeding out under high temperature and high humidity and further haze generation immediately after film formation are suppressed.

  The weight average molecular weight of the polymer X used in the present invention can be adjusted by a known molecular weight adjusting method. Examples of such a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like. The polymerization temperature is usually from room temperature to 130 ° C., preferably from 50 ° C. to 100 ° C., but this temperature or the polymerization reaction time can be adjusted.

  The measuring method of a weight average molecular weight can be based on the following method.

(Weight average molecular weight measurement method)
The weight average molecular weight Mw was measured using gel permeation chromatography.

  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: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000 to 500 calibration curves were used. Thirteen samples are used at approximately equal intervals.

  The polymer Y used in the present invention is a polymer having a weight average molecular weight of 500 or more and 3000 or less obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring. A weight average molecular weight of 500 or more is preferable because the residual monomer of the polymer is reduced. Moreover, it is preferable to set it as 3000 or less in order to maintain retardation value Rt fall performance. Ya is preferably an acrylic or methacrylic monomer having no aromatic ring.

  The polymer Y used in the present invention is represented by the following general formula (Y).

General formula (Y):-(Ya) k- (Yb) q-
More preferably, it is a polymer represented by the following general formula (Y-1).

Formula _{(Y-1): - [} CH 2 -C (-R 5) (- CO 2 R 6)] k- [Yb] q-
(In the formula, R ₅ represents H or CH _3. R ₆ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. Yb represents a monomer unit copolymerizable with Ya. K and q Represents a molar composition ratio, where k ≠ 0 and k + q = 100.)
Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Yb may be plural. k + q = 100, q is preferably 0-30.

  The ethylenically unsaturated monomer Ya constituting the polymer Y obtained by polymerizing an ethylenically unsaturated monomer having no aromatic ring is, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i- , N-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (N-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), cyclohexyl acrylate, acrylic acid (2- Ethyl hexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropiyl) ), Acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), methacrylic acid ester, the above acrylic acid ester changed to methacrylic acid ester; unsaturated acid, for example, acrylic acid, methacrylic acid And maleic anhydride, crotonic acid, itaconic acid and the like.

  Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, and vinyl caproate. Vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate and the like are preferred. Yb may be plural.

  In order to synthesize the polymers X and Y, it is difficult to control the molecular weight in normal polymerization, and it is desirable to use a method that can make the molecular weights as uniform as possible without increasing the molecular weight. Such polymerization methods include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than normal polymerization, and a mercapto compound in addition to the polymerization initiator. And a method using a chain transfer agent such as carbon tetrachloride, a method using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further disclosed in JP-A No. 2000-128911 or 2000-344823. Examples thereof include a compound having one thiol group and a secondary hydroxyl group (hydroxyl group), or a bulk polymerization method using a polymerization catalyst in which the compound and an organometallic compound are used in combination. Although it is preferably used in the present hydroxyl group (hydroxyl group), in particular, the polymer Y has a thiol group and a secondary group in the molecule. The polymerization method of using a compound having a Dorokishiru group (hydroxyl group) as a chain transfer agent is preferred. In this case, the terminal of the polymer Y has a hydroxyl group (hydroxyl group) and a thioether resulting from the polymerization catalyst and the chain transfer agent. The compatibility of Y and cellulose ester can be adjusted by this terminal residue.

  The hydroxyl values of the polymers X and Y are preferably 30 to 150 [mg KOH / g].

(Method for measuring hydroxyl (hydroxyl) value)
This measurement conforms to JIS K 0070 (1992). This hydroxyl (hydroxyl group) value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group (hydroxyl group) when 1 g of a sample is acetylated. Specifically, sample Xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml) is accurately added thereto. An air cooling tube is attached to the mouth of the flask and heated in a glycerin bath at 95-100 ° C. After 1 hour and 30 minutes, the mixture is cooled, 1 ml of purified water is added from an air condenser, and acetic anhydride is decomposed into acetic acid. Next, titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution using a potentiometric titrator, and the inflection point of the obtained titration curve is set as the end point. Further, as a blank test, titration is performed without a sample, and an inflection point of the titration curve is obtained. The hydroxyl (hydroxyl) value is calculated by the following formula.

Hydroxyl (hydroxyl group) value = {(BC) × f × 28.05 / X} + D
(Wherein B is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test (ml), and C is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the titration (ml). F is a factor of 0.5 mol / L potassium hydroxide ethanol solution, D is an acid value, and 28.05 is 1/2 of 1 mol amount of potassium hydroxide 56.11)
The above-mentioned polymer X and polymer Y are both excellent in compatibility with cellulose ester, excellent in productivity without evaporation and volatilization, good retention as a protective film for polarizing plates, low moisture permeability, and dimensional stability. Are better.

The content of the polymer X and the polymer Y in the cellulose ester film is preferably in a range satisfying the following formulas (i) and (ii). When the content of the polymer X is Xg (mass% = the mass of the polymer X / the mass of the cellulose ester × 100) and the content of the polymer Y is Yg (mass%),
Formula (i) 5 ≦ Xg + Yg ≦ 35 (mass%)
Formula (ii) 0.05 ≦ Yg / (Xg + Yg) ≦ 0.4
A preferable range of the formula (i) is 10 to 25% by mass.

  If the total amount of the polymer X and the polymer Y is 5% by mass or more, the polymer X and the polymer Y sufficiently act to reduce the retardation value Rt. Moreover, if it is 35 mass% or less as a total amount, adhesiveness with a polyvinyl alcohol-type polarizer will be favorable.

  The polymer X and the polymer Y can be directly added and dissolved as materials constituting the dope solution, or can be added to the dope solution after being previously dissolved in an organic solvent for dissolving the cellulose ester.

  Examples of the polarizer preferably used in the polarizing plate according to the present invention include a polyvinyl alcohol polarizing film, which includes a polyvinyl alcohol film dyed with iodine and a dichroic dye dyed. As the polyvinyl alcohol film, a modified polyvinyl alcohol film modified with ethylene is preferably used. For the polarizer, a polyvinyl alcohol aqueous solution is formed into a film and dyed by uniaxial stretching or dyed or uniaxially stretched and then preferably subjected to a durability treatment with a boron compound. Stretching is preferably performed uniaxially in the film forming direction, or in the direction of 45 ° obliquely with respect to the film forming direction, similarly to the λ / 4 plate described above.

  The film thickness of the polarizer is 5 to 40 μm, preferably 5 to 30 μm, and particularly preferably 5 to 20 μm. On the surface of the polarizer, the λ / 4 plate of the present invention and one side of the polarizing plate protective film B are bonded to form a polarizing plate.

  The polarizing plate can be produced by a general method. The λ / 4 plate of the present invention that has been subjected to alkali saponification treatment can be bonded to at least one surface of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. preferable. It is preferable to paste the polarizing plate protective film B on the other surface.

  The polarizing plate can be constructed by further bonding a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection.

<Liquid crystal display device>
By using the polarizing plate according to the present invention as a liquid crystal display device bonded to the surface on the viewing side of the liquid crystal cell, the display image is difficult to see depending on the direction of the polarization axis even when observed through an optical member having a polarizing action such as polarized sunglasses. Therefore, the liquid crystal display device according to the present invention having higher durability against the use environment can be manufactured. The polarizing plate according to the present invention is a reflective type, transmissive type, transflective type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. Preferably used.

  The position of the polarizing plate according to the present invention in the liquid crystal display device needs to be arranged on the viewing side with respect to the liquid crystal cell, and the linearly polarized light is circularly polarized by further arranging the λ / 4 plate of the present invention on the viewing side. It is possible to greatly improve the visibility when observed through an optical member having a polarizing action such as polarized sunglasses.

(3D image display device)
The λ / 4 plate of the present invention can be used in various modes in a stereoscopic image display device. For example, a stereoscopic image display device including a liquid crystal display device and liquid crystal shutter glasses, wherein the liquid crystal shutter glasses are provided with (1) a λ / 4 plate, a liquid crystal cell, and a polarizer in this order, or ( 2) It can be used in a stereoscopic video display device characterized by being liquid crystal shutter glasses in which a λ / 4 plate, a polarizer, a liquid crystal cell, and a polarizer are provided in this order.

  FIG. 6 shows a schematic diagram of a stereoscopic image display apparatus according to the above aspect (1) (a system in which the polarizing plate of the glasses is a single sheet). Further, FIG. 7 shows a schematic diagram of the above-described aspect (2) (system in which the polarizing plate of the glasses is one sheet).

  In any case, the front polarizing plate of the liquid crystal display device has a configuration in which a λ / 4 plate, a polarizer, an optical film cell, and a polarizer are provided in this order.

  In the present invention, the above aspect and configuration can reduce crosstalk or luminance reduction and color change when tilting the head when viewing stereoscopic (3D) video images, and maintain excellent visibility in the usage environment. Therefore, it is possible to provide a stereoscopic image display device having higher durability against the use environment.

  Hereinafter, although an example is given and the present invention is explained, the present invention is not limited to these.

Example 1
<Production of λ / 4 plate 101>
<Fine particle dispersion 1>
Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle addition liquid 1>
The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.

Methylene chloride 99 parts by mass Fine particle dispersion 1 5 parts by mass A main dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose acetate was added to a pressurized dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope solution was prepared by filtration using 244.

<Composition of main dope solution>
Methylene chloride 340 parts by mass Ethanol 64 parts by mass Cellulose acetate having an acetyl group substitution degree of 2.4 100 parts by mass Sugar ester compound 1-23 10.0 parts by mass Polyester (b) 2.5 parts by mass Ultraviolet absorber (Tinuvin 928 ( Ciba Japan Co., Ltd.)) 2.3 parts by mass Particulate additive solution 1 1 part by mass The above was put into a sealed container and dissolved while stirring to prepare a dope solution. Next, an endless belt casting apparatus was used to uniformly cast the dope solution on a stainless steel belt support at a temperature of 33 ° C. and a width of 2000 mm. The temperature of the stainless steel belt was controlled at 30 ° C.

  On the stainless steel belt support, the solvent was evaporated until the residual solvent amount in the cast (cast) film was 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.

  After peeling off the peeled cellulose acetate film, using the apparatus described in Example 1 of JP 2009-214441 (stretching machine A: FIG. 11), the temperature is 170 ° C., the magnification is 1.5 times, and the slow axis is Stretching was performed in an oblique direction so as to form 45 ° with the film width direction.

  Next, drying was terminated while the drying zone was conveyed by a number of rolls. The drying temperature was 130 ° C. and the transport tension was 100 N / m.

  As described above, a λ / 4 plate 101 having a dry film thickness of 40 μm was obtained.

<Production of λ / 4 plates 102-108, 110-114>
The λ / 4 plates 102 to 108 and 110 to 114 were produced in the same manner as the λ / 4 plate 101 except that the dope composition and manufacturing conditions were changed as shown in Tables 1 and 2.

<Production of λ / 4 plate 109>
It is the same as 108 until peeling from the stainless steel belt support. Then, with the speed difference between the part to cut the tension of the peeled part (roll) and the part to which the next transport tension is applied (roll) 1.6 times in the direction parallel to the casting direction at 170 ° C The film was conveyed while being stretched. Furthermore, it was transported for 30 minutes in a drying zone set at 130 ° C. and dried to produce a λ / 4 plate 109 having a thickness of 1500 mm, an end having a width of 1 cm and a height of 8 μm and a thickness of 80 μm.

  In addition, the synthesis | combining methods of polyester (a) and (b) used when producing various (lambda) / 4 board are as follows.

<Synthesis of polyester (a)>
In a nitrogen atmosphere, 19.2 g of dimethyl 2,6-naphthalenedicarboxylate, 14.9 g of 1,2-propylene glycol and 20 mg of tetraisopropyl titanate were mixed, and the mixture was stirred at 165 ° C. for 1 hour while distilling off the produced methanol. It was. The mixture was further stirred at 185 ° C. for 1 hour, then heated to 195 ° C. and stirred for 18 hours. Next, the temperature was lowered to 170 ° C., and unreacted 1,2-propylene glycol was distilled off under reduced pressure to obtain a polyester polyol (a).

Acid value: 0.2
Number average molecular weight: 1020
Dispersity: 1.6
Component content of molecular weight 300-1800: 48%
Hydroxyl (hydroxyl) value: 110
Hydroxyl content: 100%
It was confirmed by ¹ H-NMR that there was no methyl ester residue at the end.

<Synthesis of polyester (b)>
In a nitrogen atmosphere, 4.85 g of dimethyl terephthalate, 4.4 g of 1,2-propylene glycol, 6.8 g of p-toluic acid, and 10 mg of tetraisopropyl titanate were mixed and stirred at 140 ° C. for 2 hours. Stirring was carried out at ° C for 16 hours. Next, the temperature was lowered to 170 ° C., and unreacted 1,2-propylene glycol was distilled off under reduced pressure to obtain a comparative polyester (b).

Acid value: 0.1
Number average molecular weight: 490
Dispersity: 1.4
Component content of molecular weight 300-1800: 90%
Hydroxyl (hydroxyl) value: 0.1
Hydroxyl content: 0.04%
Since the comparison polyester 3 uses 2 times mole of monocarboxylic acid with respect to dicarboxylic acid, the terminal is toluic acid ester.

  For each of the obtained λ / 4 plates, the retardation value was measured as follows.

<Measurement of retardation Ro and Rt>
A 35 mm × 35 mm sample was cut out from the obtained film, conditioned at 23 ° C. and 55% RH for 2 hours, and the value measured at 550 nm with an automatic birefringence meter (KOBRA21DH, Oji Scientific Co., Ltd.) 550) and Rt (550). The difference between Ro (450), which is a retardation value measured at a wavelength of 450 nm, and Ro (550), which is a retardation value measured at a wavelength of 550 nm, was defined as Ro (550) -Ro (450).

<< Evaluation of Ro environmental change >>
Ro was measured at 550 nm under 23 ° C./20% RH for 24 hours and defined as Ro [20%]. Further, Ro was measured for 24 hours at 23 ° C./80% RH and measured at 550 nm under 23 ° C./80% RH, and defined as Ro [80%]. And the difference of both: Ro [20%]-Ro [80%] was evaluated as Ro environmental fluctuation value.

  Tables 1 and 2 collectively show the contents and measurement results of the various λ / 4 plates obtained above.

  As is apparent from the results shown in Tables 1 and 2, by the means of the present invention, an appropriate function as a retardation film is imparted to a cellulose acetate film having a low retardation with high retardation (retardation). It can be seen that it is possible to provide a λ / 4 plate that has a small fluctuation of the in-plane retardation value Ro with respect to environmental fluctuations and can be made thinner with an inexpensive material.

(Coating of hard coat layer)
Next, the following hard coat layer was provided on one surface of the λ / 4 plates 101 to 114 to prepare λ / 4 plates 101hc to 114hc.

<Applying hard coat layer>
The following hard coat layer coating solution is die-coated with a coating width of 1.4 m, dried at 80 ° C., and then irradiated with 120 mJ / cm ² ultraviolet light with a high-pressure mercury lamp so that the film thickness after curing is 6 μm. A layer was provided.

(Coating solution for hard coat layer)
Acetone 45 parts by mass Ethyl acetate 45 parts by mass Propylene glycol monomethyl ether 10 parts by mass Pentaerythritol triacrylate 30 parts by mass Pentaerythritol tetraacrylate 45 parts by mass Urethane acrylate (trade name U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass 1- Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Japan) 5 parts by mass 2-methyl-1- [4- (methylthio) phenyl] -2-monoforino-1-one (Irgacure 907, Ciba Japan) 3 parts by mass BYK-331 (silicone surfactant, manufactured by Big Chemie Japan Co., Ltd.)
0.5 part by mass The following antireflection layer was further provided on the prepared hard coat layer to obtain λ / 4 plates 101ar to 111ar.

<Application of antireflection layer>
(Application of medium refractive index layer)
The following medium refractive index layer coating solution is die-coated on the surface of the hard coat layer, dried at 80 ° C., and then irradiated with 120 mJ / cm ² of ultraviolet light with a high-pressure mercury lamp so that the cured film thickness becomes 110 nm. A medium refractive index layer was provided. The refractive index was 1.60.

<Medium refractive index layer coating solution>
<Preparation of particle dispersion A>
Methanol-dispersed antimony double oxide colloid (solid content 60%, zinc antimonate sol manufactured by Nissan Chemical Industries, Ltd., trade name: Celnax CX-Z610M-F2) 6.0 kg of isopropyl alcohol was gradually stirred with stirring. To prepare a particle dispersion A.

PGME (propylene glycol monomethyl ether) 40 parts by mass Isopropyl alcohol 25 parts by mass Methyl ethyl ketone 25 parts by mass Pentaerythritol triacrylate 0.9 parts by mass Pentaerythritol tetraacrylate 1.0 part by mass Urethane acrylate (trade name: U-4HA Shin-Nakamura Chemical Co., Ltd.) 0.6 parts by mass Particle dispersion A 20 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Japan) 0.4 parts by mass 2-methyl-1- [4- (methylthio) ) Phenyl] -2-monoforinopropan-1-one (Irgacure 907, manufactured by Ciba Japan) 0.2 parts by mass 10% FZ-2207, propylene glycol monomethyl ether solution (manufactured by Nihon Unicar) 0.4 mass Department (Low Application of the folding index layer)
On the medium refractive index layer, the following low refractive index layer coating solution is die-coated, dried at 80 ° C., and then irradiated with 120 mJ / cm ² of ultraviolet light with a high pressure mercury lamp so that the film thickness becomes 92 nm. A rate layer was provided to prepare an antireflection layer. The refractive index was 1.38.

(Low refractive index layer coating solution)
<Preparation of tetraethoxysilane hydrolyzate A>
After mixing 230 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol and adding 120 g of a 2% aqueous acetic acid solution thereto, the mixture is stirred for 26 hours at room temperature (25 ° C.). Silane hydrolyzate A was prepared.

Propylene glycol monomethyl ether 430 parts by mass Isopropyl alcohol 430 parts by mass Tetraethoxysilane hydrolyzate A 120 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 parts by mass Isopropyl alcohol dispersion Hollow silica sol (solid content 20%,
Silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209) 40 parts by mass Aluminum ethyl acetoacetate diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd.) 3.0 parts by mass 10% FZ-2207, propylene glycol monomethyl ether solution ( Made by Nippon Unicar Co., Ltd.) 3.0 parts by mass (production of optical film 201)
<Fine particle dispersion 1>
Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle addition liquid 1>
The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.

Methylene chloride 99 parts by mass Fine particle dispersion 1 5 parts by mass A main dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose acetate was added to a pressurized dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope solution was prepared by filtration using 244.

<Composition of main dope solution>
Methylene chloride 340 parts by weight Ethanol 64 parts by weight Cellulose acetate having an acetyl group substitution degree of 2.4 100 parts by weight Sugar ester compound 1-23 10.0 parts by weight Polyester (b) 2.5 parts by weight Ultraviolet absorber (Tinuvin 928 ( (Manufactured by Ciba Japan Co., Ltd.)) 2.3 parts by mass Fine particle additive liquid 1 1 part by mass The above composition was put into a sealed container and dissolved while stirring to prepare a dope solution. Next, an endless belt casting apparatus was used to uniformly cast the dope solution on a stainless steel belt support at a temperature of 33 ° C. and a width of 2000 mm. The temperature of the stainless steel belt was controlled at 30 ° C.

  On the stainless steel belt support, the solvent was evaporated until the residual solvent amount in the cast (cast) film was 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.

  Thereafter, the film is stretched 1.4 times in the width direction by a tenter set at 170 ° C., then dried by being transported for 30 minutes in a drying zone set at 130 ° C., 2 m wide and 1 cm wide at the end. An optical film 201 having a film thickness of 40 μm having a knurling height of 8 μm was produced and wound up at 5000 m.

  The retardation values Ro (590) and Rt (590) of the optical film 201 were 50 nm and 130 nm, respectively.

<Preparation of polarizing plates 101-108, 110-114>
A 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 polarizer.

  Next, polarizers 101 to 108 and 110 to 114 were prepared by laminating the polarizer and the λ / 4 plates 101 to 108 and 110 to 114 according to the following steps 1 to 5 and the optical film 201 on the back surface side.

  Step 1: λ / 4 plates 101 to 108, 110 to 114, which were immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to saponify the side to be bonded to the polarizer. Obtained.

  Process 2: The said polarizer was immersed in the polyvinyl alcohol adhesive tank of 2 mass% of solid content for 1-2 seconds.

  Step 3: Excess adhesive adhered to the polarizer in Step 2 was gently wiped off and placed on the λ / 4 plates 101-108, 110-114 treated in Step 1.

Step 4: The λ / 4 plates 101 to 108, 110 to 114, the polarizer, and the optical film 201 laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm ² and a conveyance speed of about 2 m / min.

  Step 5: Samples obtained by bonding the polarizer prepared in Step 4 with the λ / 4 plates 101 to 108, 110 to 114, and the optical film 201 in a dryer at 80 ° C. are dried for 2 minutes. Polarizing plates 101 to 108 and 110 to 114 corresponding to the plates 101 to 108 and 110 to 114 were produced.

<Preparation of Polarizing Plate 109>
A polarizing plate was prepared in the same manner except that 4UY manufactured by Konica Minolta was used instead of the λ / 4 plate.

  The λ / 4 plate 109 was bonded to the single wafer so that the slow axis of the λ / 4 plate and the absorption axis of the polarizer were 45 ° on the 4UY side of the obtained polarizing plate, whereby the polarizing plate 109 was obtained. .

<Production of liquid crystal display device>
A liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  Remove the pre-bonded front plate of the Sony 60-inch display BRAVIA LX900, remove the filler between the polarizing plate on the front of the panel and the front plate, and peel off the pre-bonded polarizing plate on the front side of the panel And the produced said polarizing plates 101-114 were each bonded on the front surface of the glass surface of a liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the λ / 4 film of the present invention is on the viewing side, and the absorption axis is in the same direction as the polarizing plate previously bonded. Thus, liquid crystal display devices 101 to 114 corresponding to the polarizing plates 101 to 114 were produced, respectively.

(3D glasses)
The λ / 4 plate 101 produced in Example 1 was bonded to the panel side of the SONY 3D glasses TDG-BR100.

  The manufactured liquid crystal display device was evaluated for crosstalk when tilting the neck when viewing 3D video, crosstalk without tilting the neck after continuous lighting, and visibility after a durability test.

<< Evaluation of crosstalk when tilting the head when viewing 3D images >>
Watch the 3D image with 23D and 55% RH in the 3D glasses immediately after turning on the backlight of each liquid crystal display device and tilting the neck so that the glasses are tilted 25 ° The crosstalk was evaluated according to the following criteria.
A: There is no crosstalk. O: Very weak crosstalk is visible. Δ: Weak crosstalk is visible. X: Crosstalk is clearly visible.

<< Evaluation of crosstalk environmental fluctuations during 3D video viewing >>
In an environment of 23 ° C and 20% RH, the backlight of each liquid crystal display device was lit continuously for one week, then 3D glasses were worn, 3D images were viewed without tilting the head, and crosstalk was determined according to the following criteria. evaluated.
A: There is no crosstalk. O: Very weak crosstalk is visible. Δ: Weak crosstalk is visible. X: Crosstalk is clearly visible.

(Evaluation of polarizing plate durability)
Two 100 mm × 100 mm samples were cut out from each polarizing plate, exposed to an atmosphere of 80 ° C. and 90% RH for 50 hours, and then white generated at the edge of the polarizing plate by crossed Nicols in a normal temperature and humidity atmosphere. The area of the void was observed as an area ratio with respect to the entire area, and evaluated according to the following grade.
◎: If there is no white portion or less, less than 2% of the entire area ○: White portion is 2% or more and less than 5% of the entire area Δ: White portion is based on the entire area 5% or more and less than 10% x: The white portions were 10% or more with respect to the entire area. Table 3 shows the above evaluation results.

  From the results shown in Table 3, the liquid crystal display device of the present invention has crosstalk when the head is tilted when viewing 3D video, crosstalk when the head is not tilted after continuous lighting, and visual recognition after the durability test. It is clear that the liquid crystal display device is excellent in performance.

CC control circuit LCD Liquid crystal display G Glasses for viewing 3D images (glasses)
S1 Right eye liquid crystal shutter S2 Left eye liquid crystal shutter L Linearly polarized light LC Liquid crystal layer LI Left eye image RI Right eye image P1, P2 Polarizer DR1 Feeding direction DR2 Winding direction θi Feeding angle (feeding direction and winding) Angle formed by the picking direction)
CR, CL Gripping device Wo Width of film before stretching W Width of film after stretching A Liquid crystal shutter glasses A1, A4 Polarizer A2 Liquid crystal cell A3 λ / 4 plate B Liquid crystal display device (for example, television (TV))
C Polarizing plate C1 λ / 4 plate C2 Polarizer C3 Optical film C4 Polarizer protective film D Liquid crystal cell E Polarizing plate F Backlight HC Hard coat layer AR Antireflection layer a Absorption axis b Slow axis

Claims (6)

Cellulose acetate having an acetyl group average substitution degree in the range of 2.0 to 2.6 and the following general formula A (1), and a total average substitution degree in the range of 5.0 to 6.9 A λ / 4 plate comprising a compound and having a hard coat layer on the surface.

(Wherein R _{1 to} R ₈ each independently represents a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ may be the same as each other) , May be different.)   The λ / 4 plate according to claim 1, wherein the hard coat layer is a clear hard coat layer or an antiglare hard coat layer.   The λ / 4 plate according to claim 1, wherein an antireflection layer having at least a low refractive index layer is provided on a surface of the hard coat layer.   The λ / 4 plate according to any one of claims 1 to 3, further comprising an ultraviolet absorber. any of claims 1 to 4, lambda / 4 width direction and the lambda / 4 angle of slow axis in the plane of the plate of the plate is being in the range of 40 to 50 ° The λ / 4 plate according to one item. A stereoscopic image display device comprising a polarizing plate provided on the viewing side with respect to the liquid crystal cell, a liquid crystal display device having the liquid crystal cell, and liquid crystal shutter glasses,
The polarizing plate has a total average substitution degree of 4.5 to 7.5 represented by cellulose acetate having an acetyl group average substitution degree in the range of 2.0 to 2.6 and the following general formula A (1). A polarizing plate in which a λ / 4 plate having a hard coat layer on the surface, a polarizer, and an optical film satisfying the following requirement (1) or (2) are provided in this order: ,
In the liquid crystal shutter glasses, (1) a λ / 4 plate, a liquid crystal cell, and a polarizer are provided in this order, or (2) a λ / 4 plate, a polarizer, a liquid crystal cell, and a polarizer are provided in this order. A three-dimensional image display device, characterized in that it is liquid crystal shutter glasses.

(Wherein R _{1 to} R ₈ each independently represents a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ may be the same as each other) , May be different.)
(1) The in-plane retardation value Ro (590) defined by the following formula (I) is in the range of 20 to 150 nm, and the retardation value Rt in the thickness direction defined by the following formula (II) ( 590) is in the range of 70-400 nm .
(2) The in-plane retardation value Ro (590) defined by the following formula (I) is in the range of 0 to 2 nm, and the retardation value Rt in the thickness direction defined by the following formula (II) ( 590) is within the range of -15-15 nm.
Formula (I): Ro (590) = (nx−ny) × d (nm)
Formula (II): Rt (590) = {(nx + ny) / 2−nz} × d (nm)
[In the above formula, Ro (590) represents the in-plane retardation value in the film at the measurement wavelength of 590 nm, and Rt (590) represents the retardation value in the thickness direction in the film at the measurement wavelength of 590 nm. D represents the thickness (nm) of the optical film, and nx represents the maximum in-plane refractive index at the measurement wavelength of 590 nm. ny represents the refractive index in the direction perpendicular to the slow axis in the film plane at the measurement wavelength of 590 nm, and nz represents the refractive index of the film in the thickness direction at the measurement wavelength of 590 nm. ]

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