JP5508204B2 - Humidity dependency improver for polymer film, polymer film, retardation film, polarizing plate protective film, polarizing plate and liquid crystal display device - Google Patents

Description

  The present invention relates to a humidity dependency improving agent for a polymer film, a polymer film containing the same, a polarizing plate protective film, a retardation film, a polarizing plate containing them, and a liquid crystal display device, particularly a VA (vertical aligned) mode liquid crystal display. Relates to the device. The present invention also relates to a novel compound useful for various applications such as a humidity dependency improving agent for polymer films.

  The display characteristics of liquid crystal display devices have been improved in recent years. It is known that a viewing angle characteristic of a liquid crystal display device can be remarkably improved by disposing a retardation film having specific Re and Rth between a polarizing plate and a liquid crystal cell.

  As one method for controlling Re and Rth of a retardation film, a method of adding a retardation increasing agent to a polymer film is disclosed (see Patent Document 1). The retardation increasing agent disclosed in this document is a compound capable of forming a molecular complex including a keto-enol tautomerizable structure as a constituent element. As an example, 1,3,5 such as a guanamine skeleton is used. -Compounds containing a triazine ring are disclosed. As other retardation increasing agents, discotic compounds and compounds having other structures containing a 1,3,5-triazine ring are disclosed (see Patent Documents 2 and 3).

JP 2004-109410 A JP 2001-166144 A JP 2003-344655 A

  On the other hand, the present inventors examined other characteristics of the polymer film to which such a retardation increasing agent was added. As a result, fluctuations in Re and Rth with changes in humidity in the usage environment (relationship between humidity dependence of Re and Rth) It was found to be large.

An object of the present invention is to provide a humidity-dependent improving agent for polymer films that can suppress fluctuations in Re and Rth accompanying changes in humidity in the use environment. The present invention also provides a polymer film to which the humidity dependency improver is added, a polarizing plate protective film using the polymer film, a retardation film using the polymer film, the polymer film, or the retardation. It is another object to provide a polarizing plate having a film and a liquid crystal display device.
Furthermore, this invention makes it a subject to provide a novel compound useful for various uses, such as a humidity dependence improving agent for polymer films.

  The inventors of the present invention have studied various compounds as additives for the purpose of suppressing fluctuations in Re and Rth accompanying changes in humidity in the usage environment. As a result, when a compound containing a 1,3,5-triazine ring having a substituent of a specific type and a specific arrangement is added to a polymer film substrate, the fluctuations in Re and Rth with changes in humidity in the usage environment are reduced. It came to discover that it can suppress remarkably.

  Patent Document 2 that has been found that a compound containing a 1,3,5-triazine ring having a specific substituent selected in the present invention increases Rth by paying attention to a disc-like shape (or planarity), etc. The range of preferable compounds is different from that of the compound, and is not limited to those having a disk shape.

一般式（１）中、Ｒａは、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基又は複素環基を表し；Ｑ¹は、−Ｏ−、−Ｓ−、又は−ＮＲf−を表し、Ｒfは、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基又は複素環基を表し；Ｒｂ、Ｒｃ、及びＲｅはそれぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を表し；Ｒｄは、アルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を表し；Ｘ¹、Ｘ²及びＸ^３はそれぞれ独立に、単結合又は２価の連結基を表し；Ｘ^４は、下記２価の連結基群（３）

（上記各連結基は、＊側が前記一般式（１）中の１，３，５−トリアジン環に置換しているＮ原子との連結部位である。）から選択される連結基を表す；

一般式（２）中、Ｒａ及びＲｇはそれぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基又は複素環基を表し；Ｑ¹は、−Ｏ−、−Ｓ−又は−ＮＲf−を表し、Ｒfは水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を表し、；Ｑ^２は、−Ｏ−、−Ｓ−、又は−ＮＲｈ−を表し、Ｒｈは水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を表し；Ｒｄは、アルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を表し；Ｒｅは、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を表し；Ｘ^３は、単結合又は２価の連結基を表し；Ｘ^４は、下記２価の連結基群（３）

（上記各連結基は、＊側が前記一般式（２）中の１，３，５−トリアジン環に置換しているＮ原子との連結部位であり；Ｒは水素原子又はアルキル基を表す。）から選択される連結基を表す。 Specifically, means for solving the problems are as follows.
[1] Humidity dependency improving agent for polymer film containing a compound represented by the following general formula (1) or general formula (2):

In the general formula (1), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Q ¹ represents —O—, —S—, or —NRf— Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Rb, Rc and Re each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Rd represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; X ¹ , X ^2, and X ³ each independently represent a single bond or a divalent linking group X ⁴ represents the following divalent linking group group (3):

(Each linking group represents a linking group selected from the linking site with the N atom substituted on the 1,3,5-triazine ring in the general formula (1) on the * side);

In general formula (2), Ra and Rg each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Q ¹ represents —O—, —S— or —NRf. - represents, Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group,; ^{Q 2} is, -O -, - S-, or -NRh- represent, Rh is Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; Rd represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; Re represents a hydrogen atom, Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; X ³ represents a single bond or a divalent linking group; X ⁴ represents the following divalent linking group group (3):

(Each linking group is a linking site with an N atom substituted on the 1,3,5-triazine ring in the general formula (2) on the * side; R represents a hydrogen atom or an alkyl group.) Represents a linking group selected from

一般式（４）中の各記号は、一般式（１）中の各記号と同義である。 [2] The humidity dependence improver for polymer films of [1], wherein the compound represented by the general formula (1) is a compound represented by the general formula (4):

Each symbol in general formula (4) is synonymous with each symbol in general formula (1).

一般式（５）中、Ｒ¹、Ｒ²、Ｒ^４及びＲ^３はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、カルバモイル基、スルファモイル基、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数１〜８のアルキルアミノ基、又は炭素原子数１〜８のジアルキルアミノ基を表し；Ｒａ及びＱ^１はそれぞれ、一般式（１）中のそれぞれと同義である。 [3] The humidity dependence improving agent for polymer films of [1], wherein the compound represented by the general formula (1) is a compound represented by the general formula (5):

In general formula (5), R ¹ , R ² , R ⁴ and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, or the number of carbon atoms. Represents an alkoxy group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, or a dialkylamino group having 1 to 8 carbon atoms; Ra and Q ¹ are respectively synonymous with those in the general formula (1). is there.

式中の各記号は、一般式（５）中の各記号と同義である。 [4] The humidity dependence improver for polymer films according to claim 3, wherein the compound represented by the general formula (5) is a compound represented by the following general formula (5a) or (5b).

Each symbol in the formula is synonymous with each symbol in the general formula (5).

一般式（６）中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、カルバモイル基、スルファモイル基、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数１〜８のアルキルアミノ基、又は炭素原子数１〜８のジアルキルアミノ基を表し；Ｒａ、Ｒｇ、Ｑ^１及びＱ^２は、一般式（２）中のそれぞれと同義である。 [5] The humidity dependence improver for polymer films according to any one of [1] to [4], wherein the compound represented by the general formula (2) is a compound represented by the general formula (6):

In general formula (6), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Represents an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms; Ra, Rg, Q ¹ and Q ² have the same meanings as those in formula (2).

[6] A polymer film comprising the humidity dependence improver for polymer films according to any one of [1] to [5] and at least one polymer having a hydroxyl group.
[7] The polymer film according to [6], wherein the polymer having at least one hydroxyl group is a cellulose acylate resin.
[8] The polymer film according to [7], wherein the cellulose acylate resin is a cellulose acetate resin.
[9] A retardation film comprising the polymer film of any one of [6] to [8] or including the polymer film of any of [6] to [8].
[10] A polarizing plate protective film comprising the polymer film of any one of [6] to [8] or including the polymer film of any of [6] to [8].
[11] A polarizing plate having at least a polarizer and the polymer film of any one of [6] to [8].
[12] A liquid crystal display device having at least the polymer film of [6] to [8] or the polarizing plate of [11].

一般式（５）中、Ｒａは、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基又は複素環基を表し；Ｑ¹は、−Ｏ−、−Ｓ−、又は−ＮＲf−を表し、Ｒfは水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を表し；Ｒ¹、Ｒ²、Ｒ^４及びＲ^３はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、カルバモイル基、スルファモイル基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルアミノ基、又は炭素数１〜８のジアルキルアミノ基を表す。 [13] Compound represented by general formula (5):

In the general formula (5), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Q ¹ represents -O-, -S-, or -NRf-; Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic ^{group; R 1, R 2, R} 4 and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carbamoyl group , A sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, or a dialkylamino group having 1 to 8 carbon atoms.

式中の各記号は、一般式（５）中の各記号と同義である。 [14] The compound of [13] represented by the general formula (5a) or the general formula (5b).

Each symbol in the formula is synonymous with each symbol in the general formula (5).

ADVANTAGE OF THE INVENTION According to this invention, the humidity dependence improving agent for polymer films which can suppress the fluctuation | variation of Re and Rth accompanying the humidity change of a use environment can be provided. Further, according to the present invention, a polymer film to which the humidity dependency improver is added, a polarizing plate protective film using the polymer film, a retardation film using the polymer film, the polymer film or the polymer film A polarizing plate and a liquid crystal display device each having a retardation film can be provided.
Furthermore, according to this invention, the novel compound useful for various uses, such as a humidity dependence improving agent for polymer films, can be provided.

It is a schematic diagram which shows the structure of an example of the liquid crystal display device of this invention.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

First, terms used in this specification will be described.
(Retardation (Re and Rth))
In the present specification, Re (λ) and Rth (λ) represent in-plane retardation (nm) and retardation in the thickness direction (nm) at wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).
When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film The light is incident at a wavelength of λ nm from the inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction of the rotation axis of KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the film plane is the rotation axis), Rth can also be calculated from the following formula (X) and formula (XI) based on the value, the assumed value of the average refractive index, and the input film thickness value.

注記：
上記のＲｅ（θ）は法線方向から角度θ傾斜した方向におけるレターデーション値をあらわす。また、式中、ｎｘは面内における遅相軸方向の屈折率を表し、ｎｙは面内においてｎｘに直交する方向の屈折率を表し、ｎｚはｎｘ及びｎｙに直交する方向の屈折率を表す。ｄは膜厚を表す。

Note:
The above Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction. In the formula, nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction orthogonal to nx in the plane, and nz represents the refractive index in the direction orthogonal to nx and ny. . d represents a film thickness.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is from −50 degrees to +50 degrees with respect to the normal direction of the film, with Re (λ) being the in-plane slow axis (determined by KOBRA 21ADH or WR) and the tilt axis (rotating axis). In each of the 10 degree steps, light of wavelength λ nm is incident from the inclined direction and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated.
In the above measurement, the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:
Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).
The KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

In the present invention, the “slow axis” of the retardation film or the like means a direction in which the refractive index is maximized. The “visible light region” means 380 nm to 780 nm. Further, the measurement wavelength of the refractive index is a value at λ = 589 nm in the visible light region unless otherwise specified.
Further, in the present specification, numerical values, numerical ranges, and qualitative expressions (for example, expressions such as “equivalent” and “equal”) indicating optical characteristics of each member such as a retardation film and a liquid crystal layer are liquid crystal. It shall be construed as indicating numerical values, numerical ranges and properties including generally permissible errors for the display device and the members used therefor.

1. Humidity dependency improving agent for polymer film (1-1) Structure of humidity dependency improving agent for polymer film The humidity dependency improving agent for polymer film of the present invention is represented by the general formula (1) or the general formula (2). It contains the compound represented by these, It is characterized by the above-mentioned. Conventionally, when a compound having a 1,3,5-triazine ring is added to a polymer film (for example, cellulose acylate resin), attention is paid to the flatness of the shape of the whole compound having a 1,3,5-triazine ring. Therefore, the compound having the structure represented by the general formula (1) or the general formula (2) of the present invention has received little attention as an additive for a polymer film. In the present specification, the humidity dependency improver for polymer film means that, when added to the polymer film, at least one of the change in Re or the change in Rth accompanying the change in humidity of the use environment of the added polymer film. Refers to a compound that decreases.

In the compound represented by the general formula (1) or (2) according to the present invention, at least one of the nitrogen atoms bonded to the 1,3,5-triazine ring is selected from a predetermined group of linking groups described later. There is a structural feature that it is bonded to such a linking group, and it can be presumed that the molecular structural feature contributes to the humidity dependency improving action.
Hereinafter, the general formulas (1) and (2) will be described in detail. In the present specification, the terms “alkyl group”, “alkenyl group”, and “alkynyl group” are used to mean both linear and branched chains.

In the general formula (1), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Q ¹ represents —O—, —S—, or —NRf—; Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Rb, Rc and Re each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rd represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; X ¹ , X ² and X ³ each independently represent a single bond or a divalent linking group; X ⁴ represents a linking group selected from the following divalent linking group group (3).

  Each of the linking groups is a linking site with an N atom which is substituted on the 1,3,5-triazine ring in the general formula (1) on the * side. R represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

Ra and Rg each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Q ¹ represents —O—, —S— or —NRf—, and Rf represents a hydrogen atom. Represents an atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; Q ² represents —O—, —S—, or —NRh—, and Rh represents a hydrogen atom, an alkyl group, or an alkenyl group. Represents an alkynyl group, an aryl group, or a heterocyclic group; Rd represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; Re represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl X ³ represents a single bond or a divalent linking group; X ⁴ represents a linking group selected from the following divalent linking group group (3).

  Each of the above linking groups is a linking site with an N atom substituted on the 1,3,5-triazine ring in the general formula (2) on the * side. R represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

  In the general formulas (1) and (2), Ra and Rg each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

When Ra and Rg are each an alkyl group, it is preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. When Ra and Rg are each an alkyl group, one or two or more carbon atoms that are not adjacent to each other are an oxygen atom, a sulfur atom, and a nitrogen atom (—NH— or —N (R) — (R is an alkyl group). It may be replaced by a heteroatom selected from (including group). For example, Ra and Rg may be an alkylene (eg, ethylene, propylene) oxy group.
When each of Ra and Rg is an alkenyl group, it is preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
When each of Ra and Rg is an alkynyl group, it is preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
When Ra and Rg are each an aryl group, it is preferably 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 carbon atoms from the viewpoint of improving humidity dependency. preferable.
When Ra and Rg are each a heterocyclic group, it is preferably 2 to 23 carbon atoms, more preferably 2 to 17 carbon atoms, and 2 to 6 carbon atoms for improving humidity dependency. Particularly preferable from the viewpoint. The number of ring members (members) constituting the nitrogen-containing heterocycle is preferably 4 to 24, more preferably 5 to 12, and particularly preferably 5 or 6. Specific examples include a pyrrolyl group, a pyrrolidino group, a pyrazolyl group, a pyrazolidino group, an imidazolyl group, a piperazino group, and a morpholino group.

When each of Ra and Rg represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each group may further have a substituent. Examples of the substituent include the following substituent group T.
Substituent group T:
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 group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl, cyclohexyl group, etc.), alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12, more preferably 2 to 8). For example, a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 2 carbon atoms). 8 such as propargyl group and 3-pentynyl group), aryl group (preferably having 6 to 30 carbon atoms, more preferred) 6 to 20, particularly preferably 6 to 12, and examples thereof include a phenyl group, a biphenyl group, and a naphthyl group.), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10, Particularly preferably 0 to 6, for example, amino group, methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8, for example, methoxy group, ethoxy group, butoxy group, etc.), aryloxy group (preferably 6-20 carbon atoms, more preferably 6-16, particularly Preferably they are 6-12, for example, a phenyloxy group, 2-naphthyloxy group etc. are mentioned), an acyl group (preferably carbon atom number). To 20, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms). , More preferably 2 to 16, particularly preferably 2 to 12, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7). -16, particularly preferably 7-10, for example, phenyloxycarbonyl group, etc.), acyloxy groups (preferably 2-20 carbon atoms, more preferably 2-16, particularly preferably 2-10). For example, acetoxy group, benzoyloxy group, etc.), acylamino group (preferably The number of carbon atoms is 2 to 20, more preferably 2 to 16, particularly preferably 2 to 10, and examples thereof include an acetylamino group and a benzoylamino group. ), An 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 a methoxycarbonylamino group), an aryloxycarbonylamino group ( Preferably it has 7 to 20 carbon atoms, more preferably 7 to 16 and particularly preferably 7 to 12, and examples thereof include a phenyloxycarbonylamino group, and a sulfonylamino group (preferably 1 to 20 carbon atoms). More preferably, it is 1-16, Most preferably, it is 1-12, for example, a methanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (preferably C0-20, more preferably 0). To 16, particularly preferably 0 to 12, such as sulfamoyl group, methyl Rufamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (preferably 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, for example, Carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc.), alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, Methylthio group, ethylthio group, etc.), arylthio group (preferably 6-20 carbon atoms, more preferably 6-16, particularly preferably 6-12, such as phenylthio group). A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, Is preferably 1 to 12, for example, mesyl group, tosyl group, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, For example, a methanesulfinyl group, a benzenesulfinyl group, etc.), a ureido group (preferably 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, for example, a ureido group, a methylureido group). , Phenylureido groups, etc.), phosphoric acid amide groups (preferably having 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, such as diethylphosphoric acid amide, phenylphosphoric acid Amide, etc.), 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). A hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, specifically an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, Examples thereof include a benzthiazolyl group. ) And a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms such as a trimethylsilyl group and a triphenylsilyl group).
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.

In general formulas (1) and (2), each Ra is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, alkenylene group, alkylene group or heterocyclic group; Ra is a hydrogen atom or a substituted group. Alternatively, an unsubstituted alkyl group is more preferable.
In the general formula (2), preferred examples of Rg are the same, but when Ra is other than a hydrogen atom, Rg is preferably a hydrogen atom.

In the general formulas (1) and (2), X ¹ , X ² , and X ³ each independently represent a single bond or a divalent linking group, and X ⁴ represents the following divalent linking group group (3 ) Represents a divalent linking group selected from:

  Each of the linking groups is a linking site with an N atom which is substituted on the 1,3,5-triazine ring in the general formula (1) on the * side. R represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

Examples of the divalent linking group represented by each of X ¹ , X ² , and X ³ include each linking group of the divalent linking group group (3). Furthermore, an alkylene group (preferably having 1 to 30 carbon atoms, more preferably 1 to 3 carbon atoms), an arylene group (preferably having 6 to 30 carbon atoms, more preferably 6 to 10 carbon atoms) and the like can be mentioned. it can. Especially, it is preferable that it is each coupling group of a bivalent coupling group group (3).

  In the general formulas (1) and (2), Rb, Rc, and Re each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and Rd represents an alkyl group, An alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group is represented. The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by Rb, Rc, Rd and Re are the same as the groups represented by Ra and Rg, respectively, and the preferred ranges of the number of carbon atoms are also the same. . These may have a substituent, and examples of the substituent include each substituent of the substituent group T.

In the general formulas (1) and (2), each Rd bonded to X ⁴ is preferably an aryl group, and more preferably a phenyl group. The aryl group may have one or more substituents selected from the above substituent group T. The substitution position of the substituent is not particularly limited, and any position in the ortho, meta, and para positions may be substituted with respect to X ⁴ . Examples of preferable substituents include a halogen atom, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms). , An alkylamino group (preferably an alkylamino group having 1 to 8 carbon atoms), or a dialkylamino group (preferably a dialkylamino group having 1 to 8 carbon atoms).

When each of X ¹ , X ² , and X ^{3 in} the general formulas (1) and (2) represents any of the linking groups in the divalent linking group group (3), Rb bonded to each of them , Rc, and Re are each preferably an aryl group, and more preferably a phenyl group. Examples of preferred substituents that the aryl group has are the same as those for Rd.

On the other hand, when each of X ¹ , X ² , and X ^{3 in} the general formulas (1) and (2) is not any one of the linking groups of the divalent linking group group (3), X ¹ , X ² and X ³ are each preferably a single bond, and Rb, Rc, and Re bonded to each are preferably a hydrogen atom.

  Preferable examples of the compound represented by the general formula (1) include a compound represented by the following general formula (4).

  Each symbol in general formula (4) is synonymous with each symbol in general formula (1), and its preferable range is also the same.

  Further, preferred examples of the compound represented by the general formula (1) include a compound represented by the following general formula (5).

In general formula (5), R ¹ , R ² , R ⁴ and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, or the number of carbon atoms. Represents an alkoxy group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, or a dialkylamino group having 1 to 8 carbon atoms; Ra and Q ¹ are respectively synonymous with those in the general formula (1). The preferred range is also the same.

Preferred examples of the compound represented by the general formula (5) include a compound in which Q ¹ is —NH— or —O—, that is, represented by the following general formula (5a) or (5b). Compounds are included.

  Each symbol in the formula is synonymous with each symbol in the general formula (5).

  Further, preferred examples of the compound represented by the general formula (2) include a compound represented by the following general formula (6).

In general formula (6), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Represents an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms; Ra, Rg, Q ¹ and Q ² have the same meanings as those in formula (2). Each symbol in general formula (6) is synonymous with each symbol in general formula (2), and its preferable range is also the same.

Preferred examples of the compound represented by the general formula (6) include compounds in which Q ¹ and Q ² are —NH— and Rg is a hydrogen atom, that is, a compound represented by the following general formula (6a). included.

  Specific examples of the compounds represented by the general formulas (1) and (2) are shown below, but are not limited to the following specific examples.

＊側は1，3，5−トリアジン環との連結部位である。

The * side is the linking site with the 1,3,5-triazine ring.

(1-2) Physical Properties The compound represented by the general formula (1) or (2) preferably has a molecular weight of 150 to 2000, more preferably 190 to 1000, and 190 to 500. Is particularly preferred.

(1-3) Addition amount The addition amount of the compound represented by the general formula (1) or (2) is preferably 50 parts by mass or less with respect to 100 parts by mass of the base material of the polymer film. 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass. As described above, the compound represented by the general formula (1) or (2) can sufficiently improve the humidity dependency with a small amount of use.

(1-4) Manufacturing method of compound represented by general formula (1) or general formula (2) General formula (1) or general formula (2) contained in the humidity dependence improving agent for polymer films of this invention The production method of the compound represented by () is not particularly limited, and can be synthesized by combining various synthetic reactions. For example, the compound C, which is an example of the compound represented by the general formula (1), can be synthesized via the intermediate B using the following compound A as a starting material.

Step (1) is a reaction in which a chlorine atom is substituted with —Q ¹ -Ra, for example, by reaction with a primary amine, primary aniline, primary alcohol or the like. Solvents used include water, esters (eg, ethyl acetate), hydrocarbons (eg, toluene), ethers (eg, tetrahydrofuran), amides (eg, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone) , Halogenated hydrocarbon (eg, dichloromethane), nitrile (eg, acetonitrile), or a mixed solvent thereof can be used. The reaction temperature is usually from −20 ° C. to the boiling point of the solvent used, preferably from room temperature to the boiling point of the solvent. The reaction time is usually 10 minutes to 3 days, preferably 1 hour to 1 day. The reaction may be performed under a nitrogen atmosphere or under reduced pressure. Step (2) can be synthesized by reacting compound B in an organic solvent in the presence of a base. Organic solvents include alcohols (eg, methanol, ethanol), esters (eg, ethyl acetate), hydrocarbons (eg, toluene), ethers (eg, tetrahydrofuran), amides (eg, dimethylformamide, dimethylacetamide, N-methyl) (Pyrrolidone, N-ethylpyrrolidone), halogenated hydrocarbon (eg, dichloromethane), nitrile (eg, acetonitrile) or a mixed solvent thereof can be used. Alcohols and amides are preferred, with methanol, ethanol, N-methylpyrrolidone and N-ethylpyrrolidone being particularly preferred. A mixed solvent of methanol, ethanol, N-methylpyrrolidone and N-ethylpyrrolidone is also a particularly suitable example.
As the base, any of an inorganic base (eg, potassium carbonate) and an organic base (eg, triethylamine, sodium methoxide, sodium ethoxide) can be used. Inorganic bases are preferred, and sodium methoxide is particularly preferred. The amount of the base used is preferably in the range of 0.5 to 10 equivalents, particularly preferably in the range of 1 to 3 equivalents, relative to the compound represented by the general formula (1b).
The reaction temperature is usually from −20 ° C. to the boiling point of the solvent used, preferably from room temperature to the boiling point of the solvent. The reaction time is usually 10 minutes to 3 days, preferably 1 hour to 1 day. The reaction may be performed under a nitrogen atmosphere or under reduced pressure. In particular, when the leaving group Z is an alkoxy group or an aryl group, the reaction is preferably performed under reduced pressure.

(1-5) Other components other than the compound represented by the general formula (1) or the general formula (2) In addition, the general formula (1) or the general formula (2) Other components other than the compound represented may be contained in the humidity dependence improving agent for polymer films of the present invention. As said other component, the solvent (organic solvent) which can melt | dissolve the compound represented by General formula (1) or General formula (2), a binder, and a polymeric plasticizer can be mentioned.

2. Polymer Film The present invention also relates to a polymer film containing the humidity dependency improving agent of the present invention. A preferred embodiment of the polymer film of the present invention (hereinafter also referred to as the film of the present invention) is a film containing the humidity dependency improving agent of the present invention and a polymer having a hydroxyl group. Examples of the polymer containing a hydroxyl group include polyvinyl alcohol and modified products thereof and cellulose acylate resin. In addition, in the polymer containing the hydroxyl group, a derivative in which the hydroxyl group is substituted with another substituent is also included in the examples of the polymer having the hydroxyl group, and cellulose acylate in which all the hydroxyl groups are substituted with acyl groups. Resins are also included in the examples of the polymer having a hydroxyl group.

(2-2) Cellulose Acylate Resin One aspect of the film of the present invention includes a cellulose acylate resin as the polymer having a hydroxyl group. Cellulose has free hydroxyl groups at the 2nd, 3rd and 6th positions per β-1,4 linked glucose unit. The film of this embodiment preferably contains a cellulose acylate resin as a main component. Here, “containing as a main component” means that when the cellulose acylate resin used as a material for the cellulose acylate film is one kind, it refers to the cellulose acylate resin, and when there are plural kinds, The cellulose acylate resin contained in the highest proportion.

  Examples of cellulose as a cellulose acylate raw material include cotton linter and wood pulp (hardwood pulp, softwood pulp). Cellulose acylate resins obtained from any of the raw material celluloses can be used, and they may be used as a mixture. . Detailed descriptions of these raw material celluloses can be found, for example, by Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, published by Nikkan Kogyo Shimbun (published in 1970), and the Japan Institute of Invention and Technology Publication No. 2001 The cellulose described in No. -1745 (pages 7 to 8) can be used, and the cellulose acylate film is not particularly limited.

In the cellulose acylate film, the acyl group of the cellulose acylate resin is not particularly limited, but is preferably an acetyl group, a propionyl group, or a butyryl group, and more preferably an acetyl group.
Specifically, it is preferable to contain cellulose acylate that simultaneously satisfies the following formulas (i) to (iii).
Formula (i) 2.0 <= A + B <= 3.
Formula (ii) 1.0 ≦ A ≦ 3.
Formula (iii) 0 ≦ B ≦ 1.0
In the above formulas (i) to (iii), A represents the substitution degree of the acetyl group, and B represents the sum of the substitution degree of the propionyl group and the substitution degree of the butyryl group.

More preferably, in the cellulose acylate film, the acyl substitution degree of the cellulose acylate resin simultaneously satisfies the following formulas (iv) to (vi).
Formula (iv) 2.0 ≦ A + B ≦ 3.
Formula (v) 1.5 ≦ A ≦ 3.
Formula (vi) B = 0
In the above formulas (iv) to (vi), A represents the substitution degree of the acetyl group, and B represents the sum of the substitution degree of the propionyl group and the substitution degree of the butyryl group.

  The cellulose acylate resin has an acetyl substitution degree, a propionyl substitution degree, and a butyryl substitution degree, each of which is present in a structural unit of cellulose (glucose having a (β) 1,4-glycoside bond), and three hydroxyl groups are acetylated. And the proportion of propionylation and / or butyrylation, respectively. In the present specification, the degree of substitution of the acetyl group, propionyl group, and butyryl group of the cellulose acylate resin can be calculated by measuring the amount of bound fatty acid per unit mass of cellulose. The measuring method is carried out according to “ASTM D817-91”.

  The cellulose acylate resin preferably has a polymerization degree of 350 to 800, and more preferably has a polymerization degree of 370 to 600. In addition, the cellulose acylate resin used in the present invention preferably has a number average molecular weight of 70000 to 230,000, more preferably has a number average molecular weight of 75000 to 230,000, and more preferably has a number average molecular weight of 78000 to 120,000. Further preferred.

  The cellulose acylate resin can be synthesized using an acid anhydride or acid chloride as an acylating agent. The industrially most general synthesis method is as follows. Organic acid (acetic acid, propionic acid, butyric acid) or their acid anhydrides (acetic anhydride, propionic anhydride, butyric anhydride) corresponding to acetyl group and propionyl group and / or butyryl group of cellulose obtained from cotton linter or wood pulp ) To produce a desired cellulose acylate resin.

(2-3) Other Additives The polymer film of the present invention may contain additives other than the compound represented by the general formula (1) or (2) for various purposes. These additives can be added to a polymer resin dope, for example, a cellulose acylate dope when the polymer film is produced by a solution casting method. There is no restriction | limiting in particular about the timing of addition. The additive is selected from agents that are compatible with a polymer (for example, cellulose acylate) (soluble in a cellulose acylate dope in the solution casting method). The additive is added for the purpose of adjusting the optical properties of the polymer film and other properties.

(Plasticizer)
The polymer film of the present invention preferably contains a plasticizer because the film forming property and the like are improved. When a saccharide plasticizer selected from the group of compounds consisting of saccharides and derivatives thereof, or an oligomer plasticizer selected from oligomers consisting of polycondensation esters of dicarboxylic acids and diols and derivatives thereof is used as the plasticizer. Since the environmental humidity resistance of the polymer film is improved, it is preferable. Specifically, fluctuations in Rth depending on humidity can be reduced. When both a saccharide plasticizer and an oligomer plasticizer are used in combination, the effect of reducing fluctuations in Rth depending on humidity increases.

(Sugar plasticizer)
As described above, the polymer film of the present invention preferably contains at least one compound selected from the group consisting of saccharides and derivatives thereof. Especially, the compound selected from the compound group which consists of a 1-10 mer saccharide | sugar and its derivative (s) is preferable as a plasticizer. Examples thereof include sugar derivatives in which some or all of the hydrogen atoms of OH of sugars such as glucose described in [0042] to [0065] of International Publication No. 2007/125564 pamphlet are substituted with acyl groups. . The addition amount of the saccharide plasticizer is preferably 0.1% by mass or more and less than 70% by mass, and more preferably 1% by mass or more and less than 65% by mass with respect to cellulose acylate as the main component. More preferably, it is 1 mass% or more and less than 60 mass%.

(Oligomer plasticizer)
As described above, the polymer film of the present invention preferably contains an oligomer plasticizer selected from oligomers. Preferred examples of the oligomer plasticizer include a polycondensation ester of a diol component and a dicarboxylic acid component and derivatives thereof (hereinafter sometimes referred to as “polycondensation ester plasticizer”), an oligomer of methyl acrylate (MA), and Derivatives thereof (hereinafter sometimes referred to as “MA oligomer plasticizer”) are included.

  The polycondensation ester is a polycondensation ester of a dicarboxylic acid component and a diol component. The dicarboxylic acid component may consist of only one dicarboxylic acid or may be a mixture of two or more dicarboxylic acids. Among these, as the dicarboxylic acid component, it is preferable to use a dicarboxylic acid component containing at least one aromatic dicarboxylic acid and at least one aliphatic dicarboxylic acid. On the other hand, the diol component may consist of one kind of diol component or a mixture of two or more kinds of diols. Among them, it is preferable to use ethylene glycol and / or an aliphatic diol having an average carbon atom number greater than 2.0 and 3.0 or less as the diol component.

The ratio of the aromatic dicarboxylic acid to the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 5 to 70 mol% of the aromatic dicarboxylic acid. Within the above range, the environmental humidity dependency of the optical properties of the film can be reduced, and the occurrence of bleed-out during the film forming process can be suppressed. The aromatic dicarboxylic acid in the dicarboxylic acid component is more preferably 10 to 60 mol%, and further preferably 20 to 50 mol%.
Examples of aromatic dicarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid and the like are included, and phthalic acid and terephthalic acid are preferable. Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and 1,4 -Cyclohexane dicarboxylic acid etc. are contained, and a succinic acid and adipic acid are preferable among these.

  The diol component is ethylene glycol and / or a diol having an average carbon number of more than 2.0 and 3.0 or less. In the diol component, ethylene glycol is preferably 50 mol%, and more preferably 75 mol%. Examples of the aliphatic diol include alkyl diols and alicyclic diols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1,3-butane. Diol, 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-hexa There are diol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, diethylene glycol and the like, and these are one or more kinds together with ethylene glycol. It is preferably used as a mixture of

  The diol component is preferably ethylene glycol, 1,2-propanediol, and 1,3-propanediol, and particularly preferably ethylene glycol and 1,2-propanediol.

  Further, the polycondensed ester plasticizer is preferably a derivative of the polycondensed ester in which the terminal OH of the polycondensed ester forms an ester with a monocarboxylic acid. Monocarboxylic acids used for sealing the both terminal OH groups are preferably aliphatic monocarboxylic acids, preferably acetic acid, propionic acid, butanoic acid, benzoic acid and derivatives thereof, more preferably acetic acid or propionic acid, and acetic acid. Most preferred. When the number of carbon atoms of the monocarboxylic acids used at both ends of the polycondensed ester is 3 or less, the loss on heating of the compound does not increase, and the occurrence of planar failures can be reduced. Moreover, 2 or more types of monocarboxylic acid used for sealing may be mixed. Both ends of the polycondensed ester are preferably sealed with acetic acid or propionic acid, and a polycondensed ester derivative in which both ends are acetyl ester residues by acetic acid sealing is particularly preferable.

  The polycondensed ester and derivatives thereof are preferably oligomers having a number average molecular weight of about 700 to 2000, more preferably about 800 to 1500, and still more preferably about 900 to 1200. The number average molecular weight of the polycondensed ester can be measured and evaluated by gel permeation chromatography.

  Specific examples of the polycondensed ester plasticizer are shown in Table 1 below, but are not limited thereto.

The polycondensation ester is any one of a conventional method, a hot melt condensation method by a polyesterification reaction or transesterification reaction between a dicarboxylic acid component and a diol component, or an interfacial condensation method between an acid chloride of a dicarboxylic acid component and a glycol. It can be easily synthesized by a method. The polycondensation ester according to the present invention is described in detail in Koichi Murai, “Plasticizers Theory and Application” (Koshobo Co., Ltd., first edition issued on March 1, 1973). In addition, Japanese Patent Laid-Open Nos. 05-155809, 05-155810, Japanese Patent Laid-Open Nos. 05-97073, 2006-259494, 07-330670, 2006-342227, 2007-003679. The materials described in each publication can also be used.

  The amount of the polycondensed ester plasticizer added is preferably 0.1 to 70% by weight, more preferably 1 to 65% by weight, based on the amount of cellulose acylate as a main component, More preferably, it is 60 mass%.

  The content of raw materials and by-products contained in the polycondensation ester plasticizer, specifically, aliphatic diol, dicarboxylic acid ester, diol ester, etc. in the film is preferably less than 1%, 0 Less than 5% is more preferable. Examples of the dicarboxylic acid ester include dimethyl phthalate, di (hydroxyethyl) phthalate, dimethyl terephthalate, di (hydroxyethyl) terephthalate, di (hydroxyethyl) adipate, and di (hydroxyethyl) succinate. Examples of the diol ester include ethylene diacetate and propylene diacetate.

  As the plasticizer used in the polymer film of the present invention, a methyl methacrylate (MA) oligomer plasticizer is also preferable. A combined use of an MA oligomer plasticizer and the saccharide plasticizer is also preferred. In the aspect of combined use, it is preferable to use MA oligomer type plasticizer and saccharide type plasticizer in a mass ratio of 1: 2 to 1: 5, and it is preferably used in a ratio of 1: 3 to 1: 4. More preferred. An example of the MA oligomer plasticizer is an oligomer containing the following repeating unit.

  The weight average molecular weight is preferably about 500 to 2000, more preferably about 700 to 1500, and still more preferably about 800 to 1200.

Further, the MA oligomer plasticizer may be an oligomer having at least one repeating unit derived from another monomer together with the above repeating unit derived from MA, in addition to the oligomer of MA alone. Examples of the other monomers include 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-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl) Acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl), acrylic acid (2-ethoxyethyl), etc. It includes monomers changing the ester to methacrylic acid esters. A monomer having an aromatic ring such as styrene, methylstyrene, or hydroxystyrene can also be used. As said other monomer, an acrylic ester monomer and a methacrylic ester monomer which do not have an aromatic ring are preferable.
Further, when the MA oligomer plasticizer is an oligomer having two or more kinds of repeating units, it consists of X (monomer component having a hydrophilic group) and Y (monomer component having no hydrophilic group), and X: Y ( Oligomers with a molar ratio of 1: 1 to 1:99 are preferred.

  These MA oligomers can be synthesized with reference to the method described in JP-A-2003-12859.

(Polymer plasticizer)
The polymer film of the present invention may contain another polymer plasticizer together with or in place of the saccharide plasticizer, polycondensation ester plasticizer, and MMA oligomer plasticizer described above. Other polymer plasticizers include polyester polyurethane plasticizers, aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, vinyl polymers such as polyvinyl isobutyl ether and poly N-vinyl pyrrolidone, polystyrene, poly-4 -Styrenic polymers such as hydroxystyrene, polyethers such as polyethylene oxide and polypropylene oxide, polyamides, polyurethanes, polyureas, phenol-formaldehyde condensates, urea-formaldehyde condensates, vinyl acetate and the like.

(Compound having at least two aromatic rings)
The polymer film of the present invention may contain a compound having at least two aromatic rings as long as it is not contrary to the gist of the present invention. The said compound has the effect | action which adjusts the optical characteristic of a polymer film. For example, when the polymer film of the present invention is used as an optical compensation film, stretching is effective for controlling optical characteristics, particularly Re, to a preferable value. To increase Re, it is necessary to increase the refractive index anisotropy in the film plane, and one method is to improve the main chain orientation by stretching. Further, by using a compound having a large refractive index anisotropy as an additive, the refractive index anisotropy of the film can be further increased. For example, in the compound having two or more aromatic rings, the polymer main chain is aligned by stretching, and the orientation of the compound is improved accordingly, and it becomes easy to control the desired optical characteristics.

  Examples of the compound having at least two aromatic rings include triazine compounds described in JP-A No. 2003-344655, rod-shaped compounds described in JP-A No. 2002-363343, JP-A Nos. 2005-134848 and 2007-119737. Liquid crystalline compounds described in Japanese Patent Publication No. Gazette. More preferably, the triazine compound or the rod-like compound. Two or more compounds having at least two aromatic rings can be used in combination. In addition, it is preferable that the molecular weight of the compound which has at least 2 aromatic ring is about 300-1200, and it is more preferable that it is 400-1000.

  The addition amount of the compound having at least two aromatic rings is preferably 0.05% to 10%, more preferably 0.5% to 8%, and more preferably 1% to 5% in terms of mass ratio with respect to the cellulose acylate resin. Is more preferable. The compound having two aromatic rings may also serve as the compound represented by the general formula (1) or (2) used in the present invention. On the other hand, when the compound having two aromatic rings has a 1,3,5-triazine ring structure but does not satisfy the general formula (1) or (2), from the viewpoint of improving humidity dependency, The addition amount of the compound having two aromatic rings is preferably 0.05% to 10%, more preferably 0.5% to 8%, and more preferably 1% to 5% by mass ratio with respect to the cellulose acylate resin. Particularly preferred.

(Optical anisotropy adjusting agent)
Moreover, the polymer film of the present invention may contain an optical anisotropy adjusting agent. Examples thereof include “compounds that reduce Rth” described on pages 23 to 72 of JP-A-2006-30937.

(Matting agent fine particles)
A matting agent may be added to the polymer film. Fine particles used as a matting agent include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, silica Mention may be made of magnesium and calcium phosphates. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
As fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used. Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

A fine particle dispersion can be used in the method for producing a polymer film having particles having a small secondary average particle size. For example, taking a cellulose acylate film as an example, several methods are conceivable when preparing a dispersion of fine particles. For example, a method in which a fine particle dispersion prepared by stirring and mixing a solvent and fine particles is prepared in advance, and the fine particle dispersion is added to a separately prepared small amount of cellulose acylate solution, stirred and dissolved, and further mixed with the main cellulose acylate dope solution There is. This method is a preferable preparation method in that the dispersibility of the silicon dioxide fine particles is good and the silicon dioxide fine particles are more difficult to reaggregate. In addition, a small amount of cellulose acylate is added to the solvent, and dissolved by stirring. Then, fine particles are added to the solvent and dispersed with a disperser. This is used as a fine particle additive solution. There is also a method of mixing well. Any method may be used, and the present invention is not limited to these methods.
The solvent used in the above preparation method is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film formation of a cellulose acylate.

(Low molecular plasticizer, deterioration inhibitor, release agent)
Various additives other than those described above (for example, low-molecular plasticizers, UV inhibitors, deterioration inhibitors, release agents, infrared absorbers, etc.), depending on the application in each preparation step, are used for the polymer film. Which can be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing material at 20 ° C. or lower and 20 ° C. or higher, and similarly, mixing of a plasticizer is described in, for example, JP-A-2001-151901. Furthermore, infrared absorbing dyes are described, for example, in JP-A No. 2001-194522. Moreover, the timing of the addition may be added at any timing in the dope preparation step, but may be added by adding a preparation step at the last timing of the dope preparation step. Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. Moreover, when a polymer film is formed from a multilayer, the kind and addition amount of the additive of each layer may differ. For example, it is described in Japanese Patent Application Laid-Open No. 2001-151902, and these are conventionally known techniques. For these details, materials described in detail on pages 16 to 22 in the Japan Institute of Invention Disclosure Technical Bulletin (Public Technical No. 2001-1745, published on March 15, 2001, Japan Institute of Invention) are preferably used.

(2-4) Production method of polymer film The polymer film of the present invention is preferably a film produced by a solution casting method (solvent casting method). In the solvent cast method, a dope prepared by dissolving a polymer in an organic solvent is cast on the surface of a support made of metal or the like, and dried to form a film. Thereafter, the membrane is peeled off from the support surface and subjected to a stretching treatment.
About the manufacture example of the cellulose acylate film using a solvent cast method, U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, 2,492,978, 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892, Reference can also be made to the descriptions of JP-B-45-4554, JP-A-49-5614, JP-A-60-176834, JP-A-60-203430 and JP-A-62-115035. The cellulose acylate film may be subjected to a stretching treatment. For the stretching method and conditions, see, for example, the examples described in JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, JP-A-11-48271, etc. Can be.

(2-5) Various characteristics of polymer film (Re and Rth)
The preferred range of optical properties of the polymer film of the present invention will vary depending on the application. In embodiments utilized in VA mode liquid crystal display devices, Re (589) is preferably 30 nm to 200 nm and Rth (589) is preferably 70 nm to 400 nm; Re (589) is 30 nm to 150 nm, and Rth (589) is more preferably 100 nm to 300 nm. Furthermore, it is more preferable that Re (589) is 40 nm to 100 nm and Rth (589) is 100 nm to 250 nm.
Unless otherwise specified, the Re and Rth of the film are determined after leaving the film in an environment at a temperature of 25 ° C. and a relative humidity of 60% for a sufficient time (2 hours or more, for example, 12 hours or 24 hours). It shall mean the value measured at the temperature and relative humidity.

(Re humidity dependence and Rth humidity dependence)
The polymer film of the present invention is characterized by small fluctuations in Re and / or Rth depending on humidity. Specifically, Re and Rth (also referred to as Re [25 ° C, RH10%] and Rth [25 ° C, RH10%], respectively) when the film is conditioned for 2 hours at 25 ° C and 10% relative humidity, Fluctuations in Re and Rth (also referred to as ReRe [25 ° C., RH 80%] and Rth [25 ° C., RH 80%], respectively) when humidity is adjusted for 2 hours at 25 ° C. and 80% relative humidity are small. Since the humidity dependency of the optical characteristics of the film of the present invention is reduced, fluctuations in Re and Rth are suppressed even in an environment where the humidity changes, and the above-mentioned preferable range of retardation can be exhibited.

The polymer film of the present invention preferably has a humidity dependency of Re (ΔRe = | Re [25 ° C., RH10%] − Re [25 ° C., RH80%] |) of 10 nm or less, preferably 9 nm or less. Is more preferable, and it is especially preferable that it is 7 nm or less.
The polymer film of the present invention preferably has a Rth humidity dependency (ΔRth = | Rth [25 ° C., RH10%] − Rth [25 ° C., RH80%] |) of 22 nm or less, preferably 20 nm or less. Is more preferable, and 17 nm or less is particularly preferable.

(Film thickness)
In an aspect in which the polymer film of the present invention is used as a member of a device that is desired to be thin, such as a member of a liquid crystal display device, it is preferable that the film thickness is thin. On the other hand, if the film thickness is too thin, the use is required. Optical properties cannot be achieved. In an embodiment used as an optical compensation film or a polarizing plate protective film for a liquid crystal display device, the film thickness is preferably about 20 to 80 μm. More preferably, it is about 25-70 micrometers, More preferably, it is about 30-60 micrometers.

3. Use of polymer film The polymer film of the present invention can be used in various applications. For example, it can be used for a retardation film (hereinafter also referred to as an optical compensation film) of a liquid crystal display device, a protective film for a polarizing plate, and the like.
(Retardation film)
The polymer film of the present invention can be used as a retardation film. The “retardation film or optical compensation film” is generally used for a display device such as a liquid crystal display device and means an optical material having optical anisotropy, and is synonymous with an optical compensation sheet. In a liquid crystal display device, an optical compensation film is used for the purpose of improving the contrast of a display screen or improving viewing angle characteristics and color.

  Moreover, in order to adjust to desired Re and Rth, the polymer film of this invention can be laminated | stacked several sheets, or the polymer film of this invention and another film can also be laminated | stacked and used. Lamination of the film can be performed using a pressure-sensitive adhesive or an adhesive.

(Polarizer)
The polymer film of the present invention can be used as a protective film for a polarizing plate (the polarizing plate of the present invention). An example of the polarizing plate of this invention consists of a polarizing film and two polarizing plate protective films (transparent film) which protect both surfaces, and has the polymer film of this invention as at least one polarizing plate protective film. When the polymer film of the present invention is used as a support and the surface having an optically anisotropic layer made of a liquid crystal composition is used as a protective film for a polarizing plate, The back surface of the molecular film (the surface on which the optically anisotropic layer is not formed) is preferably bonded to the surface of the polarizing film.
When the polymer film of the present invention is used as the polarizing plate protective film, the polymer film of the present invention is subjected to the surface treatment (also described in JP-A Nos. 6-94915 and 6-118232) to make it hydrophilic. For example, it is preferable to perform glow discharge treatment, corona discharge treatment, or alkali saponification treatment. In particular, when the polymer film of the present invention is a cellulose acylate film, alkali saponification treatment is most preferably used as the surface treatment.

  As the polarizing film, for example, a film obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution can be used. When using a polarizing film obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution, the surface-treated surface of the polymer film of the present invention can be directly bonded to both surfaces of the polarizing film using an adhesive. In the production method of the present invention, it is preferable that the polymer film is directly bonded to the polarizing film as described above. As the adhesive, an aqueous solution of polyvinyl alcohol or polyvinyl acetal (for example, polyvinyl butyral) or a latex of a vinyl-based polymer (for example, polybutyl acrylate) can be used. A particularly preferred adhesive is an aqueous solution of fully saponified polyvinyl alcohol.

  In general, a liquid crystal display device includes four polarizing plate protective films because a liquid crystal cell is provided between two polarizing plates. The polymer film of the present invention may be used for any of the four polarizing plate protective films, but the polymer film of the present invention is disposed between the polarizing film and the liquid crystal layer (liquid crystal cell) in the liquid crystal display device. It is particularly useful as a protective film. The protective film disposed on the opposite side of the polymer film of the present invention across the polarizing film can be provided with a transparent hard coat layer, an antiglare layer, an antireflection layer, etc. It is preferably used as a polarizing plate protective film on the outermost surface of the display side.

(Liquid crystal display device)
The polymer film of the present invention, and the optical compensation film and polarizing plate using the polymer film can be used for liquid crystal display devices in various display modes. Each liquid crystal mode in which these films are used will be described below. Among these modes, the polymer film of the present invention, and the optical compensation film and polarizing plate using the polymer film are particularly preferably used for VA mode liquid crystal display devices. These liquid crystal display devices may be any of a transmissive type, a reflective type, and a transflective type.

FIG. 1 shows a schematic cross-sectional view of an example of the liquid crystal display device of the present invention. In FIG. 1, the upper side is the observer (display surface) side, and the lower side is the backlight side.
The VA mode liquid crystal display device of FIG. 1 includes a liquid crystal cell LC (consisting of an upper substrate 1, a lower substrate 3, and a liquid crystal layer 5), and a pair of upper polarizing plates P1 disposed so as to sandwich the liquid crystal cell LC. And a lower polarizing plate P2. The polarizing film is generally incorporated in a liquid crystal display device as a polarizing plate having protective films on both surfaces, but the outer protective film of the polarizing film is omitted in FIG. The polarizing plates P1 and P2 have polarizing films 8a and 8b, respectively, and are arranged with their absorption axes 9a and 9b orthogonal to each other. The liquid crystal cell LC is a VA mode liquid crystal cell, and when displaying black, the liquid crystal layer 5 has homeotropic alignment as shown in FIG. Each of the upper substrate 1 and the lower substrate 3 has an alignment film (not shown) and an electrode layer (not shown) on the inner surface, and a color filter layer (see FIG. Not shown).

  Retardation films 10a and 10b are disposed between the upper substrate 1 and the upper polarizing film 8a and between the lower substrate 3 and the lower polarizing film 8b, respectively. The retardation films 10a and 10b are polymer films of the present invention. The retardation films 10a and 10b are arranged with their in-plane slow axes 11a and 11b orthogonal to the respective absorption axes 9a and 9b of the upper polarizing film 8a and the lower polarizing film 8b. That is, the retardation films 10a and 10b are arranged with their slow axes orthogonal to each other. The retardation films 10a and 10b made of the polymer film of the present invention contribute to the reduction of light leakage and color shift that occur in an oblique direction during black display.

(Hard coat film, antiglare film, antireflection film)
The polymer film of the present invention may be applied to a hard coat film, an antiglare film and an antireflection film as desired. For the purpose of improving the visibility of flat panel displays such as LCD, PDP, CRT, EL, etc., any or all of a hard coat layer, an antiglare layer and an antireflection layer are provided on one or both sides of the polymer film of the present invention. can do. Preferred embodiments of such an antiglare film and antireflection film are described in detail on pages 54 to 57 of the Japan Society for Invention and Innovation (Publication No. 2001-1745, published on March 15, 2001, Japan Society of Invention and Innovation). It can be preferably used in the polymer film of the present invention.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

1. Synthesis Example 1- (1) Synthesis of Exemplary Compound (43) Exemplary Compound (43) was synthesized according to the following scheme.

To 20 g of 2-chloro 4,6-diamino 1,3,5-triazine, 60 mL of a 40% methylamine aqueous solution was added and stirred at 70 ° C. for 2 hours. After cooling to room temperature, water was added to the reaction solution and the crystals were collected by filtration. The crystals were washed with isopropanol and hexane and dried to obtain 16 g of intermediate (43-1). To 200 mL of N-ethylpyrrolidone, 16 g of intermediate (43-1), 36 g of methyl 2-methylbenzoate, and 30 g of sodium methoxide were added, and the mixture was stirred at 40 ° C. for 30 minutes. After cooling to room temperature, 1N hydrochloric acid was added to the reaction solution, and the precipitated crystals were collected by filtration. The crystals were washed with water and dried. The crystals were stirred in a mixed solvent of ethyl acetate, methanol, and aqueous sodium hydrogen carbonate solution, and the crystals were collected by filtration. The crystals were washed with water and acetonitrile and dried to obtain 25 g of the desired product. It was confirmed by ¹ H-NMR that the exemplified compound (43) was obtained. The ¹ H-NMR data is shown below.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
0.85 (3H, d)
2.35 (6H, s)
7.30-7.40 (4H, m)
8.60-7.80 (4H, m)
7.80-7.90 (1H, t)
10.50 (1H, s)
10.60 (1H, s)

1- (2) Synthesis of Exemplified Compound (41) Synthesis was performed in the same manner as Exemplified Compound (43) except that the raw material was changed from methyl m-methylbenzoate to methyl benzoate to obtain the desired product. It was confirmed by ¹ H-NMR that the exemplified compound (41) was obtained. The ¹ H-NMR data is shown below.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
2.95 (3H, d)
5.95 (1H, s)
7.40-7.60 (6H, m)
7.85-8.00 (4H, m)
8.85 (1H, s)
9.30 (1H, s)

1- (3) Synthesis of Exemplified Compound (53) Synthesis was performed in the same manner as Exemplified Compound (43) except that the starting material was changed from methylamine to ethylamine to obtain the desired product. It was confirmed by ¹ H-NMR that the exemplified compound (53) was obtained. The ¹ H-NMR data is shown below.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
1.20 (3H, t)
2.40 (6H, s)
3.40-3.50 (2H, m)
5.80 (1H, m)
7.30-7.40 (4H, m)
7.70-7.80 (4H, m)
8.50 (1H, s)
9.00 (1H, s)

1- (4) Synthesis of Exemplified Compound (63) Synthesis was performed in the same manner as Exemplified Compound (43) except that the starting material was changed from methylamine to n-propylamine to obtain the desired product. It was confirmed by ¹ H-NMR that the exemplified compound (63) was obtained. The ¹ H-NMR data is shown below.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
0.85 (3H, t)
1.40-1.60 (2H, m)
2.40 (6H, s)
3.10-3.20 (2H, m)
7.30-7.40 (4H, m)
7.60-7.75 (4H, m)
8.85 (1H, t)
10.45 (1H, s)
10.55 (1H, s)

1- (5) Synthesis of Exemplified Compound (71) The same method as Exemplified Compound (43), except that the starting material was changed from methylamine to n-butylamine and methyl 2-methylbenzoate was changed to methyl benzoate. The target product was obtained. It was confirmed by ¹ H-NMR that the exemplified compound (71) was obtained. The ¹ H-NMR data is shown below.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
0.85 (3H, t)
1.25 (2H, m)
1.45 (2H, m)
3.20 (2H, m)
7.40-7.60 (6H, m)
7.80-8.00 (5H, m)
10.50 (1H, s)
10.60 (1H, s)

1- (6) Synthesis of Exemplified Compound (93) Synthesis was performed in the same manner as Exemplified Compound (43) except that the starting material was changed from methylamine to 3-ethoxypropylamine to obtain the desired product. It was confirmed by ¹ H-NMR that the exemplified compound (93) was obtained. The ¹ H-NMR data is shown below.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
1.10 (3H, t)
1.70 (2H, m)
2.40 (6H, s)
3.25 (2H, m)
3.30-3.50 (4H, m)
7.30-7.40 (4H, m)
7.60-7.75 (4H, m)
7.80 (1H, t)
10.45 (1H, s)
10.55 (1H, s)

1- (7) Synthesis of Exemplary Compound (13) Exemplary Compound (13) was synthesized according to the following scheme.

To 27 g of 2-chloro 4,6-diamino 1,3,5-triazine, 300 mL of methanol and 16 g of sodium hydroxide were added, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, water was added to the reaction solution and the crystals were collected by filtration. The crystals were washed with water and dried to obtain 17 g of intermediate (13-1). To 200 mL of N-ethylpyrrolidone, 17 g of intermediate (13-1), 38 g of methyl 2-methylbenzoate, and 33 g of sodium methoxide were added, and the mixture was stirred at 40 ° C. for 8 hours. After cooling to room temperature, 1N aqueous hydrochloric acid, ethyl acetate and hexane were added to the reaction solution, and the precipitated crystals were collected by filtration. The crystals were recrystallized from isopropanol and dried to obtain 20 g of the desired product. It was confirmed by ¹ H-NMR that Exemplified Compound (13) was obtained. The ¹ H-NMR data is shown below.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.40 (6H, s)
3.90 (3H, s)
7.30-7.50 (4H, m)
7.70-7.80 (4H, m)
11.0 (2H, s)

Ｎ−エチルピロリドン ２００ｍＬにメラミン１０ｇ、２−メチル安息香酸メチル ２４ｇ、ナトリウムメトキシド ２０ｇを加え、４０℃で８時間攪拌した。反応液を室温に戻した後、酢酸エチルで抽出し溶媒をロータリーエバポレーターで留去した。その後、カラムクロマトグラフィーにより精製を行い、目的物を得た。以下に^１Ｈ−ＮＭＲのデータを示す。
^１Ｈ−ＮＭＲ（溶媒：ＣＤＣｌ_３、基準：テトラメチルシラン）δ（ｐｐｍ）：
２．４０（６H、ｓ）
５．８５（２H、ｓ）
７．４０（４H、ｍ）
７．７０（４H、ｍ）
８．７０（２H、ｓ） 1- (8) Synthesis of Exemplified Compound (103)

To 200 mL of N-ethylpyrrolidone, 10 g of melamine, 24 g of methyl 2-methylbenzoate and 20 g of sodium methoxide were added and stirred at 40 ° C. for 8 hours. The reaction solution was returned to room temperature, extracted with ethyl acetate, and the solvent was removed by a rotary evaporator. Then, it refine | purified by column chromatography and obtained the target object. The ¹ H-NMR data is shown below.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
2.40 (6H, s)
5.85 (2H, s)
7.40 (4H, m)
7.70 (4H, m)
8.70 (2H, s)

1- (9) Synthesis of Exemplified Compound (193) To 200 mL of N-ethylpyrrolidone, 10 g of the intermediate (43-1), 11 g of methyl 2-methylbenzoate, and 12 g of sodium methoxide were added and stirred at 40 ° C. for 8 hours. The reaction solution was returned to room temperature, extracted with ethyl acetate, and the solvent was removed by a rotary evaporator. Then, it refine | purified by column chromatography and obtained the target object. The target product was confirmed by mass spectrum.

1- (10) Synthesis of Exemplified Compound (173) Synthesis was performed in the same manner as Exemplified Compound (193), except that Intermediate (13-1) was used as a starting material, to give the desired product. The target product was confirmed by mass spectrum.
1- (11) Synthesis of Exemplified Compound (254) The target product was obtained in the same manner as Exemplified Compound (43) except that methyl 3,5-dimethylbenzoate was used as a starting material. The target product was confirmed by mass spectrum.
1- (12) Synthesis of Exemplified Compound (260) The target product was obtained in the same manner as Exemplified Compound (43) except that methyl 3,4-dimethylbenzoate was used as a starting material. The target product was confirmed by mass spectrum.
1- (13) Synthesis of Exemplified Compound (267) The target product was obtained in the same manner as Exemplified Compound (53) except that methyl 3,5-dimethoxybenzoate was used as a starting material. The target product was confirmed by mass spectrum.
1- (14) Synthesis of Exemplified Compound (276) The target product was obtained in the same manner as Exemplified Compound (53) except that methyl 3,4-dimethoxybenzoate was used as a starting material. The target product was confirmed by mass spectrum.

2. Production of Cellulose Acylate Film Each exemplified compound shown in the following table was mixed in a proportion shown in the following table with respect to 100 parts by mass of cellulose acylate resin having an acetyl substitution degree shown in the following table, and 396 masses of methylene chloride as a solvent. Part of methanol and 59 parts by mass of methanol to prepare a cellulose acylate (specifically, cellulose acetate) solution. This solution was cast using a band casting machine, the obtained web was peeled from the band, and then stretched 35% in the TD direction (film width direction) under the condition of 140 ° C., and then dried. Cellulose acylate films (specifically, cellulose acetate) films each having a thickness of 50 μm were prepared.

  A film without additives was produced as a comparative film. Moreover, the film for comparative examples which used the comparative compound 1 of the structure shown below as an additive was also produced, respectively.

(Evaluation of optical properties)
About the obtained film of each Example and Comparative Example, 3 points in the width direction (center, end portion (position of 5% of the total width from both ends)) were sampled 3 times every 10 m in the longitudinal direction, and the size was 3 cm square. Nine samples were taken out and obtained from the average value of each point obtained according to the following method.
After adjusting the sample film for 24 hours at 25 ° C. and 60% relative humidity, the film surface was measured at 25 ° C. and 60% relative humidity using an automatic birefringence meter (KOBRA-21ADH: manufactured by Oji Scientific Instruments). In contrast, the retardation at a wavelength of 590 nm is measured from the direction inclined in increments of 10 ° from + 50 ° to −50 ° from the normal to the film surface with the vertical axis and the slow axis as the rotation axis. Re) and the retardation value (Rth) in the film thickness direction are calculated.
The results are shown in the table below.

Regarding the change in retardation value with humidity, Re and Rth (respectively Re and Rth calculated respectively) were measured in the same manner as above except that the film was conditioned at 25 ° C. and 10% relative humidity for 2 hours. [25 ° C, RH10%], Rth [25 ° C, RH10%]), and Re, Rth calculated and measured in the same manner as above except that the humidity was adjusted at 25 ° C and relative humidity 80% for 12 hours. From Re (25 ° C., RH 80%) and Rth [25 ° C., RH 80%], Re humidity dependency (ΔRe) and Rth humidity dependency (ΔRth) were calculated.
The results are shown in the following table as ΔRe and ΔRth, respectively.

  From the results shown in the above table, it can be understood that all the films to which the humidity dependency improving agent of the present invention is added have reduced humidity dependency of retardation as compared with the films of Comparative Examples 1 to 4. .

1 Liquid crystal cell upper substrate 3 Liquid crystal cell lower substrate 5 Liquid crystal layer (liquid crystal molecule)
8a, 8b Polarizing plate protective film 9a, 9b Polarizing plate protective film Absorption axis 10a, 10b Retardation film (polymer film of the present invention)
11a, 11b Retardation film (polymer film of the present invention) Absorption axis P1, P2 Polarizing plate LC Liquid crystal cell

Claims (9)

Humidity dependency improving agent for polymer film containing a compound represented by the following general formula (5) :

In general formula (5), R ¹ , R ² , R ⁴ and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkyl group having 1 to 8 carbon atoms, or the number of carbon atoms. Represents an alkoxy group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, or a dialkylamino group having 1 to 8 carbon atoms; Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or Q ¹ represents —O—, —S—, or —NR f —, and R f represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. The humidity dependence improving agent for polymer films according to claim 1 , wherein the compound represented by the general formula (5) is a compound represented by the following general formula (5a) or (5b).

Each symbol in the formula is synonymous with each symbol in the general formula (5). A polymer film comprising the humidity dependence improver for polymer films according to claim 1 or 2 and at least one polymer having a hydroxyl group. The polymer film according to claim 3 , wherein the polymer having at least one hydroxyl group is a cellulose acylate resin. The polymer film according to claim 4 , wherein the cellulose acylate resin is a cellulose acetate resin. A retardation film comprising the polymer film according to any one of claims 3 to 5 , or comprising the polymer film according to any one of claims 6 to 8. The polarizing plate protective film which consists of a polymer film of any one of Claims 3-5 , or contains the polymer film of any one of Claims 6-8. The polarizing plate which has a polarizer and the polymer film of any one of Claims 3-5 at least. The polymer film according to any one of claims 3-5, or at least having a liquid crystal display device the polarizing plate according to claim 8.

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