JP5543309B2 - Cellulose acylate film, retardation film, polarizing plate and liquid crystal display device - Google Patents

Description

  The present invention relates to a cellulose acylate film, a retardation film, a polarizing plate using the cellulose acylate film, and a liquid crystal display device.

  Liquid crystal display devices are increasingly used year by year as space-saving image display devices with low power consumption. Conventionally, a liquid crystal display device has a major drawback that the viewing angle dependency of a display image is large. However, a wide viewing angle liquid crystal mode such as a VA mode has been put into practical use, and thereby, a high-quality image such as a television can be obtained. In demanded markets, the demand for liquid crystal display devices is expanding rapidly.

  The basic configuration of a liquid crystal display device is one in which polarizing plates are provided on both sides of a liquid crystal cell. The polarizing plate plays a role of allowing only light having a polarization plane in a certain direction to pass through, and the performance of the liquid crystal display device is greatly influenced by the performance of the polarizing plate. The polarizing plate generally has a configuration in which transparent protective films are bonded to both front and back sides of a polarizer made of a polyvinyl alcohol film or the like on which iodine or dye is adsorbed and oriented. A cellulose acylate film typified by cellulose acetate has been widely used as a polarizing plate protective film because it has high transparency and can easily ensure adhesion with polyvinyl alcohol used in a polarizer.

  Further, it is known that a wider viewing angle can be realized, that is, display characteristics can be improved by disposing a retardation film having a specific retardation between a polarizing plate and a liquid crystal cell of a liquid crystal display device. As such a retardation film, a cellulose acylate film capable of exhibiting excellent optical performance, specifically, in-plane retardation Re (nm) and retardation Rth (nm) in the thickness direction of the retardation film. The cellulose acylate film is also used as a retardation film in a liquid crystal display device.

  There are some known additives that can be used in cellulose acylate films to improve their performance. A conventionally known compound that can be used as an additive for a cellulose acylate film includes a so-called retardation increasing agent. Patent Document 1 discloses a compound capable of forming a molecular complex containing a keto-enol tautomerizable compound as a constituent as a retardation increasing agent. As an example, 1,3 such as a guanamine skeleton is disclosed. A compound having a structure containing a 1,5-triazine ring is disclosed. Similarly, Patent Document 2 discloses a retardation increasing agent composed of a discotic compound as a compound capable of increasing Rth by adding to a cellulose acetate film. The retardation increasing agent disclosed in this document is a discotic compound. As an example, a compound having a structure containing a 1,3,5-triazine ring or a porphyrin skeleton is disclosed.

  In recent years, as the use of liquid crystal display devices has been expanded, large-size and high-quality applications such as televisions have been expanded, and higher quality is required for polarizing plates, retardation films, and polarizing plate protective films. ing. In particular, large-size and high-quality liquid crystal display devices are required to be used in harsher environments as compared to conventional liquid crystal display devices. Therefore, cellulose acylate films used in the liquid crystal display devices are optically dependent on environmental humidity. It has been desired to achieve both reduction in performance change and protection of a polarizer when aged at high temperature and high humidity.

  However, the conventional cellulose acylate film includes a cellulose acylate film to which a retardation increasing agent having a specific structure described in Patent Document 1 or 2 above is added. Reduction of optical performance change depending on environmental humidity And the protection of the polarizer when aged at high temperature and high humidity were not sufficiently achieved.

  In response to such a request, for example, in Patent Document 3, when a cellulose acylate film having a specific degree of acyl substitution is used, the optical performance changes depending on the environmental humidity, and the time is kept under high temperature and high humidity. A method for improving the performance change is disclosed.

  In addition, as a method of improving performance change due to environmental humidity and aging under high temperature and high humidity by adding additives to cellulose acylate film, polyester and polyhydric alcohol ester or aromatic terminal ester Patent Document 4 discloses a method of using a cellulose acylate film containing the above.

JP 2004-109410 A JP 2001-166144 A JP 2006-089529 A JP 2006-342227 A

  When the present inventors examined the methods described in Patent Documents 3 and 4 described above, the method described in Patent Document 3 reduced the change in optical performance depending on the environmental humidity, and the time elapsed under high temperature and high humidity. It was found that the coexistence with the protection of the polarizer was insufficient. Moreover, when the acyl substitution degree of cellulose acylate in the cellulose acylate film is limited, there is a problem that the retardation control range is narrow, and only the retardation corresponding to the liquid crystal display of a specific liquid crystal cell mode can be adjusted. Moreover, although the method described in Patent Document 4 has a certain effect, it has been found that the method is still insufficient to be used for a liquid crystal display device for high-quality applications in recent years, and further improvement is required.

  An object of the present invention is to provide a cellulose acylate film that has a small retardation change depending on environmental humidity and can suppress deterioration of a polarizer when bonded to a polarizing plate and aged at high temperature and high humidity. There is to do. Moreover, it is providing the retardation film using this cellulose acylate film, a polarizing plate, and a liquid crystal display device using the same.

  When the present inventors diligently studied for the purpose of solving the above problems, a compound having a structure similar to the compound described in Patent Document 1 or 2 is one of the compounds useful for solving the above problems. I found. Therefore, as a result of research for further improvement, it has been found that the above problem can be solved by simultaneously adding a hydrogen bonding compound and a specific hydrophobizing agent that satisfy the following requirements (A) to (C). It came to. That is, the said subject is solved by this invention of the following structures.

（一般式（Ａ−１）中、Ｒａはアルキル基、アルケニル基、アルキニル基、複素環基またはアリール基を表す。Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４はそれぞれ独立に単結合または２価の連結基を表す。Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４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、アリール基または複素環基を表す。）
［３］ 前記水素結合性化合物が下記一般式（Ｂ−１）で表される化合物である、［１］に記載のセルロースアシレートフィルム。

（一般式（Ｂ−１）中、ＲｂおよびＲｃはそれぞれ独立にアルキル基、アルケニル基、アルキニル基、複素環基またはアリール基を表す。Ｘ^５およびＸ^６はそれぞれ独立に単結合または２価の連結基を表す。Ｒ^５およびＲ^６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、アリール基または複素環基を表す。）
［４］ 前記一般式（Ａ−１）および（Ｂ−１）において、前記Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５およびＸ^６が、それぞれ独立に、単結合および下記一般式（Ｐ）で表される２価の連結基からなる群から選択されるいずれか一つであることを特徴とする［１］〜［３］のいずれか一項に記載のセルロースアシレートフィルム。

（一般式（Ｐ）中、＊側が前記一般式（Ａ−１）および（Ｂ−１）で表される化合物中の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。）
［５］ 前記水素結合性化合物が下記一般式（Ｃ−１）で表される化合物である、［１］に記載のセルロースアシレートフィルム。

（一般式（Ｃ−１）中、Ｒａ^１１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｂ^１１、Ｒｃ^１１、Ｒｄ^１１およびＲｅ^１１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、アリール基または複素環基を表す。Ｑ¹は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａと連結して環を形成してもよい。Ｘ^１１、Ｘ^１２、およびＸ^１３は、それぞれ独立に単結合または２価の連結基を表す。Ｘ^１４は、下記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。）

（一般式（Ｐ）中、＊側が前記一般式（Ｃ−１）で表される化合物中の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。）
［６］ 前記水素結合性化合物が下記一般式（Ｄ−１）で表される化合物である、［１］に記載のセルロースアシレートフィルム。

（一般式（Ｄ−１）中、Ｒａ^２１、Ｒｇ^２１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｄ^２１、およびＲｅ^２１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、アリール基または複素環基を表す。Ｑ^１１は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^２１と連結して環を形成してもよい。Ｑ^１２は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^２１と連結して環を形成してもよい。Ｘ^２３は単結合または２価の連結基を表す。Ｘ^２４は、下記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。）

（一般式（Ｐ）中、＊側が前記一般式（Ｄ−１）で表される化合物中の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。）
［７］ 前記水素結合性化合物が下記一般式（Ｅ−１）で表される化合物である［１］に記載のセルロースアシレートフィルム。

（一般式（Ｅ−１）中、Ｙ^１はメチン基、あるいは−Ｎ−を表す。Ｒａ^３１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｂ^３１、Ｒｃ^３１、Ｒｄ^３１およびＲｅ^３１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、アリール基または複素環基を表す。Ｑ^２１は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^３１と連結して環を形成してもよい。Ｘ^３１、Ｘ^３２、およびＸ^３３は、それぞれ独立に単結合または２価の連結基を表す。Ｘ^３４は、下記一般式（Ｑ）で表される２価の連結基からなる群から選択される連結基を表す。）
一般式（Ｑ）

（一般式（Ｑ）中、＊側が前記一般式（Ｅ−１）で表される化合物中の複素環に置換しているＮ原子との連結部位である。）
［８］ 前記水素結合性化合物が下記一般式（Ｆ−１）で表される化合物である［１］に記載のセルロースアシレートフィルム。

（一般式（Ｆ−１）中、Ｙ^１１はメチン基、あるいは−Ｎ−を表す。Ｒａ^４１、Ｒｇ^４１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｄ^４１、およびＲｅ^４１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、アリール基または複素環基を表す。Ｑ^３１は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^４１と連結して環を形成してもよい。Ｑ^３２は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^４１と連結して環を形成してもよい。Ｘ^４３は単結合または２価の連結基を表す。Ｘ^４４は、下記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。）

（一般式（Ｐ）中、＊側が前記一般式（Ｆ−１）で表される化合物中の複素環に置換しているＮ原子との連結部位である。）
［９］ 前記水素結合性化合物が下記一般式（Ｇ−１）で表される化合物である［１］に記載のセルロースアシレートフィルム。

（一般式（Ｇ−１）中、Ｌ^１は単結合またはヘテロ原子を含む２価の連結基を表し、Ｒ^８１は水素原子、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数６〜２０のアリール基または炭素数７〜２０のアリールアルキル基を表す。）
［１０］ 前記水素結合性化合物が下記一般式（Ｈ−１）で表される化合物である［１］に記載のセルロースアシレートフィルム。

（一般式（Ｈ−１）中、Ｌ³は単結合またはヘテロ原子を含む２価の連結基を表し、Ｒ^８５は炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数６〜２０のアリール基または炭素数７〜２０のアリールアルキル基を表す。）Ｒ^８３、Ｒ^８４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、アリール基または複素環基を表す。Ｘ^５３、Ｘ^５４はそれぞれ独立に、下記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。）

（一般式（Ｐ）中、＊側が前記一般式（Ｈ−１）で表される化合物中の複素環に置換しているＮ原子との連結部位である。）
［１１］ 前記水素結合性化合物の分子量が１００〜１０００であることを特徴とする［１］〜［１０］のいずれか一項に記載のセルロースアシレートフィルム。
［１２］ ［１］〜［１１］のいずれか一項に記載のセルロースアシレートフィルムを含むことを特徴とする位相差フィルム。
［１３］ ［１］〜［１１］のいずれか一項に記載のセルロースアシレートフィルムまたは［１２］に記載の位相差フィルムを含んでなる偏光板。
［１４］ ［１］〜［１１］のいずれか一項に記載のセルロースアシレートフィルム、［１２］に記載の位相差フィルムまたは［１３］に記載の偏光板を含んでなる液晶表示装置。 [1] A hydrogen bonding compound that satisfies the following requirements (A) to (C), at least selected from a polyhydric alcohol ester hydrophobizing agent, a polycondensation ester hydrophobizing agent, and a carbohydrate derivative hydrophobizing agent A cellulose acylate film comprising one hydrophobizing agent.
(A) It has both a hydrogen bond donor part and a hydrogen bond acceptor part in one molecule.
(B) The value obtained by dividing the molecular weight by the total number of hydrogen bond donors and hydrogen bond acceptors is 30 to 65.
(C) The total number of aromatic ring structures is 1 or more and 3 or less.
[2] The cellulose acylate film according to [1], wherein the hydrogen bonding compound is a compound represented by the following general formula (A-1).

(In the general formula (A-1), Ra represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. X ¹ , X ² , X ³ and X ⁴ are each independently a single bond or a divalent group. R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
[3] The cellulose acylate film according to [1], wherein the hydrogen bonding compound is a compound represented by the following general formula (B-1).

(In the general formula (B-1), Rb and Rc each independently represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. X ⁵ and X ⁶ each independently represent a single bond or a divalent group. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
[4] In the general formulas (A-1) and (B-1), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently a single bond and the following general formula ( The cellulose acylate film according to any one of [1] to [3], which is any one selected from the group consisting of divalent linking groups represented by P).

(In the general formula (P), the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by the general formulas (A-1) and (B-1) on the * side .)
[5] The cellulose acylate film according to [1], wherein the hydrogen bonding compound is a compound represented by the following general formula (C-1).

(In the general formula (C-1), Ra ¹¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb ¹¹ , Rc ¹¹ , Rd ¹¹ and Re ¹¹ are each independently a hydrogen atom or an alkyl group. A 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, an alkyl group, an alkenyl group, an alkynyl group, an aryl group. X ¹¹ , X ¹² , and X ¹³ each independently represents a single bond or a divalent linking group, and X ¹⁴ represents a group or a heterocyclic group, and may be linked to Ra to form a ring. Represents a linking group selected from the group consisting of divalent linking groups represented by the following general formula (P).

(In general formula (P), the * side is the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by general formula (C-1).)
[6] The cellulose acylate film according to [1], wherein the hydrogen bonding compound is a compound represented by the following general formula (D-1).

(In the general formula (D-1), Ra ²¹ and Rg ²¹ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rd ²¹ and Re ²¹ each independently represent a hydrogen atom, an alkyl group, Represents an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, Q ¹¹ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Or a heterocyclic group, which may be linked to Ra ²¹ to form a ring, Q ¹² represents —O—, —S—, or —NRh—, and Rh represents a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, an aryl group, or a heterocyclic group, which may be linked to Rg ²¹ to form a ring, X ²³ represents a single bond or a divalent linking group, and X ²⁴ represents the following general formula (P )so It represents a linking group selected from the group consisting of divalent linking group.)

(In general formula (P), the * side is the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by general formula (D-1).)
[7] The cellulose acylate film according to [1], wherein the hydrogen bonding compound is a compound represented by the following general formula (E-1).

(In General Formula (E-1), Y ¹ represents a methine group or —N—. Ra ³¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Rb ³¹ , Rc ³¹ , Rd ³¹ and Re ³¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and Q ²¹ represents a single bond, —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, and may be linked to Ra ³¹ to form a ring, X ³¹ , X ³² , and X ³³ are Each independently represents a single bond or a divalent linking group, and X ³⁴ represents a linking group selected from the group consisting of a divalent linking group represented by the following general formula (Q).
General formula (Q)

(In General Formula (Q), the * side is a linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (E-1).)
[8] The cellulose acylate film according to [1], wherein the hydrogen bonding compound is a compound represented by the following general formula (F-1).

(In General Formula (F-1), Y ¹¹ represents a methine group or —N—. Ra ⁴¹ and Rg ⁴¹ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Rd ⁴¹ , And Re ⁴¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, Q ³¹ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom. , An alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, which may be linked to Ra ⁴¹ to form a ring, and Q ³² represents —O—, —S—, or —NRh—. shows, Rh is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, linked may form a ring .X ⁴³ Ren single bond or a divalent and Rg ^41, .X ⁴⁴ represents a group represents a linking group selected from the group consisting of the divalent linking group represented by the following general formula (P).)

(In General Formula (P), the * side is the linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (F-1).)
[9] The cellulose acylate film according to [1], wherein the hydrogen bonding compound is a compound represented by the following general formula (G-1).

(In General Formula (G-1), L ¹ represents a single bond or a divalent linking group containing a hetero atom, R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Group, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.)
[10] The cellulose acylate film according to [1], wherein the hydrogen bonding compound is a compound represented by the following general formula (H-1).

(In General Formula (H-1), L ³ represents a single bond or a divalent linking group containing a hetero atom, R ⁸⁵ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon Represents an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.) R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. Represents an aryl group or a heterocyclic group. X ⁵³ and X ⁵⁴ each independently represent a linking group selected from the group consisting of a divalent linking group represented by the following general formula (P). )

(In General Formula (P), the * side is the linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (H-1).)
[11] The cellulose acylate film according to any one of [1] to [10], wherein the molecular weight of the hydrogen bonding compound is 100 to 1000.
[12] A retardation film comprising the cellulose acylate film according to any one of [1] to [11].
[13] A polarizing plate comprising the cellulose acylate film according to any one of [1] to [11] or the retardation film according to [12].
[14] A liquid crystal display device comprising the cellulose acylate film according to any one of [1] to [11], the retardation film according to [12], or the polarizing plate according to [13].

  Cellulose acylate film, retardation film, and polarizing plate that have a small retardation change depending on environmental humidity and that can suppress deterioration of the polarizer when bonded to a polarizing plate and aged under high temperature and high humidity , And a liquid crystal display device using the same.

It is the schematic which shows the example of the liquid crystal display device of this invention.

[Cellulose acylate film]
The cellulose acylate film of the present invention comprises a hydrogen bonding compound (hereinafter referred to as a hydrogen bonding compound used in the present invention) satisfying the following requirements (A) to (C), a polyhydric alcohol ester hydrophobizing agent, It contains at least one hydrophobizing agent selected from a polycondensation ester hydrophobizing agent and a carbohydrate derivative hydrophobizing agent.
(A) It has both a hydrogen bond donor part and a hydrogen bond acceptor part in one molecule.
(B) The value obtained by dividing the molecular weight by the total number of hydrogen bond donors and hydrogen bond acceptors is 25 to 65.
(C) The total number of aromatic ring structures is 1 or more and 3 or less.
By adding the hydrogen bonding compound and the specific hydrophobizing agent used in the present invention to the cellulose acylate film, the change in retardation of the cellulose acylate film accompanying a change in environmental humidity can be greatly reduced.
Furthermore, by using the cellulose acylate film as a polarizing plate protective film, the performance deterioration of the polarizer under high temperature and high humidity can be significantly improved.
Hereinafter, the hydrogen bonding compound used in the present invention, the hydrophobizing agent, and the method for producing the cellulose acylate film will be described in detail in this order.

<Hydrogen bonding compound used in the present invention>
The cellulose acylate film of the present invention is characterized by containing the hydrogen bonding compound. Hereinafter, the details of the structure of the hydrogen bonding compound used in the present invention will be described.
Without being bound by any theory, the humidity dependence of the retardation value of the cellulose acylate film is due to the fact that water molecules coordinate to the carbonyl group present in the acyl substituent of the cellulose acylate resin, and the cellulose acylate resin This is presumed to be caused by a change in the birefringence of. Similarly, without being bound by any theory, since the hydrogen bonding compound used in the present invention has a hydrogen bonding group at an appropriate position, it effectively interacts with the carbonyl group or hydroxyl group of the cellulose acylate resin. In addition, the access of water molecules to the cellulose acylate resin in a high humidity state can be inhibited. That is, the present invention focuses on the structure of the hydrogen bonding compound, particularly the arrangement of the hydrogen bonding compound in the molecule. Conventionally, when a compound having a 1,3,5-triazine ring is added to the cellulose acylate resin, attention has been paid to the planarity of the shape of the entire compound having a 1,3,5-triazine ring. The compound with the above structure has received little attention.

The hydrogen bonding compound used in the present invention satisfies the following requirements (A) to (C).
(A) It has both a hydrogen bond donor part and a hydrogen bond acceptor part in one molecule.
(B) The value obtained by dividing the molecular weight by the total number of hydrogen bond donors and hydrogen bond acceptors is 30 to 65.
(C) The total number of aromatic rings is 1 or more and 3 or less.

First, the requirement (A) will be described.
Examples of functional groups that function as a hydrogen bond donor part and a hydrogen bond acceptor part in the hydrogen bond compound used in the present invention are described in, for example, page 15 of Introduction to Hydrogen Bonding published by Oxford UP by Jeffrey, George A. In Table 2, the total number of functional groups described in this table in the hydrogen bonding compound is used as the total number of hydrogen bonding donors and hydrogen bonding acceptors.
The hydrogen-bonding compound used in the present invention has a hydrogen-bonding donor part and a hydrogen-bonding acceptor part in one molecule, thereby forming a strong hydrogen bond with water, and water is a carbonyl in cellulose acylate. Coordination to the group can be suppressed. The number of bonds connecting the hydrogen bond donor part and the hydrogen bond acceptor part is preferably 0 or more and 3 or less, from the viewpoint of hydrogen bond formation with the water, and more preferably 1 or 2.

Next, the requirement (B) will be described.
In the hydrogen bonding compound used in the present invention, the value obtained by dividing the molecular weight by the total number of hydrogen bond donors and hydrogen bond acceptors is more preferably 35 or more and 60 or less. If the value obtained by dividing the molecular weight by the total number of hydrogen bond donors and hydrogen bond acceptors is too large, it becomes difficult for hydrogen-bonding compounds to approach cellulose acylate, and the effect of improving the retardation change accompanying environmental changes becomes small. End up. On the other hand, if the value obtained by dividing the molecular weight by the total number of hydrogen bond donors and hydrogen bond acceptors is too small, the interaction between the hydrogen bonding compounds becomes too strong, resulting in solubility in the solvent and phase with cellulose acylate. Since solubility is insufficient, it is not preferable.

Next, the requirement (C) will be described.
The number of aromatic ring structures in the hydrogen bonding compound used in the present invention is 1 or more and 3 or less. Here, the aromatic ring structure includes heteroaromatic rings in addition to aromatic hydrocarbon rings. Further, the number of aromatic ring structures is counted as one in the case of a condensed ring in which aromatic rings are condensed, and is counted as a plurality when the aromatic rings are connected through a linking group. For example, an aromatic ring having 10 carbon atoms derived from naphthalene is counted as one aromatic ring structure. When the number of aromatic ring structures is 4 or more, the molecular size of the hydrogen bonding compound becomes too large, making it difficult to access the carbonyl group in cellulose acylate, and the effect of suppressing the change in optical properties due to environmental humidity becomes small. .
The hydrogen bonding compound used in the present invention preferably contains at least one heteroaromatic ring. By including a heteroaromatic ring, a heteroatom in the heteroaromatic ring and another hydrogen-bonding acceptor or hydrogen-bonding donor in the hydrogen-bonding compound are preferable because they easily form a cyclic hydrogen bond with water.

(Hydrophilicity of hydrogen bonding compounds)
The hydrophilicity / hydrophobicity of the hydrogen bonding compound used in the present invention is preferably controlled within a specific range. That is, if the additive is too hydrophobic, the compatibility with the cellulose acylate is insufficient, and the proportion of the additive that can be present in the vicinity of the cellulose acylate is reduced. On the other hand, if the additive is too hydrophilic, the solubility in the dope solvent will be insufficient.

-ClogP value-
The measurement of the octanol-water partition coefficient (log P value) can be generally carried out by a flask soaking method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163). (1989)), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)). In the present invention, the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used.
The ClogP value is a value obtained by calculating the common logarithm logP of the distribution coefficient P between 1-octanol and water. Known methods and software can be used for calculating the ClogP value. In the present invention, Daylight is used.
Chemical Information Systems system: CLOGP program embedded in PCModels was used.
Further, when the log P value of a certain compound varies depending on the measurement method or the calculation method, whether or not the compound is within the scope of the present invention is determined by the Crippen's fragmentation method.

  The hydrophilicity / hydrophobicity of the hydrogen bonding compound can be represented by an octanol-water partition coefficient (hereinafter sometimes referred to as logP). The hydrophilicity / hydrophobicity of the hydrogen bonding compound used in the present invention is controlled to be in the range of 0 to 5.5 as the ClogP value among the octanol-water partition coefficients. The ClogP value of the hydrogen bonding compound used in the present invention is more preferably 1.0 to 5.0, and most preferably 2.0 to 4.5.

The specific structure of the hydrogen bonding compound used for this invention is demonstrated below.
The hydrogen bonding compound used in the present invention is preferably a compound represented by the following general formulas (A-1) to (H-1). Each structure will be described in detail below.

(A) Hydrogen bonding compound represented by general formula (A-1) First, the compound represented by general formula (A-1) is demonstrated. In the present specification, a hydrocarbon group such as an alkyl group may be linear or branched unless it is contrary to the spirit of the present invention.

（一般式（１）中、Ｒａはアルキル基、アルケニル基、アルキニル基、複素環基またはアリール基を表す。Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４はそれぞれ独立に単結合または２価の連結基を表す。Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４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、アリール基または複素環基を表す。）

(In the general formula (1), Ra represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. X ¹ , X ² , X ³ and X ⁴ are each independently a single bond or a divalent linkage. R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

  Ra represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group, and is preferably an alkyl group or an aryl group.

When said Ra is an alkyl group, it is preferable that it is C1-C20, it is more preferable that it is C3-C15, and it is especially preferable that it is C6-C12.
When said Ra is an alkenyl group, it is preferable that it is C2-C20, it is more preferable that it is C3-C15, and it is especially preferable that it is C6-C12.
When Ra is an alkynyl group, the number of carbon atoms is preferably 2 to 20, more preferably 3 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
When said Ra is an aryl group, it is preferable that it is C6-C24, and it is more preferable that it is C6-C18.
When said Ra is a heterocyclic group, it is preferable that it is C5-C23, and it is more preferable that it is C5-C17.

The Ra may or may not further have a substituent, but it is preferable from the viewpoint of improving humidity dependence that Ra does not further have a substituent.
Examples of the substituent that Ra may have include the following substituent T. Examples of the substituent T include alkyl groups (preferably those 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- A butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl, a cyclohexyl group, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 2 carbon atoms). 12, particularly preferably 2 to 8, for example, vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 To 12, particularly preferably 2 to 8, and examples thereof include a propargyl group and a 3-pentynyl group), an aryl group (preferably The number of atoms is 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 12, for example, phenyl group, biphenyl group, naphthyl group, etc.), amino group (preferably having 0 to 20 carbon atoms). More preferably 0 to 10, particularly preferably 0 to 6, and examples thereof include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, and the like, an alkoxy group (preferably a carbon atom). The number is 1 to 20, more preferably 1 to 12, particularly preferably 1 to 8, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group.), An aryloxy group (preferably having 6 to 20 carbon atoms, More preferably, it is 6-16, Most preferably, it is 6-12, for example, a phenyloxy group, 2-naphthyloxy group, etc. are mentioned. Group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as acetyl group, benzoyl group, formyl group, and pivaloyl group), 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 group and ethoxycarbonyl group), aryloxycarbonyl group (preferably carbon atoms) The number is 7 to 20, more preferably 7 to 16, and particularly preferably 7 to 10, for example, a phenyloxycarbonyl group.), An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 2). 16, particularly preferably 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group. . ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetylamino group and benzoylamino group), alkoxycarbonylamino group ( The number of carbon atoms is preferably 2 to 20, more preferably 2 to 16, and particularly preferably 2 to 12, and examples thereof include a methoxycarbonylamino group, and an aryloxycarbonylamino group (preferably 7 to 7 carbon atoms). 20, More preferably, it is 7-16, Most preferably, it is 7-12, for example, a phenyloxycarbonylamino group etc. are mentioned, A sulfonylamino group (preferably 1-20 carbon atoms, More preferably, it is 1-16. And particularly preferably 1 to 12, for example, methanesulfonylamino group, benzenesulfonate Amino groups, etc.), sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms such as sulfamoyl group, methylsulfamoyl group, dimethylsulfa). And 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 a carbamoyl group and a 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, such as methylthio group and ethylthio group) An arylthio group (preferably having 6 to 20 carbon atoms, More preferably, it is 6-16, Most preferably, it is 6-12, for example, a phenylthio group etc. are mentioned, A sulfonyl group (Preferably 1-20 carbon atoms, More preferably, it is 1-16, Most preferably, it is 1-1. 12, for example, a mesyl group, a tosyl group, etc.), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, such as a methanesulfinyl group, A benzenesulfinyl group, etc.), a ureido group (preferably having a carbon atom number of 1-20, more preferably 1-16, particularly preferably 1-12, such as a ureido group, a methylureido group, a phenylureido group, etc. A phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12, for example, diethyl phosphoric acid amide, phenyl phosphoric acid amide and the like. ), 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 and a sulfur atom, specifically, for example, an imidazolyl group, a pyridyl group and a quinolyl group. , Furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, especially Preferably it is 3-24, for example, a trimethylsilyl group, a triphenylsilyl group, etc. are mentioned. And the like. 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.

X ¹ , X ² , X ^3, and X ⁴ each independently represent a single bond or a divalent linking group, each independently preferably a single bond, and particularly preferably all single bonds.
Examples of the divalent linking group that X ¹ , X ² , X ^3, and X ⁴ may independently represent, for example, a divalent linking group represented by the following general formula (P), an alkylene group (Preferably 1 to 30 carbon atoms, more preferably 1 to 3 carbon atoms, particularly preferably 2 carbon atoms), an arylene group (preferably 6 to 30 carbon atoms, more preferably 6 to 10 carbon atoms) and the like. be able to. Among them, a divalent linking group represented by the following general formula (P) is preferable, and a carbonyl group is more preferable.

（一般式（Ｐ）中、＊側が前記一般式（Ａ−１）で表される化合物中の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。）

(In general formula (P), the * side is the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by general formula (A-1).)

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. It is preferably a hydrogen atom, an alkyl group or an acyl group, more preferably a hydrogen atom or an alkyl group. In addition, at least one of R ¹ or R ² is preferably a hydrogen atom, and at least one of R ³ or R ⁴ is preferably a hydrogen atom.
When R ¹ , R ² , R ³ and R ⁴ are alkyl groups, it is preferably 1 to 12 carbons, more preferably 1 to 6 carbons, and 1 to 4 carbons. Is particularly preferred. The R ¹ is an alkyl group and X ¹ is —C (═O) —, the R ² is an alkyl group and X ² is —C (═O) —, the R ³ is an alkyl group, and X ³ is —C (= O)-, when R ⁴ is an alkyl group and X ⁴ is -C (= O)-, the preferred ranges of R ¹ , R ² , R ³ and R ⁴ from the viewpoint of improving humidity dependency are hydrogen atoms, It is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group or a heterocyclic group, and more preferably a substituted or unsubstituted aryl group. The preferred substituent that the aryl group has is the same as the range of R ^{31 to} R ³⁴ in the general formula (A-4) described later, that is, a halogen atom, a hydroxyl group, a carbamoyl group, a sulfamoyl group, and a carbon number of 1 to 8 An alkyl group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, and a dialkylamino group having 1 to 8 carbon atoms.
When R ¹ , R ² , R ³ and R ⁴ are alkenyl groups, it is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and 2 to 4 carbon atoms. Is particularly preferred.
When R ¹ , R ² , R ³ and R ⁴ are alkynyl groups, it is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and 2 to 4 carbon atoms. Is particularly preferred.
When R ¹ , R ² , R ³ and R ⁴ are aryl groups, it is preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and humidity of 6 carbon atoms. This is particularly preferable from the viewpoint of improving dependency.
R ¹ , R ² , R ³ and R ⁴ may or may not further have a substituent, and examples of the substituent include the substituent T.

  The compound represented by the general formula (A-1) is particularly preferably represented by the following general formula (A-2).

Ra ² represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and a preferred range is the same as the preferred range of Ra.

R ²¹ and R ²⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and a preferred range is the preferred range of R ¹ , R ² , R ³ and R ⁴ It is the same.

（一般式（Ａ−３）中、Ｒａ^３はアルキル基、アルケニル基、アルキニル基またはアリール基を表す。） The compound represented by the general formula (A-1) is more particularly preferably represented by the following general formula (A-3).

(In the general formula (A-3), Ra ³ represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group.)

Ra ³ represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and a preferred range is the same as the preferred range of Ra.
Furthermore, in the cellulose acylate film of the present invention, it is preferable that Ra ³ is an alkyl group in order to improve the humidity dependency of retardation while lowering Rth. In this case, Ra ³ is further absent. More preferred is a substituted alkyl group.

（一般式（Ａ−４）中、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４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から８のアルキル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルアミノ基、炭素数１から８のジアルキルアミノ基を表す。）前記Ｒａ⁴はアルキル基、アルケニル基、アルキニル基またはアリール基を表し、好ましい範囲は、前記Ｒａの好ましい範囲と同様である。 The compound represented by the general formula (A-1) is particularly preferably represented by the following general formula (A-4).

(In the general formula (A-4), R ³¹ , R ³² , R ³³ and R ³⁴ 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, carbon R 1 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 ⁴ represents an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and is preferable. The range is the same as the preferable range of Ra.

(B) Hydrogen bonding compound represented by general formula (B-1) Next, the compound represented by general formula (B-1) is demonstrated.

（一般式（Ｂ−１）中、ＲｂおよびＲｃはそれぞれ独立にアルキル基、アルケニル基、アルキニル基、複素環基またはアリール基を表す。Ｘ^５およびＸ^６はそれぞれ独立に単結合または２価の連結基を表す。Ｒ^５およびＲ^６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、アリール基または複素環基を表す。）

(In the general formula (B-1), Rb and Rc each independently represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. X ⁵ and X ⁶ each independently represent a single bond or a divalent group. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

  Rb and Rc each independently represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group, and the preferred range is the same as the preferred range for Ra.

X ⁵ and X ⁶ each independently represent a single bond or a divalent linking group, and preferred ranges thereof are the same as the preferred ranges of X ¹ , X ² , X ³ and X ⁴ .

R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and preferred ranges thereof are the preferred ranges of R ¹ , R ² , R ³ and R ⁴ It is the same.

The compound represented by the general formula (B-1) is particularly preferably represented by the following general formula (B-2).

Rb ² and Rc ² each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and a preferred range is the same as the preferred range of Ra.

R ²⁵ independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and a preferred range is the same as the preferred ranges of R ²¹ and R ²⁴ .

The compound represented by the general formula (B-3) is more particularly preferably represented by the following general formula (B-3).

Rb ³ and Rc ³ each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and a preferred range is the same as the preferred range of Ra.

The compound represented by the general formula (B-1) is particularly preferably represented by the following general formula (B-4).

Rb ⁴ and Rc ⁴ each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
Furthermore, in the cellulose acylate film of the present invention, it is preferable that both Rb ³ and Rc ³ are alkyl groups in order to improve the humidity dependency of retardation while lowering Rth. More preferably, Rb ³ and Rc ³ are both unsubstituted alkyl groups. Similarly, it is preferable that both Rb ⁴ and Rc ⁴ are alkyl groups.

  Specific examples of the compounds represented by the general formulas (A-1) to (B-1) are given below, but the present invention is not limited to the following specific examples.

(Method for producing compound represented by general formula (A-1) or general formula (B-1))
The method for producing the compound represented by the general formula (A-1) or the general formula (B-1) is not particularly limited, and can be produced by a known method. As a production method preferably used in the present invention, dicyanodiamide and a nitrile compound are mixed with water as described in, for example, US Pat. No. 3,478,026 and Chem. Eur. J. 2005, 11, 6616-6628. A method of forming a triazine ring by heating in alcohol in the presence of an inorganic base such as potassium oxide, or a Grignard compound and an amine compound using cyanuric chloride as a raw material as described in Tetrahedron 2000, 56, 9705-9711 In a stepwise substitution reaction, or by reaction of imidoylguanidine with a carboxylic acid chloride or ester as described in Journal of Synthetic Organic Chemistry, 1967, Vol. 25, No. 11, 1048-1051. A method of synthesizing disubstituted-s-triazines can be used.
Moreover, the compound represented by general formula (A-1) or general formula (B-1) may be obtained commercially.

（一般式（Ｃ−１）中、Ｒａ^１１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｂ^１１、Ｒｃ^１１、Ｒｄ^１１およびＲｅ^１１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、アリール基または複素環基を表す。Ｑ¹は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａと連結して環を形成してもよい。Ｘ^１１、Ｘ^１２、およびＸ^１３は、それぞれ独立に単結合または２価の連結基を表す。Ｘ^１４は、前記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。） (C) Compound Represented by General Formula (C-1) Next, the compound represented by General Formula (C-1) will be described in detail.

(In the general formula (C-1), Ra ¹¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb ¹¹ , Rc ¹¹ , Rd ¹¹ and Re ¹¹ are each independently a hydrogen atom or an alkyl group. A 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, an alkyl group, an alkenyl group, an alkynyl group, an aryl group. X ¹¹ , X ¹² , and X ¹³ each independently represents a single bond or a divalent linking group, and X ¹⁴ represents a group or a heterocyclic group, and may be linked to Ra to form a ring. And represents a linking group selected from the group consisting of divalent linking groups represented by the general formula (P).

（一般式（Ｃ−２）中、Ｒａ^１２はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｂ^１２およびＲｄ^１２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、アリール基または複素環基を表す。Ｑ^２は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^１２と連結して環を形成してもよい。Ｘ^１１、Ｘ^１２、およびＸ^１３は、それぞれ独立に単結合または２価の連結基を表す。Ｘ^１４は、前記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。） The compound represented by the general formula (C-1) is particularly preferably represented by the following general formula (C-2).

(In the general formula (C-2), Ra ¹² represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb ¹² and Rd ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. Q ² represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. the stands may be linked to form a ring with ^{Ra 12 .X 11, X 12,} and ^{X 13} are the ^{.X 14} which independently represent a single bond or a divalent linking group, the general formula ( P represents a linking group selected from the group consisting of divalent linking groups represented by P).

（一般式（Ｃ−３）中、Ｒａ^１３はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^３は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^１３と連結して環を形成してもよい。） The compound represented by the general formula (C-1) is particularly preferably represented by the following general formula (C-3).

(In the general formula (C-3), Ra ¹³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Q ³ represents —O—, —S—, or —NRf—, and Rf Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may be linked to Ra ¹³ to form a ring.

（一般式（Ｃ−４）中、Ｒ^４１、Ｒ^４２、Ｒ^４３およびＲ^４４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から８のアルキル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルアミノ基、炭素数１から８のジアルキルアミノ基を表す。Ｒａ^１４はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^４は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^１４と連結して環を形成してもよい。） The compound represented by the general formula (C-1) is particularly preferably represented by the following general formula (C-4).

(In the general formula (C-4), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, halogen atom, hydroxyl group, carbamoyl group, sulfamoyl group, alkyl group having 1 to 8 carbon atoms, carbon Represents an alkoxy group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, and a dialkylamino group having 1 to 8 carbon atoms, and Ra ¹⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Q ⁴ 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, and is linked to Ra ¹⁴ to form a ring. May be formed.)

（一般式（Ｄ−１）中、Ｒａ^２１、Ｒｇ^２１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｄ^２１、およびＲｅ^２１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、アリール基または複素環基を表す。Ｑ^１１は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^２１と連結して環を形成してもよい。Ｑ^１２は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^２１と連結して環を形成してもよい。Ｘ^２３は単結合または２価の連結基を表す。Ｘ^２４は、前記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。） (D) Compound represented by general formula (D-1) Next, the compound represented by general formula (D-1) will be described in detail.

(In the general formula (D-1), Ra ²¹ and Rg ²¹ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rd ²¹ and Re ²¹ each independently represent a hydrogen atom, an alkyl group, Represents an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, Q ¹¹ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Or a heterocyclic group, which may be linked to Ra ²¹ to form a ring, Q ¹² represents —O—, —S—, or —NRh—, and Rh represents a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, an aryl group, or a heterocyclic group, which may be linked to Rg ²¹ to form a ring, X ²³ represents a single bond or a divalent linking group, and X ²⁴ represents the above general formula (P )so It represents a linking group selected from the group consisting of divalent linking group.)

（一般式（Ｄ−２）中、Ｒａ^２２、Ｒｇ^２２はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｄ^２２は水素原子、アルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^１３は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^２２と連結して環を形成してもよい。Ｑ^１４は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^２２と連結して環を形成してもよい。Ｘ^２５は、前記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。） The compound represented by the general formula (D-1) is particularly preferably represented by the following general formula (D-2).

(In the general formula (D-2), Ra ²² and Rg ²² represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rd ²² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. Q ¹³ 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; A ring may be formed by linking with Ra ^22. Q ¹⁴ represents —O—, —S—, or —NRh—, and Rh represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or Represents a heterocyclic group, and may be linked to Rg ²² to form a ring, and X ²⁵ represents a linking group selected from the group consisting of divalent linking groups represented by formula (P). .)

（一般式（Ｄ−３）中、Ｒａ^２３、Ｒｇ^２３はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^１５は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^２３と連結して環を形成してもよい。Ｑ^１６は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^２３と連結して環を形成してもよい。） The compound represented by the general formula (D-1) is particularly preferably represented by the following general formula (D-3).

(In the general formula (D-3), Ra ²³ and Rg ²³ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Q ¹⁵ 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, and may be linked to Ra ²³ to form a ring, and Q ¹⁶ represents —O— or —S—. Or -NRh-, wherein Rh represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may be linked to Rg ²³ to form a ring.

（一般式（Ｄ−４）中、Ｒ^５１およびＲ^５２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から８のアルキル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルアミノ基、炭素数１から８のジアルキルアミノ基を表す。Ｒａ^２４、Ｒｇ^２４はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^１７は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^２４と連結して環を形成してもよい。Ｑ^１８は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^２４と連結して環を形成してもよい。） The compound represented by the general formula (D-1) is particularly preferably represented by the following general formula (D-4).

(In General Formula (D-4), R ⁵¹ and R ⁵² 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. group represents an alkylamino group having a carbon number of 1 to 8, ^.ra 24 representing a dialkylamino group having a carbon number of 1 8, ^{Rg 24} represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group ^{.Q 17} Represents —O—, —S—, or —NRf—, wherein Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and is linked to Ra ²⁴ to form a ring. Q ¹⁸ represents —O—, —S—, or —NRh—, and Rh represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. And may be linked to Rg ²⁴ to form a ring.)

Preferred compound examples of the compound represented by formula (C-1) or formula (D-1) are shown below.

（一般式（Ｅ−１）中、Ｙ^１はメチン基、あるいは−Ｎ−を表す。Ｒａ^３１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｂ^３１、Ｒｃ^３１、Ｒｄ^３１およびＲｅ^３１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、アリール基または複素環基を表す。Ｑ^２１は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^３１と連結して環を形成してもよい。Ｘ^３１、Ｘ^３２、およびＸ^３３は、それぞれ独立に単結合または２価の連結基を表す。Ｘ^３４は、下記一般式（Ｑ）
一般式（Ｑ）

（一般式（Ｑ）中、＊側が前記一般式（Ｅ−１）で表される化合物中の複素環に置換しているＮ原子との連結部位である。）
で表される２価の連結基からなる群から選択される連結基を表す。） (E) Compound Represented by General Formula (E-1) Next, the compound represented by General Formula (E-1) will be described in detail.

(In General Formula (E-1), Y ¹ represents a methine group or —N—. Ra ³¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Rb ³¹ , Rc ³¹ , Rd ³¹ and Re ³¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and Q ²¹ represents a single bond, —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, and may be linked to Ra ³¹ to form a ring, X ³¹ , X ³² , and X ³³ are Each independently represents a single bond or a divalent linking group, and X ³⁴ represents the following general formula (Q):
General formula (Q)

(In General Formula (Q), the * side is a linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (E-1).)
A linking group selected from the group consisting of divalent linking groups represented by )

（一般式（Ｅ−２）中、Ｙ^２はメチン基、あるいは−Ｎ−を表す。Ｒａ^３２はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｂ^３２、Ｒｃ^３２、Ｒｄ^３２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、アリール基または複素環基を表す。Ｑ^２２は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^３２と連結して環を形成してもよい。Ｘ^３５は、それぞれ独立に単結合または２価の連結基を表す。Ｘ^３６は、前記一般式（Ｑ）で表される２価の連結基からなる群から選択される連結基を表す。） The compound represented by the general formula (E-1) is particularly preferably represented by the following general formula (E-2).

(In General Formula (E-2), Y ² represents a methine group or —N—. Ra ³² represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Rb ³² , Rc ³² , Rd ³² each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, Q ²² represents a single bond, —O—, —S—, or —NRf—, and Rf represents Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may be linked to Ra ³² to form a ring, each of X ³⁵ being independently a single bond or a divalent linkage X ³⁶ represents a linking group selected from the group consisting of divalent linking groups represented by formula (Q).

（一般式（Ｅ−３）中、Ｙ^３はメチン基、あるいは−Ｎ−を表す。Ｒａ^３３はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^２３は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^３３と連結して環を形成してもよい。） The compound represented by the general formula (E-1) is particularly preferably represented by the following general formula (E-3).

(In General Formula (E-3), Y ³ represents a methine group or —N—. Ra ³³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Q ²³ represents a single bond, -O -, - S-, or -NRf- indicates, Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and in conjunction with ^{Ra 33} to form a ring May be good.)

（一般式（Ｅ−４）中、Ｙ^４はメチン基、あるいは−Ｎ−を表す。Ｒａ^３４はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^２４は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^３４と連結して環を形成してもよい。Ｒ^６１、Ｒ^６２、Ｒ^６３およびＲ^６４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から８のアルキル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルアミノ基、炭素数１から８のジアルキルアミノ基を表す。） The compound represented by the general formula (E-1) is particularly preferably represented by the following general formula (E-4).

(In General Formula (E-4), Y ⁴ represents a methine group or —N—. Ra ³⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Q ²⁴ represents a single bond, -O -, - S-, or -NRf- indicates, Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and in conjunction with ^{Ra 34} to form a ring R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ 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 and a dialkylamino group having 1 to 8 carbon atoms.)

（一般式（Ｅ−５）中、Ｒ^６５、Ｒ^６６、Ｒ^６７およびＲ^６８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から８のアルキル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルアミノ基、炭素数１から８のジアルキルアミノ基を表す。Ｒａ^３５はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^２５は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^３５と連結して環を形成してもよい。） The compound represented by the general formula (E-1) is particularly preferably represented by the following general formula (E-5).

(In the general formula (E-5), R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ 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, carbon Represents an alkoxy group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, and a dialkylamino group having 1 to 8 carbon atoms, and Ra ³⁵ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Q ²⁵ represents a single bond, —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, and is linked to Ra ^35. To form a ring.)

（一般式（Ｆ−１）中、Ｙ^１１はメチン基、あるいは−Ｎ−を表す。Ｒａ^４１、Ｒｇ^４１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｄ^４１、およびＲｅ^４１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、アリール基または複素環基を表す。Ｑ^３１は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^４１と連結して環を形成してもよい。Ｑ^３２は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^４１と連結して環を形成してもよい。Ｘ^４３は単結合または２価の連結基を表す。Ｘ^４４は、前記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。但し、前記一般式（Ｐ）中、＊側が前記一般式（Ｆ−１）で表される化合物中の複素環に置換しているＮ原子との連結部位である。） (F) Compound represented by general formula (F-1)

(In General Formula (F-1), Y ¹¹ represents a methine group or —N—. Ra ⁴¹ and Rg ⁴¹ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Rd ⁴¹ , And Re ⁴¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, Q ³¹ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom. , An alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, which may be linked to Ra ⁴¹ to form a ring, and Q ³² represents —O—, —S—, or —NRh—. shows, Rh is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, linked may form a ring .X ⁴³ Ren single bond or a divalent and Rg ^41, Represents a group .X ⁴⁴ represents a linking group selected from the group consisting of divalent linking group represented by the general formula (P). However, in the general formula (P), * side is the formula (It is a connection site | part with the N atom substituted by the heterocyclic ring in the compound represented by (F-1).)

（一般式（Ｆ−２）中、Ｙ^１２はメチン基、あるいは−Ｎ−を表す。Ｒａ^４２、Ｒｇ^４２はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｒｄ^４２は水素原子、アルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^３３は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^４２と連結して環を形成してもよい。Ｑ^３４は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^４２と連結して環を形成してもよい。Ｘ^４３は単結合または２価の連結基を表す。Ｘ^４５は、前記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。但し、前記一般式（Ｐ）中、＊側が前記一般式（Ｆ−１）で表される化合物中の複素環に置換しているＮ原子との連結部位である。） The compound represented by the general formula (F-1) is particularly preferably represented by the following general formula (F-2).

(In General Formula (F-2), Y ¹² represents a methine group or —N—. Ra ⁴² and Rg ⁴² represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Rd ⁴² represents Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, Q ³³ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, an aryl group, or a heterocyclic group, which may combine with Ra ⁴² to form a ring, Q ³⁴ represents —O—, —S—, or —NRh—, Rh represents a hydrogen atom, Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may combine with Rg ⁴² to form a ring, X ⁴³ represents a single bond or a divalent linking group, and X ⁴⁵ represents , The general formula Represents a linking group selected from the group consisting of a divalent linking group represented by (P), provided that in the compound represented by the general formula (F-1), the * side in the general formula (P). This is the linking site with the N atom substituted on the heterocyclic ring of

（一般式（Ｆ−３）中、Ｙ^１３はメチン基、あるいは−Ｎ−を表す。Ｒａ^４３、Ｒｇ^４３はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^３５は−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^４３と連結して環を形成してもよい。Ｑ^３６は−Ｏ−、−Ｓ−、あるいは−ＮＲｈ−を示し、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、または複素環基を表し、Ｒｇ^４３と連結して環を形成してもよい。） The compound represented by the general formula (F-1) is particularly preferably represented by the following general formula (F-3).

(In General Formula (F-3), Y ¹³ represents a methine group or —N—. Ra ⁴³ and Rg ⁴³ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and Q ³⁵ represents -O -, - S-, or -NRf- indicates, Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and in conjunction with ^{Ra 43} to form a ring Q ³⁶ represents —O—, —S—, or —NRh—, and Rh represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and is linked to Rg ^43. To form a ring.)

（一般式（Ｆ−４）中、Ｙ^１４はメチン基、あるいは−Ｎ−を表す。Ｒａ^４４およびＲｇ^４４はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^３７は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^４４と連結して環を形成してもよい。Ｑ^３８は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒｇ^４４と連結して環を形成してもよい。Ｒ^７１およびＲ^７２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から８のアルキル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルアミノ基、炭素数１から８のジアルキルアミノ基を表す。） The compound represented by the general formula (F-1) is particularly preferably represented by the following general formula (F-4).

(In General Formula (F-4), Y ¹⁴ represents a methine group or —N—. Ra ⁴⁴ and Rg ⁴⁴ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, Q ³⁷ represents A single bond, —O—, —S—, or —NRf—, wherein Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and is linked to Ra ⁴⁴ to form a ring; Q ³⁸ represents a single bond, —O—, —S—, or —NRf—, and Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. And Rg ⁴⁴ may be linked to form a ring, each of R ⁷¹ and R ⁷² is 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, a carbon number Represents an alkoxy group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, and a dialkylamino group having 1 to 8 carbon atoms.)

（一般式（Ｆ−５）中、Ｒａ^４５およびＲｇ^４５はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表す。Ｑ^３９は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒａ^４５と連結して環を形成してもよい。Ｑ^４０は単結合、−Ｏ−、−Ｓ−、あるいは−ＮＲf−を示し、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、または複素環基を表し、Ｒｇ^４５と連結して環を形成してもよい。Ｒ^７３およびＲ^７４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から８のアルキル基、炭素数１から８のアルコキシ基、炭素数１から８のアルキルアミノ基、炭素数１から８のジアルキルアミノ基を表す。） The compound represented by the general formula (F-1) is particularly preferably represented by the following general formula (F-5).

(In the general formula (F-5), Ra ⁴⁵ and Rg ⁴⁵ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Q ³⁹ represents a single bond, —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, and may be linked to Ra ⁴⁵ to form a ring, Q ⁴⁰ is a single bond,- O—, —S—, or —NRf—, wherein Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may combine with Rg ⁴⁵ to form a ring. good .R ⁷³ and R ⁷⁴ 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, 1 to 8 of carbon atoms Alkylamino group, a dialkylamino group having from 1 to 8 carbon atoms.)

  Preferred examples of the compound represented by formula (E-1) or formula (F-1) are shown below.

The compound of the said general formula (E-1) is compoundable by the method of the following scheme 1, for example. That is, it can be synthesized by reacting the compound of general formula (E-1a) and the compound of general formula (E-1b) in an organic solvent in the presence of a base. As the compounds of general formula (E-1a) and general formula (E-1b), commercially available products or synthetic products produced by known synthesis methods can be used. Examples of the organic solvent include alcohol (eg, methanol, ethanol), ester (eg, ethyl acetate), hydrocarbon (eg, toluene), ether (eg, tetrahydrofuran), amide (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, and methanol, ethanol, N-methylpyrrolidone and N-ethylpyrrolidone are 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. Organic 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 (E-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.

スキーム１中、Ｚは脱離基を表し、好ましくはハロゲン基、アルコキシ基、アリールオキシ基を表す。 Scheme 1

In Scheme 1, Z represents a leaving group, preferably a halogen group, an alkoxy group, or an aryloxy group.

  The compound of the said general formula (E-2) used for this invention is compoundable by the method of the following scheme 2, for example. That is, it can be synthesized by reacting the compound of general formula (E-2a) with the compounds of general formula (E-2b) and general formula (E-2c) in an organic solvent in the presence of a base. As the compounds of general formula (E-2a), general formula (E-2b) and general formula (E-2c), commercially available products or synthetic products produced by known synthesis methods can be used. Suitable examples of the organic solvent to be used are the same as described above. Suitable examples of the base to be used are the same as described above, but the amount of the base to be used is based on the total amount of the compound represented by the general formula (E-2b) and the compound represented by the general formula (E-2c). The range of 0.5 to 10 equivalents is preferable, and the range of 1 to 3 equivalents is particularly preferable. Suitable examples of the reaction temperature and reaction time used are the same as described above.

Scheme 2

前記一般式（Ｇ−１）中、Ｌ^１は単結合またはヘテロ原子を含む２価の連結基を表し、ヘテロ原子を含む２価の連結基であることが好ましい。前記Ｌ^１が表す前記ヘテロ原子を含む２価の連結基としては、連結に関与する２本の結合手を同一原子が有する連結基であることが好ましい。このような連結基としては、−Ｏ−、−Ｎ（Ｒ^８２）−、−Ｃ（＝Ｏ）−、−Ｓ−、−Ｓ（＝Ｏ）_２−、およびそれらの組合せからなる連結基などを挙げることができる。なお、前記Ｒ^８２の範囲は前記Ｒ^３の範囲と同様であり、前記Ｒ^８２の好ましい範囲は、水素原子または炭素数１〜１５のアルキル基（より好ましくは炭素数１〜１０、特に好ましくは炭素数１〜５、より特に好ましくはメチル基）である。
これらの中でも、−Ｏ−、−ＮＨ−および−Ｎ（ＣＨ_３）−、−Ｃ（＝Ｏ）−、およびそれらの組合せからなる連結基が好ましく、−Ｏ−、−ＮＨ−Ｃ（＝Ｏ）−および−Ｎ（ＣＨ_３）−がより好ましい。 Next, the compound represented by formula (G-1) will be described in detail.

In General Formula (G-1), L ¹ represents a divalent linking group containing a single bond or a hetero atom, and preferably a divalent linking group containing a hetero atom. The divalent linking group containing the heteroatom represented by L ¹ is preferably a linking group in which the same atom has two bonds involved in the connection. Examples of such a linking group include linking groups composed of —O—, —N (R ⁸² ) —, —C (═O) —, —S—, —S (═O) ₂ —, and combinations thereof. Can be mentioned. The range of the R ^{82 is the same as} the range of the R ³ , and the preferable range of the R ⁸² is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms (more preferably 1 to 10 carbon atoms, particularly preferably C1-C5, more preferably methyl group).
Among these, a linking group comprising —O—, —NH— and —N (CH ₃ ) —, —C (═O) —, and a combination thereof is preferable, and —O—, —NH—C (═O ) - and -N (CH ₃₎ - is more preferred.

In the general formula (G-1), R ⁸¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an alkyl group having 5 to 20 carbon atoms. It represents a heteroaryl group or an aryl group having 6 to 20 carbon atoms.
When R ⁸¹ is an alkyl group, it preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
When R ¹ and R ² are each independently an alkenyl group, it is preferably 12 to 15 carbon atoms, more preferably 12 to 10 carbon atoms, and particularly preferably 12 to 5 carbon atoms.
When R ⁸¹ is an alkynyl group, it preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 5 carbon atoms.
When R ⁸¹ is an alkyl group, an alkenyl group, or an alkynyl group, it may be cyclic, linear or branched, but is preferably linear or branched, and more preferably linear.
When R ⁸¹ is a heteroaryl group, the number of carbon atoms is preferably 5-18, and more preferably 5-12.
When R ⁸¹ is an aryl group, the number of carbon atoms is preferably 6-18, and more preferably 6-12.
When R ⁸¹ is an arylalkyl group, the number of carbon atoms is preferably 7-18, and more preferably 7-12.

R ⁸¹ may further have a substituent or may be unsubstituted. The substituent is not particularly limited as long as it is not contrary to the gist of the present invention, but is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms. And a heteroaryl group having 5 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms are preferable. Among them, an aryl group having 6 to 20 carbon atoms is more preferable, and in particular, when R ⁸¹ is an alkyl group having a substituent, the substituent is preferably a phenyl group.

Preferred combinations of L ¹ and R ⁸¹ are as follows.
When L ¹ is —O—, R ⁸¹ is preferably an alkyl group having 1 to 15 carbon atoms or an arylalkyl group, and more preferably an arylalkyl group.
When L ¹ is —NH—, R ⁸¹ is preferably an alkyl group having 1 to 15 carbon atoms or an arylalkyl group, and more preferably an arylalkyl group.
When L ¹ is —NH—C (═O) —, R ⁸¹ is preferably an alkyl group having 1 to 15 carbon atoms or an aryl group, and more preferably an alkyl group.
When L ¹ is —N (CH ₃ ) —, R ⁸¹ is preferably an alkyl group having 1 to 15 carbon atoms or an alkyl group, and more preferably an alkyl group.

R ⁸¹ is more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms from the viewpoint of suppressing retardation change with respect to environmental humidity.

  The hydrogen bonding compound used in the present invention is preferably a compound in which the number of amino groups in the purine base skeleton excluding the substituent is 0 or 1 among the compounds represented by the general formula (G-1).

In the compound represented by the general formula (G-1), the hydrogen bonding compound used in the present invention is preferably such that R ¹ is not a hydrogen atom. That is, as for the hydrogen bonding compound used for this invention, it is more preferable that the compound containing the said nucleobase skeleton is represented by the following general formula (G-2).

In General Formula (G-2), L ² represents a single bond or a divalent linking group containing a hetero atom, R ⁸² represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or the number of carbon atoms A 2-20 alkynyl group, a C6-C20 aryl group, or a C7-C20 arylalkyl group is represented.

In the general formula (G-2), a preferable range of L ^{2 is the same as} the preferable range of L ^{1 in} the general formula (G-1).

Wherein ^{R 82} is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group or an arylalkyl group having 7 to 20 carbon atoms of 6 to 20 carbon atoms The preferable carbon number range of each group is the same as the preferable carbon number range of each group in R ⁸¹ in the general formula (G-1).
R ⁸² is more preferably a methyl group, a phenyl group or a benzyl group, and particularly preferably a methyl group, a phenyl group or a benzyl group.

In the general formula (G-2), a preferable combination of L ² and R ⁸² has the same tendency as the preferable combination of L ¹ and R ⁸¹ in the general formula (G-1).

The hydrogen bonding compound may control the interaction between the compound containing the nucleobase skeleton and the cellulose acylate so as not to cause haze in the cellulose acylate film or to bleed out or volatilize from the film. preferable.
Examples of the partial structure capable of interacting with cellulose acylate by a hydrogen bond or the like that the compound containing the nucleobase skeleton preferably has include a purine base skeleton, an ether bond structure, an ester bond structure, an amide bond structure, -NH- linking group structure and the like can be mentioned.

(Specific Example of Compound Represented by General Formula (G-1) Containing Nucleobase Skeleton)
Specific examples of the compound represented by the general formula (G-1) containing the nucleobase skeleton include the following. However, the compound represented by General Formula (G-1) containing the nucleobase skeleton that can be used as the hydrogen bonding compound is not limited thereto.

（一般式（Ｈ−１）中、Ｌ^３は単結合またはヘテロ原子を含む２価の連結基を表し、Ｒ^８５は炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数６〜２０のアリール基または炭素数７〜２０のアリールアルキル基を表す。）Ｒ^８３、Ｒ^８４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、アリール基または複素環基を表す。Ｘ^５３、Ｘ^５４はそれぞれ独立に、前記一般式（Ｐ）で表される２価の連結基からなる群から選択される連結基を表す。但し、前記一般式（Ｐ）中、＊側が前記一般式（Ｈ−１）で表される化合物中の複素環に置換しているＮ原子との連結部位である。） (H) Compound Represented by General Formula (H-1) Next, the compound represented by General Formula (H-1) will be described in detail.

(In General Formula (H-1), L ³ represents a single bond or a divalent linking group containing a hetero atom, R ⁸⁵ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon Represents an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.) R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. Represents an aryl group or a heterocyclic group. X ⁵³ and X ⁵⁴ each independently represent a linking group selected from the group consisting of a divalent linking group represented by the general formula (P). However, * side in the said general formula (P) is a connection part with the N atom substituted by the heterocyclic ring in the compound represented by the said general formula (H-1). )

The preferable example of a compound represented by general formula (H-1) below is shown.

(Physical properties)
The compounds represented by the general formulas (A-1) to (H-1) preferably have a molecular weight of 100 to 1000, more preferably 150 to 700, and 150 or more and 450 or less. Most preferred.

(Addition amount)
The addition amount of the compounds represented by the general formulas (A-1) to (H-1) is preferably 30% by mass or less, and preferably 1 to 30% by mass with respect to the cellulose acylate resin. Is more preferably 2 to 20% by mass, and further preferably 3 to 15% by mass.
In the film of the present invention, the total content of the hydrogen bonding compound with respect to the cellulose acylate resin is preferably 35% by mass or less, more preferably 30% by mass or less, and 20% by mass or less. It is particularly preferred that The hydrogen bonding compound is not limited to the compounds represented by the general formulas (A-1) to (H-1).

<Hydrophobicizing agent>
The cellulose acylate film of the present invention contains at least one hydrophobizing agent selected from a polyhydric alcohol ester hydrophobizing agent, a polycondensation ester hydrophobizing agent and a carbohydrate derivative hydrophobizing agent. The hydrophobizing agent is preferably one that can reduce the water content without reducing the glass transition temperature of the film as much as possible. By using such a hydrophobizing agent, the phenomenon that the additive in the cellulose acylate film diffuses into the polarizer layer under high temperature and high humidity can be suppressed, and deterioration of the polarizer performance can be improved. Hereinafter, the hydrophobizing agent used in the present invention will be described in detail.

(Polyhydric alcohol ester hydrophobizing agent)
The polyhydric alcohol used in 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, and n represents a positive integer of 2 or more.)
Preferred examples of the polyhydric alcohol hydrophobizing agent include the following, but the present invention is not limited thereto. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane- Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  Among them, the polyhydric alcohol hydrophobizing agent is preferably a polyhydric alcohol ester using a polyhydric alcohol having 5 or more carbon atoms. Most preferably, it is C5-C20.

  There is no restriction | limiting in particular as monocarboxylic acid used for the said 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 the monocarboxylic acid used in the preferred polyhydric alcohol ester include the following, but the present invention is not limited thereto.

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

  Preferred examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecyl Acids, 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 And unsaturated fatty acids such as oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid.

  Preferred examples of the alicyclic monocarboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.

  Preferred examples of the aromatic monocarboxylic acid 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 benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. Although the aromatic monocarboxylic acid which has the above, or those derivatives can be mentioned, benzoic acid is especially preferable.

  The molecular weight of the polyhydric alcohol hydrophobizing agent is not particularly limited, but is preferably 300 to 3000, and more preferably 350 to 1500. A higher molecular weight is preferable because it is less likely to volatilize, and a lower molecular weight is preferable in terms of moisture permeability and compatibility with cellulose derivatives.

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

  Specific compounds of the polyhydric alcohol ester are shown below.

(Polycondensed ester hydrophobizing agent)
The polycondensation ester hydrophobizing agent is obtained from at least one dicarboxylic acid having an aromatic ring (also referred to as aromatic dicarboxylic acid) and at least one aliphatic diol having an average carbon number of 2.5 to 8.0. It is preferable. Moreover, it is also preferable to obtain from the mixture of aromatic dicarboxylic acid and at least 1 type of aliphatic dicarboxylic acid, and at least 1 type of aliphatic diol whose average carbon number is 2.5-8.0.

Calculation of the average carbon number of the dicarboxylic acid residue is performed separately for the dicarboxylic acid residue and the diol residue.
The value calculated by multiplying the constituent carbon number by the composition ratio (molar fraction) of the dicarboxylic acid residue is defined as the average carbon number. For example, when the adipic acid residue and the phthalic acid residue are composed of 50 mol% each, the average carbon number is 7.0.
The same applies to the diol residue, and the average carbon number of the diol residue is a value calculated by multiplying the constituent carbon number by the composition ratio (molar fraction) of the diol residue. For example, when it is composed of 50 mol% of ethylene glycol residues and 50 mol% of 1,2-propanediol residues, the average carbon number is 2.5.

The number average molecular weight of the polycondensed ester is preferably 500 to 2000, more preferably 600 to 1500, and still more preferably 700 to 1200. If the number average molecular weight of the polycondensed ester is 600 or more, the volatility is low, and film failure or process contamination due to volatilization under high temperature conditions during stretching of the cellulose ester film is less likely to occur. Moreover, if it is 2000 or less, compatibility with a cellulose ester will become high, and it will become difficult to produce the bleed-out at the time of film forming and the heat-stretching.
The number average molecular weight of the polycondensed ester can be measured and evaluated by gel permeation chromatography. Further, in the case of a polyester polyol having an unsealed terminal, it can also be calculated from the amount of hydroxyl groups per weight (hereinafter also referred to as hydroxyl value). In the present invention, the hydroxyl value is determined by measuring the amount (mg) of potassium hydroxide required for neutralizing excess acetic acid after acetylating the polyester polyol.

When a mixture of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid is used as the dicarboxylic acid component, the dicarboxylic acid component is preferably a dicarboxylic acid having an average carbon number of 5.5 to 10.0, more preferably 5 .6-8.
If the average carbon number is 5.5 or more, a polarizing plate having excellent durability can be obtained. If the average number of carbon atoms is 10 or less, the compatibility with the cellulose ester is excellent, and the occurrence of bleed out can be suppressed in the process of forming the cellulose ester film.

The polycondensation ester obtained from a diol and a dicarboxylic acid containing an aromatic dicarboxylic acid contains an aromatic dicarboxylic acid residue.
In the present specification, a residue is a partial structure of a polycondensed ester and represents a partial structure having the characteristics of a monomer forming the polycondensed ester. For example, the dicarboxylic acid residue formed from dicarboxylic acid HOOC-R-COOH is -OC-R-CO-.
The aromatic dicarboxylic acid residue ratio of the polycondensed ester used in the present invention is preferably 40 mol% or more, and more preferably 40 mol% to 95 mol%.
By setting the aromatic dicarboxylic acid residue ratio to 40 mol% or more, a cellulose ester film exhibiting sufficient optical anisotropy can be obtained, and a polarizing plate excellent in durability can be obtained. Moreover, if it is 95 mol% or less, it is excellent in compatibility with a cellulose ester, and it can make it hard to produce a bleed-out also at the time of film forming of a cellulose ester film, and the time of heat-stretching.

Examples of the aromatic dicarboxylic acid that can be used to form the polycondensation ester hydrophobizing agent that can be used in the present invention include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, and 1,4. -Naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc. can be mentioned. Of these, phthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid are preferable, phthalic acid and terephthalic acid are more preferable, and terephthalic acid is more preferable.
An aromatic dicarboxylic acid residue derived from the aromatic dicarboxylic acid used for mixing is formed in the polycondensed ester.
That is, the aromatic dicarboxylic acid residue preferably includes at least one of a phthalic acid residue, a terephthalic acid residue, and an isophthalic acid residue, more preferably at least one of a phthalic acid residue and a terephthalic acid residue. A seed, more preferably a terephthalic acid residue.
By using terephthalic acid as the aromatic dicarboxylic acid for mixing in the formation of the polycondensed ester, it is more compatible with the cellulose ester, and bleed-out is less likely to occur during film formation and heat stretching of the cellulose ester film. It can be set as a cellulose ester film. The aromatic dicarboxylic acid may be used alone or in combination of two or more. When two types are used, it is preferable to use phthalic acid and terephthalic acid.
By using together two kinds of aromatic dicarboxylic acids of phthalic acid and terephthalic acid, the polycondensation ester at normal temperature can be softened, which is preferable in terms of easy handling.
The content of the terephthalic acid residue in the dicarboxylic acid residue of the polycondensed ester is preferably 40 mol% to 100 mol%.
By setting the terephthalic acid residue ratio to 40 mol% or more, a cellulose ester film exhibiting sufficient optical anisotropy can be obtained.

A polycondensation ester obtained from a diol and a dicarboxylic acid containing an aliphatic dicarboxylic acid contains an aliphatic dicarboxylic acid residue.
Examples of the aliphatic dicarboxylic acid that can form a polycondensation ester hydrophobizing agent that can be preferably used in the present invention include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and adipic acid. , Pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid.
In the polycondensed ester, an aliphatic dicarboxylic acid residue derived from the aliphatic dicarboxylic acid used for mixing is formed.
The aliphatic dicarboxylic acid residue preferably has an average carbon number of 5.5 to 10.0, more preferably 5.5 to 8.0, and preferably 5.5 to 7.0. Further preferred. If the average carbon number of the aliphatic dicarboxylic acid residue is 10.0 or less, the heat loss of the compound can be reduced, and the occurrence of surface failure that may be caused by process contamination due to bleed-out during drying of the cellulose acylate web is prevented. be able to. Moreover, it is preferable that the aliphatic dicarboxylic acid residue has an average carbon number of 5.5 or more because it is excellent in compatibility and precipitation of the polycondensed ester hardly occurs.
Specifically, the aliphatic dicarboxylic acid residue preferably includes a succinic acid residue, and when two types are used, it preferably includes a succinic acid residue and an adipic acid residue.
That is, one kind of aliphatic dicarboxylic acid or two or more kinds may be used for mixing in the formation of the polycondensed ester. When two kinds are used, it is preferable to use succinic acid and adipic acid. When one kind of aliphatic dicarboxylic acid is used for mixing in the formation of the polycondensed ester, it is preferable to use succinic acid. The average carbon number of the aliphatic dicarboxylic acid residue can be adjusted to a desired value, which is preferable in terms of compatibility with the cellulose ester.

  In the present invention, it is preferable to use two or three dicarboxylic acids for mixing in the formation of the polycondensed ester. When using two kinds, it is preferable to use one kind of aliphatic dicarboxylic acid and one kind of aromatic dicarboxylic acid. When using three kinds, one kind of aliphatic dicarboxylic acid and two kinds of aromatic dicarboxylic acid or aliphatic dicarboxylic acid are used. Two kinds of acids and one kind of aromatic dicarboxylic acid can be used. This is because the average carbon number value of the dicarboxylic acid residue can be easily adjusted, the content of the aromatic dicarboxylic acid residue can be within a preferable range, and the durability of the polarizer can be improved.

A polycondensation ester obtained from a diol and a dicarboxylic acid containing a dicarboxylic acid contains a diol residue.
In the present specification, the diol residue formed from the diol HO—R—OH is —O—R—O—.
Examples of the diol that forms the polycondensed ester include aromatic diols and aliphatic diols. The polycondensed ester used in the hydrophobizing agent used in the present invention is preferably formed from at least an aliphatic diol.
The polycondensed ester preferably contains an aliphatic diol residue having an average carbon number of 2.5 to 7.0, more preferably an aliphatic diol residue having an average carbon number of 2.5 to 4.0. Including. When the average carbon number of the aliphatic diol residue is less than 7.0, the compatibility with the cellulose ester is improved, bleed-out is less likely to occur, and the heat loss of the compound is less likely to be increased. It is difficult for surface failures that are thought to be caused by process contamination during drying to occur. Further, the synthesis is easy if the average carbon number of the aliphatic diol residue is 2.5 or more.
Preferred examples of the aliphatic diol that can form the polycondensation ester hydrophobizing agent that can be used in the present invention include alkyl diols and alicyclic diols, such as ethylene glycol, 1,2, and the like. -Propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-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-hexa Diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10- Decanediol, 1,12-octadecanediol, diethylene glycol, cyclohexanedimethanol and the like are preferable. These are preferably used together with ethylene glycol as one or a mixture of two or more.

More preferably, the aliphatic diol is at least one of ethylene glycol, 1,2-propanediol, and 1,3-propanediol, and particularly preferably at least one of ethylene glycol and 1,2-propanediol. It is. In the case where the polycondensation ester is formed using two kinds of the aliphatic diol, it is preferable to use ethylene glycol and 1,2-propanediol. By using 1,2-propanediol or 1,3-propanediol, crystallization of the polycondensed ester can be prevented.
In the polycondensed ester, a diol residue is formed by the diol used for mixing.
That is, the polycondensation ester preferably contains at least one of an ethylene glycol residue, a 1,2-propanediol residue, and a 1,3-propanediol residue as a diol residue. More preferably, it is a 1,2-propanediol residue.
The aliphatic diol residue contained in the polycondensed ester preferably contains 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol% of ethylene glycol residue.

The terminal of the polycondensed ester may be left as it is without being blocked, and may be left as a diol or carboxylic acid, or may be further blocked with a so-called terminal by reacting with a monocarboxylic acid or monoalcohol.
As monocarboxylic acids used for sealing, acetic acid, propionic acid, butanoic acid, benzoic acid and the like are preferable. As monoalcohols used for sealing, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and the like are preferable, and methanol is most preferable. When the number of carbon atoms of the monocarboxylic acid used at the terminal of the polycondensed ester is 7 or less, the loss on heating of the compound does not increase, and no surface failure occurs.
More preferably, the end of the polycondensed ester remains as a diol residue without being sealed, or is sealed with acetic acid, propionic acid or benzoic acid.
It does not matter whether both ends of the polycondensed ester have the same sealing performance.
When both ends of the condensate are unsealed, the polycondensed ester is preferably a polyester polyol.
One aspect of the polycondensed ester is a polycondensed ester in which the aliphatic diol residue has 2.5 to 8.0 carbon atoms, and both ends of the polycondensed ester are unblocked.
When both ends of the polycondensed ester are sealed, it is preferably sealed by reacting with a monocarboxylic acid. At this time, both ends of the polycondensed ester are monocarboxylic acid residues. In the present specification, the monocarboxylic acid residue formed from the monocarboxylic acid R-COOH is R-CO-. When both ends of the polycondensed ester are sealed with a monocarboxylic acid, the monocarboxylic acid is preferably an aliphatic monocarboxylic acid residue, and the monocarboxylic acid residue is an aliphatic monocarboxylic acid having 22 or less carbon atoms. It is more preferably a carboxylic acid residue, and even more preferably an aliphatic monocarboxylic acid residue having 3 or less carbon atoms. In addition, an aliphatic monocarboxylic acid residue having 2 or more carbon atoms is preferable, and an aliphatic monocarboxylic acid residue having 2 carbon atoms is particularly preferable.
In one embodiment of the polycondensation ester, the aliphatic diol residue has a carbon number of more than 2.5 and 7.0 or less, and both ends of the polycondensation ester are capped with monocarboxylic acid residues. Mention may be made of condensed esters.
When the carbon number of the monocarboxylic acid residue sealing both ends of the polycondensed ester is 3 or less, the volatility is lowered, the weight loss due to heating of the polycondensed ester is not increased, and the occurrence of process contamination It is possible to reduce the occurrence of planar failures.
That is, the monocarboxylic acid used for sealing is preferably an aliphatic monocarboxylic acid, more preferably an aliphatic monocarboxylic acid having 2 to 22 carbon atoms, and an aliphatic monocarboxylic acid having 2 to 3 carbon atoms. A carboxylic acid is more preferable, and an aliphatic monocarboxylic acid residue having 2 carbon atoms is particularly preferable.
For example, acetic acid, propionic acid, butanoic acid, benzoic acid and derivatives thereof are preferable, acetic acid or propionic acid is more preferable, and acetic acid is most preferable.
Two or more monocarboxylic acids used for sealing may be mixed.
Both ends of the polycondensed ester are preferably sealed with acetic acid or propionic acid, and most preferably both ends are acetyl ester residues (sometimes referred to as acetyl residues).
When both ends of the polycondensed ester are sealed, a cellulose ester film that is difficult to be in a solid state at normal temperature, has good handling, and is excellent in humidity stability and polarizing plate durability can be obtained.

  Specific examples J-1 to J-38 of the polycondensed ester are shown in Table 5 below, but the present invention is not limited thereto.

  The abbreviations in Table 5 above represent the following compounds, respectively. PA: phthalic acid, TPA: terephthalic acid, AA: adipic acid, SA: succinic acid, 2,6-NPA: 2,6-naphthalenedicarboxylic acid.

  The synthesis of the polycondensed ester is performed either by a conventional method, a hot melt condensation method by a polyesterification reaction or transesterification reaction between a diol and a dicarboxylic acid, or an interfacial condensation method between an acid chloride of these acids and a glycol. Can be easily synthesized. The polycondensation ester is described in detail in Koichi Murai, “Plasticizers, Theory and Application” (Kobo Publishing Co., Ltd., first published 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.

(Carbohydrate derivative hydrophobizing agent)
The hydrophobizing agent is preferably a monosaccharide or a carbohydrate derivative containing 2 to 10 monosaccharide units (hereinafter referred to as a carbohydrate derivative hydrophobizing agent).

The monosaccharide or polysaccharide preferably constituting the carbohydrate derivative hydrophobizing agent is characterized in that a substitutable group in the molecule (for example, hydroxyl group, carboxyl group, amino group, mercapto group, etc.) is substituted. Examples of structures formed by substitution include alkyl groups, aryl groups, and acyl groups. Further, an ether structure formed by substitution with an ester structure, an ester structure formed by replacing a hydroxyl group with an acyl group, an amide structure or an imide structure formed by substitution with an amino group, and the like can be given.
Examples of the monosaccharide or carbohydrate containing 2 to 10 monosaccharide units include, for example, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, fructose, mannose, gulose, idose, galactose , Talose, trehalose, isotrehalose, neotrehalose, trehalosamine, caudibiose, nigerose, maltose, maltitol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactosamine, lactitol, lactulose, melibiose, primebelloose, rutiose , Sucrose, sucralose, turanose, vicyanose, cellotriose, cacotriose, gentianose, isomal Triose, isopanose, maltotriose, manninotriose, melezitose, panose, planteose, raffinose, solatriose, umbelliferose, lycotetraose, maltotetraose, stachyose, baltopentaose, velval course, maltohexaose, Examples include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, xylitol, sorbitol and the like.

  Preferably, ribose, arabinose, xylose, lyxose, glucose, fructose, mannose, galactose, trehalose, maltose, cellobiose, lactose, sucrose, sucralose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin Xylitol, sorbitol, more preferably arabinose, xylose, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, β-cyclodextrin, γ-cyclodextrin, particularly preferably xylose, glucose, fructose , Mannose, galactose, maltose, cellobiose, sucrose, xylitol, sorbitol.

Examples of the substituent of the carbohydrate derivative hydrophobizing agent include an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, , Methyl group, ethyl group, propyl group, hydroxyethyl group, hydroxypropyl group, 2-cyanoethyl group, benzyl group, etc.), aryl group (preferably having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 carbon atoms). To 12 aryl groups such as phenyl and naphthyl groups, acyl groups (preferably having 1 to 22 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms acyl groups such as acetyl group). , Propionyl group, butyryl group, pentanoyl group, hexanoyl group, octanoyl group, benzoyl group, toluyl group, phthalyl group, naphthal group, etc. It can be mentioned. Further, as a preferred structure formed by substitution with an amino group, an amide structure (preferably an amide having 1 to 22 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as formamide, acetamide, etc. And imide structure (preferably having 4 to 22 carbon atoms, more preferably 4 to 12 carbon atoms, and particularly preferably 4 to 8 carbon atoms, such as succinimide and phthalimide).
Among these, an alkyl group, an aryl group or an acyl group is more preferable, and an acyl group is particularly preferable.

Preferable examples of the carbohydrate derivative hydrophobizing agent include the following. However, the carbohydrate derivative hydrophobizing agent that can be used in the present invention is not limited to these.
Xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, glucose pentapropioate , Fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexapropionate, Xylose tetrabutyrate, glucose pentab Rate, fructose pentabylate, mannose pentabylate, galactose pentabylate, maltose octabutyrate, cellobiose octabutyrate, sucrose octabutyrate, xylitol pentabylate, sorbitol hexabutyrate, xylose tetrabenzoate, glucose pentabenzoate, Fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, xylitol pentabenzoate, sorbitol hexabenzoate and the like are preferable. Xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, glucose pentapropioate , Fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexapropionate, Xylose tetrabenzoate, glucose penta Nzoeto, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, xylitol pentabenzoate, sorbitol hexabenzoate is more preferable. Maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylose tetrapropionate, glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octane Propionate, sucrose octapropionate, xylose tetrabenzoate, glucose pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, xylitol pentabenzoate, sorbitol hexabenzoate, etc. Especially Masui.
The carbohydrate derivative hydrophobizing agent preferably has a pyranose structure or a furanose structure, and particularly preferably has a pyranose structure.

  As the carbohydrate derivative used in the present invention, the following compounds are particularly preferred. However, the carbohydrate derivatives that can be used in the present invention are not limited to these. In the following structural formulas, R each independently represents an arbitrary substituent, and a plurality of R may be the same or different.

(how to get)
As a method for obtaining the carbohydrate derivative, it can be obtained as a commercial product from Tokyo Kasei Co., Ltd., Aldrich, etc., or known ester derivatization methods for commercially available carbohydrates (for example, JP-A-8-245678). Can be synthesized by carrying out the method described in the publication.

  The carbohydrate derivative hydrophobizing agent can be obtained as a commercially available product from Tokyo Kasei Co., Ltd., Aldrich, etc. Can be synthesized by carrying out the method described in JP-A-8-245678.

  The addition amount of these hydrophobizing agents is preferably 1 to 20% by mass with respect to cellulose acylate. If the content is 1% by mass or more, the effect of improving the durability of the polarizer can be easily obtained, and if the content is 20% by mass or less, bleeding out hardly occurs. A more preferable addition amount is 2 to 15% by mass, and particularly preferably 5 to 15% by mass.

  The timing for adding these hydrophobizing agents to the cellulose acylate film is not particularly limited as long as it is added at the time of film formation. For example, it may be added at the time of cellulose acylate synthesis, or may be mixed with cellulose acylate during dope preparation.

<Cellulose acylate>
Next, the cellulose acylate used in the present invention will be described in detail.
The degree of substitution of cellulose acylate means the ratio of acylation of three hydroxyl groups present in the structural unit of cellulose (glucose having a (β) 1,4-glycoside bond). The degree of substitution (acylation degree) can be calculated by measuring the amount of bound fatty acid per unit mass of cellulose. In the present invention, the substitution degree of the cellulose body is determined from the peak intensity ratio of the carbonyl carbon in the acyl group by dissolving the cellulose body in a solvent such as dimethyl sulfoxide substituted with deuterium and measuring the ¹³ C-NMR spectrum. This can be calculated. This can be determined by ¹³ C-NMR measurement after substituting the remaining hydroxyl group of cellulose acylate with another acyl group different from the acyl group of cellulose acylate itself. Details of the measurement method are described in Tezuka et al. (Carbohydrate. Res., 273 (1995) 83-91).

The cellulose acylate in the present invention is preferably cellulose acetate having an acylation degree of 1.50 to 2.98. The acylation degree is more preferably 2.00 to 2.97.
As the acyl group of the cellulose acylate of the present invention, an acetyl group, a propionyl group, and a butyryl group are particularly preferable.

A mixed fatty acid ester composed of two or more kinds of acyl groups can also be preferably used as the cellulose acylate of the present invention. Also in this case, the acyl group is preferably an acetyl group and an acyl group having 3 to 4 carbon atoms. Further, the substitution degree of the acetyl group is preferably less than 2.5, and more preferably less than 1.9.
In the present invention, two types of cellulose acylates having different substituents and / or degree of substitution may be used in combination, mixed, or from a plurality of layers composed of different cellulose acylates by the co-casting method described later. A film may be formed.

  Furthermore, mixed acid esters having a fatty acid acyl group and a substituted or unsubstituted aromatic acyl group described in [0023] to [0038] of JP-A-2008-20896 can also be preferably used in the present invention.

  The cellulose acylate used in the present invention preferably has a mass average degree of polymerization of 250 to 800, more preferably 300 to 600. The cellulose acylate used in the present invention preferably has a number average molecular weight of 70000 to 230,000, more preferably 75000 to 230,000, and most preferably 78,000 to 120,000. preferable.

  The cellulose acylate used in the present invention can be synthesized using an acid anhydride or acid chloride as an acylating agent. When the acylating agent is an acid anhydride, an organic acid (for example, acetic acid) or methylene chloride is used as a reaction solvent. Further, a protic catalyst such as sulfuric acid can be used as the catalyst. When the acylating agent is an acid chloride, a basic compound can be used as a catalyst. In the most common synthetic method in the industry, cellulose is an organic acid corresponding to acetyl group and other acyl groups (acetic acid, propionic acid, butyric acid) or their acid anhydrides (acetic anhydride, propionic anhydride, butyric anhydride). A cellulose ester is synthesized by esterification with a mixed organic acid component containing.

  In the above method, cellulose such as cotton linter or wood pulp is activated with an organic acid such as acetic acid and then esterified using a mixture of organic acid components as described above in the presence of a sulfuric acid catalyst. In many cases. The organic acid anhydride component is generally used in an excess amount relative to the amount of hydroxyl groups present in the cellulose. In this esterification treatment, in addition to the esterification reaction, a hydrolysis reaction (depolymerization reaction) of the cellulose main chain (β) 1,4-glycoside bond) proceeds. When the hydrolysis reaction of the main chain proceeds, the degree of polymerization of the cellulose ester is lowered, and the physical properties of the cellulose ester film to be produced are lowered. Therefore, the reaction conditions such as the reaction temperature are preferably determined in consideration of the degree of polymerization and molecular weight of the resulting cellulose ester.

<Method for producing cellulose acylate film>
The cellulose acylate film in the present invention can be produced by a solvent cast method. In the solvent cast method, a film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent.

The organic solvent is selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to include a solvent.
The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of the ether, ketone, and ester (that is, —O—, —CO—, and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more kinds of functional groups, the number of carbon atoms is preferably within the above-described preferable range of carbon atoms of the solvent having any functional group.

Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.
Examples of the ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.
Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

The number of carbon atoms of the halogenated hydrocarbon having 1 to 6 carbon atoms is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogen atoms substituted by halogen in the halogenated hydrocarbon is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is most preferable that it is 40-60 mol%. Methylene chloride is a representative halogenated hydrocarbon.
Two or more kinds of organic solvents may be mixed and used.

  The cellulose acylate solution (dope) can be prepared by a general method comprising processing at a temperature of 0 ° C. or higher (ordinary temperature or high temperature). The cellulose acylate solution can be prepared using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent.

  The amount of cellulose acylate in the cellulose acylate solution is adjusted so that it is contained in an amount of 10 to 40% by mass in the resulting solution. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).

  The cellulose acylate solution can be prepared by stirring the cellulose acylate and the organic solvent at room temperature (0 to 40 ° C.). High concentration solutions may be stirred under pressure and heating conditions. Specifically, cellulose acylate and an organic solvent are placed in a pressure vessel and sealed, and stirred while heating to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil. The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., and more preferably 80 to 110 ° C.

  Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially. The container must be configured to allow stirring. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.

  When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.

  Stirring is preferably performed using a stirring blade provided inside the container. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.

  Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in a container. The prepared dope is taken out of the container after cooling, or taken out and then cooled using a heat exchanger or the like.

A cellulose acylate solution can also be prepared by a cooling dissolution method. As for the details of the cooling dissolution method, the techniques described in [0115] to [0122] of JP-A-2007-86748 can be used.
Then, cellulose acylate can be dissolved in an organic solvent in which it is difficult to dissolve cellulose acylate by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose acylate with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.

  In the cooling dissolution method, first, cellulose acylate is gradually added to an organic solvent with stirring at room temperature. The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Furthermore, you may add the arbitrary additive mentioned later in a mixture.

  The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). The mixture of the cellulose acylate and the organic solvent is solidified by cooling.

  The cooling rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The faster the cooling rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

  Furthermore, when the cooled mixture is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), cellulose acylate is dissolved in the organic solvent. The temperature may be increased by simply leaving it at room temperature or in a warm bath. The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The heating rate is the value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. is there.

  As described above, a uniform cellulose acylate solution is obtained. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

  In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.

  In addition, according to the measurement by a differential scanning calorimeter (DSC), the 20 mass% solution which melt | dissolved cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) in methyl acetate by the cooling dissolution method is. In the vicinity of 33 ° C., there exists a quasi-phase transition point between a sol state and a gel state, and a uniform gel state is obtained below this temperature. Accordingly, this solution is preferably kept at a temperature equal to or higher than the pseudo phase transition temperature, preferably about 10 ° C. plus the gel phase transition temperature. However, this pseudo phase transition temperature varies depending on the degree of acetylation of cellulose acetate, the degree of viscosity average polymerization, the concentration of the solution, and the organic solvent used.

  A cellulose acylate film is produced from the prepared cellulose acylate solution (dope) by a solvent cast method. It is preferable to add a retardation developer to the dope. The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. The surface of the drum or band is preferably finished in a mirror state. The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less.

  Regarding the drying method in the solvent cast method, US Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, and 2,492,978 Nos. 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892, and Japanese Patent Publication No. 45-4554 49-5614, JP-A-60-176834, JP-A-60-203430 and JP-A-62-115035. Drying on the band or drum can be performed by blowing an inert gas such as air or nitrogen.

  Further, the obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 ° C. to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

  Using the prepared cellulose acylate solution (dope), two or more layers can be cast to form a film. In this case, it is preferable to produce a cellulose acylate film by a solvent cast method. The dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is in the range of 10 to 40% by mass. The surface of the drum or band is preferably finished in a mirror state.

  When casting a plurality of cellulose acylate liquids of two or more layers, it is possible to cast a plurality of cellulose acylate solutions, and a plurality of casting ports provided at intervals in the direction of travel of the support Alternatively, a film may be produced while casting and laminating solutions containing cellulose acylate. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. Also, a film can be formed by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-104413, JP-A-61-158413, and JP-A-6-158413. The method described in each publication of No. 134933 can be used. Further, a flow of a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution and the high-low viscosity cellulose acylate solution is simultaneously extruded. A rolling method can also be used.

  Also, using two casting ports, the film formed on the support by the first casting port is peeled off, and the second casting is performed on the side in contact with the support surface to produce a film. You can also For example, the method described in Japanese Patent Publication No. 44-20235 can be mentioned.

  As the cellulose acylate solution to be cast, the same solution may be used, or two or more different cellulose acylate solutions may be used. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port. Furthermore, the cellulose acylate solution in the present invention can be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorbing layer, a polarizing layer, etc.).

  In the conventional single-layer solution, it is necessary to extrude a cellulose acylate solution having a high concentration and a high viscosity in order to obtain a necessary film thickness. In such a case, the stability of the cellulose acylate solution is poor and solid matter is generated, which often causes problems due to defects or poor flatness. As a solution to this problem, by casting a plurality of cellulose acylate solutions from the casting port, it is possible to extrude a highly viscous solution onto the support at the same time, improving the flatness and improving the planar film. Not only can be produced, but also the use of a concentrated cellulose acylate solution can reduce the drying load and increase the production speed of the film.

  Degradation inhibitors (for example, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines, etc.) may be added to the cellulose acylate film. The deterioration preventing agents are described in JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. Moreover, it is preferable that the addition amount of the said deterioration inhibitor is 0.01-1 mass% of the solution (dope) to prepare, and it is further more preferable that it is 0.01-0.2 mass%. If the addition amount is 0.01% by mass or more, the effect of the deterioration inhibitor is sufficiently exhibited, and if the addition amount is 1% by mass or less, the deterioration inhibitor bleeds out to the film surface (bleeding). And the like are less likely to occur. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

  In addition, it is preferable to add fine particles as a matting agent to the cellulose acylate film. The fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Mention may be made of calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable. The silicon dioxide fine particles preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.

  These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 μm, and these fine particles are present as aggregates of primary particles in the film, and 0.1 to 0.1 μm on the film surface. An unevenness of 3.0 μm is formed. The secondary average particle diameter is preferably 0.2 μm to 1.5 μm, more preferably 0.4 μm to 1.2 μm, and most preferably 0.6 μm to 1.1 μm. The primary and secondary particle sizes were determined by observing the particles in the film with a scanning electron microscope and determining the diameter of a circle circumscribing the particles as the particle size. In addition, 200 particles were observed at different locations, and the average value was taken as the average particle size.

  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.

  Among these, Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and while maintaining low turbidity of the optical film, friction This is particularly preferable because the effect of reducing the coefficient is great.

In order to obtain a cellulose acylate film having particles having a small secondary average particle size in the present invention, several methods are conceivable when preparing a fine particle dispersion. For example, 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 and dissolved by stirring. Further, a main cellulose acylate solution (dope solution) and There is a way to mix. This method is a preferred 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, after adding a small amount of cellulose ester to the solvent and dissolving with stirring, add the fine particles to this and disperse with a disperser, and use this as a fine particle additive solution. There is also a method of mixing. The present invention is not limited to these methods, but the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 20%. Mass% is most preferred. A higher dispersion concentration is preferable because the liquid turbidity with respect to the added amount is lowered, and haze and aggregates are improved. The addition amount of the matting agent fine particles in the final cellulose acylate dope solution is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, more preferably 0.08 to 0.16 g per m ^3. Is most preferred.
The solvent used 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 forming of a cellulose ester.

  These steps from casting to post-drying may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. The winder used for the production of the cellulose acylate film in the present invention may be one generally used, such as a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress, or the like. It can be wound up by a take-up method.

(Extension process)
The cellulose acylate film of the present invention can be stretched. A desired retardation can be imparted to the cellulose acylate film by stretching. The stretching direction of the cellulose acylate film is preferably either the width direction or the longitudinal direction.
Methods for stretching in the width direction are described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, and JP-A-11-48271. Yes.

  The film is stretched under heating conditions. The film can be stretched by a treatment during drying, and is particularly effective when the solvent remains. In the case of stretching in the longitudinal direction, for example, the film is stretched by adjusting the speed of the film transport roller so that the film winding speed is higher than the film peeling speed. In the case of stretching in the width direction, the film can also be stretched by conveying while holding the width of the film with a tenter and gradually widening the width of the tenter. After the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).

The cellulose acylate film of the present invention is preferably stretched at a temperature of (Tg-5 ° C.) to (Tg + 40 ° C.) using the glass transition temperature Tg of the cellulose acylate film, and (Tg) to (Tg + 35 ° C.). ) Is more preferable, and (Tg + 5 ° C.) to (Tg + 30 ° C.) is particularly preferable. In the case of a dry film, 130 ° C to 200 ° C is preferable.
Moreover, when extending | stretching in the state in which the dope solvent remained after casting, it becomes possible to extend | stretch at temperature lower than a dry film, In this case, 100 to 170 degreeC is preferable.

The stretch ratio of the cellulose acylate film of the present invention (elongation relative to the film before stretching) is preferably 1% to 200%, more preferably 5% to 150%. In particular, stretching in the width direction is preferably 1% to 200%, more preferably 5% to 150%, and particularly preferably 30 to 45%.
The stretching speed is preferably 1% / min to 300% / min, more preferably 10% / min to 300% / min, and most preferably 30% / min to 300% / min.

  In addition, the stretched cellulose acylate film in the present invention is stretched to the maximum stretch ratio, and then is subjected to a step of holding at a stretch ratio lower than the maximum stretch ratio for a certain time (hereinafter sometimes referred to as “relaxation process”). Preferably it is manufactured. The stretching ratio in the relaxation step is preferably 50% to 99% of the maximum stretching ratio, more preferably 70% to 97%, and most preferably 90% to 95%. Moreover, the time of the relaxation process is preferably 1 second to 120 seconds, and more preferably 5 seconds to 100 seconds.

Furthermore, the cellulose acylate film of the present invention can be preferably produced by including a shrinking step of shrinking while gripping the film in the width direction.
In the manufacturing method characterized by including a stretching process for stretching in the width direction of the film and a shrinking process for contracting in the film conveyance direction (longitudinal direction), the film width is held by a pantograph type or linear motor type tenter. The film can be shrunk by gradually narrowing the interval between the clips in the conveying direction while stretching in the direction.

  In the method described above, it can be said that at least a part of the stretching step and the shrinking step are performed simultaneously.

  In addition, Ichikin Kogyo Co., Ltd. is a stretching apparatus that specifically performs a stretching process that stretches either the longitudinal direction or the width direction of the film as described above, simultaneously shrinks the other, and simultaneously increases the film thickness of the film. A company-made FITZ machine or the like can be desirably used. This apparatus is described in (Japanese Patent Laid-Open No. 2001-38802).

The stretching ratio in the stretching step and the shrinkage rate in the shrinking step can be arbitrarily selected depending on the target in-plane retardation Re and the thickness direction retardation Rth. It is preferable that the draw ratio is 10% or more and the shrinkage rate in the shrinking step is 5% or more.
In particular, it preferably includes a stretching step of stretching 10% or more in the width direction of the film and a shrinking step of contracting the transport direction of the film by 5% or more while holding the film in the width direction of the film.
In addition, the shrinkage rate as used in the field of this invention means the ratio of the contracted length of the film after contraction with respect to the length of the film before contraction in the contraction direction.
The shrinkage rate is preferably 5 to 40%, particularly preferably 10 to 30%.

<Characteristics of cellulose acylate film>
(Retardation)
Next, the characteristics of the cellulose acylate film of the present invention will be described in detail.
The cellulose acylate film of the present invention preferably satisfies the relationships of the following formulas (1) to (4).
0 nm ≦ Re <300 nm Formula (1)
−50 nm <Rth <400 nm Formula (2)
0.1% ≦ {(Re at 25 ° C., relative humidity 10%) − (Re at 25 ° C., relative humidity 80%)} / (Re at 25 ° C., relative humidity 60%) ≦ 20% Formula ( 3)
0.1% ≦ {(Rth at 25 ° C. and relative humidity 10%) − (Rth at 25 ° C. and relative humidity 80%)} / (Rth at 25 ° C. and relative humidity 60%) ≦ 20% Formula ( 4)

In the formula (1), Re is preferably 0 nm to 200 nm, and more preferably 0 nm to 150 nm.
In formula (2), Rth is preferably −30 nm to 350 nm, and more preferably −10 nm to 300 nm.
In the formula (3), the value of {(Re at 25 ° C., relative humidity 10%) − (Re at 25 ° C., relative humidity 80%)} / (Re at 25 ° C., relative humidity 60%) is 0.1. % To 10% is more preferable.
In the formula (4), the value of {(Rth at 25 ° C., relative humidity 10%) − (Rth at 25 ° C., relative humidity 80%)} / (Rth at 25 ° C., relative humidity 60%) is 0.1. % To 10% is more preferable.
By using a cellulose film in which the Re humidity dependency and the Rth humidity dependency are set in the above ranges, a liquid crystal display device that hardly causes light leakage even when lit for a long time under high humidity can be obtained.

In this specification, Re (λ) and Rth (λ) respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. In addition, in this specification, the terms “Re” and “Rth” refer to Re and Rth at a wavelength of 548 nm, unless otherwise specified. 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) (in the absence of the slow axis, any in-plane value) 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 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) (when there is no slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (21) and (22).

Note:
The above Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction. In formula (21), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. . d represents the thickness of the film.

Rth = ((nx + ny) / 2−nz) × d Formula (22)
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 the above-mentioned Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis) from −50 degrees to +50 degrees with respect to the film normal direction. The light of wavelength λ nm is incident from each inclined direction in 10 degree steps 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, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). By inputting these assumed values of average refractive index and film thickness, KOBRA 21ADH or WR calculates nx, ny, and nz. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

(Thickness of cellulose acylate film)
The thickness of the cellulose acylate film in the present invention is preferably 30 μm to 100 μm, more preferably 30 μm to 80 μm, and most preferably 30 μm to 60 μm.

(Glass transition temperature of cellulose acylate film)
The glass transition temperature is measured by the following method. After adjusting the cellulose acylate film sample 24 mm × 36 mm of the present invention for 2 hours or more at 25 ° C. and a relative humidity of 60%, a dynamic viscoelasticity measuring device (Vibron: DVA-225 (made by IT Measurement Control Co., Ltd.)) Then, the distance between grips was 20 mm, the temperature rising rate was 2 ° C./min, the measurement temperature range was 30 ° C. to 200 ° C., and the frequency was 1 Hz. Taking the storage elastic modulus on the logarithmic axis on the vertical axis and the temperature on the linear axis on the horizontal axis, the storage elastic modulus suddenly decreases when the storage elastic modulus transitions from the solid region to the glass transition region. The glass transition temperature Tg was determined by the method described in FIG. 3 of K7121-1987.

(Moisture content of cellulose acylate film)
The equilibrium water content of the cellulose acylate film of the present invention at 25 ° C. and a relative humidity of 80% is preferably 0 to 5.0%. More preferably, it is 0.1 to 4.0%. If the equilibrium moisture content is 5.0% or less, the glass transition temperature drop of the cellulose acylate film due to the plasticizing effect of water is small, which is preferable from the viewpoint of suppressing the deterioration of the polarizer performance under high temperature and high humidity.
The moisture content was measured by measuring the cellulose acylate film sample 7 mm × 35 mm of the present invention by the Karl Fischer method using a moisture measuring device and a sample drying apparatus (CA-03, VA-05, both Mitsubishi Chemical Corporation). . It was calculated by dividing the amount of water (g) by the sample weight (g).

<Saponification treatment>
The cellulose acylate film of the present invention can be used as a polarizing plate protective film by imparting adhesion to a polarizer material such as polyvinyl alcohol by alkali saponification treatment. The saponification method is described in [0211] and [0212] of JP-A-2007-86748, and the method of making a polarizer of a polarizing plate, the optical characteristics of the polarizing plate, etc. are described in [0213] to [0255] of the same publication. Based on these descriptions, a polarizing plate using the film of the present invention as a protective film can be produced.

  For example, the alkali saponification treatment for the cellulose acylate film of the present invention is preferably carried out in a cycle in which the film surface is immersed in an alkaline solution, neutralized with an acidic solution, washed with water and dried. Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution, and the concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, and 0.5 to 4.0 mol / L. More preferably, it is in the range of L. The alkaline solution temperature is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.

[Polarizer]
A polarizing plate generally comprises a polarizer and two transparent protective films disposed on both sides thereof. As one protective film, the cellulose acylate film of the present invention can be used. The other protective film may be a normal cellulose acetate film. Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. The iodine polarizer and the dye polarizer are generally produced using a polyvinyl alcohol film. When the cellulose acylate film of the present invention is used as a polarizing plate protective film, the method for producing the polarizing plate is not particularly limited, and can be produced by a general method. There is a method in which the obtained cellulose acylate film is treated with an alkali and bonded to both sides of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed. Examples of the adhesive used to bond the protective film-treated surface and the polarizer include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and the like. The polarizing plate is composed of a polarizer and a protective film that protects both surfaces of the polarizer, and is further constructed by laminating 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. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.

The cellulose acylate film of the present invention is preferably bonded to the polarizer so that the transmission axis of the polarizer and the slow axis of the cellulose acylate film of the present invention are substantially parallel.
In the liquid crystal display device of the present invention, it is preferable that the transmission axis of the polarizing plate and the slow axis of the cellulose acylate film of the present invention are substantially parallel. Here, being substantially parallel means that the deviation between the direction of the main refractive index nx of the cellulose acylate film of the present invention and the direction of the transmission axis of the polarizing plate is within 5 °. It is preferable that the angle is within 0 °, preferably within 0.5 °. If the deviation is larger than 1 °, the polarization degree performance under the polarizing plate crossed Nicols is lowered, and light leakage occurs, which is not preferable.
The orthogonal transmittance CT of the polarizing plate was measured using UV3100PC (manufactured by Shimadzu Corporation). In the measurement, measurement was performed in the range of 380 nm to 780 nm, and the average value of 10 measurements was used.
The polarizing plate durability test was performed as follows in two types of forms in which (1) only the polarizing plate and (2) the polarizing plate were bonded to glass via an adhesive. For the measurement of only the polarizing plate of (1), two orthogonal ones are prepared in combination so that the cellulose acylate film of the present invention is sandwiched between two polarizers. In the measurement in the form in which the polarizing plate of (2) was attached to glass via an adhesive, a sample (about approximately) was attached on the glass so that the cellulose acylate film of the present invention was on the glass side. 2 cm × 5 cm). In the orthogonal transmittance measurement, the film side of this sample is set facing the light source and measured. Each of the two samples is measured, and the average value is defined as the orthogonal transmittance. In the Example of this invention, the test method of (2) was employ | adopted among the test methods of said (1) and (2).
As a preferable range of the polarization performance, the orthogonal transmittance CT is CT ≦ 2.0, and as a more preferable range, CT ≦ 1.3 (the unit is%).
In the polarizing plate durability test, the amount of change is preferably smaller. When the polarizing plate of the present invention is allowed to stand at 60 ° C. and a relative humidity of 90% for 240 hours, the change amount of orthogonal transmittance ΔCT ₂₄₀ (%) or when left at 60 ° C. and a relative humidity of 95% for 240 hours. It is preferable that the change amount ΔCT ₁₀₀₀ (%) of the orthogonal transmittance satisfies at least one of the following formulas (j) and (k).
−0.5 ≦ ΔCT ₂₄₀ ≦ 0.5 (j)
−0.5 ≦ ΔCT ₁₀₀₀ ≦ 0.5 (k)
Here, the amount of change is a value obtained by subtracting the measured value before the test from the measured value after the test.
When the above formula (j) or (k) is satisfied, it is preferable because stability of the polarizing plate can be ensured during use or storage for a long time under high temperature and high humidity.

<Functionalization of polarizing plate>
The polarizing plate in the present invention is a function that is combined with an optical film having functional layers such as an antireflection film, a brightness enhancement film, a hard coat layer, a forward scattering layer, and an antiglare (antiglare) layer for improving display visibility. It is also preferably used as a polarizing plate. The antireflection film, brightness enhancement film, other functional optical film, hard coat layer, forward scattering layer, and antiglare layer for functionalization are described in [0257] to [0276] of JP-A-2007-86748. Thus, a functionalized polarizing plate can be created based on these descriptions.

(Antireflection film)
The polarizing plate in the present invention can be used in combination with an antireflection film. As the antireflection film, either a film having a reflectivity of about 1.5% only by applying a single layer of a low refractive index material such as a fluorine-based polymer, or a film having a reflectivity of 1% or less using multilayer interference of a thin film is used. it can. In the present invention, a structure in which a low refractive index layer and at least one layer having a higher refractive index than that of the low refractive index layer (that is, a high refractive index layer and a middle refractive index layer) is laminated on a transparent support is preferably used. The In addition, Nitto Technical Report, vol. 38, no. 1, May, 2000, pages 26 to 28 and JP-A No. 2002-301783.

The refractive index of each layer satisfies the following relationship.
Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer

  As the transparent support used for the antireflection film, a transparent polymer film used for the protective film for the polarizer described above can be preferably used.

  The refractive index of the low refractive index layer is preferably 1.20 to 1.55, more preferably 1.30 to 1.50. The low refractive index layer is preferably used as an outermost layer having scratch resistance and antifouling properties. In order to improve the scratch resistance, it is also preferable to impart slipperiness to the surface using a material such as a silicone-containing compound containing a silicone group or a fluorine-containing compound containing fluorine.

Examples of the fluorine-containing compound include JP-A-9-222503 [0018] to [0026], JP-A-11-38202 [0019] to [0030], JP-A 2001-40284 [0027] to [0027]. [0028] The compounds described in JP 2000-284102 A and the like can be preferably used.
The silicone-containing compound is preferably a compound having a polysiloxane structure, such as reactive silicone (for example, Silaplane (manufactured by Chisso Corporation), polysiloxane containing silanol groups at both ends (Japanese Patent Laid-Open No. 11-258403), etc. Alternatively, an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent may be cured by a condensation reaction in the presence of a catalyst (Japanese Patent Laid-Open No. 58-86). 142958, 58-147483, 58-147484, JP-A-9-157582, 11-106704, JP-A-2000-117902, 2001-48590, 2002 -53804 publication etc.).
The low refractive index layer has an average primary particle diameter of 1 to 150 nm such as fillers (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as additives other than the above. And a low refractive index inorganic compound, organic fine particles described in [0020] to [0038] of JP-A No. 11-3820, etc.), silane coupling agents, slip agents, surfactants, and the like are preferably included. Can do.

The low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.), but may be formed by a coating method because it can be manufactured at low cost. preferable. As the coating method, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and micro gravure can be preferably used.
The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.

The medium refractive index layer and the high refractive index layer preferably have a configuration in which ultrafine particles of high refractive index having an average particle size of 100 nm or less are dispersed in a matrix material. Inorganic compound fine particles having a high refractive index include inorganic compounds having a refractive index of 1.65 or more, for example, oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and metal atoms thereof. A composite oxide or the like can be preferably used.
Such ultrafine particles may be obtained by treating the particle surface with a surface treatment agent (silane coupling agent, etc .: JP-A Nos. 11-295503, 11-153703, 2000-9908, anionic compounds) Or an organic metal coupling agent (Japanese Patent Laid-Open No. 2001-310432, etc.), a core-shell structure having high refractive index particles as a core (Japanese Patent Laid-Open No. 2001-166104, etc.), or a specific dispersant is used together (for example, , JP-A-11-153703, US Pat. No. 6,210,858B1, JP-A-2002-27776069, etc.).

As the matrix material, conventionally known thermoplastic resins, curable resin films, and the like can be used, but JP-A 2000-47004, 2001-315242, 2001-31871, 2001-296401. It is also possible to use a curable film obtained from a polyfunctional material described in JP-A-2001-293818 or a metal alkoxide composition described in JP-A-2001-293818.
The refractive index of the high refractive index layer is preferably 1.70 to 2.20. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, and more preferably 10 nm to 1 μm.
The refractive index of the medium refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.70.

  The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. Further, the strength of the film is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.

(Brightness enhancement film)
The polarizing plate in the present invention can be used in combination with a brightness enhancement film. The brightness enhancement film has a function of separating circularly polarized light or linearly polarized light, and is disposed between the polarizing plate and the backlight, and reflects or backscatters one circularly polarized light or linearly polarized light to the backlight side. Re-reflected light from the backlight part partially changes the polarization state and partially transmits when re-entering the brightness enhancement film and the polarizing plate, so the light utilization rate is improved by repeating this process. The front luminance is improved to about 1.4 times. As the brightness enhancement film, an anisotropic reflection system and an anisotropic scattering system are known, and both can be combined with the polarizing plate in the present invention.

  In the anisotropic reflection method, a brightness enhancement film having anisotropy in reflectance and transmittance is known by laminating a uniaxially stretched film and an unstretched film in multiple layers to increase the difference in refractive index in the stretching direction. Multilayer film systems using the principle of dielectric mirrors (described in the specifications of WO95 / 17691, WO95 / 17692, and WO95 / 17699) and cholesteric liquid crystals A system (European Patent No. 606940A2 specification, JP-A-8-271731) is known. DBEF-E, DBEF-D, and DBEF-M (all manufactured by 3M) are used as multi-layer brightness enhancement films using the principle of dielectric mirrors, and NIPOCS (Nitto Denko Corporation) as a cholesteric liquid crystal brightness enhancement film. )) Is preferably used in the present invention. For NIPOCS, see Nitto Giho, vol. 38, no. 1, May, 2000, pages 19 to 21 and the like.

  Further, in the present invention, the specifications of International Publication No. 97/32223, International Publication No. 97/32224, International Publication No. 97/32225, International Publication No. 97/32226, and Japanese Patent Laid-Open No. 9-274108. Used in combination with a brightness enhancement film of an anisotropic scattering method in which a positive intrinsic birefringent polymer and a negative intrinsic birefringent polymer are blended and uniaxially stretched as described in each publication of JP-A-11-174231 It is also preferable to do. As the anisotropic scattering system brightness enhancement film, DRPF-H (manufactured by 3M) is preferable.

(Other functional optical films)
The polarizing plate in the present invention is further combined with a functional optical film provided with a hard coat layer, a forward scattering layer, an antiglare (antiglare) layer, a gas barrier layer, a sliding layer, an antistatic layer, an undercoat layer, a protective layer and the like. It is also preferable to use it. These functional layers are also preferably used in combination with each other in the same layer as the antireflection layer or the optically anisotropic layer in the above-described antireflection film. These functional layers can be used by providing them on one side or both sides of the polarizer side and the side opposite to the polarizer (the side on the air side).

(Hard coat layer)
Since the polarizing plate in the present invention imparts mechanical strength such as scratch resistance, it is preferably combined with a functional optical film having a hard coat layer provided on the surface of the transparent support. When the hard coat layer is applied to the above-described antireflection film, it is particularly preferable to provide it between the transparent support and the high refractive index layer.
The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a curable compound by light and / or heat. The curable functional group is preferably a photopolymerizable functional group, or the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound. As a specific constituent composition of the hard coat layer, for example, those described in JP-A-2002-144913, JP-A-2000-9908, WO 00/46617, etc. can be preferably used.
The film thickness of the hard coat layer is preferably 0.2 μm to 100 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  As the material for forming the hard coat layer, a compound containing an ethylenically unsaturated group or a compound containing a ring-opening polymerizable group can be used, and these compounds can be used alone or in combination. Preferred examples of the compound containing an ethylenically unsaturated group include ethylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Polyacrylates of polyols such as hexaacrylate; epoxy acrylates such as diacrylate of bisphenol A diglycidyl ether, diacrylate of hexanediol diglycidyl ether; obtained by reaction of polyisocyanate and hydroxyl group-containing acrylate such as hydroxyethyl acrylate Examples of preferred compounds include urethane acrylates. Moreover, as a commercially available compound, EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (above, Daicel UCB Co., Ltd. product), UV -6300, UV-1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

  Preferred examples of the compound containing a ring-opening polymerizable group include ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, glycerol triglycidyl ether as glycidyl ethers. Triglycidyl trishydroxyethyl isocyanurate, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc. Celoxide 2021P, Celoxide 2081, Epoxide GT-301, Epolide GT-401, EHPE3150CE (above, Oxetane, OXT-121, OXT-221, OX-SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.), etc. Can be mentioned. In addition, a polymer of glycidyl (meth) acrylate or a copolymer of a monomer that can be copolymerized with glycidyl (meth) acrylate may be used for the hard coat layer.

  In the hard coat layer, oxide fine particles such as silicon, titanium, zirconium, and aluminum are used to reduce curing shrinkage of the hard coat layer, improve adhesion to the substrate, and reduce curling of the hard coat treated article in the present invention. It is also preferable to add crosslinked fine particles such as crosslinked fine particles such as polyethylene, polystyrene, poly (meth) acrylic acid esters, polydimethylsiloxane, etc., and fine organic particles such as fine crosslinked rubber particles such as SBR and NBR. The average particle size of these crosslinked fine particles is preferably 1 nm to 20000 nm. Further, the shape of the crosslinked fine particles can be used without particular limitation, such as a spherical shape, a rod shape, a needle shape, or a plate shape. The addition amount of the fine particles is preferably 60% by volume or less, more preferably 40% by volume or less of the hard coat layer after curing.

  In the case of adding the inorganic fine particles described above, since the affinity with the binder polymer is generally poor, it contains a metal such as silicon, aluminum, titanium, and the alkoxide group, carboxylic acid group, sulfonic acid group, phosphonic acid group, etc. It is also preferable to perform a surface treatment using a surface treatment agent having a functional group of

  The hard coat layer is preferably cured using heat or active energy rays. Among them, active energy rays such as radiation, gamma rays, alpha rays, electron rays, and ultraviolet rays are more preferred, and safety and productivity are improved. In view of the above, it is particularly preferable to use an electron beam or an ultraviolet ray. In the case of curing with heat, in consideration of the heat resistance of the plastic itself, the heating temperature is preferably 140 ° C. or lower, more preferably 100 ° C. or lower.

(Forward scattering layer)
The forward scattering layer is used to improve the viewing angle characteristics (hue and luminance distribution) in the vertical and horizontal directions when the polarizing plate of the present invention is applied to a liquid crystal display device. In the present invention, the forward scattering layer preferably has a configuration in which fine particles having different refractive indexes are dispersed in a binder. Japanese Patent Laid-Open No. 2000-199809, Japanese Patent Laid-Open No. 2002-107512, etc. in which the haze value is defined as 40% or more can be used. Moreover, in order to control the viewing angle characteristics of haze, the polarizing plate in the present invention should be used in combination with “Lumisty” described in Sumitomo Chemical Co., Ltd. Technical Report “Optical Functional Film” on pages 31-39. Can also be preferably performed.

(Anti-glare layer)
The antiglare (antiglare) layer is used to scatter reflected light and prevent reflection. The antiglare function is obtained by forming irregularities on the outermost surface (display side) of the liquid crystal display device. The haze of the optical film having an antiglare function is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 20%.
The method for forming irregularities on the film surface is, for example, a method of forming irregularities on the film surface by adding fine particles (for example, JP 2000-271878 A), relatively large particles (particle size 0.05-2 μm). ) Is added in a small amount (0.1 to 50% by mass) (for example, Japanese Patent Application Laid-Open Nos. 2000-281410, 2000-95893, 2001-100004, and 2001). No. 281407, etc.), a method of physically transferring the uneven shape onto the film surface (for example, as an embossing method, JP-A-63-278839, JP-A-11-183710, JP-A-2000-275401) Etc.) can be preferably used.

[Liquid Crystal Display]
Next, the liquid crystal display device of the present invention will be described.

  FIG. 1 is a schematic view showing an example of the liquid crystal display device of the present invention. In FIG. 1, a liquid crystal display device 10 includes a liquid crystal cell having a liquid crystal layer 5 and a liquid crystal cell upper electrode substrate 3 and a liquid crystal cell lower electrode substrate 6 disposed above and below, and upper polarizing plates disposed on both sides of the liquid crystal cell. 1 and the lower polarizing plate 8. A color filter may be disposed between the liquid crystal cell and each polarizing plate. When the liquid crystal display device 10 is used as a transmission type, a cold cathode or hot cathode fluorescent tube, or a backlight having a light emitting diode, a field emission element, or an electroluminescent element as a light source is disposed on the back surface.

The upper polarizing plate 1 and the lower polarizing plate 8 each have a structure in which a polarizer is sandwiched between two protective films, and the liquid crystal display device 10 of the present invention is a liquid crystal cell of one polarizing plate. The protective film on the side preferably has the characteristics of the above formulas (1) to (4). The liquid crystal display device 10 of the present invention is preferably laminated in the order of the transparent protective film, the polarizer and the cellulose acylate film of the present invention from the outside of the device (the side far from the liquid crystal cell).
The liquid crystal display device 10 includes an image direct view type, an image projection type, and a light modulation type. The present invention is effective for an active matrix liquid crystal display device using a three-terminal or two-terminal semiconductor element such as TFT or MIM. Of course, it is also effective in a passive matrix liquid crystal display device typified by STN mode called time-division driving.

(VA mode)
The liquid crystal cell of the liquid crystal display device of the present invention is preferably in the VA mode.
In the VA mode, the dielectric anisotropy between the upper and lower substrates is negative, and a liquid crystal having Δn = 0.0813 and Δε = −4.6 is rubbed to provide a director indicating the alignment direction of the liquid crystal molecules, so-called tilt angle is about Fabricate at 89 °. The thickness d of the liquid crystal layer 5 in FIG. 1 is preferably set to about 3.5 μm. Here, the brightness at the time of white display changes depending on the magnitude of the product Δnd of the thickness d and the refractive index anisotropy Δn. Therefore, in order to obtain the maximum brightness, the thickness of the liquid crystal layer is set to be in the range of 0.2 μm to 0.5 μm.

  The absorption axis 2 of the upper polarizing plate 1 of the liquid crystal cell and the absorption axis 9 of the lower polarizing plate 8 are laminated substantially orthogonally. A transparent electrode (not shown) is formed inside each alignment film of the liquid crystal cell upper electrode substrate 3 and the liquid crystal cell lower electrode substrate 6, but in a non-driving state where no driving voltage is applied to the electrodes, the liquid crystal layer 5 The liquid crystal molecules therein are aligned substantially perpendicular to the substrate surface, and as a result, the polarization state of the light passing through the liquid crystal panel hardly changes. That is, the liquid crystal display device realizes an ideal black display in the non-driven state. On the other hand, in the driving state, the liquid crystal molecules are inclined in a direction parallel to the substrate surface, and the light passing through the liquid crystal panel changes the polarization state by the inclined liquid crystal molecules. In other words, in the liquid crystal display device, white display is obtained in the driving state. In FIG. 1, reference numerals 4 and 7 denote orientation control directions.

Here, since an electric field is applied between the upper and lower substrates, it is preferable to use a liquid crystal material having a negative dielectric anisotropy so that liquid crystal molecules respond perpendicularly to the electric field direction. When an electrode is disposed on one substrate and an electric field is applied in a lateral direction parallel to the substrate surface, a liquid crystal material having a positive dielectric anisotropy is used.
In addition, in a VA mode liquid crystal display device, the addition of a chiral agent generally used in a TN mode liquid crystal display device is rarely used to degrade dynamic response characteristics, but in order to reduce alignment defects. Sometimes added.

  The features of the VA mode are high-speed response and high contrast. However, the contrast is high in the front, but there is a problem that it is deteriorated in the oblique direction. During black display, the liquid crystal molecules are aligned perpendicular to the substrate surface. When observed from the front, the liquid crystal molecules have almost no birefringence, so the transmittance is low and a high contrast can be obtained. However, when observed obliquely, birefringence occurs in the liquid crystal molecules. Further, the crossing angle of the upper and lower polarizing plate absorption axes is 90 ° perpendicular to the front, but is larger than 90 ° when viewed from an oblique direction. Because of these two factors, leakage light occurs in the oblique direction, and the contrast is lowered. In order to solve this, the cellulose acylate film of the present invention is disposed as an optical compensation sheet (retardation film).

  In addition, the liquid crystal molecules are tilted during white display, but the birefringence of the liquid crystal molecules when viewed from an oblique direction differs between the tilt direction and the opposite direction, resulting in differences in luminance and color tone. In order to solve this, it is also preferable to adopt a structure called multi-domain in which one pixel of a liquid crystal display device is divided into a plurality of regions.

(Multi-domain)
For example, in the VA system, the viewing angle characteristics are averaged by inclining liquid crystal molecules into a plurality of different regions within one pixel by applying an electric field. In order to divide the orientation within one pixel, the electrode is provided with slits or protrusions, and the electric field direction is changed or the electric field density is biased. In order to obtain a uniform viewing angle in all directions, the number of divisions may be increased, but a substantially uniform viewing angle can be obtained by dividing into four or eight or more. In particular, it is preferable that the polarizing plate absorption axis can be set at an arbitrary angle when dividing into eight.

  Also, the liquid crystal molecules are difficult to respond at the alignment division region boundary. For this reason, in normally black display, since black display is maintained, a reduction in luminance becomes a problem. Therefore, it is possible to reduce the boundary region by adding a chiral agent to the liquid crystal material.

  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.

[Example 1]
[Preparation of cellulose acylate film]
(Preparation of cellulose acylate solution)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution 1.
―――――――――――――――――――――――――――――――――――
Composition of Cellulose Acylate Solution 1 ――――――――――――――――――――――――――――――――――――
Cellulose acetate with an acetyl substitution degree of 2.76 and a polymerization degree of 350
100.0 parts by mass Polyhydric alcohol ester 4 10.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 parts by mass ――――――――――― ―――――――――――――――――――――――

(Preparation of matting agent solution 2)
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution 2.
―――――――――――――――――――――――――――――――――――
Composition of Matte Solution 2 ―――――――――――――――――――――――――――――――――――
Silica particles having an average particle size of 20 nm (AEROSIL R972,
Nippon Aerosil Co., Ltd.) 2.0 parts by weight Methylene chloride (first solvent) 75.0 parts by weight Methanol (second solvent) 12.7 parts by weight The cellulose acylate solution 1 10.3 parts by weight ―――――――――――――――――――――――――――――――

(Preparation of hydrogen bonding compound solution 3)
The following composition was put into a mixing tank, stirred while heating to dissolve each component, and a hydrogen bonding compound solution 3 was prepared.

―――――――――――――――――――――――――――――――――――
Composition of hydrogen bonding compound solution 3 ――――――――――――――――――――――――――――――――――――
Hydrogen bonding compound (A-16) 20.0 parts by mass Methylene chloride (first solvent) 67.2 parts by mass Methanol (second solvent) 10.0 parts by mass The cellulose acylate solution 1 12.8 parts by mass ―――――――――――――――――――――――――――――――――

  1.3 parts by mass of the matting agent solution 2 and 3.1 parts by mass of the hydrogen bonding compound solution 3 were mixed using an in-line mixer after filtration, and 95.6 parts by mass of the cellulose acylate solution 1 was added. And mixed using an in-line mixer. The mixed solution was cast using a band casting machine, dried at 100 ° C. to a residual solvent content of 40%, and then the film was peeled off. The peeled film was stretched transversely at a draw ratio of 35% using a tenter when the residual solvent content reached 20% at an atmospheric temperature of 140 ° C., and further held at 130 ° C. for 3 minutes. Thereafter, the clip holding the film was removed and the film was dried at 130 ° C. for 30 minutes to produce a cellulose acylate film of Example 1. The produced cellulose acylate film had a residual solvent amount of 0.1% and a film thickness of 60 μm.

[Examples 2 to 10, Comparative Examples 1 to 14]
[Production of Cellulose Acylate Films of Examples 2 to 10 and Comparative Examples 1 to 14]
In Example 1, the substitution degree of cellulose acylate, the kind and amount of each additive, the stretching temperature and the stretching ratio, and the film thickness were changed in the same manner as described in Tables 11 to 14 below. 10 and Comparative Examples 1 to 14 were prepared.

  In addition, in the following Tables 11-14, the addition amount of an additive represents the mass part with respect to 100 mass parts of cellulose acylate resins.

  About the cellulose acylate films of Examples 1 to 10 and Comparative Examples 1 to 14 manufactured as described above, relative humidity was measured at 25 ° C. with an automatic birefringence meter (KOBRA-WR, manufactured by Oji Scientific Instruments). Re and Rth at a wavelength of 548 nm in each case of 10%, 60%, and 80% were measured.

Further, from the measured values of Re and Rth, Re humidity dependency and Rth humidity dependency were obtained by the following calculation.
Re humidity dependency = {(Re at 25 ° C., relative humidity 10%) − (Re at 25 ° C., relative humidity 80%)} / (Re at 25 ° C., relative humidity 60%)
Rth humidity dependency = {(Rth at 25 ° C., relative humidity 10%) − (Rth at 25 ° C., relative humidity 80%)} / (Rth at 25 ° C., relative humidity 60%)
The obtained results are shown in Tables 11 to 14 below.

[Saponification treatment of cellulose acylate film]
The produced cellulose acylate film of Example 1 was immersed in a 2.3 mol / L sodium hydroxide aqueous solution at 55 ° C. for 3 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. In this way, the surface of the cellulose acylate film of Example 1 was saponified.

[Preparation of polarizing plate]
A polarizer was produced by adsorbing iodine to a stretched polyvinyl alcohol film.
The saponified cellulose acylate film of Example 1 was attached to one side of the polarizer using a polyvinyl alcohol-based adhesive. A commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was subjected to the same saponification treatment, and the prepared cellulose acylate film of Example 1 was attached using a polyvinyl alcohol adhesive. A cellulose triacetate film after saponification treatment was attached to the surface of the polarizer on the opposite side.
At this time, the transmission axis of the polarizer and the slow axis of the prepared cellulose acylate film of Example 1 were arranged in parallel. Further, the transmission axis of the polarizer and the slow axis of the commercially available cellulose triacetate film were arranged so as to be orthogonal to each other.
Thus, the polarizing plate of Example 1 was produced.

  For the cellulose acylate films of Examples 2 to 10 and the cellulose acylate films of Comparative Examples 1 to 14, the saponification treatment and the polarizing plate were prepared in the same manner as in Example 1, and the polarizing plates of Examples 2 to 10 and The polarizing plate of Comparative Examples 1-14 was produced.

(Evaluation of polarizing plate durability)
About the polarizing plate of Examples 1-10 produced above and Comparative Examples 1-14, the orthogonal transmittance | permeability of the polarizer in wavelength 410nm was measured by the method described in this specification.
Thereafter, for the polarizing plates of Examples 1, 2, 6 and Comparative Examples 1-3, 7, 8, 11, and 13, the orthogonal transmittance after storage for 1000 hours in an environment of 60 ° C. and relative humidity of 95% was obtained. It was measured. The change of the orthogonal transmittance before and after the aging was obtained, and this was described in Table 11 and Table 13 below as the polarizer durability (1).
On the other hand, for other polarizing plates, the orthogonal transmittance after storage for 240 hours in an environment of 60 ° C. and 90% relative humidity was measured, and the change of the orthogonal transmittance before and after aging was similarly determined. The results are shown in Table 12 and Table 14 below as durability (2).

From the results of Tables 11 to 14, the polarizing plate using the cellulose acylate film of the present invention is a case where a cellulose acylate resin having the same acyl substitution degree is used, and includes a hydrophobizing agent within the scope of the present invention. In comparison with the polarizing plate using the cellulose acylate film of Comparative Examples (that is, Comparative Examples 2 to 4, 6, 7, and 9) containing a hydrogen bonding compound within the scope of the present invention, it was dependent on environmental humidity. It was found that the change in Re and Rth was small, and the deterioration of the polarizer after aging under high temperature and high humidity was small. Further, the polarizing plate using the cellulose acylate film of the present invention is a case where a cellulose acylate resin having the same acyl substitution degree is used, including a hydrophobizing agent within the scope of the present invention, and a hydrogen within the scope of the present invention. Compared with the polarizing plate using the cellulose acylate film of the comparative example not containing the binding compound (ie, Comparative Examples 1, 5, 8 and 10), it depended on the environmental humidity while maintaining the polarizer durability. It was found that the changes in Re and Rth were significantly improved. Furthermore, the polarizing plate using the cellulose acylate film of the present invention is more polarizing than the polarizing plate using the cellulose acylate films of Comparative Examples 11 to 14 in which neither a hydrophobizing agent nor a hydrogen bonding compound is added. It was found that changes in Re and Rth depending on the environmental humidity were remarkably improved while maintaining the child durability. Moreover, when comparing Comparative Examples 11 to 14 with a comparative example in which only a hydrophobizing agent is added or a comparative example in which only a hydrogen bonding compound is added, either one of the additives It has also been found that the addition is insufficiently improved.
That is, the polarizing plate using the cellulose acylate film of the present invention has a small retardation change depending on the environmental humidity, and the polarizer is deteriorated when it is bonded to the polarizing plate and aged at high temperature and high humidity. I found that it can be suppressed.

[Example 11]
[Production of liquid crystal display device]
The polarizing plate of the present invention using the cellulose acylate film of Example 8 on the viewer side and the backlight side is peeled off from two polarizing plates of a commercially available liquid crystal television (BRAVIA J5000 from Sony Corporation). 8 pieces of cellulose acylate films were attached to the observer side and the backlight side one by one through an adhesive so that each would be on the liquid crystal cell side. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. The liquid crystal display device of the present invention produced in this way has a small contrast change and color change when observed from an oblique direction even when the environmental humidity is changed compared to a commercially available liquid crystal television, and for a long time under high temperature and high humidity. Even when used, the decrease in contrast was small and preferred.

[Example 401]
(Preparation of cellulose acylate)
Cellulose acylate was synthesized by the method described in JP-A-10-45804 and 08-231761, and the degree of substitution was measured. Specifically, sulfuric acid (7.8 parts by mass with respect to 100 parts by mass of cellulose) was added as a catalyst, carboxylic acid serving as a raw material for the acyl substituent was added, and an acylation reaction was performed at 40 ° C. At this time, the kind and substitution degree of the acyl group were adjusted by adjusting the kind and amount of the carboxylic acid. In addition, aging was performed at 40 ° C. after acylation. Further, the low molecular weight component of the cellulose acylate was removed by washing with acetone.

(Preparation of cellulose acylate solution C01 for low substitution layer)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution having a solid concentration of 22% by mass. The viscosity of the cellulose acylate solution was 60 Pa · s.
-Cellulose acetate (substitution degree 2.45) 100.0 parts by mass-Polycondensation polyester J-35 16.0 parts by mass-Hydrogen bonding compound 3.0 parts by mass-Methylene chloride 365.5 parts by mass-Methanol 54.6 Parts by mass

  Polycondensation polyester A-35 is a terephthalic acid / succinic acid / propylene glycol / ethylene glycol copolymer (copolymerization ratio [mol%] = 27.5 / 22.5 / 25/25).

(Preparation of cellulose acylate solution S01 for high substitution layer)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution. The amount of the solvent (methylene chloride and methanol) was appropriately adjusted so that the solid content concentration of each cellulose acylate solution had the value described in Table 2 below.
Cellulose acetate (substitution degree 2.79) 100.0 parts by mass Polycondensation polyester J-35 19.0 parts by mass Silica fine particles R972 (manufactured by Nippon Aerosil) 0.15 parts by mass Methylene chloride 395.0 parts by mass Methanol 59.0 parts by mass The obtained cellulose acylate solution S01 for a high substitution degree layer had a solid content concentration of 20.0% by mass and a viscosity of 30 Pa · s.

(Creation of polarizing plate protective film 401)
The cellulose acylate solution C01 for the low substitution layer has a film thickness of 56 μm, and the cellulose acylate solution S01 for the high substitution layer has a film thickness of 2 μm and each has a skin A layer and a skin B layer. Each cast. The obtained web (film) was peeled from the band, sandwiched between clips, and stretched 1.08 times at 140 ° C. using a tenter when the amount of residual solvent relative to the mass of the entire film was 20 to 5%. Then, after removing the clip from the film and drying at 130 ° C. for 20 minutes, the film was further stretched 1.2 times again at 180 ° C. using a tenter to produce the polarizing plate protective film 401 of the present invention.
The residual solvent amount was determined according to the following formula.
Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is a mass of the web at an arbitrary time point, and N is a mass when the web of which M is measured is dried at 120 ° C. for 2 hours.

[Examples 402-420 and Comparative Examples 501-508, 511, 512]
In Example 401, the same procedure as in Example 401 was performed, except that the type of hydrophobizing agent added to the cellulose acylate solution for the low substitution degree layer and / or the type of hydrogen bonding compound was changed to the contents shown in Table 15. The polarizing plate protective film of Examples 402-420 and the polarizing plate protective film of Comparative Examples 501-508, 511, 512 were produced.
In Comparative Example 507 in Table 15, Compound U-6 was not dissolved in the dope.

Compound U-5 ;: Penta-O-acetyl-β-D-galactopyranose; manufactured by Tokyo Chemical Industry Co., Ltd.

[Example 421]
(Creation of polarizing plate protective film 421)
The low-substituted-layer cellulose acylate solution C01 prepared in Example 421 was formed to have a film thickness of 90 μm, and the high-substituted-layer cellulose acylate solution S01 was formed into a skin A layer and a skin B having a film thickness of 3 μm each. Each was cast to form a layer. The obtained web (film) was peeled from the band, sandwiched between clips, and stretched 1.3 times at 140 ° C. using a tenter when the amount of residual solvent relative to the total mass of the film was 20 to 5%. Thereafter, the clip was removed from the film and dried at 130 ° C. for 20 minutes to produce the polarizing plate protective film 410 of the present invention.
The residual solvent amount was determined according to the following formula.
Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is a mass of the web at an arbitrary time point, and N is a mass when the web of which M is measured is dried at 120 ° C. for 2 hours.

[Examples 422 to 430 and Comparative Examples 521 and 522]
In Example 421, the same procedure as in Example 421 was performed, except that the type of hydrophobizing agent added to the cellulose acylate solution for the low substitution degree layer and / or the type of hydrogen bonding compound was changed to the contents of Table 16. The polarizing plate protective films 421 to 430 of Examples 422 to 430 and the polarizing plate protective films 521 and 522 of Comparative Examples 521 and 522 were produced.

  For the cellulose acylate film thus prepared, the wavelength when Re and Rth measurements, polarizing plate preparation, and the polarizing plate were stored in an environment at a temperature of 60 ° C. and a relative humidity of 95% was performed in the same manner as in Example 1. The change in cross transmittance at 410 nm was measured. The results are shown in Table 17.

  From the results of Table 17, the polarizing plate using the cellulose acylate film of the present invention does not contain the hydrophobizing agent within the scope of the present invention, and the cellulose acylate film of the comparative example includes the hydrogen bonding compound within the scope of the present invention. It was found that the change in Re and Rth depending on the environmental humidity was small and the deterioration of the polarizer after aging under high temperature and high humidity was small as compared with the polarizing plate using. In addition, the polarizing plate using the cellulose acylate film of the present invention includes a hydrophobizing agent within the scope of the present invention, and a polarized light using the cellulose acylate film of the comparative example not including the hydrogen bonding compound within the scope of the present invention. It was found that the change in Re and Rth depending on the environmental humidity was significantly improved while maintaining the durability of the polarizer as compared with the plate.

[Synthesis Example: Synthesis of Compound Represented by General Formula (A-2)]
The said hydrogen bondable compound used for this invention represented by the following general formula (A-2) was synthesize | combined.

Synthesis of Compound (3-1) To a solution of 10 g (32 mmol) of acetoguanamine in 50 mL of pyridine was added 9.9 g (70 mmol) of benzoyl chloride and heated to reflux for 8 hours. The temperature of the reaction system was returned to room temperature, ethyl acetate and water were added for liquid separation, and the organic layer was washed with 1N hydrochloric acid and water in this order. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain compound (3-1).
The NMR spectrum of the obtained compound (3-1) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.50 (3H, s)
7.45-7.55 (4H, m)
7.60-7.65 (2H, m)
7.90-8.00 (4H, m)
11.20 (2H, s)

Synthesis of Compound (3-2) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to o-methylbenzoic acid chloride.
The NMR spectrum of the obtained compound (3-2) is as follows.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
2.50 (6H, s)
2.60 (3H, s)
7.20-7.30 (4H, m)
7.35-7.45 (2H, m)
7.50-7.60 (2H, m)
8.55 (2H, s)

Synthesis of Compound (3-3) Synthesis was performed in the same manner as for Compound (3-1) except that the starting material was changed from benzoyl chloride to p-methylbenzoic acid chloride.
The NMR spectrum of the obtained compound (3-3) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.35 (6H, s)
2.50 (3H, s)
7.30 (4H, d)
7.85 (4H, d)
11.10 (2H, s)

Synthesis of Compound (3-4) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to p-methoxybenzoic acid chloride.
The NMR spectrum of the obtained compound (3-4) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.50 (3H, s)
3.80 (6H, s)
7.00 (4H, d)
7.95 (4H, d)
11.00 (2H, s)

Synthesis of Compound (3-5) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to m-methoxybenzoic acid chloride.
The NMR spectrum of the obtained compound (3-5) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.50 (3H, s)
3.80 (6H, s)
7.10-7.20 (2H, m)
7.35-7.45 (2H, m)
7.50-7.60 (4H, m)
11.20 (2H, s)

Synthesis of Compound (3-6) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to p-tert-butylbenzoic acid chloride.
The NMR spectrum of the obtained compound (3-6) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
1.30 (18H, s)
2.50 (3H, s)
7.55 (4H, d)
7.95 (4H, d)
11.10 (2H, s)

Synthesis of Compound (3-7) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to m-methylbenzoic acid chloride.
The NMR spectrum of the obtained compound (3-7) is as follows.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
2.40 (6H, s)
2.65 (3H, s)
7.35-7.45 (4H, m)
7.70-7.80 (4H, m)
8.80 (2H, s)

Synthesis of Compound (3-8) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to p-chlorobenzoic acid chloride.
The NMR spectrum of the obtained compound (3-8) is as follows.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
2.60 (3H, s)
7.40-7.50 (4H, m)
7.90-8.00 (4H, m)
9.10 (2H, s)

Synthesis of Compound (3-9) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to o-chlorobenzoic acid chloride.
The NMR spectrum of the obtained compound (3-9) is as follows.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
2.50 (3H, s)
7.30-7.50 (6H, m)
7.60-7.70 (2H, m)
8.95 (2H, s)

Synthesis of Compound (3-10) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to m-chlorobenzoic acid chloride.
The NMR spectrum of the obtained compound (3-10) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.50 (3H, s)
7.55 (2H, m)
7.70 (2H, m)
7.90 (2H, m)
8.00 (2H, s)
11.35 (2H, s)

Synthesis of Compound (3-11) Synthesis was performed in the same manner as Compound (3-1) except that the starting material was changed from benzoyl chloride to o-methoxybenzoic acid chloride.
The NMR spectrum of the obtained compound (3-11) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.40 (3H, s)
3.80 (6H, s)
7.00-7.20 (4H, m)
7.55 (2H, m)
7.65 (2H, m)
10.70 (2H, s)

Synthesis of Compound (3-12) The compound (3-12) was synthesized in the same manner as Compound (3-1) except that the starting acid chloride was changed. The target product was confirmed by MS spectrum.

Synthesis of Compound (3-13) The compound (3-13) was synthesized in the same manner as Compound (3-1) except that the raw material acid chloride was changed. The target product was confirmed by MS spectrum.

Synthesis of Compound (3-14) The compound (3-14) was synthesized in the same manner as Compound (3-1) except that the raw material acid chloride was changed.
The NMR spectrum of the obtained compound (3-14) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.40 (3H, s)
4.00 (4H, s)
7.20-7.30 (10H, m)
10.90 (2H, s)

Synthesis of Compound (3-15) The compound (3-15) was synthesized in the same manner as Compound (3-1) except that the raw material acid chloride was changed.
The NMR spectrum of the obtained compound (3-15) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
2.40 (3H, s)
3.80 (3H, s)
7.15 (1H, m)
7.35-7.55 (5H, m)
7.75 (2H, m)
11.10 (1H, s)
11.20 (1H, s)

Synthesis of Compound (3-16) Synthesis was performed in the same manner as for Compound (3-1) except that benzoguanamine and p-tert-butylbenzoic acid chloride were used as raw materials.
The NMR spectrum of the obtained compound (3-16) is as follows.
¹ H-NMR (solvent: heavy DMSO, standard: tetramethylsilane) δ (ppm):
1.35 (18H, s)
7.50-7.60 (7H, m)
7.90-8.00 (4H, m)
7.30 (2H, m)
11.20 (2H, s)

Ｃｈｅｍｉｓｔｒｙ−Ａ Ｅｕｒｏｐｅａｎ Ｊｏｕｒｎａｌ， ２００５， ｖｏｌ．１１， ＃２２ ｐ．６６１６〜６６２８の方法に従い中間体３−１７−１を合成し、化合物（３−７）と同様に合成を行った。目的物はＭＳスペクトルで確認した。 Synthesis of compound (3-17)

Chemistry-A European Journal, 2005, vol. 11, # 22 p. Intermediate 3-17-1 was synthesized according to the methods of 6616-6628, and was synthesized in the same manner as compound (3-7). The target product was confirmed by MS spectrum.

Synthesis of Compound (3-18) Synthesis was performed in the same manner as for Compound (3-17), and the target product was confirmed by MS spectrum.

ジメチルアセトアミド３００ｍｌに２−クロロ−４，６−ジアミノ−１，３，５−トリアジン５０ｇ、モルホリン６０ｇ、炭酸カリウム９５ｇを加え１００℃で３時間攪拌した。室温に冷却後、反応液に食塩水１Ｌを加え１０℃に冷却し、析出した結晶を濾取した。この結晶を水、アセトニトリルで洗浄し、乾燥することで中間体（３−１）を５５ｇ得た。N−エチルピロリドン４００ｍｌに中間体（３−１）４０ｇ、２−メチル安息香酸メチル６４ｇ、ナトリウムメトキシド５５ｇを加え４０℃で３０分攪拌した。室温に冷却後、反応液に１N塩酸水を加え、析出した結晶を濾取した。この結晶を水で洗浄し乾燥した。この結晶を酢酸エチル、メタノール、炭酸水素ナトリウム水溶液の混合溶媒中で攪拌し、結晶を濾取した。この結晶を水、アセトニトリルで洗浄し、乾燥することで目的物を６０ｇ得た。
¹Ｈ−ＮＭＲ（溶媒：ＣＤＣｌ₃、基準：テトラメチルシラン）δ（ｐｐｍ）： Synthesis of compound (C-103)

To 300 ml of dimethylacetamide, 50 g of 2-chloro-4,6-diamino-1,3,5-triazine, 60 g of morpholine and 95 g of potassium carbonate were added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 1 L of brine was added to the reaction solution and cooled to 10 ° C., and the precipitated crystals were collected by filtration. The crystals were washed with water and acetonitrile, and dried to obtain 55 g of intermediate (3-1). To 400 ml of N-ethylpyrrolidone, 40 g of the intermediate (3-1), 64 g of methyl 2-methylbenzoate and 55 g of sodium methoxide were added and stirred at 40 ° C. for 30 minutes. After cooling to room temperature, 1N aqueous 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 60 g of the desired product.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):

２−クロロ−４，６−ジアミノ−１，３，５−トリアジン２０ｇに４０％メチルアミン水溶液を６０ｍｌ加え７０℃で２時間攪拌した。室温に冷却後、反応液に水を加え結晶を濾取した。この結晶をイソプロパノール、ヘキサンで洗浄し、乾燥することで中間体（４３−１）を１６ｇ得た。その後の操作は化合物（Ｃ−１０３）の合成と同様に行い目的物を得た。
¹Ｈ−ＮＭＲ（溶媒：ＣＤＣｌ₃、基準：テトラメチルシラン）δ（ｐｐｍ）： Synthesis of compound (C-153)

To 20 g of 2-chloro-4,6-diamino-1,3,5-triazine, 60 ml of 40% aqueous methylamine 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). Subsequent operations were carried out in the same manner as in the synthesis of compound (C-103) to obtain the desired product.
¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):

Synthesis of Compound (C-113) 300 ml of methanol and 16 g of sodium hydroxide were added to 27 g of 2-chloro-4,6-diamino-1,3,5-triazine, 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 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.

DESCRIPTION OF SYMBOLS 1 Upper polarizing plate 2 Upper polarizing plate Absorption axis direction 3 Liquid crystal cell upper electrode substrate 4 Upper substrate alignment control direction 5 Liquid crystal layer 6 Liquid crystal cell lower electrode substrate 7 Lower substrate alignment control direction 8 Lower polarizing plate 9 Lower polarization Direction of plate absorption axis 10 Liquid crystal display device

Claims (15)

Hydrogen bonding compound satisfying requirements (A) to (C) below and ClogP value of 0 to 5.5, polyhydric alcohol ester hydrophobizing agent, polycondensation ester hydrophobizing agent and carbohydrate derivative hydrophobizing agent at least one hydrophobizing agent selected from among, seen containing a cellulose acylate resin,
The addition amount of the hydrogen bonding compound is 1 to 30% by mass with respect to the cellulose acylate resin,
The cellulose acylate film , wherein an amount of the hydrophobizing agent is 1 to 20% by mass with respect to the cellulose acylate resin .
(A) It has both a hydrogen bond donor part and a hydrogen bond acceptor part in one molecule.
(B) The value obtained by dividing the molecular weight by the total number of hydrogen bond donors and hydrogen bond acceptors is 30 to 65.
(C) The total number of aromatic ring structures is 1 or more and 3 or less. The hydrogen bonding compound is represented by the following general formula (A-1), general formula (B-1), general formula (C-1), general formula (D-1), general formula (E-1), general formula ( The cellulose acylate film according to claim 1, which is a compound represented by any one of F-1), general formula (G-1), and general formula (H-1).

(In the general formula (A-1), Ra represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. X ¹ , X ² , X ³ and X ⁴ are each independently a single bond or a divalent group. R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

(In the general formula (B-1), Rb and Rc each independently represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. X ⁵ and X ⁶ each independently represent a single bond or a divalent group. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

(In the general formula (C-1), Ra ¹¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb ¹¹ , Rc ¹¹ , Rd ¹¹ and Re ¹¹ are each independently a hydrogen atom or an alkyl group. A 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, an alkyl group, an alkenyl group, an alkynyl group, an aryl group. group or a heterocyclic group, may be linked to form a ring with Ra .X ^11, X ^12, and X ¹³ are the .X ¹⁴ which independently represent a single bond or a divalent linking group, Represents a linking group selected from the group consisting of divalent linking groups represented by the following general formula (P).

(In general formula (P), the * side is the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by general formula (C-1).)

(In the general formula (D-1), Ra ²¹ and Rg ²¹ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rd ²¹ and Re ²¹ are each independently a hydrogen atom, an alkyl group, An alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, Q ¹¹ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Or a heterocyclic group, which may be linked to Ra ²¹ to form a ring, Q ¹² represents —O—, —S—, or —NRh—, and Rh represents a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, an aryl group, or a heterocyclic group, which may be linked to Rg ²¹ to form a ring, X ²³ represents a single bond or a divalent linking group, and X ²⁴ represents the following general formula (P A divalent linking group represented by Represents a linking group selected from the group.)

(In general formula (P), the * side is the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by general formula (D-1).)

(In General Formula (E-1), Y ¹ represents a methine group or —N—. Ra ³¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Rb ³¹ , Rc ³¹ , Rd ³¹ and Re ³¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and Q ²¹ represents a single bond, —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, and may be linked to Ra ³¹ to form a ring, and X ³¹ , X ³² , and X ³³ are Each independently represents a single bond or a divalent linking group, and X ³⁴ represents a linking group selected from the group consisting of a divalent linking group represented by the following general formula (Q).
General formula (Q)

(In General Formula (Q), the * side is a linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (E-1).)

(In General Formula (F-1), Y ¹¹ represents a methine group or —N—. Ra ⁴¹ and Rg ^{41 each} represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rd ⁴¹ , And Re ⁴¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, Q ³¹ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom. Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may be linked to Ra ⁴¹ to form a ring, and Q ³² represents —O—, —S—, or —NRh—. Rh represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may be linked to Rg ⁴¹ to form a ring X ⁴³ is a single bond or a divalent linkage X ⁴⁴ represents the following general group This represents a linking group selected from the group consisting of divalent linking groups represented by formula (P).)

(In General Formula (P), the * side is the linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (F-1).)

(In General Formula (G-1), L ¹ represents a single bond or a divalent linking group containing a hetero atom, R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Group, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.)

(In General Formula (H-1), L ³ represents a single bond or a divalent linking group containing a hetero atom, R ⁸⁵ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon Represents an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.) R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. Represents an aryl group or a heterocyclic group. X ⁵³ and X ⁵⁴ each independently represent a linking group selected from the group consisting of a divalent linking group represented by the following general formula (P). )

(In General Formula (P), the * side is the linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (H-1).) The cellulose acylate film according to claim 1 or 2, wherein the hydrogen bonding compound is a compound represented by the following general formula (A-1).

(In the general formula (A-1), Ra represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. X ¹ , X ² , X ³ and X ⁴ are each independently a single bond or a divalent group. R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. The cellulose acylate film according to claim 1 or 2, wherein the hydrogen bonding compound is a compound represented by the following general formula (B-1).

(In the general formula (B-1), Rb and Rc each independently represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. X ⁵ and X ⁶ each independently represent a single bond or a divalent group. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. In the general formulas (A-1) and (B-1), the X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently a single bond or the following general formula (P) The cellulose acylate film according to any one of claims 2 to 4, wherein the cellulose acylate film is any one selected from the group consisting of divalent linking groups represented.

(In the general formula (P), the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by the general formulas (A-1) and (B-1) on the * side .) The cellulose acylate film according to claim 1 or 2, wherein the hydrogen bonding compound is a compound represented by the following general formula (C-1).

(In the general formula (C-1), Ra ¹¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb ¹¹ , Rc ¹¹ , Rd ¹¹ and Re ¹¹ are each independently a hydrogen atom or an alkyl group. A 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, an alkyl group, an alkenyl group, an alkynyl group, an aryl group. group or a heterocyclic group, may be linked to form a ring with Ra .X ^11, X ^12, and X ¹³ are the .X ¹⁴ which independently represent a single bond or a divalent linking group, Represents a linking group selected from the group consisting of divalent linking groups represented by the following general formula (P).

(In general formula (P), the * side is the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by general formula (C-1).) The cellulose acylate film according to claim 1 or 2, wherein the hydrogen bonding compound is a compound represented by the following general formula (D-1).

(In the general formula (D-1), Ra ²¹ and Rg ²¹ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rd ²¹ and Re ²¹ are each independently a hydrogen atom, an alkyl group, An alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, Q ¹¹ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Or a heterocyclic group, which may be linked to Ra ²¹ to form a ring, Q ¹² represents —O—, —S—, or —NRh—, and Rh represents a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, an aryl group, or a heterocyclic group, which may be linked to Rg ²¹ to form a ring, X ²³ represents a single bond or a divalent linking group, and X ²⁴ represents the following general formula (P A divalent linking group represented by Represents a linking group selected from the group.)

(In general formula (P), the * side is the linking site with the N atom substituted on the 1,3,5-triazine ring in the compound represented by general formula (D-1).) The cellulose acylate film according to claim 1 or 2, wherein the hydrogen bonding compound is a compound represented by the following general formula (E-1).

(In General Formula (E-1), Y ¹ represents a methine group or —N—. Ra ³¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Rb ³¹ , Rc ³¹ , Rd ³¹ and Re ³¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and Q ²¹ represents a single bond, —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, and may be linked to Ra ³¹ to form a ring, and X ³¹ , X ³² , and X ³³ are Each independently represents a single bond or a divalent linking group, and X ³⁴ represents a linking group selected from the group consisting of a divalent linking group represented by the following general formula (Q).
General formula (Q)

(In General Formula (Q), the * side is a linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (E-1).) The cellulose acylate film according to claim 1 or 2, wherein the hydrogen bonding compound is a compound represented by the following general formula (F-1).

(In General Formula (F-1), Y ¹¹ represents a methine group or —N—. Ra ⁴¹ and Rg ^{41 each} represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rd ⁴¹ , And Re ⁴¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, Q ³¹ represents —O—, —S—, or —NRf—, and Rf represents a hydrogen atom. Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may be linked to Ra ⁴¹ to form a ring, and Q ³² represents —O—, —S—, or —NRh—. Rh represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and may be linked to Rg ⁴¹ to form a ring X ⁴³ is a single bond or a divalent linkage X ⁴⁴ represents the following general group This represents a linking group selected from the group consisting of divalent linking groups represented by formula (P).)

(In General Formula (P), the * side is the linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (F-1).) The cellulose acylate film according to claim 1 or 2, wherein the hydrogen bonding compound is a compound represented by the following general formula (G-1).

(In General Formula (G-1), L ¹ represents a single bond or a divalent linking group containing a hetero atom, R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Group, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.) The cellulose acylate film according to claim 1 or 2, wherein the hydrogen bonding compound is a compound represented by the following general formula (H-1).

(In General Formula (H-1), L ³ represents a single bond or a divalent linking group containing a hetero atom, R ⁸⁵ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon Represents an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.) R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. Represents an aryl group or a heterocyclic group. X ⁵³ and X ⁵⁴ each independently represent a linking group selected from the group consisting of a divalent linking group represented by the following general formula (P). )

(In General Formula (P), the * side is the linking site with the N atom substituted on the heterocyclic ring in the compound represented by General Formula (H-1).)   The cellulose acylate film according to any one of claims 1 to 11, wherein the molecular weight of the hydrogen bonding compound is 100 to 1,000.   A retardation film comprising the cellulose acylate film according to claim 1.   A polarizing plate comprising the cellulose acylate film according to claim 1 or the retardation film according to claim 13.   A liquid crystal display device comprising the cellulose acylate film according to claim 1, the retardation film according to claim 13, or the polarizing plate according to claim 14.

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