JP6275191B2 - Retardation film, polarizing plate, and liquid crystal display device - Google Patents

Description

  The present invention relates to a retardation film suitable for optical compensation of liquid crystal display devices of various alignment modes, an optical film having a retardation layer formed by fixing the alignment state of a liquid crystal compound used in a polarizing plate, and a method for producing the same. .

In a liquid crystal display device, optical compensation is performed to improve image quality such as wide viewing angle, contrast improvement, and color shift suppression. Optical compensation means the function of correcting the birefringence that occurs when light passes through a member having birefringence that is configured when the liquid crystal display device displays an image, and cancels the generated birefringence. This is done by arranging an optically anisotropic layer.
This optically anisotropic layer can be obtained by developing the birefringence of a material having birefringence.
For example, a method for obtaining an optically anisotropic layer (retardation layer) as a film by forming a material exhibiting birefringence such as cyclic polyolefin or cellulose, or by aligning a liquid crystal compound having birefringence and causing retardation Methods for obtaining layers are known.
The latter retardation layer has higher retardation than the former retardation layer and often takes the form of a retardation film formed on a support such as a film.
For example, in Patent Document 1, a laminated retardation film in which an alignment film (intermediate layer) containing a polyvinyl alcohol resin and a layer in which a rod-like liquid crystal compound is vertically aligned are provided on a cellulose acylate film (support). Is disclosed.
Patent Document 2 discloses a retardation film using a support containing a cyclic olefin resin.

JP 2007-279083 A JP 2010-42623 A

However, as in Patent Document 1, when a liquid crystal layer is provided on a cellulose acylate film (support), the cellulose acylate is saponified and a polyvinyl alcohol (PVA) film is applied thereon, and then the liquid crystal layer is formed. Further application was necessary. As a result, the saponification treatment, the water washing step, the PVA film coating, and the liquid crystal layer coating require a large number of necessary treatments and are complicated operations, and therefore, improvement is required from the viewpoint of productivity. Furthermore, since the PVA layer is water-soluble, there is a problem that the liquid crystal layer is peeled off when rubbed with a cloth after being immersed in hot water (warm water). In addition, in the saponification treatment and washing process, water removal after washing becomes uneven and optical unevenness occurs from that part, and handling of thin film (60 μm or less) in the washing process is also a problem. There was a need to solve these problems.
In addition, in a support made of a cyclic olefin resin as in Patent Document 2, it is disclosed that a polyimide resin is used as an alignment film for aligning a liquid crystal layer. However, polyimide is yellowish and expensive. It is generally known that it is a new material.

Accordingly, in view of the above circumstances, the present invention provides a retardation film having excellent optical properties suitable for optical compensation of a liquid crystal display device, which is excellent in productivity, adhesion, surface shape, abrasion resistance in hot water, and handling in a thin film. The purpose is to provide.
Moreover, it aims at providing the polarizing plate and liquid crystal display device which have such a phase difference film.

一般式（４）及び（５）において、ｍは０〜４の整数を表す。Ｒ^３〜Ｒ^６は各々独立に、水素原子又は炭素数１〜１０の炭化水素基を表す。Ｘ^２、Ｘ^３、Ｙ^２、Ｙ^３は各々独立に、水素原子、炭素数１〜１０の炭化水素基、ハロゲン原子、ハロゲン原子で置換された炭素数１〜１０の炭化水素基、−（ＣＨ_２）_ｎＣＯＯＲ^１１、−（ＣＨ_２）_ｎＯＣＯＲ^１２、−（ＣＨ_２）_ｎＮＣＯ、−（ＣＨ_２）_ｎＮＯ_２、−（ＣＨ_２）_ｎＣＮ、−（ＣＨ_２）_ｎＣＯＮＲ^１３Ｒ^１４、−（ＣＨ_２）_ｎＮＲ^１３Ｒ^１４、−（ＣＨ_２）_ｎＯＺ、−（ＣＨ_２）_ｎＷ、またはＸ^２とＹ^２、あるいは、Ｘ^３とＹ^３から構成された（−ＣＯ）_２Ｏ、（−ＣＯ）_２ＮＲ^１５を示す。なお、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、及びＲ^１５は各々独立に、水素原子、炭素数１〜２０の炭化水素基、Ｚは炭化水素基またはハロゲンで置換された炭化水素基、ＷはＳｉＲ^１６ _ｐＤ_３−ｐ（Ｒ^１６は炭素数１〜１０の炭化水素基、Ｄはハロゲン原子、−ＯＣＯＲ^１６または−ＯＲ^１６、ｐは０〜３の整数を示す）、ｎは０〜１０の整数を示す。
＜７＞
前記位相差層を形成する重合性液晶化合物が下記一般式（ＩＩＡ）で表される化合物、及び下記一般式（ＩＩＢ）で表される化合物からなる群より選択される少なくとも１種の化合物である、＜１＞〜＜６＞のいずれか１項に記載の位相差フィルム。

Ｒ_１〜Ｒ_４は、各々独立に、−（ＣＨ_２）_ｎ−ＯＯＣ−ＣＨ＝ＣＨ_２で、ｎは２〜５の整数を表す。Ｘ及びＹは各々独立に、水素原子又はメチル基を表す。
＜８＞
前記位相差層が、前記一般式（ＩＩＡ）で表される化合物、及び前記一般式（ＩＩＢ）で表される化合物をそれぞれ、位相差層の全固形分に対して３質量％以上含む、＜７＞に記載の位相差フィルム。
＜９＞
前記位相差層に含まれる垂直配向剤が、下記一般式（Ｉ）で表されるオニウム化合物である、＜１＞〜＜８＞のいずれか１項に記載の位相差フィルム。

一般式（Ｉ）中、環Ａは含窒素複素環からなる第４級アンモニウムイオンを表し、Ｘはアニオンを表し；Ｌ¹は二価の連結基を表し；Ｌ²は単結合又は二価の連結基を表し；Ｙ¹は５又は６員環を部分構造として有する２価の連結基を表し；Ｚは２〜２０のアルキレン基を部分構造として有する２価の連結基を表し；Ｐ¹及びＰ²はそれぞれ独立に重合性エチレン性不飽和基を有する一価の置換基を表す。
＜１０＞
前記位相差層中に臭素、ホウ素、及び珪素から選択される少なくとも１種の元素を含む、＜１＞〜＜９＞のいずれか１項に記載の位相差フィルム。
＜１１＞
前記位相差層において、臭素、ホウ素、及び珪素から選択される少なくとも１種の元素が、前記アクリル樹脂層に近い側に多く偏在している、＜１０＞に記載の位相差フィルム。
＜１２＞
前記位相差層の膜厚が、０．５μｍ〜２．０μｍである、＜１＞〜＜１１＞のいずれか１項に記載の位相差フィルム。
＜１３＞
前記支持体のＲｅが８０ｎｍ〜１５０ｎｍであり、Ｒｔｈは、Ｒｅよりも大きく、かつ８０ｎｍ〜１５０ｎｍである、＜１＞〜＜１２＞のいずれか１項に記載の位相差フィルム。
ここで、Ｒｅ及びＲｔｈは、それぞれ、２５℃、６０％ＲＨで波長５５０ｎｍの光で測定した面内レターデーション値及び厚み方向のレターデーション値である。
＜１４＞
前記位相差層において、Ｒｅが−１０ｎｍ〜１０ｎｍであり、Ｒｔｈが−２５０ｎｍ〜−１００ｎｍである、＜１＞〜＜１３＞のいずれか１項に記載の位相差フィルム。
ここで、Ｒｅ及びＲｔｈは、それぞれ、２５℃、６０％ＲＨで波長５５０ｎｍの光で測定した面内レターデーション値及び厚み方向のレターデーション値である。
＜１５＞
偏光膜と該偏光膜の両面を保護する２枚の保護フィルムを有する偏光板であって、該保護フィルムの少なくとも一方が＜１＞〜＜１４＞のいずれか１項に記載の位相差フィルムである偏光板。
＜１６＞
前記２枚の保護フィルムのうち、一方が＜１＞〜＜１４＞のいずれか１項に記載の位相差フィルムであり、他方がアクリル樹脂からなるフィルムである、＜１５＞に記載の偏光板。
＜１７＞
膜厚が５０μｍ〜１２０μｍである＜１５＞又は＜１６＞に記載の偏光板。
＜１８＞
＜１＞〜＜１４＞のいずれか１項に記載の位相差フィルム、又は、＜１５＞〜＜１７＞のいずれか１項に記載の偏光板を有する液晶表示装置。
＜１９＞
＜１＞〜＜１４＞のいずれか１項に記載の位相差フィルムを用いた横電界モードの液晶表示装置。
＜２０＞
＜１５＞〜＜１７＞のいずれか１項に記載の偏光板を用いた横電界モードの液晶表示装置。
なお、本発明は上記＜１＞〜＜２０＞に関するものであるが、参考のためその他の事項（下記［１］〜［２９］に記載した事項等）についても記載した。
Therefore, the present inventors have studied various methods for homeotropic alignment of liquid crystal compounds in a simplified form of layer formation. As a result, an acrylic resin layer having a polar group is provided between the support and the liquid crystal layer. By providing an intermediate layer in which both materials are mixed between the acrylic resin layer and the support, and further by adding a vertical alignment agent to the retardation layer in which the alignment state of the liquid crystal compound is fixed, the support layer, acrylic A simple method for producing a retardation film that does not peel off at any interface between the resin layer and the alignment layer of the liquid crystal compound, has little tint, has high transparency, and is excellent in scuff resistance in warm water It was found that it can be manufactured.
That is, the present invention has the following configuration.
<1>
A support, an acrylic resin layer, and an intermediate layer including a main component of the support and a main component of the acrylic resin layer between the support and the acrylic resin layer; A retardation film having a retardation layer directly fixing the alignment state of the liquid crystal compound on the surface opposite to the intermediate layer,
The support contains a cyclic olefin resin,
The acrylic resin layer contains an acrylic resin having at least one polar group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, and a cyano group,
The intermediate layer has a thickness of 0.1 μm or more and 10 μm or less,
The retardation layer, Ri Na comprise polymers of polymerizable liquid crystal compound with a vertical alignment agent,
The retardation layer is a layer that fixes the polymerizable liquid crystal compound in a homeotropic alignment state,
The retardation film has Re of -10 nm to 10 nm .
Here, Re is an in-plane retardation value measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH.
<2>
The retardation film according to <1>, wherein the optical characteristics of the retardation film satisfy the following formulas (1), (2), and (3).
80 nm ≦ Re ≦ 150 nm (1)
−100 nm ≦ Rth ≦ 10 nm Formula (2)
0.05 ≦ | Rth / Re | ≦ 0.5 Formula (3)
Here, R e及 beauty Rth, respectively, is 25 ° C., a retardation value measured in-plane retardation value and the thickness direction by light with a wavelength of 550nm at 60% RH.
<3>
The retardation film according to <1> or <2>, wherein a water droplet contact angle on the surface of the acrylic resin layer is 25 ° or more and 60 ° or less.
<4>
The retardation film according to any one of <1> to <3>, wherein the polar group of the acrylic resin is a hydroxyl group.
<5>
The retardation film according to any one of <1> to <4>, wherein the acrylic resin layer is a layer formed from a composition containing at least one acrylate monomer having two or more functional groups.
<6>
The retardation film according to any one of <1> to <4>, wherein the cyclic olefin resin includes a structural unit represented by the following general formula (4) or (5).

In general formula (4) and (5), m represents the integer of 0-4. R ^{3 to} R ⁶ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. X ² , X ³ , Y ² and Y ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom,-( _{^{CH 2) n COOR 11, -}} (CH 2) n OCOR 12, - (CH 2) n NCO, - (CH 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 13 R ¹⁴ , — (CH ₂ ) _n NR ¹³ R ¹⁴ , — (CH ₂ ) _n OZ, — (CH ₂ ) _n W, or X ² and Y ² , or X ³ and Y ³ (—CO ) ₂ O, (—CO) ₂ NR ¹⁵ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with a halogen, W is SiR ¹⁶ _p D _3-p (R ¹⁶ is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, —OCOR ¹⁶ or —OR ¹⁶ , p is an integer of 0 to 3), and n is 0 An integer of -10 is shown.
<7>
The polymerizable liquid crystal compound forming the retardation layer is at least one compound selected from the group consisting of a compound represented by the following general formula (IIA) and a compound represented by the following general formula (IIB). <1>-<6> The retardation film according to any one of <6>.

R _{1 to} R ₄ are each independently — (CH ₂ ) _n —OOC—CH═CH ₂ , and n represents an integer of 2 to 5. X and Y each independently represent a hydrogen atom or a methyl group.
< 8 >
The retardation layer contains 3% by mass or more of the compound represented by the general formula (IIA) and the compound represented by the general formula (IIB) with respect to the total solid content of the retardation layer, respectively. 7> The retardation film described in 7>.
< 9 >
The retardation film according to any one of <1> to < 8 >, wherein the vertical alignment agent contained in the retardation layer is an onium compound represented by the following general formula (I).

In general formula (I), ring A represents a quaternary ammonium ion composed of a nitrogen-containing heterocycle, X represents an anion; L ¹ represents a divalent linking group; L ² represents a single bond or a divalent group. Y ¹ represents a divalent linking group having a 5- or 6-membered ring as a partial structure; Z represents a divalent linking group having 2 to 20 alkylene groups as a partial structure; P ¹ and P ² independently represents a monovalent substituent having a polymerizable ethylenically unsaturated group.
< 10 >
The retardation film according to any one of <1> to < 9 >, wherein the retardation layer contains at least one element selected from bromine, boron, and silicon.
< 11 >
The retardation film according to < 10 >, wherein in the retardation layer, at least one element selected from bromine, boron, and silicon is unevenly distributed closer to the acrylic resin layer.
< 12 >
The retardation film according to any one of <1> to < 11 >, wherein a film thickness of the retardation layer is 0.5 μm to 2.0 μm.
< 13 >
The retardation film according to any one of <1> to < 12 >, wherein Re of the support is 80 nm to 150 nm, Rth is larger than Re, and is 80 nm to 150 nm.
Here, R e及 beauty Rth, respectively, is 25 ° C., a retardation value measured in-plane retardation value and the thickness direction by light with a wavelength of 550nm at 60% RH.
< 14 >
The retardation film according to any one of <1> to < 13 >, wherein Re is -10 nm to 10 nm and Rth is -250 nm to -100 nm in the retardation layer.
Here, R e及 beauty Rth, respectively, is 25 ° C., a retardation value measured in-plane retardation value and the thickness direction by light with a wavelength of 550nm at 60% RH.
< 15 >
A polarizing plate having a polarizing film and two protective films protecting both surfaces of the polarizing film, wherein at least one of the protective films is the retardation film according to any one of <1> to < 14 >. A polarizing plate.
< 16 >
The polarizing plate according to < 15 >, wherein one of the two protective films is the retardation film according to any one of <1> to < 14 >, and the other is a film made of an acrylic resin. .
< 17 >
The polarizing plate as described in < 15 > or < 16 > whose film thickness is 50 micrometers-120 micrometers.
< 18 >
<1>-< 14 > The phase difference film of any one of < 14 >, or the liquid crystal display device which has a polarizing plate of any one of < 15 >-< 17 >.
< 19 >
<1>-< 14 > The liquid crystal display device of the horizontal electric field mode using the retardation film of any one of <1>.
< 20 >
< 15 >-< 17 > The horizontal electric field mode liquid crystal display device using the polarizing plate of any one of < 17 >.
In addition, although this invention is related to said <1>-< 20 >, the other matter (The matter described in the following [1]-[29] etc.) was also described for reference.

[1]
A support, an acrylic resin layer, and an intermediate layer including a main component of the support and a main component of the acrylic resin layer between the support and the acrylic resin layer; A retardation film having a retardation layer directly fixing the alignment state of the liquid crystal compound on the surface opposite to the intermediate layer,
The support contains at least one resin selected from cellulose acylate resin, cyclic olefin resin, polycarbonate resin, acrylic resin, and styrene resin,
The acrylic resin layer contains an acrylic resin having at least one polar group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, and a cyano group, and the intermediate layer , Having a thickness of 0.1 μm or more and 10 μm or less,
The retardation layer comprises a polymer of a vertical alignment agent and a polymerizable liquid crystal compound.
Retardation film.
[2]
The retardation film according to [1], wherein the optical characteristics of the retardation film satisfy the following formulas (1), (2), and (3).
80 nm ≦ Re ≦ 150 nm (1)
−100 nm ≦ Rth ≦ 10 nm Formula (2)
0.05 ≦ | Rth / Re | ≦ 0.5 Formula (3)
Here, Re and Rth are an in-plane retardation value and a retardation value in the thickness direction, respectively, measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH.
[3]
The retardation film according to [1] or [2], wherein a contact angle of water droplets on the surface of the acrylic resin layer is 25 ° or more and 60 ° or less.
[4]
The retardation film according to any one of [1] to [3], wherein the polar group of the acrylic resin is a hydroxyl group.
[5]
The retardation film according to any one of [1] to [4], wherein the acrylic resin layer is a layer formed from a composition containing at least one acrylate monomer having two or more functional groups.
[6]
The retardation film according to any one of [1] to [5], wherein the support contains cellulose acylate.
[7]
The retardation film according to [6], wherein the cellulose acylate is cellulose acetate.
[8]
The retardation film according to [6] or [7], wherein an average acyl group substitution degree DS of the cellulose acylate satisfies 2.0 <DS <2.6.
[9]
The said support body contains cyclic olefin resin, The said cyclic olefin resin contains the structural unit represented by following General formula (4) or (5), Any one of [1]-[5]. Retardation film.

In general formula (4) and (5), m represents the integer of 0-4. R ^{3 to} R ⁶ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. X ² , X ³ , Y ² and Y ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom,-( _{^{CH 2) n COOR 11, -}} (CH 2) n OCOR 12, - (CH 2) n NCO, - (CH 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 13 R ¹⁴ , — (CH ₂ ) _n NR ¹³ R ¹⁴ , — (CH ₂ ) _n OZ, — (CH ₂ ) _n W, or X ² and Y ² , or X ³ and Y ³ (—CO ) ₂ O, (—CO) ₂ NR ¹⁵ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with a halogen, W is SiR ¹⁶ _p D _3-p (R ¹⁶ is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, —OCOR ¹⁶ or —OR ¹⁶ , p is an integer of 0 to 3), and n is 0 An integer of -10 is shown.
[10]
The support contains an acrylic resin, and the acrylic resin contains at least one structural unit selected from the group consisting of a lactone ring unit, a maleic anhydride unit, and a glutaric anhydride unit. The retardation film according to any one of [5].
[11]
The retardation film according to any one of [1] to [5], wherein the support contains a styrene resin, and the styrene resin includes a structural unit represented by the following general formula (S).
General formula (S)

In the general formula (S), R _{S1 to} R _S3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, or a carbon atom having 1 to 3 carbon atoms substituted with a halogen atom. Represents a hydrocarbon group.
[12]
The polymerizable liquid crystal compound forming the retardation layer is at least one compound selected from the group consisting of a compound represented by the following general formula (IIA) and a compound represented by the following general formula (IIB). [1] to [11] The retardation film according to any one of [11].

R _{1 to} R ₄ are each independently — (CH ₂ ) _n —OOC—CH═CH ₂ , and n represents an integer of 2 to 5. X and Y each independently represent a hydrogen atom or a methyl group.
[13]
The retardation film according to any one of [1] to [12], wherein the retardation layer is a layer in which the polymerizable liquid crystal compound is fixed in a homeotropic alignment state.
[14]
The retardation layer contains 3% by mass or more of the compound represented by the general formula (IIA) and the compound represented by the general formula (IIB), respectively, based on the total solid content of the retardation layer. [12] or [13].
[15]
The retardation film according to any one of [1] to [14], wherein the vertical alignment agent contained in the retardation layer is an onium compound represented by the following general formula (I).

In general formula (I), ring A represents a quaternary ammonium ion composed of a nitrogen-containing heterocycle, X represents an anion; L ¹ represents a divalent linking group; L ² represents a single bond or a divalent group. Y ¹ represents a divalent linking group having a 5- or 6-membered ring as a partial structure; Z represents a divalent linking group having 2 to 20 alkylene groups as a partial structure; P ¹ and P ² independently represents a monovalent substituent having a polymerizable ethylenically unsaturated group.
[16]
The retardation film according to any one of [1] to [15], wherein the retardation layer contains at least one element selected from bromine, boron, and silicon.
[17]
The retardation film according to [16], wherein in the retardation layer, at least one element selected from bromine, boron, and silicon is unevenly distributed on the side closer to the acrylic resin layer.
[18]
The retardation film according to any one of [1] to [17], wherein the retardation layer has a thickness of 0.5 μm to 2.0 μm.
[19]
The retardation film according to any one of [1] to [18], wherein Re of the support is from 80 nm to 150 nm, Rth is larger than Re, and is from 80 nm to 150 nm.
Here, Re and Rth are an in-plane retardation value and a retardation value in the thickness direction, respectively, measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH.
[20]
The retardation film according to any one of [1] to [19], wherein Re is -10 nm to 10 nm and Rth is -250 nm to -100 nm in the retardation layer.
Here, Re and Rth are an in-plane retardation value and a retardation value in the thickness direction, respectively, measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH.
[21]
A polarizing plate having a polarizing film and two protective films protecting both surfaces of the polarizing film, wherein at least one of the protective films is the retardation film according to any one of [1] to [20]. A certain polarizing plate.
[22]
A polarizing plate, wherein one of the two protective films is the retardation film according to any one of [1] to [20], and the other is a film made of an acrylic resin.
[23]
The polarizing plate as described in [21] or [22] whose film thickness is 50 micrometers-120 micrometers.
[24]
A liquid crystal display device comprising the retardation film according to any one of [1] to [20] or the polarizing plate according to any one of [21] to [23].
[25]
A liquid crystal display device in a transverse electric field mode using the retardation film according to any one of [1] to [20].
[26]
A liquid crystal display device in a transverse electric field mode using the polarizing plate according to any one of [21] to [23].
[27]
A support, an acrylic resin layer, and an intermediate layer including a main component of the support and a main component of the acrylic resin layer between the support and the acrylic resin layer; A method for producing a retardation film having a retardation layer in which an alignment state of a liquid crystal compound is directly fixed on a surface opposite to the support,
On the support, a step of applying an acrylic resin layer forming composition in which an acrylic resin layer forming material is dissolved in a solvent having a dissolving ability and a swelling ability in the supporting material;
Providing a region where the support material and the acrylic resin layer forming material are mixed;
A step of curing the acrylic resin layer forming material,
A step of applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound and at least one vertical alignment agent on the acrylic resin layer, and forming a liquid crystal layer in which the alignment state is fixed by polymerization. Film manufacturing method.
[28]
The method for producing a retardation film according to [27], wherein the solvent having solubility and swelling ability with respect to the support is selected from at least one of methyl acetate, methyl ethyl ketone, and acetone.
[29]
The support is subjected to a stretching treatment of at least 30% and not more than 150% in at least one direction, the support layer has optical characteristics of Re = 80 nm to 150 nm, Rth is at least larger than Re, and satisfies 80 nm to 150 nm The method for producing a laminated optical film according to [27] or [28].
Here, Re and Rth are an in-plane retardation value and a retardation value in the thickness direction measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH (relative humidity 60%), respectively.

According to the present invention, a retardation film having excellent optical properties suitable for optical compensation of a liquid crystal display device in a transverse electric field mode, which is excellent in productivity, adhesion, planarity, abrasion resistance in hot water, and handling in a thin film. Can be provided.
Moreover, it aims at providing the polarizing plate and liquid crystal display device which have such a phase difference film.
According to the present invention, a retardation film excellent in adhesion of a support, an acrylic resin layer and a retardation layer, a liquid crystal alignment property of a retardation layer in which an alignment state of a liquid crystal compound is fixed, and a retardation layer surface shape can be obtained. .
Further, since the retardation film of the present invention can be easily thinned, it can contribute to thinning of the polarizing plate and the liquid crystal display device.
Furthermore, an optical film provided with a hydrophilic acrylic resin layer is excellent in durability under a high-temperature and high-humidity environment and has a good surface shape. In addition, since the hardness of the acrylic resin layer is larger than that of the PVA alignment film, when the film is continuously formed, the film having a PVA layer is hardly wound in a wound shape, and is easily generated in a normal wound shape. It is possible to obtain a high-quality film with few defective parts with good handling properties such as unevenness (referred to as knicking or tape copying) such as curling and transfer of steps.

It is a schematic diagram which shows an example of the embodiment of the retardation film of this invention. It is a schematic diagram which shows an example of the embodiment of the polarizing plate of this invention. It is a schematic diagram for demonstrating the measurement of the average content rate of the support body component of an intermediate | middle layer in the retardation film of this invention.

  Hereinafter, the present invention will be described in detail. In the present specification, when numerical values represent physical property values, characteristic values, etc., the descriptions “(numerical value 1) to (numerical value 2)” and “(numerical value 1) to (numerical value 2)” are “(numeric value 1) ) ”(Numerical value 2) or less”. The “retardation layer in which the alignment state of the liquid crystal compound is fixed” may be abbreviated as “retardation layer”.

The retardation film of the present invention has a support, an acrylic resin layer, and an intermediate layer including the main component of the support and the main component of the acrylic resin layer between the support and the acrylic resin layer. Further, a retardation film having a retardation layer directly fixing the alignment state of the liquid crystal compound on the surface of the acrylic resin layer opposite to the intermediate layer,
The support contains at least one resin selected from cellulose acylate resin, cyclic olefin resin, polycarbonate resin, acrylic resin, and styrene resin,
The acrylic resin layer contains an acrylic resin having at least one polar group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, and a cyano group, and the intermediate layer , Having a thickness of 0.1 μm or more and 10 μm or less,
The retardation layer comprises a polymer of a vertical alignment agent and a polymerizable liquid crystal compound.
It is a retardation film.

The retardation film of the present invention is an optical film formed by laminating a support, an acrylic resin layer, and a retardation layer. The support film and the acrylic resin layer are mixed at the interface between the support and the acrylic resin layer. There is an intermediate layer.
Each of the following configurations will be described in detail.

<Support>
The support of the retardation film of the present invention contains at least one resin selected from cellulose acylate resins, cyclic olefin resins, polycarbonate resins, acrylic resins, and styrene resins.

[Cellulose acylate resin]
The support of the retardation film of the present invention is preferably a support (cellulose acylate film) containing cellulose acylate as a main component.
Examples of the cellulose acylate resin (also referred to as “cellulose acylate”) include a cellulose acylate compound and a compound having an acyl-substituted cellulose skeleton obtained by introducing a functional group biologically or chemically using cellulose as a raw material. It is done.

  Cellulose acylate is an ester of cellulose and acid. As the acid constituting the ester, an organic acid is preferable, a carboxylic acid is more preferable, a fatty acid having 2 to 22 carbon atoms is further preferable, and a lower fatty acid having 2 to 4 carbon atoms is most preferable.

[Cellulose acylate raw material cotton]
Cellulose acylate raw material cellulose used in the present invention includes cotton linter and wood pulp (hardwood pulp, softwood pulp), etc., and any cellulose acylate obtained from any raw material cellulose can be used, optionally mixed. May be. Detailed descriptions of these raw material celluloses can be found in, for example, “Plastic Materials Course (17) Fibrous Resin” (Marusawa, Uda, Nikkan Kogyo Shimbun, published in 1970) and JIII Journal of Technical Disclosure 2001-1745 (7 The cellulose described in pages 8 to 8) can be used, and the cellulose acylate used in the present invention is not particularly limited.

[Degree of acyl substitution of cellulose acylate]
In the present invention, the cellulose acylate is obtained by acylating a hydroxyl group of cellulose, and the substituent is preferably an acyl group having 2 to 22 carbon atoms and an acyl group having 2 to 4 carbon atoms. A group can be preferably used.
The support in the present invention preferably contains, as a main component, cellulose acylate having an average acyl group substitution degree DS satisfying 2.0 <DS <2.6.
Here, “as the main component” means that the support is composed of a single polymer, and when the support is composed of a plurality of polymers, the most of the polymers constituting the support. Indicates a polymer with a high mass fraction.
Although there is no particular limitation on the measurement of the degree of substitution of cellulose with a hydroxyl group in cellulose acylate, the degree of substitution of acetic acid and / or a fatty acid having 3 or more carbon atoms to be substituted with a hydroxyl group of cellulose is measured, and the degree of substitution is obtained by calculation. be able to. As a measuring method, it can implement according to ASTMD-817-91.

When the acyl substitution degree of cellulose acylate is DS, in the present invention, 2.00 <DS <2.60, 2.00 <DS <2.55 is preferable, and 2.10 <DS <2.50. Is more preferable, and 2.20 <DS <2.45 is still more preferable.
If the acyl substitution degree of cellulose acylate is larger than 2.00, it is sufficient in terms of humidity stability and polarizing plate durability. A cellulose acylate having excellent compatibility with a polycondensate that is excellent, has solubility in an organic solvent, and may be used as an additive is preferable.

  The acyl group possessed by cellulose acylate may be either an aliphatic acyl group or an aromatic acyl group, and is not particularly limited, and may be a single group or a mixture of two or more types. The number of carbon atoms of the acyl group is preferably 2 to 22, and 2 or 3 is particularly preferable. Examples of the acyl group include cellulose alkylcarbonyl ester, alkenylcarbonyl ester, aromatic carbonyl ester, and aromatic alkylcarbonyl ester, which may each further have a substituted group. These preferred acyl groups include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl I-butanoyl group, t-butanoyl group, cyclohexanecarbonyl group, oleoyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group and the like. Among these, acetyl group, propionyl group, butanoyl group, dodecanoyl group, octadecanoyl group, t-butanoyl group, oleoyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group and the like are preferable, and acetyl group, propionyl group, butanoyl group are preferable. Groups are more preferred. Further preferred groups are an acetyl group and a propionyl group, and the most preferred group is an acetyl group.

[Degree of polymerization of cellulose acylate]
The degree of polymerization of cellulose acylate preferably used in the present invention is 180 to 700 in terms of viscosity average polymerization degree, and in cellulose acetate, 180 to 550 is more preferable, 180 to 400 is more preferable, and 180 to 350 is particularly preferable. . If the degree of polymerization is not more than the upper limit, the viscosity of the cellulose acylate dope solution does not become too high, and a film can be easily produced by casting. If the degree of polymerization is equal to or greater than the lower limit, it is preferable because there is no inconvenience such as a decrease in strength of the produced film. The viscosity average degree of polymerization can be measured by Uda et al.'S intrinsic viscosity method {Kazuo Uda, Hideo Saito, "Journal of the Textile Society," Vol. 18, No. 1, pages 105-120 (1962)}. This method is also described in detail in JP-A-9-95538.

  The molecular weight distribution of cellulose acylate preferably used in the present invention is evaluated by gel permeation chromatography, and its polydispersity index Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) is small, and the molecular weight A narrow distribution is preferred. The specific value of Mw / Mn is preferably 1.0 to 4.0, more preferably 2.0 to 4.0, and most preferably 2.3 to 3.4. preferable.

[Method for producing cellulose acylate film]
The method for producing a cellulose acylate film includes a film-forming step of casting a dope on a casting support such as a metal support and evaporating the solvent to form a cellulose acylate film, and then stretching to stretch the film. It is preferable to have a step of drying the film obtained thereafter, and a step of heat-treating at a temperature of 150 to 200 ° C. for 1 minute or longer after the drying step.

(Film forming process)
In the present invention, a method for forming a known cellulose acylate film or the like can be widely adopted, and it is preferably produced by a solution casting film forming method. In the solution casting film forming method, a film can be produced using a solution (dope) obtained by dissolving cellulose acylate in an organic solvent.
The organic solvent is a solvent 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 contain. The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of 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 types of functional groups, the number of carbon atoms may be within the specified range of the compound 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 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 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 organic solvents may be mixed and used.

A cellulose acylate solution can be prepared by a general method. A general method means processing at a temperature of 0 ° C. or higher (ordinary temperature or high temperature). The solution can be prepared by using a dope preparation method and apparatus in a normal solution casting film forming 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 is adjusted so as to be contained in the obtained solution in an amount of 10 to 40% by mass. 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 solution can be prepared by stirring the cellulose acylate and the organic solvent at room temperature (0 to 40 ° C.). The high concentration solution 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 needs to be configured so that it can be stirred. 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.
It is preferable to provide a stirring blade inside the container and stir using this. 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 film can be produced from the prepared cellulose acylate solution (dope) by a solution casting film forming method.
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% by mass. The surface of the drum or band is preferably finished in a mirror state. Regarding casting and drying methods in the solution casting film-forming method, U.S. Pat. 640731, 736892, JP-B 45-4554, 49-5614, JP-A-60-176834, 60-203430, 62-1215035 .

  The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less. After casting, it is preferable to dry it by applying air for 2 seconds or more. 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.

(Co-casting)
The cellulose acylate film used in the present invention is preferably produced by stretching after film formation by a solution casting film formation method. Moreover, it is preferable that a solution casting film is a multilayer casting film by co-casting simultaneously or sequentially. It is because it can be set as the film which has a desired retardation value. In the present invention, the obtained cellulose acylate solution may be cast as a single layer liquid on a smooth band or drum as a metal support, or a plurality of cellulose acylate solutions of two or more layers may be cast. May be. When casting a plurality of cellulose acylate solutions, produce a film while casting and laminating a solution containing cellulose acylate from a plurality of casting openings provided at intervals in the traveling direction of the metal support. For example, the methods described in JP-A-61-158414, JP-A-1-122419, JP-A-11-198285 and the like can be applied. Further, it may be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, It can be carried out by the methods described in JP-A Nos. 61-104813, 61-158413, and 6-134933. Further, 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- and low-viscosity cellulose acylate solutions are simultaneously extruded. A casting method may be used. Furthermore, it is also a preferable aspect that the surface side solution described in JP-A-61-94724 and JP-A-61-94725 contains a larger amount of an alcohol component which is a poor solvent than the inner solution. .

  Alternatively, by using two casting ports, the film cast on the metal support is peeled off by the first casting port, and the second casting is performed on the side in contact with the metal support surface. Further, a film may be prepared, for example, a method described in Japanese Patent Publication No. 44-20235. The cellulose acylate solutions to be cast may be the same solution or different cellulose acylate solutions, and are not particularly limited. 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. Further, the cellulose acylate solution used in the present invention may be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer). sell.

  In conventional single-layer liquids, it is preferable to extrude a cellulose acylate solution with a high concentration and a high viscosity in order to obtain the required film thickness. In this case, the stability of the cellulose acylate solution is poor and solids are generated. In many cases, however, it becomes a problem due to a failure or poor flatness. As a solution to this, by casting a plurality of cellulose acylate solutions from a casting port, a highly viscous solution can be extruded onto a metal support at the same time. Not only can it be produced, but also the use of a concentrated cellulose acylate solution can reduce the drying load and increase the film production speed.

  In the case of co-casting, the thickness of the inner side and the surface side is not particularly limited, but preferably the surface side is preferably 1 to 50% of the total film thickness, more preferably 2 to 30%. Here, in the case of co-casting of three or more layers, the total thickness of the outermost layer in contact with the casting metal support and the outermost layer in contact with the air side is defined as the thickness on the surface side.

  In the case of co-casting, a cellulose acylate film having a laminated structure can be produced by co-casting cellulose acylate solutions having different degrees of substitution. Also, a cellulose acylate film having a laminated structure can be produced by co-casting cellulose acylate solutions having different additive concentrations such as a plasticizer, an ultraviolet absorber, and fine particles described later. For example, fine particles can be contained in the surface layer in a large amount or only in the surface layer. The plasticizer and the ultraviolet absorber can be contained in the inner layer more than the surface layer, and may be contained only in the inner layer. Also, the type of plasticizer and UV absorber can be changed between the inner layer and the surface layer. For example, the surface layer contains a low-volatile plasticizer and / or UV absorber, and the inner layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption. Moreover, it is also a preferable aspect to contain a release agent only in the surface layer on the metal support side. Moreover, in order to cool a metal support body by a cooling drum method and to gelatinize a solution, it is also preferable to add more alcohol which is a poor solvent to a surface layer than an internal layer. The Tg of the surface layer and the inner layer may be different, and the Tg of the inner layer is preferably lower than the Tg of the surface layer. The viscosity of the solution containing cellulose acylate during casting may be different between the surface layer and the inner layer, and the viscosity of the surface layer is preferably smaller than the viscosity of the inner layer. It may be smaller than the viscosity.

  The support includes a cellulose acylate having an average acyl substitution degree DS satisfying 2.0 <DS <2.6, which is a main component, and a cellulose acylate having an average acyl substitution degree of 2.6 to 3.0. A support formed by laminating a rate is preferable from the viewpoint of ease of peeling from the metal support.

(Drying process, stretching process)
A method of drying a web formed and peeled on a drum or belt, which is a metal support for casting, will be described. The web peeled at the peeling position just before the drum or belt makes one round is conveyed by alternately passing through a group of rolls arranged in a staggered manner, or the both ends of the peeled web are gripped by clips or the like and are not contacted. It is conveyed by the method of conveying it automatically. Drying is performed by a method of applying wind at a predetermined temperature to both sides of the web (film) being conveyed or a method using a heating means such as a microwave. Since rapid drying may impair the flatness of the film to be formed, it is preferable to dry at a temperature at which the solvent does not foam in the initial stage of drying, and to dry at a high temperature after the drying proceeds. In the drying process after peeling from the support, the film tends to shrink in the longitudinal direction or the width direction by evaporation of the solvent. Shrinkage increases with drying at higher temperatures. Drying while suppressing this shrinkage as much as possible is preferable for improving the flatness of the finished film. From this point, for example, as shown in Japanese Patent Laid-Open No. 62-46625, a method in which all or part of the drying process is performed while holding the width at both ends of the web with clips or pins in the width direction. (Tenter method) is preferable. It is preferable that the drying temperature in the said drying process is 100-145 degreeC. The drying temperature, the amount of drying air, and the drying time vary depending on the solvent used, but may be appropriately selected according to the type and combination of the solvents used. In the production of the cellulose acylate film used in the present invention, the web (film) peeled from the support is preferably stretched when the residual solvent amount in the web is less than 120% by mass.

The residual solvent amount can be expressed by the following formula.
Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of the web at an arbitrary point in time, and N is the mass when the web of which M is measured is dried at 110 ° C. for 3 hours. If the amount of residual solvent in the web is too large, the effect of stretching cannot be obtained, and if it is too small, stretching becomes extremely difficult and the web may break. The more preferable range of the residual solvent amount in the web is 70% by mass or less, more preferably 10% by mass to 50% by mass, and particularly preferably 12% by mass to 35% by mass. Further, if the stretching ratio is too small, a sufficient phase difference cannot be obtained, and if it is too large, stretching may become difficult and breakage may occur.
The draw ratio is preferably 1.3 to 1.9, and more preferably 1.4 to 1.7.
The stretching may be performed in the longitudinal direction, in the lateral direction, or in both directions. In addition, since tension | tensile_strength is applied with respect to a conveyance direction when peeling a web from the metal support body for casting, the effect similar to extending | stretching may arise on the peeling conditions in which strong tension | tensile_strength applies. Taking these effects into consideration, stretching conditions are determined. The cellulose acylate film used in the present invention is preferably obtained by stretching in the width direction, and the stretching ratio is preferably 5% or more and 100% or less in the direction perpendicular to the transport direction. By setting the draw ratio to 30% or more, Re can be expressed more appropriately, and the bowing can be improved. Moreover, by setting the draw ratio to 70% or less, a film having a tear strength of 1.5 to 6.0 [g · cm / cm] can be obtained while the haze is lowered.
In the present invention, the solution cast film can be stretched without being heated to a high temperature as long as the residual solvent amount is in a specific range, but it is preferable because drying and stretching can shorten the process. . However, since the plasticizer volatilizes when the temperature of the web is too high, a range of room temperature (15 ° C) to 145 ° C or less is preferable. Further, stretching in the biaxial directions perpendicular to each other is an effective method for bringing the refractive indexes Nx, Ny, and Nz of the film within the scope of the present invention. In this case, it can be improved by suppressing the width shrinkage of the film or stretching in the width direction. When stretching in the width direction, the refractive index may be distributed with a width. This is sometimes seen when using, for example, the tenter method, but it is a phenomenon that occurs when the film is stretched in the width direction and contraction force is generated at the center of the film and the end is fixed. It is thought to be called the Boeing phenomenon. Even in this case, by stretching in the casting direction, the bowing phenomenon can be suppressed, and the distribution of the width retardation can be improved. Furthermore, the film thickness fluctuation | variation of the film obtained by extending | stretching to the biaxial direction orthogonal to each other can be reduced. If the film thickness variation of the optical film is too large, the retardation will be uneven. The film thickness variation of the optical film is preferably in the range of ± 3%, and more preferably ± 1%. For the purposes as described above, a method of stretching in the biaxial directions orthogonal to each other is effective, and the stretching ratios in the biaxial directions orthogonal to each other are 1.2 to 2.0 times and 0.7 to 1.0, respectively. It is preferable that the range be doubled. Here, stretching to 1.2 to 2.0 times with respect to one direction and making the other perpendicular to 0.7 to 1.0 times means that the distance between the clip or pin supporting the film is This means that the distance is 0.7 to 1.0 times the interval before stretching.

In general, when a biaxial stretching tenter is used to stretch in the width direction so as to have an interval of 1.2 to 2.0 times, a contracting force acts in the longitudinal direction, which is the perpendicular direction.
Therefore, if the force is applied in only one direction and the stretching is continued, the width in the perpendicular direction is reduced, which means that the amount of shrinkage is suppressed with respect to the amount that shrinks without restricting the width. This means that the interval between the clip or pin whose width is restricted is restricted to a range of 0.7 to 1.0 times that before stretching. At this time, in the longitudinal direction, a force is exerted to shrink the film by stretching in the width direction. By taking the interval between the clips or pins in the longitudinal direction, an excessive tension is not applied in the longitudinal direction. There is no particular limitation on the method of stretching the web. For example, a method in which a difference in peripheral speed is applied to a plurality of rolls, and the roll peripheral speed difference is used to stretch in the longitudinal direction between the rolls. And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, these methods may be used in combination. In the case of the so-called tenter method, driving the clip portion by a linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced.

(Heat treatment process)
The method for producing a cellulose acylate film used in the present invention preferably includes a heat treatment step after the drying step. The heat treatment in the heat treatment step may be performed after completion of the drying step, and may be performed immediately after the drying step after performing the stretching step, or may be performed only after the winding step by the method described later after the drying step. May be provided separately. In the present invention, it is preferable to provide the heat treatment step again after the drying step is once cooled to room temperature to 100 ° C. or less. This is because a film having better thermal dimensional stability can be obtained. For the same reason, it is preferable that the amount of residual solvent is dried to less than 2% by mass, preferably less than 0.4% by mass immediately before the heat treatment step.
Although the reason why the shrinkage rate of the film can be reduced by such treatment is not clear, in the film that has undergone the treatment to be stretched in the stretching process, the residual stress in the stretching direction is large, so the residual stress is eliminated by heat treatment. Thus, it is presumed that the shrinkage force in the region below the heat treatment temperature is reduced.

The heat treatment is performed by a method of applying a wind at a predetermined temperature to the film being conveyed or a method using a heating means such as a microwave.
The heat treatment is preferably performed at a temperature of 150 to 200 ° C., more preferably 160 to 180 ° C. The heat treatment is preferably performed for 1 to 20 minutes, more preferably 5 to 10 minutes.
When the heat treatment temperature exceeds 200 ° C. for a long time, the amount of scattering of volatile components such as a plasticizer contained in the film increases, which may be problematic because it becomes difficult to control the post-process and adjust physical properties. is there.

  In the heat treatment step, the film tends to shrink in the longitudinal direction or the width direction. It is preferable to heat-treat while suppressing the shrinkage as much as possible in order to improve the flatness of the finished film, and a method in which the width ends of the web are held with clips or pins in the width direction (tenter method). Is preferred. Furthermore, it is preferable to extend | stretch 0.9 to 1.5 times in the width direction and conveyance direction of a film, respectively.

  As the winder for winding the obtained film, a commonly used winder can be used, such as a constant tension method, a constant torque method, a taper tension method, and a program tension control method with a constant internal stress. It can be wound up by a take-up method. In the optical film roll obtained as described above, the slow axis direction of the film is preferably ± 2 ° with respect to the winding direction (longitudinal direction of the film), and further within the range of ± 1 °. Preferably there is. Alternatively, it is preferably ± 2 degrees with respect to the direction perpendicular to the winding direction (film width direction), and more preferably within a range of ± 1 degree. In particular, the slow axis direction of the film is preferably within ± 0.1 degrees with respect to the winding direction (longitudinal direction of the film). Alternatively, it is preferably within ± 0.1 degrees with respect to the width direction of the film.

[Heating steam treatment]
In addition, the stretched film may be manufactured through a process of spraying water vapor heated to 100 ° C. or higher. By passing through this water vapor spraying step, the residual stress of the cellulose acylate film to be produced is relaxed, and the dimensional change is reduced, which is preferable. The temperature of the water vapor is not particularly limited as long as it is 100 ° C. or higher, but considering the heat resistance of the film, it is preferable to select the water vapor temperature of 200 ° C. or lower.

  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 used in the present invention may be a commonly used winder such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress. It can be wound up by a take-up method.

(Film thickness)
The film thickness of the cellulose acylate film that is the support in the retardation film of the present invention is preferably 20 μm to 60 μm, more preferably 20 μm to 50 μm, and even more preferably 20 μm to 45 μm. A film thickness of 20 μm or more is preferable in terms of handling properties when processing into a polarizing plate or the like and curling suppression of the polarizing plate. Further, the film thickness unevenness of the cellulose ester film used in the present invention is preferably 0 to 2% in both the transport direction and the width direction, more preferably 0 to 1.5%, and 0 to 1%. Is particularly preferred.

(Retardation of cellulose acylate film)
In the present specification, Re (λ) and Rth (λ) respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re is measured by making light with a wavelength of λ nm incident in the normal direction of the film in KOBRA21ADH (manufactured by Oji Scientific Instruments). Rth is a letter measured by making light of wavelength λ nm incident from a direction inclined + 40 ° with respect to the film normal direction with the slow axis in the plane (determined by KOBRA21ADH) as the tilt axis (rotation axis). The retardation value and the retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH is calculated based on the retardation value measured in (1). Here, 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 the assumed value of the average refractive index and the film thickness, KOBRA 21ADH calculates nx, ny, and nz. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.
Note that Re = (nx−ny) × d and Rth = {(nx + ny) / 2−nz} × d. nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film, and d is the thickness of the film. (Nm).

The cellulose acylate film is preferably used as a protective film for a polarizing plate, and can be particularly preferably used as a retardation film corresponding to various liquid crystal modes.
The cellulose acylate film used as the support for the retardation film of the present invention preferably has a Re of 30 to 200 nm, more preferably 80 to 150 nm. Rth is preferably 70 to 400 nm, more preferably 80 to 150 nm.
When Re is greater than Rth, it is necessary to increase the draw ratio, and the tear strength may decrease. From the viewpoint of maintaining the tear strength at the required strength, Re of the support is 80 nm to 150 nm, and Rth Is preferably larger than Re and 80 nm to 150 nm.
Here, Re and Rth are an in-plane retardation value and a retardation value in the thickness direction, respectively, measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH.

(Haze of film)
The hazes of the cellulose acylate film and retardation film used in the present invention are preferably 0.01 to 1.0%. More preferably, it is 0.05 to 0.8%, and further preferably 0.1 to 0.7%. High transparency of the film as the optical film is preferable because the amount of light from the light source can be used without waste. The haze can be measured according to JIS K-6714 using a haze meter “HGM-2DP” {manufactured by Suga Test Instruments Co., Ltd.}.

(Spectral characteristics, spectral transmittance)
A transmittance of a cellulose acylate film sample 13 mm × 40 mm at a wavelength of 300 to 450 nm can be measured with a spectrophotometer “U-3210” {Hitachi, Ltd.} at 25 ° C. and 60% RH. The inclination width can be obtained at a wavelength of 72% -5%. The limiting wavelength can be represented by a wavelength of (gradient width / 2) + 5%, and the absorption edge can be represented by a wavelength having a transmittance of 0.4%. From this, the transmittances at 380 nm and 350 nm can be evaluated.

(Glass-transition temperature)
The glass transition temperature of the cellulose acylate film used in the present invention is preferably 120 ° C. or higher, and more preferably 140 ° C. or higher.
The glass transition temperature is a temperature at which the base line derived from the glass transition of the film starts to change and a temperature at which it returns to the base line again when measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). It can be calculated as an average value. Moreover, the measurement of a glass transition temperature can also be calculated | required using the following dynamic viscoelasticity measuring apparatuses. A cellulose acylate film sample (unstretched) 5 mm × 30 mm used in the present invention was conditioned at 25 ° C. and 60% RH for 2 hours or more, and then a dynamic viscoelasticity measuring device (Vibron: DVA-225 (IT Measurement Control Co., Ltd.) ))), Measured at a distance between grips of 20 mm, a heating rate of 2 ° C./minute, a measurement temperature range of 30 ° C. to 250 ° C. and a frequency of 1 Hz, the logarithmic axis is the storage elastic modulus, and the horizontal axis is the linear axis. When the temperature (° C.) is taken, the straight line 1 is drawn in the solid region, and the straight line 2 is drawn in the glass transition region, when the storage elastic modulus shifts from the solid region to the glass transition region. When the temperature rises, the intersection of the straight line 1 and the straight line 2 is the temperature at which the storage elastic modulus suddenly decreases and the film begins to soften, and the temperature at which the film begins to move to the glass transition region. Viscoelasticity To.

(Water permeability of film)
The moisture permeability of the film can be measured under conditions of 60 ° C. and 95% RH based on JIS Z-0208.
The moisture permeability decreases as the thickness of the cellulose acylate film increases, and increases as the thickness decreases. Therefore, for samples having different film thicknesses, it is necessary to convert the reference to 40 μm. The film thickness can be converted according to the following mathematical formula. Mathematical formula: moisture permeability in terms of 40 μm = measured moisture permeability × measured film thickness (μm) / 40 (μm)

  The measurement method of water vapor transmission rate is “Polymer Physical Properties II” (Polymer Experiment Course 4, Kyoritsu Shuppan), pages 285-294 “Measurement of vapor permeation amount (mass method, thermometer method, vapor pressure method, adsorption amount method) Can be applied.

Moisture permeability of the cellulose acylate film and the retardation film used in the present invention is preferably 400~2500g ^/ m ^2/24 hours. More preferably 400~2350g ^/ m ^2/24 hours, and particularly preferably 400~2200g ^/ m ^2/24 hours. If less moisture permeability 2200g ^/ m ^2/24 hours, Re value of the film, the absolute value of humidity dependency of Rth value without causing inconvenience such as greater than RH 0.5 nm /%, preferably.

(Dimension change rate of film)
The dimensional stability of the cellulose acylate film used in the present invention is the dimensional change rate after standing for 24 hours under the conditions of 60 ° C. and 90% RH (high humidity), and the conditions of 80 ° C. and 5% RH. It is preferable that the dimensional change rate after standing for 24 hours (low temperature) is 0.5% or less.
More preferably, it is 0.3% or less, More preferably, it is 0.15% or less.

(Configuration of cellulose acylate film)
The cellulose acylate film used in the present invention may have a single layer structure or a plurality of layers, but preferably has a single layer structure. Here, the “single layer structure” film does not mean that a plurality of film materials are bonded together, but means a single cellulose acylate film. A case where a single cellulose acylate film is produced from a plurality of cellulose acylate solutions using a sequential casting method or a co-casting method is also included in the “single layer structure”.

  In this case, a cellulose acylate film having a distribution in the thickness direction can be obtained by appropriately adjusting the type and blending amount of additives, the molecular weight distribution of cellulose acylate, the type of cellulose acylate, and the like. Moreover, what has various functional parts, such as an optical anisotropy part, a glare-proof part, a gas barrier part, and a moisture resistance part, in those one film is also contained in a "single layer structure."

(Additive)
The support of the retardation film of the present invention can contain at least one compound selected from the group consisting of i) and ii) below. Addition of these compounds facilitates adjustment of moisture permeability and moisture content by imparting hydrophobicity and adjustment of mechanical properties by imparting plasticity.
i) a polycondensed ester containing a dicarboxylic acid residue having an average carbon number of 5.5 or more and 10.0 or less containing at least one aromatic dicarboxylic acid residue ii) a pyranose in which at least one hydroxyl group is aromatically esterified Sugar ester containing 1 to 12 structures or furanose structures

  Although the compounds i) and ii) have a function as a plasticizer, these compounds are added to cellulose acylate in which the acyl group substitution degree DS satisfies 2.0 <DS <2.6. Polarizing plate durability can be improved by using a retardation film containing a cellulose acylate film as a polarizing plate protective film.

[I) Polycondensed ester]
i) A polycondensation ester (also referred to as “i) polycondensation ester” containing a dicarboxylic acid residue having an average carbon number of 5.5 or more and 10.0 or less containing at least one aromatic dicarboxylic acid residue will be described. .
i) The polycondensed ester is obtained from at least one dicarboxylic acid having an aromatic ring (also referred to as aromatic dicarboxylic acid) and at least one diol.

(Aromatic dicarboxylic acid residue)
The aromatic dicarboxylic acid residue is contained in a polycondensed ester obtained from a diol and a dicarboxylic acid containing an aromatic dicarboxylic acid.
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 (R represents a hydrocarbon group) is -OC-R-CO-.
The content ratio of aromatic dicarboxylic acid residues in the polycondensed ester (aromatic dicarboxylic acid residue ratio) is preferably 40 mol% or more, more preferably 40 mol% to 95 mol%, and 45 mol% to 70 mol%. More preferably, it is particularly preferably 50 mol% to 70 mol%.
By setting the aromatic dicarboxylic acid residue ratio to 40 mol% or more, a cellulose acylate film exhibiting sufficient optical anisotropy can be obtained, and a polarizing plate excellent in durability can be obtained. Moreover, if the aromatic dicarboxylic acid residue ratio is 95 mol% or less, the compatibility with cellulose acylate is excellent, and bleed-out can be made difficult to occur even when the cellulose acylate film is formed and heated.

Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,8-naphthalenedicarboxylic acid. Alternatively, 2,6-naphthalenedicarboxylic acid can be used. Phthalic acid, terephthalic acid and isophthalic acid are preferred, phthalic acid and terephthalic acid are more preferred, and terephthalic acid is even more preferred.
i) In the polycondensed ester, an aromatic dicarboxylic acid residue is formed by the aromatic dicarboxylic acid used as a raw material. Specifically, 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 a phthalic acid residue or a terephthalic acid residue. It contains at least one, and more preferably contains a terephthalic acid residue.
By using terephthalic acid as the aromatic dicarboxylic acid, it is possible to obtain a cellulose acylate film that is more compatible with cellulose acylate and is less likely to bleed out during film formation and heat stretching of the cellulose acylate film. it can. Moreover, 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 95 mol%, preferably 45 mol% to 70 mol%, and preferably 50 mol% to 70 mol%. .
By setting the terephthalic acid residue ratio to 40 mol% or more, a cellulose acylate film exhibiting sufficient optical anisotropy can be obtained. Moreover, if it is 95 mol% or less, it is excellent in compatibility with a cellulose acylate, and it can make it hard to produce a bleed-out also at the time of film formation of a cellulose acylate film and the time of heat-stretching.

(Aliphatic dicarboxylic acid residue)
i) The polycondensation ester may contain an aliphatic dicarboxylic acid residue in addition to the aromatic dicarboxylic acid residue.
The aliphatic dicarboxylic acid residue is contained in a polycondensed ester obtained from a diol and a dicarboxylic acid containing an aliphatic dicarboxylic acid.
Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid or 1,4- And cyclohexanedicarboxylic acid.
The aliphatic dicarboxylic acid may be used alone or in combination of two or more. When two kinds are used, it is preferable to use succinic acid and adipic acid. When using 1 type, it is preferable to use a succinic acid. This is preferable in terms of compatibility with the cellulose acylate because the average carbon number of the diol residue can be adjusted to a desired value.

  i) The average carbon number of the dicarboxylic acid residue contained in the polycondensed ester is 5.5 or more and 10.0 or less. The dicarboxylic acid residue preferably has an average carbon number of 5.5 to 8.0, and more preferably 5.5 to 7.0. If the average carbon number of the dicarboxylic acid residue is 5.5 or more, a polarizing plate having excellent durability can be obtained. If the average carbon number of the dicarboxylic acid residue is 10.0 or less, the compatibility with cellulose acylate is excellent, and the occurrence of bleed-out can be suppressed in the process of forming a cellulose acylate film.

  The average carbon number of the dicarboxylic acid residue is calculated by multiplying the constituent carbon number by the composition ratio (molar fraction) of the dicarboxylic acid residue 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 a diol residue. The average carbon number of an aliphatic diol residue is a value calculated by multiplying the constituent carbon number by the composition ratio (molar fraction) of the aliphatic 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.

(Aliphatic diol)
The aliphatic diol residue is contained in a polycondensed ester obtained from an aliphatic diol and a dicarboxylic acid.
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 diol residue formed from the diol HO—R—OH is —O—R—O—.
i) The diol that forms the polycondensed ester includes aromatic diols and aliphatic diols, and preferably contains at least an aliphatic diol.
i) The polycondensation ester preferably contains an aliphatic diol residue having an average carbon number of 2.5 or more and 7.0 or less, more preferably an aliphatic diol having an average carbon number of 2.5 or more and 4.0 or less. Residue. If the average carbon number of the aliphatic diol residue is 7.0 or less, the compatibility with cellulose acylate is high, bleed-out is unlikely to occur, the weight loss of the compound is small, and the cellulose acylate web is dried. Since there is little process contamination, surface failure is unlikely to occur. Moreover, it is preferable from a synthetic | combination viewpoint that the average carbon number of an aliphatic diol residue is 2.5 or more.
Examples of the aliphatic diol used in the present invention include alkyl diols and alicyclic diols, such as ethylene glycol, 1,2-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-hexanediol, 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, etc. Is preferably used together with ethylene glycol as one or a mixture of two or more.

The preferred 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. . When two types are used, 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.
i) In the polycondensed ester, a diol residue is formed by the diol used as a raw material.
The diol residue preferably includes at least one of an ethylene glycol residue, a 1,2-propanediol residue, and a 1,3-propanediol residue, and an ethylene glycol residue or a 1,2-propanediol residue It is more preferable that

(End sealing)
The terminal of i) polycondensation ester used in the present invention is not capped and remains as a hydroxyl group or a carboxylic acid, or a so-called end capping may be carried out by reacting monocarboxylic acid or monoalcohol. .
As monocarboxylic acids used for end-capping, acetic acid, propionic acid, butanoic acid, benzoic acid and the like are preferable, acetic acid or propionic acid is more preferable, and acetic acid is most 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 3 or less, the loss on heating of the compound does not increase, and no surface failure occurs.
The end of i) polycondensed ester used in the present invention is more preferably not capped and remains a diol residue, or more preferably capped with acetic acid or propionic acid.
The both ends of i) polycondensed ester according to the present invention may be sealed or unsealed.
When both ends of the condensate are unsealed, the polycondensed ester is preferably a polyester polyol.
One aspect of i) polycondensed ester according to the present invention is a polycondensed ester in which the aliphatic diol residue has 2.5 to 7.0 carbon atoms, and both ends of the condensate are unsealed. Can be mentioned.
When both ends of the condensate 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, 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 monocarboxylic acid residue formed from monocarboxylic acid R—COOH is R—CO—. The monocarboxylic acid residue is preferably an aliphatic monocarboxylic acid residue, more preferably an aliphatic monocarboxylic acid residue having 22 or less carbon atoms, and more preferably 3 or less carbon atoms. More preferably, it is an aliphatic monocarboxylic acid residue. 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 i) polycondensed ester according to the present invention, the aliphatic diol residue has a carbon number of more than 2.5 and 7.0 or less, and both ends of the condensate are monocarboxylic acid residues. Mention may be made of condensed esters.
i) When the number of carbon atoms of the monocarboxylic acid residue at both ends of the polycondensed ester is 3 or less, the volatility decreases, the weight loss due to heating of the polycondensed ester does not increase, process contamination and surface failure occur. Can be reduced.
That is, the monocarboxylic acid used for sealing is preferably an aliphatic monocarboxylic acid. More preferably, the monocarboxylic acid is an aliphatic monocarboxylic acid having 2 to 22 carbon atoms, more preferably an aliphatic monocarboxylic acid having 2 to 3 carbon atoms, and an aliphatic monocarboxylic acid residue having 2 carbon atoms. Particularly preferred is a group.
As the aliphatic monocarboxylic acid, for example, acetic acid, propionic acid, butanoic 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 used in the present invention are preferably sealed with acetic acid or propionic acid, and most preferably both ends become acetyl ester residues (sometimes referred to as acetyl residues) by acetic acid sealing.
When both ends are sealed, the cellulose acylate film can be obtained in which the state at normal temperature is unlikely to be in a solid form, the handling becomes good, and the humidity stability and polarizing plate durability are excellent.

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

  Specific examples A-1 to A-31 and B-1 to B-10 of i) polycondensed ester according to the present invention are shown in Table 1 below, but are not limited thereto.

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

  The content of i) polycondensed ester in the cellulose acylate film is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and 5 to 20% by mass with respect to the cellulose acylate. More preferably it is.

i) The content of the aliphatic diol, dicarboxylic acid ester, or diol ester, which is a by-product that can be synthesized when synthesizing the polycondensed ester, in the cellulose acylate film is preferably less than 1% by mass, Less than mass% is more preferable. Examples of the dicarboxylic acid ester include dimethyl phthalate, di (hydroxyethyl) phthalate, dimethyl terephthalate, di (hydroxyethyl) terephthalate, di (hydroxyethyl) adipate, and di (hydroxyethyl) succinate. Examples of the diol ester include ethylene diacetate and propylene diacetate.
I) The types and ratios of the dicarboxylic acid residue, diol residue, and monocarboxylic acid residue contained in the polycondensation ester used in the present invention should be measured by H-NMR by a usual method. Can do. Usually, deuterated chloroform can be used as a solvent.
For measurement of the hydroxyl value of the polycondensed ester, the acetic anhydride method described in Japanese Industrial Standard JIS K3342 (discontinued) can be applied. When the polycondensate is a polyester polyol, the hydroxyl value is preferably from 50 to 190, and more preferably from 50 to 130.

[Ii) sugar ester]
ii) A sugar ester containing 1 to 12 pyranose structures or furanose structures in which at least one hydroxyl group is aromatically esterified (also referred to as “ii) sugar ester”) will be described.
ii) By adding the sugar ester compound to the cellulose acylate film, the optical properties are not deteriorated, and the internal haze when the wet heat treatment is performed after stretching is not deteriorated. By using the phase difference film in a liquid crystal display device, the front contrast can be greatly improved.

  The ii) sugar ester compound includes a structure derived from a monosaccharide or a disaccharide or higher polysaccharide constituting the sugar ester compound (hereinafter also referred to as a sugar residue). The structure of the sugar residue per monosaccharide is referred to as the structural unit of the sugar ester compound. The structural unit of the sugar ester compound includes 1 to 12 pyranose structural units or furanose structural units, and may include a sugar residue other than the pyranose structural unit or the furanose structural unit. Is preferably a pyranose structural unit or a furanose structural unit. Moreover, when the said ii) sugar ester is comprised from polysaccharide, it is preferable that both a pyranose structural unit and a furanose structural unit are included.

  The ii) sugar residue of the sugar ester compound may be derived from pentose or hexose, but is preferably derived from hexose.

  The number of structural units contained in the ii) sugar ester compound is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 or 2.

  In the present invention, the ii) sugar ester compound is a sugar ester compound containing 1 to 12 pyranose structural units or furanose structural units in which at least one hydroxyl group is aromatic esterified, and at least one of the hydroxyl groups is aromatic. It is preferably a sugar ester compound containing one or two pyranose structural units or furanose structural units that are group-esterified.

  Examples of the monosaccharide or saccharide containing 2 to 12 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, isomaltoto Ose, isopanose, maltotriose, manninotriose, melezitoose, panose, planteose, raffinose, solatriose, umbelliferose, lycotetraose, maltotetraose, stachyose, maltopentaose, bellbass 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. The ii) sugar ester compound has a glucose skeleton or a sucrose skeleton, which is described as compound 5 in [0059] of JP-A-2009-1696 and has a maltose skeleton used in Examples of the same document. Compared with the sugar ester compound etc. which have, it is especially preferable from a compatible viewpoint with a cellulose acylate.

-Substituent structure-
The ii) sugar ester compound used in the present invention more preferably has a structure represented by the following general formula (1) including the substituent used.
Formula _{(1) (OH) p -G-} (L 1 -R 11) q (O-R 12) r
In general formula (1), G represents a sugar residue, L ¹ represents any ^one of —O—, —CO—, and —NR ¹³ —, and R ¹¹ represents a hydrogen atom or a monovalent substituent. R ¹² represents a monovalent substituent bonded by an ester bond. p, q, and r each independently represent an integer of 0 or more, and p + q + r is equal to the number of hydroxyl groups on the assumption that G is an unsubstituted saccharide having a cyclic acetal structure.

  The preferable range of G is the same as the preferable range of the sugar residue.

L ¹ is preferably —O— or —CO—, and more preferably —O—. When L ¹ is —O—, it is particularly preferably a linking group derived from an ether bond or an ester bond, and more preferably a linking group derived from an ester bond.
Further, when there are a plurality of L ^{1 s} , they may be the same or different.

At least one of R ¹¹ and R ¹² preferably has an aromatic ring.

In particular, when L ¹ is —O— (that is, when R ¹¹ and R ¹² are substituted on the hydroxyl group in the sugar ester compound), R ¹¹ , R ¹² and R ¹³ are substituted or unsubstituted. Are preferably selected from the group consisting of acyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted amino groups, substituted or unsubstituted acyl groups, substituted or unsubstituted A substituted alkyl group or a substituted or unsubstituted aryl group is more preferable, and an unsubstituted acyl group, a substituted or unsubstituted alkyl group, or an unsubstituted aryl group is particularly preferable.
When there are a plurality of R ¹¹ , R ¹² and R ¹³ , they may be the same as or different from each other.

The p represents an integer of 0 or more, and the preferred range is the same as the preferred range of the number of hydroxyl groups per monosaccharide unit described later, but in the present invention, the p is preferably zero.
The r preferably represents a number larger than the number of pyranose structural units or furanose structural units contained in the G.
Q is preferably 0.
Moreover, since p + q + r is equal to the number of hydroxyl groups assuming that G is an unsubstituted saccharide having a cyclic acetal structure, the upper limit values of p, q and r are uniquely determined according to the structure of G. Is done.

  Preferred examples of the substituent of the sugar ester compound include an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, An ethyl group, a propyl group, a hydroxyethyl group, a hydroxypropyl group, a 2-cyanoethyl group, a benzyl group, etc.), an aryl group (preferably having a carbon number of 6 to 24, more preferably 6 to 18 and particularly preferably 6 to 12). A group such as a phenyl group or a naphthyl group, an acyl group (preferably having a carbon number of 1 to 22, more preferably a carbon number of 2 to 12, particularly preferably a carbon number of 2 to 8, such as an acetyl group or a propionyl group, Butyryl group, pentanoyl group, hexanoyl group, octanoyl group, benzoyl group, toluyl group, phthalyl group), amide group (preferred) Or an amide group (preferably 4 to 22 carbon atoms, more preferably an amide having 2 to 12 carbon atoms, particularly preferably an amide having 2 to 8 carbon atoms, such as a formamide group or an acetamide group). Is an amide group having 4 to 12 carbon atoms, particularly preferably 4 to 8 carbon atoms, such as a succinimide group and a phthalimide group, and an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, particularly Preferred examples include 7 to 13 aryl groups such as benzyl group. Among these, an alkyl group or an acyl group is more preferable, a methyl group, an acetyl group, a benzoyl group, or a benzyl group is more preferable, and an acetyl group and a benzyl group are particularly preferable. Furthermore, among them, when the constituent sugar of the sugar ester compound has a sucrose skeleton, a sugar ester compound having an acetyl group and a benzyl group as substituents is described as compound 3 in [0058] of JP2009-1696A. Therefore, it is more preferable from the viewpoint of compatibility with the polymer, compared with the sugar ester compound having a benzoyl group used in the examples of the document.

  The number of hydroxyl groups per structural unit in the sugar ester compound (hereinafter also referred to as hydroxyl group content) is preferably 3 or less, more preferably 1 or less, and zero. Particularly preferred. By controlling the hydroxyl group content within the above range, the migration of the sugar ester compound to the polarizer layer and the destruction of the PVA-iodine complex at high temperature and high humidity can be suppressed, and the polarizer performance (polarizing plate at high temperature and high humidity) can be suppressed. It is preferable from the viewpoint of suppressing deterioration in durability.

The sugar ester compound used in the cellulose acylate film used in the present invention preferably has no unsubstituted hydroxyl group, and the substituent consists only of an acetyl group and / or a benzyl group.
The ratio of acetyl groups to benzyl groups in the sugar ester compound tends to increase the value of wavelength dispersion ΔRe and ΔRe / Re (550) of the cellulose acylate film obtained when the ratio of benzyl groups is somewhat small. The change in blackness when incorporated in a liquid crystal display device is small, which is preferable. Specifically, the ratio of the benzyl group to the sum of all unsubstituted hydroxyl groups and all substituents in the sugar ester compound is preferably 60% or less, and preferably 40% or less.

  As the method for obtaining the sugar ester compound, commercially available products such as those manufactured by Tokyo Chemical Industry Co., Ltd., Aldrich, etc., or known ester derivatization methods for commercially available carbohydrates (for example, Japanese Patent Laid-Open No. Hei. Can be synthesized by carrying out the method described in JP-A-8-245678.

  The sugar ester compound has a number average molecular weight of preferably 200 to 3500, more preferably 200 to 3000, and particularly preferably 250 to 2000.

Specific examples of the sugar ester compound that can be preferably used in the present invention are listed below, but the present invention is not limited to the following embodiments.
In the following structural formulae, R each independently represents an arbitrary substituent, and a plurality of R may be the same or different. In the following structure, each of the substituents 1 and 2 represents an arbitrary R. The degree of substitution represents the number of R represented by the substituent. “None” represents that R is a hydrogen atom.

The ii) sugar ester compound is preferably contained in an amount of 2 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass relative to the cellulose acylate.
Further, when an additive having a negative intrinsic birefringence, which will be described later, is used in combination with the ii) sugar ester compound, the amount of the ii) sugar ester compound added to the additive amount (part by mass) of the additive having a negative intrinsic birefringence. (Mass part) is preferably added 2 to 10 times (mass ratio), more preferably 3 to 8 times (mass ratio).
Moreover, when using together the polyester plasticizer mentioned later with the said ii) sugar ester compound, the addition amount (mass part) of the said ii) sugar ester compound with respect to the addition amount (mass part) of a polyester plasticizer is 2-2. It is preferable to add 10 times (mass ratio), and more preferably 3 to 8 times (mass ratio).
In addition, the said ii) sugar ester compound may be used independently, or may use 2 or more types together.

  In the cellulose acylate film, various low molecular and polymer additives (for example, deterioration inhibitors, UV inhibitors, retardation (optical anisotropy) modifiers, release accelerators, Plasticizers, infrared absorbers, particulates, etc.) can be added, which can be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing materials having a melting point of less than 20 ° C. and 20 ° C. or more, and similarly mixing of a deterioration inhibitor. Furthermore, infrared absorbing dyes are described, for example, in JP-A No. 2001-194522. Moreover, the addition time may be added at any time in the cellulose acylate solution (dope) preparation step, but it may be added by adding a preparation step to the final preparation step of the dope preparation step. Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. Moreover, when a cellulose acylate resin layer is formed from a multilayer, the kind and addition amount of the additive of each layer may differ.

(Retardation expression agent)
In order to express the retardation value, a compound having at least two aromatic rings can be used as a retardation enhancer.
The compound having at least two or more aromatic rings preferably exhibits optically positive uniaxiality when uniformly oriented, and the two aromatic rings form a rigid portion and further exhibit liquid crystallinity It is preferable that
The molecular weight of the compound having at least two or more aromatic rings is preferably 300 to 1200, more preferably 400 to 1000.
Stretching is effective for controlling optical characteristics, particularly Re, to a preferred value. To increase Re, it is necessary to increase the refractive index anisotropy in the film plane, and one method is to improve the main chain orientation of the polymer film by stretching. Further, by using a compound having a large refractive index anisotropy as an additive, the refractive index anisotropy of the film can be further increased. For example, the compound having two or more aromatic rings described above is improved in the orientation of the compound by transmitting the force of aligning the polymer main chains by stretching, and can easily be controlled to have desired optical characteristics.

Examples of the compound having at least two aromatic rings include triazine compounds described in JP-A No. 2003-344655, rod-like compounds described in JP-A No. 2002-363343, JP-A Nos. 2005-134848 and 2007-119737. Examples thereof include liquid crystal compounds described in the publication. More preferably, the triazine compound or the rod-like compound.
Two or more compounds having at least two aromatic rings can be used in combination.

  The support in the retardation film of the present invention preferably contains a compound represented by the following general formula (IIIA) or (IIIB) as a retardation developer. By including the compound represented by the following general formula (IIIA) or (IIIB), the expression of optical characteristics per unit film thickness is improved, and it can contribute to thinning.

R _{5 to} R ₇ each independently represent —OCH ₃ or —CH ₃ .
R ₅ ′ to R ₇ ′ each independently represent —OCH ₃ or —CH ₃ .

  The addition amount of the compound having at least two aromatic rings is preferably 0.05% or more and 10% or less, more preferably 0.5% or more and 8% or less, more preferably 1% by mass ratio with respect to the cellulose acylate in the support. More preferably, it is 5% or less.

[Other additives]
In addition to the cellulose acylate film, additives such as an antioxidant, a peeling accelerator, and fine particles can be added.

[Antioxidant]
The retardation film of the present invention can use an antioxidant in order to prevent deterioration such as depolymerization due to oxidation. Examples of usable antioxidants include phenol-based or hydroquinone-based antioxidants and phosphorus-based antioxidants described in paragraph [0120] of JP2012-181516A. The addition amount of the antioxidant is preferably 0.05 to 5.0 parts by mass with respect to 100 parts by mass of cellulose acylate.

(Peeling accelerator)
As additives for reducing the peel resistance of the cellulose acylate film, many surfactants having a remarkable effect are found. As preferred release agents, phosphate ester surfactants, carboxylic acid or carboxylate surfactants, sulfonic acid or sulfonate surfactants, and sulfate ester surfactants are effective. A fluorine-based surfactant in which part of the hydrogen atoms bonded to the hydrocarbon chain of the surfactant is substituted with fluorine atoms is also effective. As specific examples, the compounds described in paragraphs (0124) to [0138] (organic acid) of JP2012-181516A can be referred to.
The addition amount of the release agent is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass, and most preferably 0.1 to 0.5% by mass with respect to the cellulose acylate.

[Fine particles]
The retardation film of the present invention can contain fine particles from the viewpoint of film slipperiness and stable production. These fine particles are sometimes referred to as matting agents, and may be inorganic compounds or organic compounds.
Preferable examples of these fine particles include, as specific examples, paragraphs (0024) to [0027] (matte agent fine particles) in JP2012-177894A, paragraphs of JP2012-181516A [ Reference can be made to the fine particles described in the section (Matting Agent) of [0122] to [0123].
Since these fine particles are smaller than the wavelength of light, the haze of the film does not increase unless they are added in a large amount. When actually used in LCDs, inconveniences such as a decrease in contrast and generation of bright spots are unlikely to occur. If the amount is too small, the above-mentioned creaking and scratch resistance can be realized. From these viewpoints, it is preferably included in the cellulose acylate film at a ratio of 0.01 to 5.0% by weight, more preferably included at a ratio of 0.03 to 3.0% by weight, It is particularly preferable to include it at a ratio of 1.0% by weight.

  The support that the retardation film has may contain a cyclic olefin resin. The cyclic olefin resin preferably contains a structural unit represented by the following general formula (4) or (5).

In general formula (4) and (5), m represents the integer of 0-4. R ^{3 to} R ⁶ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. X ² , X ³ , Y ² and Y ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom,-( _{^{CH 2) n COOR 11, -}} (CH 2) n OCOR 12, - (CH 2) n NCO, - (CH 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 13 R ¹⁴ , — (CH ₂ ) _n NR ¹³ R ¹⁴ , — (CH ₂ ) _n OZ, — (CH ₂ ) _n W, or X ² and Y ² , or X ³ and Y ³ (—CO ) ₂ O, (—CO) ₂ NR ¹⁵ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with a halogen, W is SiR ¹⁶ _p D _3-p (R ¹⁶ is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, —OCOR ¹⁶ or —OR ¹⁶ , p is an integer of 0 to 3), and n is 0 An integer of -10 is shown.

The support that the retardation film has may contain a styrene resin. The styrene resin preferably contains a structural unit represented by the following general formula (S).
General formula (S)

In the general formula (S), R _{S1 to} R _S3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, or a carbon atom having 1 to 3 carbon atoms substituted with a halogen atom. Represents a hydrocarbon group.

The support that the retardation film has may contain an acrylic resin. As the acrylic resin, a known acrylic resin can be used.
Moreover, the support body which a phase difference film has may contain polycarbonate resin. A known acrylic resin can be used as the polycarbonate resin.

[Acrylic resin layer]
The acrylic resin layer which the retardation film of this invention has is demonstrated.
The acrylic resin layer contains an acrylic resin having at least one polar group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, and a cyano group.

(Acrylic resin with polar group)
In the present invention, “acrylic resin” includes “methacrylic resin” and is also referred to as “(meth) acryloyl group” as a generic term for acryloyl group and methacryloyl group.
As a material for the acrylic resin layer, an acrylic resin having a polar group can be used. When the acrylic resin layer is formed using an acrylic resin having a polar group, sufficient adhesion can be obtained without subjecting the cellulose acylate film as a support to saponification treatment. This is preferable from the viewpoint of productivity.

The acrylic resin having a polar group is preferably a resin containing a repeating unit derived from a compound containing a polar group and a (meth) acryloyl group.
The polar group is preferably a hydroxyl group.
The acrylic resin having a polar group in the present invention may contain a repeating unit having no polar group, or may contain a repeating unit other than a repeating unit derived from a compound containing a (meth) acryloyl group. Good.

  The acrylic resin having a polar group is composed of a repeating unit derived from a compound having three or more functional groups in one molecule, a polar group and one (meth) acryloyl group from the viewpoint of improving the adhesion to the support. It is preferable that it is resin which has a repeating unit derived from the compound containing this.

(Compound having 3 or more functional groups in one molecule)
As a compound having three or more functional groups in one molecule, a compound having a polymerizable functional group (polymerizable unsaturated double bond) such as a (meth) acryloyl group, a vinyl group, a styryl group, or an allyl group. Among them, a compound having a (meth) acryloyl group and —C (O) OCH═CH ₂ is preferable. Particularly preferred are compounds containing three or more (meth) acryloyl groups in one molecule described below.

  Specific examples of the compound having a polymerizable functional group include (meth) acrylic acid diesters of alkylene glycol, (meth) acrylic acid diesters of polyoxyalkylene glycol, (meth) acrylic acid diesters of polyhydric alcohol, Examples include (meth) acrylic acid diesters of adducts of ethylene oxide or propylene oxide, epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and the like.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO Modified tri (meth) acrylate phosphate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, urethane acrylate Polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.

  A commercially available compound may be used as the compound having three or more functional groups in one molecule. For example, examples of the polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARAD PET30, KAYARAD DPHA, DPCA-30, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd. Examples of the urethane acrylate include U15HA manufactured by Shin-Nakamura Chemical Co., Ltd., U4HA, A-9300, and EB5129 manufactured by Daicel UCB.

  The acrylic resin is a layer obtained by crosslinking an acrylic monomer with light or heat, and the polar group is particularly preferably a hydroxyl group. Thereby, the rod-like liquid crystal compound can be effectively homeotropically aligned in a retardation layer (retardation layer) in which the alignment state of the liquid crystal compound described later is fixed.

(Method for forming acrylic resin layer and intermediate layer)
As a method for forming an acrylic resin layer, a film in which the above-mentioned acrylic resin is formed on a support is bonded as an acrylic resin layer, or a composition for forming an acrylic resin layer is applied directly or through another layer, It can be formed by drying and curing as necessary.
As a forming method, a composition for forming an acrylic resin layer having a solvent capable of dissolving and swelling with respect to a support material and an acrylic monomer described above is applied and cured on the support in terms of forming an intermediate layer described later. It is preferable to form by.
In the composition for forming an acrylic resin layer, it is preferable to use a solvent having a dissolving ability or a swelling ability with respect to a material forming the support.
As the solvent having a swelling capacity for the material forming the support swells the surface of the support, a compound that forms an acrylic resin having a polymerizable group penetrates the support. In addition, a compound that forms a support that forms an acrylic resin having a polymerizable group with the base material diffused on the acrylic resin layer side by dissolving the support with a solvent having a solubility in the base material that forms the support. A mixed region occurs.
By providing a region including the main component of the support and the main component of the acrylic resin layer (hereinafter referred to as “intermediate layer”), the material at the interface between the support and the acrylic resin layer is entangled to produce an anchor effect, thereby providing close contact Improves.
Here, the “main component” refers to the support when the support is made of a single polymer, as described above, and when the support is made of a plurality of polymers, the support is used. Among the polymers constituting the polymer, the polymer having the highest mass fraction is shown. For the acrylic resin layer, when the acrylic resin layer is obtained from a single monomer, it indicates that monomer, and when it is obtained from a plurality of monomers, among the monomers for constituting the acrylic resin layer, Indicates the monomer with the highest mass fraction.
The intermediate layer preferably has a thickness of 0.1 μm to 10 μm, more preferably 0.3 μm to 5.0 μm, and still more preferably 0.5 μm to 4 μm. The thickness can be selected in consideration of the adhesion between the support and the acrylic resin layer.
As thickness control, a solvent having a desired dissolving ability and swelling ability is used, or a solvent having neither dissolving ability nor swelling ability, which will be described later, is mixed and used to control the dissolving ability and swelling ability of the solvent. it can.
Thereby, it is excellent in the adhesiveness of a support body and an acrylic resin layer, even if it does not give the adhesiveness improvement process to the support body surface.
From the viewpoint of inhibiting the orientation of the outermost liquid crystal layer when the support component is too much, the content of the support component in the intermediate layer is 1% by mass or more and 50% by mass or less with respect to the total solid content of the intermediate layer. Is preferred.
Hereinafter, the case where the support is cellulose acylate will be described as an example.

[Solvent having solubility in cellulose acylate]
The solvent having the ability to dissolve cellulose acylate is obtained by immersing a cellulose acylate film having a size of 24 mm × 36 mm (thickness 80 μm) in a 15 cm ³ bottle containing the solvent at room temperature (25 ° C.) for 60 seconds. When taken out, the soaked solution is analyzed by gel permeation chromatography (GPC), which means a solvent having a cellulose acylate peak area of 400 mV / sec or more. Alternatively, a cellulose acylate film with a size of 24 mm × 36 mm (thickness 80 μm) is aged for 24 hours at room temperature (25 ° C.) in a 15 cm ³ bottle containing the solvent, and the film is completely shaken by appropriately shaking the bottle. What loses its shape when dissolved in a solution means a solvent having a solubility in cellulose acylate.
As the solvent having the ability to dissolve cellulose acylate, one kind or two or more kinds may be used.

  Examples of the solvent capable of dissolving cellulose acylate include methyl acetate, acetone, and methylene chloride, and methyl acetate and acetone are preferable.

[Solvent having swelling ability for cellulose acylate]
A solvent having a swelling ability for cellulose acylate is a cellulose acylate film having a size of 24 mm × 36 mm (thickness 80 μm) placed vertically in a 15 cm ³ bottle containing the solvent and immersed at 25 ° C. for 60 seconds. Observe while shaking the bottle as appropriate, meaning a solvent that can be bent or deformed (the film is observed as bent or deformed due to changes in the size of the swollen part. Changes such as bending or deformation in a solvent without swelling ability. Is not seen).

As the solvent having swelling ability for cellulose acylate, the solvents described in paragraph [0026] of JP-A-2008-112177 can be used.
For example, ethers having 3 to 12 carbon atoms such as dibutyl ether and tetrahydrofuran, carbons having 3 to 12 carbon atoms such as acetone, methyl ethyl ketone, diethyl ketone, cyclopentanone and cyclohexanone, carbon such as methyl acetate and ethyl acetate Solvents such as esters having a number of 3 to 12 and organic solvents having two or more types of functional groups can be used, and these can be used alone or in combination of two or more.
In addition, in order to control the effect of the solvent, a solvent having neither a dissolving ability nor a swelling ability can be used in combination with the cellulose acylate film.
As the solvent having neither dissolving ability nor swelling ability, the solvents described in paragraph [0027] of JP-A-2008-112177 can be used.
For example, methyl isobutyl ketone (MIBK), methanol, ethanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-propanol, 2-methyl-2-butanol, cyclohexanol, 2-octanone, 2 -Pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone, 4-heptanone, isobutyl acetate.
The amount of the solvent having neither dissolving ability nor swelling ability is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less with respect to the total solvent used.

  From the viewpoint of swelling the support and improving adhesion, the solvent preferably contains at least one of methyl acetate, acetone, and methyl ethyl ketone. A mixed solvent containing methyl acetate or acetone and methyl ethyl ketone is preferable.

From the viewpoint of the balance between the solubility of the appropriate support and the adhesion force, the ratio of the content of the solvent having the ability to dissolve or swell the cellulose acylate and the solvent not having the ability to swell to cellulose acylate is 10: It is preferable that it is 90-60: 40.
Further, the solvent having solubility and swelling ability with respect to the support containing the styrene resin is the same as the solvent having solubility and swelling ability with respect to the support containing the cellulose acylate.

  The total amount of solvent in the composition for forming an acrylic resin layer is such that the solid content in the composition is preferably in the range of 1 to 70% by mass, more preferably in the range of 2 to 50% by mass, and further preferably 3 to 40%. Mass% is preferred.

In addition to the above-mentioned cellulose resin, as a solvent that can be used to form an intermediate layer when a cyclic olefin resin, an acrylic resin, or a polycarbonate resin is used as a material for forming the support, the solvent is soluble in each resin. Or a known solvent having swelling ability can be used.
For example, in the cyclic olefin resin, as solvents having both solubility and swelling ability, ketones having 3 to 12 carbon atoms such as cyclopentanone and cyclohexanone, dichloromethane, toluene and the like are known, and in particular, cyclohexanone and dichloromethane. Are preferably used, and examples of the solvent having neither dissolving ability nor swelling ability include methyl isobutyl ketone (MIBK), methanol, ethanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2- Propanol, 2-methyl-2-butanol, cyclohexanol, 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone, 4-heptanone, isobutyl acetate, ethanol Can be preferably used.
In the acrylic resin, as solvents having both dissolving ability and swelling ability, ketones having 3 to 12 carbon atoms such as chloroform, tetrahydrofuran, cyclopentanone, cyclohexanone, dichloromethane, toluene, etc. are known, in particular tetrahydrofuran, Dichloromethane can be preferably used, and solvents having no dissolving ability or swelling ability include methyl isobutyl ketone (MIBK), methanol, ethanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2 -Propanol, 2-methyl-2-butanol, cyclohexanol, 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone, 4-heptanone, isobutyl acetate are known, Ethanol is preferred It is possible to have.
In polycarbonate resins, solvents that have both solubility and swelling ability include, but are not limited to, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, and combinations thereof. Typically, the solvent is toluene or dichloromethane.
Solvents having neither solubility nor swelling ability include methyl isobutyl ketone (MIBK), methanol, ethanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-propanol, 2-methyl-2- Butanol, cyclohexanol, 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone, 4-heptanone, and isobutyl acetate are known, and ethanol can be preferably used.

(Water drop contact angle of acrylic resin layer)
The water droplet contact angle of the acrylic resin layer is that the film is conditioned for 2 hours or more at 25 ° C. and a relative humidity of 60%, and then a drop of pure water having a diameter of 3 mm is dropped on the surface, and the film surface and the water droplet formed after 20 seconds. Find from the corner. The water droplet contact angle of the acrylic resin layer is preferably 25 ° to 60 °, more preferably 35 ° to 57 °, and still more preferably 40 ° to 54 °.

[Retardation layer with fixed alignment state of liquid crystal compound (retardation layer)]
The retardation layer (retardation layer) which fixed the orientation state of the liquid crystal compound which the retardation film of this invention has is demonstrated.
The retardation film of the present invention has a retardation layer in which the alignment state of the liquid crystal compound is directly fixed on the surface of the acrylic resin layer opposite to the intermediate layer. That is, in the retardation film of the present invention, the acrylic resin and the retardation layer are adjacent to each other.
The retardation layer is a layer containing a polymer of a vertical alignment agent and a polymerizable liquid crystal compound.
The retardation layer is preferably a layer in which the liquid crystal compound is fixed in a homeotropic alignment state.
Homeotropic alignment is an alignment state in which liquid crystal molecules are aligned in the normal direction of the layer and the slow axis is parallel to the normal direction of the layer. Note that the slow axis of the retardation layer is particularly preferably parallel to the normal direction of the layer, but may have an inclination depending on the alignment state of the liquid crystal molecules. If this inclination is within 3.5 °, the in-plane retardation can be made 10 nm or less, which is preferable.

(Liquid crystal compound)
As the liquid crystal compound, from the viewpoint of the optical properties of the retardation film, a layer in which the homeotropic alignment of the composition containing the rod-shaped liquid crystal compound as a main component is fixed is preferable.
The layer in which the homeotropic alignment of the rod-like liquid crystal compound is fixed can function as a positive C-plate.

  Usable rod-like liquid crystal compounds are described in, for example, [0045] to [0066] of JP-A-2009-217256, and can be referred to. The additive that can be used in the retardation layer, the alignment film that can be used in the present invention, and the method for forming the homeotropic liquid crystal layer are described in, for example, [0076] to [0079] of JP-A-2009-237421. There is a reference.

  From the viewpoint of optical developability, the polymerizable liquid crystal compound forming the retardation layer (retardation layer) in which the alignment state of the liquid crystal compound is fixed is a compound represented by the following general formula (IIA), and the following general formula (IIB) It is preferable that it is at least 1 type of compound selected from the group which consists of a compound represented by these.

R _{1 to} R ₄ each independently represent — (C) _n —OOC—C═C, and n represents an integer of 2 to 5. X and Y each independently represent a hydrogen atom or a methyl group.

From the viewpoint of inhibiting crystal precipitation, in the general formula (IIA) or (IIB), X and Y preferably represent a methyl group. If n is an integer of 2 to 5, crystal formation starting from a foreign substance does not occur, which is preferable.
Further, from the viewpoint of suppressing crystallization and precipitation, the liquid crystal compound forming the retardation layer is preferably contained in the retardation by 70% by mass or more, particularly preferably 80% by mass or more. Furthermore, as the liquid crystal compound, any of the compound represented by the general formula (IIA) and the compound represented by the general formula (IIB) is 3% by mass with respect to the total solid content of the retardation layer. The content is preferably 5% by mass or more, and more preferably 8% by mass or more.

(Onium compound represented by general formula (I))
The retardation layer (retardation layer) in which the alignment state of the liquid crystal compound included in the retardation film of the present invention is fixed preferably includes an onium compound represented by the following general formula (I). The onium compound acts as a vertical alignment agent that promotes homeotropic alignment at the alignment film interface of the liquid crystal compound, and at the interface between the retardation layer (retardation layer) that fixes the alignment state of the liquid crystal compound and the acrylic resin layer. Contributes to improved adhesion. The retardation layer (retardation layer) in which the alignment state of the liquid crystal compound is fixed includes an air interface side alignment control agent (for example, a repeating unit having a fluoroaliphatic group) that controls the alignment on the air interface side as necessary. A copolymer).
The onium compound represented by the general formula (I) is added for the purpose of controlling the orientation of the liquid crystal compound at the acrylic resin layer interface, and has the effect of increasing the tilt angle in the vicinity of the acrylic resin layer interface of the molecules of the liquid crystal compound. is there.

In general formula (I), ring A represents a quaternary ammonium ion composed of a nitrogen-containing heterocycle, X represents an anion; L ¹ represents a divalent linking group; L ² represents a single bond or a divalent group. Y ¹ represents a divalent linking group having a 5- or 6-membered ring as a partial structure; Z represents a divalent linking group having 2 to 20 alkylene groups as a partial structure; P ¹ and P ² each independently represents a hydrogen atom, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, a cyano group, or a monovalent substituent having a polymerizable ethylenically unsaturated group.

  Ring A represents a quaternary ammonium ion composed of a nitrogen-containing heterocyclic ring. Examples of ring A include pyridine ring, picoline ring, 2,2′-bipyridyl ring, 4,4′-bipyridyl ring, 1,10-phenanthroline ring, quinoline ring, oxazole ring, thiazole ring, imidazole ring, pyrazine ring , Triazole ring, tetrazole ring and the like, preferably quaternary imidazolium ion and quaternary pyridinium ion.

  X represents an anion. Examples of X include a halogen anion (for example, fluorine ion, chlorine ion, bromine ion, iodine ion, etc.), sulfonate ion (for example, methanesulfonate ion, trifluoromethanesulfonate ion, methylsulfate ion, vinylsulfonate ion) , Allyl sulfonate ion, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion, p-vinylbenzene sulfonate ion, 1,3-benzene disulfonate ion, 1,5-naphthalene disulfonate ion, 2,6- Naphthalenedisulfonate ion), sulfate ion, carbonate ion, nitrate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, benzoate ion, p-vinylbenzoate ion, formate ion The trifle B acetate ion, phosphoric acid ion (e.g., hexafluorophosphate ion), such as a hydroxide ion. Preferred are halogen anions, sulfonate ions, and hydroxide ions. In particular, chlorine ion, bromine ion, iodine ion, methanesulfonic acid ion, vinylsulfonic acid ion, p-toluenesulfonic acid ion, and p-vinylbenzenesulfonic acid ion are preferable.

L ¹ represents a divalent linking group. Examples of L ¹ include an alkylene group, —O—, —S—, —CO—, —SO ₂ —, —NRa— (where Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. ), A divalent linking group having 1 to 20 carbon atoms, which is a combination with an alkenylene group, an alkynylene group or an arylene group. L ¹ is preferably -AL-, -O-AL-, -CO-O-AL-, or -O-CO-AL- having 1 to 10 carbon atoms, and -AL having 1 to 10 carbon atoms. -And -O-AL- are more preferable, and -AL- and -O-AL- having 1 to 5 carbon atoms are most preferable. AL represents an alkylene group.

L ² represents a single bond or a divalent linking group. Examples of L ² include an alkylene group, —O—, —S—, —CO—, —SO ₂ —, —NRa— (where Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. ), A divalent linking group having 1 to 10 carbon atoms consisting of a combination with an alkenylene group, an alkynylene group or an arylene group, a single bond, —O—, —O—CO—, —CO—O—, —O -AL-O-, -O-AL-O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O-CO-, -CO -O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO-, -O-CO-AL-CO-O-, and the like can be given. AL represents an alkylene group. L ² is preferably a single bond, -AL- having 1 to 10 carbon atoms, -O-AL-, or -NRa-AL-O-, a single bond, -AL- having 1 to 5 carbon atoms, —O—AL— and —NRa—AL—O— are more preferable, and —O—AL— and —NRa—AL—O— having a single bond and 1 to 5 carbon atoms are most preferable.

Y ¹ represents a divalent linking group having a 5- or 6-membered ring as a partial structure. Examples of Y ¹ include a cyclohexyl ring, an aromatic ring or a heterocyclic ring. Examples of the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, a biphenyl ring, and a pyrene ring, and a benzene ring, a biphenyl ring, and a naphthalene ring are particularly preferable. The hetero atom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. For example, a furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole Ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, dioxane ring, dithiane ring, thiine ring, pyridine ring, piperidine ring, oxazine ring Morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. The heterocycle is preferably a 6-membered ring. The divalent linking group having a 5- or 6-membered ring represented by Y ¹ as a partial structure may further have a substituent.

  Examples of the substituent include a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 10, more preferably 1 to 5), and 2 to 12 carbon atoms (more preferably). An alkenyl group having 2 to 10 and more preferably 2 to 5), an alkoxy group having 1 to 12 carbon atoms (more preferably 1 to 10, more preferably 1 to 5), and the like can be mentioned. The alkyl group and the alkoxy group have an acyl group having 2 to 12 carbon atoms (more preferably 2 to 10 and more preferably 2 to 5) or 2 to 12 carbon atoms (more preferably 2 to 10 and more preferably). May be substituted with an acyloxy group of 2-5). The acyl group is represented by —CO—R, the acyloxy group is represented by —O—CO—R, and R is an aliphatic group (alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group) or aromatic. Group (aryl group, substituted aryl group). R is preferably an aliphatic group, and more preferably an alkyl group or an alkenyl group.

The divalent linking group represented by Y ¹ is preferably a divalent linking group having two or more 5- or 6-membered rings, and preferably has a structure in which two or more rings are connected by a linking group. More preferred. Examples of linking groups include linking groups represented by L ¹ and L ^2, and —C≡C—, —CH═CH—, —CH═N—, —N═CH—, —N═N— and the like. Can be mentioned.

Z represents a divalent linking group having a combination of —O—, —S—, —CO—, and —SO ₂ — with a C 2-20 alkylene group as a partial structure, and an alkylene group May have a substituent. Examples of the divalent linking group include an alkyleneoxy group and a polyalkyleneoxy group. The number of carbon atoms of the alkylene group represented by Z is more preferably 2 to 16, more preferably 2 to 12, and particularly preferably 2 to 8.

P ¹ and P ² each independently represent a hydrogen atom, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, a cyano group, or a monovalent substituent having a polymerizable ethylenically unsaturated group. . Examples of the monovalent substituent having the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-8). That is, the monovalent substituent having a polymerizable ethylenically unsaturated group may be a substituent consisting only of an ethenyl group as in (M-8).

In formulas (M-3) and (M-4), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. Among the above formulas (M-1) to (M-8), (M-1), (M-2) and (M-8) are preferable, and (M-1) or (M-8) is more preferable. . In particular, (M-1) is preferable as P ¹ . P ² is preferably (M-1) or (M-8), and in the compound in which ring A is a quaternary imidazolium ion, P ² is (M-8) or (M-1). And in compounds where ring A is a quaternary pyridinium ion, P ² is preferably (M-1).

  The onium compounds represented by the general formula (I) include onium compounds represented by the following general formulas (I-1) and (I-2).

The definition of each symbol of general formula (I-1) and (I-2) is synonymous with each in general formula (I); L < ³ > and L < ⁴ > represent a bivalent coupling group each independently; Y ² and Y ³ are each independently a 6-membered ring optionally having a substituent; m represents 1 or 2, and when m is 2, two L ⁴ and two Y ³ are They may be the same or different; p represents an integer of 1 to 10.

L ³ represents a divalent linking group, and examples of L ³ include a single bond, —O—, —O—CO—, —CO—O—, —O—AL—O—, —O—AL. -O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO-, and -O-CO-AL-CO-O-. Note that AL represents an alkylene group having 1 to 10 carbon atoms. L ³ represents a single bond, —O—, —O—AL—O—, —O—AL—O—CO—, —O—AL—CO—O—, —CO—O—AL—O—, — CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO-, -O-CO- AL-CO-O- is preferable, a single bond or -O- is more preferable, and -O- is most preferable.

L ⁴ represents a divalent linking group, and examples of L ⁴ include a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, -CH = N-, -N = CH-, -N = N-, -NH-CO-, -CO-NH-. L ⁴ is preferably a single bond, —O—CO—, —CO—O—, —C≡C—, —NH—CO—, —CO—NH—, and preferably a single bond, —O—CO—, —CO. —O— is more preferable, and —O—CO— and —CO—O— are most preferable.

Y ² and Y ³ each independently represent a 6-membered ring optionally having a substituent, and the 6-membered ring includes an aliphatic ring, an aromatic ring (benzene ring) and a heterocyclic ring. Examples of the aliphatic 6-membered ring include a cyclohexane ring, a cyclohexene ring, and a cyclohexadiene ring. Examples of the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, a biphenyl ring, and a pyrene ring. Examples of 6-membered heterocycles include pyran ring, dioxane ring, dithiane ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, triazine ring Etc. Further, another 6-membered ring or a 5-membered ring may be condensed with the 6-membered ring. Y ² and Y ³ are preferably a cyclohexane ring, a pyridine ring, a pyrimidine ring or a benzene ring, more preferably a pyrimidine ring or a benzene ring, and most preferably a benzene ring.

Examples of the substituent include a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 10, more preferably 1 to 5), an alkoxy group having 1 to 12 carbon atoms, and the like. Is mentioned. The alkyl group and the alkoxy group may be substituted with an acyl group having 2 to 12 carbon atoms or an acyloxy group having 2 to 12 carbon atoms. The acyl group is represented by —CO—R, the acyloxy group is represented by —O—CO—R, and R is an aliphatic group (alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group) or aromatic. Group (aryl group, substituted aryl group). R is preferably an aliphatic group, and more preferably an alkyl group or an alkenyl group.
In formulas (I-1) and (I-2), at least one Y ³ is preferably a substituted benzene ring, preferably a benzene ring having one or more halogen groups, alkyl groups or alkoxy groups. Is more preferable, and a benzene ring having two or more alkyl groups or alkenyl groups is more preferable.

m represents an integer of 1 or 2, and when m is 2, two L ⁴ and two Y ³ may be different.

C _p H _2p represents a chain alkylene group which may have a branched structure. C _p H _2p is preferably a linear alkylene group (— (CH ₂ ) _p —).

  p represents an integer of 1 to 10, more preferably 1 to 5, and most preferably 1 to 2.

  The onium compounds represented by the general formula (I) include onium compounds represented by the following general formulas (I-3) and (I-4).

  The definition of each symbol of general formula (I-3) and (I-4) is synonymous with each in general formula (I-1) or (I-2); R 'represents a substituent; b represents an integer of 1 to 4.

Examples of R ′ are the same as the examples of the substituent of the 6-membered ring represented by Y ² and Y ³ in general formula (I-1) or (I-2), and the preferred ranges are also the same. . That is, R ′ is preferably a halogen group, an alkyl group or an alkoxy group.
b represents an integer of 1 to 4, more preferably 1 to 3, and still more preferably 2 to 3.

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

  The onium compound of the general formula (I) can be generally synthesized by alkylating a nitrogen-containing heterocycle (Menstokin reaction).

  From the viewpoint that the vertical alignment agent tends to be unevenly distributed in the acrylic resin layer having a polar group, the retardation layer preferably contains at least one element selected from bromine, boron, and silicon, and bromine, boron, and silicon. More preferably, at least one element selected from is unevenly distributed on the side closer to the acrylic resin layer.

(Optical properties of retardation layer with fixed alignment state of liquid crystal compound)
The Re value of the retardation layer is preferably 0 to 10 nm, more preferably 0 to 3 nm, and still more preferably 0 to 1 nm.
Rth of the retardation layer is preferably −100 to −250 nm, more preferably −120 to −230 nm, and further preferably −140 to −210 nm.
The retardation of the retardation layer can be measured by measuring the value of the film applied on the glass plate in the order of the acrylic resin layer and the retardation layer.
Here, Re and Rth are an in-plane retardation value and a retardation value in the thickness direction, respectively, measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH.

(Thickness of retardation layer (retardation layer) in which alignment state of liquid crystal compound is fixed)
The thickness of the retardation layer (retardation layer) in which the alignment state of the liquid crystal compound is fixed is preferably 0.5 to 2.0 μm from the viewpoint that it can contribute to thinning and improve curling of the film. -2.0 micrometers is more preferable.

[Phase difference film]
The retardation film of the present invention is a retardation film having at least the support, the acrylic resin layer, and a retardation layer (retardation layer) in which the alignment state of the liquid crystal compound is fixed. That is, the retardation film of the present invention is a laminated retardation film. FIG. 1 is a schematic diagram showing an example of the retardation film of the present invention.

(Optical characteristics of retardation film)
The optical characteristics of the retardation film of the present invention preferably satisfy the following formulas (1), (2), and (3).
80 nm ≦ Re ≦ 150 nm (1)
−100 nm ≦ Rth ≦ 10 nm Formula (2)
0.05 ≦ | Rth / Re | ≦ 0.5 Formula (3)
Here, Re and Rth are an in-plane retardation value (nm) and a retardation value in the thickness direction (nm), respectively, measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH.

Rth of the retardation film is preferably from -100 nm to 10 nm, and more preferably from -50 nm to -10 nm.
| Rth / Re | of the retardation film is preferably 0.05 to 1.0, more preferably 0.1 to 0.5.

(Thickness of retardation film)
The film thickness of the retardation film is preferably 20 μm to 50 μm, more preferably 22 to 50 μm, and even more preferably 25 to 45 μm from the viewpoint that it can cope with the recent thinning.

The retardation film preferably has a tear strength of 1.5 to 6.0 g · cm / cm from the viewpoint of making the film having no problem in handling and punching.
Since the tear strength is particularly affected by the orientation state of the cellulose acylate of the support, it is necessary to pay attention to the stretching conditions.

(Method for producing retardation film)
The retardation film of the present invention can be formed by the following method, but is not limited to this method.
First, a support is prepared.
Next, an acrylic resin layer forming composition is prepared, and the composition is supported by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method, or the like. Apply on top, heat and dry. A micro gravure coating method, a wire bar coating method, and a die coating method (see US Pat. No. 2,681,294 and JP-A-2006-122889) are more preferable, and a die coating method is particularly preferable.
After the acrylic resin layer forming composition is applied, it is dried and cured by light irradiation to form an acrylic resin layer.
Subsequently, a composition for a retardation layer is prepared, applied onto an acrylic resin layer, and a polymerizable group is reacted and cured to form a retardation layer.
Thus, the retardation film of the present invention is obtained. Further, other layers can be provided as necessary. In the method for producing a retardation film of the present invention, a plurality of layers may be applied simultaneously or sequentially.
In forming the acrylic resin layer and the retardation layer, the polymerization of the acrylic resin layer is not completed and an unreacted polymerizable group is left in the acrylic resin layer, and the acrylic resin is subjected to polymerization curing of the retardation layer. It is also possible to use a technique in which a polymerization reaction occurs at the interface between the acrylic resin layer and the retardation layer by combining the unreacted polymerizable groups in the layer and reacting, thereby improving the adhesion at the interface.

[Protective film for polarizing plate]
When the retardation film is used as a surface protective film (polarizing plate protective film) for a polarizing film (polarizer), a saponification treatment is performed to hydrophilize the surface of the support, that is, the surface to be bonded to the polarizing film. Thus, it is possible to improve adhesion with a polarizing film containing polyvinyl alcohol as a main component.

[Polarizer]
The polarizing plate of the present invention is a polarizing plate having a polarizing film and two protective films protecting both surfaces of the polarizing film, and at least one of the protective films is the retardation film of the present invention. FIG. 2 is a schematic diagram showing an example of the polarizing plate of the present invention.
Of the two protective films, one is the retardation film of the present invention, and the other is preferably a film made of an acrylic resin from the viewpoint of curling of the polarizing plate after polarizing plate processing. Examples of the film made of acrylic resin include acrylylene (manufactured by Mitsubishi Rayon Co., Ltd.), technoloy (manufactured by Sumitomo Chemical Co., Ltd.), and kenduren (manufactured by Kaneka Corporation).
Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine-based polarizing film and the dye-based polarizing film can be generally produced using a polyvinyl alcohol film.

  A structure in which the cellulose acylate film of the retardation film is adhered to the polarizing film through an adhesive layer made of polyvinyl alcohol, if necessary, and a protective film is also provided on the other side of the polarizing film. The surface of the other protective film opposite to the polarizing film may have an adhesive layer.

  The total film thickness of the polarizing plate (total film thickness of retardation film, polarizing film and protective film) is preferably 80 to 120 μm.

[Liquid Crystal Display]
The liquid crystal display device of the present invention has the retardation film or polarizing plate of the present invention.
The retardation film of the present invention can be advantageously used in a transverse electric field mode liquid crystal display device.

A liquid crystal cell having two cell substrates and a liquid crystal layer sandwiched between them and aligned in parallel with the substrate in the vicinity of the cell substrate when no voltage is applied; A pair of disposed polarizing plates, a first retardation film disposed between one polarizing plate and the cell substrate, and a second retardation film disposed between the other polarizing plate and the cell substrate The slow retardation axis of the first retardation film is arranged so as to be orthogonal to the major axis of the liquid crystal molecules in the vicinity of the inner side of the cell substrate adjacent to the first retardation film when no voltage is applied. In the liquid crystal display device operating in the transverse electric field mode, it is preferable that either the first retardation film or the second retardation film is the retardation film of the present invention.
Further, another preferred embodiment of the liquid crystal display device of the present invention is as follows:
A first substrate on which unit pixels are arranged; a second substrate facing the first substrate; a liquid crystal layer formed between the first substrate and the second substrate and arranged in a first direction; A first polarizing plate formed outside the first substrate and having a polarization transmission axis parallel to the first direction, and a first polarizing plate formed outside the second substrate and having a polarization transmission axis perpendicular to the first direction. The first polarizing plate includes a polyvinyl alcohol film having a polarizing function, and a triacetyl cellulose film or an acrylic film on the inner and outer surfaces of the polyvinyl alcohol film, and the second polarizing plate. The polarizing plate is a polyvinyl alcohol film having a polarizing function, and a triacetyl cellulose film or an acrylic film on one surface of the polyvinyl alcohol film. Comprising the polyvinyl retardation film formed on the other surface of alcohol film, the laminated retardation film is a liquid crystal display device is a retardation film of the present invention.

  The present invention will be described more specifically with reference to the following 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 is not limited to the specific examples shown below.

1. Production of Support (1) Production of Cellulose Acylate Film Cellulose acylate films were produced by the following methods.

(1) -1 Preparation of Dope Preparation Cellulose Acylate Solution:
The main agent, additive and solvent described in the following table are put into a mixing tank, stirred to dissolve each component, further heated to 90 ° C. for about 10 minutes, then filtered with an average pore size of 34 μm and baked with an average pore size of 10 μm. It filtered with the metal filter.
In addition, the addition amount of the additive was represented by the mass part with respect to 100 mass parts of the main ingredients in the table. The composition ratio of the solvent 1 and the solvent 2 is described in the table as a mass ratio. Further, the solid content concentration (unit mass%) of the cellulose acylate solution is described in the column of “Concentration” in the table.

Preparation of fine particle dispersion:
Next, the following components including each cellulose acylate solution prepared by the above method were charged into a disperser to prepare a fine particle dispersion.
―――――――――――――――――――――――――――――――――――
Fine particle dispersion ――――――――――――――――――――――――――――――――――――
・ Inorganic fine particles (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.)
0.2 parts by mass, 72.4 parts by mass of methylene chloride, 10.8 parts by mass of methanol, 10.3 parts by mass of each cellulose acylate solution ――――――――――――――――――― ――――――――――――――――

  100 parts by mass of each cellulose acylate solution and the fine particle dispersion were mixed in an amount such that the inorganic fine particles were 0.02 parts by mass with respect to cellulose acylate to prepare a dope for film formation.

(1) -2 Casting The above-mentioned dope was cast using a band casting machine. The band was made of stainless steel.

(1) -3 Drying After the web (film) obtained by casting was peeled from the band, the pass roll was conveyed and dried at a drying temperature of 120 ° C. for 20 minutes. In addition, the drying temperature here means the film surface temperature of a film.

(1) -4 Stretching The obtained web (film) is peeled from the band, sandwiched between clips, and in the direction of film transport (MD) using a tenter at the stretching temperature and stretch ratio shown in the table under the conditions of fixed-end uniaxial stretching. ) In a direction (TD) orthogonal to the above.
The stretch ratio and stretch temperature are described in the following table.

(2) Production of Support Made of Other Resins Supports 12 to 18 were produced using a resin other than cellulose acylate shown in Table 6.

The compounds used are shown below.
In the table, “CTA” represents cellulose triacetate, and the numerical value represents the degree of substitution of acetyl groups.
“Ring 1” is “Appear 3000” (cyclic olefin resin) manufactured by Ferrania.
"Ring 2" is "ZF14" (cyclic olefin resin) manufactured by Nippon Zeon.
“P1” is “Dianar BR88” (acrylic resin) manufactured by Mitsubishi Rayon Co., Ltd.
“P2” is “styrene-maleic anhydride copolymer D332” (styrene resin) manufactured by NOVA Chemicals.
“P3” is “Panlite L1225” (polycarbonate resin) manufactured by Teijin.
“P4” is “Teleflex FT7” (polyethylene terephthalate resin) manufactured by Teijin DuPont.
“S1” is a polyester oligomer having the following components and composition. The number average molecular weight of S1 was 1000.

In the above table, Ac represents an acetyl group.
“S2” is a polyester oligomer having the following structure. N represents the number of repeating units, and n = 2.

  Sugar 1 is a compound having the following structure. Ac represents an acetyl group.

In sugar 2, in formula (10) below, six Rs are substituted with the following substituents (benzoyl group), and the remaining two Rs are hydrogen atoms.
In sugar 3, in the following general formula (10), five Rs are substituted with the following substituents (benzoyl group), and the remaining three Rs are hydrogen atoms.

  TPP represents triphenyl phosphate and BDP represents biphenyl diphenyl phosphate. TPP / BDP indicates that TPP and BDP are included at a ratio of 3: 2 (mass ratio).

2. Formation of Acrylic Resin Layer and Intermediate Layer An acrylate compound described in the following table and a solvent were mixed to prepare an acrylic resin layer forming composition. More specifically, an acrylic resin layer forming composition was prepared as follows.
Acrylic compound (total of two when two types are used) 100 parts by mass, photopolymerization initiator (Irgacure 127, manufactured by Ciba Specialty Chemicals Co., Ltd.) 4 parts by mass, and a solvent are mixed, and an acrylic resin layer A forming composition was prepared.
In addition, the composition ratio of the acrylate compound and the solvent is shown in the table as a mass ratio. Moreover, the solid content concentration (unit mass%) of the composition for forming an acrylic resin layer is described in the column of “Concentration” in the table.
The acrylic resin layer-forming composition thus prepared was applied onto a support, the acrylic layer-forming composition was applied with a wire bar coater # 1.6, dried at 60 ° C. for 0.5 minutes, and then a high pressure of 120 W / cm. Using a mercury lamp, UV irradiation was performed at 30 ° C. for 30 seconds to crosslink the acrylic resin layer. The film thickness of the obtained acrylic resin layer was described in the table.
Further, the solvent contained in the composition for forming an acrylic resin layer dissolves the support, whereby an intermediate layer containing the main component of the support and the main component of the acrylic resin layer is formed between the support and the acrylic resin layer. Been formed. The thickness of the intermediate layer was obtained by cutting a cross section of the film with a microtome to prepare a sample, dyed with osmic acid vapor for one day, and then observing the film thickness profile of the cured layer with a scanning electron microscope.

The average content (% by mass) of the support component in the intermediate layer was determined as follows.
(Quantification of support components)
As shown in FIG. 3, the secondary ionic strength I1 of the surface was measured with respect to the film surface using TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry).
Next, when the cross section of the film was cut with a microtome, a slice was cut out at an inclination angle of 87 ° when the film thickness direction was 0 ° and the in-plane direction was 90 °. The secondary ion intensity I2 at the intermediate layer portion was measured with respect to the cut surface cut out by the above method.
Next, the average content (mass%) of the support component was determined from the average content = I2 / I1 × 100.
(Measurement method of secondary ion intensity in TOF-SIMS)
The measurement of TOF-SIMS can be observed, for example, by detecting fragments of components present on the film surface using TRIFT II type TOF-SIMS (trade name) manufactured by Phi Evans. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan.
For example, for a film using a cellulose-based support, the intensity of secondary ions derived from acetyl groups can be detected.

The compounds used are shown below.
IPA: isopropyl alcohol MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone

  A1: KAYARAD PET30: Nippon Kayaku Co., Ltd., a mixture of compounds having the following structure. The weight average molecular weight is 298, and the number of functional groups in one molecule is 3.4 (average).

  A2: Blemmer GLM: NOF Corporation, compound having the following structure.

  A3: Urethane monomer: Compound having the following structure. The weight average molecular weight is 596, and the number of functional groups in one molecule is 4.

  A4: EB5129: manufactured by Daicel UCB Corporation. A compound having the following structure.

  A5: Glycerol 1,3-diglycerolate diacrylate: Aldrich, a compound having the following structure.

  A6: allyl α-D-galactopyranoside: a compound having the following structure, manufactured by Aldrich.

(Measurement method of water droplet contact angle)
The water droplet contact angle was determined by adjusting the film for 2 hours or more at 25 ° C. and 60% relative humidity, dropping a 3 mm diameter pure water droplet on the surface of the acrylic resin layer, and 20 seconds later. It was calculated from the angle formed.
When a representative film was measured by the above method, the acrylic resin layer No. 5 has a water droplet contact angle of 50 °, an acrylic resin layer no. The film having 12 had a contact angle of 61 °.

3. Formation of Retardation Layer On the acrylic resin layer, 1.8 g of a liquid crystal compound described in the following table, 0.06 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), sensitizer (Kayacure DETX, Nippon Kayaku ( Co., Ltd.) 0.02 g, a solution obtained by dissolving 0.002 g of the vertical alignment agent described in the table below in the solvent in the table was applied with a wire bar of # 3.2. This was affixed to a metal frame and heated in a constant temperature bath at 100 ° C. for 2 minutes to align the rod-like liquid crystal compound. Next, after cooling to 50 ° C., using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% under a nitrogen purge, an illuminance of 190 mW / cm ² and an irradiation amount of 300 mJ The coating layer was cured by irradiating UV light of / cm ² . Then, it stood to cool to room temperature. In the table, “phr” represents mass% with respect to the total solid content of the retardation layer forming composition.
For example, “S1 + S2_1.0 + 0.5 phr” means that “S1 is included in an amount of 1.0 mass% with respect to the total solid content of the retardation layer forming composition, and S2 is the total solid content of the retardation layer forming composition. "0.5% by mass is included".

The retardation layer 32 was whitened when the liquid crystal layer was applied after the acrylic resin layer was applied, and the liquid crystal compound was not aligned.
Since the retardation layer 33 did not contain a vertical alignment agent, the liquid crystal compound was not aligned. The non-oriented film was whitened and the optical properties could not be measured.
The retardation layer 29 is not provided with a retardation layer.

  The compounds used are shown below.

S3: Compound I-1
S4: Compound I-2
S5: Compound I-7
S6: Compound I-15

  In this manner, laminated retardation films each having a retardation layer composed of a homeotropic liquid crystal layer on an acrylic resin layer were produced.

<Evaluation of retardation film>
About each obtained retardation film, thickness, Re, Rth, haze, surface shape, adhesiveness, and the abrasion resistance in warm water were evaluated.

(Measure haze)
The haze of the obtained film was measured according to JIS K-6714 using a haze meter “HGM-2DP” {manufactured by Suga Test Instruments Co., Ltd.}.

(Surface evaluation)
A film was placed on a black cloth, and the transparency and smoothness were visually evaluated in a fluorescent light reflecting environment.

(Evaluation of adhesion)
The adhesion between the retardation layer of the film and the acrylic resin layer was examined by a cross-cut peel test. 100 grids of 2 mm × 2 mm square were prepared with a cutter, Nitto Cello Tape (registered trademark) was applied, and then peeled, and the number remaining on the film without peeling was scored based on the following index. The larger the number, the higher the adhesion.
A: 80 or more B: 1 or more and 40 or less C: 0

(Evaluation of abrasion resistance in warm water)
The scuff resistance in warm water between the retardation layer and the acrylic resin layer of the film was examined by a cross-cut peel test. Make 100 grids of 2mm x 2mm square with a cutter, soak it in warm water at 40 ° C for 30 minutes, and then use BEMCOT, M-3II manufactured by Asahi Kasei so that a 1 kg load is applied immediately after removal. A rub test was performed. The results were evaluated according to the following indicators.
A: Not peeled B; 1-30 pieces peeled off but no problem C; 31-100 pieces peeled off

  The following table shows the evaluation results.

4). Production of polarizing plate The retardation film samples 10, 14, 39 and 42 produced above were bonded using a polyvinyl alcohol polarizer and an adhesive, and on the opposite surface of the polarizer in the same manner, FUJIFILM Corporation's Fujitac TD60UL (thickness: 60 μm) was bonded to prepare polarizing plates. When laminating the retardation film and the polarizer, the surface of the cellulose acylate film as the support and the surface of the polarizer were laminated.
In all cases, the retardation film was disposed between the liquid crystal cell and the polarizer when mounted on the liquid crystal display device.

  In addition, each produced said polarizing plate was used as a display surface side polarizing plate so that it might mention later. As a backlight side polarizing plate used in combination with this, Z-TAC (manufactured by Fuji Film Co., Ltd.) is formed on one surface of the polarizer, and Fujitac TD60UL (thickness 60 μm) is produced on the other surface by Fuji Film Co., Ltd. A polarizing plate produced by laminating each of was used. When mounted on a liquid crystal display device, a Z-TAC film was disposed between the liquid crystal cell and the polarizer.

[Preparation of polarizing plate with adhesive layer]
(Formation of adhesive layer)
The following pressure-sensitive adhesive layer composition used between the polarizing plate and the liquid crystal cell was used as a coating solution, applied to a separate film surface-treated with a silicone release agent using a die coater, and dried at 90 ° C. for 5 minutes. An acrylate pressure-sensitive adhesive layer was formed. The film thickness of the adhesive layer at that time was 20 μm.

(Creation of adhesive)
The acrylate polymer used for the pressure-sensitive adhesive was prepared according to the following procedure.
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 100 parts by mass of butyl acrylate, 3 parts by mass of acrylic acid, and 0.3 parts by mass of 2,2′-azobisisobutyronitrile are acetic acid. It was added together with ethyl to a solid content concentration of 30% by mass, and reacted at 60 ° C. for 4 hours under a nitrogen gas stream to obtain an acrylate polymer (A1).
Next, using the acrylate polymer (A1) obtained, an acrylate pressure-sensitive adhesive was produced according to the following procedure.
Acrylate polymer (A1) 2 parts by mass of trimethylolpropane tolylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., Coronate L) and 0.1 part by mass of 3-glycidoxypropyltrimethoxysilane per 100 parts by mass of solid content are added. The film was coated on a separate film surface-treated with a release agent using a die coater and dried at 150 ° C. for 3 hours to obtain an acrylate-based pressure-sensitive adhesive. Coronate L (Japanese polyurethane), which is a cross-linking agent, is a cross-linking agent having two or more aromatic rings.

(Transfer and aging of adhesive layer)
This pressure-sensitive adhesive layer was transferred to one side of the polarizing plate produced above and aged for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a polarizing plate with a pressure-sensitive adhesive layer. In this way, a polarizing plate with an adhesive layer was obtained.
The polarizing plates produced in this manner were incorporated as the polarizing plate 10, polarizing plate 14, polarizing plate 39, and polarizing plate 42 in the following liquid crystal display device, and the display performance was evaluated.

5. Production and evaluation of liquid crystal display device <Evaluation of liquid crystal display device>
(Preparation of liquid crystal cell)
A liquid crystal panel is taken out from new-iPad (registered trademark) [trade name; manufactured by Apple Inc.] equipped with an IPS mode liquid crystal cell, and placed on the front side (display side) and rear side (backlight side) of the liquid crystal cell. The optical film that had been removed was removed only on the front side (display surface side), and the surface glass surface of the liquid crystal cell was washed.
(5) Production of liquid crystal display device A polarizing plate with a retardation film was bonded to the display surface side surface of the IPS mode liquid crystal cell.
In this way, an IPS mode liquid crystal display device LCD was produced.
(6) Evaluation of liquid crystal display device The produced LCD was returned to new-iPad (registered trademark), and the following evaluation was performed.

(Front contrast evaluation)
For each of the produced IPS mode liquid crystal display devices, the luminance at the time of black display and white display was measured using a measuring device (EZ-Contrast XL88, manufactured by ELDIM), and the front contrast ratio (CR) was calculated. However, the front contrast of any polarizing plate was stable between 950 and 1000.

(Viewing angle brightness evaluation)
For each of the IPS mode liquid crystal display devices produced above, a backlight was installed, and for each, using a measuring device (EZ-Contrast XL88, manufactured by ELDIM), the luminance during black display was measured in a dark room, and the polar angle The black luminance value of each point was evaluated by 0 ° to 80 ° and an azimuth angle of 0 ° to 360 ° by 5 °.
Films 10 and 14 have a maximum black luminance of 0.15 cd / m ² , and some light leakage occurs, whereas films 39 and 42 have black luminance of 0.1 cd / m ² or less in any part. Almost no light leaked.

Claims (20)

A support, an acrylic resin layer, and an intermediate layer including a main component of the support and a main component of the acrylic resin layer between the support and the acrylic resin layer; A retardation film having a retardation layer directly fixing the alignment state of the liquid crystal compound on the surface opposite to the intermediate layer,
The support contains a cyclic olefin resin,
The acrylic resin layer contains an acrylic resin having at least one polar group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, and a cyano group,
The intermediate layer has a thickness of 0.1 μm or more and 10 μm or less,
The retardation layer, Ri Na comprise polymers of polymerizable liquid crystal compound with a vertical alignment agent,
The retardation layer is a layer that fixes the polymerizable liquid crystal compound in a homeotropic alignment state,
The retardation film has Re of -10 nm to 10 nm .
Here, Re is an in-plane retardation value measured with light having a wavelength of 550 nm at 25 ° C. and 60% RH. The retardation film according to claim 1, wherein the optical properties of the retardation film satisfy the following formulas (1), (2), and (3).
80 nm ≦ Re ≦ 150 nm (1)
−100 nm ≦ Rth ≦ 10 nm Formula (2)
0.05 ≦ | Rth / Re | ≦ 0.5 Formula (3)
Here, R e及 beauty Rth, respectively, is 25 ° C., a retardation value measured in-plane retardation value and the thickness direction by light with a wavelength of 550nm at 60% RH.   The retardation film according to claim 1, wherein a water droplet contact angle on the surface of the acrylic resin layer is 25 ° or more and 60 ° or less.   The retardation film according to claim 1, wherein the polar group of the acrylic resin is a hydroxyl group.   The retardation film according to any one of claims 1 to 4, wherein the acrylic resin layer is a layer formed from a composition containing at least one acrylate monomer having two or more functional groups. The retardation film according to claim 1, wherein the cyclic olefin resin includes a structural unit represented by the following general formula (4) or (5).

In general formula (4) and (5), m represents the integer of 0-4. R ^{3 to} R ⁶ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. X ² , X ³ , Y ² and Y ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom,-( _{^{CH 2) n COOR 11, -}} (CH 2) n OCOR 12, - (CH 2) n NCO, - (CH 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 13 R ¹⁴ , — (CH ₂ ) _n NR ¹³ R ¹⁴ , — (CH ₂ ) _n OZ, — (CH ₂ ) _n W, or X ² and Y ² , or X ³ and Y ³ (—CO ) ₂ O, (—CO) ₂ NR ¹⁵ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with a halogen, W is SiR ¹⁶ _p D _3-p (R ¹⁶ is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, —OCOR ¹⁶ or —OR ¹⁶ , p is an integer of 0 to 3), and n is 0 An integer of -10 is shown. The polymerizable liquid crystal compound forming the retardation layer is at least one compound selected from the group consisting of a compound represented by the following general formula (IIA) and a compound represented by the following general formula (IIB). The retardation film according to any one of claims 1 to 6.

R _{1 to} R ₄ are each independently — (CH ₂ ) _n —OOC—CH═CH ₂ , and n represents an integer of 2 to 5. X and Y each independently represent a hydrogen atom or a methyl group.   The retardation layer contains 3% by mass or more of the compound represented by the general formula (IIA) and the compound represented by the general formula (IIB), respectively, based on the total solid content of the retardation layer. Item 8. A retardation film according to Item 7. The retardation film according to any one of claims 1 to 8 , wherein the vertical alignment agent contained in the retardation layer is an onium compound represented by the following general formula (I).

In general formula (I), ring A represents a quaternary ammonium ion composed of a nitrogen-containing heterocycle, X represents an anion; L ¹ represents a divalent linking group; L ² represents a single bond or a divalent group. Y ¹ represents a divalent linking group having a 5- or 6-membered ring as a partial structure; Z represents a divalent linking group having 2 to 20 alkylene groups as a partial structure; P ¹ and P ² independently represents a monovalent substituent having a polymerizable ethylenically unsaturated group. Bromine in the retardation layer, comprising boron, and at least one element selected from silicon, the retardation film according to any one of claims 1-9. The retardation film according to claim 10 , wherein in the retardation layer, at least one element selected from bromine, boron, and silicon is unevenly distributed closer to the acrylic resin layer. The thickness of the retardation layer is a 0.5Myuemu～2.0Myuemu, retardation film according to any one of claims 1 to 11. The Re of the support is 80Nm～150nm, Rth is greater than Re, and a 80Nm～150nm, retardation film according to any one of claims 1 to 12.
Here, R e及 beauty Rth, respectively, is 25 ° C., a retardation value measured in-plane retardation value and the thickness direction by light with a wavelength of 550nm at 60% RH. The retardation film according to any one of claims 1 to 13 , wherein Re is -10 nm to 10 nm and Rth is -250 nm to -100 nm in the retardation layer.
Here, R e及 beauty Rth, respectively, is 25 ° C., a retardation value measured in-plane retardation value and the thickness direction by light with a wavelength of 550nm at 60% RH. A polarizing plate having a polarizing film and two protective films protecting both surfaces of the polarizing film, wherein at least one of the protective films is the retardation film according to any one of claims 1 to 14. Board. The polarizing plate according to claim 15 , wherein one of the two protective films is the retardation film according to any one of claims 1 to 14 , and the other is a film made of an acrylic resin. The polarizing plate according to claim 15 or 16 , which has a thickness of 50 µm to 120 µm. A liquid crystal display device comprising the retardation film according to any one of claims 1 to 14 or the polarizing plate according to any one of claims 15 to 17 . The liquid crystal display device of transverse electric field mode using the retardation film according to any one of claims 1-14. A liquid crystal display device in a transverse electric field mode using the polarizing plate according to any one of claims 15 to 17 .

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