JP2011150314A - Composite retardation plate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thinner composite retardation plate capable of performing uniform polarization conversion in a broader wavelength range. <P>SOLUTION: The composite retardation plate includes a retardation plate (1) obtained by polymerizing a liquid crystal compound having a polymerizable group and a retardation plate (2) containing an organic modified clay composite and a binder resin, wherein the birefringence index Δn(λ) of the plate to light at a wavelength of λ (nm) satisfies expressions (3):Δn(451)/Δn(549)≤1.04 and (4):0.98≤Δn(628)/Δn(549). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composite retardation plate and a method for manufacturing the same.

The composite retardation plate includes a plurality of retardation plates such as a circularly polarizing plate obtained by bonding a λ / 4 plate and a λ / 2 plate, and is used in a liquid crystal display device or the like. In recent years, liquid crystal display devices are required to be further reduced in size, and composite retardation plates are also required to be thinner.
Patent Document 1 discloses a composite phase difference plate obtained by laminating a λ / 4 plate made of a stretched film of a cyclic polyolefin-based resin to a phase difference plate containing an organically modified clay composite and a binder resin. It is disclosed.

JP 2005-338215 A

  A composite obtained by laminating a retardation plate containing a conventional organic modified viscosity composite and a binder resin as disclosed in the above document and a retardation film made of a stretched film of a cyclic polyolefin resin with an adhesive. The retardation plate has a thickness and is not always satisfactory for downsizing of the liquid crystal display device. An object of the present invention is to provide a composite retardation plate that is thinner than a conventional composite retardation plate.

［式（Ａｒ−６）中、Ｚ^１は、ハロゲン原子、炭素数１〜６のアルキル基、シアノ基、ニトロ基、−ＮＲ^７Ｒ^８、−ＳＲ^７を表す。ｎが２以上の整数である場合、複数のＺ^１は互いに同一であっても異なっていてもよい。
Ｒ^７及びＲ^８は、水素原子又は炭素数１〜６のアルキル基を表す。
Ｑ^１は、−Ｓ−、−Ｏ−又は−ＮＲ^９−を表す。
Ｒ^９は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｙ^２は、置換基を有していてもよい炭素数６〜１２の芳香族炭化水素基、又は置換基を有していてもよい炭素数３〜１２の芳香族複素環式基を表す。
ｎは、０〜２の整数を表す。］
［６］Ｇ^１及びＧ^２が、ともにシクロヘキサン−１，４−ジイル基である前記［２］記載の複合位相差板。
［７］Ａ^１及びＡ^２が、それぞれ独立に、ｐ−フェニレン基又はシクロヘキサン−１，４−ジイル基である前記［３］記載の複合位相差板。
［８］Ａ^１のみと結合しているＢ^１、及びＡ^２のみと結合しているＢ^２が、それぞれ独立に、−ＣＨ_２−ＣＨ_２−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−Ｏ−ＣＨ_２−、−ＣＨ_２−Ｏ−又は単結合であり、かつ
Ｆ^１と結合しているＢ^１、及びＦ^２と結合しているＢ^２が、それぞれ独立に、−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−又は単結合である前記［３］〜［７］のいずれかに記載の複合位相差板。
［９］重合性基が、それぞれ独立に、アクリロイルオキシ基及びメタクリロイルオキシ基からなる群から選ばれる１種以上である［１］〜［８］のいずれかに記載の複合位相差板。
［１０］有機修飾粘土複合体が、４級アンモニウム塩とスメクタイト族に属する粘土鉱物とを含み、該粘土鉱物に含まれるマグネシウムとケイ素４原子との原子比（Ｍｇ／Ｓｉ_４）が０．０１以上２．７３未満である前記［１］記載の複合位相差板。
［１１］位相差板（２）が、負の一軸性の位相差板である前記［１］又は［１０］記載の複合位相差板。
［１２］位相差板（１）と位相差板（２）とが接合してなる前記［１］〜［１１］のいずれかに記載の複合位相差板。
［１３］さらに、プライマー層を、位相差板（１）と位相差板（２）との間に含む前記［１］〜［１１］のいずれかに記載の複合位相差板。
［１４］波長５５０ｎｍにおける正面位相差値が、１１３ｎｍ以上１６３ｎｍ以下である前記［１］〜［１３］のいずれかに記載の複合位相差板。
［１５］偏光板及び前記［１］〜［１４］のいずれかに記載の複合位相差板を含む偏光部材。
［１６］液晶セル及び前記［１５］記載の偏光部材を含む液晶表示装置。
［１７］カラーフィルター及び、前記［１］〜［１４］のいずれかに記載の複合位相差板を含む光学部材。
［１８］下記（i）〜（v）の工程を有する複合位相差板の製造方法。
（i）重合性基を有する液晶化合物と有機溶媒とを混合して溶液を得る工程
（ii）工程（i）で得られた溶液から塗工膜を得る工程
（iii）工程（ii）で得られた塗工膜に含まれる重合性基を有する液晶化合物を重合させて、位相差板（１）を得る工程
（iv）有機修飾粘土複合体とバインダー樹脂と有機溶媒とを混合して塗工液を得る工程
（v）工程（iv）で得られた塗工液を、得られた位相差板（１）に塗布して、複合位相差板を得る工程
［１９］下記（i）〜（iv）および（vi）〜（vii）の工程を有する複合位相差板の製造方法。
（i）重合性基を有する液晶化合物と有機溶媒とを混合して溶液を得る工程
（ii）工程（i）で得られた溶液から塗工膜を得る工程
（iii）工程（ii）で得られた塗工膜に含まれる重合性基を有する液晶化合物を重合させて、位相差板（１）を得る工程
（iv）有機修飾粘土複合体とバインダー樹脂と有機溶媒とを混合して塗工液を得る工程
（vi）得られた位相差板（１）に、プライマーを塗布して、位相差板（１）上にプライマー層を形成する工程
（vii）工程（iv）で得られた塗工液を、プライマー層上に塗布して、複合位相差板を得る工程
［２０］（i）重合性基を有する液晶化合物と有機溶媒とを混合して溶液を得る工程において、さらに重合開始剤を混合して溶液を得る前記［１８］又は［１９］記載の複合位相差板の製造方法。 The present invention provides the following [1] to [20].
[1] A retardation plate (1) obtained by polymerizing a liquid crystal compound having a polymerizable group, and a retardation plate (2) containing an organically modified clay composite and a binder resin, and having a wavelength λ (nm) A composite phase difference plate in which the birefringence Δn (λ) in the light satisfies the expressions (3) and (4).
Δn (451) / Δn (549) ≦ 1.04 (3)
0.98 ≦ Δn (628) / Δn (549) (4)
[2] The composite retardation plate according to [1], wherein the liquid crystal compound having a polymerizable group is a compound represented by the formula (A).

^{L 1 -G 1 -D 1 -Ar-} D 2 -G 2 -L 2 (A)

[In the formula (A), Ar represents a divalent group having an aromatic ring, and the number of π electrons contained in the aromatic ring is 12 or more and 22 or less.
D ¹ and D ² are each independently a single bond, —CO—O—, —O—CO—, —C (═S) —O—, —O—C (═S) —, —CR ¹ R ^{2 -, - CR 1 R 2} -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 R ² —O—CO—, —O—CO—CR ¹ R ² —, —CR ¹ R ² —O—CO—CR ³ R ⁴ —, —CR ¹ R ² —CO—O—CR ³ R ⁴ — , —NR ¹ —CR ² R ³ —, —CR ¹ R ² —NR ³ —, —CO—NR ¹ —, or —NR ¹ —CO—.
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, — S— or —NH— may be substituted, and —CH (—) — contained in the alicyclic hydrocarbon group may be substituted with —N (—) —.
L ¹ and L ² each independently represents an organic group, and at least one selected from the group consisting of L ¹ and L ² represents a group having a polymerizable group. ]
[3] The composite phase difference plate according to [2], wherein L ¹ is a group represented by the formula (B) and L ² is a group represented by the formula (C).

P ¹ -F ^1- (B ¹ -A ¹ ) _k -E ^1- (B)
P ² -F ^2- (B ² -A ² ) ₁ -E ^2- (C)

Wherein (B) and ^{(C), B 1, B} 2, E 1 and ^{E 2,} each _{^{independently, -CR 5 R 6 -, -}} CH 2 -CH 2 -, - O -, - S- , -CO-O-, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -O-C (= S)- ^{O -, - CO-NR 5} -, - NR 5 -CO -, - O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - represents a CH 2 -S- or a single bond. If k is an integer of 2 or more, plural B ¹ represents may be the same or different from each other. When l is an integer greater than or equal to ² , several B2 may mutually be same or different.
R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon —CH ₂ — contained in the group may be replaced by —O—, —S— or —NH—, and —CH (—) — contained in the alicyclic hydrocarbon group represents —N (-)-May be replaced. When k is an integer of 2 or more, the plurality of A ¹ may be the same as or different from each other. When l is an integer greater than or equal to ² , several A2 may mutually be same or different.
k and l each independently represents an integer of 0 to 3.
F ¹ and F ² represents a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
P ¹ represents a polymerizable group.
P ² represents a hydrogen atom or a polymerizable group. ]
[4] The composite phase difference plate according to [3], wherein the compound represented by the formula (A) is a compound satisfying the formulas (5) and (6).
( _Nπ- 4) / 3 <k + 1 + 4 (5)
12 ≦ N _π ≦ 22 (6)
[In Formula (5) and Formula (6), N _π represents the number of π electrons contained in the aromatic ring of Ar. k and l represent the same meaning as in formulas (B) and (C). ]
[5] The composite phase difference plate according to [2], wherein Ar is a divalent group represented by the formula (Ar-6).

[In Formula (Ar-6), Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, —NR ⁷ R ⁸ , or —SR ⁷ . If n is an integer of 2 or more, a plurality of Z ¹ may be the being the same or different.
R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Q ¹ represents —S—, —O— or —NR ⁹ —.
R ⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ² represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent.
n represents an integer of 0 to 2. ]
[6] The composite phase difference plate according to [2], wherein G ¹ and G ² are both cyclohexane-1,4-diyl groups.
[7] The composite phase difference plate according to [3], wherein A ¹ and A ² are each independently a p-phenylene group or a cyclohexane-1,4-diyl group.
[8] ^{B 1} which is bound to only ^{A 1,} and ^{A 2} only bonded to that ^{B 2} is an _{independently, -CH 2 -CH 2 -, -} CO-O -, - O-CO- , -CO-NH -, - NH -CO -, - O-CH 2 -, - is CH 2 -O- or a single bond, and bonded to ^{B 1,} and ^{F 2} which is bound to F ¹ Each B ² independently represents —O—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NH—, —NH—CO— or a single bond. [3] The composite retardation plate according to any one of [7].
[9] The composite phase difference plate according to any one of [1] to [8], wherein the polymerizable group is independently one or more selected from the group consisting of an acryloyloxy group and a methacryloyloxy group.
[10] The organically modified clay complex includes a quaternary ammonium salt and a clay mineral belonging to the smectite group, and an atomic ratio (Mg / Si ₄ ) between magnesium and silicon 4 atoms contained in the clay mineral is 0.01. The composite retardation plate according to [1], which is less than 2.73.
[11] The composite retardation plate according to [1] or [10], wherein the retardation plate (2) is a negative uniaxial retardation plate.
[12] The composite retardation plate according to any one of [1] to [11], wherein the retardation plate (1) and the retardation plate (2) are joined.
[13] The composite phase difference plate according to any one of [1] to [11], further including a primer layer between the phase difference plate (1) and the phase difference plate (2).
[14] The composite phase difference plate according to any one of [1] to [13], wherein a front phase difference value at a wavelength of 550 nm is 113 nm or more and 163 nm or less.
[15] A polarizing member comprising a polarizing plate and the composite retardation plate according to any one of [1] to [14].
[16] A liquid crystal display device comprising a liquid crystal cell and the polarizing member according to [15].
[17] An optical member including a color filter and the composite retardation plate according to any one of [1] to [14].
[18] A method for producing a composite retardation plate comprising the following steps (i) to (v):
(I) Step for obtaining a solution by mixing a liquid crystal compound having a polymerizable group and an organic solvent (ii) Step for obtaining a coating film from the solution obtained in step (i) (iii) Obtaining in step (ii) (Iv) a step of obtaining a retardation plate (1) by polymerizing a liquid crystal compound having a polymerizable group contained in the coated film, and coating by mixing an organically modified clay complex, a binder resin and an organic solvent Step of obtaining liquid (v) Step of obtaining the composite phase difference plate by applying the coating liquid obtained in step (iv) to the obtained phase difference plate (1) [19] The following (i) to ( A method for producing a composite phase difference plate, comprising the steps of iv) and (vi) to (vii).
(I) Step for obtaining a solution by mixing a liquid crystal compound having a polymerizable group and an organic solvent (ii) Step for obtaining a coating film from the solution obtained in step (i) (iii) Obtaining in step (ii) (Iv) a step of obtaining a retardation plate (1) by polymerizing a liquid crystal compound having a polymerizable group contained in the coated film, and coating by mixing an organically modified clay complex, a binder resin and an organic solvent Step (vi) for obtaining a solution Step (vii) of applying a primer to the obtained retardation plate (1) to form a primer layer on the retardation plate (1) The coating obtained in step (iv) Step [20] of applying a working solution on the primer layer to obtain a composite retardation plate (i) In the step of mixing a liquid crystal compound having a polymerizable group and an organic solvent to obtain a solution, a polymerization initiator is further added. The method for producing a composite retardation plate as described in [18] or [19] above, wherein a solution is obtained by mixing.

  According to the present invention, it is possible to obtain a composite retardation plate that is further thinned and can perform uniform polarization conversion in a wider wavelength range.

FIG. 1 is a schematic cross-sectional view schematically showing a composite retardation plate. FIG. 2 is a schematic cross-sectional schematic view of a composite retardation plate including an alignment film and / or a supporting substrate. FIG. 3 is a schematic cross-sectional schematic diagram of a polarizing member including a composite retardation plate. FIG. 4 is a schematic cross-sectional schematic diagram of a liquid crystal display device including a polarizing member and a liquid crystal cell. FIG. 5 is a schematic cross-sectional schematic diagram of an optical member including a composite retardation plate and a color filter.

Hereinafter, the present invention will be described in detail.
The composite retardation plate of the present invention comprises a retardation plate (1) obtained by polymerizing a liquid crystal compound having a polymerizable group (hereinafter sometimes referred to as “liquid crystal monomer”), an organically modified clay composite, and a binder. A birefringence index Δn (λ) with respect to light having a wavelength λ (nm) satisfies the expressions (3) and (4).
Δn (451) / Δn (549) ≦ 1.04 (3)
0.98 ≦ Δn (628) / Δn (549) (4)

  In this specification, a retardation film is an object that can transmit light and has an optical function. The optical function means refraction, birefringence and the like. The phase difference plate is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converting circularly polarized light or elliptically polarized light into linearly polarized light.

  The phase difference (Re (λ)) of the retardation plate given by the light of wavelength λnm is represented by the product of the birefringence Δn and the thickness d of the retardation plate (Re (λ) = Δn × d). The wavelength dispersion is the wavelength dependence of the phase difference Re, and the reverse wavelength dispersion characteristic is a property in which the phase difference Re increases as the wavelength increases. For example, the wavelength dispersion is represented by a value (Re (λ) / Re (549)) obtained by dividing the phase difference value Re (λ) at a certain wavelength λnm by the phase difference value Re (549) at 549 nm. (Re (λ) / Re (549)) is a wavelength region close to 1 (for example, 0.98 to 1.04), or [Re (451) / Re (549)] ≦ 1.04 (preferably 0.8. 8 ≦ [Re (451) / Re (549)] ≦ 1.04) and [Re (628) / Re (549)] ≧ 0.98 (preferably 0.98 ≦ [Re (628) / Re (549) )] ≦ 1.1), uniform polarization conversion is possible in the wavelength region showing the reverse wavelength dispersion characteristic.

[Phase difference plate (1)]
The retardation plate (1) of the present invention is preferably a retardation plate obtained by polymerizing a compound represented by the formula (A) (hereinafter sometimes referred to as “compound (A)”).

^{L 1 -G 1 -D 1 -Ar-} D 2 -G 2 -L 2 (A)
[In the formula (A), Ar represents a divalent group having an aromatic ring, and the number N _{π of} π electrons contained in the aromatic ring is 12 or more and 22 or less.
D ¹ and D ² are each independently a single bond, —CO—O—, —O—CO—, —C (═S) —O—, —O—C (═S) —, —CR ¹ R ^{2 -, - CR 1 R 2} -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 R ² —O—CO—, —O—CO—CR ¹ R ² —, —CR ¹ R ² —O—CO—CR ³ R ⁴ —, —CR ¹ R ² —CO—O—CR ³ R ⁴ — , —NR ¹ —CR ² R ³ —, —CR ¹ R ² —NR ³ —, —CO—NR ¹ —, or —NR ¹ —CO—.
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, — S— or —NH— may be substituted, and —CH (—) — contained in the alicyclic hydrocarbon group may be substituted with —N (—) —.
L ¹ and L ² each independently represents an organic group, and at least one selected from the group consisting of L ¹ and L ² represents a group having a polymerizable group. ]
In the present specification, -CH (-)-means a methine group, and -N (-)-means a nitrilo group.

Ar, which is a divalent group having an aromatic ring, is preferably a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The total number N _π of π electrons of the aromatic ring contained in the divalent group is preferably 12 or more, more preferably 13 or more, and preferably 22 or less.

  Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring. Examples of the aromatic heterocycle include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole. A ring etc. are mentioned. Among these, a benzene ring, a thiazole ring or a benzothiazole ring is preferable.

  Examples of Ar include divalent groups represented by formulas (Ar-1) to (Ar-13).

[In Formula (Ar-1) to Formula (Ar-13), Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 alkylsulfonyl groups, carboxy groups, 1 to 6 carbon fluoroalkyl groups, 1 to 6 alkoxy groups, 1 to 6 alkylsulfanyl groups, and 1 to 6 carbon atoms N-alkylamino Group, a C2-C12 N, N-dialkylamino group, a C1-C6 N-alkylsulfamoyl group or a C2-C12 N, N-dialkylsulfamoyl group.
Q ¹ and Q ³ each independently represent —CR ⁹ R ¹⁰ —, —S—, —NR ⁹ —, —CO— or —O—.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
W ^a and W ^b each independently represent a hydrogen atom, a cyano group, a methyl group, or a halogen atom.
m represents an integer of 0-6.
n represents an integer of 0 to 2. ]

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom, a chlorine atom, or a bromine atom is preferable.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. Among them, an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

  Examples of the alkylsulfinyl group having 1 to 6 carbon atoms include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, pentylsulfinyl group Group, hexylsulfinyl group and the like. Among them, an alkylsulfinyl group having 1 to 4 carbon atoms is preferable, an alkylsulfinyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfinyl group is particularly preferable.

  Examples of the alkylsulfonyl group having 1 to 6 carbon atoms include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl Group, hexylsulfonyl group and the like. Among them, an alkylsulfonyl group having 1 to 4 carbon atoms is preferable, an alkylsulfonyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfonyl group is particularly preferable.

  Examples of the fluoroalkyl group having 1 to 6 carbon atoms include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group. Of these, a fluoroalkyl group having 1 to 4 carbon atoms is preferable, a fluoroalkyl group having 1 to 2 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable.

  Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, and hexyloxy group. It is done. Among these, an alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

  Examples of the alkylsulfanyl group having 1 to 6 carbon atoms include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, isobutylsulfanyl group, sec-butylsulfanyl group, tert-butylsulfanyl group, pentylsulfanyl group Group, hexylsulfanyl group and the like. Among them, an alkylsulfanyl group having 1 to 4 carbon atoms is preferable, an alkylsulfanyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfanyl group is particularly preferable.

  Examples of the N-alkylamino group having 1 to 6 carbon atoms include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group, N-hexylamino group and the like can be mentioned. Among them, an N-alkylamino group having 1 to 4 carbon atoms is preferable, an N-alkylamino group having 1 to 2 carbon atoms is more preferable, and an N-methylamino group is particularly preferable.

  Examples of the N, N-dialkylamino group having 2 to 12 carbon atoms include N, N-dimethylamino group, N-methyl-N-ethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dipentylamino group, N, N-dihexylamino group and the like can be mentioned. Among them, an N, N-dialkylamino group having 2 to 8 carbon atoms is preferable, an N, N-dialkylamino group having 2 to 4 carbon atoms is more preferable, and an N, N-dimethylamino group is particularly preferable.

  Examples of the N-alkylsulfamoyl group having 1 to 6 carbon atoms include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N- Butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-hexylsulfamoyl group, etc. Is mentioned. Among them, an N-alkylsulfamoyl group having 1 to 4 carbon atoms is preferable, an N-alkylsulfamoyl group having 1 to 2 carbon atoms is more preferable, and an N-methylsulfamoyl group is particularly preferable.

  Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include N, N-dimethylsulfamoyl group, N-methyl-N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-dipropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N, N-dipentylsulfamoyl group, N, N-dihexylsulfamoyl group and the like can be mentioned. Among them, an N, N-dialkylsulfamoyl group having 2 to 8 carbon atoms is preferable, an N, N-dialkylsulfamoyl group having 2 to 4 carbon atoms is more preferable, and an N, N-dimethylsulfamoyl group is particularly preferable. .

Z ^{1 in} formulas (Ar-1) to (Ar-13) is particularly a halogen atom, a methyl group, a cyano group, a nitro group, a carboxy group, a methylsulfonyl group, a trifluoromethyl group, a methoxy group, a methylsulfanyl group, N-methylamino group, N, N-dimethylamino group, N-methylsulfamoyl group or N, N-dimethylsulfamoyl group is preferred.

Examples of the alkyl group having 1 to 4 carbon atoms in R ⁹ and R ¹⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. Among these, an alkyl group having 1 to 2 carbon atoms is preferable, and a methyl group is more preferable.

Q ¹ in the formulas (Ar-1) to (Ar-13) is preferably —S—, —CO—, —NH— or —N (CH ₃ ) —, and Q ³ represents —S—. Or it is preferable that it is -CO-.

Examples of the aromatic hydrocarbon group and aromatic heterocyclic group represented by Y ¹ , Y ² and Y ³ include a monocyclic aromatic hydrocarbon group, a monocyclic aromatic heterocyclic group, a polycyclic aromatic hydrocarbon group, and Examples include polycyclic aromatic heterocyclic groups.
Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. Of these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. As the aromatic heterocyclic group, at least one hetero atom such as nitrogen atom, oxygen atom, sulfur atom such as furyl group, pyrrolyl group, thienyl group, pyridinyl group, thiazolyl group, benzothiazolyl group, benzofuryl group, benzothienyl group, etc. Examples thereof include an aromatic heterocyclic group having 4 to 20 carbon atoms. Of these, a furyl group, a thienyl group, a thiazolyl group, a benzothiazolyl group, a benzofuryl group, and a benzothienyl group are preferable.

  Such an aromatic hydrocarbon group and aromatic heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, and a carbon number. An alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, C1-C6 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C6 N-alkylsulfamoyl group, C2-C12 N, N- And dialkylsulfamoyl groups.

A halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms An alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, and an N-alkylsulfamoyl group having 1 to 6 carbon atoms Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include the same groups as those described above for Z ¹ .

  Examples of the substituent include a halogen atom, an alkyl group having 1 to 2 carbon atoms, a cyano group, a nitro group, an alkylsulfonyl group having 1 to 2 carbon atoms, a fluoroalkyl group having 1 to 2 carbon atoms, and 1 to 2 carbon atoms. Alkoxy group having 1 to 2 carbon atoms, N-alkylamino group having 1 to 2 carbon atoms, N, N-dialkylamino group having 2 to 4 carbon atoms, alkylsulfamoyl having 1 to 2 carbon atoms Groups are preferred.

  Examples of the monocyclic aromatic hydrocarbon group or the monocyclic aromatic heterocyclic group include groups represented by formulas (Y-1) to (Y-6).

[In formula (Y-1) to formula (Y-6), * represents a bond, Z ² represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, or 1 to 6 carbon atoms. Alkylsulfinyl group, C1-6 alkylsulfonyl group, carboxy group, C1-6 fluoroalkyl group, C1-6 alkoxy group, C1-6 alkylsulfanyl group, C1 -6 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C6 N-alkylsulfamoyl group or C2-C12 N, N-dialkylsulfa Represents a moyl group.
a ¹ is an integer of 0 to 5, a ² is an integer of 0 to 4, b ¹ is an integer of 0 to 3, b ² is an integer of 0 to 2, and R is a hydrogen atom or a methyl group. . ]

A halogen atom in Z ² , an alkyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms Alkoxy group having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfone having 1 to 6 carbon atoms Examples of the famoyl group or the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms are the same as those in Z ¹ described above.

Z ² is particularly a halogen atom, methyl group, cyano group, nitro group, sulfone group, carboxy group, trifluoromethyl group, methoxy group, methylsulfanyl group, N, N-dimethylamino group or N-methylamino group. preferable.

Y ¹ , Y ² and Y ³ are each particularly preferably a group represented by the formula (Y-1) or the formula (Y-3) in terms of the production process and cost.

Examples of the polycyclic aromatic hydrocarbon group or the polycyclic aromatic heterocyclic group include groups represented by formulas (Y ¹ -1) to (Y ¹ -7).

[In formulas (Y ¹ -1) to (Y ¹ -7), * represents a bond, and Z ³ is independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a nitro group. , An alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl having 1 to 6 carbon atoms Sulfanyl group, N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms, N having 2 to 12 carbon atoms , N-dialkylsulfamoyl group.
V ¹ and V ² each independently represent —CO—, —S—, —NR ¹¹ —, —O—, —Se— or —SO ₂ —.
W ^{1 to} W ⁵ each independently represent —CH═ or —N═.
However, at least one of V ¹ , V ² and W ^{1 to} W ⁵ represents a group containing S, N, O or Se.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
a represents the integer of 0-3 each independently.
b represents the integer of 0-2 each independently. ]

Furthermore, any group represented by the formula (Y ¹ -1) to the formula (Y ¹ -7) is a group represented by the formula (Y ³ -1) to the formula (Y ³ -6). Is preferred.

[In formula (Y ³ -1) to formula (Y ³ -6), *, Z ³ , a, b, V ¹ , V ² and W ¹ represent the same meaning as described above. ]

Z ³ includes a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, and 1 to 1 carbon atoms. 6 fluoroalkyl groups, alkoxy groups having 1 to 6 carbon atoms, alkylsulfanyl groups having 1 to 6 carbon atoms, N-alkylamino groups having 1 to 6 carbon atoms, N, N-dialkylamino groups having 2 to 12 carbon atoms And an N-alkylsulfamoyl group having 1 to 6 carbon atoms and an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
A halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms An alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, and an N-alkylsulfamoyl group having 1 to 6 carbon atoms Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include the same groups as those described above for Z ¹ .

Z ³ includes, among others, a halogen atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a cyano group, a nitro group, a sulfone group, a nitroxyd group, a carboxy group, a trifluoromethyl group, a methoxy group, a methylsulfanyl group, N, N-dimethylamino group or N-methylamino group is preferable, halogen atom, methyl group, ethyl group, isopropyl group, sec-butyl group, cyano group, nitro group, trifluoromethyl group are more preferable, methyl group, An ethyl group, isopropyl group, sec-butyl group, pentyl group, and hexyl group are particularly preferable.

Further, V ¹ and V ² are preferably each independently -S-, -NR ¹¹ -or -O-, and W ^{1 to} W ⁵ are each independently -CH = or -N =. is there.
In addition, at least one of V ¹ , V ² and W ^{1 to} W ⁵ preferably represents a group containing S, N or O.
a is preferably 0 or 1, and b is preferably 0.

Specific examples of Ar include the following groups.
For example, specific examples of the groups represented by formula (Ar-1) to formula (Ar-4) include groups represented by formula (ar-1) to formula (ar-29).

  Specific examples of the group represented by the formula (Ar-5) include groups represented by the formula (ar-30) to the formula (ar-39).

  Specific examples of the group represented by Formula (Ar-6) or Formula (Ar-7) include groups represented by Formula (ar-40) to Formula (ar-119).

  Specific examples of the group represented by formula (Ar-8) or formula (Ar-9) include groups represented by formula (ar-120) to formula (ar-129).

  Specific examples of the group represented by the formula (Ar-10) include groups represented by the formula (ar-130) to the formula (ar-149).

  Specific examples of the group represented by the formula (Ar-11) include groups represented by the formula (ar-150) to the formula (ar-159).

  Specific examples of the group represented by the formula (Ar-12) include groups represented by the formula (ar-160) to the formula (ar-179).

  Specific examples of the group represented by the formula (Ar-13) include groups represented by the formula (ar-180) to the formula (ar-189).

  Ar in the compound (A) is particularly preferably a divalent group represented by the formula (Ar-6) because the compound is easily synthesized and the wavelength dispersion of the retardation is easily obtained.

D ¹ and D ² in the formula (A) are * —O—CO—, * —O—C (═S) —, * —O—CR ¹ R ² —, * —NR ¹ —CR ² R ^3. — Or * —NR ¹ —CO— (* represents a bond to Ar) is preferable. More preferably, D ¹ and D ² are * —O—CO—, * —O—C (═S) — or * —NR ¹ —CO— (* represents a bond to Ar). .

R ¹ , R ² , R ³ and R ⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of G ¹ and G ² in the formula (A) include alicyclic hydrocarbon groups that may include a hetero atom represented by the formula (g-1) to the formula (g-10). It is preferably a 6-membered alicyclic hydrocarbon group.

  The hydrogen atom contained in the groups represented by the above formulas (g-1) to (g-10) is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a tert-butyl group; a methoxy group An alkoxy group having 1 to 4 carbon atoms such as ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; a fluoroalkoxy group having 1 to 4 carbon atoms such as trifluoromethoxy group; a cyano group; Group; may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

G ¹ and G ² are preferably alicyclic hydrocarbon groups composed of a 6-membered ring represented by the formula (g-1). Among these, both G ¹ and G ² are more preferably a cyclohexane-1,4-diyl group, and particularly preferably a trans-cyclohexane-1,4-diyl group.

L ¹ and L ² in the formula (A) are organic groups, and at least one selected from the group consisting of L ¹ and L ² is a group having a polymerizable group.
The organic group L ¹ is preferably a group represented by the formula (B), and L ² is preferably a group represented by the formula (C).
P ¹ -F ^1- (B ¹ -A ¹ ) _k -E ^1- (B)
P ² -F ^2- (B ² -A ² ) ₁ -E ^2- (C)
Wherein (B) and ^{(C), B 1, B} 2, E 1 and ^{E 2,} each _{^{independently, -CR 5 R 6 -, -}} CH 2 -CH 2 -, - O -, - S- , -CO-O-, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -O-C (= S)- ^{O -, - CO-NR 5} -, - NR 5 -CO -, - O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - represents a CH 2 -S- or a single bond. If k is an integer of 2 or more, plural B ¹ represents may be the same or different from each other. When l is an integer greater than or equal to ² , several B2 may mutually be same or different.
R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon —CH ₂ — contained in the group may be replaced by —O—, —S— or —NH—, and —CH (—) — contained in the alicyclic hydrocarbon group represents —N (-)-May be replaced. When k is an integer of 2 or more, the plurality of A ¹ may be the same as or different from each other. When l is an integer greater than or equal to ² , several A2 may mutually be same or different.
k and l each independently represents an integer of 0 to 3.
F ¹ and F ² represents a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
P ¹ represents a polymerizable group.
P ² represents a hydrogen atom or a polymerizable group. ]

Examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms or the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms in A ¹ and A ² include the above formulas (g-1) to (g -10) or an alicyclic hydrocarbon group composed of a 5-membered ring or a 6-membered ring, or a divalent aromatic hydrocarbon represented by the following formulas (a-1) to (a-8): Groups.

In addition, as A ¹ and A ² , the hydrogen atom contained in the exemplified group is an alkyl group having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, or a t-butyl group; a methoxy group Or an alkoxy group having about 1 to 4 carbon atoms such as an ethoxy group; a trifluoromethyl group; a trifluoromethoxy group; a cyano group; a nitro group; and a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom. .

A ¹ and A ² are each independently preferably a monocyclic 1,4-phenylene group or cyclohexane-1,4-diyl group, and in particular, since the production of the compound (A) is easy, A 1,4-phenylene group is preferred. Further, A ¹ and A ² are preferably the same type of group because the compound (A) tends to be easily produced.

B ¹ and B ² are preferably the same type of group because the production of the compound (A) tends to be easy. Further, since the production of the compound (A) becomes easier, ^{B 1} which is bound to only ^{A 1,} and ^{A 2} only bonded to that ^{B 2} is an _{independently,} -CH 2 -CH ₂ -, - CO-O -, - O-CO -, - CO-NH -, - NH-CO -, - O-CH 2 -, - is preferably CH 2 -O- or a single bond. In particular, -CO-O- or -O-CO- is preferable because it exhibits high liquid crystallinity. Further, B ¹ bonded to F ¹ and B ² bonded to F ² are each independently —O—, —CO—O—, —O—CO—, —O—CO—O. -, -CO-NH-, -NH-CO- or a single bond is more preferable.

  From the viewpoint of liquid crystallinity, k and l preferably each independently represent an integer of 0 to 3, and k and l are more preferably 0 to 2. The total of k and l is preferably 5 or less, and more preferably 4 or less.

F ¹ and F ² are preferably alkylene groups having 1 to 12 carbon atoms. An unsubstituted alkylene group is particularly preferable. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. In addition, —CH ₂ — contained in the alkylene group may be substituted with —O— or —CO—.

P ¹ is a polymerizable group, and P ² is a hydrogen atom or a polymerizable group. Since the hardness of the obtained retardation plate tends to be excellent, it is preferable that both P ¹ and P ² are polymerizable groups.

Here, the polymerizable group means a substituent capable of polymerizing the compound (A), specifically, vinyl group, p-stilbene group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group. Carboxy group, methylcarbonyl group, hydroxy group, amide group, alkylamino group having 1 to 4 carbon atoms, amino group, epoxy group, oxetanyl group, aldehyde group, isocyanate group and thioisocyanate group.
As the polymerizable group, a radical polymerizable group and a cationic polymerizable group suitable for photopolymerization are preferable, and since they are particularly easy to handle and easy to manufacture, acryloyl group, methacryloyl group, acryloyl group are preferable. An oxy group and a methacryloyloxy group are preferred. Among them, the polymerizable group is preferably each independently an acryloyloxy group or a methacryloyloxy group, and particularly preferably an acryloyloxy group.

Specific examples of * -D ¹ -G ¹ -L ¹ (* represents a bond to Ar) when L ¹ is a group represented by the formula (B) include the following formula (R— Examples include groups represented by 1) to formula (R-120) and formula (R-129) to formula (R-131). As a specific example of * -D ² -G ² -L ² (* represents a bond to Ar) when L ² is a group represented by the formula (C), the following formula (R -1) to groups represented by formula (R-134), and the like.
In the formulas (R-1) to (R-134), n represents an integer of 2 to 12.

The compound (A) is preferably a compound that satisfies the formulas (5) and (6).
( _Nπ- 4) / 3 <k + 1 + 4 (5)
12 ≦ N _π ≦ 22 (6)
[In Formula (5) and Formula (6), N _π represents the number of π electrons contained in the aromatic ring of Ar. k and l represent the same meaning as in formulas (B) and (C). ]

Examples of the compound (A) include the following compound (i) to compound (xxxiv). Incidentally, R1 in the ^table, the -D ^{1 -G} 1 -L 1, R2 ^represents -D ^{2 -G} 2 -L 2.

  In Table 1 above, compound (xvii) is a compound in which Ar is a group represented by the formula (ar-78) or a compound in which Ar is a group represented by the formula (ar-79) or Ar is represented by the formula (ar-78). ) Is a mixture of a compound which is a group represented by formula (ar-79) and a compound which is a group represented by formula (ar-79).

  In Table 1 above, the compound (xxx) is a compound in which Ar is a group represented by the formula (ar-120) or a compound in which Ar is a group represented by the formula (ar-121) or Ar is represented by the formula (ar-120). ) Is a mixture of a compound which is a group represented by formula (ar-121) and a compound which is a group represented by formula (ar-121). Similarly, the compound (xxxi) is a compound in which Ar is a group represented by the formula (ar-122) or a compound in which Ar is a group represented by the formula (ar-123), or Ar is represented by the formula (ar-122). Means a mixture of a compound that is a group represented by formula (ar-123) and a compound that is a group represented by formula (ar-123).

  Specific examples of the compounds in Table 1 include the following compounds. Compound (i), Compound (ii), Compound (iv), Compound (v), Compound (vi), Compound (ix), Compound (x), Compound (xi), Compound (xvi), Compound (xviii) ), Compound (xix), Compound (xx), Compound (xxi), Compound (xxiii), Compound (xxiv), Compound (xxv), Compound (xxvi), Compound (xxvii), Compound (xxviii) and Compound (xxix) ) Is a typical structural formula.

  Furthermore, examples of the compound (A) include the following.

  Furthermore, examples of the compound (A) include compounds represented by the formulas (A1-1) to (A68-8). In the formula, * represents a bond, for example, the compound represented by the formula (A1-1) is a compound represented as follows.

  In the retardation film (1) of the present invention, a plurality of different types of compounds (A) may be used in combination.

Compound (A) is a known organic synthesis reaction described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. (for example, condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama reaction, Buchwald-Heartwig reaction, Friedel-Craft reaction, Heck reaction, Aldol reaction, etc. ) Can be manufactured by appropriately combining depending on the structure.

For example, when D ¹ and D ² of the compound (A) are * —O—CO—, the formula (1-1)

［式中、Ａｒは上記と同一の意味を表わす。］
で示される化合物と式（１−２）

[Wherein Ar represents the same meaning as described above. ]
And a compound represented by formula (1-2)

［式中、Ｇ^１、Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１、Ｐ^１及びｋは上記と同一の意味を表わす。］
で示される化合物とを反応させることにより、式（１−３）

[Wherein, G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as described above. ]
Is reacted with a compound represented by formula (1-3)

［式中、Ａｒ、Ｇ^１、Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１、Ｐ^１及びｋは上記と同一の意味を表わす。］
で示される化合物を得て、得られた式（１−３）で示される化合物と式（１−４）

[Wherein Ar, G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as described above. ]
And a compound represented by the formula (1-3) and a formula (1-4)

［式中、Ｇ^２、Ｅ^２、Ａ^２、Ｂ^２、Ｆ^２、Ｐ^２及びｌは上記と同一の意味を表わす。］
で示される化合物とを反応させることにより製造することができる。

[Wherein, G ² , E ² , A ² , B ² , F ² , P ² and l represent the same meaning as described above. ]
It can manufacture by making the compound shown by react.

  The reaction between the compound represented by the formula (1-1) and the compound represented by the formula (1-2) and the reaction between the compound represented by the formula (1-3) and the compound represented by the formula (1-4) It is preferable to carry out in the presence of an esterifying agent.

  Examples of esterifying agents include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide met-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- Carbodiimides such as (3-dimethylaminopropyl) carbodiimide hydrochloride (partially water-soluble carbodiimide: commercially available as WSC), bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, diphenylphosphoryl azide, 1 (4-nitrobenzenesulfonyl) ) -1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N, N ′, N′-tetramethyl-O— (N-succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzoxysuccinimide, O- (6-chlorobenzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (6-chlorobenzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophos 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1- Examples thereof include methylpyridinium iodide, 2-chloro-1-methylpyridinium paratoluenesulfonate, 2-fluoro-1-methylpyridinium paratoluenesulfonate, and trichloroacetic acid pentachlorophenyl ester. Among them, from the viewpoint of reactivity, cost, and usable solvent, as the condensing agent, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide Hydrochloride, bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, and 2,2′-carbonylbis-1H-imidazole are preferred.

  The retardation plate (1) of the present invention comprises a compound (A) and a liquid crystal compound having a polymerizable group and different from the compound (A) (hereinafter sometimes referred to as a liquid crystal compound (A1)). A phase difference plate obtained by copolymerization may be used.

Specific examples of the liquid crystal compound (A1) are: Chapter 3 of Liquid Crystal Handbook (Edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000) 3.2 Non-chiral rod-like liquid crystal with molecular structure and liquid crystallinity Among the compounds described in Molecule, 3.3 Chiral rod-like liquid crystal molecule, there are compounds having a polymerizable group.
A plurality of different compounds may be used in combination as the liquid crystal compound (A1). Of these, compounds having a polymerizable group and exhibiting liquid crystallinity are preferred.

  Examples of the liquid crystal compound (A1) include a compound containing a group represented by the formula (D) (hereinafter sometimes referred to as “compound (D)”).

^{P 11 -B 11 -E 11 -B 12} -A 11 -B 13 - (D)
[In formula (D), P ¹¹ represents a polymerizable group.
A ¹¹ represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or It may be substituted with a nitro group. The hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
B ¹¹ is —O—, —S—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NR ¹⁶ —, —NR ¹⁶ —CO—, —CO—, -CS- or a single bond is represented. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B ¹² and ^{B 13} are each _{independently, -C≡C -, - CH = CH} -, - CH 2 -CH 2 -, - O -, - S -, - C (= O) -, - C ( = O) -O-, -OC (= O)-, -O-C (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C ( ═O) —NR ¹⁶ —, —NR ¹⁶ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O ) —O—, —O—C (═O) —CH═CH— or a single bond.
E ¹¹ represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. A hydrogen atom contained in the alkyl group and alkoxy group may be substituted with a halogen atom, and a methylene group contained in the alkylene group may be substituted with -O- or -CO-. ]

For example, photopolymerization may be used to cure the retardation plate. Therefore, P ¹¹ is preferably a radical polymerizable group or a cationic polymerizable group suitable for photopolymerization. In particular, the groups represented by the following formulas (P-1) to (P-5) are preferable because they are easy to handle and easy to produce.

［式（Ｐ−１）〜（Ｐ−５）中、Ｒ^１７〜Ｒ^２１はそれぞれ独立に、炭素数１〜６のアルキル基又は水素原子を表す。＊は、Ｂ^１１との結合手を表す。］

[In formulas (P-1) to (P-5), R ^{17 to} R ²¹ each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. * ^Represents a bond to ^{B 11.} ]

Further, P ¹¹ is preferably a group represented by formula (P-6) to formula (P-10), and is a vinyl group, p-stilbene group, epoxy group, oxetanyl group, isocyanate group, and thioisocyanate group. Etc.

In particular, P ¹¹ -B ^11- is preferably an acryloyloxy group or a methacryloyloxy group.

Carbon number of the aromatic hydrocarbon group and alicyclic hydrocarbon group in A ¹¹ is, for example, 3 to 18, preferably 5 to 12, and particularly preferably 5 or 6. A ¹¹ is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.

E ¹¹ is preferably an alkylene group having 1 to 12 carbon atoms which is not branched into two or more. The methylene group contained in the alkylene group may be substituted with -O-.

Specific examples of E ¹¹ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decalene group, undecalene group, dodecylene group, —CH ₂ —CH. _{2 -O-CH 2 -CH 2 -} , - CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 - and _{CH 2 -CH 2 -O-CH 2} -CH 2 -O _{-CH 2 -CH 2 -O-CH 2} -CH 2 - and the like.

  Examples of compound (D) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI).

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -A ¹⁴ -B ¹⁶ -E ¹² -B ¹⁷ -P ¹² (I)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -A ¹⁴ -F ¹¹ (II)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -E ¹² -B ¹⁷ -P ¹² (III)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -F ¹¹ (IV)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -E ¹² -B ¹⁷ -P ¹² (V)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -F ¹¹ (VI)
[Wherein, P ¹² represents the same meaning as P ¹¹ .
A ^{12 to} A ¹⁴ represent the same meaning as A ¹¹ .
B ^{14 to} B ¹⁶ have the same meaning as B ¹² and B ¹⁷ has the same meaning as B ¹¹ .
E ^{12 represents} the same meaning as ^{E 11.}
F ¹¹ is a hydrogen atom, an alkyl group of 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a nitrile group, a nitro group, a trifluoromethyl group, dimethylamino group, hydroxy group, a methylol group, an aldehyde group, a sulfonic An acid group, a carboxy group, a carboxy group esterified with an alcohol having 1 to 10 carbon atoms, or a halogen atom is represented. The methylene group contained in the alkyl group and alkoxy group may be substituted with -O-. ]

  Examples of the compound (D) include compounds represented by the following formulas. These liquid crystal compounds are preferable because they are commercially available and can be easily obtained and can be easily synthesized. In the formula, k1 and k2 represent an integer of 2 to 12.

  The content of the compound (A) is preferably 10 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more, with respect to 100 parts by mass of the total amount of the compound (A) and the liquid crystal compound (A1). 100 parts by mass or less. When the content of the compound (A) is within the above range, it tends to exhibit a larger reverse wavelength dispersion characteristic, which is preferable.

  The wavelength dispersion characteristic of the composite retardation plate of the present invention is determined by the content of the structural unit derived from the compound (A) and the content of the structural unit derived from the compound (A1) in the retardation plate (1). Can do. In the retardation plate (1), when the content of the structural unit derived from the compound (A) is increased, the reverse wavelength dispersion characteristic is further exhibited.

  Specifically, the wavelength dispersion characteristic of the composite retardation plate of the present invention can be determined as follows. First, about 2 to 5 types of compositions having different contents of structural units derived from the compound (A) are prepared. As will be described later for each composition, a retardation plate having the same film thickness is produced, and the retardation value of the obtained retardation plate is determined. From the result, the correlation between the content of the structural unit derived from the compound (A) and the retardation value of the retardation plate is obtained, and from the obtained correlation, the desired retardation value is obtained in the retardation plate at the above film thickness. The content of the structural unit derived from the compound (A) necessary for providing the above is determined.

Hereinafter, at least one selected from the group consisting of the compound (A) and the liquid crystal compound (A1) may be collectively referred to as “liquid crystal monomer”.
The phase difference plate (1) was obtained by, for example, applying a solution containing a liquid crystal monomer and an organic solvent on a support substrate, an alignment film, etc., and then removing the organic solvent to obtain a coating film. It can be produced by polymerizing the liquid crystal monomer in the coating film. An alignment film may be formed on the support substrate.

Hereinafter, the manufacturing method of a phase difference plate (1) is demonstrated.
[(I) Step of mixing liquid crystal monomer and organic solvent to obtain a solution]
First, a solution containing a liquid crystal monomer and an organic solvent (hereinafter abbreviated as solution (1)) is prepared by dissolving the liquid crystal monomer in an organic solvent. If necessary, additives such as a polymerization initiator, a polymerization inhibitor, a photosensitizer, a crosslinking agent, and a leveling agent may be contained in the solution (1). In particular, it preferably contains a polymerization initiator because it has a function of curing the obtained retardation plate. The solution (1) may be mixed with a compound other than the liquid crystal monomer for the purpose of controlling the optical characteristics of the retardation plate.

[Organic solvent]
As the organic solvent, any organic solvent that can dissolve the liquid crystal monomer can be used without particular limitation. Specifically, alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, phenol; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, Ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; Non-chlorine aliphatic hydrocarbon solvents such as pentane, hexane, and heptane Non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; tetrahydrofuran, dimethoxy Ether solvents such as Tan; chloroform, chlorinated hydrocarbon solvents such as chlorobenzene and the like. These organic solvents may be used alone or in combination of two or more. The organic solvent may contain water.
In particular, since the liquid crystal monomer described above is excellent in compatibility, an alcohol solvent, an ester solvent, a ketone solvent, a non-chlorine aliphatic hydrocarbon solvent, and a non-chlorine system can be used without using a chlorine-based hydrocarbon solvent such as chloroform. It can be dissolved in an aromatic hydrocarbon solvent, and the solution (1) can be prepared.
The content of the organic solvent is usually 50 to 95% by mass, preferably 60 to 95% by mass, and more preferably 70 to 90% by mass with respect to the solution (1). When the content of the organic solvent is within the above range, coating unevenness is unlikely to occur and the desired film thickness tends to be easily obtained.

[Polymerization initiator]
As described above, the solution (1) preferably contains a polymerization initiator for polymerizing the liquid crystal monomer. Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, and the like. A photopolymerization initiator is preferable in that a liquid crystal monomer can be stably polymerized at a low temperature.
Examples of thermal polymerization initiators include azo initiators such as 2,2′-azobis (isobutyronitrile) and 4,4′-azobis (4-cyanovaleric acid), peroxides such as benzoyl peroxide, and the like. Can be mentioned.
Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, iodonium salts, sulfonium salts and the like. Specifically, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, and Irgacure 369 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), Sake All BZ, Sake All Z, Sake All BEE (all All Seiko) Chemical Co., Ltd.), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152, Adekaoptomer SP-170 (all manufactured by ADEKA), etc. Is mentioned.
Content of a polymerization initiator is 0.1 mass part-30 mass parts normally with respect to a total of 100 mass parts of a liquid crystal monomer, Preferably it is 0.5 mass part-10 mass parts. When the content of the polymerization initiator is within the above range, it is preferable because polymerization can be performed without disturbing the orientation of the liquid crystal monomer.

[Polymerization inhibitor]
The solution (1) may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone compounds having substituents such as hydroquinone and alkoxy groups (for example, methoxy group), catechol compounds having substituents such as alkoxy groups (for example, methoxy group) such as butylcatechol, and pyrogallol. Examples thereof include compounds, radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinyloxy radical, thiophenol compounds, β-naphthylamine compounds, β-naphthol compounds and the like.
By using a polymerization inhibitor, the polymerization of the liquid crystal monomer can be easily controlled, and the stability of the obtained retardation plate and the stability of the solution (1) can be improved. Content of a polymerization inhibitor is 0.1 mass part-30 mass parts normally with respect to a total of 100 mass parts of a liquid crystal monomer, Preferably it is 0.5 mass part-10 mass parts. When the content of the polymerization inhibitor is within the above range, it is preferable because polymerization can be performed without disturbing the orientation of the liquid crystal monomer.

[Photosensitizer]
Solution (1) may contain a photosensitizer. Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone, anthracene, anthracene compounds having a substituent such as an alkoxy group (for example, methoxy group), phenothiazine, and rubrene.
By using a photosensitizer, the liquid crystal monomer can be polymerized with higher sensitivity.
Content of a photosensitizer is 0.1 mass part-30 mass parts normally with respect to a total of 100 mass parts of a liquid crystal monomer, Preferably it is 0.5 mass part-10 mass parts. It is preferable that the content of the photosensitizer is in the above range because polymerization can be performed without disturbing the orientation of the liquid crystal monomer.

[Leveling agent]
Solution (1) may contain a leveling agent. As leveling agents, additives for radiation-curing coatings (BYK-352: BYK-352, BYK-353, BYK-361N), coating additives (Toray Dow Corning: SH28PA, DC11PA, ST80PA), coating additives Agents (manufactured by Shin-Etsu Silicone Co., Ltd .: KP321, KP323, X22-161A, KF6001), fluorine-based additives (manufactured by DIC Corporation: F-445, F-470, F-479) and the like.
By using a leveling agent, a smoother retardation plate can be obtained. Furthermore, in the manufacturing process of the phase difference plate, the fluidity of the solution (1) can be controlled, and the crosslinking density of the phase difference plate can be adjusted. Content of a leveling agent is 0.01 mass part-30 mass parts normally with respect to a total of 100 mass parts of a liquid crystal monomer, Preferably it is 0.01 mass part-10 mass parts. It is preferable that the content of the leveling agent is in the above range because polymerization can be performed without disturbing the orientation of the liquid crystal monomer.

The solution (1) is usually adjusted to a viscosity of 10 mPa · s or less, preferably about 0.1 to 7 mPa · s so that it can be easily applied after mixing and dissolving the above components.
The solid content in the solution (1) is usually 5 to 50% by mass, preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. Here, solid content means the total amount of the component remove | excluding the solvent from the solution (1).

[(Ii) Step of obtaining a coating film from the solution obtained in step (i)]
A coating film is obtained by applying the solution (1) obtained in the step (i) on a support base material, an alignment film or the like and then removing the organic solvent. Preferably, after applying the solution (1) on the alignment film, the organic solvent is removed to obtain a coating film.

[Alignment film]
The alignment film has solvent resistance that does not dissolve in the solution (1), has heat resistance in the heat treatment for removing the organic solvent and adjusting the alignment of the liquid crystal monomer, and does not peel off due to rubbing friction or the like. It is necessary to satisfy that.
The alignment film contains a polymer. Examples of the polymer include polyamide and gelatin having an amide bond in the molecule, polyimide having an imide bond in the molecule, and a hydrolyzate thereof, polyamic acid, polyvinyl alcohol, and alkyl-modified polyvinyl alcohol. , Polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid esters. These polymers may be used alone, or may be used by mixing two or more kinds or making a copolymer. These polymers can be easily obtained by polycondensation such as dehydration and deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

  Such a polymer is usually dissolved in a solvent and applied onto a supporting substrate. Although it does not restrict | limit as a solvent, For example, Water; Alcohol solvents, such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve; Ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, (gamma) -butyrolactone, propylene Ester solvents such as glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; Toluene, xylene , Aromatic hydrocarbon solvents such as chlorobenzene, nitrile solvents such as acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran Down, ether solvents such as dimethoxyethane; halogenated hydrocarbon solvents such as chloroform and the like. These organic solvents may be used alone or in combination of two or more.

In order to form the alignment film, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries), Optomer (registered trademark, manufactured by JSR), and the like.
If such an alignment film is used, the alignment of the liquid crystal monomer is facilitated, so that in-plane variation in birefringence is reduced. Therefore, there is an effect that it is possible to provide a large retardation plate that can cope with an increase in the size of the FPD. In addition, alignment control becomes easier depending on the material of the alignment film, rubbing conditions, etc., and various alignments such as horizontal alignment, vertical alignment, hybrid alignment, and tilt alignment can be obtained, improving the viewing angle of various liquid crystal panels. Can be used for etc.

The alignment film can be formed, for example, by applying a commercially available alignment film material or a solution of a compound serving as a material of the alignment film on a supporting substrate, and then annealing.
The thickness of the alignment film is usually 10 nm to 10000 nm, preferably 10 nm to 1000 nm. When the thickness of the alignment film is in the above range, the liquid crystal monomer can be aligned in a desired direction or angle on the alignment film when the solution (1) is applied, which is preferable.

These alignment films are usually irradiated with rubbing or polarized ultraviolet rays. By using the alignment film subjected to these treatments, the liquid crystal monomer can be aligned in a desired direction or angle.
Examples of the method for rubbing the alignment film include a method in which a rubbing cloth is wound and a rotating rubbing roll is brought into contact with the alignment film on the support substrate which is carried on the stage.

  Examples of the method for preparing the alignment film by applying the alignment film material on the supporting substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, the method of apply | coating using coaters, such as a dip coater, a bar coater, a spin coater, is also mentioned.

The support substrate may be any material that can form an alignment film on the support substrate. For example, glass, a plastic sheet, a plastic film, a translucent film, etc. are mentioned. Translucent films include polyolefin films such as polyethylene, polypropylene, norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylate films, polyacrylate films, cellulose ester films, polyethylene naphthalate films, polycarbonate films , Polysulfone film, polyether sulfone film, polyether ketone film, polyphenylene sulfide film, polyphenylene oxide film and the like.
The retardation plate (1) of the present invention is usually a thin film. For example, when the composite retardation plate of the present invention is joined to another member or the retardation plate (1) is transported and stored. Even when equal film strength is required, it can be easily handled without tearing or the like by using a supporting substrate.

Examples of the method for applying the solution (1) to the alignment film include the same application method as described above for applying the alignment film material to the supporting substrate.
By appropriately adjusting the coating amount of the solution (1) and the amount of the organic solvent in the solution (1), the thickness of the retardation plate (1) can be adjusted so as to give a desired retardation. Since the retardation value (retardation value, R ₀ (λ)) in the front direction in the retardation plate (1) is determined by the equation (7), in order to obtain a desired R ₀ (λ), a film The thickness d may be adjusted.
R ₀ (λ) = d × Δn (λ) (7)
[Wherein R ₀ (λ) represents a retardation value at a wavelength of λ nm, d represents a film thickness, and Δn (λ) represents a refractive index anisotropy at a wavelength of λ nm. ]

  What is necessary is just to select suitably the phase difference value of the phase difference plate (1) obtained from the range of about 30-300 nm by the use of a composite phase difference plate. For example, when the composite retardation plate is applied to a relatively small liquid crystal display device such as a mobile phone or a portable information terminal, it is advantageous that the retardation plate (1) is a λ / 4 plate.

For example, in order to use the retardation plate (1) as a broadband λ / 4 plate or λ / 2 plate, the content of the structural unit derived from the liquid crystal monomer is appropriately selected, and the retardation plate according to the formula (7) What is necessary is just to adjust the film thickness of (1). The film thickness in the retardation plate (1) is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm from the viewpoint of reducing photoelasticity.
Specifically, in the case of a λ / 4 plate, R ₀ (550) of the obtained retardation plate (1) may be adjusted to 113 to 163 nm, preferably 130 to 150 nm. In such a case, R ₀ (550) of the obtained retardation plate may be adjusted to 250 to 300 nm, preferably 265 to 285 nm. In order to obtain a desired retardation value, the film thickness is also adjusted.

  The organic solvent is removed simultaneously with or after the application of the solution (1). Examples of the method for removing the organic solvent include natural drying, ventilation drying, and drying under reduced pressure. As removal temperature, it is preferable that it is 10-150 degreeC, and it is more preferable that it is 25-120 degreeC. The removal time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When the removal temperature and the removal time are within the above ranges, it is preferable because a support substrate and an alignment film having relatively low heat resistance can be used.

  The coating film obtained by removing the organic solvent is composed of an unpolymerized liquid crystal monomer. The coating film usually has birefringence due to monodomain alignment because the liquid crystal monomer gives a phase exhibiting liquid crystallinity such as a nematic phase. The coating film is usually oriented at a low temperature of about 0 to 150 ° C., preferably 25 to 120 ° C. After removing the organic solvent, heating may be further performed to adjust the alignment state of the liquid crystal monomer.

[(Iii) Step of obtaining a retardation plate (1) by polymerizing a liquid crystal monomer]
The coating film obtained in step (ii) contains an unpolymerized liquid crystal monomer, and the phase difference plate (1) is obtained by polymerizing this. Specifically, the obtained coating film is irradiated with light, or the coating film is heated, or the coating film is irradiated with light and heated to polymerize the liquid crystal monomer, thereby causing retardation plate (1). Can be obtained.
If the polymerizable group contained in the liquid crystal monomer is photopolymerizable, the polymerization is carried out by irradiating with light such as visible light, ultraviolet light, laser light or the like. Moreover, if this polymeric group is thermopolymerizable, it will be implemented by heating. Photopolymerization is preferred from the viewpoint of film formability, and polymerization by ultraviolet light is more preferred from the viewpoint of handleability.

The obtained retardation plate (1) preferably exhibits positive uniaxiality. In order for the retardation film (1) to exhibit positive uniaxiality, it is usually sufficient to use a liquid crystal monomer having a rod-like molecular shape.
The rod-like molecular shape of the liquid crystal monomer is a compound having two or more divalent mesogenic groups and a group connecting the mesogenic group and the mesogenic group.

[Phase difference plate (2)]
The retardation plate (2) used in the present invention contains an organically modified clay complex and a binder resin, and includes a coating liquid (hereinafter referred to as coating) containing an organically modified clay complex, a binder resin, and an organic solvent. It can be obtained by removing the organic solvent from the liquid (abbreviated as liquid (2)).
An organically modified clay complex is a complex of an organic substance and a clay mineral, specifically, a complex of a clay mineral having a layered structure and an organic compound, which can be dispersed in an organic solvent. is there.

Examples of the clay mineral having a layered structure include a smectite group, a swellable mica, and the like, and complexation with an organic compound is possible due to its cation exchange ability. In particular, a clay mineral belonging to the smectite group is preferable because of its excellent transparency. Examples of the clay mineral belonging to the smectite group include hectorite, montmorillonite, and bentonite. Among them, a chemically synthesized product is preferable in that it has few impurities and is excellent in transparency. In particular, synthetic hectorite having a controlled particle size is preferably used because scattering of visible light is suppressed.
In particular, an organically modified clay complex having an atomic ratio (Mg / Si ₄ ) between magnesium and silicon 4 atoms belonging to the smectite group of 0.01 or more and less than 2.73 is preferable.

Examples of the organic substance that can be combined with the clay mineral include a compound that can react with an oxygen atom or a hydroxy group of the clay mineral, or an ionic compound that can be exchanged with an exchangeable cation. Specifically, a nitrogen-containing compound in which 1 to 4 hydrocarbon groups having 1 to 30 carbon atoms are bonded to a nitrogen atom, a phosphonium salt in which 4 hydrocarbon groups having 1 to 30 carbon atoms are bonded to a phosphorus atom, Examples thereof include a sulfonium salt in which three hydrocarbon groups having 1 to 30 carbon atoms are bonded to a sulfur atom. Examples of the nitrogen-containing compound include primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
As a C1-C30 hydrocarbon group, a C1-C30 alkyl group, a C1-C30 alkylene group, a C7-C30 aralkyl group, etc. are mentioned. It is preferable that at least one is a hydrocarbon group having 4 to 20 carbon atoms, and it is more preferable that at least one is a hydrocarbon group having 6 to 10 carbon atoms. As the nitrogen-containing compound, a quaternary ammonium salt is preferable.

Two or more organic modified clay composites can be used in combination. Commercially available products of suitable organically modified clay composites include composites of synthetic hectorite and quaternary ammonium salts sold under the trade names “Lucentite STN” and “Lucentite SPN” by Corp Chemical Co., Ltd. Etc.
Depending on its origin, the organically modified clay complex may contain chlorine in the form of chlorine ions, and the chlorine content in the coating liquid (2) is 2,000 ppm or less, for example, The organically modified clay complex is preferably washed with water.

  The binder resin is a resin in which an organically modified clay complex is dispersed and dissolved in an organic solvent such as toluene, xylene, acetone, or ethyl acetate. Particularly, a resin having a glass transition temperature of room temperature or lower (about 20 ° C. or lower). preferable. Preferred binder resins include polyvinyl acetal resins such as polyvinyl butyral and polyvinyl formal, cellulose resins such as cellulose acetate butyrate, acrylic resins such as butyl acrylate, urethane resins, methacrylic resins, epoxy resins and polyester resins. Can be mentioned.

  Commercially available binder resins include polyvinyl alcohol aldehyde-modified resins sold under the trade name “Denkabutyral # 3000-K” by Denki Kagaku Kogyo Co., Ltd., and “Aron S1601” from Toagosei Co., Ltd. Examples include acrylic resins sold under the name, isophorone diisocyanate-based urethane resins sold under the trade name “SBU Lacquer 0866” by Sumika Bayer Urethane Co., Ltd.

  The mass ratio of the organic modified clay complex to the binder resin (organic modified clay complex: binder resin) in the phase difference plate (2) is usually 1: 2 to 10: 1, preferably 1: 1 to 2: 1. .

  The organic solvent in the coating liquid (2) is not particularly limited as long as it is an organic solvent that can disperse the organic modified clay complex and dissolve the binder resin. Specifically, methanol, ethanol, ethylene glycol, isopropyl Alcohol solvents such as alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, phenol; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; non-chlorine aliphatic hydrocarbon solvents such as pentane, hexane and heptane Nitrile solvents such as acetonitrile; tetrahydrofuran, ether solvents such as dimethoxyethane: toluene, non-chlorinated aromatic hydrocarbon solvents such as xylene chloroform, chlorinated hydrocarbon solvents such as chlorobenzene and the like. These organic solvents may be used alone or in combination of two or more.

  The retardation plate (2) thus obtained exhibits negative uniaxiality.

[Composite retardation plate]
In the composite retardation plate of the present invention, the retardation plate (1) and the retardation plate (2) may be joined, or a primer layer between the retardation plate (1) and the retardation plate (2). May be provided.
The composite phase difference plate in which the phase difference plate (1) and the phase difference plate (2) are joined can be manufactured by, for example, the following method.

[(Iv) Step of preparing coating liquid (2)]
A coating liquid (2) is prepared by mixing the organically modified clay complex, the binder resin, and the organic solvent. Usually, the binder resin is dissolved in an organic solvent, and the organic modified clay complex is dispersed in the organic solvent. The total concentration of the organically modified clay complex and the binder resin in the coating liquid (2) may be diluted to such an extent that the coating liquid (2) does not gel or become cloudy as long as there is no practical problem. 3 to 15% by mass. The optimum concentration differs depending on the types of the organically modified clay complex and the binder resin and the composition ratio of the two, and may be set for each composition. Moreover, you may add various additives, such as a viscosity modifier for improving the applicability | paintability at the time of film forming, and a crosslinking agent for improving hydrophobicity and / or durability further.

  The chlorine content in the coating liquid (2) is preferably 2,000 ppm or less. When the chlorine content in the coating liquid (2) is 2,000 ppm or less, the liquid crystal cell glass tends to be strongly bonded to the surface of the obtained retardation plate (2) via the adhesive layer. Yes, it is preferable. In order to adjust the chlorine content in the coating liquid (2) to 2,000 ppm or less, as described above, a method of washing the organically modified clay complex with water and the like can be mentioned.

  The moisture content of the coating liquid (2) measured with a Karl Fischer moisture meter is preferably in the range of 0.15 to 0.35% by mass. When the water content is 0.35% by mass or less, the coating liquid (2) tends to be difficult to separate into an aqueous phase and an organic phase, and when the water content is 0.15% by mass or more, a retardation plate ( It is preferable because it tends to suppress the haze value of 2).

[(V) Step of applying composite liquid (2) to retardation plate (1) to obtain a composite retardation plate]
Examples of a method for applying the coating liquid (2) onto the retardation plate (1) include coating methods such as a direct gravure method, a reverse gravure method, a die coating method, a comma coating method, and a bar coating method.

The refractive index anisotropy in the thickness direction of the retardation plate (2) is represented by a thickness direction retardation value _Rth defined by the equation (8), and this value tilts the in-plane fast axis. It can be calculated from the phase difference value R ₄₀ measured with the axis tilted by 40 degrees and the in-plane phase difference value R ₀ . That is, the retardation value R _{th in the} thickness direction according to the equation (8) is the in-plane retardation value R ₀ , the retardation value R ₄₀ measured by tilting 40 degrees with the fast axis as the tilt axis, and the film thickness d. , and using the mean refractive index n ₀ of the film to obtain the n _x, n _y and n _z numerically from the following equation (9) to (11), these are substituted into equation (8), is calculated be able to.

_Rth = [( _nx + _ny ) / 2- _nz ] * d (8)
_{R 0 = (n x -n y} ) × d (9)
R ₄₀ = (n _x −ny _y ) × d / cos (φ) (10)
(n _x + _ny + _nz ) / 3 = n ₀ (11)
here,
φ = sin ⁻¹ [sin (40 °) / n ₀ ]
n _y ′ = _ny × _nz / [ _ny ² × sin ² (φ) + _nz ² × cos ² (φ)] ^1/2

The thickness direction retardation R _th retardation plate (2) is, from the range of about 40 to 300 nm, their use, in particular according to the characteristics of the liquid crystal cell is preferably selected as appropriate. The thickness direction retardation value _Rth is preferably 50 nm or more and 200 nm or less.

Next, the obtained coating film is heated to remove the organic solvent, whereby a composite retardation plate in which the retardation plate (1) and the retardation plate (2) are joined can be obtained.
The heating temperature is usually 0 to 150 ° C, preferably 25 to 120 ° C.

  The composite phase difference plate of the present invention includes the phase difference plate (1) and the phase difference plate (2), and may include an alignment film, a support base material, a primer layer, and the like. For example, as shown in FIGS. 1 (a), 2 (a), 2 (c) and 2 (e), the retardation plate (1) 11 and the retardation plate (2) 12 are joined. For example, as shown in FIGS. 1 (b), 2 (b), 2 (d) and 2 (f), the phase difference plate (1) and the phase difference plate (1) The primer layer 13 may be provided between the phase difference plate (2).

  As shown in FIG. 2A, in the composite retardation plate of the present invention, the retardation plate (1) and the retardation plate (2) are joined, and the retardation plate (1) of the retardation plate (1) ( The support base material 14 may be bonded to the surface opposite to the surface to which 2) is bonded. As shown in FIGS. 2C and 2E, the phase difference plate (1) and the phase difference plate (2) are joined, and the phase difference plate (2) of the phase difference plate (1) is joined. The alignment film 15 may be bonded to the surface opposite to the surface. As shown in FIG.2 (c), the support base material 14 may be joined to the surface on the opposite side to the surface where the phase difference plate (1) of the alignment film was joined.

As shown in FIG. 2 (b), the composite phase difference plate of the present invention has a primer layer 13 formed between the phase difference plate (1) and the phase difference plate (2). The support base material 14 may be bonded to the surface opposite to the surface where the primer layer 13 is bonded. As shown in FIGS. 2D and 2F, a primer layer 13 is formed between the phase difference plate (1) and the phase difference plate (2), and the primer layer 13 of the phase difference plate (1). The alignment film 15 may be bonded to the surface opposite to the surface to which is bonded. As shown in FIG. 2D, the support base material 14 may be bonded to the surface of the alignment film 15 opposite to the surface to which the retardation film (1) is bonded.
The composite phase difference plate shown in FIGS. 2A to 2F may be used as it is, or may be used after peeling and transferring the support base or the support base and the alignment film. Good.
As a method of peeling and transferring the support substrate or the support substrate and the alignment film, a pressure-sensitive adhesive layer to be described later is laminated on the support substrate to which the composite retardation plate of the present invention is laminated, and then the support substrate and the orientation are aligned. Examples include a method in which the film is peeled off at the same time, or only the supporting substrate is peeled off and bonded to the pressure-sensitive adhesive layer.

The composite retardation plate of the present invention can discuss the shape of the refractive index ellipsoid of the retardation plate with a numerical value called an Nz coefficient. The Nz coefficient is calculated by the following equation (12).
_{Nz = (n x -n z)} / (n x -n y) (12)
A composite retardation plate having an Nz coefficient of 1.1 to 2.0, preferably 1.2 to 1.8 is a circularly polarized mode, and is bonded to a liquid crystal cell of a vertical alignment (VA) mode to be a medium-to-small size. It is suitably used for a liquid crystal panel for a liquid crystal display device. A composite retardation plate having an Nz coefficient of 2.0 to 5.0, preferably 2.5 to 4.5 is a linearly polarized mode, and is bonded to a liquid crystal cell in a vertical alignment (VA) mode, It is suitably used for a liquid crystal panel for a liquid crystal display device.
Since the Nz coefficient is adjusted for each liquid crystal panel, a composite retardation plate having a desired Nz coefficient is prepared simply by adjusting the thickness of the retardation plate (1) and the thickness of the retardation plate (2). can do.

  The composite retardation plate of the present invention is usually a significantly thinned composite retardation plate in which a positive uniaxial retardation plate and a negative uniaxial retardation plate are laminated. In addition, the composite retardation plate is reduced in weight because it is thin.

[Primer layer]
The primer layer is usually formed from a primer that is a transparent resin. It is preferable to provide a primer layer because defects and coating unevenness at the time of film formation of the retardation plate (2) formed by coating can be suppressed. Moreover, it is preferable to provide a primer layer also from the point that the influence to the phase difference plate (1) by the organic solvent in the coating liquid (2) can be prevented.
The primer layer can be formed by applying a primer layer resin solution on the retardation plate (1) and removing the solvent. As the primer, a primer excellent in coating property, particularly excellent in transparency and adhesion after layer formation is preferable.

  The primer may be dissolved in a solvent, or the resin may be diluted with a solvent in order to adjust the film thickness. Aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc .; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate, isobutyl acetate; methylene chloride, trichloroethylene, chloroform, etc. A common organic solvent such as ethanol, 1-propanol, 2-propanol, 1-butanol and other alcohol solvents can be used, but a primer layer is formed using a solution containing the organic solvent. Then, since the optical properties of the retardation plate (1) may be affected, it is preferable to form the primer layer using a solution containing water as a solvent.

  As the resin for the primer layer, polyvinyl alcohol resin, epoxy resin, polyvinyl acetal resin (for example, polyvinyl butyral, polyvinyl formal, etc.), cellulose resin (for example, cellulose acetate butyrate), (meth) acrylic resin (for example, polybutyl acrylate) , Urethane resin, polyester resin and the like. Among these, polyvinyl alcohol resin and epoxy resin are preferable. As the epoxy resin, a one-component curing type or a two-component curing type may be used. A water-soluble epoxy resin is particularly preferable. As a water-soluble epoxy resin, a polyamide epoxy resin obtained by reacting epichlorohydrin with a polyamide polyamine obtained by reacting a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid. Is mentioned. Commercially available products of such polyamide epoxy resins include “Smileys Resin (registered trademark) 650 (30)” and “Smileys Resin (registered trademark) 675” (registered trademark) sold by Sumika Chemtex Co., Ltd. Is mentioned.

  When a water-soluble epoxy resin is used as the primer, it is preferable to use other water-soluble resin such as polyvinyl alcohol resin in combination in order to further improve the coatability. Polyvinyl alcohol resins are modified polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxy group modified polyvinyl alcohol, acetoacetyl group modified polyvinyl alcohol, methylol group modified polyvinyl alcohol, amino group modified polyvinyl alcohol. Alcohol-based resin may be used. Examples of suitable commercially available polyvinyl alcohol resins include “KL-318” (trade name), which is an anionic group-containing polyvinyl alcohol sold by Kuraray Co., Ltd.

  When forming a primer layer from the solution containing a water-soluble epoxy resin, it is preferable that an epoxy resin shall be the range of about 0.2-1.5 mass parts with respect to 100 mass parts of water. Moreover, when mix | blending a polyvinyl alcohol-type resin with this solution, it is preferable that the quantity shall be about 1-6 mass parts with respect to 100 mass parts of water. The thickness of the primer layer is preferably in the range of about 0.1 to 10 μm.

  The method for forming the primer layer is not limited, and various known coating methods such as a direct gravure method, a reverse gravure method, a die coating method, a comma coating method, and a bar coating method can be used.

[(Vi) Step of forming primer layer on retardation plate (1)]
For example, a primer layer can be obtained by applying a solution of a primer dissolved in water or an organic solvent on the retardation plate (1) and drying it. A drying temperature is about 0-150 degreeC normally, Preferably it is 25-120 degreeC.

[(Vii) Step of forming retardation plate (2) on primer layer]
A composite phase difference plate can be obtained by applying the coating liquid (2) onto the obtained primer layer and drying it.

[Polarizing member]
The polarizing member of the present invention includes the composite retardation plate and the polarizing plate of the present invention. The polarizing member is usually a composite retardation plate, a pressure-sensitive adhesive layer, and a polarizing plate laminated in this order, and specific examples thereof include the polarizing members shown in (a) to (f) of FIG. It is done.
The polarizing member 18 in FIG. 3A is a polarizing member in which the composite retardation plates 11 and 12, the pressure-sensitive adhesive layer 16, and the polarizing plate 17 in FIG. 1A are laminated in this order. The polarizing member in FIG. 3B is a polarizing member in which the composite retardation plate, the pressure-sensitive adhesive layer, and the polarizing plate in FIG. 1B are laminated in this order.
The polarizing member in FIG. 3C is a polarizing member in which the composite retardation plate, the pressure-sensitive adhesive layer, and the polarizing plate in FIG. 2E are laminated in this order. The polarizing member in FIG. 3D is a polarizing member in which the composite retardation plate, the pressure-sensitive adhesive layer, and the polarizing plate in FIG. 2F are laminated in this order. The polarizing member in FIG. 3 (e) is a polarizing member in which the composite retardation plate, the pressure-sensitive adhesive layer, and the polarizing plate in FIG. 2 (c) are laminated in this order. The polarizing member in FIG. 3 (f) is a polarizing member in which the composite retardation plate, the pressure-sensitive adhesive layer, and the polarizing plate in FIG. 2 (d) are laminated in this order.

  The polarizing plate may be any material that transmits linearly polarized light having a vibration surface in one direction within the plane and absorbs linearly polarized light having a vibration surface in a direction perpendicular to the surface within the surface. For example, a film having a polarizer stretched by adsorbing iodine or dichroic dye on a polyvinyl alcohol film, a film having a polarizer stretched by adsorbing iodine or dichroic dye, etc. Can be mentioned. Moreover, although such a polarizer may be utilized alone as a polarizing plate, it is preferable to use a polarizer in which a protective film is bonded to at least one side (one side or both sides) of the polarizer. As this protective film, a cellulose resin such as triacetyl cellulose, a cyclic polyolefin resin using a polycyclic cyclic olefin such as norbornene as a monomer, and the like are used.

  The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer can be composed of an acrylic polymer, a silicone polymer, polyester, polyurethane, polyether, or the like as a base polymer. In particular, like acrylic pressure-sensitive adhesives, it has excellent optical transparency, retains appropriate wettability and cohesion, has excellent adhesion to substrates, and has weather resistance and heat resistance. It is preferable to select and use one that does not cause peeling problems such as floating and peeling under the conditions of heating and humidification. In the acrylic adhesive, a functional group comprising an alkyl ester of acrylic acid having an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, or a butyl group, and (meth) acrylic acid or hydroxyethyl (meth) acrylate. An acrylic copolymer having a weight average molecular weight of 100,000 or more, in which a glass transition temperature is preferably 25 ° C. or lower, more preferably 0 ° C. or lower, is useful as a base polymer. It is.

[Optical member]
The optical member of the present invention includes the composite retardation plate and the color filter of the present invention.
Specifically, as shown in FIG. 5A, a color filter layer 20 is formed on a support substrate, and a retardation plate (1) and a retardation plate (2) are formed thereon as described above. The optical member obtained by forming sequentially is mentioned. Further, as shown in FIG. 5B, the color filter layer 20 is formed on the support substrate 14, and the retardation plate (1), the primer layer 13 and the retardation plate (2) are formed thereon as described above. And an optical member obtained by sequentially forming a). Further, as shown in FIG. 5C, an optical member in which the support base material 14, the color filter layer 20, the alignment film 15, the retardation plate (1), and the retardation plate (2) are laminated in this order. As shown in FIG. 5 (d), the support substrate 14, the color filter layer 20, the alignment film 15, the retardation plate (1), the primer layer 13 and the retardation plate (2) are laminated in this order. The optical member etc. which become are also mentioned.
In addition, as shown in FIG. 5 (e), an optical member formed by laminating a color filter layer 20 on a composite retardation plate including a support substrate 14, a retardation plate (1) and a retardation plate (2), As shown in FIG. 5 (f), an optical member formed by laminating a support substrate 14, a retardation plate (1), a primer layer 13, a retardation plate (2) and a color filter layer 20 in this order, 5 (g), an optical member in which the support base material 14, the alignment film 15, the retardation film (1), the retardation film (2), and the color filter layer 20 are laminated in this order, As shown in (h), the support member 14, the alignment film 15, the retardation film (1), the primer layer 13, the retardation film (2), and the color filter layer 20 are laminated in this order. Etc.

A liquid crystal cell can be produced by a conventional method using the optical member of the present invention. In addition, a liquid crystal display (LCD) can also be manufactured by a conventional method using the manufactured liquid crystal cell.
A liquid crystal cell including the optical member of the present invention has improved viewing angle and color reproducibility.

[Liquid Crystal Display]
The liquid crystal display device of the present invention (hereinafter sometimes referred to as LCD) includes the polarizing member and the liquid crystal cell of the present invention. Specifically, the LCD and polarizing member in which the polarizing member is disposed on one surface of the liquid crystal cell LCD which is arranged on both sides of the liquid crystal cell.
As shown in FIG. 4, the polarizing member 18 and the liquid crystal cell 19 are usually laminated via the pressure-sensitive adhesive layer 16.
The polarizing member of the present invention is disposed on one surface of the liquid crystal cell, and a polarizing member (for example, a polarizing plate) other than the polarizing member of the present invention is disposed on the other surface of the liquid crystal cell with the same adhesive layer as described above. It may be provided. Further, the polarizing member of the present invention is disposed on one side of the liquid crystal cell, and the other phase of the liquid crystal cell is a composite retardation plate of the present invention, a composite retardation plate other than the present invention, or a normal retardation plate. May be joined. According to the above configuration, when a voltage is applied to the liquid crystal panel using an electrode (not shown), the liquid crystal molecules are driven to produce an optical shutter effect.
Examples of the liquid crystal cell include a TN (Twisted Nematic) method, an STN (Super Twisted Nematic) method, a VA (Vertical Alignmen) method, an IPS (In-plane Switching) method, an ECB (Electrically Controlled Bireviringence) method, and the like. The VA method and the ECB method are preferable, and the VA method is particularly preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples. In the examples, the part representing the content or amount used is based on mass unless otherwise specified. The compositions of the solution (1) and the coating solution (2) used in the following examples are as follows.

[Solution (1)]
Each component was mixed so that it might become a composition shown in Table 2, and after stirring the obtained solution at 80 degreeC for 1 hour, it cooled to room temperature and prepared the solution (1).

Photopolymerization initiator: Irgacure 819 (manufactured by Ciba Japan)
Leveling agent: BYK361N (by Big Chemie Japan)
Organic solvent: Chloroform Liquid crystal compound:

[Coating fluid (2)]
The following components were mixed, and the resulting mixture was stirred and then filtered through a filter having a pore size of 1 μm to prepare a coating liquid (2).
Organic modified clay complex: Complex of synthetic hectorite and trioctylmethylammonium ion ("Lucentite STN" (trade name) manufactured by Coop Chemical Co., Ltd.) 7.2 parts Binder resin: Polyurethane resin based on isophorone diisocyanate Resin varnish with a solid content of 30% <SBU Lacquer 0866 (trade name) manufactured by Sumika Bayer Urethane Co., Ltd.> 16.0 parts Organic solvent: 76.8 parts of toluene Other: 0.3 parts of water

The chlorine content in the “Lucentite STN” (trade name) used was 1,111 ppm.
The water content in the coating liquid (2) was measured with a Karl Fischer moisture meter and found to be 0.25%. Moreover, the mass ratio of the organic modified clay complex and the binder resin in the coating liquid (2) was 6/4.

Example 1
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) is applied to a glass substrate (supporting base material), and then heated and dried at 100 ° C. for 5 minutes to obtain a glass substrate. A polyvinyl alcohol film having a thickness of 89 nm was obtained thereon. Subsequently, the surface of the polyvinyl alcohol film was rubbed to obtain a laminate of the alignment film and the supporting substrate. The solution (1) having the composition shown in Table 2 was applied to the surface of the obtained laminate subjected to the rubbing treatment by a spin coating method. The layered product coated with the solution (1) is dried on a hot plate at 100 ° C. for 1 minute, and then heated with UV irradiation apparatus (Unicure (Ushio Electric Co., Ltd.)) at 2400 mJ / cm ² of ultraviolet rays. Was applied to produce a laminate on which the retardation plate (1) was laminated. Next, the coating liquid (2) was applied onto the retardation plate (1) by a spin coating method.
The laminate coated with the coating liquid (2) is heated and dried at 80 ° C. for 5 minutes, and the glass substrate (support base material), the alignment film, the retardation plate (1) and the retardation plate (2) are in this order. The composite phase difference plate laminated | stacked by was obtained.

<Measurement of optical properties>
The incident angle dependence of the retardation value at a wavelength of 549 nm of the composite retardation plate obtained above was measured using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments). The results are shown in Table 3, with the phase difference value measured without tilting the support (ie, the front phase difference value) as R ₀ and the phase difference value measured with the support tilted 40 degrees as R ₄₀ . In addition, since R ₀ and R ₄₀ of the laminate composed only of the alignment film and the supporting base material (glass substrate) were both 0 nm, the laminate had no phase difference and was obtained with a measuring instrument. The phase difference values R ₀ and R ₄₀ of the composite phase difference plate can be regarded as being due to the phase difference derived from the phase difference plate (1) and the phase difference plate (2) of the composite phase difference plate. confirmed.
In addition, the phase difference plate (1) and the phase difference plate (2) are partially separated from the composite phase difference plate, and the thickness d (of the composite phase difference plate including only the phase difference plate (1) and the phase difference plate (2) is obtained. μm) was measured using a laser microscope (LEXT, Olympus). The average refractive index of the composite retardation plate _{(n 0)} as 1.6, from the formulas (9) to _(11), determine the n x, _{n y} and _{n z,} the following equation (12):
_{Nz = (n x -n z)} / (n x -n y) (12)
Thus, the Nz coefficient was calculated. The above results are shown in Table 3.
Further, retardation values Re (451), Re (549), and Re (628) of the composite retardation plate at wavelengths of 451 nm, 549 nm, and 628 nm were measured. From the phase difference value, [Re (451) / Re (549)] (referred to as α) and [Re (628) / Re (549)] (referred to as β) were calculated. The results are shown in Table 4.

(Example 2)
A composite retardation plate was obtained in the same manner as in Example 1 except that the thickness of the retardation plate (2) was changed. Tables 3 and 4 show the results of optical characteristics of the obtained composite retardation plate.

(Examples 3 to 11)
In the same manner as in Example 1, the coating liquid (2) was applied on the retardation plate (1) obtained by applying the solution (1) having the composition shown in Table 2, and the retardation plate (2) was obtained. A composite retardation plate was obtained by laminating. Tables 3 and 4 show the results of optical characteristics of the obtained composite retardation plate.

(Comparative Example 1)
On a retardation film (uniaxially stretched film WRF-S (modified polycarbonate resin), retardation value 141 nm, thickness 50 μm, manufactured by Teijin Chemicals Ltd.), polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, Wako Pure Chemical Industries, Ltd.) 2 mass% aqueous solution (made by Co., Ltd.) was applied and then dried by heating to obtain a 79 nm thick polyvinyl alcohol film on the retardation film. Subsequently, after rubbing the surface of the polyvinyl alcohol film, the film was bonded to a glass substrate (support base material) with an adhesive. Subsequently, the coating liquid (2) is applied to the surface subjected to the rubbing treatment by a spin coating method and dried by heating, whereby a supporting substrate, an adhesive layer, a retardation film, an alignment film, and a retardation plate ( 2) obtained a composite retardation plate laminated in this order.

<Measurement of optical properties>
The incident angle dependence of the retardation value at a wavelength of 549 nm of the composite retardation plate obtained above was measured by the same method as in the example. Incidentally, R ₀ and R ₄₀ of the supporting substrate (glass substrate), since both were 0 nm, no phase difference to the supporting substrate, the phase difference value of the composite retardation plate obtained by the machine is It was confirmed that it can be considered to be due to the retardation derived from the retardation film, the alignment film and the retardation plate (2).
Further, the Nz coefficient was calculated in the same manner as in Example 1 by setting the average refractive index (n ₀ ) of the composite retardation plate to 1.6. Further, similarly to Example 1, Re (451), Re (549), and Re (628) of the composite retardation plate were measured, and α and β were calculated from the values of the phase difference values. The results are shown in Table 4.

(Comparative Example 2)
A composite retardation plate was obtained in the same manner as in Comparative Example 1 except that the thickness of the retardation plate (2) was changed.
Tables 3 and 4 show the results of optical characteristics of the obtained composite retardation plate.

(Comparative Example 3)
Using a retardation film (lateral uniaxially stretched escina (norbornene resin)), retardation value 140 nm, thickness 26.7 μm, manufactured by Sekisui Chemical Co., Ltd., a composite retardation plate is obtained in the same manner as in Comparative Example 1. It was. Tables 3 and 4 show the results of optical characteristics of the obtained composite retardation plate.

(Comparative Example 4)
A composite retardation plate was obtained in the same manner as in Comparative Example 3 except that the thickness of the retardation plate (2) was changed. Tables 3 and 4 show the results of optical characteristics of the obtained composite retardation plate.

(Examples 12 to 18)
In the same manner as in Example 1, on the retardation plate (1) obtained by applying the solution (1) having the composition shown in Table 2, polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, Wako Pure Chemical Industries, Ltd. ( After applying a 2% by weight aqueous solution (made by Co., Ltd.), a primer layer having a thickness of 90 nm was formed by heat drying at 100 ° C. for 5 minutes. Next, the coating liquid (2) is applied by a spin coating method and heated and dried at 80 ° C. for 5 minutes, whereby a glass substrate (support base material), an alignment film, a retardation plate (1), a primer layer, and The phase difference plate (2) obtained the composite phase difference plate laminated | stacked in this order. The optical property results of the obtained composite retardation plate were measured by the same method as in Example 1. It shows in Table 5 and Table 6.

  According to Tables 3 to 6, the composite retardation plate of the present invention shows excellent optical characteristics equivalent to the composite retardation plate of the comparative example with respect to the wavelength dispersion characteristics of the Nz coefficient and the retardation value, and the thickness is An order of magnitude smaller and thinner.

  The composite retardation plate of the present invention can obtain a thin composite retardation plate and can perform uniform polarization conversion in a wide wavelength range.

Claims (20)

A phase difference plate (1) obtained by polymerizing a liquid crystal compound having a polymerizable group, and a phase difference plate (2) containing an organically modified clay complex and a binder resin, and having a wavelength λ (nm) A composite retardation plate having a birefringence index Δn (λ) satisfying Expressions (3) and (4).
Δn (451) / Δn (549) ≦ 1.04 (3)
0.98 ≦ Δn (628) / Δn (549) (4) The composite retardation plate according to claim 1, wherein the liquid crystal compound having a polymerizable group is a compound represented by the formula (A).

^{L 1 -G 1 -D 1 -Ar-} D 2 -G 2 -L 2 (A)

[In the formula (A), Ar represents a divalent group having an aromatic ring, and the number of π electrons contained in the aromatic ring is 12 or more and 22 or less.
D ¹ and D ² are each independently a single bond, —CO—O—, —O—CO—, —C (═S) —O—, —O—C (═S) —, —CR ¹ R ^{2 -, - CR 1 R 2} -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 R ² —O—CO—, —O—CO—CR ¹ R ² —, —CR ¹ R ² —O—CO—CR ³ R ⁴ —, —CR ¹ R ² —CO—O—CR ³ R ⁴ — , —NR ¹ —CR ² R ³ —, —CR ¹ R ² —NR ³ —, —CO—NR ¹ —, or —NR ¹ —CO—.
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, — S— or —NH— may be substituted, and —CH (—) — contained in the alicyclic hydrocarbon group may be substituted with —N (—) —.
L ¹ and L ² each independently represents an organic group, and at least one selected from the group consisting of L ¹ and L ² represents a group having a polymerizable group. ] The composite retardation plate according to claim 2, wherein L ¹ is a group represented by the formula (B) and L ² is a group represented by the formula (C).

P ¹ -F ^1- (B ¹ -A ¹ ) _k -E ^1- (B)
P ² -F ^2- (B ² -A ² ) ₁ -E ^2- (C)

Wherein (B) and ^{(C), B 1, B} 2, E 1 and ^{E 2,} each _{^{independently, -CR 5 R 6 -, -}} CH 2 -CH 2 -, - O -, - S- , -CO-O-, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -O-C (= S)- ^{O -, - CO-NR 5} -, - NR 5 -CO -, - O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - represents a CH 2 -S- or a single bond. If k is an integer of 2 or more, plural B ¹ represents may be the same or different from each other. When l is an integer greater than or equal to ² , several B2 may mutually be same or different.
R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon —CH ₂ — contained in the group may be replaced by —O—, —S— or —NH—, and —CH (—) — contained in the alicyclic hydrocarbon group represents —N (-)-May be replaced. When k is an integer of 2 or more, the plurality of A ¹ may be the same as or different from each other. When l is an integer greater than or equal to ² , several A2 may mutually be same or different.
k and l each independently represents an integer of 0 to 3.
F ¹ and F ² represents a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
P ¹ represents a polymerizable group.
P ² represents a hydrogen atom or a polymerizable group. ] The compound phase difference plate of Claim 3 whose compound represented by Formula (A) is a compound which satisfy | fills Formula (5) and Formula (6).
( _Nπ- 4) / 3 <k + 1 + 4 (5)
12 ≦ N _π ≦ 22 (6)
[In Formula (5) and Formula (6), N _π represents the number of π electrons contained in the aromatic ring of Ar. k and l represent the same meaning as in formulas (B) and (C). ] The composite retardation plate according to claim 2, wherein Ar is a divalent group represented by the formula (Ar-6).

[In Formula (Ar-6), Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, —NR ⁷ R ⁸ , or —SR ⁷ . If n is an integer of 2 or more, a plurality of Z ¹ may be the being the same or different.
R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Q ¹ represents —S—, —O— or —NR ⁹ —.
R ⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ² represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent.
n represents an integer of 0 to 2. ] The composite phase difference plate according to claim ² , wherein G ¹ and G ² are both cyclohexane-1,4-diyl groups. The composite phase difference plate according to claim 3, wherein A ¹ and A ² are each independently a p-phenylene group or a cyclohexane-1,4-diyl group. B ¹ bonded only to A ¹ and B ² bonded only to A ² are each independently —CH ₂ —CH ₂ —, —CO—O—, —O—CO—, —CO. -NH -, - NH-CO - , - O-CH 2 -, - CH 2 -O- or a single bond, and ^{B 1} which is bound to F ^1, and ^{F 2} and bonded to that ^{B 2} Are each independently —O—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NH—, —NH—CO— or a single bond. 8. The composite retardation plate according to any one of 7 above.   The composite retardation plate according to claim 1, wherein the polymerizable group is independently one or more selected from the group consisting of an acryloyloxy group and a methacryloyloxy group. The organically modified clay complex includes a quaternary ammonium salt and a clay mineral belonging to the smectite group, and the atomic ratio (Mg / Si ₄ ) between magnesium and silicon 4 atoms contained in the clay mineral is 0.01 or more. The composite phase difference plate according to claim 1, which is less than 73.   The composite retardation plate according to claim 1 or 10, wherein the retardation plate (2) is a negative uniaxial retardation plate.   The composite phase difference plate according to claim 1, wherein the phase difference plate (1) and the phase difference plate (2) are joined. Furthermore, the composite phase difference plate in any one of Claims 1-11 which contains a primer layer between a phase difference plate (1) and a phase difference plate (2).   The composite phase difference plate according to any one of claims 1 to 13, wherein a front phase difference value at a wavelength of 550 nm is 113 nm or more and 163 nm or less.   A polarizing member comprising a polarizing plate and the composite retardation plate according to claim 1.   A liquid crystal display device comprising a liquid crystal cell and the polarizing member according to claim 15.   The optical member containing a color filter and the composite phase difference plate in any one of Claims 1-14. The manufacturing method of the composite phase difference plate which has the process of following (i)-(v).
(I) Step for obtaining a solution by mixing a liquid crystal compound having a polymerizable group and an organic solvent (ii) Step for obtaining a coating film from the solution obtained in step (i) (iii) Obtaining in step (ii) (Iv) a step of obtaining a retardation plate (1) by polymerizing a liquid crystal compound having a polymerizable group contained in the coated film, and coating by mixing an organically modified clay complex, a binder resin and an organic solvent Step of obtaining liquid (v) Step of applying the coating liquid obtained in step (iv) to the obtained retardation plate (1) to obtain a composite retardation plate The manufacturing method of the composite phase difference plate which has the process of following (i)-(iv) and (vi)-(vii).
(I) Step for obtaining a solution by mixing a liquid crystal compound having a polymerizable group and an organic solvent (ii) Step for obtaining a coating film from the solution obtained in step (i) (iii) Obtaining in step (ii) (Iv) a step of obtaining a retardation plate (1) by polymerizing a liquid crystal compound having a polymerizable group contained in the coated film, and coating by mixing an organically modified clay complex, a binder resin and an organic solvent Step (vi) for obtaining a solution Step (vii) of applying a primer to the obtained retardation plate (1) to form a primer layer on the retardation plate (1) The coating obtained in step (iv) A process of applying a working fluid on a primer layer to obtain a composite retardation plate   The method for producing a composite retardation plate according to claim 18 or 19, wherein (i) in the step of obtaining a solution by mixing a liquid crystal compound having a polymerizable group and an organic solvent, a polymerization initiator is further mixed to obtain a solution.

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