JP6672961B2 - Manufacturing method of optical compensation film - Google Patents

Description

  The present invention relates to a method for producing an optical compensation film. In particular, the present invention relates to a manufacturing method capable of efficiently manufacturing a high-quality optical compensation film having uniform orientation of constituent molecules.

  2. Description of the Related Art An optical compensation technique using a phase difference plate has been known for the purpose of increasing the viewing angle and increasing the contrast of a liquid crystal display (LCD). A stretched film in which birefringence is controlled by stretching a polymer film has been used as such a retardation plate.

Liquid crystal compounds having a polymerizable group are used for optical compensation films.
Examples of the optical compensation film include a reflection type polarizing plate and a retardation plate. The optical compensation film exhibits birefringence, for example, optical anisotropy, and the liquid crystal compound exhibits birefringence in a liquid crystal state. The orientation of the liquid crystal compound is fixed by polymerization. The orientation of the polymer is fixed, and the polymer is in an orientation state such as homogeneous (horizontal orientation), tilt (tilted orientation), homeotropic (vertical orientation), and twist (twisted orientation). A retardation plate obtained by using a polymerizable liquid crystal compound exhibits a large birefringence as compared with a conventionally used stretched film, and thus can be made thinner.

  An optical compensation film having a homogeneous orientation can be used as a composite retardation plate or a circularly polarizing plate by combining with a half-wave plate, a quarter-wave plate, or a film having another optical function (Patent Reference 1).

  An optical compensation film having homeotropic alignment has an optical axis direction in the nz direction, and a refractive index in the optical axis direction is larger than a refractive index in a direction orthogonal to the optical axis direction. Is done. By combining this positive C-plate with a film having another optical function, it can be applied to optical compensation of a horizontally aligned liquid crystal mode, so-called IPS (In-Plane Switching) mode, for example, to improve the viewing angle characteristics of a polarizing plate. (Non-Patent Documents 1 to 3, Patent Documents 2 and 3).

  In an optical compensation layer composed of a rod-shaped liquid crystal compound, the two refractive indices ne (an extraordinary refractive index in a direction parallel to the molecular long axis) and no (an ordinary refractive index in a direction perpendicular to the molecular long axis) of anisotropic molecules are: It decreases as the wavelength increases. Normally, since the refractive index change rate with respect to wavelength is larger in ne than in no, the refractive index anisotropy (Δn = ne−no) decreases as the applied wavelength increases. Such a chromatic dispersion characteristic is called positive chromatic dispersion.

  The light source of a display device such as a liquid crystal display (LCD) is white light composed of light having a wavelength of about 380 to 800 nm. When a λλ or λλ plate or the like is formed using the optically anisotropic layer exhibiting the positive wavelength dispersion as described above, a change in the polarization state occurs depending on the wavelength due to the wavelength dispersion described above. A problem arises in that the desired light becomes colored.

  In order to prevent this problem, it is necessary to control the wavelength dispersion so that the phase difference is designed at each wavelength. The use of a material having a low dependence of the refractive index anisotropy on the wavelength or a material having a large refractive index anisotropy with an increase in the wavelength solves the problem that light that is originally desired to be white becomes colored. A material having a low dependence of the refractive index anisotropy on the wavelength has a low wavelength dispersion characteristic. A material whose refractive index anisotropy increases as the wavelength increases has an inverse wavelength dispersion characteristic.

  In order to obtain an optical compensation layer having an inverse wavelength dispersion characteristic, a method has been proposed in which two retardation layers are laminated at an angle in the direction of refractive index anisotropy (Patent Documents 5 and 6). ). However, in such a laminate, two retardation layers are required, and it is necessary to adjust the anisotropy angle of the two retardation layers. Therefore, there is a problem that manufacturing for forming the laminate becomes complicated and the optical compensation layer becomes thick.

  In order to solve such a problem, an optical compensation layer having reverse wavelength dispersion without being laminated is required, and liquid crystal compounds having reverse wavelength dispersion have been proposed (Patent Documents 7 to 11).

However, as the liquid crystal compound having the reverse wavelength dispersion characteristic, a compound having a small aspect ratio and having a bulky structure in a direction perpendicular to the long axis of the molecule as compared with a normal rod-shaped liquid crystal molecule is used. However, a compound having a small aspect ratio has a problem that the liquid crystallinity is poor and it is difficult to control the alignment uniformity.
In general, a rod-shaped liquid crystal compound tends to exhibit a liquid crystal phase as the aspect ratio increases, and tends to exhibit a large refractive index anisotropy. Since the liquid crystal compound having a small aspect ratio has small refractive index anisotropy, it is necessary to increase the thickness of the optical compensation layer. However, when the film thickness is large, disorder of the orientation becomes more remarkable.

JP 2002-372623 A International Publication No. 05/38517 US Patent Application Publication No. 2006/182900 JP-A-8-321381 JP-A-10-068816 JP 2001-004837 A JP 2010-522893 A JP 2009-179563 A International Publication No. 2012/169424 JP 2010-031223 A JP 2014-63143 A

M.S.Park et al, IDW '04 FMC8-4 M.Nakata et al, SID '06 P-58 K.J.Kim et al, SID '06 Digest p.1158-1161

  An object of the present invention is to provide a method for producing an optical compensation film that can efficiently produce a high-quality optical compensation film with uniform orientation of constituent molecules.

In order to achieve the above object, the inventor of the present application efficiently manufactures a high-quality optical compensation film with uniform orientation of constituent molecules by precisely controlling the temperature control in the production process of the optical compensation film, particularly the cooling process. I found what I could do.
That is, the manufacturing method of the optical compensation film according to the present invention includes a coating step of coating a polymerizable liquid crystal composition on a supporting substrate, a coating film obtained by coating step is heated at a temperature T _H, the solvent includes a heating step of evaporating a cooling step of cooling the coating film obtained in the heating step to room temperature T _R, a polymerization step of polymerizing by irradiation of light to the coating film obtained in said cooling step, a polymerizable liquid crystal A polymerizable liquid crystal, wherein the composition has a rod-shaped molecular structure, and the aspect ratio (L / D) is 3 or less when the length of the major axis in the molecular structure is L and the length of the minor axis is D. A liquid crystal compound containing at least one compound, a photopolymerization initiator, a surfactant, and a solvent are included. The cooling step satisfies at least one of the following conditions (i) and (ii). That includes (i) prior to the coating film is cooled to T _R, the duration of holding at a temperature T _i 30 seconds or more, at least once. Here, the temperature T _i is T _H > T _i ≧ T _R + 20 ° C. Further, (ii) the average cooling rate to the coating film is cooled to room temperature T _R from the temperature T _H is 20 ° C. / min or less.

式（１−１）〜式（１−４）中、
Ｘ^１、Ｘ^３およびＸ^４は、それぞれ独立して−Ｏ−または−Ｓ−であり、
Ｘ^２は、−ＣＨ＝または−Ｎ＝であり、
Ｗ^１は、単結合または−Ｃ≡Ｃ−によって連結した芳香環（該芳香環中の水素がフッ素、塩素、シアノ、ニトロ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルキルエステル、炭素数１〜５のアルカノイル、または炭素数１〜５のチオアルキルに置換されているものも含む）であって、非局在化している電子数が６〜１６である一価の基であり、
Ｗ^２は、酸素、硫黄、または炭素数５〜１０の単環もしくは縮合環（ただし該単環または縮合環において、−ＣＨ＝は−Ｎ＝に置き換えられてもよく、−ＣＨ_２−は−Ｏ−、−ＮＨ−、−Ｓ−または−ＣＯ−に置き換えられてもよく、炭素または窒素上の水素が、フッ素、塩素、シアノ、ニトロ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルキルエステル、炭素数１〜５のアルカノイル、または炭素数１〜５のチオアルキルに置換されているものも含む）であり、
Ｗ^３は、それぞれ独立してシアノ、炭素数１〜１０のアルコキシカルボニルまたは炭素数１〜１０のアルカノイルであり、該アルコキシカルボニルおよびアルカノイルにおいて少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、
Ｗ^４は、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、ヘテロ原子を含んでもよい芳香環またはそれら
の組み合わせからなる群より選ばれる二価の連結基を表し、
Ｒ^１は、それぞれ独立して式（２−１）で表される基であり、

式（２−１）中、Ａ^１はそれぞれ独立して１，４−フェニレンまたは１，４−シクロへキシレンであり、この１，４−フェニレンにおいて、少なくとも一つの水素はフッ素、シアノ、ホルミル、トリフルオロアセチル、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニルまたは炭素数１〜５のアルカノイルで置き換えられてもよく、Ｚ^１はそれぞれ独立して単結合、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＯＣＨ_２ＣＨ_２Ｏ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＯＣＯ−または−ＣＯＯＣＨ_２ＣＨ_２−であり、ｍはそれぞれ独立して１または２の整数であり、Ｙ^１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯＯ−であり、Ｑ^１は単結合または炭素数１〜２０を有するアルキレンであり、該アルキレンにおいて少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、ＰＧは式（ＰＧ−１）〜式（ＰＧ−８）のいずれか１つで表される重合性の基である。

式（ＰＧ−１）〜式（ＰＧ−８）中、Ｒ^３はそれぞれ独立して水素、ハロゲン、メチル、エチルまたはトリフルオロメチルであり、
式（１−１）〜式（１−４）中、
Ｒ^２はそれぞれ独立して式（２−２）で表される基であり、

式（２−２）中、Ａ^２はそれぞれ独立して１，４−フェニレンまたは１，４−シクロへキシレンであり、１，４−フェニレンにおいて、少なくとも一つの水素はフッ素、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニルまたは炭素数１〜５のアルカノイルで置き換えられてもよく、Ｚ^２は
単結合であり、ｎはそれぞれ独立して０〜３の整数であり、Ｒ^４は水素、フッ素、トリフルオロメチル、トリフルオロメトキシ、シアノ、炭素数１〜２０のアルキル、炭素数２〜２０のアルケニル、炭素数１〜２０のアルコキシまたは炭素数１〜２０のアルコキシカルボニルである。
また、前記式（２−１）におけるＺ^１は、それぞれ独立して−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２ＣＨ_２ＣＯＯ−または−ＯＣＯＣＨ_２ＣＨ_２−であり、ＰＧが式（ＰＧ−１）で表される重合性の基であることを特徴とする。
また、前記重合性液晶化合物が、式（１−１）または式（１−３）で表される化合物であることを特徴とする。
また、光学素子は、前記光学補償フィルムの製造方法により製造された光学補償フィルムと偏光板を有し、また、液晶表示装置は、前記光学補償フィルムの製造方法により製造された光学補償フィルムを液晶セルの内面または外面に有する。また、液晶表示装置および有機ＥＬ表示装置は、前記光学素子を有する。 When the phase transition temperature from the liquid crystal phase to the isotropic phase of the coating film obtained in the heating step after the coating step is T _NI , T _H , T _i , T _R , and T _NI are represented by the following ( It is characterized in that the relationship satisfies the conditions of a) and (b). That is, _{(a) T H ≧ T NI} + 10 ℃, and _{(b) T H -10 ℃ ≧} T i ≧ room temperature _T R + 20 ℃.
Further, T _i and T _NI are characterized by satisfying the following conditions (c) and (d). That is, (c) T _NI ≧ 45 ° C. and (d) T _NI + 5 ° C. ≧ T _i ≧ 45 ° C.
In the light irradiation in the polymerization step, the birefringence Δn (λ) with respect to light having a wavelength of λ nm is characterized by Δn (450) / Δn (550) ≦ 1.05.
Further, the polymerizable liquid crystal compound contains at least one selected from the group consisting of compounds represented by formulas (1-1) to (1-4).

In the formulas (1-1) to (1-4),
X ¹ , X ³ and X ⁴ are each independently -O- or -S-;
X ² is -CH = or -N =;
W ¹ represents a single bond or an aromatic ring connected by —C≡C— (where hydrogen in the aromatic ring is fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbons, carbon (Alkoxy having 1 to 5 carbon atoms, alkyl ester having 1 to 5 carbon atoms, alkanoyl having 1 to 5 carbon atoms, or thioalkyl having 1 to 5 carbon atoms) Is a monovalent group having 6 to 16 electrons,
W ² is oxygen, sulfur, or the monocyclic or condensed (provided that the monocyclic or condensed ring having 5 to 10 carbon atoms, -CH = may be replaced by -N =, -CH ₂ - is - O-, -NH-, -S- or -CO- may be substituted and hydrogen on carbon or nitrogen is replaced with fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, carbon number 1-5. Alkyl, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons, alkanoyl having 1 to 5 carbons, or thioalkyl having 1 to 5 carbons),
W ³ is each independently cyano, alkoxycarbonyl having 1 to 10 carbon atoms or alkanoyl having 1 to 10 carbon atoms, and at least one of —CH ₂ — in the alkoxycarbonyl and alkanoyl is —O—, —COO— , -OCO-, -CH = CH- or -C≡C-,
W ⁴ represents a divalent linking group selected from the group consisting of —CH ＝ CH—, —C≡C—, an aromatic ring optionally containing a hetero atom, or a combination thereof;
R ¹ is each independently a group represented by the formula (2-1),

In the formula (2-1), A ¹ is each independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, at least one hydrogen atom is fluorine, cyano, formyl, trifluoroacetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, may be replaced by alkoxycarbonyl, or alkanoyl of 1 to 5 carbon atoms of 1 to 5 carbon atoms, Z ¹ is each independently represent a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - OCH 2 CH 2 O —, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO— or —COOCH ₂ CH ₂ —, and m is each independently 1 or 2 An integer, Y ¹ is a single bond, —O—, —COO—, —OCO— or —OCOO—; Q ¹ is a single bond or an alkylene having 1 to 20 carbon atoms; One of _-CH 2 - is -O -, - COO -, - OCO -, - CH = CH- or -C≡C-, PG formula (PG-1) ~ formula (PG-8 ) Is a polymerizable group represented by any one of the above.

In the formulas (PG-1) to (PG-8), each R ³ is independently hydrogen, halogen, methyl, ethyl or trifluoromethyl;
In the formulas (1-1) to (1-4),
R ² is independently a group represented by the formula (2-2),

In Formula (2-2), A ² is each independently 1,4-phenylene or 1,4-cyclohexylene, and in 1,4-phenylene, at least one hydrogen atom is fluorine, trifluoromethyl, May be replaced by alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkoxycarbonyl having 1 to 5 carbon atoms or alkanoyl having 1 to 5 carbon atoms, Z ² is a single bond, and n is each independently R ⁴ is hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons Alternatively, it is an alkoxycarbonyl having 1 to 20 carbon atoms.
Z ¹ in the formula (2-1) is independently —COO—, —OCO—, —CH ₂ CH ₂ COO—, or —OCOCH ₂ CH ₂ —, and PG is a group represented by the formula (PG-1). ) Is a polymerizable group.
Further, the polymerizable liquid crystal compound is a compound represented by Formula (1-1) or Formula (1-3).
The optical element has an optical compensation film manufactured by the method for manufacturing an optical compensation film and a polarizing plate, and the liquid crystal display device includes an optical compensation film manufactured by the method for manufacturing an optical compensation film. Have on the inner or outer surface of the cell. Further, the liquid crystal display device and the organic EL display device have the optical element.

  According to the present invention, it is possible to efficiently produce a high-quality optical compensation film having uniform orientation of constituent molecules. Further, it can be applied to the production of an optical compensation film having excellent wavelength dispersion characteristics.

5 is a retardation measurement result of the optical compensation film manufactured in Example 1. 5 is a graph of wavelength dispersion characteristics (measured value of wavelength _λ nm (Re _λ ) ÷ wavelength dependence of measured value of wavelength 550 nm (Re ₅₅₀ )) of the optical security film manufactured in Example 1.

“Liquid crystal compound” is a general term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. The liquid crystal phase is a nematic phase, a smectic phase, a cholesteric phase or the like, and often means a nematic phase. The polymerizable means that the polymer has the ability to polymerize by means of light, heat, a catalyst or the like to change into a polymer having a larger molecular weight, or contains a functional group having the ability. The compound (1) means a compound represented by the formula (1). Compounds represented by other formulas are referred to according to the same simplified method.
The meaning of "liquid crystallinity" is not limited only to having a liquid crystal phase. Even if it does not have a liquid crystal phase per se, it can be used as a component of a liquid crystal composition when mixed with another liquid crystal compound.
"Aromatic ring" is a unit of a molecule (including condensed rings and ring assemlies) that has been constrained in a cyclic manner. Means a ring structure that is more thermodynamically stable. The ring structure includes those having an oxygen, nitrogen, or sulfur atom.
A substituent whose bonding position to the carbon constituting the ring is not clear means that the bonding position can be selected within a range that does not cause any chemical problem.
The case where the compound has one polymerizable group is called monofunctional. When the compound has a plurality of polymerizable groups, it is referred to by a name corresponding to the number of polyfunctional or polymerizable groups.

また、化学式として、下記Ｃに示すような基の記載があった場合には、波線部が基としての結合位置であることを意味するものとする。

In the case where the following content is described as a chemical formula, the straight line from B to A means a bond, the hydrogen in A is replaced by a group B, and the position is arbitrary. Means. X indicates the number of groups B to be replaced. When X is 0, it indicates that B does not exist and has not been replaced.

Further, when a group represented by the following C is described as a chemical formula, it means that a wavy line portion is a bonding position as a group.

<Production method of optical compensation film>
The method for manufacturing an optical compensation film according to one embodiment of the present invention includes four steps. The first step is a coating step of coating a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, a photopolymerization initiator, a surfactant, and a solvent on a supporting substrate. The second step is a heating step of heating the coating film obtained by a coating process in order to evaporate the solvent to a temperature T _H. Third step, the coating film after the heating step is a step of cooling to room temperature T _R. The fourth step is a polymerization step of irradiating the coating film having undergone the cooling step with light to polymerize the polymerizable liquid crystal compound contained therein.
The present invention is characterized in that the cooling step satisfies at least one of the following conditions (i) and (ii).
Before (i) the coating film is cooled to room temperature T _R, the duration of holding at a temperature T _i includes one or more times, and the period of holding at temperatures T _i is respectively more than 30 seconds. That is, the period of holding at temperatures _{T i} 30 seconds or more, at least once.
Here, the temperature _{T i} satisfies _{T H> T i ≧ T R} + 20 ℃.
(Ii) the average cooling rate to the coating film is cooled to room temperature T _R from the temperature T _H is 20 ° C. / min or less.
"Production method of the present invention" refers to a method for producing an optical compensation film.
By controlling the cooling process in the manufacturing process of the optical compensation film as described in (i) and (ii) above, and controlling the cooling conditions, the orientation of the constituent molecules is more uniform and good quality as compared with the conventional case without control. It has been found that a suitable optical compensation film can be obtained. This method can be applied relatively easily, and can be said to be an excellent method capable of producing a high-quality optical compensation film without impairing productivity. Also, this method has a feature that it can be applied to the production of an optical compensation film having excellent wavelength dispersion control characteristics.

(Coating process)
The coating step refers to a step of coating a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, a photopolymerization initiator, a surfactant, and a solvent on a supporting substrate. The coating method includes, but is not limited to, spin coating, microgravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating, and die coating. By applying a wire bar coating method or the like in which a shear stress is applied to the solution at the time of coating, the orientation of the polymerizable liquid crystal compound can be controlled without performing a surface treatment of the substrate by rubbing or the like.
Here, the polymerizable liquid crystal compound has a rod-shaped molecular structure, and the aspect ratio (L / D) when the length of the major axis in the molecular structure is L and the length of the minor axis is D is 3 or less. It is.

(Heating process)
The heating step is a step of heating the coating film obtained by a coating process in order to evaporate the solvent to a temperature T _H. As the heating method, known methods and conditions can be appropriately selected. The heating method includes, but is not limited to, a method using a hot plate, a drying oven, a hot air / hot air blowing device, or the like. In this case, the substrate surface temperature, or the temperature of the set temperature of the device and the temperature T _H.
Temperature T _H can be appropriately selected depending on the polymerizable liquid crystal compound and the type of solvent and the like. Temperature T _H is preferably a polymerizable liquid crystal compound is a temperature at which uniform alignment.
The temperature _{T H,} and preferably 45 ° C. to 200 DEG ° C., more preferably 60 ° C. to 150 DEG ° C., more preferably from 80 ° C. to 120 ° C.. If the heating temperature is too low, it is difficult to ensure uniformity of orientation. On the other hand, if the heating temperature is too high, the productivity decreases.
The time of the coating film from the start to warm up the coating to a temperature T _H and the heating time.
The heating time is generally 5 seconds to 2 hours, preferably 10 seconds to 30 minutes, more preferably 20 seconds to 10 minutes. When the content is within the above range, it becomes easy to efficiently produce an optical compensation film having a uniform orientation of constituent molecules. If the heating time is too short, it is difficult to ensure uniformity of orientation. If the heating time is too long, the productivity will decrease.
Further, the polymerizable liquid crystal composition is coated on a supporting substrate, the phase transition temperature to isotropic phase from the liquid crystal phase of the coating film obtained by evaporating the solvent and the temperature T _NI, and the temperature T _H it is preferable that the temperature _{T NI} is _{T H> T NI.} More preferably _{T H ≧ T NI + 10 ℃} , more preferably from _{T H ≧ T NI + 15 ℃} . Here, when it is within the above range, it becomes easier to produce an optical compensation film in which the orientation of the constituent molecules is uniform.

(Cooling process)
Cooling step, the coating film after the heating step is a step of cooling to room temperature T _R, wherein at least one satisfy the following condition (i) and (ii).
(I) before the coating is cooled to room temperature T _R, the duration of holding at a temperature T _i includes one or more times, and the period of holding at temperatures T _i is greater than or equal to 30 seconds. Here, the temperature _{T i} satisfies _{T H> T i ≧ T R} + 20 ℃.
(Ii) the average cooling rate to the coating film is cooled to room temperature T _R from the temperature T _H is 20 ° C. / min or less.
Here, room temperature _{T R} means a 20 ° C. ~ 28 ° C.. Room temperature T _R is intended to mean the surface temperature or the temperature of the laboratory, the supporting substrate coating is formed.

The first aspect of the cooling step (i), holding the liquid crystal composition is a coating film is heated to a temperature higher than the temperature exhibiting an isotropic phase, and then at a temperature T _i within the temperature range showing a nematic liquid crystal phase by heating step doing, generally to complete the nematic orientation in the liquid crystal composition in the coating film, by further lowering the temperature to room temperature T _R and then a method for the orientation was even more ordered.
Here, the term “hold at the temperature T _i ” means the temperature of the substrate surface or the set temperature of an apparatus used for heating the coating film.
Further, “temperature T _i ” means the temperature when the temperature is maintained, and when the temperature is maintained a plurality of times, the temperatures are assumed to be T ₁ , T ₂ , T _{3 ,.}
The temperature T _i is not particularly limited as long as it satisfies _TH > T _i > T _R + 20 ° C., but preferably T _H −10 ° C. ≧ T _i ≧ T _R + 20 ° C. When the content is within the above range, it becomes easy to efficiently produce an optical compensation film having a uniform orientation of constituent molecules.
The holding period of the temperature _{T i} is preferably from 30 seconds to 30 minutes, more preferably 30 seconds to 10 minutes, more preferably from 10 minutes 1 minute. When the content is within the above range, it becomes easy to efficiently produce an optical compensation film having a uniform orientation of constituent molecules.
Further, the polymerizable liquid crystal composition is coated on a supporting substrate, and the solvent is evaporated, and the phase transition temperature from the liquid crystal phase to the isotropic phase of the coating film obtained is set to a temperature T _{i with} respect to the temperature T _NI . Is preferably T _NI + 5 ° C. ≧ T _i ≧ 45 ° C., and more preferably T _NI ≧ T _i ≧ 45 ° C. Further, T _NI is preferably a polymerizable liquid crystal composition satisfying T _NI ≧ 45 ° C.

In the second mode (ii) of the cooling step, similarly to the first mode, in order to obtain uniform alignment, the coating film is heated to a temperature T _NI or higher at which the liquid crystal composition exhibits an isotropic phase by a heating step. warming, followed by lowering slowly to room temperature T _R, it is a method for the alignment orderly.
The "average cooling rate until cooled to room temperature T _R from the coating temperature T _H", as shown in the following formulas, the temperature T _H and the room T the temperature difference _R, the coating temperature T _H It means a value obtained by dividing the total time to be cooled to room temperature T _R from.
(Average cooling rate) = (temperature _{T H} - RT _T R) / (total time to cool [min])
The average cooling rate until the coating is cooled to room temperature T _R from the temperature T _H is a 20 ° C. / min or less, preferably 15 ° C. / min or less.
The cooling step may be performed by holding the substrate in the air and cooling it, or by leaving it on a base or the like made of a material having low thermal conductivity such as rubber. In order not to lower the productivity, it is preferable to set the heating period to 2 hours or less.

(Polymerization step)
The polymerization step is a polymerization step of irradiating the coating film having undergone the cooling step with light to polymerize the polymerizable liquid crystal compound contained therein. This polymerization fixes the orientation of the constituent molecules.
The type of light irradiated with light in the polymerization step is not particularly limited. This light includes ultraviolet light, visible light, infrared light (heat ray), and the like. The specific wavelength is preferably from 150 nm to 500 nm. 250 nm to 450 nm is more desirable. 300 nm to 400 nm is more desirable. When the content is within the above range, it becomes easy to produce a stronger optical compensation film in order to adapt to the absorption wavelength of the polymerization initiator.
Light sources include low pressure mercury lamps (germicidal lamps, fluorescent chemical lamps, black lights), high pressure discharge lamps (high pressure mercury lamps, metal halide lamps), short arc discharge lamps (ultra high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. . Metal halide lamps, xenon lamps, ultra-high pressure mercury lamps, and high pressure mercury lamps are preferred.
The amount of light applied to the coating film is preferably from 2 to 5000 mJ / cm ² . It is more preferably from 10 to 3000 mJ / cm ² . 100 to 2000 mJ / cm ² is more preferred. If the amount of light is too small, the curability tends to be insufficient. On the other hand, if the light amount is too large, the productivity is reduced.
The polymerization step may be performed under any atmosphere such as an inert gas (nitrogen, argon, etc.), air and the like. It is preferable to carry out in an inert gas atmosphere from the viewpoint of improving the curability.
Thus, the optical compensation film of the present invention is obtained.

(Polymerizable liquid crystal compound)
In calculating the aspect ratio of a molecular structure, the length of the major axis means the maximum length of the molecular model when the molecular structure is optimized, and the length of the minor axis is the maximum length in the direction perpendicular to the major axis. Means.
The “aspect ratio” is a value L / D obtained by dividing the length L of the major axis by the length D of the minor axis.
For the optimization of the molecular structure, a molecular calculation technique is used, such as B3LYP / 6-31G (d). In the present invention, using GAMSS (MW Schmidt et al., J. Comput. Chem. 14, 1347 (1993).), The molecular structure was optimized by the method of B3LYP / 6-31G (d).
The production method of the present invention is suitable when a polymerizable liquid crystal compound having an aspect ratio of 3 or less is used, and the aspect ratio is usually 1.2 or more, preferably 1.5 or more.
The polymerizable liquid crystal compound may be a compound in which at least one polymerizable liquid crystal compound exhibits a nematic phase and the aspect ratio of the molecular structure is 3 or less.
The polymerizable liquid crystal compound is not limited to one type, and two or more types may be used in combination. When two or more polymerizable liquid crystal compounds are included, at least one of them may be a compound having an aspect ratio of a molecular structure of 3 or less.

式（１−１）〜式（１−４）中、
Ｘ^１、Ｘ^３およびＸ^４はそれぞれ独立して−Ｏ−または−Ｓ−であり；
Ｘ^２は−ＣＨ＝または−Ｎ＝であり；
Ｗ^１は、単結合または−Ｃ≡Ｃ−によって連結した芳香環（該芳香環中の水素がフッ素、塩素、シアノ、ニトロ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルキルエステル、炭素数１〜５のアルカノイル、または炭素数１〜５のチオアルキルに置換されているものも含む）であって、非局在化している電子数が６〜１６である一価の基であり、
Ｗ^２は酸素、硫黄、または、炭素数５〜１０の単環もしくは縮合環（ただし該単環または縮合環において、−ＣＨ＝は−Ｎ＝に置き換えられてもよく、−ＣＨ_２−は−Ｏ−、−ＮＨ−、−Ｓ−または−ＣＯ−に置き換えられてもよく、炭素または窒素上の水素が、フッ素、塩素、シアノ、ニトロ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルキルエステル、炭素数１〜５のアルカノイル、または炭素数１〜５のチオアルキルに置換されているものも含む）であり、
Ｗ^３はそれぞれ独立してシアノ、炭素数１〜１０のアルコキシカルボニルまたは炭素数１〜１０のアルカノイルであり、該アルコキシカルボニルおよびアルカノイルにおいて少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、
Ｗ^４は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、ヘテロ原子を含んでもよい芳香環またはそれらの組み合わせからなる群より選ばれる二価の連結基を表し、
Ｒ^１はそれぞれ独立して式（２−１）で表される基であり、

式（２−１）中、Ａ^１はそれぞれ独立して１，４−フェニレンまたは１，４−シクロへキシレンであり、この１，４−フェニレンにおいて、少なくとも一つの水素はフッ素、シアノ、ホルミル、トリフルオロアセチル、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニルまたは炭素数１〜５のアルカノイルで置き換えられてもよく、Ｚ^１はそれぞれ独立して単結合、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＯＣＨ_２ＣＨ_２Ｏ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＯＣＯ−または−ＣＯＯＣＨ_２ＣＨ_２−であり、ｍはそれぞれ独立して１または２の整数であり、Ｙ^１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯＯ−であり、Ｑ^１は単結合または炭素数１〜２０を有するアルキレンであり、該アルキレンにおいて少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、ＰＧは式（ＰＧ−１）〜式（ＰＧ−８）のい
ずれか１つで表される重合性の基である。

式（ＰＧ−１）〜式（ＰＧ−８）中、Ｒ^３はそれぞれ独立して水素、ハロゲン、メチル、エチルまたはトリフルオロメチルであり；
式（１−１）〜式（１−４）中、
Ｒ^２はそれぞれ独立して式（２−２）で表される基であり、

式（２−２）中、Ａ^２はそれぞれ独立して１，４−フェニレンまたは１，４−シクロへキシレンであり、１，４−フェニレンにおいて、少なくとも一つの水素はフッ素、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニルまたは炭素数１〜５のアルカノイルで置き換えられてもよく、Ｚ^２は単結合であり、ｎはそれぞれ独立して０〜３の整数であり、Ｒ^４は水素、フッ素、トリフルオロメチル、トリフルオロメトキシ、シアノ、炭素数１〜２０のアルキル、炭素数２〜２０のアルケニル、炭素数１〜２０のアルコキシまたは炭素数１〜２０のアルコキシカルボニルである。 Examples of the polymerizable liquid crystal compound include compounds represented by Formulas (1-1) to (1-4).

In the formulas (1-1) to (1-4),
X ¹ , X ³ and X ⁴ are each independently -O- or -S-;
X ² is -CH = or -N =;
W ¹ represents a single bond or an aromatic ring connected by —C≡C— (where hydrogen in the aromatic ring is fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbons, carbon (Alkoxy having 1 to 5 carbon atoms, alkyl ester having 1 to 5 carbon atoms, alkanoyl having 1 to 5 carbon atoms, or thioalkyl having 1 to 5 carbon atoms) Is a monovalent group having 6 to 16 electrons,
W ² is oxygen, sulfur, or a monocyclic or condensed ring having 5 to 10 carbon atoms (however, in the monocyclic or condensed ring, -CH = may be replaced by -N =, and -CH _2- is- O—, —NH—, —S— or —CO— may be replaced by hydrogen on carbon or nitrogen, wherein fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, C 1-5 Alkyl, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons, alkanoyl having 1 to 5 carbons or thioalkyl having 1 to 5 carbons),
W ³ is each independently cyano, alkoxycarbonyl having 1 to 10 carbon atoms or alkanoyl having 1 to 10 carbon atoms, and in the alkoxycarbonyl and alkanoyl, at least one —CH ₂ — is —O—, —COO—, -OCO-, -CH = CH- or -C≡C-
W ⁴ represents a divalent linking group selected from the group consisting of —CH ＝ CH—, —C≡C—, an aromatic ring optionally containing a hetero atom, or a combination thereof;
R ¹ is independently a group represented by the formula (2-1),

In the formula (2-1), A ¹ is each independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, at least one hydrogen atom is fluorine, cyano, formyl, trifluoroacetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, may be replaced by alkoxycarbonyl, or alkanoyl of 1 to 5 carbon atoms of 1 to 5 carbon atoms, Z ¹ is each independently represent a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - OCH 2 CH 2 O —, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO— or —COOCH ₂ CH ₂ —, and m is each independently 1 or 2 An integer, Y ¹ is a single bond, —O—, —COO—, —OCO— or —OCOO—; Q ¹ is a single bond or an alkylene having 1 to 20 carbon atoms; One of _-CH 2 - is -O -, - COO -, - OCO -, - CH = CH- or -C≡C-, PG formula (PG-1) ~ formula (PG-8 ) Is a polymerizable group represented by any one of the above.

In the formulas (PG-1) to (PG-8), R ³ is each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl;
In the formulas (1-1) to (1-4),
R ² is independently a group represented by the formula (2-2),

In Formula (2-2), A ² is each independently 1,4-phenylene or 1,4-cyclohexylene, and in 1,4-phenylene, at least one hydrogen atom is fluorine, trifluoromethyl, May be replaced by alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkoxycarbonyl having 1 to 5 carbon atoms or alkanoyl having 1 to 5 carbon atoms, Z ² is a single bond, and n is each independently R ⁴ is hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons Alternatively, it is an alkoxycarbonyl having 1 to 20 carbon atoms.

As the compounds represented by the formulas (1-1) to (1-4), Z ¹ in the formula (2-1) is independently —COO—, —OCO—, or —CH ₂ CH ₂ COO. - or -OCOCH ₂ CH ₂ - and are; PG compound is a polymerizable group represented by the formula (PG-1) it is preferable.
Further, it is more preferable that the polymerizable liquid crystal compound contains at least one compound represented by the formula (1-1) or the formula (1-3).
When the polymerizable liquid crystal compound has the formula (1-1) or the formula (1-3), the liquid crystallinity is high and the wavelength dispersion characteristics tend to be easily controlled.

式（Ｗ^１−１）〜式（Ｗ^１−１２）中、少なくとも一つの水素はフッ素、塩素、シアノ、ニトロ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルキルエステル、炭素数１〜５のアルカノイル、または炭素数１〜５のチオアルキルで置き換えられてもよい。 In the formula (1-1), W ¹ is more preferably selected from the groups represented by the formulas (W ¹ -1) to (W ¹ -12). When W ¹ is a group represented by the formulas (W ¹ -1) to (W ¹ -12), control of chromatic dispersion characteristics is easy, and synthesis is easy.

Wherein ^(W 1 -1) ~ formula ^(W 1 -12), at least one hydrogen is fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl of 1 to 5 carbon atoms, 1 to carbon atoms It may be replaced by an alkoxy having 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms, an alkanoyl having 1 to 5 carbon atoms, or a thioalkyl having 1 to 5 carbon atoms.

式（Ｗ^２−１）〜式（Ｗ^２−１２）中、少なくとも一つの水素はフッ素、塩素、シアノ、ニトロ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルキルエステル、炭素数１〜５のアルカノイル、または炭素数１〜５のチオアルキルで置き換えられてもよい。 In the formula (1-2), W ² is more preferably selected from oxygen, sulfur, and groups represented by the formulas (W ² -1) to (W ² -12). If W ² is a group represented by the formula ^(W 2 -1) ~ formula ^(W 2 -12), it is easy to control the wavelength dispersion characteristics, synthesis is facilitated.

Wherein ^(W 2 -1) ~ formula ^(W 2 -12), at least one hydrogen is fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl of 1 to 5 carbon atoms, 1 to carbon atoms It may be replaced by an alkoxy having 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms, an alkanoyl having 1 to 5 carbon atoms, or a thioalkyl having 1 to 5 carbon atoms.

In the formula (1-4), ^{W 4} can be selected from the group represented by the formula ^(W 4 -1) ~ formula ^(W 4 -3) is further preferred. If W ⁴ is a group represented by formula ^(W 4 -1) ~ formula ^(W 4 -3), it is easy to control the wavelength dispersion characteristics, synthesis is facilitated.

Hereinafter, preferable examples of the compound represented by the formula (1-1) are shown.

Hereinafter, preferable examples of the compound represented by the formula (1-2) are shown.

Hereinafter, preferable examples of the compound represented by the formula (1-3) are shown.

Hereinafter, preferable examples of the compound represented by the formula (1-4) are shown.

In the formulas (1-1-1) to (1-4-4), R ⁴ is hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, or alkyl having 2 to 20 carbons. Alkenyl, alkoxy having 1 to 20 carbons or alkoxycarbonyl having 1 to 20 carbons, wherein R ⁵ is hydrogen, fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbons, C 1-5 alkoxy, C 1-5 alkyl ester, C 1-5 alkanoyl, or C 1-5 thioalkyl, and Y ¹ is a single bond, —O—, —COO—, -OCO- or a -OCOO-, ^{Q 1} is alkylene having a single bond or 1 to 20 carbon atoms, at least one -CH ₂ - in the alkylene - is -O -, - OO-, -OCO-, -CH = CH- or -C≡C-, and PG is a polymer represented by any one of formulas (PG-1) to (PG-8). Is a sex group.

式（ＰＧ−１）〜式（ＰＧ−８）中、Ｒ^３はそれぞれ独立して水素、ハロゲン、メチル、エチルまたはトリフルオロメチルである。

In the formulas (PG-1) to (PG-8), R ³ is each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl.

Other polymerizable liquid crystal compounds include a compound represented by the following formula (M1) and a compound represented by (M2).

式（Ｍ１）および（Ｍ２）中、Ａ^Ｍはそれぞれ独立して１，４−フェニレン、１，４−シクロへキシレン、１−シクロヘキセン−１，４−イレン、２−シクロヘキセン−１，４−イレン、３−シクロヘキセン−１，４−イレン、ピリジン−２，５−ジイル、ナフタレン−２，６−ジイルまたはフルオレン−２，７−ジイルであり、これらにおいて、少なくとも一つの水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニルまたは炭素数１〜５のアルカノイルで置き換えられてもよく、Ｚ^Ｍはそれぞれ独立して単結合、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−、−ＯＣＯＯ−、−ＣＯＮＨ−、−ＮＨ
ＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＣＨ_３−、−ＣＣＨ_３＝Ｎ−、−Ｎ＝Ｎ−、−Ｃ≡Ｃ−または−Ｃ≡Ｃ−Ｃ≡Ｃ−であり、Ｘ^Ｍは水素、フッ素、塩素、トリフルオロメチル、トリフルオロメトキシ、シアノ、炭素数１〜２０のアルキル、炭素数１〜２０のアルケニル、炭素数１〜２０のアルコキシまたは炭素数１〜２０のアルコキシカルボニルであり、ｑは１〜４の整数であり、
ａは０〜２０の整数であり、Ｒ^Ｍは水素またはメチルであり、Ｙ^Ｍは単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯＯ−である。ここで、ｑが２以上である場合、このＡ^ＭおよびＺ^Ｍはその繰り返し毎に異なっていてもよい。

In the formulas (M1) and (M2), A ^M is each independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene , 3-cyclohexene-1,4-ylene, pyridine-2,5-diyl, naphthalene-2,6-diyl or fluorene-2,7-diyl, wherein at least one hydrogen atom is fluorine, chlorine, cyano , Hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons or alkanoyl having 1 to 5 carbons is well also, ^{Z M} each independently represent a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - OS -, - SCO -, - OCOO -, - CONH -, - NH
_{CO -, - CF 2 O -} , - OCF 2 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH _{2 CH 2 -, - CH =} CH -, - N = CH -, - CH = N -, - N = CCH 3 -, - CCH 3 = N -, - N = N -, - C≡C- or - a C≡C-C≡C-, ^{X M} is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, 1 to carbon atoms 20 alkoxy or alkoxycarbonyl having 1 to 20 carbon atoms, q is an integer of 1 to 4,
a is an integer from 0 to 20, ^{R M} is hydrogen or methyl, ^{Y M} is a single bond, -O -, - COO -, - OCO- or -OCOO-. Here, when q is 2 or more, A ^M and Z ^M may be different for each repetition.

In the formula (M1), A ^M is each independently 1,4-phenylene, 1,4-cyclohexylene, or naphthalene-2,6-diyl, and at least one of A ^M is 1,4 -Cyclohexylene, wherein in the 1,4-phenylene or 1,4-cyclohexylene, at least one hydrogen is fluorine, chlorine, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons. , ^C 1-5 alkoxy, ^C 1-5 alkoxycarbonyl or ^C 1-5 alkanoyl, and Z ^M each independently represents a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ CH ₂ COO— or —OCOCH ₂ CH ₂ —, and q is an integer of 1 or 2. X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons or 1 carbon a 20 alkoxycarbonyl, a is an integer of 0 to 20, ^{R M} is hydrogen or methyl, ^{Y M} is a single bond, -O -, - COO -, - OCO- or -OCOO- Compounds are preferred.

式（Ｍ３）中、Ａ^Ｍはそれぞれ独立して１，４−フェニレンまたは１，４−シクロへキシレンであり、これらにおいて、少なくとも一つの水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニルまたは炭素数１〜５のアルカノイルで置き換えられてもよく、Ｚ^Ｍはそれぞれ独立して単結合、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−、−ＯＣＯＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＣＨ_３−、−ＣＣＨ_３＝Ｎ−、−Ｎ＝Ｎ−または−Ｃ≡Ｃ−であり、ｃおよびｄはそれぞれ０〜３の整数であり、かつ１≦ｃ＋ｄ≦４の関係であり、ａは０〜２０の整数であり、Ｒ^Ｍは水素またはメチルであり、Ｙ^Ｍは単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯＯ−であり、Ｑ^Ｍは単結合、−Ｏ−または−ＣＯＯ−である。ここで、ｃ、ｄが２以上である場合、このＡ^ＭおよびＺ^Ｍはその繰り返し毎に異なっていても
よい。 Other polymerizable liquid crystal compounds include compounds represented by the following formula (M3).

In the formula (M3), ^AM is each independently 1,4-phenylene or 1,4-cyclohexylene, wherein at least one hydrogen atom is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl. , Difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons or alkanoyl having 1 to 5 carbons, and Z ^M is each independently represent a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - COS -, - SCO -, - OCOO -, - CONH -, - NHCO -, - CF 2 O _{-, - OCF 2 -, -} CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO- _{, -OCOCH 2 CH 2 -, -} CH = CH -, - N = CH -, - CH = N -, - N = CCH 3 -, - CCH 3 = N -, - N = N- or -C≡C And c and d are each an integer of 0 to 3 and have a relationship of 1 ≦ c + d ≦ 4, a is an integer of 0 to 20, R ^M is hydrogen or methyl, and Y ^M is single bond, -O -, - COO -, - OCO- or a -OCOO-, ^{Q M} represents a single bond, -O- or -COO-. Here, when c and d are 2 or more, A ^M and Z ^M may be different for each repetition.

The compound represented by the formula (M1) is a monofunctional polymerizable liquid crystal compound, and can control the liquid crystal temperature range, optical characteristics, and alignment of the liquid crystal composition. The compound represented by the formula (M2) is a bifunctional polymerizable liquid crystal compound. This polymer has a three-dimensional structure. Therefore, the polymer is harder than the compound represented by the formula (M1) having one polymerizable group. The compound represented by the formula (M3) is a trifunctional polymerizable liquid crystal compound. This polymer can form a stronger network. Therefore, this polymer becomes a harder polymer as compared with a compound having one and two polymerizable groups. Compound with xylene in at least one 1,4-cyclohexylene Of A ^M in formula (M1) ~ (M2), in order to show a lower wavelength dispersion characteristics, more likely to control the wavelength dispersion characteristics. In the future, the compounds represented by the formulas (M1), (M2) and (M3) and the compounds derived therefrom may be collectively referred to as the formula (M).

  Hereinafter, preferable examples of the compound represented by the formula (M1) are shown.

式（Ｍ１−１）〜（Ｍ１−２４）において、Ｒ^Ｍはそれぞれ独立して水素またはメチルであり、ａはそれぞれ独立して１〜１２の整数である。

In the formulas (M1-1) to (M1-24), R ^M is each independently hydrogen or methyl, and a is each independently an integer of 1 to 12.

  Hereinafter, preferable examples of the compound represented by the formula (M2) are shown.

式（Ｍ２−１）〜（Ｍ２−３１）において、Ｒ^Ｍはそれぞれ独立して水素またはメチルであり、ａはそれぞれ独立して１〜１２の整数である。式中に２つ以上のａがあるとき、任意の２つのａは同一でもよく、異なっていてもよい。

In the formulas (M2-1) to (M2-31), R ^M is each independently hydrogen or methyl, and a is each independently an integer of 1 to 12. When there are two or more a's in the formula, any two a's may be the same or different.

  Hereinafter, preferable examples of the compound represented by the formula (M3) are shown.

式（Ｍ３−１）〜（Ｍ３−１０）において、Ｒ^Ｍはそれぞれ独立して水素またはメチルであり、ａはそれぞれ独立して１〜１２の整数である。式中に２つ以上のａがあるとき、任意の２つのａは同一でもよく、異なっていてもよい。

In the formulas (M3-1) to (M3-10), R ^M is each independently hydrogen or methyl, and a is each independently an integer of 1 to 12. When there are two or more a's in the formula, any two a's may be the same or different.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is from 5 to 95% by weight. 10 to 70% by weight is preferred. 15 to 60% by weight is more preferred.
When the compounds represented by the formulas (1-1) to (1-4) are included as the polymerizable liquid crystal compound, it is easy to control the wavelength dispersion of the refractive index anisotropy, and it is possible to secure good coating properties. Therefore, it is preferable that the compounds represented by the formulas (1-1) to (1-4) are contained in an amount of 10 to 100% by weight based on the total content of the polymerizable liquid crystal compound. More preferably, the content is 50 to 100% by weight.

(Polymerization initiator)
The polymerizable liquid crystal composition contains a photopolymerization initiator. More specifically, a photo-radical polymerization initiator is included.
Examples of the photoradical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173), 1-hydroxycyclohexylphenylketone (Irgacure 184), 2,2-dimethoxy-1,2 -Diphenylethane-1-one (Irgacure 651), Irgacure 127, Irgacure 500 (mixture of Irgacure 184 and benzophenone), Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 1870, Dalocure 4265, Dalocure MBF, Dalocure TP , Irgacure 784, Irgacure 754, and the like. Both Darocur and Irgacure are the names of products sold by BASF Japan Ltd.

As the photoradical polymerization initiator, a photopolymerization initiator having an oxime ester may be used. The photopolymerization initiator having an oxime ester is illustrated below.
Specifically, compound Nos. 1 to No. 108, a compound described in JP-T-2004-534797, a compound described in International Publication WO2009 / 147031, a compound described in JP-A-2000-80068, and an oxime ester moiety described in JP-A-2006-251374. Compounds, compounds having an oxime ester site described in JP-A-2009-286976, compounds having an oxime ester site described in JP-A-2009-29929, and the like can be mentioned.

  Among the photoradical polymerization initiators, NCI-930, N-1919 (all manufactured by ADEKA Corporation), Irgacure 907, Irgacure OXE01, Irgacure OXE02, Irgacure 369, and Irgacure 379 are exemplified. These are manufactured by BASF Japan Ltd.

As the photoradical polymerization initiator, a photoradical polymerization initiator can also be used.
The photo-radical polymerization initiator is p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenyl Acridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethylketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, and a benzophenone / methyltriethanolamine mixture. .

  The content of the photopolymerization initiator in the polymerizable liquid crystal composition is preferably from 0.1 to 20% by weight based on the total weight of the polymerizable liquid crystal compound. 0.5 to 10% by weight is more preferred. More preferred is 1 to 8% by weight.

  These photopolymerization initiators may be used in combination with a sensitizer. Examples of the sensitizer include isopropylthioxanthone, diethylthioxanthone, ethyl-4 dimethylaminobenzoate (Darocur EDB), and 2-ethylhexyl-4-dimethylaminobenzoate (Darocur EHA).

  The photopolymerization initiator and the sensitizer may be used alone or in combination of two or more.

(Surfactant)
The polymerizable liquid crystal composition contains a surfactant. The surfactant can adjust the form and uniformity of the orientation, the coating properties, the recoating properties, and the like.
Surfactants include ionic and non-ionic surfactants. The surfactant is not limited to one type, and two or more types may be used in combination. From the viewpoint of compatibility with the polymerizable liquid crystal compound and solubility in a solvent, it is more preferable to use a nonionic surfactant.

  Ionic surfactants include titanate compounds, imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and its esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate Amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, lauryl amide propyl betaine, lauryl amino acetate betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, Compounds such as fluoroalkyl sulfonates and perfluoroalkyl carboxylate are exemplified.

  Examples of the type of the nonionic surfactant include a vinyl type, a silicone type, a fluorine type, and a hydrocarbon type.

Examples of the vinyl surfactant include polyalkyl acrylate, polyalkyl methacrylate, polyalkyl vinyl ether, polybutadiene, polyolefin, and polyvinyl ether. For example, polyflow No. 7, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 75, polyflow no. 77, polyflow no. 85HF, Polyflow No. 90, polyflow no. 95, polyflow no. 99C, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, BYK-399, BYK-Silenan 3700, TEGOFlow300, TEGOFlow370, And TEGOFlowZFS460.

  Examples of the silicone surfactant include polydimethylsiloxane, polyphenylsiloxane, specially modified siloxane, fluorine-modified siloxane, and surface-treated siloxane. For example, polyflow KL-400HF, polyflow KL-401, polyflow KL-402, polyflow KL-403, polyflow KL-404, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315. , BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-344, BYK-345, BYK -346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-371, BYK-375, BYK-377, BYK-378, BYK-3455, BYK-3500, BYK-3510, BYK-3530 , BYK-3570, BYK-Si clean3720, and TEGOFlow425, and the like.

  Examples of the fluorine-based surfactant include a fluorine-based polymer. For example, BYK-340, FUJANT 251, FUJANT 212M, FUJANT 215M, FUJANT 250, FUJANT 222F, FUJANT 245F, FUJANT 208G, FUJANT 240G, FUJANT 220P, FUJANT 228P, FUJANT FTX- 218, FUTAGEN DFX-18, FUTAGEN 710FL, FUTAGEN 710FM, FUTAGEN 710FS, FUTAGEN 730LM, MEGAFAK F-251, MEGAFAK F-410, MEGAFAK F-430, MEGAFAK F-444, MEGAFAK F-577, Megafac F-551, Megafac F-553, Megafac F-554, Megafac F-556, Megafac F-557, Mega Fac F-558, Mega Fac F-559, Mega Fac F-562, Mega Fac F-563, Mega Fac F-565, Mega Fac F-570, Mega Fac R-40, Mega Fac R-41, Mega Fac R -43, or Megafac R-94.

  Examples of the hydrocarbon surfactant include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin.

  The content of the surfactant in the solution containing the polymerizable liquid crystal compound is usually from 0.001 to 5.0% by weight based on the weight of the entire polymerizable liquid crystal compound. Preferably it is 0.003 to 4.0% by weight, more preferably 0.005 to 3.0% by weight. When it is within the above range, the wavelength dispersion control of the refractive index anisotropy is easy, and good coatability can be secured.

(solvent)
The type of the solvent is not particularly limited as long as it can dissolve the polymerizable liquid crystal compound, but specifically, ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ethers Solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogenated aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, and acetate solvents Solvents and the like. The solvent is not limited to one type, and two or more types may be used in combination.
From the viewpoint of solubility of the polymerizable liquid crystal compound, the solvent is preferably an amide solvent, an aromatic hydrocarbon solvent, or a ketone solvent, and in consideration of the boiling point of the solvent, an ester solvent, an alcohol solvent, an ether solvent, or glycol. It is also preferable to use a monoalkyl ether-based solvent in combination. In addition, when a photo-alignment film is used as the alignment film, it is necessary to lower the heating temperature so as not to erode the photo-alignment film or to reduce solvent damage. Solvents preferably used in such a case include aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, alcohol solvents, acetate solvents, and glycol monoalkyl ether solvents.

  Examples of the ester solvent include alkyl acetate (eg, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate), cyclohexyl acetate, ethyl trifluoroacetate, Alkyl propionates (eg, methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and butyl propionate), alkyl butyrate (eg, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propyl butyrate) , Dialkyl malonate (eg, diethyl malonate), alkyl glycolate (eg, methyl glycolate and ethyl glycolate), alkyl lactate (eg, methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate) Le lactate and ethylhexyl lactate), alkyl pyruvate (e.g. ethyl pyruvate) monoacetin, .gamma.-butyrolactone and .gamma.-valerolactone.

  Examples of the amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N-dimethylacetamide dimethyl acetal, N-methylcaprolactam, dimethylimidazolidinone and the like.

  Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, and 4-hydroxy-4-methyl. -2-pentanone (diacetone alcohol), n-hexanol, n-heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, Glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, 1,3-butanedi Diol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol and Methyl cyclohexanol and the like can be mentioned.

  Examples of the ether solvent include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, bis (2-propyl) ether, 1,3-dioxolan, 1,4-dioxane, and tetrahydrofuran (THF).

Examples of glycol monoalkyl ether solvents include ethylene glycol monoalkyl ether (eg, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (eg, diethylene glycol monoethyl ether), triethylene glycol monoalkyl ether, and propylene glycol. Monoalkyl ether (eg, propylene glycol monomethyl ether, propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (eg, dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether acetate (eg, ethylene glycol monobutyl ether acetate), diethylene glycol Monoalkyl ether Acetate (example: diethylene glycol monoethyl ether acetate), triethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate (example: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene Glycol monoalkyl ether acetate (eg, dipropylene glycol monomethyl ether acetate), diethylene glycol methyl ethyl ether, and the like.

Examples of aromatic hydrocarbon solvents include benzene, toluene, anisole, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, and terpene derivatives. (P-cymene, 1,4-cineole, 1,8-cineole, D-limonene, D-limonene oxide, p-menthane, α-pinene, β-pinene, γ-terpinene, terpinolene) and tetralin. .
Examples of the halogenated aromatic hydrocarbon solvent include chlorobenzene.
Hexane and heptane are mentioned as an aliphatic hydrocarbon solvent.
Examples of the halogenated aliphatic hydrocarbon solvent include chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene and tetrachloroethylene.
Examples of the alicyclic hydrocarbon-based solvent include cyclohexane and decalin.

  Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, cyclopentanone, and methyl propyl ketone.

  Examples of the acetate-based solvent include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, and 1-methoxy-2-propyl acetate.

  The content of the solvent in the polymerizable liquid crystal composition is usually 5% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and usually 95% by weight or less, preferably 90% by weight or less, more preferably Is not more than 85% by weight. The lower limit of the above range is a numerical value in consideration of the solubility of the polymerizable liquid crystal compound and its optimum viscosity when applying this solution. The upper limit is a numerical value in consideration of the economic cost such as the cost of the solvent and the amount of time and heat required for evaporating the solvent.

  The polymerizable liquid crystal composition may contain a compound other than a polymerizable liquid crystal compound, a photopolymerization initiator, a surfactant, and a solvent. Specific examples include a non-liquid crystalline polymerizable compound, a silane coupling agent, a chain transfer agent, an antioxidant, an ultraviolet absorber, a light stabilizer (radical scavenger), and an optically active compound. Hereinafter, each additive will be described in detail with reference to specific examples.

(Non-liquid crystalline polymerizable compound)
The polymerizable liquid crystal composition may contain a non-liquid crystal polymerizable compound (a polymerizable compound other than the polymerizable liquid crystal compound).
The non-liquid crystalline polymerizable compound is a compound such as a vinyl derivative, a styrene derivative, a (meth) acrylic acid derivative, an oxirane derivative, an oxetane derivative, a sorbic acid derivative, a fumaric acid derivative, and an itaconic acid derivative. Some do not. The other polymerizable compounds having no liquid crystallinity include compounds having one polymerizable group, compounds having two polymerizable groups, and polyfunctional compounds having three or more polymerizable groups. The polymerizable compound other than the polymerizable liquid crystal compound is not limited to one type, and two or more types may be used in combination.

  Examples of the compound having one polymerizable group include styrene, nuclear-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, fatty acid vinyl (eg, vinyl acetate), α, β-ethylenically unsaturated carboxylic acid (eg, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), alkyl ester of (meth) acrylic acid (alkyl having 1 to 18 carbon atoms), (meth) acrylic Hydroxyalkyl esters of acids (hydroxyalkyl having 1 to 18 carbon atoms), aminoalkyl esters of (meth) acrylic acid (1 to 18 carbon atoms of aminoalkyl), alkyl oxygen-containing alkyl esters of (meth) acrylic acid (ether oxygen C3-C18 of alkyl contained, for example: methoxyethyl ester, ethoxy Xyethyl ester, methoxypropyl ester, methyl carbyl ester, ethyl carbyl ester, and butyl carbyl ester), N-vinylacetamide, pt-butyl vinyl benzoate, N, N-dimethylamino vinyl benzoate, vinyl benzoate, Vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, Dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, dicyclopentenyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl Phthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol having a polymerization degree of 1 to 100, polypropylene glycol, copolymer of ethylene oxide and propylene oxide, etc. Mono (meth) acrylate or di (meth) acrylate of polyalkylene glycol, or polyethylene glycol or polypropylene glycol having a degree of polymerization of 1 to 100 and having a terminal capped by an alkyl group having 1 to 6 carbon atoms - le, and polyalkylene glycol having a copolymer of ethylene oxide and propylene oxide - such as Le mono (meth) acrylic acid esters.

  Examples of the compound having two polymerizable groups include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, and dimethylol tricyclo. Decane diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO addition diacrylate, bisphenol A glycidyl diacrylate (Biscoat V # 700), polyethylene glycol diacrylate Examples include acrylates and methacrylate compounds of these compounds.

Examples of the compound having three or more polymerizable groups include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol EO-added tri (meth) acrylate, and tris (meth) acryloyloxyethyl phosphite. Fate, tris ((meth) acryloyloxyethyl) isocyanurate, alkyl-modified dipentaerythritol tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa ( (T) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, Biscoat V # 802 (functional groups = 8), Biscoat V # 1000 (functional groups = average 14), etc. No. "Viscort" is a trade name of Osaka Organic Chemicals Co., Ltd. Those having 16 or more functional groups can be obtained by acrylizing Boltorn H20 (16 functions), Boltorn H30 (32 functions), and Boltorn H40 (64 functions), which are sold by Perstorp Specialty Chemicals.

式（α−１）〜（α−３）において、Ｒ^αはそれぞれ独立して水素またはメチルであり、ｓはそれぞれ独立して０〜４の整数である。式中に２つ以上のｓがあるとき、任意の２つのｓは同一でもよく、異なっていてもよい。 The polymerizable compound other than the polymerizable liquid crystal compound further includes a polymerizable fluorene derivative having a cardo structure. These compounds are suitable for controlling the orientation direction and further increasing the degree of curing of the polymer. Examples of the polymerizable fluorene derivative having a cardo structure are shown in formulas (α-1) to (α-3).

In the formulas (α-1) to (α-3), R ^α is each independently hydrogen or methyl, and s is each independently an integer of 0 to 4. When there are two or more s in the formula, any two s may be the same or different.

Further, examples of the polymerizable compound other than the polymerizable liquid crystal compound include a polymerizable compound having a bisphenol structure. These compounds are suitable for assisting in film forming ability and alignment uniformity. Examples of the polymerizable bisphenol derivative are shown in formulas (N-1) to (N-6).

  The content of the non-liquid crystal polymerizable compound in the polymerizable liquid crystal composition may be added as long as the liquid crystal phase is not impaired. Preferably, the weight ratio to the total weight of the polymerizable liquid crystal compound is 0.01 or more and 0.50 or less, and more preferably 0.03 or more and 0.30 or less.

(Silane coupling agent)
The polymerizable liquid crystal composition may contain a silane coupling agent, for example, for controlling adhesion to a substrate.
Examples of the silane coupling agent include vinyl trialkoxysilane, 3-isocyanatopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrialkoxysilane, N- (1,3-dimethylbutylidene) -3- (Trialkoxysilyl) -1-propanamine, 3-glycidoxypropyl trialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrialkoxysilane, and the like. In these compounds, dialkoxymethylsilane in which one of alkoxy (three) is replaced with methyl can also be used as a silane coupling agent.

  The content of the silane coupling agent in the polymerizable liquid crystal composition is usually 0.01 or more, preferably 0.03 or more, and usually 0.2 or less, preferably 0.2% by weight based on the total weight of the polymerizable liquid crystal compound. 0.1 or less. These silane coupling agents may be used alone or as a mixture of two or more.

(Chain transfer agent)
The polymerizable liquid crystal composition may contain a chain transfer agent, for example, for controlling the polymerization reaction rate, adhesion, or mechanical properties of the polymer. By including a chain transfer agent, the length of the polymer chain or the length of two crosslinked polymer chains in the polymer film can be controlled. These lengths can be controlled simultaneously. Increasing the amount of chain transfer agent decreases the rate of polymerization and decreases the length of the polymer chains. Preferred chain transfer agents are thiol compounds and styrene dimers. These chain transfer agents may be used alone or in combination of two or more.

  Examples of the thiol chain transfer agent include dodecanethiol, monofunctional thiol compounds such as 2-ethylhexyl- (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), and pentaerythritol Tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MTPE1), and 1,3 And polyfunctional thiol compounds such as 1,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Karenz MT NR1). "Karenz" is a trade name of Showa Denko KK Examples of the outer thiol compound include the thiol compounds described in paragraphs 0042 to 0043 of International Publication No. 2013/080855 and the eleventh line to p.23 of p.23 of International Publication No. 2008/077261. Examples of the styrene dimer include α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene) and 1,1-diphenylethylene, and Quinoexter QE-2014. "Kino Exter" is a trade name of Kawasaki Kasei Kogyo Co., Ltd.

  Examples of the styrene dimer chain transfer agent include 2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-1-butene.

(Antioxidant)
The polymerizable liquid crystal composition may contain an antioxidant for improving storage stability and weather resistance. As the antioxidant, a phenolic antioxidant, a sulfuric antioxidant, and a phosphoric acid antioxidant can be used. These antioxidants may be used alone or in combination of two or more.

  Examples of the antioxidant include Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 manufactured by ADEKA, Sumilizer BHT and Sumilizer BBM sold by Sumitomo Chemical Co., Ltd. -S, and Sumilizer GA-80, as well as Irganox1010 sold by BASF Japan (Co.), Irganox1035, Irganox1076, Irganox1098, Irganox1135, Irganox1330, Irganox1425, Irganox1520, Irganox1726, Irganox245, Irganox259, Irganox3114, Irganox3790, such as Irganox5057 and Irganox565 Is mentioned.

(UV absorber)
The polymerizable liquid crystal composition may contain an ultraviolet absorber for improving, for example, weather resistance. Examples of the ultraviolet absorber include Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 384-2, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479, Tinuvin 5236, Hostabin PR-25, Hostabin B-CAP, Hostabin VSU,
Adekastab LA-32, Adekastab LA-34, Adekastab LA-36, Adekastab LA-31, Adekastab 1413, and Adekastab LA-51. “Tinuvin” is a trade name of BASF Japan Co., Ltd., “Hostabine” is a trade name of Clariant Japan Co., Ltd., and “Adeka Stub” is a trade name of ADEKA. These UV absorbers may be used alone or in combination of two or more.

(Light stabilizer)
The solution containing the polymerizable liquid crystal compound may contain a light stabilizer (radical scavenger) for improving, for example, weather resistance.
Light stabilizers include Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, 5060, Tinuvin 5151, Chimasorb 119FL, Chimassorb 944FL, Chimassorb 944LD, Adekastab LA-52, Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63P, Adekastab LA-68LD, Adekastab LA-77, Adekastab LA-82, Adecastab LA And Scisorb UV-3346 manufactured by Scitech, and Goodlight UV-3034 manufactured by Goodrich. "Kimasorb" is a trade name of BASF Japan Ltd. These light stabilizers may be used alone or in combination of two or more.

(Optically active compound)
The polymerizable liquid crystal composition may contain a chiral compound, that is, an optically active compound. Examples of the optically active compound include compounds represented by formulas (Op-1) to (Op-25).

In the formulas (Op-1) to (Op-25), Ak represents alkyl having 1 to 15 carbons or alkoxy having 1 to 15 carbons, and Me, Et and Ph represent methyl, ethyl and phenyl, respectively. P ² is a polymerizable group, and is preferably a group containing (meth) acryloyloxy, vinyloxy, oxiranyl, or oxetanyl.
Examples of the optically active compound include those described in JP-A-2011-148762, p. 70 paragraphs 0159-p. 81, paragraph 0170.

  A solution containing an optically active compound or a solution containing an optically active polymerizable compound is coated on an oriented support base material and polymerized to give a helical structure (twist structure). A film is obtained. This helical structure is fixed by the polymerization of the polymerizable liquid crystal compound. The characteristics of the obtained liquid crystal film depend on the helical pitch of the obtained helical structure. The helical pitch length can be adjusted by the type and the amount of the optically active compound. One optically active compound may be added, but a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the helical pitch.

As the polymerizable liquid crystal composition, according to the production method of the present invention, a coating film obtained by applying the polymerizable liquid crystal composition on a supporting substrate and evaporating the solvent to produce a high-quality optical compensation film. When the phase transition temperature from the liquid crystal phase to the isotropic phase is T _NI , it is preferable that 120 ° C. ≧ T _NI ≧ 45 ° C. When T _NI is higher than 120 ° C., crystallization and uniformity of orientation tend to be reduced at room temperature. When T _NI is less than 45 ° C., it is difficult to obtain a uniform orientation.

(Supporting substrate)
The support substrate on which the polymerizable liquid crystal composition is applied is not particularly limited, and a known substrate can be appropriately selected. Examples of the material include plastic, metals such as aluminum, iron, and copper, alkali glass, and borosilicate. Glass, such as glass and flint glass, may be used.

  Examples of plastics include polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. , Polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose and partially saponified products thereof, epoxy resin, phenol resin, and cycloolefin resin.

  Examples of the cycloolefin-based resin include a norbornene-based resin and a dicyclopentadiene-based resin, but are not limited thereto. Among them, those having no unsaturated bond or hydrogenated unsaturated bond are preferably used. For example, hydrogenated ring-opening (co) polymer of one or more norbornene-based monomers, addition (co) polymer of one or more norbornene-based monomers, norbornene-based monomers and olefin-based monomers (Ethylene, α-olefin, etc.), addition copolymers of norbornene-based monomers and cycloolefin-based monomers (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and the like. Modified products, and the like, specifically, ZEONEX, ZEONOR (both trade names, manufactured by Zeon Corporation), ARTON (trade name, manufactured by JSR Corporation), TOPAS (trade name, manufactured by Ticona), APEL (trade name, manufactured by Mitsui Chemicals, Inc.), Ssina (trade name, manufactured by Sekisui Chemical Co., Ltd.), OPTOREZ (trade name) Manufactured by Hitachi Chemical Co., Ltd.) and the like.

The form of the support substrate is usually a sheet or film.
In the case of a film-like support substrate, it may be a uniaxially stretched film or a biaxially stretched film.
The film may have been subjected to a surface treatment such as a hydrophilization treatment such as a corona treatment or a plasma treatment, or a hydrophobic treatment. The method for the hydrophilization treatment is not particularly limited, but corona treatment or plasma treatment is preferred, and a particularly preferred method is plasma treatment. For the plasma treatment, a method described in JP-A-2002-226616, JP-A-2002-121648, or the like may be used. Further, an anchor coat layer may be formed to improve the adhesion between the liquid crystal film and the plastic film. As long as such an anchor coat layer enhances the adhesiveness between the liquid crystal film and the plastic film, there is no problem whether it is an inorganic material or an organic material. Further, the plastic film may be a laminated film.

When forming a homogeneous alignment or hybrid alignment optical compensation film on the support substrate, a physical or mechanical surface treatment such as rubbing may be performed before applying the polymerizable liquid crystal composition. When forming an optical compensation film having homeotropic alignment, surface treatment such as rubbing is not often performed, but rubbing may be performed in order to prevent alignment defects and the like. Any method can be used for the rubbing treatment.However, usually, a rubbing cloth made of a material such as rayon, cotton, or polyamide is wound around a metal roll or the like, and the roll is rotated while being in contact with the supporting substrate or the polymer film. A method of moving the supporting base material while the roll is fixed, and the like. The rubbing treatment may be performed directly on the support substrate, or a polymer film such as polyimide generally referred to as an alignment film may be provided on the support substrate in advance, and the polymer film may be subjected to the rubbing treatment. The rubbing method is as described above. Depending on the type of the supporting base material, silicon oxide can be obliquely vapor-deposited on the surface to impart orientation ability.

  In addition, when forming an optical compensation film of a homogeneous orientation and a hybrid orientation, in addition to performing physical and mechanical surface treatment such as rubbing, a polyimide or polyacrylate generally called a photo-alignment film on a support substrate in advance. Or the like, and a polarized UV treatment may be applied to the polymer film.

<Optical compensation film>
The production method of the present invention is a production method capable of producing an optical compensation film in which the orientation of constituent molecules is uniform. You can choose.
The orientation of the constituent molecules of the optical compensation film is classified into homogenous (parallel), homeotropic (vertical), tilted (tilted), twisted (twisted), etc. based on the size of the tilt angle. Is done. The tilt angle is an angle between the orientation of the constituent molecules and the supporting substrate. Homogeneous refers to a state in which the alignment state is parallel to the base material and arranged in one direction. An example of the tilt angle of the homogeneous orientation is 0 ° to 5 °. Homeotropic refers to a state in which the orientation state is perpendicular to the substrate. Examples of tilt angles in homeotropic alignment are 85 ° to 90 °. Tilt refers to a state where the orientation rises from parallel to vertical as the orientation state moves away from the substrate. An example of the tilt angle (tilt angle) in the tilt orientation is 5 ° to 85 °. The twist refers to a state in which the orientation state is parallel to the base material, but is twisted in a stepwise manner around a helical axis. Examples of the tilt angle in the twist orientation are 0 ° to 5 °.

  In the case of forming a film by coating on a plastic that has been subjected to an alignment treatment such as a rubbing treatment or on a supporting substrate whose surface is coated with a plastic thin film, for example, the orientation of the constituent molecules is controlled by a homogeneous alignment or a hybrid alignment. Compensation films can be manufactured. When the above-mentioned optically active compound is added to a solution, a twist-oriented optical compensation film can be produced. Furthermore, when a compound having a cardo structure described above or a monofunctional liquid crystal compound is added to the solution, an optical compensation film having homeotropic alignment can be produced. The tilt angle can be controlled by adjusting, for example, the type, composition ratio, and the like of the polymerizable liquid crystal compound, the solvent, and the compound added to the solution. The tilt angle can also be controlled by the type of the support substrate and the coating, the rubbing conditions, the drying and heat treatment conditions of the coating, the irradiation atmosphere in the polymerization step, the temperature during irradiation, and the like.

The form, physical properties, and the like of the optical compensation film produced by the production method of the present invention are not particularly limited, and can be appropriately selected depending on the purpose.
The thickness of the optical compensation film is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and is usually 500 μm or less, preferably 300 μm or less, more preferably 200 μm or less.
The birefringence Δn (550) of the optical compensation film is usually 0.03 or more, preferably 0.04 or more, more preferably 0.05 or more, and usually 0.5 or less, preferably 0.4 or more, and more preferably Is 0.3 or less.
The thickness can be reduced as the birefringence (value indicating optical anisotropy) of the optical compensation film is higher. The smaller the thickness, the better the optical characteristics such as haze value and transmittance tend to be.
The optical compensation film preferably has a birefringence index Δn (λ) for light having a wavelength of λ nm of Δn (450) / Δn (550) ≦ 1.05, and Δn (450) / Δn (550) ≦ 1. 00 is more preferable, and it is further preferable that Δn (450) / Δn (550) ≦ 0.95. When it is in the above range, it can be used for various uses as an optical compensation film having excellent wavelength dispersion control characteristics.

The optical compensation film manufactured by the manufacturing method of the present invention may have a selective reflection characteristic of selectively reflecting visible light. In the selective reflection characteristic, a helical structure acts on incident light to reflect circularly polarized light or elliptically polarized light. Since the selective reflection characteristic is represented by λ = n · Pitch (λ is the central wavelength of selective reflection, n is the average refractive index, and Pitch is a helical pitch), the central wavelength (λ) and wavelength width can be changed by changing n or Pitch. (Δλ) can be adjusted appropriately. To improve the color purity, the wavelength width (Δλ) may be reduced, and when broadband reflection is desired, the wavelength width (Δλ) may be increased.
By making the helical pitch shorter than the wavelength of visible light, a negative C plate (Negative C plate) described in WH de Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980) can be prepared. Shortening the helical pitch can be achieved by using an optically active compound having a large torsional force (HTP: helical twisting power) and further increasing the amount thereof. Specifically, by setting λ to 350 nm or less, preferably 200 nm or less, a negative C plate can be prepared. This negative type C plate is an optical compensation film suitable for a display device such as a VAN type, a VAC type, and an OCB type among liquid crystal display devices. Further, the optical compensation film is a reflection film in which the reflection wavelength region is set to near infrared (wavelength 800 to 2500 nm) as described in JP-A-2004-333671 by making the helical pitch longer than visible light. Can be used. In order to lengthen the helical pitch, for example, it can be achieved by using an optically active compound having a small twisting power or by reducing the amount of the optically active compound added.
As the optically active compound, any optically active compound may be used as long as it induces a helical structure and can be appropriately mixed with a liquid crystal composition serving as a base. Further, either a polymerizable compound or a non-polymerizable compound may be used, and an optimum compound can be added according to the purpose. In consideration of heat resistance and solvent resistance, a polymerizable compound is more preferable. Further, among the optically active compounds, those having a large twisting power (HTP: helical twisting power) are suitable for shortening the helical pitch. Representative examples of compounds having a large torsional force are disclosed in GB-A-2298202 and DE-A-10221175.

<Optical element, liquid crystal display, organic EL display>
The use of the optical compensation film produced by the production method of the present invention is not particularly limited. ) And organic EL display devices

As an example of application to a liquid crystal display device, impurities are eluted very little into the liquid crystal filled in the liquid crystal cell of the liquid crystal display device, and therefore, it can be disposed inside the liquid crystal cell. For example, if the method disclosed in Japanese Patent Application Laid-Open No. 2008-01943 is applied, the function of the color filter can be further improved by forming the polymerizable liquid crystal layer of the present invention on the color filter.
When used as an optical element integrated with a polarizing plate or the like, it is arranged outside the liquid crystal cell. The type of the polarizing plate is not particularly limited, but examples thereof include an absorption type polarizing plate doped with iodine and a reflection type polarizing plate such as a wire grid polarizing plate. When the polarizing plate includes a stretched film as a component, it is disposed outside the liquid crystal cell. When the polarizing plate comprises an inorganic film as a component, it may be arranged either outside the liquid crystal cell or inside the liquid crystal cell.
Types of liquid crystal display devices include IPS type (in-plane switching), OCB type (optically compensated birefringence), TN type (twisted nematic), STN type (super twisted nematic), ECB Type (electrically controlled birefringence), DAP type (deformation effect of aligned phase), CSH type (color super homeotropic), VAN / VAC type (vertically oriented nematic / cholesteric), OMI type (optical Mode interference), SBE type (super birefringence effect) and the like. Further, an optical compensation film can be used as a phase retarder for a display element of a guest-host type, a ferroelectric type, an antiferroelectric type or the like.

The method for manufacturing the liquid crystal display device is not particularly limited, and a known method can be appropriately selected. For example, a transparent electrode such as ITO is formed on the optical compensation film manufactured by the manufacturing method of the present invention by a vacuum film forming method such as sputtering, and an alignment film in a vertical alignment mode is formed after the electrode is formed. A liquid crystal display device having a vertical alignment mode can be obtained by injecting and bonding a liquid crystal having a negative dielectric anisotropy. Since the optical compensation film becomes strong due to the additional heat curing treatment, it can be arranged in the liquid crystal cell, and is used to bond the stretched type optical compensation film and the liquid crystal cell which have been used so far. No adhesive is required. As a result, a decrease in contrast due to interfacial reflection of the adhesive can be prevented, which is useful for increasing the contrast (higher quality) of the liquid crystal display in the vertical alignment mode.
In addition, the optimal values of the parameters such as the helical pitch and the thickness of the twist alignment required for the optically anisotropic body having the twist alignment strongly depend on the type of liquid crystal display device to be compensated and its optical parameters. different.

  As an example of application to an organic EL display device, it is used as a circularly polarizing plate integrated with a polarizing plate or the like for the purpose of preventing reflection. Since an organic EL display device has a highly reflective metal layer, problems such as reflection of external light and reflection of a background are likely to occur. Therefore, an object is to prevent these problems by providing a circularly polarizing plate on the viewing side. In order to exhibit the function as a circularly polarizing plate, it is preferable that the optical compensation film is designed as a 波長 wavelength plate.

  The optical compensation film may contain an additive such as a dichroic dye. As the dichroic dye, a dye composed of anthraquinone, naphthoquinone or azobenzene is preferable. A liquid crystal film of a homogeneous alignment which is complexed with a dichroic dye can also be used as an absorption type polarizing plate. Further, a homogeneously oriented liquid crystal film complexed with a fluorescent dye can also be used as a polarized light emitting film.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

<Phase transition temperature>
The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, heated at a rate of 3 ° C./min, and the temperature at which a transition from a nematic phase to an isotropic liquid was measured. T _NI = 50 ° C. indicates a transition from a nematic phase to an isotropic liquid at 50 ° C.
The sample can be obtained by applying the polymerizable liquid crystal composition on a supporting substrate and substantially removing the solvent by heat treatment or hot-air drying.

<Confirmation of substrate surface temperature>
The surface temperature of the substrate was measured using a portable digital temperature and humidity indicator DFT-700-M (manufactured by Shinko Technos Co.) and using PCE-707L as a sensor.

<Confirmation of cooling rate>
The production method of the optical compensation film of the present invention is characterized in that the cooling step is important and satisfies at least one of the following conditions (i) and (ii).
Coating film after the heating step in (i) the temperature T _H is, before being cooled to room temperature T _R, the temperature T _i includes one or more times the length of time to keep at, and duration each 30 holding at a temperature T _i Seconds or more. Here, the temperature _{T i} satisfies _{T H> T i ≧ T R} + 20 ℃.
(Ii) a coating film formed through a heating step to evaporate the solvent at a temperature T _H is the average cooling rate from the temperature T _H to be cooled to room temperature T _R is 20 ° C. / min or less.
In the present invention, the cooling step is (ii) the coating film, when the average cooling rate from the temperature T _H to be cooled to room temperature T _R is 20 ° C. / min or less, confirming a cooling rate is necessary. The supporting substrate is heated at the hot plates set at a temperature T _H, the surface temperature T _S1 was measured using a temperature sensor of the contact type, it was confirmed that T _H and T _S1 is substantially equal. Thereafter, the supporting base material is removed from the hot plate, placed on a metal plate for cooling, the surface temperature T _S2 is measured in the same manner, and a period t _c until the temperature T _R becomes substantially equal to the previously measured room temperature TR. Was measured, and the average cooling rate was calculated by (T _S1 −T _S2 ) / t _c . In addition, the change in the surface temperature of the supporting substrate when placed on a rubber plate instead of the metal plate was similarly measured, and the cooling rate was calculated.
The temperature _{T A} and the temperature _{T B} is "approximately equal" _| was _{≦ 2 ℃ | T A -T B} . In the present invention, when the cooling rate exceeds 20 ° C./min, “rapid cooling” is used, and when the cooling rate is 20 ° C./min or less, “slow cooling” is used.
Further, the cooling step (i) is maintained at a temperature T _i ( _TH > T ₁ , T ₂ , T ₃ ,..., T _i ≧ room temperature T _R + 20 ° C.) before the coating film is cooled to the room temperature TR. In the case where the time period for holding the temperature T _i is one or more times and the time periods for holding at the temperature Ti are 30 seconds or more, the condition (ii) may not be satisfied.

<Confirmation of room temperature>
Room temperature T _R is determined using Shigumamini α temperature and humidity recorder (manufactured by SATO meter Seisakusho). The operations described in the examples were performed in an environment where temperature and humidity were controlled, and were always 25 ° C.

<Polymerization conditions>
Under a nitrogen atmosphere, light having an intensity of 19 mW / cm ² (365 nm) was irradiated for 26 seconds at room temperature using a 250 W ultra-high pressure mercury lamp (manufactured by Ushio Inc., Multilight-250).

<Evaluation of orientation>
(1) Preparation of glass substrate with rubbed alignment film with spin coating Polyamic acid for low pretilt angle (horizontal alignment mode) (Rixon aligner: PIA-5370 JNC) is spin-coated on a glass substrate having a thickness of 1.1 mm. After the solvent was removed from the spin-coated coating film on a hot plate at 80 ° C., the coating film was baked in an oven at 230 ° C. for 30 minutes and rubbed using a rayon cloth.

(2) Visual Observation Method A substrate on which a retardation film was formed was sandwiched between two polarizing plates arranged in crossed Nicols and observed, and the substrate was rotated in a horizontal plane to confirm a bright and dark state. The substrate on which the retardation film was formed was observed with a polarizing microscope, and the presence or absence of alignment defects was confirmed. When there was a portion where light could be seen in the dark state, or when both the bright state and the dark state could not be confirmed, it was determined that the alignment defect.

(3) Measurement by Polarization Analyzer Using a polarization analyzer OPTIPRO manufactured by Shintec Co., Ltd., the substrate on which the retardation film was formed was irradiated with light having wavelengths of 550 nm and 450 nm. The retardation was measured while reducing the incident angle of these lights from 90 ° with respect to the film surface. Retardation (retardation; also called phase retardation) is represented by Δn × d. The symbol Δn is the optical anisotropy value, and the symbol d is the thickness of the optical compensation film.

<Film thickness measurement>
The layer of the optical compensation film of the glass substrate with the optical compensation film was cut out, and the level difference was measured using a fine shape measuring device (alpha step IQ manufactured by KLA TENCOR CORPORATION).

<Evaluation of optical anisotropy (Δn)>
The optical anisotropy (Δn) = retardation (Re) / thickness (d) is obtained from the retardation and the thickness when the incident angle of light obtained for the liquid crystal film having a homogeneous orientation is 90 ° with respect to the film surface. Calculated.

<Evaluation of wavelength dispersion characteristics>
As a characteristic of chromatic dispersion, a value obtained from the following equation was used as an index.
Characteristics of wavelength dispersion = retardation (Re450 nm) measured with light of 450 nm / retardation (Re550 nm) measured with light of 550 nm.
In other words, the smaller the characteristic value of the chromatic dispersion is, the higher the low chromatic dispersion property is, and when the value is 1 or less, it indicates that the chromatic dispersion has the inverse chromatic dispersion property.

<Polymerizable liquid crystal compound>
The following compounds were used as polymerizable liquid crystal compounds in Examples and Comparative Examples. In addition, the aspect ratio of the molecular structure of the following compounds was calculated from the molecular model optimized by the molecular calculation method using B3LYP / 6-31G (d).
-Compound (1-1-2a)
Compound (1-1-2a) is a compound (1-1-2) in which R ⁵ is hydrogen, Y ¹ is each —O—, Q ¹ is each alkylene having 6 carbon atoms, and PG Are each PG-1, and R ^{3 in} PG-1 is each hydrogen.
In addition, the compound (1-1-2a) had an aspect ratio of 1.98 determined by molecular calculation.

-Compound (1-1-2b)
In the compound (1-1-2b), in the compound (1-1-2), R ⁵ is chlorine bonded to the p-position, Y ¹ is each —O—, and Q ¹ is each 6 carbon atoms. Wherein PG is each PG-1 and R ^{3 in} PG-1 is each hydrogen.
In addition, the compound (1-1-2b) had an aspect ratio of 1.97 determined by molecular calculation.

-Compound (1-1-6a)
Compound (1-1-6a) is a compound (1-1-6) wherein R ⁵ is hydrogen, Y ¹ is each —O—, Q ¹ is each alkylene having 6 carbon atoms, and PG Are each PG-1, and R ^{3 in} PG-1 is each hydrogen.
Note that the compound (1-1-6a) had an aspect ratio L / D of 1.96 determined by molecular calculation.

-Compound (1-1-14a)
The compound (1-1-14a) is a compound (1-1-14) in which R ⁵ is hydrogen, Y ¹ is each —O—, Q ¹ is alkylene having 6 carbon atoms, and PG Are each PG-1, and R ^{3 in} PG-1 is each hydrogen.
In addition, the compound (1-1-14a) had an aspect ratio of 1.98 determined by molecular calculation.

-Compound (1-4-1a)
In the compound (1-4-1a), in the compound (1-4-1), each of R ⁴ is alkyl having 3 carbon atoms, each Y ¹ is —O—, and each Q ¹ has 6 carbon atoms. alkylene, PG is PG-1, respectively, ^{R 3} in the PG-1 is hydrogen, respectively.
In addition, as the compound (1-4-1a), two types of optimal molecular structures obtained by molecular calculation were obtained. These are due to differences in conformation, and are referred to as Structure 1 and Structure 2, respectively, as shown below. The aspect ratio of Structure 1 was 2.09, and the aspect ratio of Structure 2 was 1.36.

-Compound (1-2-3a)
In the compound (1-2-3a), in the compound (1-2-3), each of Y ¹ is —O—, each of Q ¹ is alkylene having 6 carbon atoms, and each of PG is PG-1. , ^{R 3} in the PG-1 is hydrogen, respectively.
In addition, the compound (1-2-3a) had an aspect ratio of 1.98 determined by molecular calculation.

-Compound (1-3-3a)
In the compound (1-3-3a), in the compound (1-2-3), each of Y ¹ is —O—, each of Q ¹ is alkylene having 6 carbon atoms, and each of PG is PG-1. , ^{R 3} in the PG-1 is hydrogen, respectively.
In addition, the compound (1-3-3a) had an aspect ratio determined by molecular calculation of 2.00.

次にこの重合性液晶化合物の混合物（ＭＩＸ−１）１００重量部に対して、重合開始剤としてＩｒｇａｃｕｒｅ１８４（商品名、ＢＡＳＦジャパン株式会社製）を３重量部、界面活性剤としてＴＥＧＯＦＬＯＷ３７０（商品名、エボニック社製）を１．５重量部添加して、これを室温（２５℃）で撹拌し、シクロヘキサノンに溶解し（ＭＩＸ−１）の濃度が２５重量％の溶液を調製した。この溶液を（ＰＬＣ−１）とする。 <Preparation of polymerizable liquid crystal composition (PLC-1)>
Compound (1-1-2a) 90 wt%, in the compounds (M2-7) is a = 4, ^{R M} is hydrogen, a mixture of compound (M2-7a) consisting of 10 wt% polymerizable liquid crystal compound (MIX- 1) was prepared.

Next, with respect to 100 parts by weight of the polymerizable liquid crystal compound mixture (MIX-1), 3 parts by weight of Irgacure 184 (trade name, manufactured by BASF Japan Co., Ltd.) as a polymerization initiator, and TEGOFLOW 370 (trade name, as a surfactant) 1.5 parts by weight (Evonik) were added, and the mixture was stirred at room temperature (25 ° C.) and dissolved in cyclohexanone to prepare a solution having a concentration of (MIX-1) of 25% by weight. This solution is designated as (PLC-1).

<Preparation of polymerizable liquid crystal compositions (PLC-2 to PLC-10)>
PLC-2 to PLC-10 were prepared in the same manner as PLC-1. The compounds and compositions used are summarized in Table 1. Incidentally, a compound a = 4, ^{R M} is hydrogen in the compounds in Table (m2-1a) compound (M2-1), a = 6 in the compound (M1-24a) compound (M1-24) , ^RM are hydrogen.

[Example 1]
<When the cooling step satisfies the above (i)>
In this example, as shown in Table 3, using the polymerizable liquid crystal composition (PLC-1), an optical compensation film was manufactured in the following order.
(1) Spin coating on a rubbed glass substrate with an alignment film.
(2) This glass substrate is heated at 90 ° C. for 1 minute. (90 ° C / 1 minute)
(3) Then, hold 1 min at _{60 ℃ (≧ T R + 20} ℃). (60 ° C / 1 minute)
(4) Leave still for 30 seconds on a metal plate having a thickness of about 1.6 cm placed at room temperature (25 ° C).
(5) Thereafter, the coating film from which the solvent has been removed is polymerized in the air by ultraviolet rays.
(6) The optical compensation film is inserted between two polarizing plates arranged in a polarizing microscope (cross Nicol).
(7) When the substrate is in a dark field state, it is confirmed that there is no light leakage, and a bright and dark state is confirmed.
As a result, it was determined that the orientation was uniform.
As shown in FIG. 1, the retardation of the optical compensation film was determined to be horizontal because the retardation from the vertical direction was the largest as shown in FIG.
The thickness was 1.9 μm. When the phase transition temperature of the polymerizable liquid crystal composition (PLC-1) after the solvent removal treatment was confirmed with a polarizing microscope, T _NI was 62 ° C.

[Comparative Example 1]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 1, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-1). However, in Comparative Example 1, in the heating step, 40 ° C. <were changed to hold one minute at a temperature of T R ₊ 20 ℃).
In this case, it was determined that the orientation was non-uniform. At that time, the film thickness was 1.9 μm.

[Example 2]
<When the cooling step satisfies the condition (ii)>
As shown in Table 3, in Example 2, the optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-2). However, in Example 1, after heating in the cooling step, the room temperature (25 ° C.) allowed to stand for 4 minutes to put a thick rubber board approximately 0.6cm in), the period until the temperature of annealing (substrate the substrate from T _H to room temperature T _R is room temperature in 4 minutes Yes, average cooling rate of substrate is 16.3 ° C
/ Min at 20 ° C / min. ) Was implemented.
As a result, it was determined that the orientation was uniform.
Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined that the film was in a horizontal orientation.
Further, the film thickness was 1.3 μm. When the phase transition temperature was confirmed in the same manner as in Example 1, T _NI was 75 ° C.

[Comparative Example 2]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 2, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-2). ) and allowed to stand 2.5 min placed a thickness of about 1.6cm of the metal plate on during the subsequent period of the substrate from T _H to quenching to room temperature T _R (temperature of the substrate is room temperature Is 2.5 minutes, and the average cooling rate of the substrate is 26 ° C./min, which exceeds 20 ° C./min.).
As a result, it was determined that the orientation was non-uniform. At that time, the film thickness was 1.3 μm.

[Example 3]
<When the cooling step satisfies the above (i)>
As shown in Table 3, in Example 3, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-3). The test was carried out with a change to hold for 1 minute.
As a result, it was determined that the orientation was uniform. Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined that the film was in a horizontal orientation.
Further, the film thickness was 1.3 μm. When the phase transition temperature was confirmed in the same manner as in Example 1, T _NI was 85 ° C.

[Comparative Example 3]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 3, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-3). after heating for 1 minute, in the cooling step, it was changed to hold 20 seconds at _{60 ℃ (≧ T R + 20} ℃).
As a result, when the substrate was placed in a dark field state, a region where light leaked was confirmed, and it was determined that the orientation was non-uniform. At that time, the film thickness was 1.3 μm.

[Example 4]
<When the cooling step satisfies the above (i)>
As shown in Table 3, in Example 4, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-4). after heating for one minute at a temperature, in the cooling step was performed by changing the operation to hold 1 min at _{60 ℃ (≧ T R + 20} ℃).
As a result, it was determined that the orientation was uniform.
As a result of measuring the retardation of the optical compensation film, the same graph as in Example 1 was obtained, and the retardation from the vertical direction was the maximum.
Further, the film thickness was 1.7 μm. When the phase transition temperature was confirmed in the same manner as in Example 1, T _NI was 65 ° C.

[Comparative Example 4]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 4, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-4), but in Example 1, the substrate was heated at a temperature of 80 ° C. in the heating step. after heating for 1 minute, in the cooling step, allowed to stand for 1 minute at room temperature (25 ° C.) placed a thickness of about 1.6cm of the metal plate on during, until the temperature of the substrate to room temperature T _R from T _H The operation of rapid cooling (the period until the temperature of the substrate reaches room temperature is 1 minute, and the average cooling rate of the substrate is 55 ° C./min and exceeds 20 ° C./min) was performed by changing the operation.
As a result, when the substrate was placed in a dark field state, a region where light leaked was confirmed, and it was determined that the orientation was non-uniform. At that time, the film thickness was 1.7 μm.

[Example 5]
<When the cooling step satisfies the condition (ii)>
As shown in Table 3, in Example 5, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-5), but in Example 1, the substrate was heated at a temperature of 100 ° C. in the heating step. after heating for 1 minute, in the cooling step, allowed to stand for 4 minutes at room temperature (25 ° C.) to put the thickness rubber plate on about 0.6 cm, Xu temperature of the substrate is from T _H to room temperature T _R The cooling was performed so that the period until the temperature of the substrate reached room temperature was 4 minutes, and the average cooling rate of the substrate was 18.8 ° C./min and 20 ° C./min or less.
As a result, it was determined that the orientation was uniform. Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined to be in the horizontal direction.
The thickness was 1.2 μm. When the phase transition temperature was observed in the same manner as in Example 1, the T _NI was 59 ° C.

[Comparative Example 5]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 5, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-5). After heating for 1 minute, the cooling step was performed by changing the operation of maintaining the temperature at 40 ° C. (≧ room temperature T _R + 20 ° C.) for 1 minute.
As a result, when the substrate was placed in a dark field state, a region where light leaked was confirmed, and it was determined that the orientation was non-uniform. At that time, the film thickness was 1.2 μm.

[Example 6]
<When the cooling step satisfies the condition (ii)>
As shown in Table 3, in Example 6, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-6). ) and allowed to stand for 4 minutes to put a thick rubber plate on about 0.6cm in, the temperature of annealing (substrate temperature of the substrate is from T _H to room temperature T _R is the period until the room temperature 4 minutes, and the average cooling rate of the substrate was 16.3 ° C./min and 20 ° C./min or less.)
As a result, it was determined that the orientation was uniform. Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined to be in the horizontal direction.
The thickness was 1.2 μm. When the phase transition temperature was confirmed in the same manner as in Example 1, T _NI was 71 ° C.

[Comparative Example 6]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 6, it was prepared an optical compensation film using a polymerizable liquid crystal composition (PLC-6), from Example 1, in the cooling step, the temperature 40 ℃ (<T _R (+ 20 ° C.) for 1 minute, and then changed to rest on a metal plate having a thickness of about 1.6 cm placed at room temperature (25 ° C.) for 1 minute.
As a result, it was determined that the orientation was non-uniform. At that time, the film thickness was 1.2 μm.

[Example 7]
<When the cooling step satisfies the above (i)>
As shown in Table 3, in Example 7, the optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-7). The test was carried out by changing the temperature to 1 minute.
As a result, it was determined that the orientation was uniform. Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined that the film was in a horizontal orientation.
The thickness was 2.0 μm. When the phase transition temperature was observed in the same manner as in Example 1, the _TNI was 57 ° C.

[Comparative Example 7]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 7, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-7). However, in Example 1, the substrate was heated to 80 ° C. in the heating step and the cooling step. after heating at the temperature for 1 minute, temperature _{40 ℃ (<T R + 20} ℃) was maintained for 1 minute, 1 minute standing to room temperature (25 ° C.) placed a thickness of about 1.6cm of the metal plate on during Was implemented.
As a result, when the substrate was placed in a dark field state, a region where light leaked was confirmed, and it was determined that the orientation was non-uniform. At that time, the film thickness was 2.0 μm.

Example 8
<When the cooling step satisfies the above (i)>
As shown in Table 3, in Example 8, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-8). However, in Example 1, the heating of the substrate was performed at 100 ° C. in the heating step. after heating for one minute at a temperature, in the cooling _{step, 60 ℃ (> T R +} 20 ℃) was maintained for 1 minute at room temperature (25 ° C.) for 1 minute to put the thickness of about 1.6cm of the metal plate on during The test was carried out by changing to stand still.
As a result, it was determined that the orientation was uniform. Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined that the film was in a horizontal orientation.
The thickness was 2.0 μm. When the phase transition temperature was observed in the same manner as in Example 1, T _NI was 65 ° C.

[Comparative Example 8]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 8, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-8), but in Example 1, the substrate was heated at a temperature of 100 ° C. in the heating step. after heating for 1 minute, in the cooling step, and held for 20 seconds at a temperature _{60 ℃ (> T R + 20} ℃), static 1 minutes at room temperature (25 ° C.) placed a thickness of about 1.6cm of the metal plate on during It was carried out by changing it to be placed.
As a result, when the substrate was placed in a dark field state, a region where light leaked was confirmed, and it was determined that the orientation was non-uniform. At that time, the film thickness was 2.0 μm.

[Example 9]
<When the cooling step satisfies the above (i)>
As shown in Table 3, in Example 9, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-9), but in Example 1, the substrate was heated at a temperature of 100 ° C. in the heating step. after heating for 1 minute, in the cooling step, and held for one minute at a temperature _{60 ℃ (> T R + 20} ℃), static 1 minutes at room temperature (25 ° C.) placed a thickness of about 1.6cm of the metal plate on during It was carried out by changing it to be placed.
As a result, it was determined that the orientation was uniform. Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined that the film was in a horizontal orientation.
Further, the film thickness was 1.7 μm. When the phase transition temperature was observed in the same manner as in Example 1, the _TNI was 77 ° C.

[Example 10]
<When the cooling step satisfies the above (i)>
As shown in Table 3, in Example 10, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-10). However, in Example 1, the substrate was heated at 100 ° C. in the heating step. after heating for one minute at a temperature, in the cooling _{step, 60 ℃ (> T R +} 20 ℃) was maintained for 1 minute at room temperature (25 ° C.) for 1 minute to put the thickness of about 1.6cm of the metal plate on during The test was carried out by changing to stand still.
As a result, it was determined that the orientation was uniform. Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined that the film was in a horizontal orientation.
The thickness was 1.7 μm. When the phase transition temperature was observed in the same manner as in Example 1, the T _NI was 82 ° C.

[Example 11]
<When the cooling step satisfies the above (i)>
As shown in Table 3, in Example 11, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-11). In Example 1, the heating of the substrate was performed at 100 ° C. in the heating step. after heating for one minute at a temperature, in the cooling _{step, 50 ℃ (> T R +} 20 ℃) was maintained for 3 minutes at room temperature (25 ° C.) for 1 minute to put the thickness of about 1.6cm of the metal plate on during The test was carried out by changing to stand still.
As a result, it was determined that the orientation was uniform. Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined that the film was in a horizontal orientation.
Further, the film thickness was 2.0 μm. When the phase transition point was observed in the same manner as in Example 1, the _TNI was 58 ° C.

[Comparative Example 9]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 9, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-9), but in Example 1, the substrate was heated at a temperature of 100 ° C. in the heating step. after heating for 1 minute, in the cooling step, allowed to stand for 1 minute at room temperature (25 ° C.) placed a thickness of about 1.6cm of the metal plate on during, until the temperature of the substrate to room temperature T _R from T _H Rapid cooling was performed (the period until the temperature of the substrate reached room temperature was 1 minute, and the average cooling rate of the substrate was 60 ° C./min and exceeded 20 ° C./min).
As a result, when the optical anisotropy of the substrate was confirmed, a film having optical anisotropy was not obtained because the substrate was not in a dark field state when viewed from any angle, and the orientation was non-uniform. Was. The thickness was 2.0 μm.

[Example 12]
<When the cooling step satisfies the above (i)>
As shown in Table 3, in Example 12, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-12), but in Example 1, the substrate was heated at a temperature of 100 ° C. in the heating step. after heating for 1 minute, in the cooling _{step, 50 ℃ (> T R +} 20 ℃) was maintained for 3 minutes, 1 minute standing to room temperature (25 ° C.) placed a thickness of about 1.6cm of the metal plate on during Was implemented.
As a result, it was determined that the orientation was uniform.
Since the same graph as in Example 1 was obtained from the measurement result of the retardation of the optical compensation film, it was determined that the film was in a horizontal orientation.
Further, the film thickness was 2.0 μm. When the phase transition temperature was observed in the same manner as in Example 1, the _TNI was 58 ° C.

[Comparative Example 10]
<When the cooling step does not satisfy the above (i) and (ii)>
As shown in Table 4, in Comparative Example 10, an optical compensation film was manufactured using the polymerizable liquid crystal composition (PLC-10), but in Example 1, the substrate was heated at 100 ° C. in the heating step. after heating for 1 minute, in the cooling step, and held at a temperature _{40 ℃ (<T R + 20} ℃) 3 minutes, the static 1 minutes at room temperature (25 ° C.) placed a thickness of about 1.6cm of the metal plate on during It was carried out by changing it to be placed.
As a result, when the optical compensation film was confirmed, no dark field state was obtained, and a film having optical anisotropy was not obtained because the orientation was non-uniform. The thickness was 2.0 μm.

The production conditions of the optical compensation films produced in Examples 1 to 12 and Comparative Examples 1 to 10 are shown in Tables 3 and 4.

<Optical properties of optical compensation film>
FIG. 2 shows the wavelength dispersion characteristics of the retardation at 90 ° with respect to the film surface of the optical compensation film produced in Example 1 (measured value at wavelength _λ nm (Re _λ ) / measured value at wavelength 550 nm (Re ₅₅₀ )). .
Further, the wavelength dispersion characteristics of the retardation at 90 ° with respect to the film surface of the optical compensation film produced in Examples 1 to 12 (measured value at 450 nm (Re ₄₅₀ ) / measured value at 550 nm (Re ₅₅₀ )), film thickness Table 5 shows Δn at a wavelength of 550 nm.

The production method of the present invention can efficiently produce a high-quality optical compensation film having uniform orientation of constituent molecules. Further, it can be applied to the production of an optical compensation film having excellent wavelength dispersion control characteristics. Therefore, the optical compensation film produced by the production method of the present invention includes, for example, a retardation film, an optical compensation film, a reflection film, a selective reflection film, an antireflection film, a viewing angle compensation film, a liquid crystal alignment film, a polarizing element, and a circular element. It is suitable for a polarizing element, an elliptically polarizing element, and the like, and a display element having these films or elements.

Claims (6)

A coating step of coating the polymerizable liquid crystal composition on a support substrate,
The coating film obtained in the coating step was heated at a temperature T _H, a heating step to evaporate the solvent,
A cooling step of holding the coating film obtained in the heating step in the air or leaving the coating film to stand on a rubber base and cooling to room temperature TR _;
Including a polymerization step of polymerizing the coating film obtained in the cooling step by light irradiation,
When the polymerizable liquid crystal composition has a rod-shaped molecular structure, and the length of the major axis in the molecular structure is L and the length of the minor axis is D, the aspect ratio (L / D) is 3 or less. At least one of a certain polymerizable liquid crystal compound, a photopolymerization initiator, a surfactant, and a polymerizable liquid crystal composition containing a solvent, in the method for producing an optical compensation film,
The polymerizable liquid crystal compound contains at least one selected from the group consisting of compounds represented by the following formulas (1-1) to (1-4);
The method for producing an optical compensation film, wherein the cooling step satisfies at least one of the following conditions (i) and (ii).
Before (i) the coating film is cooled to room temperature T _R, the duration of holding at a temperature T _i 30 seconds or more, at least once. Here, the temperature T _i is T _H > T _i ≧ T _R + 20 ° C.
(Ii) the average cooling rate to the coating film is cooled to room temperature T _R from the temperature T _H is 20 ° C. / min or less.

In the formulas (1-1) to (1-4),
X ¹ , X ³ and X ⁴ are each independently -O- or -S-;
X ² is -CH = or -N =;
W ¹ represents a single bond or an aromatic ring connected by —C≡C— (where hydrogen in the aromatic ring is fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbons, carbon (Alkoxy having 1 to 5 carbon atoms, alkyl ester having 1 to 5 carbon atoms, alkanoyl having 1 to 5 carbon atoms, or thioalkyl having 1 to 5 carbon atoms) Is a monovalent group having 6 to 16 electrons,
W ² is oxygen, sulfur, or a monocyclic or condensed ring having 5 to 10 carbon atoms (however, in the monocyclic or condensed ring, -CH = may be replaced by -N =, and -CH ₂ -is -O -, -NH-, -S- or -CO-, wherein hydrogen on carbon or nitrogen is selected from fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-5 Alkyl, alkoxy having 1 to 5 carbon atoms, alkyl ester having 1 to 5 carbon atoms, alkanoyl having 1 to 5 carbon atoms, or thioalkyl having 1 to 5 carbon atoms).
W ³ is each independently cyano, alkoxycarbonyl having 1 to 10 carbon atoms or alkanoyl having 1 to 10 carbon atoms, and at least one of —CH ₂ — in the alkoxycarbonyl and alkanoyl is —O—, —COO— , -OCO-, -CH = CH- or -C≡C-,
W ⁴ represents a divalent linking group selected from the group consisting of —CH ＝ CH—, —C≡C—, an aromatic ring optionally containing a hetero atom, or a combination thereof;
R ¹ is each independently a group represented by the formula (2-1),

In the formula (2-1), A ¹ is each independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, at least one hydrogen atom is fluorine, cyano, formyl, trifluoroacetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, may be replaced by alkoxycarbonyl, or alkanoyl of 1 to 5 carbon atoms of 1 to 5 carbon atoms, Z ¹ is each independently represent a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - OCH 2 CH 2 O —, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO— or —COOCH ₂ CH ₂ —, and m is each independently 1 or 2 An integer, Y ¹ is a single bond, —O—, —COO—, —OCO— or —OCOO—; Q ¹ is a single bond or an alkylene having 1 to 20 carbon atoms; One of _-CH 2 - is -O -, - COO -, - OCO -, - CH = CH- or -C≡C-, PG formula (PG-1) ~ formula (PG-8 ) Is a polymerizable group represented by any one of the above.

In the formulas (PG-1) to (PG-8), each R ³ is independently hydrogen, halogen, methyl, ethyl or trifluoromethyl;
In the formulas (1-1) to (1-4),
R ² is independently a group represented by the formula (2-2),

In Formula (2-2), A ² is each independently 1,4-phenylene or 1,4-cyclohexylene, and in 1,4-phenylene, at least one hydrogen atom is fluorine, trifluoromethyl, May be replaced by alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkoxycarbonyl having 1 to 5 carbon atoms or alkanoyl having 1 to 5 carbon atoms, Z ² is a single bond, and n is each independently R ⁴ is hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons Alternatively, it is an alkoxycarbonyl having 1 to 20 carbon atoms. Assuming that the phase transition temperature from the liquid crystal phase to the isotropic phase of the coating film obtained in the heating step is T _NI , T _H , T _i , T _R , and T _NI satisfy the following (a) and (b): 2. The method for producing an optical compensation film according to claim 1, wherein the relationship satisfies the following condition.
_{(A) T H ≧ T NI} + 10 ℃
_{(B) T H -10 ℃ ≧} T i ≧ T R + 20 ℃ 3. The method of manufacturing an optical compensation film according to claim 1, wherein the _Ti and T _NI satisfy a relationship satisfying the following conditions (c) and (d). 4.
(C) T _NI ≧ 45 ° C.
(D) T _NI + 5 ° C. ≧ T _i ≧ 45 ° C.   The method according to any one of claims 1 to 3, which is a method for producing an optical compensation film having a birefringence Δn (λ) for light having a wavelength of λnm, wherein Δn (450) / Δn (550) ≦ 1.05. A method for producing an optical compensation film. ^{Z 1} in the formula (2-1) are each independently _{-COO -, - OCO -, -} CH 2 CH 2 COO- or -OCOCH ₂ CH ₂ - and is, PG is the formula (PG-1) The method for producing an optical compensation film according to any one of claims 1 to 4 , which is a polymerizable group represented. The method for producing an optical compensation film according to any one of claims 1 to 5 , wherein the polymerizable liquid crystal compound is a compound represented by Formula (1-1) or Formula (1-3).

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