KR20220140835A - Polymerizable liquid crystal composition, retardation film, elliptically polarizing plate and optical display - Google Patents

Abstract

로 나타내는 중합성 액정 화합물을 적어도 2 종 포함하는 중합성 액정 조성물로서, 상기 중합성 액정 화합물로서, 식 (1) 중의 G¹ 및 G² 가, 각각, 1,4-trans-시클로헥산디일기인 중합성 액정 화합물 (1-1) 과, 상기 중합성 액정 화합물 (1-1) 과 식 (1) 중의 G¹ 및 G² 의 적어도 일방이 1,4-cis-시클로헥산디일기인 것만에 있어서 분자 구조가 상이한 중합성 액정 화합물 (1-2) 를 포함하고, 액체 크로마토그래피에 의해 측정되는, 중합성 액정 화합물 (1-1) 과 중합성 액정 화합물 (1-2) 의 전체 피크 면적에 대한 중합성 액정 화합물 (1-2) 의 피크 면적의 비율이 0.01 ％ 이상 10 ％ 이하인, 중합성 액정 조성물.They have the same molecular weight, but different molecular structures, and also have the formula (1):

A polymerizable liquid crystal composition comprising at ^{least two} polymerizable liquid crystal compounds represented by In the case where at least one of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-1) and G ¹ and G ² in the formula (1) is a 1,4-cis-cyclohexanediyl group, With respect to the total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), including the polymerizable liquid crystal compound (1-2) having different molecular structures, measured by liquid chromatography The polymerizable liquid crystal composition, wherein the ratio of the peak area of the polymerizable liquid crystal compound (1-2) is 0.01% or more and 10% or less.

Description

Polymerizable liquid crystal composition, retardation film, elliptically polarizing plate and optical display

The present invention relates to a polymerizable liquid crystal composition, a retardation film composed of a cured product of the polymerizable liquid crystal composition, and an elliptically polarizing plate and an optical display comprising the retardation film.

As an optical film, such as retardation film used for a flat panel display device (FPD), there exists an optical film obtained by superposing|polymerizing, after apply|coating to a support base material the coating liquid obtained by melt|dissolving a polymeric liquid crystal compound in a solvent, for example. As a polymerizable liquid crystal compound for forming such an optical film, the nematic liquid crystal compound etc. of the rod-shaped structure in which 2-4 6-membered rings were connected are known, for example.

On the other hand, the retardation film is required to be capable of constant polarization conversion in the wavelength region as one of its characteristics. In a wavelength range where the value [Re(λ)/Re(550)] obtained by dividing the value Re(550) is close to 1, or in a wavelength range showing reverse wavelength dispersion of [Re(450)/Re(550)] < 1, , it is known that, in theory, a constant polarization conversion is possible. The polymerizable liquid crystal compound capable of constituting such a retardation film is disclosed in Patent Documents 1 and 2, for example.

Japanese Patent Laid-Open No. 2011-207765 Japanese Patent Laid-Open No. 2015-143788

In a solution (coating solution) obtained by dissolving a polymerizable liquid crystal compound in a solvent to be used for production of an optical film, the solubility to various solvents may be insufficient due to the molecular structure of the polymerizable liquid crystal compound. Such a low solubility polymerizable liquid crystal compound may precipitate in the coating solution or crystallize and precipitate. Such precipitation and precipitation of the polymerizable liquid crystal compound not only deteriorates film forming properties, but is also obtained It can cause orientation defects in the optical film. Therefore, development of the polymeric liquid crystal composition containing the polymeric liquid crystal which shows the more improved solubility with respect to a solvent is anticipated.

An object of this invention is to provide the polymeric liquid crystal composition excellent in the solubility with respect to a solvent.

The present invention provides the following preferred embodiments.

[1] The molecular weight is the same but has a different molecular structure, and the formula (1):

[Formula 1]

[In formula (1),

Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent,

D ¹ , D ² , E ¹ , E ² , B ¹ and B ² are each independently -CR ¹¹ R ¹² -, -CH ₂ CH ₂ -, -O-, -S-, -CO-O- , -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, R ¹¹ and R ¹² are each independently , a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms,

G ¹ and G ² each represent a 1,4-cyclohexanediyl group,

A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group is , a halogen atom, -R ¹³ , -OR ¹³ , may be substituted with a cyano group or a nitro group, R ¹³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,

F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁴ or a halogen atom, and R ¹⁴ is a carbon number 1 to 4 represents the alkyl group, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, -CH ₂ - contained in the alkanediyl group may be substituted with -O- or -CO-,

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ¹ and P ² is a polymerizable group)]

A polymerizable liquid crystal composition comprising at least two polymerizable liquid crystal compounds represented by

As the polymerizable liquid crystal compound, G ¹ and G ² in Formula (1) are each a 1,4-trans-cyclohexanediyl group, the polymerizable liquid crystal compound (1-1), and the polymerizable liquid crystal compound (1) -1) and a polymerizable liquid crystal compound (1-2) having a different molecular structure only when at least one of G ¹ and G ² in Formula (1) is a 1,4-cis-cyclohexanediyl group;

The ratio of the peak area of the polymerizable liquid crystal compound (1-2) to the total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) measured by liquid chromatography is 0.01% The polymerizable liquid crystal composition is 10% or more.

[2] The polymerizable liquid crystal compound (1-2) is a polymerizable liquid crystal compound (1-2a) wherein either one of G ¹ and G ² in the formula (1) is a 1,4-cis-cyclohexanediyl group and a polymerizable liquid crystal compound (1-2b) in which both G ¹ and G ² in Formula (1) are 1,4-cis-cyclohexanediyl groups. The polymerizable liquid crystal composition according to [1] above. .

[3] The polymerizable liquid crystal composition according to the above [1] or [2], wherein Ar in the formula (1) is a group represented by any of the formulas (2-1) to (2-5).

[Formula 2]

[During the ceremony,

* represents a bonding portion of D ¹ or D ² ;

Q ¹ represents -S-, -O- or -NR ¹⁵ -, R ¹⁵ represents a hydrogen atom or an optionally substituted C1-C6 alkyl group,

Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;

W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹⁵ -, and R ¹⁵ represents a hydrogen atom or an optionally substituted C1-C6 alkyl group;

Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group, and the hydrogen atom contained in the alkyl group, the aromatic hydrocarbon group or the aromatic heterocyclic group may be substituted with a halogen atom , -CH ₂ - contained in the alkyl group may be substituted with -O-, -CO-, -O-CO- or -CO-O-,

Y ² represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and -CH ₂ - contained in the alkyl group is -O- , -CO-, -O-CO-, or -CO-O- may be substituted;

Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms; represents a halogen atom, a cyano group, a nitro group, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , Z ¹ and Z ² may be bonded to each other to form an aromatic ring or an aromatic heterocycle, and R ¹⁵ and R ¹⁶ are each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, Ay is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, Ax and Ay may combine to form a ring;

Y ³ and Y ⁴ are, each independently, the following formula (Y-1):

[Formula 3]

[in formula (Y-1),

M ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the alkyl group may be substituted with one or more substituents X ³ , and the substituent X ³ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a penta Fluorosulfolanyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thio Socyano group, or one -CH ₂ - or two or more -CH ₂ - not adjacent to each other are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO- S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH= CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- represents a linear or branched alkyl group having 1 to 20 carbon atoms, and Any hydrogen atom may be substituted with a fluorine atom, or may be a contribution represented by -B ¹¹ -F ¹¹ -P ¹¹ , and B ¹¹ , F ¹¹ and P ¹¹ are respectively B ¹ , F ¹ in the formula (1). and P ¹ , and may be the same as or different from those of B ¹ , F ¹ and P ¹ ;

U ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and the aromatic hydrocarbon group may be substituted with one or more substituents X ³ . become ;

T ¹ is, -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ² - or -O-NU ² -, U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group (the aromatic hydrocarbon group an organic group having 2 to 30 carbon atoms, or (E ¹¹ -A ¹¹ ) _q -B ¹² -F ¹² -P ¹² , an alkyl group, a cycloalkyl group, or a cyclo The alkenyl group and the aromatic hydrocarbon group may each be unsubstituted or substituted with one or more substituents X ³ , the alkyl group may be substituted with the cycloalkyl group or cycloalkenyl group, and one of the alkyl groups -CH ₂ - or two or more -CH ₂ - which are not adjacent are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO- , -SO ₂ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- may be substituted, and one of the cycloalkyl groups or cycloalkenyl groups -CH ₂ - or 2 not adjacent or more -CH ₂ - may be each independently substituted with -O-, -CO-, -COO-, -OCO- or -O-CO-O-, E ¹¹ , A ¹¹ , B ¹² , F ¹² and P ¹² are respectively defined the same as E ¹ , A ¹ , B ¹ , F ¹ and P ¹ in Formula (1), respectively, and are the same as E ¹ , A ¹ , B ¹ , F ¹ and P ¹ , respectively. You may or may differ, q represents the integer of 0-4, and ^when two or more E11 and/or ^A11 exist, each They may be the same or different, and U ¹ and U ² may combine to form a ring]

represents a group selected from.]

[4] The above [1] to [3], wherein A ¹ and A ² in the formula (1) are each independently a 1,4-cyclohexanediyl group or a 1,4-phenylenediyl group. A polymerizable liquid crystal composition.

[5] The polymerizable liquid crystal composition according to any one of [1] to [4], wherein each of P ¹ and P ² in Formula (1) is an acryloyl group.

[6] The polymerizable liquid crystal composition according to any one of [1] to [5], further comprising a photopolymerization initiator.

[7] The polymerizable liquid crystal composition according to any one of [1] to [6], further comprising an organic solvent.

[8] A retardation film comprising a liquid crystal cured film which is a cured product of the polymerizable liquid crystal composition according to any one of [1] to [7].

[9] Liquid crystal cured film, formula (i):

0.75 ≤ Re(450)/Re(550) < 1.00 (i)

[In formula (i), Re(λ) represents the in-plane retardation value at the wavelength λ nm of the liquid crystal cured film]

The retardation film according to [8], which satisfies

[10] An elliptically polarizing plate comprising the retardation film according to [8] or [9].

[11] An optical display comprising the elliptically polarizing plate according to [10].

[12] A flexible image display device comprising the elliptically polarizing plate according to [10].

ADVANTAGE OF THE INVENTION According to this invention, the polymeric liquid crystal composition excellent in the solubility with respect to a solvent can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made within a range that does not impair the spirit of the present invention.

<Polymerizable liquid crystal composition>

The polymerizable liquid crystal composition of the present invention includes at least two polymerizable liquid crystal compounds having the same molecular weight, but different molecular structures, and represented by the formula (1). High solubility to a solvent can be ensured by including the at least 2 types of polymeric liquid crystal compound mutually similar as molecular structure represented by Formula (1) with the same molecular structure while mutually different molecular structures.

[Formula 4]

[In formula (1),

Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent,

D ¹ , D ² , E ¹ , E ² , B ¹ and B ² are each independently -CR ¹¹ R ¹² -, -CH ₂ CH ₂ -, -O-, -S-, -CO-O- , -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, R ¹¹ and R ¹² are each independently , a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms,

G ¹ and G ² each represent a 1,4-cyclohexanediyl group,

A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group is , a halogen atom, -R ¹³ , -OR ¹³ , may be substituted with a cyano group or a nitro group, R ¹³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,

F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁴ or a halogen atom, and R ¹⁴ is a carbon number 1 to 4 represents the alkyl group, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, -CH ₂ - contained in the alkanediyl group may be substituted with -O- or -CO-,

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ¹ and P ² is a polymerizable group)].

The polymerizable liquid crystal composition of the present invention is the at least two polymerizable liquid crystal compounds, wherein each of G ¹ and G ² in Formula (1) is a 1,4-trans-cyclohexanediyl group ( 1-1) (hereinafter also referred to as "polymerizable liquid crystal compound (1-1)"), and at least one of G ¹ and G ² in the polymerizable liquid crystal compound (1-1) and Formula (1) is 1; The polymerizable liquid crystal compound (1-2) (hereinafter also referred to as “polymerizable liquid crystal compound (1-2)”) having a different molecular structure only in the case of a 4-cis-cyclohexanediyl group is included. In the present invention, the polymerizable liquid crystal composition may contain only one polymerizable liquid crystal compound (1-1), or may contain two or more polymerizable liquid crystal compounds (1-1). When a plurality of polymerizable liquid crystal compounds (1-1) are included, the polymerizable liquid crystal composition of the present invention contains at least one polymerizable liquid crystal compound (1-2) corresponding to at least one polymerizable liquid crystal compound (1-1). What is necessary is just to contain, with respect to the some polymerizable liquid crystal compound (1-1) constituting the polymerizable liquid crystal composition, respectively, the corresponding polymerizable liquid crystal compound (1-2) may be included.

The polymerizable liquid crystal compound (1-1) differs from the polymerizable liquid crystal in molecular structure only when at least one of G ¹ and G ² in Formula (1) is a 1,4-cis-cyclohexanediyl group, that is, an isomer. By including the compound (1-2) in combination, the solubility of the polymerizable liquid crystal compound (1-1) in a solvent can be improved. In other words, when the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) are included in combination, compared with the case where the polymerizable liquid crystal compound (1-1) is dissolved alone in a solvent, the same It becomes possible to easily dissolve more polymerizable liquid crystal compound (1-1) with respect to an amount or a smaller amount of solvent. Thereby, an undissolved polymeric liquid crystal compound is hard to remain|survive in a coating liquid, and precipitation, precipitation, and stacking of a polymeric liquid crystal compound in a coating liquid can be suppressed. The improvement of the solubility of the polymerizable liquid crystal compound (1-1) in a solvent leads to suppression of an orientation defect resulting from an undissolved polymerizable liquid crystal compound, a precipitate, or the like, or an improvement in storage stability.

The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) are each represented by Formula (1):

[Formula 5]

It is a polymerizable liquid crystal compound represented by . The compound having a structure represented by the formula (1) is usually a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion birefringence when polymerized in a unidirectionally oriented state, and constant polarization conversion is possible in a wide wavelength range. Therefore, by using the polymerizable liquid crystal compound represented by the formula (1), when a retardation film or an elliptically polarizing plate formed of the polymerizable liquid crystal compound is used for an optical display such as a display device, a polymerizable liquid crystal capable of imparting good display properties composition can be obtained.

In Formula (1), G ¹ and G ² each independently represent a 1,4-cyclohexanediyl group. Both of the two polymerizable liquid crystal compounds (1-1) and (1-2) constituting the polymerizable liquid crystal composition of the present invention have structures represented by G ¹ and G ² in Formula (1). It is a 1,4-trans-cyclohexanediyl group, or differs from each other in whether one or both of G ¹ and G ² is a 1,4-cis-cyclohexanediyl group.

In formula (1), D ¹ , D ² , E ¹ , E ² , B ¹ and B ² are each independently -CR ¹¹ R ¹² -, -CH ₂ CH ₂ -, -O-, -S- , -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, - CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond. Here, R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom or a C1-C4 alkyl group, and it is preferable that they are a hydrogen atom, a methyl group, or an ethyl group.

In formula (1), D ¹ and D ² are each independently, preferably -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, -O-CH ₂ -, -CH ₂ -O-, -CO-NR ¹¹ - or -NR ¹¹ -CO-, more preferably -CO-O-, -O-CO-, -CO-NR ¹¹ - or -NR ¹¹ -CO-, particularly preferably -CO-O-, -O-CO-. R ¹¹ is preferably a hydrogen atom, a methyl group, or an ethyl group. In Formula (1), D ¹ and D ² may be the same as or different from each other. In addition, that D ¹ and D ² are identical to each other means that the structures of D ¹ and D ² when viewed centering on Ar are identical to each other. Hereinafter, the same applies to the relationships between E ¹ and E ² , A ¹ and A ² , B ¹ and B ² , and F ¹ and F ² .

In formula (1), E ¹ , E ² , B ¹ and B ² are each independently, preferably -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -CO-NR ¹¹ -, -NR ¹¹ -CO- or a single bond, More preferably -O-, -O-CO- or -CO-O-. R ¹¹ is preferably a hydrogen atom, a methyl group, or an ethyl group. In Formula (1), E ¹ and E ² , and B ¹ and B ² may be the same as or different from each other.

In Formula (1), A ¹ and A ² each independently represent a C3-C16 divalent alicyclic hydrocarbon group or a C6-C20 divalent aromatic hydrocarbon group. Here, the hydrogen atom contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ¹³ , -OR ¹³ , a cyano group or a nitro group, and R ¹³ represents an alkyl group having 1 to 4 carbon atoms. , the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

In formula (1), A ¹ and A ² are each independently 1,4-phenyl which may be substituted with at least one substituent preferably selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a rendiyl group, a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenyl substituted with a methyl group a rendiyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-cyclohexanediyl group, particularly preferably an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4- It is a cyclohexanediyl group, Especially preferably, it is an unsubstituted 1, 4- phenylenediyl group. In Formula (1), A ¹ and A ² may be mutually the same or different.

In Formula (1), F ¹ and F ² each independently represent a C1-C12 alkanediyl group. Here, the hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁴ or a halogen atom, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. do. Moreover, -CH ₂ - contained in the alkanediyl group may be substituted with -O- or -CO- (however, when two or more -O- exist, these are not mutually adjacent).

In Formula (1), F ¹ and F ² each independently represent an optionally substituted alkanediyl group having 4 to 12 carbon atoms. In Formula (1), F ¹ and F ² may be the same as or different from each other.

Examples of the polymerizable group represented by P ¹ or P ² include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyl group, a methacryloyl group, an oxiranyl group, and a jade group. A cetanyl group etc. are mentioned. Among these, an acryloyl group, a methacryloyl group, a vinyl group, and a vinyloxy group are preferable, an acryloyl group and a methacryloyl group are more preferable, and an acryloyl group is still more preferable. In Formula (1), P ¹ and P ² may be the same as or different from each other as long as either one is a polymerizable group, but it is preferable that both P ¹ and P ² are polymerizable groups, and both P ¹ and P ² are acrylic groups. It is more preferable that it is a royl group.

In Formula (1), Ar represents the divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group which may have a substituent. In the present invention, the divalent aromatic hydrocarbon group which may have a substituent means a divalent linking group containing at least one aromatic hydrocarbon ring, and the divalent aromatic heterocyclic group which may have a substituent includes at least one aromatic heterocycle. It means a divalent linking group containing a dog. An aromatic hydrocarbon ring and an aromatic heterocyclic ring as used herein means that the number of π electrons in the ring structure is [4n + 2] (n represents an integer) according to Hukel's law (in the case of an aromatic heterocycle, -N= or - It satisfies the Hewkel's rule by including a non-covalent pair of electrons on a hetero atom such as S-. Ar may contain one aromatic hydrocarbon ring or aromatic heterocyclic ring, and may contain two or more. When one aromatic hydrocarbon ring or one aromatic heterocyclic ring is included, Ar may be a divalent aromatic hydrocarbon group which may have a substituent, or the divalent aromatic heterocyclic group which may have a substituent may be sufficient as it. When two or more aromatic hydrocarbon rings or aromatic heterocycles are included, only an aromatic hydrocarbon ring or only a plurality of aromatic heterocycles may be included, and one or more aromatic hydrocarbon rings and aromatic heterocycles may be included, respectively. The two or more aromatic hydrocarbon rings and/or aromatic heterocycles may be mutually bonded by a single bond or a divalent bonding group such as -CO-O- or -O-.

As an aromatic hydrocarbon ring which may be contained in Ar, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned, for example, A benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, and an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring. When Ar contains a nitrogen atom, it is preferable that the nitrogen atom has π electrons.

Among them, Ar preferably has an aromatic heterocyclic ring containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and has a thiazole ring, a benzothiazole ring or a benzofuran ring It is more preferable, and it is still more preferable to have a benzothiazole ring. Further, when Ar has an aromatic heterocycle containing at least ^two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and ^a sulfur atom, the aromatic heterocycle is directly It may be bonded to form a divalent linking group, or may be included as a substituent for a divalent linking group directly bonded to D ¹ and D ² , but the entire Ar group including the aromatic heterocycle is in a direction substantially orthogonal to the molecular orientation direction. It is preferable that it is three-dimensionally arranged.

In formula (1), the total number of _pi electrons contained in the divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group which may have a substituent represented by Ar is preferably 8 or more, more preferably 12 or more, particularly Preferably it is 16 or more, Especially preferably, it is 20 or more. Moreover, Preferably it is 36 or less, More preferably, it is 32 or less, More preferably, it is 30 or less, Especially preferably, it is 26 or less, Especially preferably, it is 24 or less.

As the divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group which may have a substituent represented by Ar in formula (1), groups represented by the following formulas (2-1) to (2-5) are exemplified.

[Formula 6]

In formulas (2-1) to (2-5), * represents a bonding portion with D ¹ or D ² .

In formula (2-1), Q ¹ represents -S-, -O- or -NR ¹⁵ -, and R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. In formulas (2-3) and (2-4), Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

In formula (2-2), W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹⁵ -, and R ¹⁵ is a hydrogen atom or carbon number which may have a substituent. An alkyl group of 1-6 is shown.

In the formula (2-1), Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group, an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms and 3 to carbon atoms. A 12 aromatic heterocyclic group is preferable, and a C6-C12 aromatic hydrocarbon group and a C3-C12 aromatic heterocyclic group are more preferable. In Formula (2-2), Y< ² > represents a C1-C12 alkyl group which may have a CN group or a substituent. Here, the hydrogen atom contained in the alkyl group aromatic heterocyclic group or aromatic heterocyclic group may be substituted with a halogen atom, and -CH ₂ - contained in the alkyl group is -O-, -CO-, -O-CO- Or it may be substituted with -CO-O-.

In formulas (2-1) to (2-5), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group, or an alicyclic group having 3 to 20 carbon atoms. represents a hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , Z ¹ and Z ² are bonded to each other to form an aromatic ring or an aromatic hetero You may form a ring. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formulas (2-3) and (2-4), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ay is a hydrogen atom , an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, Ax and Ay are bonded to You may form a ring.

Although it does not specifically limit as group represented by Formula (2-1) - (2-4), Specifically, the group described in Unexamined-Japanese-Patent No. 2011-207765, Unexamined-Japanese-Patent No. 2008-107767, WO2014/010325, etc. can be heard

In formula (2-5), Y ³ and Y ⁴ each independently represent the following formula (Y-1):

[Formula 7]

selected from the group represented by

In formula (Y-1), M< ¹ > represents a hydrogen atom or a C1-C6 alkyl group. The alkyl group may be substituted with one or more substituents X ³ .

Substituent X ³ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfolanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, A diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH ₂ - or two or more non-adjacent -CH ₂ - are each independently -O-, - S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH= which may be substituted with CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- A linear or branched alkyl group having 1 to 20 carbon atoms is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or may be a contribution represented by -B ¹¹ -F ¹¹ -P ¹¹ , B ¹¹ , F ¹¹ and P ¹¹ are respectively defined the same as B ¹ , F ¹ , and P ¹ in Formula (1), and may be the same as or different from B ¹ , F ¹ and P ¹ , respectively.

The substituent X ³ is preferably a fluorine atom, a chlorine atom, -CF ₃ , -OCF ₃ or a cyano group. M ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms substituted with a hydrogen atom or one or more fluorine atoms, more preferably a hydrogen atom.

U ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group. Any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and U ¹ is an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. . The aromatic hydrocarbon group may be substituted with one or more of the above-mentioned substituents X ³ .

It is preferable that U< ¹ > is the organic group which has an aromatic heterocyclic ring by which 1 or more of carbon atoms are substituted by the hetero atom at the point which wavelength dispersion property becomes favorable. It is more preferable that U< ¹ > is an organic group which has an aromatic heterocyclic ring which is a condensed ring of a 5-membered ring and a 6-membered ring from the point which wavelength-dispersion property is favorable and will show high birefringence.

Specifically, as U ¹ , it is preferable to have a group represented by the following formula. In addition, in the following formula, these groups have a bond with T ¹ at an arbitrary position.

[Formula 8]

T ¹ is, -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ² - or -O-NU ² -, U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group (the aromatic hydrocarbon group arbitrary carbon atoms may be substituted with a hetero atom); an organic group having 2 to 30 carbon atoms; or (E ¹¹ -A ¹¹ ) _q -B ¹² -F ¹² -P ¹² . Each of the alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents X ³ , and the alkyl group may be substituted with the cycloalkyl group or the cycloalkenyl group. do. One -CH ₂ - or two or more non-adjacent -CH ₂ - in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO- S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- may be substituted, and one -CH of the cycloalkyl group or cycloalkenyl group ₂ - or two or more non-adjacent -CH ₂ -s may each independently be substituted with -O-, -CO-, -COO-, -OCO- or O-CO-O-. E ¹¹ , A ¹¹ , B ¹² , F ¹² , and P ¹² are respectively defined the same as E ¹ , A ¹ , B ¹ , F ¹ and P ¹ in Formula (1), and E ¹ , A ¹ , B ¹ , F ¹ and P ¹ may be the same as or different from each other, q represents an integer of 0 to 4, and when two or more E ¹¹ and/or A ¹¹ exist, they may be the same or different, respectively.

T ¹ is preferably -O-, -S-, -N=CU ² - or -NU ² - from the viewpoint of good birefringence and easy synthesis, and from the viewpoint of easily improving wavelength dispersion and birefringence, -O-, -S- or -NU ² - is more preferable.

U ² may be substituted with one or more substituents X ³ , and one -CH ₂ - or two or more non-adjacent -CH ₂ - are each independently -O-, -CO-, -COO -, -OCO- or -O-CO-O-, a C1-C20 alkyl group or alkenyl group, a C3-C12 cycloalkyl group, or a C3-C12 cycloalkenyl group, or; It is preferable that it is the said alkyl group or alkenyl group which may be substituted by the said cycloalkyl group, a cycloalkenyl group, or an aryl group.

Among them, in U ² , from the viewpoint of birefringence and solvent solubility, a hydrogen atom may be substituted with a fluorine atom, and one -CH ₂ - or two or more non-adjacent -CH ₂ - are each independently -O-, -CO It is more preferable that it is a C1-C20 linear alkyl group which may be substituted by -, -COO-, or -OCO-.

U ¹ and U ² may be bonded to each other to form a ring. In that case, for example, a cyclic group represented by -NU ¹ U ² or a cyclic group represented by -N=CU ¹ U ² can be mentioned.

From the viewpoint of easy availability of raw materials, good solubility and high birefringence, it is particularly preferred that Y ³ and Y ⁴ each represent a group selected from the following formulas (Y-1') to (Y-47'). desirable.

[Formula 9]

[Formula 10]

It is preferable that the molecular structure of the polymerizable liquid crystal compound (1) becomes symmetrical from the viewpoints of improving the orientation of the polymerizable liquid crystal compound (1), facilitating industrial production, and improving productivity. Specific examples of the group represented by the formula (2-5) include the following groups. * in the following (2-5a) to (2-5t) represents a bonding portion with D ¹ or D ² .

[Formula 11]

[Formula 12]

[Formula 13]

Among formulas (2-1) to (2-5), formula (2-1), formula (2-3), formula (2-4), and formula (2-5) are preferable, and formula (2-1) ) and Formula (2-5) are more preferable, and Formula (2-1) is especially preferable.

In this invention, as a polymeric liquid crystal compound represented by Formula (1), the compound as described in Unexamined-Japanese-Patent No. 2019-003177, Unexamined-Japanese-Patent No. 2019-073496, etc. is mentioned, for example.

The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention are 1 represented by G ¹ and G ² in the structure represented by the formula (1). They differ from each other only in the structure of the ,4-cyclohexanediyl group. In the polymerizable liquid crystal compound (1-1), both G ¹ and G ² in the formula (1) are 1,4-trans-cyclohexanediyl groups, and the polymerizable liquid crystal compound (1-2) is the polymerizable liquid crystal Based on the structure of the compound (1-1), the polymerizable liquid crystal compound (1-1) differs only in that at least one of G ¹ and G ² is a 1,4-cis-cyclohexanediyl group.

In the present invention, as for the polymerizable liquid crystal compound (1-2), either one of G ¹ and G ² in the formula (1) is a 1,4-trans-cyclohexanediyl group, and the other is 1,4-cis- The polymerizable liquid crystal compound (1-2a) (hereinafter also referred to as "polymerizable liquid crystal compound (1-2a)) which is a cyclohexanediyl group may be sufficient, and both G ¹ and G ² in Formula (1) are 1,4-cis - The polymerizable liquid crystal compound (1-2b) which is a cyclohexanediyl group (henceforth "polymerizable liquid crystal compound (1-2b)") may be sufficient. The polymerizable liquid crystal composition of the present invention may contain either one of the polymerizable liquid crystal compound (1-2a) and the polymerizable liquid crystal compound (1-2b), or may contain both.

The polymerizable liquid crystal composition of the present invention contains the polymerizable liquid crystal compound (1-2) with respect to the total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) as measured by liquid chromatography. ) in an amount such that the ratio of the peak area (hereinafter also referred to as "area percentage value") is 0.01% or more and 10% or less, and contains the polymerizable liquid crystal composition (1-1) and the polymerizable liquid crystal compound (1-2) do. The polymerizable liquid crystal compound represented by Formula (1) having a so-called T-structure in which constituent molecules are arranged in a direction intersecting the long axis direction serving as the main chain of the compound and the long axis direction is G ¹ and When all of G ² are 1,4-trans-cyclohexanediyl groups (ie, polymerizable liquid crystal compound (1-1)), usually at least one of G ¹ and G ² in Formula (1) is 1,4 Since it is molecularly structurally more stable than the polymerizable liquid crystal compound (1-2) which is a -cis- cyclohexanediyl group, and it is easy to orientate in a desired direction, an optical film with few orientation defects can be manufactured. For this reason, from a viewpoint of orientation or an optical characteristic, it is thought that a polymeric liquid crystal compound (1-1) is advantageous as a polymeric liquid crystal compound represented by Formula (1). In the present invention, by setting the amount of the polymerizable liquid crystal compound (1-2) to the polymerizable liquid crystal compound (1-1) within a specific range, without affecting the orientation of the polymerizable liquid crystal compound (1-1) , the solubility of the polymerizable liquid crystal compound (1-1) in a solvent can be sufficiently improved.

When the area percentage value of the polymerizable liquid crystal compound (1-2) is less than the above lower limit, it is difficult to improve the solubility of the polymerizable liquid crystal compound (1-1) in a solvent, but the area of the polymerizable liquid crystal compound (1-2) is There exists a tendency for the solubility with respect to the solvent of a polymeric liquid crystal compound (1-1) to fully improve that a percentage value is more than the said lower limit. In addition, when the area percentage value of the polymerizable liquid crystal compound (1-2) is equal to or less than the upper limit, the alignment state of the liquid crystal at the time of manufacturing an optical film such as a retardation film from the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound Since it can hold|maintain favorably, the optical film excellent in an optical characteristic can be obtained, suppressing an orientation defect. In the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) is more preferably 9% or less, still more preferably 8% or less, particularly preferably 7% or less, particularly preferably 6% or less. is below. In the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) is preferably 0.1% or more, more preferably 0.5% or more, and still more preferably 2.5% or more. On the other hand, in the present invention, even when the polymerizable liquid crystal compound (1-2) is contained in a small amount, since the effect of greatly improving the solubility of the polymerizable liquid crystal compound (1-1) in a solvent is excellent, the present invention In an aspect of easy to get

Further, when a plurality of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1-1) and/or the polymerizable liquid crystal compound (1-2) are contained, the area percentage value of the polymerizable liquid crystal compound (1-2) is , computed with respect to the total peak area of all polymerizable liquid crystal compounds (1-2) and all polymerizable liquid crystal compounds (1-1). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and can be measured and calculated by the method described in the Example mentioned later in detail.

The method for producing the polymerizable liquid crystal compound represented by the formula (1) such as the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention is not particularly limited, Methoden der Organischen Chemie, Organic Reactions, OrganicSyntheses, Comprehensive Organic Synthesis, and known organic synthesis reactions (e.g., condensation reaction, esterification reaction, Williamson reaction, Ulman reaction, Wittich reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Burwald-Hart reaction, Friedelcraft reaction, Heck reaction, Aldol reaction, etc.) to the structure Therefore, it can manufacture by combining suitably.

For example, D ¹ and D ² in Formula (1) are *-O-CO- (* represents a bonding portion with Ar), G ¹ and G ² are 1,4-trans-cyclohexanediyl groups, , having a symmetrical structure around Ar (that is, E ¹ and E ² , A ¹ and A ² , B ¹ and B ² , F ¹ and F ² , P ¹ and P ² are each the same) -One) :

[Formula 14]

The polymerizable liquid crystal compound (1-1) represented by

Formula (B):

HO-Ar-OH (B)

an alcohol compound (B) represented by

Formula (C):

[Formula 15]

It can manufacture by performing the esterification reaction of the carboxylic acid compound (C) represented by. In addition, Ar, E ¹ , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ in Formulas (A-1), (B) and (C) and P ² is the same as defined in the formula (1), and is determined corresponding to the structure of the polymerizable liquid crystal compound (1-1) represented by the formula (A-1).

The alcohol compound (B) may be a compound in which two hydroxyl groups are bonded to the aromatic group Ar corresponding to the aromatic group Ar in the formula (1) in the desired polymerizable liquid crystal compound (1-1). As aromatic group Ar, it is the same as what was prescribed|regulated previously, For example, the compound which is two * addition hydroxyl groups in said Formula (2-1) - (2-5) is mentioned.

As a carboxylic acid compound (C), it has a structure corresponding to P ¹ -F ¹ -B ¹ -A ¹ -E ¹ -G ¹ - in Formula (1) in the desired polymerizable liquid crystal compound (1-1). What is necessary is just a compound which the carboxyl group couple|bonded with respect to the 1, 4- trans- cyclohexanediyl group couple|bonded as G< ¹ >.

The polymerizable liquid crystal compound (1-2a) in which either one of G ¹ and G ² in Formula (1) is a 1,4-cis-cyclohexanediyl group is, for example, the alcohol compound (B) and the carboxyl group. By reacting the acid compound (C), the following formula (D):

[Formula 16]

To obtain a compound represented by, the compound and the following formula (C'):

[Formula 17]

It can manufacture by making the carboxylic acid compound (C') represented by react. In addition, Ar, E ¹ , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² in the formulas (C′) and (D) are the formulas It is the same as that prescribed|regulated by (1), and it determines corresponding to the structure of the polymeric liquid crystal compound (1-1) represented by Formula (A-1).

Further, the polymerizable liquid crystal compound (1-2b) in which both G ¹ and G ² in the formula (1) is a 1,4-cis-cyclohexanediyl group is, for example, a polymerizable liquid crystal compound (1-1) In the method illustrated as a manufacturing method, it can manufacture by using a carboxylic acid compound (C') instead of a carboxylic acid compound (C).

The esterification reaction of the alcohol compound (B) with the carboxylic acid compound (C) and/or the carboxylic acid compound (C') is preferably performed in the presence of a condensing agent. By performing the esterification reaction in the presence of a condensing agent, the esterification reaction can be performed efficiently and quickly.

Examples of the condensing agent include 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-para-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1- Ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), bis(2,6-di Carbodiimide compounds such as isopropylphenyl)carbodiimide and bis(trimethylsilyl)carbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1; 1'-oxalyldiimidazole, diphenylphosphorylazide, 1 (4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidino Phosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimidyl ) Uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzoxysuccinimide, O- (6-chlorobenzotriazole) -1-yl)-N,N,N',N'-tetramethyluroniumtetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'- Tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimida Jolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate and trichloroacetic acid pentachlorophenyl ester.

The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention can be used as a liquid crystal mixture by preparing each separately and then mixing them. Further, by a method comprising reacting the reactive group R ² of the compound represented by the following formula (I), the reactive group R ² of the compound represented by the formula (II), and R ¹ of the compound represented by the formula (III) , a polymerizable liquid crystal compound (1-1) and a polymerizable liquid crystal compound (1-2a) and/or a liquid crystal mixture containing a polymerizable liquid crystal compound (1-2b).

[Formula 18]

[Wherein, R ¹ and R ² each independently represent a reactive group,

Ar, E ¹ , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² are Ar, E ¹ , E ² , A ¹ , A in Formula (1) ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² have the same meaning.]

In the former method, it is easy to control the content of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) in the polymerizable liquid crystal composition, and in the latter method, the synthesis is simple and the polymerizable liquid crystal composition There is an advantage that can be manufactured more efficiently.

Ar, E ¹ , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² in Formula (I), Formula (II) and Formula (III) represent the desired polymerization It is determined according to the corresponding molecular structures of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2).

Formula (1) wherein R ¹ in formula (III) and R ² in formulas (I) and (II) react with each other to represent a polymerizable liquid crystal compound (1-1) and a polymerizable liquid crystal compound (1-2) What is necessary is just to be able to form ^the structure ^shown by D1 and D2 in ). For example, as the reactive group represented by R ¹ and/or R ² , a hydroxyl group, a carboxyl group, an amino group, etc. are exemplified, and the reactive group represented by R ¹ and R ² depending on the reaction used for the production of the polymerizable liquid crystal compound. You can select each.

From the viewpoints of easiness of reaction, material handling property, availability, etc., typically, as a compound represented by Formula (III), for example, an alcohol compound in which R ¹ in Formula (III) is a hydroxyl group, and Formula (I) The polymerizable liquid crystal composition of the present invention is constituted by carrying out an esterification reaction using ^a compound represented by A polymerizable liquid crystal compound (liquid crystal mixture) can be prepared. The esterification reaction can be performed according to the method similar to the esterification reaction which can be used in order to manufacture the polymeric liquid crystal compound etc. represented by Formula (I), For example, the method mentioned above, or Unexamined-Japanese-Patent No. The method or conditions described in No. 2019-003177 or the like can be employed.

A polymerizable liquid crystal compound (1-1), a polymerizable liquid crystal compound (1-2a) and The content ratio of the polymerizable liquid crystal compound (1-2b) is controllable. By using a plurality of carboxylic acid compounds in a method for reacting R ¹ and R ² , a plurality of compounds can be synthesized simultaneously.

The polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) as long as the effects of the present invention are not affected. . Examples of the polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) include a polymerizable liquid crystal compound having no molecular structure represented by the formula (1), for example, alignment Polymerizable liquid crystal compounds generally exhibiting positive wavelength dispersion when polymerized by polymerization, for example, "3.8.6 Network ( fully crosslinked type)", "6.5.1 liquid crystal material b. Polymeric nematic liquid crystal material", the compound etc. which have a polymeric group among the compounds described in it are mentioned.

When the polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), from the viewpoint of obtaining a liquid crystal cured film having a high degree of alignment order , The ratio of the polymerizable liquid crystal compound (1) to the total mass of all the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition is preferably 51 mass% or more, more preferably 70 mass% or more, and still more preferably Preferably, it is 90 mass % or more, and 100 mass % may be sufficient.

When two or more polymerizable liquid crystal compounds (1-1) are included, at least one polymerizable liquid crystal compound (1-2) corresponding to the polymerizable liquid crystal compound (1-1) may be included. The content of the polymerizable liquid crystal compound (1-1) in which the polymerizable liquid crystal compound (1-2) is present and the polymerizable liquid crystal compound (1-2) corresponding thereto is determined by the total mass of all the polymerizable liquid crystal compounds. It is preferable that it is 60 mass % or more, More preferably, it is 70 mass % or more, More preferably, it is 80 mass % or more.

The content of the polymerizable liquid crystal compound (total amount of all the polymerizable liquid crystal compounds) in the polymerizable liquid crystal composition is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is a mass part, More preferably, it is 85-98 mass parts, More preferably, it is 90-95 mass parts. It is advantageous from a viewpoint of the orientation of the liquid crystal cured film obtained as content of a polymeric liquid crystal compound is in the said range. In addition, in this specification, the solid content of a polymeric liquid crystal composition means all the components except volatile components, such as an organic solvent, from a polymeric liquid crystal composition.

The polymerizable liquid crystal composition of the present invention contains, in addition to the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), a photopolymerization initiator, an organic solvent, a polymerization inhibitor, a photosensitizer, and a leveling agent. You may further contain an additive. These components may be used individually by only 1 type, and may be used in combination of 2 or more type.

It is preferable that the polymeric liquid crystal composition of this invention contains a polymerization initiator. A polymerization initiator is a compound which produces|generates reactive active species by the contribution of heat|fever or light, and can initiate polymerization reaction, such as a polymerizable liquid crystal. As reactive active species, active species, such as a radical, a cation, or an anion, are mentioned. Especially, the photoinitiator which generate|occur|produces a radical by light irradiation from a viewpoint that reaction control is easy is preferable.

Examples of the photopolymerization initiator include a benzoin compound, a benzophenone compound, a benzyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a triazine compound, an iodonium salt, and a sulfonium salt. . Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, manufactured by BASF Japan Co., Ltd.), Sakeol BZ, Sakeol Z, Sakeol BEE (above, manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 ( Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Corporation), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Optomer N-1919 Deca Accruz NCI-831, Adeca Accruz NCI-930 (above, manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, manufactured by Nippon Shibel Hegner) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) can be heard

In this invention, it is preferable that the polymeric liquid crystal composition contains at least 1 type of photoinitiator, and may contain 2 or more types of photoinitiators.

A photoinitiator can fully utilize the energy emitted from a light source, and since it is excellent in productivity, it is preferable in it being 300 nm - 400 nm of maximum absorption wavelength, It is more preferable in it being 300 nm - 380 nm, Especially, α- An acetophenone-type polymerization initiator and an oxime-type photoinitiator are preferable.

Examples of the α-acetophenone polymerization initiator include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl). )-2-benzylbutan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, more preferably 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one can be heard As a commercial item of (alpha)-acetophenone compound, Irgacure 369, 379EG, 907 (above, BASF Japan Co., Ltd. make), Sikol BEE (made by Seiko Chemicals), etc. are mentioned.

An oxime-type photoinitiator produces|generates a methyl radical by irradiating light. By this methyl radical, superposition|polymerization of the polymeric liquid crystal compound in the liquid crystal cured film deep part formed advances suitably. Moreover, it is preferable to use the photoinitiator which can utilize the ultraviolet-ray with a wavelength of 350 nm or more efficiently from a viewpoint of advancing the polymerization reaction in the deep part of the liquid crystal cured film formed more efficiently. As a photoinitiator which can utilize the ultraviolet-ray of wavelength 350nm or more efficiently, a triazine compound and an oxime ester type carbazole compound are preferable, and an oxime ester type carbazole compound is more preferable from a viewpoint of a sensitivity. Examples of the oxime ester-type carbazole compound include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2) -Methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), etc. are mentioned. As a commercial item of an oxime ester type carbazole compound, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, BASF Japan Co., Ltd. make), Adeca Optomer N-1919, Adeka Accruz NCI-831 (above, manufactured by ADEKA Corporation) etc. are mentioned.

The addition amount of a photoinitiator is 0.1 mass part or more and 30 mass parts or less normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.5 mass part or more, More preferably, it is 1 mass part or more, Preferably It is 20 mass parts or less, More preferably, it is 15 mass parts or less. If it is in the said range, reaction of a polymeric group fully advances, and the orientation of a polymeric liquid crystal compound is hard to be disturbed.

In the present invention, since the polymerizable liquid crystal composition is usually applied to a substrate or the like in a state dissolved in a solvent, it is preferable to include a solvent. As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition, such as the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), is preferable. It is preferable that it is an inactive solvent for the polymerization reaction of a liquid crystal compound. Examples of the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and propylene. Alcohol solvents, such as glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents, such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; and amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used individually or in combination of 2 or more types. Among these, organic solvents are preferable, and alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are more preferable.

To [ content of the solvent in a polymeric liquid crystal composition / 100 mass parts of polymeric liquid crystal composition ], Preferably it is 50-98 mass parts, More preferably, it is 70-95 mass parts. Therefore, 2-50 mass parts is preferable and, as for solid content which occupies for 100 mass parts of polymeric liquid crystal compositions, 5-30 mass parts is more preferable. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition tends to be low, the thickness of the film becomes substantially uniform, and there is a tendency for non-uniformity to occur easily. The said solid content can consider the thickness of the liquid crystal cured film to manufacture, and can determine it suitably.

By mix|blending a polymerization inhibitor, the polymerization reaction of a polymerizable liquid crystal compound is controllable. Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone and alkyl ether; catechols having a substituent such as an alkyl ether such as butyl catechol; radical scavengers such as pyrogallols and 2,2,6,6-tetramethyl-1-piperidinyloxy radicals; thiophenols; β-naphthylamines and β-naphthols are mentioned. In order to polymerize the polymerizable liquid crystal compound without disturbing the orientation, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the polymerizable liquid crystal compound, More preferably, it is 0.1-3 mass parts.

Moreover, a photoinitiator can be made highly sensitive by using a sensitizer. As a photosensitizer, For example, xanthone, such as a xanthone and a thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; Rubrene can be mentioned. As a photosensitizer, For example, xanthone, such as a xanthone and a thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; Rubrene can be mentioned. Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts.

Moreover, the polymeric liquid crystal composition of this invention may contain the leveling agent. A leveling agent is an additive which has the function of adjusting the fluidity|liquidity of a polymeric liquid crystal composition and making the film|membrane obtained by apply|coating this flatter, For example, silicone type, polyacrylate type, and perfluoroalkyl type|system|group leveling agent are mentioned. can Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (above, all manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341 , X22-161A, KF6001 (above, all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (above, all are Momentive Performance Materials Japan joint venture) Manufactured), fluorinert (registered trademark) FC-72, copper FC-40, copper FC-43, copper FC-3283 (above, all manufactured by Sumitomo 3M Co., Ltd.), Megapac (registered trademark) R -08, East R-30, East R-90, East F-410, East F-411, East F-443, East F-445, East F-470, East F-477, East F-479, East F -F-482, copper F-483 (above, all manufactured by DIC Co., Ltd.), FTOP (trade name) EF301, copper EF303, copper EF351, copper EF352 (above, all manufactured by Mitsubishi Material Electronics Co., Ltd.), SURFRON ( Registered trademarks) S-381, Dong S-382, Dong S-383, Dong S-393, Dong SC-101, Dong SC-105, KH-40, SA-100 (all above, AGC Semi Chemical Co., Ltd.) manufactured), trade names E1830, copper E5844 (manufactured by Daikin Fine Chemical Research Institute), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: manufactured by BM Chemie), etc. can be heard Especially, a polyacrylate type leveling agent and a perfluoroalkyl type leveling agent are preferable.

0.01-5 mass parts is preferable with respect to 100 mass parts of polymeric liquid crystal compounds, and, as for content of the leveling agent in a polymeric liquid crystal composition, 0.05-3 mass parts is more preferable. It becomes easy to orientate a polymeric liquid crystal compound as content of a leveling agent is in the said range, and since there exists a tendency for the liquid crystal cured film obtained to become smoother, it is preferable. The polymerizable liquid crystal composition may contain two or more types of leveling agents.

The polymerizable liquid crystal composition of the present invention is added to the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) as needed with a solvent, a photoinitiator, a polymerization inhibitor, a photosensitizer, or a leveling agent. It can prepare by adding additives, such as these, and stirring and mixing at predetermined temperature.

<Retardation film>

Since the polymerizable liquid crystal composition of the present invention has high solubility in solvents of the polymerizable liquid crystal compound, it is possible to suppress the occurrence of alignment defects resulting from precipitation, precipitation, etc. of undissolved polymerizable liquid crystal compounds or polymerizable liquid crystal compounds during storage. The effect is excellent. For this reason, by using the polymeric liquid crystal composition of this invention, it becomes possible to form into a film without reducing the optical characteristic which a polymeric liquid crystal compound can express originally, and it becomes possible to obtain the liquid crystal cured film which has the outstanding optical characteristic. Accordingly, the present invention relates to a retardation film comprising, as a cured product (liquid crystal cured film) of the polymerizable liquid crystal composition of the present invention, a liquid crystal cured film in which the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is cured in an aligned state. it is also The retardation film comprised from the said liquid crystal cured film can fully express the optical characteristic which the polymeric liquid crystal compound used can fully express, and it can become the retardation film which has high optical performance.

The liquid crystal cured film constituting the retardation film of the present invention may be composed of a homopolymer of the polymerizable liquid crystal compound (1-1) in an aligned state and a homopolymer of the polymerizable liquid crystal compound (1-2), and You may be comprised from the copolymer in the orientation state of the mixture of a liquid crystal compound (1-1) and a polymeric liquid crystal compound (1-2). Since the polymerization reaction is easy and it is easy to obtain a uniform liquid crystal cured film, the liquid crystal cured film which comprises the retardation film of this invention is orientation of the mixture of a polymeric liquid crystal compound (1-1) and a polymeric liquid crystal compound (1-2) It is preferable to be comprised from the copolymer in a state.

In one aspect of the present invention, the retardation film of the present invention comprises a liquid crystal cured film which is a cured product of the polymerizable liquid crystal composition of the present invention, and the liquid crystal cured film has the following formula (i):

0.75 ≤ Re(450)/Re(550) < 1.0 (i)

[In formula (i), Re(λ) represents the in-plane retardation value at the wavelength λ nm of the liquid crystal cured film]

It is preferable to have an optical characteristic represented by .

When a liquid crystal cured film satisfy|fills Formula (i), the said liquid crystal cured film shows what is called reverse wavelength dispersion in which the in-plane retardation value in a short wavelength becomes smaller than the in-plane retardation value in a long wavelength. Re(450)/Re(550) is more preferably 0.76 or more, still more preferably 0.78 or more, and more preferably Re(450)/Re(550) from the viewpoint of improving the reverse wavelength dispersion and further improving the optical properties of the retardation film. preferably 0.92 or less, more preferably 0.90 or less, particularly preferably 0.87 or less, more particularly preferably 0.86 or less, particularly preferably 0.85 or less.

In one aspect of the present invention, the retardation film of the present invention, the following formula (ii):

1.00 ≤ Re(650)/Re(550) (ii)

[In formula (ii), Re(λ) represents the in-plane retardation value at the wavelength λ nm of the retardation film]

It is preferable to contain the liquid crystal cured film which has the optical characteristic represented by. From a viewpoint of the optical characteristic of retardation film, Re(650)/Re(550) becomes like this. More preferably, it is 1.01 or more, More preferably, it is 1.02 or more.

Further, in one aspect of the present invention, the retardation film of the present invention, the following formula (iii):

100 nm ≤ Re(550) ≤ 180 nm (iii)

[In formula (iii), Re(λ) represents the in-plane retardation value at the wavelength λ nm of the retardation film]

It is preferable to contain the liquid crystal cured film which has the optical characteristic shown by. The liquid crystal cured film satisfying the above formula (iii) functions as a λ/4 plate, and an elliptically polarizing plate having a retardation film including the liquid crystal cured film is applied to an optical display, etc. effect) is excellent. A more preferable range of the in-plane retardation value is 120 nm ≤ Re(550) ≤ 170 nm, and a more preferable range is 130 nm ≤ Re(550) ≤ 150 nm.

The said in-plane retardation value can be adjusted with the thickness d of a liquid crystal cured film. Since the in-plane retardation value is determined by the above formula Re(λ) = (nx(λ) - ny(λ)) × d, a desired in-plane retardation value (Re(λ): liquid crystal curing at a wavelength λ (nm)) In order to obtain the in-plane retardation value of the film), the three-dimensional refractive index and the film thickness d may be adjusted. In addition, in said formula, d represents the thickness of the liquid crystal cured film made into object, nx is the refractive index ellipsoid formed by the liquid crystal cured film. WHEREIN: The principal refractive index in the wavelength λ nm of the direction parallel to the plane of the liquid crystal cured film. In the refractive index ellipsoid formed by the liquid crystal cured film, ny represents the refractive index at a wavelength λ nm in a direction parallel to the plane of the liquid crystal cured film and orthogonal to the nx direction.

The retardation film of the present invention, for example,

forming a coating film of the polymerizable liquid crystal composition of the present invention, drying the coating film, and further aligning the polymerizable liquid crystal compound in the polymerizable liquid crystal composition;

Process of polymerizing a polymerizable liquid crystal compound by light irradiation while maintaining an orientation state, and forming a liquid crystal cured film

It can be prepared by a method comprising

The coating film of a polymeric liquid crystal composition can be formed by apply|coating a polymeric liquid crystal composition on the base material, the alignment film mentioned later, etc.

As a base material, although a glass base material, a film base material, etc. are mentioned, for example, From a viewpoint of workability, a resin film base material is preferable. As resin which comprises a film base material, For example, Polyolefin like polyethylene, a polypropylene, and a norbornene-type polymer; Cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; polyacrylic acid ester; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; and plastics such as polyphenylene sulfide and polyphenylene oxide. Such a resin can be formed into a film by known means such as a solvent casting method and a melt extrusion method to be used as a substrate. The surface of the substrate may have a protective layer formed of an acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and surface treatment such as silicone treatment, release treatment, corona treatment, plasma treatment, etc. may be performed.

A commercially available product may be used as the substrate. As a commercially available cellulose-ester base material, For example, a Fuji Photo Film Co., Ltd. cellulose-ester base material like Fujitac film; and "KC8UX2M", "KC8UY", and "KC4UY" Konica Minolta Opto Co., Ltd. cellulose ester base material etc. are mentioned. Examples of commercially available cyclic olefin-based resins include cyclic olefin-based resins manufactured by Ticona Corporation (Germany) such as “Topas (registered trademark)”; Cyclic olefin resin by JSR Corporation like "Aton (trademark)"; Cyclic olefin resins manufactured by Nippon Zeon Corporation such as “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; Cyclic olefin resin by Mitsui Chemicals, Inc. like "Apel" (trademark) is mentioned. A commercially available cyclic olefin-based resin substrate can also be used. As a commercially available cyclic olefin resin base material, Sekisui Chemical Industry Co., Ltd. product cyclic olefin resin base material like "Sucina (trademark)" and "SCA40 (trademark)"; Cyclic olefin resin base material by Optes Corporation like "ZEONOA film (trademark)"; The cyclic olefin resin base material by JSR Corporation like "Aton Film (trademark)" is mentioned.

From the viewpoints of thickness reduction of the retardation film, ease of peeling of the base material, handling properties of the base material, and the like, the thickness of the base material is usually 5 to 300 µm, preferably 10 to 150 µm.

As a method of applying the polymerizable liquid crystal composition to a substrate, etc., a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, a coating method such as an applicator method, and a printing method such as a flexographic method are known. method can be found.

Then, a dry coating film is formed by removing a solvent by drying etc. As a drying method, the natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method, etc. are mentioned. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent is removed from the coating film by drying, and the polymerizable liquid crystal compound can be oriented in a desired direction (eg, horizontal or vertical direction) with respect to the plane of the coating film. . The heating temperature of the coating film can be appropriately determined in consideration of the materials such as the polymerizable liquid crystal compound to be used and the base material for forming the coating film. It needs to be temperature. In order to bring the polymerizable liquid crystal compound into a desired alignment state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smectic phase transition temperature) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. or nematic phase transition temperature) or higher. In addition, the liquid crystal phase transition temperature can be measured using, for example, a polarization microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), etc. In the polymerizable liquid crystal composition of the present invention comprising at least two kinds of polymerizable liquid crystal compounds, the phase transition temperature is the ratio of all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition to the composition in the polymerizable liquid crystal composition. It means a temperature measured using a mixture of polymerizable liquid crystal compounds mixed with

The polymerizable liquid crystal composition of the present invention contains at least two kinds of a polymerizable liquid crystal compound (1-1) and a polymerizable liquid crystal compound (1-2), and is usually a single polymerizable liquid crystal compound (1-1). ) or the polymerizable liquid crystal compound (1-2) may undergo liquid crystal phase transition at a temperature lower than the transition temperature to the liquid crystal phase. For this reason, in manufacture of the retardation film using the polymeric liquid crystal composition of this invention, excessive consumption of thermal energy can be suppressed and productive efficiency can be improved. Moreover, since a liquid-crystal phase transition can be performed by heating at a comparatively low temperature, there also exists an advantage that the choice of the support base material which apply|coats a polymeric liquid crystal composition expands.

The heating time can be appropriately determined depending on the heating temperature, the type of the polymerizable liquid crystal compound to be used, the type of solvent, its boiling point, its quantity, and the like, but is usually 15 seconds to 10 minutes, and preferably 0.5 to 5 minutes.

Although the removal of the solvent from a coating film may be performed simultaneously with the heating to the liquid crystal phase transition temperature of a polymeric liquid crystal compound or more, and may be performed separately, it is preferable to perform simultaneously from a viewpoint of productivity improvement. Prior to heating the polymerizable liquid crystal compound above the liquid crystal phase transition temperature, a preliminary drying step for appropriately removing the solvent in the coating film under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize You can prepare Examples of the drying method in this preliminary drying step include a natural drying method, a ventilation drying method, heat drying, and a reduced pressure drying method. It can determine suitably according to the kind, the kind of solvent, its boiling point, its quantity, etc.

Subsequently, in the obtained dry coating film, the polymerizable liquid crystal compound is polymerized by irradiation with light while maintaining the alignment state of the polymerizable liquid crystal compound, thereby forming a liquid crystal cured film which is a polymer of the polymerizable liquid crystal compound present in a desired alignment state. . Since the polymerizable liquid crystal composition of the present invention can be highly polymerized by irradiation with light such as high-intensity ultraviolet rays while suppressing damage to the polymerizable liquid crystal compound, a photopolymerization method is usually used as a polymerization method. . Photopolymerization WHEREIN: As light irradiated to a dry coating film, it selects suitably according to the kind of polymerization initiator contained in the said dry coating film, the kind and quantity of a polymerizable liquid crystal compound. Specific examples thereof include at least one light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays and active electron beams. Among them, ultraviolet light is preferable from the viewpoint of being easy to control the progress of the polymerization reaction and being widely used in the field as a photopolymerization device, and it is polymerizable so that photopolymerization is possible with the ultraviolet light. It is preferable to select the kind of a polymeric liquid crystal compound and polymerization initiator contained in a liquid crystal composition. Moreover, at the time of superposition|polymerization, superposition|polymerization temperature can also be controlled by irradiating with light, cooling a dry coating film with an appropriate cooling means. When a polymerizable liquid crystal compound is superposed|polymerized at low temperature by employ|adoption of such a cooling means, even if it uses the thing with comparatively low heat resistance as a base material, a liquid crystal cured film can be formed suitably. Moreover, the polymerization reaction can also be accelerated|stimulated by making the polymerization temperature high in the range which does not generate|occur|produce the problem by the heat at the time of light irradiation (transformation by heat of a base material, etc.). At the time of photopolymerization, the patterned cured film can also be obtained by performing masking or image development.

Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, a wavelength range of 380 An LED light source emitting light of -440 nm, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, etc. are mentioned.

Ultraviolet irradiation intensity|strength is 10-3,000 mW/cm<2> normally. Ultraviolet irradiation intensity|strength, Preferably it is intensity|strength in the wavelength range effective for activation of a photoinitiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, still more preferably 0.1 second to 1 minute. When irradiated once or multiple times with such ultraviolet irradiation intensity, the accumulated light quantity is 10-3,000 mJ/cm<2>, Preferably it is 50-2,000 mJ/cm<2>, More preferably, it is 100-1,000 mJ/cm<2>.

The thickness of a liquid crystal cured film can be suitably selected according to the applied optical display etc. Preferably it is 0.2-3 micrometers, More preferably, it is 0.2-2 micrometers.

The coating film of the polymerizable liquid crystal composition may be formed on the alignment film. An aligning film has the orientation regulating force which liquid-crystal-aligns a polymeric liquid crystal compound in a desired direction. For example, there are a horizontal alignment film, an alignment film having an orientation regulating force for aligning the polymerizable liquid crystal compound in the horizontal direction, a vertical alignment film, and the like. The orientation regulating force can be arbitrarily adjusted according to the type of orientation film, surface state, rubbing conditions, etc., and when the orientation film is formed of a photo-alignable polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc.

As an alignment film, it is preferable that it has solvent resistance which does not melt|dissolve by application|coating of a polymeric liquid crystal composition, etc., and has heat resistance in the heat processing for the removal of a solvent, or orientation of a polymeric liquid crystal compound mentioned later. Examples of the alignment film include an alignment film containing an alignment polymer, a photo alignment film, a groove alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the alignment direction, and the like, from the viewpoint of the precision and quality of the alignment angle. A photo-alignment film is preferable.

Examples of the orientation polymer include polyamide and gelatin having an amide bond in the molecule, polyimide having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacryl which is a hydrolyzate thereof. amide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Especially, polyvinyl alcohol is preferable. An orientation polymer can be used individually or in combination of 2 or more types.

An alignment film containing an alignment polymer is usually prepared by applying a composition in which an alignment polymer is dissolved in a solvent (hereinafter, sometimes referred to as an “oriented polymer composition”) to a substrate to remove the solvent, or the alignment polymer composition is applied to the substrate. It is obtained by apply|coating to, removing a solvent, and rubbing (rubbing method). As a solvent, the thing similar to the solvent illustrated above as a solvent which can be used for a polymeric liquid crystal composition is mentioned.

The concentration of the orientation polymer in the orientation polymer composition should just be in a range in which the orientation polymer material can be completely dissolved in the solvent. desirable.

As the orientation polymer composition, a commercially available orientation film material may be used as it is. Examples of commercially available alignment film materials include SunEver (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.), Optimer (registered trademark, manufactured by JSR Corporation), and the like.

As a method of apply|coating an orientation polymer composition to a base material, the thing similar to what was illustrated as a method of apply|coating a polymeric liquid crystal composition to a base material is mentioned.

As a method of removing the solvent contained in an orientation polymer composition, the natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method, etc. are mentioned.

In order to provide an orientation regulating force to an orientation film, a rubbing process can be performed as needed (rubbing method). As a method of imparting an orientation regulating force by the rubbing method, a rubbing cloth is wound and a rotating rubbing roll is coated with an oriented polymer composition on a substrate and annealed to make contact with a film of an oriented polymer formed on the surface of the substrate. . When performing a rubbing process, if masking is performed, a some area|region (pattern) from which an orientation direction differs can also be formed in an orientation film.

The photo-alignment film is usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as "composition for photo-alignment film formation") to a substrate, and after removing the solvent, polarized light (preferably, polarized UV light) ) is obtained by irradiating A photo-alignment film is advantageous also at the point which can control the direction of an orientation regulating force arbitrarily by selecting the polarization direction of the polarization|polarized-light to irradiate.

A photoreactive group means group which produces liquid-crystal orientation ability by irradiating with light. Specific examples include groups involved in photoreactions that cause alignment of molecules generated by light irradiation, or which are the origins of liquid crystal alignment ability, such as isomerization, dimerization, photocrosslinking, or photolysis. Especially, group which participates in dimerization reaction or photocrosslinking reaction is preferable at the point excellent in orientation. As the photoreactive group, a group having an unsaturated bond, especially a double bond, is preferable, and a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N A group having at least one selected from the group consisting of a bond) and a carbon-oxygen double bond (C=O bond) is particularly preferred.

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C=N bond include a group having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N=N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Examples of the photoreactive group having a C=O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, or a halogenated alkyl group.

Among them, a photoreactive group involved in the photodimerization reaction is preferable, the amount of polarized light irradiation required for photoalignment is relatively small, and a photoalignment film excellent in thermal stability and temporal stability is easy to be obtained, so cinnamoyl group and chalcone groups are preferred. As a polymer which has a photoreactive group, it is especially preferable that the terminal part of the said polymer side chain has a cinnamoyl group used as a cinnamic acid structure.

By applying the composition for forming a photo-alignment film on the substrate, the photo-alignment inducing layer can be formed on the substrate. Examples of the solvent contained in the composition include the same solvents as those exemplified above as solvents usable in the polymerizable liquid crystal composition, and can be appropriately selected according to the solubility of the polymer or monomer having a photoreactive group.

Although content of the polymer or monomer which has a photoreactive group in the composition for photo-alignment film formation can be suitably adjusted according to the kind of polymer or monomer, or the thickness of the photo-alignment film made into the objective, with respect to the mass of the composition for photo-alignment film formation, at least 0.2 mass % is preferable, and the range of 0.3-10 mass % is more preferable. In the range in which the characteristic of a photo-alignment film is not impaired remarkably, the composition for photo-alignment film formation may contain polymeric materials, such as polyvinyl alcohol and a polyimide, and a photosensitizer.

As a method of apply|coating the composition for photo-alignment film formation to a base material, the method similar to the method of apply|coating an orientation polymer composition to a base material is mentioned. As a method of removing a solvent from the apply|coated composition for photo-alignment film formation, a natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method etc. are mentioned, for example.

In order to irradiate the polarized light, from the composition for forming a photo-alignment film applied on the substrate, the solvent may be directly irradiated with polarized UV light, or the polarized light may be irradiated from the substrate side, and the polarized light may be transmitted and irradiated. . Moreover, the said polarization|polarized-light is especially preferable if it is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength range where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength of 250 to 400 nm is particularly preferable. Examples of the light source used for polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps and metal halide lamps. is more preferable. Among these, a high-pressure mercury-vapor lamp, an ultra-high pressure mercury lamp, and a metal halide lamp are preferable because the light emission intensity of the ultraviolet-ray of wavelength 313nm is large. Polarized UV can be irradiated by irradiating the light from the said light source through a suitable polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as Glan Thompson or Glan Taylor, or a wire grid type polarizer can be used.

Moreover, when performing rubbing or polarized light irradiation and masking, the some area|region (pattern) from which the direction of a liquid-crystal orientation differs can also be formed.

A groove alignment film is a film|membrane which has an uneven|corrugated pattern or a plurality of grooves (grooves) on the film surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of straight grooves arranged at equal intervals, the liquid crystal molecules are aligned in a direction along the grooves.

As a method of obtaining a groove alignment film, a method of forming an uneven pattern by developing and rinsing after exposure through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film, a method of forming an uneven pattern on the surface A method of forming a layer of UV-curing resin before curing, transferring the formed resin layer to a substrate, and then curing, and pressing a roll-shaped disk having a plurality of grooves on a film of UV-curing resin formed on the substrate before curing The method of forming an unevenness|corrugation and hardening after that is mentioned.

The thickness of the alignment film (orientation film or photo-alignment film containing an alignment polymer) is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 500 nm or less, still more preferably is in the range of 10 to 300 nm, particularly preferably 50 to 250 nm.

<Elliptical Polarizer>

The present invention includes an elliptically polarizing plate comprising the retardation film of the present invention. The elliptically polarizing plate of the present invention contains the retardation film and the polarizing film of the present invention.

A polarizing film is a film which has a polarizing function, and the film etc. which contain as a polarizer the stretched film which made the dye which has absorption anisotropy adsorb|suck, and the film which apply|coated the dye which has absorption anisotropy are mentioned. As a dye which has absorption anisotropy, a dichroic dye is mentioned, for example.

A film comprising a stretched film to which a dye having absorption anisotropy is adsorbed as a polarizer is usually used in a step of uniaxially stretching a polyvinyl alcohol-based resin film, by dyeing the polyvinyl alcohol-based resin film with a dichroic dye, the dichroic dye At least one side of the polarizer manufactured through a step of adsorbing the polyvinyl alcohol-based resin film to which the dichroic dye has been adsorbed, a step of treating the polyvinyl alcohol-based resin film with an aqueous solution of boric acid, and a step of washing with water after treatment with an aqueous solution of boric acid through an adhesive It is manufactured by sandwiching it with a transparent protective film.

Polyvinyl alcohol-type resin is obtained by saponifying polyvinyl acetate-type resin. As polyvinyl acetate-type resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, the copolymer of vinyl acetate and other monomer copolymerizable to it is used. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The saponification degree of polyvinyl alcohol-type resin is about 85-100 mol% normally, Preferably it is 98 mol% or more. The polyvinyl alcohol-type resin may be modified|denatured, for example, polyvinyl formal and polyvinyl acetal modified|denatured with aldehydes can also be used. The polymerization degree of polyvinyl alcohol-type resin is about 1,000-10,000 normally, Preferably it is the range of 1,500-5,000.

What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of a polarizing film. The method of forming a polyvinyl alcohol-type resin into a film is not specifically limited, A film can be formed by a well-known method. The film thickness of a polyvinyl alcohol-type raw film can be about 10-150 micrometers, for example.

Uniaxial stretching of a polyvinyl alcohol-type resin film can be performed before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing|staining. When performing uniaxial stretching after dyeing|staining, this uniaxial stretching may be implemented before a boric-acid process, and may be implemented during a boric-acid process. Moreover, it is also possible to perform uniaxial stretching in these several steps. At the time of uniaxial stretching, you may extend|stretch uniaxially between rolls from which circumferential speed differs, and you may extend|stretch uniaxially using a hot roll. Moreover, uniaxial stretching may be dry extending|stretching extending|stretching in air|atmosphere, and wet extending|stretching which extends|stretches in the state which swelled the polyvinyl alcohol-type resin film using a solvent may be sufficient as it. The draw ratio is usually about 3 to 8 times.

The dyeing|staining by the dichroic dye of a polyvinyl alcohol-type resin film is performed by the method of immersing a polyvinyl alcohol-type resin film in the aqueous solution containing a dichroic dye, for example.

Specifically, iodine or a dichroic organic dye is used as a dichroic dye. As a dichroic organic dye, the dichroic direct dye which consists of a disazo compound, such as C.I. DIRECT RED 39, and a dichroic direct dye which consists of compounds, such as trisazo and tetrakis azo, etc. are mentioned. It is preferable that a polyvinyl alcohol-type resin film performs the immersion process with respect to water before a dyeing process.

When using an iodine as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing an iodine and potassium iodide is usually employ|adopted. Content of the iodine in this aqueous solution is about 0.01-1 mass part normally per 100 mass parts of water. Moreover, content of potassium iodide is about 0.5-20 mass parts normally per 100 mass parts of water. The temperature of the aqueous solution used for dyeing is about 20-40 degreeC normally. Moreover, the immersion time (dyeing time) with respect to this aqueous solution is about 20 to 1,800 second normally.

On the other hand, when using a dichroic organic dye as a dichroic dye, the method of dyeing by immersing a polyvinyl alcohol-type resin film in the aqueous solution containing a water-soluble dichroic dye is usually employ|adopted. Content of the dichroic organic dye in this aqueous solution is about 1x10 ^-4 - 10 mass parts normally per 100 mass parts of water, Preferably it is 1x10 ^-3 - 1 mass part, More preferably, 1 x 10 ^-3 to 1 x 10 ^-2 parts by mass. This aqueous solution may contain inorganic salts, such as sodium sulfate, as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is about 20-80 degreeC normally. Moreover, the immersion time (dyeing time) with respect to this aqueous solution is about 10 to 1,800 second normally.

The boric acid treatment after dyeing|dyeing with a dichroic dye can be performed by the method of immersing the dyed polyvinyl alcohol-type resin film in boric-acid aqueous solution normally. Content of the boric acid in this boric-acid aqueous solution is about 2-15 mass parts normally per 100 mass parts of water, Preferably it is 5-12 mass parts. When iodine is used as a dichroic dye, it is preferable that this aqueous boric acid solution contains potassium iodide, and content of potassium iodide in that case is about 0.1-15 mass parts normally per 100 mass parts of water, Preferably it is 5 -12 parts by mass. The immersion time with respect to boric-acid aqueous solution is about 60 to 1,200 second normally, Preferably it is 150 to 600 second, More preferably, it is 200 to 400 second. The temperature of a boric acid process is 50 degreeC or more normally, Preferably it is 50-85 degreeC, More preferably, it is 60-80 degreeC.

The polyvinyl alcohol-type resin film after a boric acid process is water washing process normally. The water washing process can be performed by the method of immersing the polyvinyl alcohol-type resin film by which the boric acid process was carried out, for example in water. The temperature of the water in a water washing process is about 5-40 degreeC normally. Moreover, immersion time is about 1-120 second normally.

A drying process is performed after water washing, and a polarizer is obtained. A drying process can be implemented using a hot-air dryer or a far-infrared heater, for example. The temperature of a drying process is about 30-100 degreeC normally, Preferably it is 50-80 degreeC. The time of a drying process is about 60 to 600 second normally, Preferably it is 120 to 600 second. By a drying process, the moisture content of a polarizer is reduced to a practical use grade. The moisture content is normally about 5-20 mass %, Preferably it is 8-15 mass %. It has moderate flexibility as a moisture content is the said range, and the polarizer excellent in thermal stability is easy to be obtained.

In this way, the thickness of the polarizer obtained by making a polyvinyl alcohol-type resin film uniaxially stretching, dyeing with a dichroic dye, a boric acid treatment, water washing, and drying becomes like this. Preferably it is 5-40 micrometers.

As a film to which the dye which has absorption anisotropy is apply|coated, the film obtained by apply|coating the composition containing the dichroic dye which has liquid crystallinity, or the composition containing the dichroic dye and a polymerizable liquid crystal compound, etc. are mentioned. The said film, Preferably, it has a protective film on the single side|surface or both surfaces. As the said protective film, the thing similar to the resin film illustrated above as a base material which can be used for manufacture of a liquid crystal cured film is mentioned.

The film coated with the dye having absorption anisotropy is preferably thinner, but from the viewpoint of strength and workability, the thickness of the film is usually 20 µm or less, preferably 5 µm or less, and more preferably 0.5 to 3 µm. to be.

As a film which apply|coated the pigment|dye which has the said absorption anisotropy, the film of Unexamined-Japanese-Patent No. 2013-33249 etc. is mentioned specifically,.

Thus, a polarizing film is obtained by laminating|stacking a transparent protective film on the at least one surface of the obtained polarizer through an adhesive agent. As a transparent protective film, the same transparent film as the resin film illustrated above as a base material which can be used for manufacture of the liquid crystal cured film which comprises retardation film can be used preferably.

The elliptically polarizing plate of the present invention is constituted by including the retardation film and the polarizing film of the present invention, for example, by laminating the retardation film and the polarizing film of the present invention through an adhesive layer or an adhesive layer, the elliptically polarizing plate of the present invention A polarizing plate can be obtained.

In one aspect of the present invention, when the retardation film of the present invention including the liquid crystal cured film and the polarizing film are laminated, the angle formed between the slow axis (optical axis) of the liquid crystal cured film constituting the retardation film and the absorption axis of the polarizing film is 45 It is preferable to laminate it so that it may become ± 5 degrees.

The elliptically polarizing plate of this invention may have the structure with which the conventional general elliptically polarizing plate or a polarizing film and retardation film are equipped. In such a configuration, for example, an adhesive layer (sheet) for bonding an elliptically polarizing plate to a display element constituting an optical display, etc., a polarizing film or retardation film Used for the purpose of protecting the surface from scratches and contamination The protection film etc. which become used are mentioned.

The elliptically polarizing plate of the present invention can be used for various display devices, particularly optical displays.

A display device is a device which has a display element, and contains a light emitting element or a light emitting device as a light emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a flexible image display device, a touch panel display device, an electron emission display device (eg, an electric field Emission display device (FED), surface field emission display device (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (eg grating light valve (GLV) display device) , a display device having a digital micromirror device (DMD)), a piezoelectric ceramic display, etc. The liquid crystal display device includes a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, and a direct view type liquid crystal display device. and projection type liquid crystal display device, etc. These display devices may be a display device that displays a two-dimensional image or a stereoscopic display device that displays a three-dimensional image. In particular, the elliptically polarizing plate of the present invention is an organic electroluminescent device. It can be suitably used in ness (EL) display device and inorganic electroluminescence (EL) display device.These display devices (optical display) are provided with the elliptically polarizing plate of the present invention excellent in optical properties, and thus have good image display characteristics can be expressed.

It is preferable that the flexible image display apparatus which has an elliptically polarizing plate of this invention further has a window and a touchscreen touch sensor.

A flexible image display apparatus consists of, for example, the laminated body for flexible image display apparatuses, and an organic electroluminescent display panel, The laminated body for flexible image display apparatuses is arrange|positioned on the visual recognition side with respect to an organic electroluminescent display panel, and it is comprised so that it can bend. has been As the laminate for a flexible image display device, in addition to the elliptically polarizing plate of the present invention described above, a window, a touch panel touch sensor, and the like may be included. Although their lamination order is arbitrary, it is preferable to laminate|stack in the order of a window, an elliptically polarizing plate, and a touch panel touch sensor, or a window, a touch panel touch sensor, and an elliptically polarizing plate from the viewing side.

When the elliptically polarizing plate exists on the visual recognition side of a touch panel touch sensor, since the pattern of a touch panel touch sensor becomes hard to be visually recognized and the visibility of a display image becomes favorable, it is preferable. Each member can be laminated using an adhesive, a pressure-sensitive adhesive, or the like. Moreover, the laminated body for flexible image display apparatuses can be equipped with the light-shielding pattern formed in at least one surface of any layer of the said window, an elliptically polarizing plate, and a touchscreen touch sensor.

A window is arrange|positioned on the visual recognition side of a flexible image display apparatus, and plays the role of protecting other components from external impact or environmental changes, such as temperature and humidity. Conventionally, although glass has been used as such a protective layer, the window in a flexible image display apparatus is not rigid and rigid like glass, and has a flexible characteristic. The said window consists of a flexible transparent base material, and may contain the hard-coat layer in at least one surface.

The transparent substrate preferably has a visible light transmittance of 70% or more, and more preferably 80% or more of a visible light transmittance. As the transparent substrate, any polymer film having transparency may be used. Among them, polyamide films, polyamideimide films or polyimide films, polyester films, olefin films, acrylic films, and cellulose films, which are excellent in transparency and heat resistance, are preferable. It is also preferable to disperse inorganic particles such as silica, organic fine particles, rubber particles, and the like in the polymer film.

The thickness of the said transparent base material becomes like this. Preferably it is 5-200 micrometers, More preferably, it is 20-100 micrometers.

A hard coat layer may be formed on at least one surface of the transparent substrate constituting the window. The thickness of a hard-coat layer is not specifically limited, For example, 2-100 micrometers may be sufficient. If the thickness of the said hard-coat layer is in the said range, it will be easy to ensure sufficient impact resistance, abrasion resistance, and bending resistance.

Although the said hard-coat layer can be formed by hardening of the composition for hard-coat formation containing the reactive material which irradiates an active energy ray or thermal energy to form a crosslinked structure, it is preferable that it is by active energy ray hardening. An active energy ray is defined as an energy ray capable of generating active species by decomposing a compound that generates active species. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays, and electron beams, and ultraviolet rays are particularly preferable. The said composition for hard-coat formation contains the at least 1 sort(s) of compound of a radically polymerizable compound and a cationically polymerizable compound, and a polymerization initiator normally. It does not specifically limit as a radically polymerizable compound, a cationically polymerizable compound, and a polymerization initiator, A conventionally well-known thing is mentioned. The hard coat composition may further include one or more selected from the group consisting of solvents and additives. As the solvent, as long as it can dissolve or disperse the polymerizable compound or the polymerization initiator, a solvent known as a solvent for a composition for forming a hard coat in the field of an optical film can be used without limitation. Examples of the additive include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, and antifouling agents.

A touch panel touch sensor is used as an input means. As a touch panel touch sensor, various styles, such as a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and a capacitive method, are proposed, and any method may be used. Among them, the electrostatic capacitive method is preferable. The capacitive touch panel touch sensor is divided into an active area and an inactive area located outside the active area. The active area is an area corresponding to an area (display unit) in which a screen is displayed on the display panel, and is an area in which a user's touch is sensed, and the inactive area is an area corresponding to an area in which a screen is not displayed (non-display unit) of the display device. . A touch panel touch sensor comprises: a board|substrate which has a flexible characteristic; a sensing pattern formed in the active region of the substrate; Each sensing line is formed in the non-active area of the substrate and connected to an external driving circuit through the sensing pattern and the pad part.

The substrate having flexible characteristics, the sensing pattern, and each sensing line are not particularly limited, and each applicable material in the art may be selected.

As the substrate having flexible characteristics, for example, a substrate made of the same material as the transparent substrate of the window can be used. It is preferable from the point of crack suppression of a touchscreen touch sensor that toughness is 2,000 MPa% or more, and, as for the board|substrate of a touchscreen touch sensor, it is more preferable that toughness is 2,000 MPa% - 30,000 MPa%. Here, the toughness is defined as the area under the curve from the stress-strain curve to the fracture point obtained through a tensile test of a polymer material.

Each layer (window, elliptically polarizing plate, touch panel touch sensor) forming the laminate for a flexible image display device and the film member (polarizing film, retardation film, etc.) constituting each layer can be formed with an adhesive agent. Examples of adhesives include water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent volatilization adhesives, moisture-curing adhesives, heat-curing adhesives, anaerobic curing adhesives, active energy ray curing adhesives, hardener mixture adhesives, hot melt adhesives, What is generally used, such as a pressure-sensitive adhesive (adhesive) and a rewritable adhesive, can be used. Especially, an aqueous solvent volatilization type adhesive agent, an active energy ray hardening type adhesive agent, and an adhesive are used preferably. Although the thickness of an adhesive agent layer can be suitably adjusted according to the adhesive force calculated|required etc., it is 0.01 micrometer - 500 micrometers normally, Preferably they are 0.1 micrometer - 300 micrometers. When two or more adhesive agent layers exist in the said laminated body for flexible image display devices, the kind and thickness of the adhesive agent which comprise each adhesive agent layer may be same or different.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. In addition, unless otherwise indicated, "%" and "part" in an example mean mass % and mass part, respectively.

1. Preparation of polymerizable liquid crystal compound and liquid crystal mixture

Production Example 1: Preparation of a polymerizable liquid crystal compound represented by the formula (A-1)

A polymerizable liquid crystal compound (hereinafter, referred to as "polymerizable liquid crystal compound (A-1)") represented by the following formula (A-1) was synthesized according to the following scheme.

[Formula 19]

11.02 g of compound (E-1) synthesized with reference to Patent Literature (Japanese Patent Application Laid-Open No. 2010-31223) in a 100 mL-4 neck flask equipped with a Dimroth cooling tube and a thermometer, in a nitrogen atmosphere, Patent Literature ( 4.00 g of compound (D-1) synthesized with reference to JP 2011-207765), 0.02 g of DMAP (manufactured by Wako Pure Chemical Industries, Ltd.), 0.20 g of BHT (manufactured by Wako Pure Chemical Industries, Ltd.), and chloroform After adding and mixing 58 g (manufactured by Kanto Chemical Co., Ltd.), 4.05 g of IPC (manufactured by Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel, and these were reacted at 0°C overnight. After completion of the reaction, insoluble components were removed by filtration. The obtained chloroform solution was dripped at 3 times the weight of acetonitrile (made by Wako Pure Chemical Industries, Ltd.) with respect to the weight of the chloroform contained in the solution, and solid was deposited. Subsequently, the precipitated solid was taken out by filtration, washed 3 times with 20 g of acetonitrile, and then dried under reduced pressure at 30°C to obtain 11.43 g of a polymerizable liquid crystal compound (A-1). The yield of the polymerizable liquid crystal compound (A-1) was 80% based on the compound (D-1).

Preparation Example 2: Preparation of liquid crystal mixture (A')

A liquid crystal mixture (hereinafter also referred to as "liquid crystal mixture (A')") containing a polymerizable liquid crystal compound represented by the following formulas (A-1) to (A-3) was synthesized according to the following scheme.

[Formula 20]

[Formula 21]

With reference to the patent document (Japanese Patent Application Laid-Open No. 2010-31223), trans-1,4-cyclohexanedicarboxylic acid was changed to cis-1,4-cyclohexanedicarboxylic acid, and the compound (E-2) was 27.02 g of the mixture shown was synthesized. Compound (E-1) of Production Example 1 was mixed with compound (E-2) and compound (E-1) using a mixture of the obtained compound (E-2) and compound (E-1) at a ratio of 10/90. 10.57g of liquid-crystal mixture (A') was obtained by changing to the said mixture of and performing a synthesis|combination. As a result of analyzing the obtained liquid crystal mixture (A') by HPLC measurement, the liquid crystal mixture contains the compound (A-1), the compound (A-2), and the compound (A-3), and the compound (A) The sum of the peak areas of -2) and compound (A-3) was 3.00% with respect to 100% of the total peak areas of compound (A-1), compound (A-2), and compound (A-3).

[HLPC Measurement]

You may perform HPLC measurement on any condition as long as the peak derived from a polymeric liquid crystal compound can be isolate|separated. The HPLC measurement conditions used for the analysis in the Example and comparative example of this invention are shown below.

(Measuring conditions)

Measurement device: HPLC LC-10AT (manufactured by Shimadzu Corporation)

Column: L-Column ODS (inner diameter 3.0 mm, length 150 mm, particle diameter 3 μm)

Temperature: 40℃

Mobile phase A: 0.1% (v/v) - TFA/water

Mobile phase B: 0.1% (v/v) - TFA/acetonitrile

Gradient: 0 min 70 % - B

30 min 100% - B

60 min 100% - B

60.01 min 70 % - B

75 min 70 % - B

Flow rate: 0.5 mL/min

Injection volume: 5 μL

Detection wavelength: 254 nm

Production Example 3: Preparation of a polymerizable liquid crystal compound represented by the formula (B-1)

A polymerizable liquid crystal compound represented by the following formula (B-1) (hereinafter referred to as “polymerizable liquid crystal compound (B-1)”) was synthesized according to the following scheme.

[Formula 22]

All reacted similarly to the method of manufacture example 1 except having changed into 4.22g of compound (D-2), and 11.75g of polymerizable liquid crystal compounds (B-1) were obtained. The yield of the polymerizable liquid crystal compound (B-1) was 81% based on the compound (D-2).

Preparation Example 4: Preparation of liquid crystal mixture (B')

A liquid crystal mixture (hereinafter also referred to as "liquid crystal mixture (B')") containing a polymerizable liquid crystal compound represented by the following formulas (B-1) to (B-3) was synthesized according to the following scheme.

[Formula 23]

Except having changed into 4.22 g of compound (D-2), all reacted similarly to the method of manufacture example 2, and 10.88g of liquid-crystal mixtures (B') were obtained. As a result of analyzing the obtained liquid crystal mixture (B') under the HPLC measurement conditions, the liquid crystal mixture contains the compound (B-1), the compound (B-2) and the compound (B-3), and the compound The sum total of the peak areas of (B-2) and (B-3) was 5.23% with respect to 100% of the total peak areas of compound (B-1), compound (B-2), and compound (B-3).

Preparation Example 5: Preparation of liquid crystal mixture (C')

The reaction was carried out in the same manner as in Preparation Example 4 except that the mixing ratio of the compound (E-2) and the compound (E-1) used in Preparation Example 4 was changed to 20/80, and the liquid crystal mixture (C' ) was obtained as 10.44 g. As a result of analyzing the obtained liquid crystal mixture (C') under the HPLC measurement conditions, the liquid crystal mixture contains the compound (B-1), the compound (B-2) and the compound (B-3), and the compound The sum of the peak areas of (B-2) and compound (B-3) was 12.3% with respect to 100% of the total peak areas of compound (B-1), compound (B-2), and compound (B-3).

Further, in Production Examples 1 to 5, the compound (A-1) and the compound (B-1) each correspond to the polymerizable liquid crystal compound (1-1) in the present invention, and the compound (A- 2) and compound (B-2) correspond to the polymerizable liquid crystal compound (1-2a) in the present invention, respectively, and compound (A-3) and compound (B-3) are, respectively, the present invention It corresponds to the polymerizable liquid crystal compound (1-2b) in

2. Polymerizable liquid crystal compounds/mixtures of Examples and Comparative Examples

(1) Example 1: Preparation of liquid crystal mixture (1)

The liquid crystal mixture (A') obtained in Preparation Example 2 and the polymerizable liquid crystal compound (A-1) obtained in Preparation Example 1 were subjected to the above HPLC measurement conditions, compound (A-1), compound (A-2) ) and compound (A-3) were mixed so that the peak area of the compound (A-2) and the compound (A-3) with respect to 100% of the total peak area of the compound (A-3) became 0.1 %, and the liquid crystal mixture (1) was obtained.

(2) Example 2: The liquid crystal mixture (A') obtained in Preparation Example 2 was used as the liquid crystal mixture (2).

(3) Example 3: Preparation of liquid crystal mixture (4)

The liquid crystal mixture (B') obtained in Preparation Example 4 and the polymerizable liquid crystal compound (B-1) obtained in Preparation Example 3 were subjected to the above HPLC measurement conditions, compound (B-1), compound (B-2) And it mixed so that the peak area of compound (B-2) and compound (B-3) with respect to 100% of the total peak area of compound (B-3) might become 0.4 %, and the liquid crystal mixture (3) was obtained.

(4) Example 4: The liquid crystal mixture (B') obtained in Preparation Example 4 was used as the liquid crystal mixture (4).

(5) Comparative Example 1: The polymerizable liquid crystal compound (A-1) obtained in Production Example 1 was used as the liquid crystal compound (1).

(6) Comparative Example 2: The polymerizable liquid crystal compound (B-1) obtained in Production Example 3 was used as the liquid crystal compound (2).

(7) Comparative Example 3: The liquid crystal mixture (C') obtained in Production Example 5 was used as the liquid crystal mixture (5).

3. Solubility Assessment

Liquid crystal mixture prepared in Examples 1 to 4 and Comparative Examples 1 to 3, while putting N-methylpyrrolidone (NMP) and a stirrer in a vial tube and stirring with a magnetic stirrer (HS-30DN, Asone) (1) to (5), and the liquid crystal compounds (1) and (2) were respectively added until the dissolution residue was visually confirmed. At the time when the dissolution residue was confirmed, the solubility of each liquid crystal mixture and the polymerizable liquid crystal compound in NMP was determined by (weight of each liquid crystal mixture and polymerizable liquid crystal compound)/(weight of each liquid crystal mixture and polymerizable liquid crystal compound + NMP weight) was calculated as weight percent concentration. A result is shown in Table 2.

4. Orientation defect evaluation

(1) Preparation of optical film (retardation film)

An optical film (retardation film) was produced according to the following procedure.

(i) Preparation of a composition for forming a photo-alignment film

The composition for photo-alignment film formation was obtained by mixing the following component and stirring the obtained mixture at 80 degreeC for 1 hour.

A photo-aligning material (5 parts) represented by the following formula (number average molecular weight about 28000):

[Formula 24]

Solvent (95 parts): cyclopentanone

(ii) Preparation of polymerizable liquid crystal composition

Cycloolefin polymer film (COP) (ZF-14, manufactured by Nippon Zeon Co., Ltd.) was prepared by using a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) at an output of 0.3 kW and a processing speed of 3 m/min. times were treated. On the corona-treated surface, the composition for forming a photo-alignment film was applied with a bar coater, dried at 80° C. for 1 minute, and 100 mJ using a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) Polarized UV exposure was performed with an accumulated light quantity of /cm<2>. It was 100 nm when the film thickness of the obtained photo-alignment film was measured with the laser microscope (LEXT, the Olympus Co., Ltd. make).

Next, the liquid crystal mixture (1) prepared in Example 1 is put into a vial tube, and a photopolymerization initiator, a leveling agent, a polymerization inhibitor and a solvent are injected according to the composition shown in Table 1, and the carousel is used and stirred at 80°C for 30 minutes to obtain a polymerizable liquid crystal composition.

In addition, the compounding quantity of a solvent was set so that mass % of a liquid crystal mixture might be 13 % with respect to the whole quantity of a polymeric liquid crystal composition (solution).

Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan)

Leveling agent: polyacrylate compound (BYK-361N; manufactured by Big Chemie Japan)

Polymerization inhibitor: BHT (manufactured by Wako Pure Chemical Industries, Ltd.)

Solvent: N-methylpyrrolidone (NMP; manufactured by Kanto Chemical Co., Ltd.)

(iii) manufacture of optical film

The obtained polymerizable liquid crystal composition was applied onto the alignment film using a bar coater, dried at 120°C for 1 minute, and then irradiated with ultraviolet light using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Corporation). The optical film was manufactured by carrying out (in nitrogen atmosphere, wavelength: 365 nm, the accumulated light quantity in wavelength 365 nm: 1000 mJ/cm<2>).

In addition, in place of the liquid crystal mixture (1), the liquid crystal mixtures (2) to (5) and liquid crystal compounds (1) and (2) prepared in Examples 2 to 5 and Comparative Examples 1 to 3 were respectively used, and Table 1 shows A polymerizable liquid crystal composition and an optical film were prepared in the same manner as above except that a photopolymerization initiator, a leveling agent, a polymerization inhibitor and a solvent were added according to the composition described above.

(2) Evaluation of orientation defects

The obtained optical film was cut out to 10 cm square, and the number of objects of the orientation defect on a screen was visually confirmed using the polarization microscope (LEXT, the product made by Olympus), and it evaluated according to the following evaluation criteria. A result is shown in Table 1.

(Evaluation criteria for orientation defects)

1: Orientation defects occur on the entire surface (>100)

2: 11 ~ 100 pieces

3 : 1 ~ 10 pieces

4: No defects

As shown in Table 1, the polymerizable liquid crystal compositions (Examples 1-4) according to the present invention contain a specific amount of the polymerizable liquid crystal compound (1-2) with respect to the polymerizable liquid crystal compound (1-1). It was confirmed that the solubility with respect to the solvent of a polymeric liquid crystal compound (1-1) could be improved, suppressing an orientation defect by carrying out.

Claims (12)

They have the same molecular weight, but different molecular structures, and also have the formula (1):

[In formula (1),
Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent,
D ¹ , D ² , E ¹ , E ² , B ¹ and B ² are each independently -CR ¹¹ R ¹² -, -CH ₂ CH ₂ -, -O-, -S-, -CO-O- , -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, R ¹¹ and R ¹² are each independently , a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms,
G ¹ and G ² each represent a 1,4-cyclohexanediyl group,
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group is , a halogen atom, -R ¹³ , -OR ¹³ , may be substituted with a cyano group or a nitro group, R ¹³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁴ or a halogen atom, and R ¹⁴ is a carbon number 1 to 4 represents the alkyl group, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, -CH ₂ - contained in the alkanediyl group may be substituted with -O- or -CO-,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ¹ and P ² is a polymerizable group)]
A polymerizable liquid crystal composition comprising at least two polymerizable liquid crystal compounds represented by
As the polymerizable liquid crystal compound, G ¹ and G ² in Formula (1) are each a 1,4-trans-cyclohexanediyl group, the polymerizable liquid crystal compound (1-1), and the polymerizable liquid crystal compound (1) -1) and a polymerizable liquid crystal compound (1-2) having a different molecular structure only when at least one of G ¹ and G ² in Formula (1) is a 1,4-cis-cyclohexanediyl group;
The ratio of the peak area of the polymerizable liquid crystal compound (1-2) to the total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) measured by liquid chromatography is 0.01% The polymerizable liquid crystal composition is 10% or more. The method of claim 1,
The polymerizable liquid crystal compound (1-2) is a polymerizable liquid crystal compound (1-2a) in which either one of G ¹ and G ² in Formula (1) is a 1,4-cis-cyclohexanediyl group; A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound (1-2b) in which both G ¹ and G ² in (1) are 1,4-cis-cyclohexanediyl groups. 3. The method according to claim 1 or 2,
A polymerizable liquid crystal composition wherein Ar in formula (1) is a group represented by any of formulas (2-1) to (2-5).

[During the ceremony,
* represents a bonding portion of D ¹ or D ² ;
Q ¹ represents -S-, -O- or -NR ¹⁵ -, R ¹⁵ represents a hydrogen atom or an optionally substituted C1-C6 alkyl group,
Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹⁵ -, and R ¹⁵ represents a hydrogen atom or an optionally substituted C1-C6 alkyl group;
Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group, and the hydrogen atom contained in the alkyl group, the aromatic hydrocarbon group or the aromatic heterocyclic group may be substituted with a halogen atom , -CH ₂ - contained in the alkyl group may be substituted with -O-, -CO-, -O-CO- or -CO-O-,
Y ² represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and -CH ₂ - contained in the alkyl group is -O- , -CO-, -O-CO-, or -CO-O- may be substituted;
Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms; represents a halogen atom, a cyano group, a nitro group, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , Z ¹ and Z ² may be bonded to each other to form an aromatic ring or an aromatic heterocycle, and R ¹⁵ and R ¹⁶ are each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, Ay is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, Ax and Ay may combine to form a ring;
Y ³ and Y ⁴ are, each independently, the following formula (Y-1):

[in formula (Y-1),
M ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the alkyl group may be substituted with one or more substituents X ³ , and the substituent X ³ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a penta Fluorosulfolanyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thio Socyano group, or one -CH ₂ - or two or more -CH ₂ - not adjacent to each other are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO- S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH= CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- represents a linear or branched alkyl group having 1 to 20 carbon atoms, and Any hydrogen atom may be substituted with a fluorine atom, or may be a contribution represented by -B ¹¹ -F ¹¹ -P ¹¹ , and B ¹¹ , F ¹¹ and P ¹¹ are respectively B ¹ , F ¹ in the formula (1). and P ¹ , and may be the same as or different from those of B ¹ , F ¹ and P ¹ ;
U ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and the aromatic hydrocarbon group may be substituted with one or more substituents X ³ . become ;
T ¹ is, -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ² - or -O-NU ² -, U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group (the aromatic hydrocarbon group an organic group having 2 to 30 carbon atoms, or (E ¹¹ -A ¹¹ ) _q -B ¹² -F ¹² -P ¹² , an alkyl group, a cycloalkyl group, or a cyclo The alkenyl group and the aromatic hydrocarbon group may each be unsubstituted or substituted with one or more substituents X ³ , the alkyl group may be substituted with the cycloalkyl group or cycloalkenyl group, and one of the alkyl groups -CH ₂ - or two or more -CH ₂ - which are not adjacent are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO- , -SO ₂ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- may be substituted, and one of the cycloalkyl groups or cycloalkenyl groups -CH ₂ - or 2 not adjacent or more -CH ₂ - may be each independently substituted with -O-, -CO-, -COO-, -OCO- or -O-CO-O-, E ¹¹ , A ¹¹ , B ¹² , F ¹² and P ¹² are respectively defined the same as E ¹ , A ¹ , B ¹ , F ¹ and P ¹ in Formula (1), respectively, and are the same as E ¹ , A ¹ , B ¹ , F ¹ and P ¹ , respectively. may or may differ, q represents the integer of 0-4, and when two or more E ¹¹ and/or A ¹¹ exist, each may be same It may be different, and U ¹ and U ² may combine to form a ring]
represents a group selected from.] 4. The method according to any one of claims 1 to 3,
A ¹ and A ² in Formula (1) are each independently a 1,4-cyclohexanediyl group or a 1,4-phenylenediyl group, The polymerizable liquid crystal composition. 5. The method according to any one of claims 1 to 4,
The polymerizable liquid crystal composition in which P ¹ and P ² in Formula (1) are each an acryloyl group. 6. The method according to any one of claims 1 to 5,
A polymerizable liquid crystal composition further comprising a photopolymerization initiator. 7. The method according to any one of claims 1 to 6,
A polymerizable liquid crystal composition further comprising an organic solvent. Retardation film containing the liquid crystal cured film which is hardened|cured material of the polymeric liquid crystal composition in any one of Claims 1-7. 9. The method of claim 8,
Liquid crystal cured film, formula (i):
0.75 ≤ Re(450)/Re(550) < 1.00 (i)
[In formula (i), Re(λ) represents the in-plane retardation value at the wavelength λ nm of the liquid crystal cured film]
Satisfying the retardation film. An elliptically polarizing plate comprising the retardation film according to claim 8 or 9. An optical display comprising the elliptically polarizing plate according to claim 10. The flexible image display apparatus containing the elliptically polarizing plate of Claim 10.