TWI808131B - Polymerizable liquid crystal composition, liquid crystal cured film, retardation film, elliptically polarizing plate, and display device - Google Patents

Abstract

The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound, a polymerization initiator, and an organic solvent, and satisfies the following formula (1): 0.15≦cV≦0.65

[wherein, cV represents the product of the solid content c (mass fraction) of the polymerizable liquid crystal composition and the viscosity V (mPa·s) at 23° C. of the polymerizable liquid crystal composition at 48 hours after mixing all the components contained in the polymerizable liquid crystal composition].

Description

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

The present invention relates to a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound, a polymerization initiator, and an organic solvent, a liquid crystal cured film formed by curing the polymerizable liquid crystal composition, a retardation film comprising the liquid crystal cured film, an elliptical polarizing plate comprising the retardation film and a polarizing film, and a display device comprising the elliptically polarizing plate.

Optical films such as polarizing films and retardation films are used in flat panel displays (FPDs). In recent years, from the viewpoint of thinning, a retardation film including a liquid crystal cured film obtained by curing a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, a polymerization initiator, and an organic solvent has been known (for example, JP-A-2017-027058).

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-027058

In order to form such a liquid crystal cured film continuously, it is necessary to prepare the above-mentioned polymerizable liquid crystal composition And long-term storage. However, according to the studies of the present inventors, it can be seen that when the polymerizable liquid crystal composition is stored for a long period of time, the polymerizable liquid crystal compound in the composition reacts under the influence of light, and thus gels. Moreover, it is also known that even if the gelation of the polymerizable liquid crystal compound does not proceed, if a liquid crystal cured film is formed after storage, unevenness in film thickness may occur.

Accordingly, an object of the present invention is to provide a polymerizable liquid crystal composition capable of suppressing the occurrence of alignment defects and uneven film thickness of the obtained liquid crystal cured film even after long-term storage, a liquid crystal cured film obtained by curing the polymerizable liquid crystal composition, a retardation film including the liquid crystal cured film, an elliptically polarizing plate including the retardation film and a polarizing film, and a display device including the elliptically polarizing plate.

The inventors of the present invention have conducted intensive research to solve the above-mentioned problems. As a result, they found that if the product of the solid content c (mass fraction) of the polymerizable liquid crystal composition and the viscosity V (mPa.s) at 23° C. of the polymerizable liquid crystal composition 48 hours after mixing all the components contained in the polymerizable liquid crystal composition in a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, a polymerization initiator, and an organic solvent is 0.15 or more and 0.65 or less, the above-mentioned problem can be solved, thereby completing the present invention. invention. That is, the following are included in the present invention.

[1] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound, a polymerization initiator, and an organic solvent, and satisfying The following formula (1) 0.15≦cV≦0.65 (1)

[wherein, cV represents the product of the solid content c (mass fraction) of the polymerizable liquid crystal composition and the viscosity V (mPa·s) at 23° C. of the polymerizable liquid crystal composition at 48 hours after mixing all the components contained in the polymerizable liquid crystal composition].

[2] The polymerizable liquid crystal composition as described in [1], wherein the polymerizable liquid crystal compound is a liquid crystal compound having a photopolymerizable group.

[3] The polymerizable liquid crystal composition as described in [1] or [2], wherein the maximum absorption wavelength of the polymerization initiator is 300 to 400 nm.

[4] The polymerizable liquid crystal composition according to any one of [1] to [3], wherein the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm.

[5] The polymerizable liquid crystal composition according to any one of [1] to [4], further comprising a polymerization inhibitor.

[6] The polymerizable liquid crystal composition as described in [5], wherein the content of the polymerization inhibitor is 0.1 to 10 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

[7] The polymerizable liquid crystal composition according to [5] or [6], wherein the polymerization inhibitor is a primary antioxidant.

[8] A cured liquid crystal film obtained by curing the polymerizable liquid crystal composition described in any one of [1] to [7], wherein the polymerizable liquid crystal compound is polymerized in an aligned state.

[9] A retardation film comprising the liquid crystal cured film as described in [8].

[10] An elliptically polarizing plate comprising the phase difference film and a polarizing film as described in [9].

[11] A display device comprising the elliptically polarizing plate as described in [10].

The polymerizable liquid crystal composition of the present invention can suppress the occurrence of alignment defects and uneven film thickness of the obtained liquid crystal cured film even after long-term storage.

[Polymerizable Liquid Crystal Composition]

The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound, a polymerization initiator, and an organic solvent, and satisfies the following formula (1): 0.15≦cV≦0.65 (1)

[wherein, cV represents the product of the solid content c (mass fraction) of the polymerizable liquid crystal composition and the viscosity V (mPa·s) at 23° C. of the polymerizable liquid crystal composition at 48 hours after mixing all the components contained in the polymerizable liquid crystal composition].

If the relationship of the formula (1) is satisfied, it is surprising that even after long-term storage, the generation of alignment defects and uneven film thickness of the obtained liquid crystal cured film can be suppressed. Therefore, the cured liquid crystal film obtained by curing the polymerizable liquid crystal composition of the present invention can have excellent alignment and uniform film thickness. On the other hand, when cV is less than 0.15, the film thickness unevenness of the obtained liquid crystal cured film may generate|occur|produce. Moreover, when cV exceeds 0.65, the alignment defect of the obtained liquid crystal cured film may generate|occur|produce.

In formula (1), the so-called solid content of the polymerizable liquid crystal composition means all components in the polymerizable liquid crystal composition except volatile components such as organic solvents. The so-called solid content concentration c (mass fraction) represents the content of the solid content relative to the quality of the polymerizable liquid crystal composition, which is divided by the quality of the solid content contained in the polymerizable liquid crystal composition The value derived from the mass of the compound.

The solid content concentration c (mass fraction) of the polymerizable liquid crystal composition is not limited as long as it satisfies the formula (1), preferably 0.01-0.5, more preferably 0.03-0.3, further preferably 0.05-0.25, especially preferably 0.07-0.15. When the solid content concentration c is within the above range, good applicability of the polymerizable liquid crystal composition can be obtained, and generation of uneven film thickness of the obtained liquid crystal cured film can be easily suppressed.

In the formula (1), the viscosity V represents the viscosity (mPa·s) at 23° C. of the polymerizable liquid crystal composition when 48 hours have elapsed after mixing all the components contained in the polymerizable liquid crystal composition. As a method of mixing the polymerizable liquid crystal composition, stirring etc. are mentioned, for example, and 48 hours after completion of mixing means 48 hours after completion of mixing, for example, stirring. The storage after the completion of mixing until 48 hours passed was carried out in an airtight container at 23°C under a fluorescent lamp (40W).

The viscosity V is not limited as long as it satisfies the formula (1), but it is preferably 1~15mPa. s, more preferably 1~10mPa. s, and more preferably 1~5mPa. s. When viscosity V is more than the said lower limit, the generation|occurrence|production of the film thickness unevenness of the obtained liquid crystal cured film will be suppressed easily, and if it is below the said upper limit, the generation|occurrence|production of the alignment defect of the obtained liquid crystal cured film will be suppressed easily.

In formula (1), cV which is the product of the above-mentioned c and the above-mentioned V is preferably 0.17 to 0.60, more preferably 0.20 to 0.57. When cV is more than the said lower limit, generation|occurrence|production of the unevenness of the film thickness of the obtained liquid crystal cured film will be suppressed easily, and if it is below the said upper limit, the generation|occurrence|production of the alignment defect of the obtained liquid crystal cured film will be suppressed easily. In addition, when the obtained liquid crystal cured film is a retardation film, if there exists film thickness unevenness in this liquid crystal cured film, the unevenness of retardation may generate|occur|produce. Therefore, the so-called suppressable The generation of uneven film thickness can also be said to suppress the generation of uneven retardation, and the uneven film thickness can be evaluated by measuring the uneven retardation of the liquid crystal cured film, for example, as described in the examples.

<Polymerizable liquid crystal compound>

The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention means a liquid crystal compound having a polymerizable group, especially a photopolymerizable group, and as the polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound previously known in the field of retardation films can be used. The photopolymerizable group refers to a group that can participate in a polymerization reaction by a reactive species generated from a photopolymerization initiator, such as an active radical or an acid. Examples of photopolymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxiranyl, and oxetanyl groups. Among them, acryloxy, methacryloxy, vinyloxy, oxiranyl and oxetanyl are preferred, and acryloxy is more preferred. Liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, and a thermotropic liquid crystal is preferable at the point which can realize dense film thickness control. In addition, as the phase order structure in the thermotropic liquid crystal, it may be a nematic liquid crystal or a smectic liquid crystal. The polymerizable liquid crystal compound can be used alone or in combination of two or more.

Examples of the polymerizable liquid crystal compound include compounds satisfying all of the following (1) to (4).

(1) A compound that can form a nematic phase;

(2) Having π electrons in the long axis direction (a) of the polymerizable liquid crystal compound.

(3) There are π electrons in a direction [crossing direction (b)] intersecting with the major axis direction (a).

(4) The π-electron density in the long-axis direction (a) of the polymerizable liquid crystal compound defined by the following formula (i), where the total of π-electrons present in the long-axis direction (a) is N(πa), and the total of molecular weights present in the long-axis direction is N(Aa): D(πa)=N(πa)/N(Aa) (i), and the π-electron density in the crossing direction (b) of the polymerizable liquid crystal compound defined by the following formula (ii): D(πb)=N(πb)/N(Ab) (ii)

0≦[D(πa)/D(πb)]≦1

The relationship [that is, the π-electron density in the cross direction (b) is greater than the π-electron density in the long-axis direction (a)].

Furthermore, the polymerizable liquid crystal compound that satisfies all of the above (1) to (4) can form a nematic phase by coating on an alignment film and heating to a temperature above the phase transition temperature. In the nematic phase formed by the alignment of the polymerizable liquid crystal compound, the alignment is usually carried out in such a manner that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis direction becomes the alignment direction of the nematic phase.

Generally, many polymerizable liquid crystal compounds having the above-mentioned characteristics exhibit inverse wavelength dispersion. As a compound that satisfies the characteristics of the above-mentioned (1) to (4), specifically, the following formula (I) can be exemplified:

The indicated compound.

In formula (I), Ar represents a divalent aromatic group which may have a substituent. The so-called aromatic group here refers to a base with a planar ring structure, and the number of π electrons in the ring structure is based on Hückel's rule (Hückel's rule) is [4n+2]. Here, n represents an integer. In the case of forming a ring structure including heteroatoms such as -N= or -S-, it also includes the case of including non-covalent bond electron pairs on these heteroatoms, satisfying Huckel's law and having aromaticity. The divalent aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom.

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbons, a fluoroalkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, a cyano group or a nitro group, and the carbon atoms constituting the divalent aromatic group or alicyclic hydrocarbon group may be substituted by an oxygen atom, a sulfur atom or a nitrogen atom.

L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.

k and l independently represent integers from 0 to 3, satisfying the relationship of 1≦k+l. Here, in the case of 2≦k+l, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other.

E ¹ and E ² independently represent an alkanediyl group with 1 to 17 carbon atoms, where the hydrogen atoms contained in the alkanediyl group may be substituted by halogen atoms, and the -CH ₂ - contained in the alkanediyl group may be substituted by -O-, -S-, or -Si-.

^P1 and ^P2 independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

^G1 and ^G2 are each independently preferably 1,4-benzenediyl which may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbons, 1,4-cyclohexanediyl which may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbons, more preferably 1,4-benzenediyl substituted by methyl, unsubstituted 1,4-benzenediyl, or unsubstituted 1,4-trans Formula-cyclohexanediyl, especially unsubstituted 1,4-benzenediyl or unsubstituted 1,4-trans-cyclohexanediyl.

Also, it is preferable that at least one of the plurality of G ¹ and G ² is a divalent alicyclic hydrocarbon group, and more preferably at least one of the G ^{1 and} G 2 bonded to L ¹ or L ² is a divalent alicyclic hydrocarbon group.

L ¹ and L ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, -R ^a7 OC=OOR ^a8 -, -N=N-, -CR ^c =CR ^d -, or -C≡C-. Here, R ^a1 to R ^a8 independently represent a single bond or an alkylene group having 1 to 4 carbons, and R ^c and R ^d represent an alkyl group having 1 to 4 carbons or a hydrogen atom. L ¹ and L ² are each independently more preferably a single bond, -OR ^a2-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a4-1 -, or -OCOR ^a6-1 -. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent any of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. L ¹ and L ² are each independently further preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or -OCO-.

B ¹ and B ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10 -, -R ^a11 COOR ^a12 -, -R ^a13 OCOR ^a14 -, or -R ^a15 OC=OOR ^a16 -. Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are each independently more preferably a single bond, -OR ^a10-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a12-1 -, or -OCOR ^a14-1 -. Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent any of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. B ¹ and B ² are each independently a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO-, or -OCOCH ₂ CH ₂ -.

From the viewpoint of expressing inverse wavelength dispersion, k and l are preferably in the range of 2≦k+l≦6, preferably k+l=4, more preferably k=2 and l=2. If k=2 and l=2, since a symmetrical structure is formed, it is preferable.

E ¹ and E ² are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, more preferably an alkanediyl group having 4 to 12 carbon atoms.

Examples of the polymerizable group represented by ^P1 or ^P2 include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxirane, and oxetanyl groups. Among them, acryloxy, methacryloxy, vinyloxy, oxiranyl and oxetanyl are preferred, and acryloxy is more preferred.

環、嘧啶環、三唑環、三

環、吡咯啉環、咪唑環、吡唑環、噻唑環、苯并噻唑環、噻唑并噻唑環、

唑環、苯并

唑環、及啡啉環等。其中，較佳為具有噻唑環、苯并噻唑環、或苯并呋喃環，進而較佳為具有苯并噻唑基。又，於Ar中包含氮原子之情形時，該氮原子較佳為具有π電子。 Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and the like, preferably a benzene ring and a naphthalene ring. Examples of the aromatic heterocycle include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridine ring,

ring, pyrimidine ring, triazole ring, three

ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thiazolothiazole ring,

Azole ring, benzo

Azole ring, and phenanthroline ring, etc. Among them, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazolyl group. Also, when Ar contains a nitrogen atom, it is preferable that the nitrogen atom has π electrons.

In the formula (I), the total number N _π of π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, further preferably 14 or more, particularly preferably 16 or more. Moreover, it is preferably 30 or less, more preferably 26 or less, and still more preferably 24 or less.

As an aromatic group represented by Ar, the following groups are mentioned, for example.

In Formula (Ar-1)~Formula (Ar-23), the symbol * represents the linking part, Z⁰,Z¹and Z²Respectively independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbons, a cyano group, a nitro group, an alkylsulfinyl group with 1 to 12 carbons, an alkylsulfonyl group with 1 to 12 carbons, a carboxyl group, a fluoroalkyl group with 1 to 12 carbons, Alkoxy with 1 to 6 carbons, alkylthio with 1 to 12 carbons, N-alkylamino with 1 to 12 carbons, N,N-dialkylamino with 2 to 12 carbons, N-alkylsulfamoyl with 1 to 12 carbons or N,N-dialkylsulfamoyl with 2 to 12 carbons.

Q ¹ , Q ² and Q ³ independently represent -CR ^2' R ^3' -, -S-, -NH-, -NR ^2' -, -CO- or -O-, and R ^2' and R ^3' independently represent a hydrogen atom or an alkyl group with 1 to 4 carbons.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

W ¹ and W ² independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0-6.

The aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups with 6 to 20 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl, preferably phenyl and naphthyl, more preferably phenyl. Examples of the aromatic heterocyclic group include: furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl, and other aromatic heterocyclic groups with 4 to 20 carbon atoms containing at least one nitrogen atom, oxygen atom, sulfur atom, etc., preferably furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl.

Y ¹ , Y ² and Y ³ may each independently be a substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from a collection of aromatic rings. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group, or a group derived from a collection of aromatic rings.

Z ⁰ , Z ¹ and Z ² are independently preferably a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbons, a cyano group, a nitro group, an alkoxy group with 1 to 12 carbons, Z ⁰ is further preferably a hydrogen atom, an alkyl group with 1 to 12 carbons, and a cyano group, and Z ¹ and Z ² are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group.

Q ¹ , Q ² and Q ³ are preferably -NH-, -S-, -NR ^2' -, -O-, and R ^2' is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferable.

Among formulas (Ar-1) to (Ar-23), formula (Ar-6) and formula (Ar-7) are preferable from the viewpoint of molecular stability.

環、嘧啶環、吲哚環、喹啉環、異喹啉環、嘌呤環、吡咯啶環等。該芳香族雜環基可具有取代基。又，Y¹可與其所鍵結之氮原子及Z⁰一起形成上述可經取代之多環系芳香族烴基或多環系芳香族雜環基。例如可列舉苯并呋喃環、苯并噻唑環、苯并

唑環等。 In the formulas (Ar-16)~(Ar-23), Y ¹ can form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . As the aromatic heterocyclic group, those mentioned above as the aromatic heterocyclic ring that Ar may have are mentioned, for example, pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrroline ring,

ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. This aromatic heterocyclic group may have a substituent. In addition, Y ¹ may form the above-mentioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . For example, benzofuran ring, benzothiazole ring, benzo

Azole ring etc.

Among the polymerizable liquid crystal compounds, polymerizable liquid crystal compounds with a maximum absorption wavelength of 300-400 nm are preferred. The polymerization initiator contained in the polymerizable liquid crystal composition is preferably at 300~ 400nm has an absorption wavelength, and more preferably has a maximum absorption wavelength at 300~400nm, so there is a risk of absorbing ultraviolet light during storage of the composition, thereby generating reactive species such as active free radicals to carry out the polymerization reaction and gelation of the polymerizable liquid crystal compound. However, if the composition contains a polymerizable liquid crystal compound with a maximum absorption wavelength of 300 to 400 nm as described above, even if it is exposed to ultraviolet light during storage, the polymerizable liquid crystal compound will absorb the exposure light, and the generation of reactive species caused by the photopolymerization initiator and the progress of polymerization and gelation of the polymerizable liquid crystal compound caused by the reactive species can be effectively suppressed. Therefore, if a polymerizable liquid crystal compound with a maximum absorption wavelength of 300 to 400 nm is included in the polymerizable liquid crystal composition, it is advantageous in terms of long-term stability of the polymerizable liquid crystal composition, and the alignment and uniformity of film thickness of the obtained liquid crystal cured film can be improved. Furthermore, the maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent that can dissolve the polymerizable liquid crystal compound, and examples thereof include chloroform and the like.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film that content of a polymeric liquid crystal compound exists in the said range. In addition, in this specification, the solid content of a polymeric liquid crystal composition means all components except the volatile components, such as an organic solvent, from a polymeric liquid crystal composition.

<polymerization initiator>

The polymerizable liquid crystal composition of the present invention contains a polymerization initiator. The polymerization initiator is a reactive species generated by the action of heat or light, which can start the polymerization reaction of polymerizable liquid crystal compounds, etc. compound. Examples of the reactive species include active species such as radicals and cations or anions. Among them, a photopolymerization initiator that generates radicals (active radicals) by light irradiation is preferable from the viewpoint of easy reaction control.

化合物、錪鹽及鋶鹽。具體而言，可列舉：豔佳固(Irgacure，註冊商標)907、豔佳固184、豔佳固651、豔佳固819、豔佳固250、豔佳固369、豔佳固379、豔佳固127、豔佳固2959、豔佳固754、豔佳固379EG(以上由BASF Japan股份有限公司製造)，Seikuol BZ、Seikuol Z、Seikuol BEE(以上由精工化學股份有限公司製造)，卡亞固(kayacure)BP100(日本化藥股份有限公司製造)，卡亞固UVI-6992(Dow公司製造)，Adeka Optomer SP-152、Adeka Optomer SP-170、Adeka Optomer N-1717、Adeka Optomer N-1919、Adeka arc LUZ NCI-831、Adeka arc LUZ NCI-930(以上由ADEKA股份有限公司製造)，TAZ-A、TAZ-PP(以上由Nihon Siber Hegner公司製造)及TAZ-104(三和化學公司製造)。光聚合起始劑可單獨使用或組合兩種以上使用。 Examples of photopolymerization initiators include benzoin compounds, benzophenone compounds, benzoyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds,

Compounds, Odonium salts and Conium salts. 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 (manufactured by BASF Japan Co., Ltd.), Seikuol BZ, Seikuol Z, Seikuol Kuol BEE (manufactured by Seiko Chemical Co., Ltd. above), kayacure BP100 (manufactured by 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 arc LUZ NCI-831 , Adeka arc LUZ NCI-930 (manufactured by ADEKA Co., Ltd. above), TAZ-A, TAZ-PP (manufactured by Nihon Siber Hegner Co., Ltd. above), and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.). A photopolymerization initiator can be used individually or in combination of 2 or more types.

From the viewpoint of making full use of the energy emitted from the light source, ensuring a sufficient polymerization rate of the polymerizable liquid crystal compound, and obtaining a cured liquid crystal film having sufficient hardness as a retardation film, the photopolymerization initiator preferably has a maximum absorption wavelength of 300 to 400 nm, more preferably 300 to 380 nm. On the other hand, if a polymerizable liquid crystal compound having a maximum absorption wavelength of 300 to 400 nm is included in the composition as described above, the initiation of photopolymerization during long-term storage can be effectively suppressed. The generation of reactive species caused by the agent and the progress of the polymerization reaction and gelation of the polymerizable liquid crystal compound caused by the reactive species. Also from this point of view, it is preferable to use a photopolymerization initiator having a maximum absorption wavelength of 300-400 nm. Furthermore, the maximum absorption wavelength of the photopolymerization initiator can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent that can dissolve the polymerizable liquid crystal compound, and examples thereof include chloroform and the like.

Among photopolymerization initiators, α-acetophenone-based photopolymerization initiators and oxime-based photopolymerization initiators are preferable.

啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲胺基-1-(4-

啉基苯基)-2-苄基丁烷-1-酮及2-二甲胺基-1-(4-

啉基苯基)-2-(4-甲基苯基甲基)丁烷-1-酮等，更佳為2-甲基-2-

啉基-1-(4-甲基硫基苯基)丙烷-1-酮及2-二甲胺基-1-(4-

啉基苯基)-2-苄基丁烷-1-酮。作為α-苯乙酮系光聚合起始劑之市售品，可列舉豔佳固369、379EG、907(以上由BASF Japan(股)製造)及Seikuol BEE(精工化學公司製造)等。 Examples of α-acetophenone-based photopolymerization initiators include: 2-methyl-2-

Linyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4-

Linylphenyl)-2-benzylbutan-1-one and 2-dimethylamino-1-(4-

Linylphenyl)-2-(4-methylphenylmethyl)butan-1-one, etc., more preferably 2-methyl-2-

Linyl-1-(4-methylthiophenyl)propan-1-one and 2-dimethylamino-1-(4-

Linylphenyl)-2-benzylbutan-1-one. Examples of commercially available α-acetophenone-based photopolymerization initiators include ENGAGOL 369, 379EG, and 907 (manufactured by BASF Japan Co., Ltd.), Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.), and the like.

化合物或肟酯型咔唑化合物，就感度之觀點而言，更佳為肟酯型咔唑化合物。作為肟酯型咔唑化合物，例如可列舉：1,2-辛烷二酮、1-[4-(苯硫基)2-(O- 苯甲醯肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯肟)等。作為肟酯型咔唑化合物之市售品，可列舉：豔佳固OXE-01、豔佳固OXE-02、豔佳固OXE-03(以上由BASF Japan股份有限公司製造)，Adeka Optomer N-1919、Adeka arc LUZ NCI-831(以上由ADEKA股份有限公司製造)等。 Oxime-based photopolymerization initiators generate methyl radicals by irradiating light. Polymerization of the polymerizable liquid crystal compound in the deep part of the liquid crystal cured film preferably proceeds by the methyl radical. Moreover, it is preferable to use the photoinitiator which can utilize the ultraviolet-ray of wavelength 350nm or more efficiently from a viewpoint of advancing the polymerization reaction of the deep part of a liquid crystal cured film more efficiently. As a photopolymerization initiator capable of efficiently utilizing ultraviolet light with a wavelength of 350 nm or more, three

The compound or the oxime ester type carbazole compound is more preferably an oxime ester type carbazole compound from the viewpoint of sensitivity. Examples of oxime ester-type carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)2-(O-benzoyloxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like. Commercially available products of the oxime ester-type carbazole compound include Encacur OXE-01, Encargo OXE-02, Encaracur OXE-03 (the above are manufactured by BASF Japan Co., Ltd.), Adeka Optomer N-1919, Adeka arc LUZ NCI-831 (the above are manufactured by ADEKA Co., Ltd.) and the like.

The content of the polymerization initiator can be appropriately adjusted according to the type and amount of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, and is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. When content of a polymerization initiator is more than the said lower limit, reaction of a polymeric group will fully progress, and a polymerization rate can be raised. The long-term storage stability of a polymeric liquid crystal composition will become easy to improve that content of a polymerization initiator is below the said upper limit.

<Organic solvent>

The polymerizable liquid crystal composition of the present invention contains an organic solvent. The organic solvent is preferably a solvent that can dissolve the polymerizable liquid crystal compound and is inactive to the polymerization reaction of the polymerizable liquid crystal compound, as long as it is properly selected according to the polymerizable liquid crystal compound used.

Specifically, for example, alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene 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 alkanes; 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 amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone, etc. These organic solvents can be used individually or in combination of 2 or more types. Among them, from the viewpoint of film coating, it is preferable to use at least one selected from alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents, and it is more preferable to use at least one selected from ester solvents, ketone solvents, and amide solvents from the viewpoint of solubility of polymerizable liquid crystal compounds.

The content of the organic solvent in 100 parts by mass of the polymerizable composition is preferably 50-99 parts by mass, more preferably 70-97 parts by mass, still more preferably 75-95 parts by mass, especially preferably 85-93 parts by mass. When the content of the organic solvent is within the above range, good applicability of the polymerizable liquid crystal composition can be obtained, and it is easy to suppress the occurrence of uneven film thickness of the obtained liquid crystal cured film.

<polymerization inhibitor>

The polymerizable liquid crystal composition of the present invention preferably contains a polymerization inhibitor. The progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled by the polymerization inhibitor. Therefore, by adjusting the content of the polymerization inhibitor contained in the composition, the above-mentioned viscosity V at 23° C. of the polymerizable liquid crystal composition at 48 hours after the completion of mixing all the components contained in the polymerizable liquid crystal composition can be controlled. When the content of the polymerization inhibitor contained in the composition increases, the polymerization reaction of the polymerizable liquid crystal compound is inhibited, so the viscosity V tends to decrease. On the other hand, if the content of the polymerization inhibitor contained in the composition decreases, the polymerization reaction of the polymerizable liquid crystal compound will easily proceed, so the above-mentioned viscosity V tends to increase. Furthermore, the above-mentioned viscosity V can also be controlled by appropriately adjusting the types and amounts of the above-mentioned organic solvent, the above-mentioned polymerization initiator, and the above-mentioned polymerizable liquid crystal composition.

As the polymerization inhibitor, conventionally known polymerization inhibitors used in the field of retardation films can be used, and examples thereof include primary antioxidants such as phenolic antioxidants, amine antioxidants, quinone antioxidants, and nitroso antioxidants; secondary antioxidants such as phosphorus antioxidants and sulfur antioxidants, and the like. A polymerization inhibitor can be used individually or in combination of 2 or more types. Among these, primary antioxidants such as phenolic antioxidants are preferred from the viewpoint of capturing free radicals derived from polymerization initiators, and primary antioxidants with a molecular weight of 500 or less are more preferred from the viewpoint of not inhibiting the polymerization of the cured liquid crystal film after drying.

The so-called phenolic antioxidant is an antioxidant having a phenolic hydroxyl group in the molecule, preferably having an alkyl group adjacent to the phenolic hydroxyl group. In this specification, antioxidants having both a phenolic hydroxyl group and a phosphate ester structure or a phosphite structure are classified as phosphorus-based antioxidants.

-2,4,6(1H,3H,5H)-三酮、1,3,5-三((4-第三丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮、硫代二伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、苯丙酸3,5-雙(1,1-二甲基乙基)-4-羥基C7-C9側鏈烷基酯、4,6-雙(辛硫基甲基)-鄰甲酚、Irganox(註冊商標)3125(BASF公司製造)、2,4-雙(正辛硫基)-6-(4-羥 基-3',5'-二-第三丁基苯胺基)-1,3,5-三

、3,9-雙(2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基)-1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷、二丁基羥基甲苯(2,6-二-第三丁基-對甲酚，有時稱為BHT)、Sumilizer(註冊商標)BHT(住友化學(股)製造)、Sumilizer(註冊商標)GA-80(住友化學(股)製造)、Sumilizer(註冊商標)GS(住友化學(股)製造)、Cyanox(註冊商標)1790(Cytec(股)製造)及Vitamin E(Eisai(股)製造)等。 Examples of phenolic antioxidants include: 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, acrylic acid 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)- 4-methylphenyl ester, (tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl ester, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene -2,4,6-triyl)tri-p-cresol, 1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-trione, 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-trione, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,5-bis(1,1-dimethylethyl)-4-hydroxy C7-C9 side chain alkyl phenylpropionate, 4,6-bis(octylthiomethyl)-o-cresol, Irganox (registered trademark) 3125 (manufactured by BASF Corporation), 2,4- Bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-tri

, 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol, sometimes called BHT), Sumilizer (registered trademark) BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered Trademark) GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (manufactured by Cytec Co., Ltd.), Vitamin E (manufactured by Eisai Co., Ltd.), etc.

、N-甲基啡噻

、N-乙基啡噻

、3,7-二辛基啡噻

、啡噻

羧酸酯、啡硒

(phenoselenazine)等啡噻

系抗氧化劑。 The so-called amine-based antioxidants are antioxidants with amine groups in the molecule. Examples of amine antioxidants include: 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, phenyl-2-naphthylamine and other naphthylamine antioxidants; β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine and other phenylenediamine-based antioxidants; dipyridylamine, diphenylamine, p,p'-di-n-butyldiphenylamine, p, p'-di-tert-butyldiphenylamine, p,p'-di-tert-pentyldiphenylamine, p,p'-dioctyldiphenylamine, p,p'-dinonyldiphenylamine, p,p'-didecyldiphenylamine, p,p'-di-dodecyldiphenylamine, p,p'-distyryldiphenylamine, p,p'-dimethoxydiphenylamine, 4,4'-bis(4-α,α-dimethylbenzoyl)diphenylamine Diphenylamine-based antioxidants such as phenylamine, p-isopropoxydiphenylamine, and dipyridylamine;

, N-Methylphenidate

, N-Ethyl phenanthrene

, 3,7-Dioctylphenanthil

, morphine

Carboxylate, phenselenium

(phenoselenazine)

Department of antioxidants.

The so-called phosphorus antioxidants are antioxidants having a phosphate structure or a phosphite structure. Examples of phosphorus-based antioxidants include: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphopine, tris(2,4-di-tert-butylphenyl)phosphite, diphenylisooctyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite , diphenylisodecyl phosphite, diphenylisodecyl phosphite, triphenyl phosphate, tributyl phosphate, distearyl pentaerythritol diphosphite, cyclic neopentanetetrayl bis(2,6-di-tert-butyl-4-methylphenyl) phosphite, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butylbenzo[d,f][1,3,2]dioxyl Phosphoheptene, Tris(nonylphenyl)phosphite, Tris(mono-&dinonylphenyl)phosphite, Diphenylmono(tridecyl)phosphite, 2,2'-Ethylenebis(4,6-di-tert-butylphenol)fluorophosphite, Phenyl diisodecyl phosphite, Tris(2-ethylhexyl)phosphite, Tris(isodecyl)phosphite, Tris(tridecyl)phosphite, Tetrakis(2,4-di-tert-butylphenyl)phosphite -4,4'-biphenylene-bis-phosphonite, 4,4'-isopropylidenediphenyltetraalkyl(C12-C15) diphosphite, 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-didecyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol-di-phosphite, cyclic neopentanetetraylbis(2,6 -di-tert-butyl-4-methylphenyl-phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl)butane, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylene diphosphinate, tris(2-ethylhexyl) phosphite, triisodecyl phosphite, tristearyl phosphite, phenyl diisodecyl phosphite, trilauryl trithiophosphite ester, distearyl pentaerythritol diphosphite, tris(nonylated phenyl) phosphite (TRIS(NONYLATED PHENYL)PHOSPHITE)), tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl Ester phosphorous acid, Adekastab (registered trademark) 329K (ADEKA (stock) manufactured), Adekastab (registered trademark) PEP36 (manufactured by ADEKA Co., Ltd.), Adekastab (registered trademark) PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab (registered trademark) P-EPQ (manufactured by Clariant Company), Weston (registered trademark) 618 (manufactured by GE Company), Weston (registered trademark) 619G (manufactured by GE Company), Ultranox (registered trademark) 626 (manufactured by GE Company), 6-[3 -(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphapane and the like.

The so-called sulfur-based antioxidants are antioxidants with sulfur atoms in their molecules. Examples of sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; β-alkylmercaptopropionate compounds of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane; and the like.

When the polymerizable liquid crystal composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.1 to 10 parts by mass, more preferably 0.15 to 7 parts by mass, further preferably 0.2 to 5 parts by mass, and especially preferably 0.2 to 1 part by mass, based on 100 parts by mass of the polymerizable liquid crystal compound. When the content of the polymerization inhibitor is more than the above-mentioned lower limit, the polymerization reaction and gelation of the polymerizable liquid crystal compound during storage can be effectively suppressed, so it is easy to suppress the occurrence of alignment defects in the obtained cured liquid crystal film. When content of a polymerization inhibitor is below the said upper limit, the cured liquid crystal film of sufficient degree of polymerization as a retardation film can be obtained.

<levelling agent>

The polymerizable liquid crystal composition of the present invention may contain a leveling agent. The leveling agent has the function of adjusting the fluidity of the polymerizable liquid crystal composition and making the liquid crystal cured film obtained by coating the composition more flat able. As a leveling agent, a silicone type leveling agent, a polyacrylate type leveling agent, a perfluoroalkyl type leveling agent etc. are mentioned, for example. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161 A. KF6001 (all of the above are manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of the above are manufactured by Momentive Performance Materials Japan contract company), Fluorinert (registered trademark) FC-72, Fluorin ert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (all of the above are manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) R-08, Megafac R-30, Megafac R-90, Megafac F-410, Megafac F-411, Megafac F-443, Megafac F-445, Megafac F-47 0. Megafac F-477, Megafac F-479, Megafac F-482, Megafac F-483 (all of the above are manufactured by DIC), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all of the above are manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all of the above are manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, trade name E5844 (manufactured by Daikin Precision Chemical Laboratories Co., Ltd.), BM-10 00, BM-1100, BYK-352, BYK-353, and BYK-361N (all trade names: manufactured by BM Chemie Co., Ltd.), etc. These leveling agents can be used individually or in combination of 2 or more types. Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferable.

The content of the leveling agent is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. parts by mass, more preferably 0.05 to 3 parts by mass. When content of a leveling agent is the said range, since it exists in the tendency which horizontally aligns a polymeric liquid crystal compound easily, and the obtained liquid crystal cured film becomes smoother, it is preferable. The polymerizable liquid crystal composition may contain two or more leveling agents.

<Photosensitizer>

酮、9-氧硫

等

酮類；蒽及具有烷基醚等取代基之蒽類；啡噻

；紅螢烯。光增感劑可單獨使用或組合兩種以上使用。光增感劑之含量相對於聚合性液晶化合物100質量份，較佳為0.01~10質量份，更佳為0.05~5質量份，進而較佳為0.1~3質量份。 The polymerizable liquid crystal composition of the present invention may contain a photosensitizer. A photosensitizer can sensitize a photopolymerization initiator. Examples of photosensitizers include:

Ketone, 9-oxosulfur

wait

Ketones; anthracenes and anthracenes with substituents such as alkyl ethers; phenanthrene

; rubrene. A photosensitizer can be used individually or in combination of 2 or more types. The content of the photosensitizer is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, and still more preferably from 0.1 to 3 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound.

<additive>

The polymerizable liquid crystal composition of the present invention may contain additives such as adhesion improving agents, release agents, stabilizers, coloring agents such as bluing agents, flame retardants, and lubricants. The content of the additive is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the mass of the solid content of the polymerizable liquid crystal composition.

The polymerizable liquid crystal composition of the present invention can be prepared by mixing the above-mentioned polymerizable liquid crystal compound, the above-mentioned polymerization initiator, the above-mentioned organic solvent, and if necessary, the above-mentioned polymerization inhibitor, the above-mentioned leveling agent, the above-mentioned photosensitizer, and the above-mentioned additives by a known method, such as stirring.

[Liquid crystal cured film and retardation film]

The present invention includes a liquid crystal cured film obtained by curing the above-mentioned polymerizable liquid crystal composition, and a retardation film including the liquid crystal cured film. The cured liquid crystal film is a cured film formed by polymerizing a polymerizable liquid crystal compound in an aligned state. The cured liquid crystal film and retardation film of the present invention are formed from the above-mentioned polymerizable liquid crystal composition, so they exhibit excellent alignment and have a uniform film thickness. Therefore, there is no deviation in phase difference, and it has excellent optical characteristics.

The cured liquid crystal film of the present invention is preferably a film having three-dimensional refractive index anisotropy. The three-dimensional refractive index ellipsoid formed by the cured liquid crystal film may have biaxiality, but preferably has uniaxiality. The liquid crystal cured film can be a horizontally aligned liquid crystal cured film formed by polymerizing a polymerizable liquid crystal compound aligned in a horizontal direction with respect to the plane of the liquid crystal cured film, or a vertically aligned liquid crystal cured film formed by polymerizing a polymerizable liquid crystal compound aligned in a vertical direction (film thickness direction of the liquid crystal cured film) relative to the plane of the liquid crystal cured film, or a hybrid aligned liquid crystal cured film or an obliquely aligned liquid crystal cured film.

In a preferred aspect of the present invention, the cured liquid crystal film of the present invention is a cured liquid crystal film formed by curing the above-mentioned polymerizable liquid crystal composition, and is a cured liquid crystal film formed by polymerizing the polymerizable liquid crystal compound in a state aligned horizontally with respect to the plane of the cured liquid crystal film.

The above-mentioned horizontally oriented liquid crystal cured film preferably satisfies the optical characteristics shown in the following formula (2) with respect to the in-plane retardation of light with a wavelength of λ nm, i.e. R(λ), more preferably satisfies the optical characteristics shown in the following formula (3) and the following formula (4).

100nm≦Re(550)≦160nm...(2)

[In the formula, Re(550) represents the in-plane retardation value (in-plane retardation) for light with a wavelength of 550nm]

Re(450)/Re(550)≦1.0...(3)

1.00≦Re(650)/Re(550)…(4)

[In the formula, Re(450) represents the in-plane retardation value for light with a wavelength of 450nm, Re(550) represents the in-plane retardation value for light with a wavelength of 550nm, and Re(650) represents the in-plane retardation value for light with a wavelength of 650nm]

When "Re(450)/Re(550)" of the cured liquid crystal film exceeds 1.0, light leakage on the short wavelength side of the elliptically polarizing plate including the cured liquid crystal layer tends to increase. More preferably, it is 0.95 or less, and still more preferably, it is 0.92 or less.

The in-plane retardation value of the liquid crystal cured layer can be adjusted by the thickness of the liquid crystal cured layer. The in-plane retardation value is determined by the following formula (5), so in order to obtain the required in-plane retardation value (Re(λ)), it is only necessary to adjust Δn(λ) and film thickness d. The thickness of the horizontal alignment liquid crystal cured layer is preferably 0.5-5 μm, more preferably 1-3 μm. The thickness of the horizontally aligned liquid crystal hardened layer can be measured by an interference film thickness meter, a laser microscope or a stylus film thickness meter. Furthermore, Δn(λ) depends on the molecular structure of the polymerizable liquid crystal compound described below.

Re(λ)=d×△n(λ)...(5)

(In the formula, Re(λ) represents the in-plane retardation value at a wavelength of λ nm, d represents the film thickness, △n(λ) represents the complex refractive index at a wavelength of λ nm)

The polymerization rate of the liquid crystal cured film is preferably at least 70%, more preferably at least 75%, and still more preferably at least 80%. If the polymerization rate of the liquid crystal cured film is more than the above value, it can have a phase difference Sufficient hardening degree for film application. In addition, the polymerization rate can be measured by the method described in an Example.

The cured liquid crystal film of the present invention is preferably formed on a substrate or an alignment film. The retardation film of the present invention only needs to include the above liquid crystal cured film, and may further include a substrate or an alignment film, preferably further include a substrate and an alignment film. Such a retardation film can be produced by a method comprising the following steps: a step of applying the above-mentioned polymerizable liquid crystal composition on a substrate or an alignment film to obtain a coating layer (hereinafter also referred to as “coating step”); a step of removing the solvent from the obtained above-mentioned coating layer and aligning the polymerizable liquid crystal compound (hereinafter also referred to as “drying step”);

Furthermore, when the polymerizable liquid crystal composition is formed on an alignment film, the alignment film is preferably formed on a substrate.

In the coating step, as a method of coating the above-mentioned polymerizable liquid crystal composition on a substrate or an alignment film, for example, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, a slit coating method, a die coating method, etc. can be mentioned. Moreover, the method etc. which apply using coaters, such as a dip coater, a bar coater, and a spin coater, are also mentioned. Among these, the CAP coating method, the inkjet method, the dip coating method, the slit coating method, the die coating method, and the coating method using a bar coater are preferable in terms of continuous coating in a roll-to-roll (Roll to Roll) form. In the case of roll-to-roll coating, the composition for forming an alignment film may be applied to a substrate to form an alignment film, and the polymerizable liquid crystal composition may be continuously coated on the obtained alignment film.

烯系聚合物等聚烯烴；環狀烯烴系樹脂；聚乙烯醇；聚對苯二甲酸乙二酯；聚甲基丙烯酸酯；聚丙烯酸酯；三乙醯纖維素、二乙醯纖維素及乙酸丙酸纖維素等纖維素酯；聚萘二甲酸乙二酯；聚碳酸酯；聚碸；聚醚碸；聚醚酮；聚苯硫醚及聚苯醚等樹脂。 Examples of the base material include a glass base material and a film base material, preferably a film base material from the viewpoint of processability, and more preferably a long roll-shaped film because continuous production is possible. Examples of the resin constituting the film substrate include polyethylene, polypropylene,

Polyolefins such as vinyl polymers; Cyclic olefin resins; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylate; Polyacrylate; Triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate and other cellulose esters; Polyethylene naphthalate; Polycarbonate; Polyethylene;

Examples of commercially available cellulose ester substrates include "Fujitac Film" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (above, manufactured by Konica Minolta Opto Co., Ltd.).

Examples of commercially available cyclic olefin-based resins include "Topas" (registered trademark) (manufactured by Ticona, Inc.), "ARTON" (registered trademark) (manufactured by JSR Corporation), "ZEONOR" (registered trademark), "ZEONEX" (registered trademark) (the above are manufactured by Japan ZEON Co., Ltd.), and "APEL" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). Such a cyclic olefin-based resin can be formed into a film by a known method such as a solvent casting method or a melt extrusion method to obtain a base material. Commercially available cyclic olefin-based resin substrates can also be used. Examples of commercially available cyclic olefin-based resin substrates include "S-SINA" (registered trademark), "SCA40" (registered trademark) (manufactured by Sekisui Chemical Industry Co., Ltd.), "ZEONOR FILM" (registered trademark) (manufactured by Japan Zeon Co., Ltd.), and "ARTON FILM" (registered trademark) (manufactured by JSR Co., Ltd.).

Regarding the thickness of the base material, it is preferable to be thin in terms of quality to the extent that practical handling is possible, but if it is too thin, the strength tends to decrease and the workability tends to be poor. The thickness of the substrate is usually 5-300 μm, preferably 20-200 μm. In addition, by transferring the cured liquid crystal film alone or transferring the laminated body of the cured liquid crystal film and the alignment film by peeling off the base material, a further thinning effect can be obtained.

The term "alignment film" refers to a film having an alignment-regulating force for aligning the above-mentioned polymerizable liquid crystal compound in a desired direction. As an alignment film, it is preferable to have solvent resistance that does not dissolve due to coating of a polymerizable liquid crystal composition, etc., and heat resistance for removal of a solvent or heat treatment for alignment of a polymerizable liquid crystal compound described below. Examples of the alignment film include a rubbed alignment film, a photo-alignment film, a trench alignment film having a concave-convex pattern or a plurality of grooves on the surface, and a stretched film. When applied to a long roll-shaped film, a photo-alignment film is preferable at the point that the alignment direction can be easily controlled.

Such an alignment film facilitates the alignment of the polymerizable liquid crystal compound. In addition, various alignment controls such as vertical alignment, horizontal alignment, hybrid alignment, and oblique alignment can be performed according to the type of alignment film, rubbing conditions, or light irradiation conditions.

The film thickness of the alignment film is usually 10-10000 nm, preferably 10-1000 nm, and more preferably 50-300 nm.

唑、聚乙烯亞胺、聚苯乙烯、聚乙烯吡咯啶酮、聚丙烯酸及聚丙烯酸酯類。配向性聚合物可單獨使用或組合兩種以上使用。 As the alignment polymer used for the rubbed alignment film, for example, polyamide or gelatin having an amide bond, polyimide having an amide bond and polyamic acid as its hydrolyzate, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyamide, etc.

Azole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. The alignment polymer can be used alone or in combination of two or more.

The rubbed alignment film can generally be coated on a substrate with a composition of an alignment polymer dissolved in a solvent (hereinafter also referred to as an alignment polymer composition), remove the solvent to form a coating film, and rub the coating film to impart alignment restriction force.

The concentration of the alignment polymer in the alignment polymer composition may be a range in which the alignment polymer is completely dissolved in the solvent. The content of the alignment polymer relative to the alignment polymer composition is preferably 0.1-20% by mass, more preferably 0.1-10% by mass.

Aligning polymer compositions are commercially available. Examples of commercially available alignment polymer compositions include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optomer (registered trademark, manufactured by JSR Corporation), and the like.

As a method of applying the alignment polymer composition to a substrate, the same method as the method of applying the above-mentioned polymerizable liquid crystal composition to a substrate or an alignment film may be mentioned. Examples of methods for removing the solvent contained in the alignment polymer composition include natural drying, air drying, heat drying, and reduced pressure drying.

As a method of a rubbing process, the method of bringing the said coating film into contact with the rubbing roll which wound the rubbing cloth and rotated is mentioned, for example. If masking is performed during the rubbing process, a plurality of regions (patterns) having different alignment directions can also be formed on the alignment film.

The photo-alignment film generally includes polymers or oligomers or monomers with photoreactive groups. At When continuously forming a cured liquid crystal film, a polymer having a molecular weight of 5,000 or more is preferable from the viewpoint of solvent resistance, and an acrylic polymer is preferable when the polymerizable liquid crystal compound has a (meth)acryl group from the viewpoint of affinity. The photo-alignment film can be obtained by applying a composition containing a polymer or oligomer or a monomer with a photoreactive group or a monomer and a solvent (hereinafter also referred to as "photo-alignment film-forming composition") to a substrate, drying and removing the solvent, and then irradiating polarized light (preferably polarized UV). The photo-alignment film is more preferable in that the direction of the alignment-regulating force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

The so-called photoreactive group refers to a group that generates alignment ability by light irradiation. Specifically, the groups involved in the following reactions: photoreactions that are the origin of the alignment ability, such as an alignment induction reaction of molecules generated by light irradiation, an isomerization reaction, a photodimerization reaction, a photocrosslinking reaction, or a photodecomposition reaction. As the photoreactive group, it is preferably a group having an unsaturated bond, especially a double bond, and especially preferably a group having at least one selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond) and a carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyalkenyl group, a stilbene group, a styrylpyridinyl group, a styrylpyridinium group, a chalcone group, and a cinnamyl group. As a photoreactive group which has a C=N bond, the group which has structures, such as an aromatic Schiff base and an aromatic hydrazone, is mentioned, for example. As the photoreactive group having an N=N bond, for example, an azophenyl group, an azonaphthyl group, an aromatic heterocyclic azo group, a disazo group, a formazan group, and a group having an oxyazobenzene structure may be mentioned. As a photoreactive group which has a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group are mentioned, for example. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, halogenated alkyl and the like.

A group that participates in a photodimerization reaction or a photocrosslinking reaction is preferable in terms of being excellent in alignment. Among them, photoreactive groups that participate in photodimerization reactions are preferable, and cinnamyl groups and chalcone groups are preferable in terms of easily obtaining a photoalignment film that requires relatively less amount of polarized light irradiation required for alignment and has excellent thermal stability or stability over time. As a polymer having a photoreactive group, one having a cinnamoyl group in which the terminal portion of the polymer side chain becomes a cinnamic acid structure or a cinnamate ester structure is particularly preferable.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be adjusted according to the type of polymer or monomer or the thickness of the target photoalignment film, preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass.

As a method of applying the composition for photoalignment film formation to a base material, the method similar to the method of applying the above-mentioned polymerizable liquid crystal composition to a base material or an alignment film is mentioned. As a method of removing the solvent from the applied composition for forming a photo-alignment film, the same method as the method of removing the solvent from the self-aligning polymer composition may be mentioned.

When irradiating polarized light, it may be a form in which polarized light is irradiated directly to the solvent-removed composition from the composition for forming an optical alignment film coated on the substrate, or a form in which polarized light is irradiated from the substrate side and transmitted through the substrate. Also, the polarized light is preferably substantially parallel light. The wavelength of the irradiated polarized light is preferably in the wavelength region 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 nm to 400 nm is particularly preferable. Examples of light sources for irradiating the polarized light include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, gold It belongs to halide lamp, KrF, ArF and other ultraviolet lasers. Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because the luminous intensity of ultraviolet rays with a wavelength of 313 nm is relatively large. By irradiating light from the above-mentioned light source through an appropriate polarizing element, polarized light UV can be irradiated. Examples of the polarizing element include polarizing filters, polarizing filters such as Glan-Thompson and Glan-Taylor, and wire grids. Among them, a wire grid type polarizing element is preferable from the viewpoint of increasing the area and resistance to heat. Furthermore, if masking is performed when rubbing or polarized light irradiation is performed, a plurality of regions (patterns) in which liquid crystal alignment directions are different can also be formed.

The groove (groove) alignment film is a film with a concave-convex 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 linear grooves arranged at equal intervals, the liquid crystal molecules are aligned along the grooves.

As a method of obtaining a trench alignment film, the following methods can be listed: a method of exposing the surface of a photosensitive polyimide film through an exposure mask having a pattern-shaped slit, and then developing and washing to form a concave-convex pattern; a method of forming a layer of a UV curable resin before hardening on a plate-like master with grooves on the surface, and moving the resin layer to a substrate and then hardening; , followed by hardening method.

As a method of removing the solvent from the coating layer obtained in the coating step in the drying step, for example, natural drying, ventilation drying, heat drying, reduced-pressure drying, and a method of combining these are mentioned. Among them, natural drying or heating drying is preferable. The drying temperature is preferably in the range of 0 to 200°C, more preferably in the range of 20 to 150°C, and still more preferably in the range of 50 to 130°C. Dry The drying time is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes.

In the hardening step, polymerization of the polymerizable liquid crystal compound aligned by the drying step can be performed by a known method for polymerizing a compound having a polymerizable group, for example, photopolymerization by irradiation of active energy rays can be used.

The active energy ray to be irradiated is appropriately selected according to the type of polymerizable liquid crystal compound (especially the type of photopolymerizable functional group contained in the polymerizable liquid crystal compound), the type of photopolymerization initiator, and the amount thereof. Specifically, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be used. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and can be used by a wide range of users in this field as a photopolymerization device, and it is preferable to select the type of polymerizable liquid crystal compound so that photopolymerization by ultraviolet light can be performed.

Examples of light sources for the active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED (light emitting diode) light sources that emit light in a wavelength range of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW/cm ² . The intensity of ultraviolet irradiation is preferably an intensity in a wavelength region effective for activation of the photopolymerization initiator. The light irradiation time is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, further preferably 0.1 second to 1 minute. If the ultraviolet irradiation intensity is irradiated once or multiple times, the cumulative light intensity is 10~3,000mJ/cm ² , preferably 50~2,000mJ/cm ² , more preferably 100~1,000mJ/cm ² . When the integrated light quantity is within this range, sufficient curing of the obtained cured liquid crystal film tends to be obtained, and coloring of the cured liquid crystal film can be prevented.

The film thickness of the liquid crystal cured film of the present invention is preferably from 0.5 to 5 μm, more preferably from 1 to 3 μm, from the viewpoint of thinning. Furthermore, the film thickness of the liquid crystal cured film and retardation film can be measured by an interference film thickness meter, a laser microscope, or a stylus film thickness meter.

[Elliptic polarizer and display device]

The elliptically polarizing plate of the present invention includes the above retardation film and polarizing film. The elliptically polarizing plate can be obtained by bonding the retardation film and the polarizing film together via an adhesive.

In one embodiment of the present invention, when a retardation film is laminated on a polarizing film, it is preferable to laminate such that the retardation axis (optical axis) of the retardation film and the absorption axis of the polarizing film become substantially 45°. By laminating so that the retardation axis (optical axis) of the retardation film and the absorption axis of the polarizing film become substantially 45°, a function as an elliptically polarizing plate can be obtained. In addition, the so-called substantial 45° is usually in the range of 45±5°.

As the polarizing film, a polarizing element having a polarizing function is included. Examples of the polarizing element include a stretched film on which a dye with absorption anisotropy is adsorbed, or a film on which a dye with absorption anisotropy is coated and aligned. Examples of dyes having absorption anisotropy include dichroic dyes.

A stretched film adsorbed with a pigment having absorption anisotropy is usually produced through the following steps: a step of uniaxially stretching a polyvinyl alcohol-based resin film; A step of dyeing with a dichroic dye to adsorb the dichroic dye, a step of treating the polyvinyl alcohol-based resin film having the dichroic dye adsorbed thereon with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution. A polarizing film is obtained by bonding the polarizing element obtained in this way to a transparent protective film. Examples of dichroic dyes include iodine and dichroic organic dyes. Examples of dichroic organic dyes include dichroic direct dyes containing disazo compounds such as C.I. Direct Red 39 and dichroic direct dyes containing compounds such as trisazo and tetrasazo. The thickness of the polarizing element obtained by uniaxially stretching a polyvinyl alcohol-based resin film, dyeing with a dichroic dye, treating with boric acid, washing with water, and drying as described above is preferably 5 to 40 μm.

Examples of the film on which the absorbing anisotropic dye is coated include a film coated with a composition containing a liquid crystalline dichroic dye, or a film coated with a composition containing a dichroic dye and a polymerizable liquid crystal compound. The film coated with the pigment with absorption anisotropy should be thinner, but if it is too thin, the strength will decrease and the processability will tend to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, more preferably 0.5-3 μm. In terms of being obtainable as a hard film, it is preferable to apply a composition comprising a dichroic dye and a polymerizable liquid crystal compound, and to form a polymer film in a state in which the polymerizable liquid crystal compound is aligned. In terms of obtaining high polarizing performance, it is more preferable to use a film in which the polymerizable liquid crystal compound has a smectic liquid crystal phase and forms a polymer in the state of the smectic liquid crystal phase. Specific examples of such polarizing elements include those described in Japanese Patent No. 4719156, Japanese Patent No. 4937252, Japanese Patent No. 5776063, Japanese Patent No. 5923941, Japanese Patent No. 5982762, Japanese Patent No. 6006485, Japanese Patent No. 6036452, Japanese Patent No. 6098053, and Japanese Patent No. 6132049. The polarizing element.

Furthermore, the elliptically polarizing plate of the present invention may include layers other than the retardation film, the polarizing film, and the adhesive (adhesive layer). As another layer, an isotropic protective film, a hard coat layer, etc. are mentioned, for example.

The present invention includes a display device including the above-mentioned elliptically polarizing plate. The display device can be obtained by laminating an elliptical polarizer, preferably a retardation film of an elliptical polarizer, to the display device through an adhesive. The so-called display device refers to a device having a display mechanism, which includes a light emitting element or a light emitting device as a light emitting source. As a display device, it can be listed: LCD display device, mechanical electrical light emitting (EL) display device, inorganic electrical light (EL) display device, touch panel display device, electronic launch display device (field launch display device (FED, etc.), surface -conducting electronic launch display device (SED)), electronic paper (display device using electronic ink or electrical parts), plasma display device, projection The display device (grating light valve (GLV) display device, display device with digital microscope devices (DMD)), and voltage ceramic display. The liquid crystal display device includes any one of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection type liquid crystal display device. These display devices may be display devices that display two-dimensional images, or may be stereoscopic display devices that display three-dimensional images. In particular, as a display device including the elliptically polarizing plate of the present invention, an organic EL display device and a touch panel display device are preferable.

As the adhesive used to bond the polarizing film and the retardation film in the formation of the elliptically polarizing plate, or the adhesive used to bond the elliptical polarizing plate and the display device in the formation of the display device, pressure-sensitive adhesives, dry-curable adhesives, and chemical reaction adhesives are listed. As a chemical reaction type adhesive agent, an active energy ray hardening type adhesive agent is mentioned, for example. As an adhesive in the formation of an elliptical polarizing plate, it is preferably a pressure-sensitive adhesive, a dry-curing adhesive Adhesive layer formed by adhesive, active energy ray-curable adhesive, preferably a pressure-sensitive adhesive or active energy ray-curable adhesive as an adhesive in the formation of a display device.

Pressure sensitive adhesives usually contain polymers and may contain solvents.

Examples of the polymer include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyethers, and the like. Among them, acrylic-based adhesives containing acrylic-based polymers are preferred due to their excellent optical transparency, moderate wettability or cohesive force, excellent adhesiveness, high weather resistance and heat resistance, and are less prone to swelling or peeling under heating or humidification.

As an acrylic polymer, it is preferable that the alkyl group of the ester part is a (meth)acrylic ester (meth)acrylic acid ester (acrylic acid ester and methacrylic acid ester are sometimes collectively referred to as (meth)acrylic acid ester, and acrylic acid and methacrylic acid ester are collectively referred to as (meth)acrylic acid ester) in which the alkyl group of the ester part is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl or butyl, and a copolymer of (meth)acrylic monomers having functional groups such as (meth)acrylic acid or hydroxyethyl (meth)acrylate.

A pressure-sensitive adhesive containing such a copolymer is preferable because it has excellent adhesiveness and can be removed relatively easily after being attached to a display device without causing paste residue on the display device. The glass transition temperature of the acrylic polymer is preferably at most 25°C, more preferably at most 0°C. The mass average molecular weight of such acrylic polymer is preferably more than 100,000.

As a solvent, the solvent etc. which were mentioned as the said organic solvent are mentioned. The pressure-sensitive adhesive may contain a light diffusing agent. A light diffusing agent is an additive that imparts light diffusing properties to the adhesive, as long as it is Fine particles having a refractive index different from that of the polymer contained in the adhesive are sufficient. As a light-diffusion agent, the fine particle containing an inorganic compound, and the fine particle containing an organic compound (polymer) are mentioned. Including acrylic polymers, most polymers included in the adhesive as an active ingredient have a refractive index of about 1.4 to 1.6, so it is preferable to select appropriately from light diffusing agents whose refractive index is 1.2 to 1.8. The difference in refractive index between the polymer contained in the adhesive as an active ingredient and the light diffusing agent is usually 0.01 or more, and preferably 0.01 to 0.2 from the viewpoint of brightness and displayability of the display device. The microparticles used as the light diffusing agent are preferably spherical microparticles, spherical microparticles close to monodisperse, more preferably microparticles with an average particle diameter of 2-6 μm. The refractive index is measured by the usual minimum declination method or Abbe's refractometer.

Examples of fine particles containing an inorganic compound include aluminum oxide (refractive index: 1.76), silicon oxide (refractive index: 1.45), and the like. Examples of fine particles containing organic compounds (polymers) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate/styrene copolymer resin beads (refractive index 1.50 to 1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46) , and polysiloxane beads (refractive index 1.46), etc. Content of a light-diffusion agent is 3-30 mass parts normally with respect to 100 mass parts of polymers.

The thickness of the pressure-sensitive adhesive is determined according to its adhesion, etc., so there is no special limitation, and it is usually 1-40 μm. In terms of processability, durability, and the like, the thickness is preferably from 3 to 25 μm, more preferably from 5 to 20 μm. By setting the thickness of the adhesive layer formed by the adhesive to 5-20 μm, the brightness when the display device is viewed from the front or viewed from an oblique direction can be maintained, and blurring or blurring of the display image is less likely to occur.

The dry-curable adhesive may contain a solvent.

Examples of dry-curable adhesives include polymers or urethane resins containing monomers having protonic functional groups such as hydroxyl groups, carboxyl groups, or amine groups, and ethylenically unsaturated groups as main components, and compositions containing crosslinking agents such as polyaldehydes, epoxy compounds, epoxy resins, melamine compounds, zirconia compounds, and zinc compounds, or curable compounds. Examples of polymers of monomers having protonic functional groups such as hydroxyl groups, carboxyl groups, or amine groups and ethylenically unsaturated groups include ethylene-maleic acid copolymers, itaconic acid copolymers, acrylic acid copolymers, acrylamide copolymers, saponified products of polyvinyl acetate, and polyvinyl alcohol-based resins.

Examples of polyvinyl alcohol-based resins include polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, methylol-modified polyvinyl alcohol, and amino-modified polyvinyl alcohol. The content of the polyvinyl alcohol-based resin in the water-based adhesive is usually 1 to 10 parts by mass, preferably 1 to 5 parts by mass, relative to 100 parts by mass of water.

Examples of the urethane resin include polyester-based ionomer-type urethane resins and the like. Here, the polyester-based ionomer-type urethane resin is a urethane resin having a polyester skeleton into which a small amount of an ionic component (hydrophilic component) is introduced. The ionomer type urethane resin is emulsified in water to form an emulsion without using an emulsifier, so it can be used as a water-based adhesive. When using a polyester-based ionomer type urethane resin, it is effective to prepare a water-soluble epoxy compound as a crosslinking agent.

Examples of epoxy resins include those obtained by reacting epichlorohydrin with polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetramine with dicarboxylic acids such as adipic acid. Polyamide epoxy resin, etc. Commercially available products of the polyamide epoxy resin include "Sumirez Resin (registered trademark) 650" and "Sumirez Resin 675" (manufactured by Sumika Chemtex Co., Ltd.), "WS-525" (manufactured by Japan PMC Co., Ltd.), and the like. When compounding an epoxy resin, the addition amount is 1-100 mass parts normally with respect to 100 mass parts of polyvinyl-alcohol-type resins, Preferably it is 1-50 mass parts.

The thickness of the adhesive layer formed by the dry-curable adhesive is usually 0.001-5 μm, preferably 0.01-2 μm, and more preferably 0.01-0.5 μm. If the adhesive layer formed by the dry-curable adhesive is too thick, the optically anisotropic layer tends to have poor appearance.

The active energy ray-curable adhesive may contain a solvent. The so-called active energy ray-curable adhesive refers to an adhesive that is cured by irradiation with active energy rays.

Examples of active energy ray-curable adhesives include cationically polymerizable adhesives containing epoxy compounds and cationic polymerization initiators; radically polymerizable adhesives containing acrylic curing components and radical polymerization initiators; adhesives containing both cationically polymerizable curing components such as epoxy compounds and radically polymerizable curing components such as acrylic compounds, further containing cationic polymerization initiators and radical polymerization initiators;

Among them, a radically polymerizable active energy ray-curable adhesive containing an acrylic curing component and a radical polymerization initiator, and a cationically polymerizable active energy ray-curable adhesive containing an epoxy compound and a cationic polymerization initiator are preferred. Examples of the acrylic curing component include (meth)acrylates such as methyl (meth)acrylate and hydroxyethyl (meth)acrylate, and (meth) Acrylic etc. The active energy ray-curable adhesive containing an epoxy compound may further contain compounds other than the epoxy compound. As a compound other than an epoxy compound, an oxetane compound, an acrylic compound, etc. are mentioned.

As a radical polymerization initiator, the said photoinitiator is mentioned. Commercially available cationic polymerization initiators include: "Kayarad" (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.), "Cyracure UVI" series (manufactured by Dow Chemical Co., Ltd.), "CPI" series (manufactured by San-Apro Co., Ltd.), "TAZ", "BBI" and "DTS" (the above are manufactured by Midori Kagaku Co., Ltd.), "Adeka Optomer" series (manufactured by ADEKA Co., Ltd.), "RHODORSIL" (registered trademark) ) (manufactured by Rhodia Co., Ltd.), etc. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass relative to 100 parts by mass of the active energy ray-curable adhesive.

The active energy ray-curable adhesive may further contain ion scavengers, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, defoamers, and the like.

In this specification, the so-called active energy rays are defined as energy rays that can decompose compounds that generate active species to generate active species. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays, electron beams, and the like, preferably ultraviolet rays and electron beams. Preferable irradiation conditions of ultraviolet rays are the same as those for the polymerization of the above-mentioned polymerizable liquid crystal compound.

[Example]

The present invention will be described in more detail below by way of examples. "%" and "parts" in the examples refer to mass % and mass parts unless otherwise specified.

The apparatuses, measurement methods, and evaluation methods used in the examples are as follows.

[Measurement of Film Thickness]

The film thicknesses of the substrates, photo-alignment films, and liquid crystal cured films in Examples and Comparative Examples were measured using an ellipsometer M-220 manufactured by JASCO Corporation.

[Determination of viscosity]

In Examples and Comparative Examples, the viscosity V and the viscosity of the solvent used 48 hours after mixing all the components contained in the polymerizable liquid crystal composition were measured using a vibrating viscometer VM-10A-L manufactured by CBC Materials Co., Ltd. in accordance with "JIS 8803Z: 2011 Viscosity Measuring Method for Liquids".

[Determination of maximum absorption wavelength λ _max (LC)]

The maximum absorption wavelengths of the polymerizable liquid crystal compounds (A) and (B), photopolymerization initiators, and liquid crystal cured films were measured in chloroform using an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation).

[Measurement of Polymerization Rate]

The liquid crystal cured films obtained in Examples and Comparative Examples were measured for infrared total reflection absorption spectrum ("model 670-IR" manufactured by Agilent Corporation) (incident angle 45°), and from the obtained measurement results (values of peak intensity I(1) of in-plane bending vibration (1408 cm ^-1 ) derived from ethylenically unsaturated bonds and peak intensity I(2) of stretching vibration (1504 cm ^-1 ) of unsaturated bonds derived from aromatic rings) to calculate P' (relative to liquid crystal hardening P value of the surface irradiated with ultraviolet rays among the surfaces perpendicular to the thickness direction of the film).

Furthermore, a solution obtained by dissolving the polymerizable liquid crystal compound (A) in chloroform was dropped on germanium crystals and dried to obtain a thin layer of the polymerizable liquid crystal compound (A). The obtained thin layer was measured for infrared total reflection absorption spectrum, and P0 (P value of the polymerizable liquid crystal compound (A)) was calculated from the obtained measurement results.

The polymerization rate defined by (1-P'/P0)×100 was calculated from the values of P' and P0. The larger the numerical value, the higher the degree of curing of the liquid crystal cured film.

[Evaluation of Orientation]

The cured liquid crystal films obtained in Examples and Comparative Examples were observed at a magnification of 400 times using a polarizing microscope (BX51, manufactured by Olympus Co., Ltd.). Those with good alignment were set to "◯", and those with insufficient alignment such as poor alignment visible on the surface were set to "×".

[Evaluation of uneven film thickness]

Overlap a pair of linear polarizers on a light table to form crossed polarizers. The cured liquid crystal films obtained in Examples and Comparative Examples were placed between linear polarizers placed on a light-transmitting table as described above. At this time, it is set so that the slow axis of a cured liquid crystal film may become substantially 45 degrees with respect to the absorption axis of a polarizing element as viewed from the thickness direction. Thereafter, observation was performed visually. According to the uniformity of the observed image (uniformity of phase difference), those that were substantially uniform over the entire surface and no unevenness was observed were rated as "○", and those where unevenness was confirmed were rated as "×".

[Example 1]

<Preparation of composition for photoalignment film formation>

5 parts of the photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent) were mixed as components, and the resulting mixture was stirred at 80° C. for 1 hour to obtain a composition (1) for forming a photo-alignment film.

Photoalignment material:

<Preparation of polymerizable liquid crystal composition>

A polymerizable liquid crystal compound (A) having the following structure, dibutylhydroxytoluene (polymerization inhibitor) (BHT; manufactured by Wako Pure Chemical Industries, Ltd.), polyacrylate compound (leveling agent) (BYK-361N; manufactured by BYK-Chemie Corporation), and the following photopolymerization initiator were mixed according to the composition shown in Table 1. Next, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration of the polymerizable liquid crystal composition became 9%, and it stirred at 80 degreeC for 1 hour, and the polymerizable liquid crystal composition (1) was obtained.

After the stirring was completed, that is, after the mixing of all the components contained in the polymerizable liquid crystal composition was completed, the polymerizable liquid crystal composition (1) was stored in an airtight container at 23° C. under a fluorescent lamp (40 W) for 48 hours. The viscosity V at 23°C of the polymerizable liquid crystal composition 48 hours after the completion of mixing was 2.53 mPa. s. Furthermore, the viscosity of NMP at 23°C is 1.89mPa. s.

Polymerizable liquid crystal compound (A): [Chem. 4]

The polymerizable liquid crystal compound (A) was synthesized by the method described in JP-A-2010-31223. Furthermore, the maximum absorption wavelength λ _max (LC) of the polymerizable liquid crystal compound (A) measured in chloroform was 350 nm.

Content of dibutylhydroxytoluene (polymerization inhibitor) in a polymeric liquid crystal composition is 0.3 part with respect to 100 parts of polymeric liquid crystal compounds (A).

The content of the polyacrylate compound (leveling agent) in the polymerizable liquid crystal composition is 0.01 part with respect to 100 parts by mass of the polymerizable liquid crystal compound (A).

The following 2 types were used as a photoinitiator, and the following photoinitiator was added in the following addition amount with respect to 100 parts of polymerizable liquid crystal compounds (A).

． Oxime ester type carbazole compound (Yanjiagu OXE-03 (made by BASF Japan Co., Ltd.)): 7.5 parts with respect to 100 parts of polymerizable liquid crystal compounds (A). Furthermore, the maximum absorption wavelengths of the initiator measured in chloroform are 305 nm and 350 nm.

啉基苯基)丁烷-1-酮(豔佳固369(Irg369)；BASF Japan股份有限公司製造)：相對於聚合性液晶化合物(A)100份為3份。再者，於氯仿中測定之該起始劑之極大吸收波長為320nm。 ． 2-Dimethylamino-2-benzyl-1-(4-

Linylphenyl)butan-1-one (Irgagon 369 (Irg369); manufactured by BASF Japan Co., Ltd.): 3 parts per 100 parts of the polymerizable liquid crystal compound (A). Furthermore, the maximum absorption wavelength of the initiator measured in chloroform was 320 nm.

<Manufacture of liquid crystal cured film and retardation film>

A cycloolefin polymer (COP) film (Zeonor Film (registered trademark) "ZF-14" manufactured by ZEON Japan Co., Ltd., film thickness 23 μm) as a substrate was subjected to corona treatment using a corona treatment device ("AGF-B10" manufactured by Kasuga Electric Co., Ltd.). Next, the above-mentioned photoalignment film-forming composition (1) was coated on the surface of the corona-treated COP film (substrate) using a bar coater, dried at 80°C for 1 minute, and then polarized UV exposure was performed with a cumulative light amount of 100 mJ/cm2 using a polarized UV irradiation device ("SPOT CURE SP- ⁷ with a polarizing element unit" manufactured by Ushio Electric Co., Ltd.) to obtain a photoalignment film. The film thickness of the obtained photo-alignment film was 100 nm. In addition, the above-mentioned corona treatment was performed once under conditions of an output of 0.3 kW and a treatment speed of 3 m/min using the above-mentioned corona treatment apparatus.

Next, the polymerizable liquid crystal composition (1) 48 hours after the above-mentioned mixing was coated on the photo-alignment film using a bar coater, dried at 120°C for 1 minute, and then irradiated with ultraviolet rays (accumulated light intensity at a wavelength of 313 nm of 500 mJ/cm ² in a nitrogen atmosphere) from the coating surface side of the coating solution using a high-pressure mercury lamp ("Unicure VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.) to form a hardened liquid crystal. film. The film thickness of the liquid crystal cured film was 2 μm. The retardation film comprising the above-mentioned base material, the above-mentioned photo-alignment film and the above-mentioned liquid crystal cured film was obtained in the above-mentioned manner. The film thickness of the retardation film was 25 μm. Furthermore, the maximum absorption wavelength of the obtained liquid crystal cured film was 350 nm.

[Example 2]

A polymerizable liquid crystal composition (2), a liquid crystal cured film, and a retardation film were obtained in the same manner as in Example 1 except that the solid content concentration of the polymerizable liquid crystal composition was 13%.

[Example 3]

A polymerizable liquid crystal composition (3), a liquid crystal cured film, and a retardation film were obtained in the same manner as in Example 1 except that the solid content concentration of the polymerizable liquid crystal composition was 15%.

[Example 4]

Except having used cyclopentanone as a solvent, it carried out similarly to Example 1, and obtained the polymeric liquid crystal composition (4), liquid crystal cured film, and retardation film. Furthermore, the viscosity of cyclopentanone at 23°C is 1.08mPa. s.

[Example 5]

The polymerizable liquid crystal compound is set to LC242 (manufactured by BASF Japan Co., Ltd.), the solvent is set to propylene glycol monomethyl ether acetate (PGMEA), the solid content concentration is set to 13%, and the content of dibutylhydroxytoluene is set to 2%. In addition, the polymerizable liquid crystal composition (5), a liquid crystal cured film, and a retardation film are obtained in the same manner as in Example 1. Furthermore, the viscosity of PGMEA at 23°C is 1.10mPa. s.

[Example 6]

A polymerizable liquid crystal composition (6), a liquid crystal cured film, and a retardation film were obtained in the same manner as in Example 1 except that the content of dibutylhydroxytoluene was 5%.

[Example 7]

Except having used the polymerizable liquid crystal compound as the polymerizable liquid crystal compound (B) of the following structure, it carried out similarly to Example 1, and obtained the polymerizable liquid crystal composition (7), liquid crystal cured film, and retardation film. The polymerizable liquid crystal compound (B) was synthesized by the method described in JP-A-2010-24438. Furthermore, the maximum absorption wavelength λ _max (LC) of the polymerizable liquid crystal compound (B) measured in chloroform was 330 nm.

Polymerizable liquid crystal compound (B):

[Comparative example 1~3]

Except that the solid content concentration and the content of dibutylhydroxytoluene (polymerization inhibitor) are set as described in Table 1, polymerizable liquid crystal compositions (8) to (10), liquid crystal cured films, and retardation films were obtained in the same manner as in Example 1. Furthermore, the viscosity of the polymerizable liquid crystal composition (8) prepared in Comparative Example 1 at 23°C immediately after mixing was 3.12 mPa. s.

[Comparative example 4, 5]

The polymerizable liquid crystal compound was LC242 (manufactured by BASF Japan Co., Ltd.), the solvent was propylene glycol monomethyl ether acetate (PGMEA), the solid content concentration was 13%, and the content of dibutylhydroxytoluene (polymerization inhibitor) was set as described in Table 1. Polymerizable liquid crystal compositions (11) and (12) were obtained in the same manner as in Example 1 except that. If the polymerizable liquid crystal compositions (11) and (12) were stored in an airtight container at 23° C. under a fluorescent lamp (40 W) for 48 hours, they all gelled, the viscosity could not be measured, and the cured liquid crystal film and retardation film could not be formed.

Table 1 shows the solid content c (mass fraction), the content (mass %) of the polymerization inhibitor, the viscosity V (mPa.s) and cV of the polymerizable liquid crystal compositions obtained in Examples and Comparative Examples after 48 hours of mixing. Moreover, the evaluation of the orientation of the liquid crystal cured film obtained by the Example and the comparative example, and film thickness unevenness, and the polymerization rate are shown in Table 1.

As shown in Table 1, it can be seen that the evaluation of alignment and film thickness unevenness of the liquid crystal cured film obtained from the polymerizable liquid crystal composition of Examples 1 to 7 is good, so even after long-term storage of the polymerizable liquid crystal composition, it can also suppress the occurrence of alignment defects and film thickness unevenness of the obtained liquid crystal cured film. Moreover, it turns out that the polymerization rate of the liquid crystal cured film of Examples 1-7 is all 72% or more, and it has the degree of hardening sufficient as a retardation film use. On the other hand, it can be seen that the alignment of the cured liquid crystal films obtained from the polymerizable liquid crystal compositions of Comparative Examples 1 to 3 were poorly evaluated in terms of alignment and film thickness unevenness, so the polymerizable liquid crystal compositions of Comparative Examples 1 to 3 could not suppress the occurrence of alignment defects or film thickness unevenness of the obtained liquid crystal cured films. In addition, the cured liquid crystal films obtained from the polymerizable liquid crystal compositions of Comparative Examples 4 and 5 were unable to measure the viscosity at 48 hours after mixing due to gelation as described above, and the cured liquid crystal films and retardation films could not be formed.

Claims (11)

A polymerizable liquid crystal composition, which comprises a polymerizable liquid crystal compound, a polymerization initiator, and an organic solvent, and satisfies the following formula (1) 0.15≦cV≦0.65 (1) [wherein, cV represents the solid content c (mass fraction) of the polymerizable liquid crystal composition, and 23% of the polymerizable liquid crystal composition after mixing all the components contained in the polymerizable liquid crystal composition in an airtight container at 23°C under a fluorescent lamp (40W) for 48 hours The product of the viscosity V (mPa.s) at ℃], the viscosity V is 1~15mPa. s, the solid content concentration c of the polymerizable liquid crystal composition is 0.01 to 0.5 in terms of mass fraction, and the polymerizable liquid crystal composition comprises a compound represented by the following formula (I),

式(I)中，Ar表示二價之芳香族基，G ¹及G ²分別獨立表示二價之芳香族基或二價之脂環式烴基，該二價之芳香族基或二價之脂環式烴基中所含之氫原子可任意被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基或硝基，構成該二價之芳香族基或二價之脂環式烴基之碳原子可任意被取代為氧原子、硫原子或氮原子，L ¹ 、L ² 、B ¹及B ²分別獨立為單鍵或二價之連結基，k、l分別獨立表示0~3之整數，且滿足1≦k+l之關係，於2≦k+l之情形時，B ¹及B ² 、G ¹及G ²分別可相互相同亦可不同， E ¹及E ²分別獨立表示碳數1~17之烷二基，烷二基中所含之氫原子可任意被鹵素原子取代，該烷二基中所含之-CH ₂ -可任意被-O-、-S-、-Si-取代，P ¹及P ²相互獨立地表示聚合性基或氫原子，且至少1個為聚合性基。 The polymerizable liquid crystal composition according to claim 1, wherein the polymerizable liquid crystal compound is a liquid crystal compound having a photopolymerizable group. The polymerizable liquid crystal composition according to claim 1 or 2, wherein the maximum absorption wavelength of the polymerization initiator is 300-400 nm. The polymerizable liquid crystal composition according to claim 1 or 2, wherein the maximum absorption wavelength of the polymerizable liquid crystal compound is 300-400 nm. The polymerizable liquid crystal composition according to claim 1 or 2, further comprising a polymerization inhibitor. The polymerizable liquid crystal composition according to Claim 5, wherein the content of the polymerization inhibitor is 0.1-10 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. The polymerizable liquid crystal composition according to claim 5, wherein the polymerization inhibitor is a primary antioxidant. A liquid crystal cured film, which is formed by curing the polymerizable liquid crystal composition according to any one of claims 1 to 7, and is formed by polymerizing the above polymerizable liquid crystal compound in an aligned state. A retardation film comprising the liquid crystal cured film according to claim 8. An elliptically polarizing plate comprising the phase difference film and polarizing film according to claim 9. A display device comprising the elliptical polarizer according to Claim 10.