阅读说明：本技术 化合物、聚合性组合物、固化物、光学膜、偏振片及图像显示装置 (Compound, polymerizable composition, cured product, optical film, polarizing plate, and image display device ) 是由 福岛悠贵 稻田宽 鹫见聪一 加藤峻也 市桥光芳 于 2020-03-24 设计创作，主要内容包括：本发明的课题在于提供一种能够减小液晶分子的倾斜角的化合物以及使用该化合物的聚合性组合物、固化物、光学膜、偏振片及图像显示装置。本发明的化合物为由下述式(I)表示的化合物。P-Sp-Z-G～(1)-(X～(1)-Cy～(1))n-(X～(2)-A～(1))m-X～(3)-A～(2)……(I)。(The invention provides a compound capable of reducing the tilt angle of liquid crystal molecules and use thereofA polymerizable composition, a cured product, an optical film, a polarizing plate and an image display device using the compound. The compound of the present invention is a compound represented by the following formula (I). P-Sp-Z-G 1 ‑(X 1 ‑Cy 1 )n‑(X 2 ‑A 1 )m‑X 3 ‑A 2 ……(I)。)

1. A compound represented by the following formula (I),

P-Sp-Z-G¹-(X¹-Cy¹)n-(X²-A¹)m-X³-A² (I)

here, in the formula (I),

sp represents a single bond, -CH, or a C1-12 linear or branched alkylene group₂1 or more of-2-valent linking groups substituted with-O-, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, Q represents a substituent,

z represents a single bond, -O-, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, Q represents a substituent,

X¹、X²and X³Each independently represents a single bond, -COO-, -OCO-, -CO-NH-or-NH-CO-,

G¹represents an aromatic ring which may have a substituent or a1, 4-cyclohexylene group which may have a substituent,

Cy¹the representation may haveA substituted 1, 4-cyclohexylene group,

A¹represents an aromatic ring which may have a substituent,

A²represents an aromatic ring or a cyclohexane ring which may have a substituent R which represents a linear or branched alkoxy group having 1 to 11 carbon atoms, a linear or branched alkyl group having 1 to 12 carbon atoms or-Z-Sp-P, wherein Z and Sp are the same as above, respectively, and when A is²When it is a 6-membered aromatic ring, it is substituted with X³Wherein the substituent R is not present at the para-position, and when the substituent R is-Z-Sp-P, Z, Sp and P, each of which is present in 2, may be the same or different from each other,

n represents 0 or 1, m represents an integer of 0 to 2, n + m represents an integer of 1 to 3, and when m is 2, 2X's are present in the formula²And A¹May be the same as or different from each other,

p represents a polymerizable group, wherein when A represents²In the case where the substituent R is an aromatic ring having-Z-Sp-P, one of the 2P atoms present in the formula represents a polymerizable group, and the other represents a hydrogen atom or a polymerizable group,

wherein, when G¹Is an optionally substituted aromatic ring, when n is 0 and m is 1, X³represents-COO-, -OCO-, -CO-NH-or-NH-CO-,

and when G is¹Is an optionally substituted aromatic ring, n is 1, m is 0, A²When Z is a single bond, Z represents a single bond, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and Q represents a substituent, wherein when Z is a single bond, the substituent is bonded to G in a 2-valent linking group constituting Sp¹The adjacent atom is not an oxygen atom.

2. The compound of claim 1, wherein,

the sum of n and m in the formula (1) is 1.

3. The compound according to claim 1 or 2, wherein,

sp in the formula (1) is a straight-chain or branched alkylene group having 1-3 carbon atoms.

4. The compound according to any one of claims 1 to 3, wherein,

a in the formula (1)²Is an aromatic ring which may have the substituent R.

5. The compound according to any one of claims 1 to 4, wherein,

a in the formula (1)²Is relative to X³Has a 6-membered aromatic ring of the substituent R in the ortho-or meta-position.

6. The compound according to any one of claims 1 to 5, wherein,

and the substituent R is-Z-Sp-P.

7. The compound according to any one of claims 1 to 3, wherein,

a in the formula (1)²Is an unsubstituted 6-membered aromatic ring.

8. The compound according to any one of claims 1 to 7, wherein,

a in the formula (1)²Is a benzene ring which may have the substituent R.

9. The compound according to any one of claims 1 to 8, wherein,

m in the formula (1) is 0.

10. The compound according to any one of claims 1 to 9, wherein,

n in the formula (1) is 1.

11. The compound according to any one of claims 1 to 8, wherein,

n in the formula (1) is 0.

12. The compound according to any one of claims 1 to 11, wherein,

p in the formula (1) is a polymerizable group represented by any one of the following formulas (P-1) to (P-9),

13. the compound according to any one of claims 1 to 12, wherein,

g in the formula (1)¹Is a1, 4-cyclohexylene group which may have a substituent.

14. The compound according to any one of claims 1 to 12, wherein,

g in the formula (1)¹Is an aromatic ring which may have a substituent.

15. A polymerizable composition containing the compound according to any one of claims 1 to 14.

16. The polymerizable composition according to claim 15, wherein the polymerizable composition contains a polymerizable liquid crystal compound different from the compound.

17. The polymerizable composition according to claim 16,

the compound and the polymerizable liquid crystal compound have different polymerizable groups from each other.

18. The polymerizable composition according to any one of claims 15 to 17, wherein the polymerizable composition contains a polymerization initiator.

19. A cured product obtained by curing the polymerizable composition according to any one of claims 15 to 18.

20. An optical film comprising the cured product according to claim 19.

21. A polarizing plate comprising the optical film according to claim 20 and a polarizer.

22. An image display device having the optical film of claim 20 or the polarizing plate of claim 21.

Technical Field

The present invention relates to a compound, a polymerizable composition, a cured product, an optical film, a polarizing plate, and an image display device.

Background

Optical films such as optical compensation sheets and retardation films are used in various image display devices in order to eliminate image coloration and to enlarge a viewing angle.

A stretched birefringent film is used as the optical film, but in recent years, it has been proposed to use an optical film having an optically anisotropic layer made of a liquid crystalline compound instead of the stretched birefringent film.

As such an optically anisotropic layer, for example, patent document 1 describes "an optically anisotropic layer in which a polymerizable composition containing 1 or more polymerizable rod-like liquid crystal compounds exhibiting a smectic phase is fixed in a state exhibiting a smectic phase, and the slope between the direction in which the refractive index of the optically anisotropic layer is maximized and the optically anisotropic layer plane is 10 ° or less. "([ claim 1 ]).

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 2015-assisted 200861

Disclosure of Invention

Technical problem to be solved by the invention

As a result of studies on the optically anisotropic layer described in patent document 1, the present inventors have found that the following space exists: by selecting a compound to be blended together with the polymerizable liquid crystal compound, the angle (hereinafter, simply referred to as "tilt angle") formed by the director of the liquid crystal molecules and the layer plane of the optically anisotropic layer can be further reduced.

Accordingly, an object of the present invention is to provide a compound capable of reducing the tilt angle of liquid crystal molecules, and a polymerizable composition, a cured product, an optical film, a polarizing plate, and an image display device using the compound.

Means for solving the technical problem

As a result of intensive studies to achieve the above object, the present inventors have found that the tilt angle of liquid crystal molecules can be reduced by using a compound having a predetermined structure, and have completed the present invention.

That is, it has been found that the above-mentioned problems can be achieved by the following configuration.

[1] A compound represented by the following formula (I).

P-Sp-Z-G¹-(X¹-Cy¹)n-(X²-A¹)m-X³-A²……(I)

Here, in the above formula (I),

sp represents a single bond, -CH, or a group consisting of a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms₂1 or more of-2-valent linking groups substituted with-O-, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and Q represents a substituent.

Z represents a single bond, -O-, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and Q represents a substituent.

X¹、X²And X³Each independently represents a single bond, -COO-, -OCO-, -CO-NH-or-NH-CO-.

G¹Represents an aromatic ring which may have a substituent or a1, 4-cyclohexylene group which may have a substituent.

Cy¹Represents a1, 4-cyclohexylene group which may have a substituent.

A¹Represents an aromatic ring which may have a substituent.

A²Represents an optionally substituted groupR is an aromatic ring or a cyclohexane ring, wherein the substituent R represents a linear or branched alkoxy group having 1 to 11 carbon atoms, a linear or branched alkyl group having 1 to 12 carbon atoms or-Z-Sp-P, and Z and Sp are the same as described above. Wherein, when A²When it is a 6-membered aromatic ring, it is substituted with X³The bonding position of (2) has no substituent R at the para position. When the substituent R is-Z-Sp-P, Z, Sp and P, each of which is present in 2, may be the same or different from each other.

n represents 0 or 1, m represents an integer of 0 to 2, and n + m represents an integer of 1 to 3. When m is 2, there are 2X's in the formula²And A¹May be the same as or different from each other.

P represents a polymerizable group. Wherein, when A²In the case of an aromatic ring having-Z-Sp-P as a substituent R, one of 2P atoms present in the formula represents a polymerizable group, and the other represents a hydrogen atom or a polymerizable group.

Wherein, when G¹Is an optionally substituted aromatic ring, when n is 0 and m is 1, X³represents-COO-, -OCO-, -CO-NH-or-NH-CO-.

And when G is¹Is an optionally substituted aromatic ring, n is 1, m is 0, A²When the group is an aromatic ring which may have a substituent R, Z represents a single bond, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and Q represents a substituent. Wherein, when Z is a single bond, the group bonded to G in the 2-valent linking group constituting Sp¹The adjacent atom is not an oxygen atom.

[2] The compound according to [1], wherein,

in the formula (1), n and m are 1 in total.

[3] The compound according to [1] or [2], wherein,

sp in the formula (1) is a linear or branched alkylene group having 1 to 3 carbon atoms.

[4] The compound according to any one of [1] to [3], wherein,

a in the above formula (1)²Is an aromatic ring which may have a substituent R.

[5] The compound according to any one of [1] to [4], wherein,

a in the above formula (1)²Is relative to X³The bonding position of (b) is a 6-membered aromatic ring having a substituent R at the ortho-or meta-position.

[6] The compound according to any one of [1] to [5], wherein,

the substituent R is-Z-Sp-P.

[7] The compound according to any one of [1] to [3], wherein,

a in the above formula (1)²Is an unsubstituted 6-membered aromatic ring.

[8] The compound according to any one of [1] to [7], wherein,

a in the above formula (1)²Is a benzene ring which may have a substituent R.

[9] The compound according to any one of [1] to [8], wherein,

m in the above formula (1) is 0.

[10] The compound according to any one of [1] to [9], wherein,

n in the above formula (1) is 1.

[11] The compound according to any one of [1] to [8], wherein,

n in the above formula (1) is 0.

[12] The compound according to any one of [1] to [11], wherein,

p in the above formula (1) is a polymerizable group represented by any one of the following formulas (P-1) to (P-9),

[ chemical formula 1]

[13] The compound according to any one of [1] to [12], wherein,

g in the above formula (1)¹Is a1, 4-cyclohexylene group which may have a substituent.

[14] The compound according to any one of [1] to [12], wherein,

g in the above formula (1)¹Is an aromatic ring which may have a substituent.

[15] A polymerizable composition comprising the compound according to any one of [1] to [14 ].

[16] The polymerizable composition according to [15], which contains a polymerizable liquid crystal compound different from the above-mentioned compound.

[17] The polymerizable composition according to [16], wherein,

the compound and the polymerizable liquid crystal compound have different polymerizable groups from each other.

[18] The polymerizable composition according to any one of [15] to [17], which contains a polymerization initiator.

[19] A cured product obtained by curing the polymerizable composition according to any one of [15] to [18 ].

[20] An optical film comprising the cured product according to [19 ].

[21] A polarizing plate having the optical film according to [20] and a polarizer.

[22] An image display device having the optical film of [20] or the polarizing plate of [21 ].

Effects of the invention

According to the present invention, a compound capable of reducing the tilt angle of liquid crystal molecules, and a polymerizable composition, a cured product, an optical film, a polarizing plate, and an image display device using the compound can be provided.

Drawings

Fig. 1A is a schematic cross-sectional view showing an example of the optical film of the present invention.

Fig. 1B is a schematic cross-sectional view showing an example of the optical film of the present invention.

Fig. 1C is a schematic cross-sectional view showing an example of the optical film of the present invention.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, the numerical range expressed by the term "to" means a range in which the numerical values described before and after the term "to" are included as the lower limit value and the upper limit value.

In the present specification, 1 kind of substance corresponding to each component may be used alone or 2 or more kinds may be used in combination. Here, in the case where 2 or more substances are simultaneously used with respect to each component, the content with respect to the component refers to the total content of the substances simultaneously used unless otherwise specified.

[ Compound ]

The compound of the present invention is a compound represented by the following formula (I) (hereinafter, also simply referred to as "compound (I)").

P-Sp-Z-G¹-(X¹-Cy¹)n-(X²-A¹)m-X³-A²……(I)

In the present invention, as described above, the tilt angle of the liquid crystal molecules can be reduced by using the compound (I).

Although details thereof are not clear, the present inventors presume as follows.

First, from the viewpoint of fixing the alignment state, it is considered that the polymerizable liquid crystal compound is usually polymerized after alignment, but the liquid crystal molecules are deformed by shrinkage during curing accompanying the polymerization, and as a result, a tilt angle is generated.

Therefore, in the present invention, it is considered that the compound (I) enters the gap or interlayer of the polymerizable liquid crystal compound and participates in the polymerization reaction after alignment, whereby the deformation of the liquid crystal molecules observed only when the liquid crystal compound is polymerized can be suppressed, and therefore the tilt angle of the liquid crystal molecules can be reduced.

The structure of the above formula (I) will be described in detail below with respect to the compound of the present invention.

As described above, the compound of the present invention is a compound represented by the following formula (I).

P-Sp-Z-G¹-(X¹-Cy¹)n-(X²-A¹)m-X³-A²……(I)

In the formula (I), Sp represents a single bond, -CH, or a C1-12 linear or branched alkylene group₂1 or more of-2-valent linking groups substituted with-O-, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and Q represents a substituent.

In the formula (I), Z represents a single bond, -O-, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and Q represents a substituent.

And, in the above formula (I), X¹、X²And X³Each independently represents a single bond, -COO-, -OCO-, -CO-NH-or-NH-CO-.

And, in the above formula (I), G¹Represents an aromatic ring which may have a substituent or a1, 4-cyclohexylene group which may have a substituent.

And, in the above formula (I), Cy¹Represents a1, 4-cyclohexylene group which may have a substituent.

In the above formula (I), A¹Represents an aromatic ring which may have a substituent.

In the above formula (I), A²The aromatic ring or cyclohexane ring may have a substituent R which is a linear or branched alkoxy group having 1 to 11 carbon atoms, a linear or branched alkyl group having 1 to 12 carbon atoms or-Z-Sp-P, wherein Z and Sp are the same as described above. Wherein, when A²When it is a 6-membered aromatic ring, it is substituted with X³The bonding position of (2) has no substituent R at the para position. When the substituent R is-Z-Sp-P, Z, Sp and P, each of which is present in 2, may be the same or different from each other.

In the formula (I), n represents 0 or 1, m represents an integer of 0 to 2, and n + m represents an integer of 1 to 3. When m is 2, there are 2X's in the formula²And A¹May be the same as or different from each other,

in the formula (I), P represents a polymerizable group. Wherein, when A²When the substituent R is an aromatic ring having-Z-Sp-P, any of 2P's present in the formula represents polymerizabilityThe other of the groups represents a hydrogen atom or a polymerizable group.

Wherein, in the formula (I), when G is¹Is an optionally substituted aromatic ring, when n is 0 and m is 1, X³represents-COO-, -OCO-, -CO-NH-or-NH-CO-.

And, in the above formula (I), when G is¹Is an optionally substituted aromatic ring, n is 1, m is 0, A²When the group is an aromatic ring which may have a substituent R, Z represents a single bond, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and Q represents a substituent. Wherein, when Z is a single bond, the group bonded to G in the 2-valent linking group constituting Sp¹The adjacent atom is not an oxygen atom.

In the formula (I), examples of the linear or branched alkylene group having 1 to 12 carbon atoms which is represented by one embodiment of Sp include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, and a heptylene group.

As described above, Sp may be-CH which constitutes a linear or branched alkylene group having 1 to 12 carbon atoms₂1 or more of-2-valent linking groups substituted with-O-, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and the substituent represented by Q is the group corresponding to G described later¹The same substituents may be present.

In the present invention, Sp in the formula (I) is preferably a linear or branched alkylene group having 1 to 3 carbon atoms because the tilt angle of the liquid crystal molecules can be further reduced.

In the formula (I), Z represents a single bond, -O-, -S-, -NH-, -N (Q) -, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-, and Q represents a substituent. Further, examples of the substituent represented by Q include G described later¹The same substituents may be present.

Among these, a single bond, -CO-, -COO-, -OCO-, -CO-NH-or-NH-CO-is preferable because it facilitates synthesis. In particular, in the following G¹In the case of an aromatic ring which may have a substituent, a single bond is preferable.

In the above formula (I), X¹、X²And X³Each independently represents a single bond, -COO-, -OCO-, -CO-NH-or-NH-CO-.

Among these, with respect to X¹Wherein n in the above formula (I) is 1, and G described later¹In the case of an optionally substituted aromatic ring, the ring is preferably a single bond, n in the formula (I) is 1, and G described later¹When the aromatic ring may have a substituent, it is preferably-COO-or-OCO-.

And, with respect to X²Wherein, in the case where m in the above formula (I) is 1 or 2, with respect to X²preferably-COO-or-OCO-.

And, with respect to X³When m in the above formula (I) is 0, the following G is added¹Is preferably-COO-or-OCO-, and in the case where m is 1 or 2, is preferably a single bond.

In the above formula (I), as G¹The aromatic ring represented by the above embodiment includes, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, phenanthroline ring, etc.; an aromatic heterocyclic ring such as a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, an oxadiazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, a pyrazole ring, a triazole ring, a furazan ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine (triazine) ring, a tetrazine ring, and a benzothiazole ring. Among them, benzene rings (e.g., 1, 4-phenyl group, etc.) are preferred.

And, with respect to G¹Examples of the substituent that the aromatic ring or the 1, 4-cyclohexylene group may have include an alkyl group, an alkoxy group, and a halogen atom.

The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclohexyl group, etc.), further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (e.g., methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group), still more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.

In the present invention, G is because the tilt angle of the liquid crystal molecules can be further reduced¹Preferred is a1, 4-cyclohexylene group which may have a substituent.

Further, G is considered to be a factor of further reducing the tilt angle of the liquid crystal molecules¹Preferred is an aromatic ring which may have a substituent.

In the above formula (I), Cy¹Represents a1, 4-cyclohexylene group which may have a substituent. Further, examples of the substituent include the above-mentioned G¹The same substituents may be present.

In the above formula (I), as A¹The aromatic ring may be the same as the above-mentioned G¹The same groups as those in the aromatic ring of (1).

And, with respect to A¹Examples of the substituent which may be contained in the aromatic ring include the above-mentioned G¹The same substituents may be present.

In the above formula (I), A²The aromatic ring or cyclohexane ring may have a substituent R, but from the reason that the tilt angle of the liquid crystal molecules can be further reduced, the aromatic ring may have a substituent R is preferable, and the benzene ring may have a substituent R is more preferable.

Here, as A²The aromatic ring represented by the above-mentioned embodiment is the same as the above-mentioned A¹The same groups as those in the aromatic ring of (1). In addition, when A²When it is a 6-membered aromatic ring, it is substituted with X³The bonding position of (2) has no substituent R at the para position.

And, as described above, A²The substituent R which the aromatic ring may have represents a linear or branched alkoxy group having 1 to 11 carbon atoms, a linear or branched alkyl group having 1 to 12 carbon atoms or a group represented by formula (II)Sp-P. Z and Sp are the same as the above groups, and P is described below.

Specific examples of the linear or branched alkoxy group having 1 to 11 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and the like.

Specific examples of the linear or branched alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and cyclohexyl.

Among these substituents R, the substituent is preferably-Z-Sp-P because of the improved durability of the cured product of the present invention described later. When the substituent R is-Z-Sp-P, Z, Sp and P, which are 2 substituents in the formula (I), may be the same or different from each other.

In the present invention, A²Preferably with respect to X³The bonding position of (b) is a 6-membered aromatic ring having a substituent R at the ortho-or meta-position.

And, A²Preferably an unsubstituted 6-membered aromatic ring.

In the formula (I), n represents 0 or 1, m represents an integer of 0 to 2, and n + m represents an integer of 1 to 3. When m is 2, there are 2X's in the formula²And A¹May be the same as or different from each other.

In the present invention, the total of n and m is preferably 1 or 2, and more preferably 1, from the viewpoint of further reducing the tilt angle of the liquid crystal molecules.

Further, m is preferably 0 or 1, and more preferably 0, from the viewpoint of enabling the tilt angle of the liquid crystal molecules to be further reduced.

Further, n is preferably 0 or 1 from the viewpoint of further reducing the tilt angle of the liquid crystal molecules.

In the formula (I), P represents a polymerizable group. Wherein, when A²In the case of an aromatic ring having-Z-Sp-P as a substituent R, one of 2P atoms present in the formula represents a polymerizable group, and the other represents a hydrogen atom or a polymerizable group.

Here, as the polymerizable group, a polymerizable group capable of radical polymerization or cationic polymerization is preferable.

As the radical polymerizable group, a well-known radical polymerizable group can be used, and as a preferred radical polymerizable group, an acryloyloxy group or a methacryloyloxy group can be mentioned. In this case, it is known that the polymerization rate of an acryloyloxy group is generally high, and an acryloyloxy group is preferable from the viewpoint of improving productivity, but a methacryloyloxy group can be similarly used as a polymerizable group.

As the cationically polymerizable group, known cationically polymerizable groups can be used, and specific examples thereof include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups. Among them, an alicyclic ether group or an ethyleneoxy group is preferable, and an epoxy group, an oxetanyl group or an ethyleneoxy group is particularly preferable.

In the present invention, the polymerizable group is preferably a polymerizable group represented by any one of the following formulae (P-1) to (P-9).

[ chemical formula 2]

Specific examples of the compound (I) include the following compounds.

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

The method for synthesizing the compound (I) is not particularly limited, and a general synthesis method can be employed. For example, in the case of using the esterification reaction, there may be mentioned acid chlorination, tosylation, benzenesulfonylation, mesylation, a method using a condensing agent, and the like, in which an alcohol is used as a raw material, and in the case of using the amidation reaction, there may be mentioned a method using an amine as a raw material in place of an alcohol.

Examples of the solvent used for the reaction, the post-treatment and the purification include ester solvents such as methyl acetate, ethyl acetate and butyl acetate; ether solvents such as tetrahydrofuran, dioxane, and diethyl ether; hydrocarbon solvents such as toluene, xylene, n-hexane, n-heptane, cyclohexane and the like; halogen-based solvents such as methylene chloride and chloroform; alcohol solvents such as methanol, ethanol, and isopropanol; water; and the like.

Examples of the base used in the reaction include triethylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, and N-methylimidazole.

As the post-treatment step, separation and purification can be performed by a usual method such as liquid separation, crystallization, recrystallization, and silica gel column chromatography.

In the liquid separation purification, as a method for removing impurities, separation and purification using hydrochloric acid water, an aqueous sodium bicarbonate solution, a saline solution, or the like can be used.

In the case of crystallization purification, separation and purification can be carried out using the general-purpose solvents described above.

[ polymerizable composition ]

The polymerizable composition of the present invention is a polymerizable composition containing the compound (I).

[ polymerizable liquid Crystal Compound ]

The polymerizable composition of the present invention preferably contains a polymerizable liquid crystal compound different from the compound (I).

Here, the polymerizable liquid crystal compound refers to a liquid crystal compound having a polymerizable group.

Generally, liquid crystal compounds can be classified into rod-like types and disk-like types according to their shapes. And, respectively, have low molecular and high molecular types. The polymer generally refers to a polymer having a polymerization degree of 100 or more (polymer physical/phase transition kinetics, Tujing, 2 nd page, Shibo bookshop, 1992).

In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound is preferably used, and a rod-like liquid crystal compound is more preferably used.

In the present invention, from the viewpoint of immobilizing the liquid crystal compound, the polymerizable liquid crystal compound preferably has 2 or more polymerizable groups in one molecule.

The type of the polymerizable group is not particularly limited, and a functional group capable of addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a cyclopolymerizable group is preferable. More specifically, it preferably includes acryloyl, methacryloyl, vinyl, styryl, allyl, and the like, and acryloyl and methacryloyl are more preferred.

Among these polymerizable groups, the polymerizable group contained in the polymerizable liquid crystal compound is preferably a polymerizable group different from the polymerizable group contained in the compound (I) because the tilt angle of the liquid crystal molecules can be further reduced.

As the rod-like liquid crystalline compound, for example, the compounds described in claim 1 of Japanese patent application laid-open No. 11-513019 or paragraphs [0026] to [0098] of Japanese patent application laid-open No. 2005-289980 can be preferably used, and as the disk-like liquid crystalline compound, for example, the compounds described in paragraphs [0020] to [0067] of Japanese patent application laid-open No. 2007-laid-open No. 108732 or paragraphs [0013] to [0108] of Japanese patent application laid-open No. 2010-laid-open No. 244038 can be preferably used, but not limited thereto.

In the present invention, as the polymerizable liquid crystal compound, a polymerizable smectic liquid crystal compound is preferably used.

Here, the "polymerizable smectic liquid crystal compound" is a compound having a polymerizable group and showing a liquid crystal state of a smectic phase.

The liquid crystal state represented by the polymerizable smectic liquid crystal compound is preferably a higher order smectic phase. The higher order smectic phases described herein are smectic a phase, smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and smectic L phase, among which smectic a phase, smectic B phase, smectic F phase, smectic I phase, tilted smectic F phase and tilted smectic I phase are preferred, and smectic a phase and smectic B phase are more preferred.

Examples of such polymerizable smectic liquid crystal compounds include those described in paragraphs [0043] to [0055] of Japanese patent application laid-open No. 2013-033249.

In the present invention, a reverse wavelength dispersive liquid crystal compound can be used as the polymerizable liquid crystal compound.

In the present specification, the term "reverse wavelength dispersion liquid crystal compound" means that when the in-plane retardation (Re) value at a specific wavelength (visible light range) of a retardation film produced using the compound is measured, the Re value becomes equal or higher as the measurement wavelength becomes longer.

Further, as long as the reverse wavelength-dispersive liquid crystal compound is a compound capable of forming a reverse wavelength-dispersive thin film as described above, examples of the compound include, but are not limited to, compounds represented by the general formula (I) described in jp 2008-297210 a (in particular, compounds described in paragraphs [0034] to [0039 ]), compounds represented by the general formula (1) described in jp 2010-084032 a (in particular, compounds described in paragraphs [0067] to [0073 ]), compounds represented by the general formula (II) described in jp 2016-3709 a (in particular, compounds described in paragraphs [0036] to [0043 ]), and compounds represented by the general formula (1) described in jp 2016-081035 a (in particular, compounds described in paragraphs [0043] to [0055 ]).

From the viewpoint of enhancing the reverse wavelength dispersion property, preferable examples of the polymerizable liquid crystal compound include compounds represented by the following formulae (1) to (22), and specifically, K (side chain structure) in the formulae (1) to (22) includes compounds having side chain structures shown in the following tables 1 to 3.

In tables 1 to 3, each "+" indicated by the side chain structure of K indicates a bonding position to an aromatic ring.

In the side chain structures represented by 1-2 in table 2 and 2-2 in table 3, the groups adjacent to the acryloyloxy group and the methacryloyl group respectively represent propylene groups (groups in which methyl groups are substituted with ethylene groups), and represent a mixture of positional isomers in which the positions of the methyl groups are different.

[ chemical formula 16]

[ Table 1]

[ Table 2]

[ Table 3]

In the present invention, a positive wavelength dispersive liquid crystal compound can be used as the polymerizable liquid crystal compound. In particular, it is preferable to use a positive wavelength dispersive liquid crystal compound together with the reverse wavelength dispersive liquid crystal compound.

In the present specification, the term "positive wavelength dispersion liquid crystal compound" means that when the in-plane retardation (Re) value at a specific wavelength (visible light range) of a retardation film produced using the compound is measured, the Re value becomes lower as the measurement wavelength becomes longer.

Examples of the positive wavelength dispersive liquid crystal compound include compounds represented by the following formulas (30) to (53), and specifically, examples of K (side chain structure) in the following formulas (30) to (53) include compounds having side chain structures shown in the above tables 2 and 3.

In tables 2 and 3, the "+" indicated by the side chain structure of K indicates the bonding position with the benzene ring, piperazine ring or cyclohexane ring in the following formulae (30) to (53).

In the side chain structures represented by 1-2 in table 2 and 2-2 in table 3, the groups adjacent to the acryloyloxy group and the methacryloyl group respectively represent propylene groups (groups in which methyl groups are substituted with ethylene groups), and represent a mixture of positional isomers in which the positions of the methyl groups are different.

[ chemical formula 17]

[ polymerization initiator ]

The polymerizable composition of the present invention preferably contains a polymerization initiator.

The polymerization initiator to be used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.

Examples of the photopolymerization initiator include an α -carbonyl compound (described in U.S. Pat. Nos. 2367661 and 2367670), an acyloin ether (described in U.S. Pat. No. 2448828), an α -hydrocarbon-substituted aromatic acyloin compound (described in U.S. Pat. No. 2722512), a polynucleoquinone compound (described in U.S. Pat. Nos. 3046127 and 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (described in U.S. Pat. No. 3549367), an acridine and phenazine compound (described in Japanese patent application laid-open No. Sho 60-105667 and U.S. Pat. No. 4239850), an oxadiazole compound (described in U.S. Pat. No. 4212970), an acylphosphine oxide compound (described in Japanese patent publication No. Sho 63-40799, Japanese patent publication No. Hei 5-29234, a-O-n, Japanese patent laid-open Nos. H10-95788 and H10-29997).

In the present invention, the polymerization initiator is also preferably an oxime-type polymerization initiator, and specific examples thereof include the initiators described in paragraphs [0049] to [0052] of International publication No. 2017/170443.

[ solvent ]

The polymerizable composition of the present invention preferably contains a solvent from the viewpoint of workability in forming a cured product (for example, an optically anisotropic layer) of the present invention described later.

Specific examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, etc.), one of them may be used alone or 2 or more may be used simultaneously.

[ leveling agent ]

The polymerizable composition of the present invention preferably contains a leveling agent from the viewpoint of keeping the surface of the cured product of the present invention described below smooth and facilitating alignment control.

As such a leveling agent, a fluorine-based leveling agent or a silicon-based leveling agent is preferable because the leveling effect is high with respect to the amount added, and a fluorine-based leveling agent is more preferable because bleeding (blooming, bleeding) is less likely to occur.

As the leveling agent, specifically, examples thereof include compounds described in paragraphs [0079] to [0102] of Japanese patent laid-open No. 2007-069471, compounds described in paragraphs [0020] to [0032] of Japanese patent laid-open No. 2013-047204, compounds described in general formula (I) of Japanese patent laid-open No. 2012-211306 (particularly, compounds described in paragraphs [0022] to [0029 ]), liquid crystal alignment improvers described in Japanese patent laid-open No. 2002-129162 (particularly, compounds described in paragraphs [0076] to [0078] and [0082] to [0084 ]), and compounds described in paragraphs [ I), (II) and (III) of general formula (I), (II) and (III) of Japanese patent laid-open No. 2005-099248 (particularly, compounds described in paragraphs [0092] 0096), and the like. Further, the functional group may also function as an alignment control agent described later.

[ orientation controlling agent ]

The polymerizable composition of the present invention may contain an orientation controlling agent, if necessary.

The orientation control agent can form various orientation states such as homeotropic orientation (Vertical orientation), tilt orientation, hybrid orientation, and cholesteric orientation in addition to uniform orientation, and can control and realize a specific orientation state more uniformly and more precisely.

As the orientation control agent for promoting uniform orientation, for example, a low molecular orientation control agent or a high molecular orientation control agent can be used.

As the low-molecular orientation controlling agent, for example, the descriptions of paragraphs [0009] to [0083] of Japanese patent laid-open No. 2002-.

Further, as the orientation controlling agent for the polymer, for example, paragraphs [0021] to [0057] of Japanese patent laid-open No. 2004-198511 and paragraphs [0121] to [0167] of Japanese patent laid-open No. 2006-106662 are referred to and are incorporated herein by reference.

Examples of the orientation control agent for forming or promoting the vertical orientation include boric acid compounds and onium salt compounds, and specifically, compounds described in paragraphs [0023] to [0032] of Japanese patent laid-open No. 2008-225281, paragraphs [0052] to [0058] of Japanese patent laid-open No. 2012-208397, paragraphs [0024] to [0055] of Japanese patent laid-open No. 2008-026730, and paragraphs [0043] to [0055] of Japanese patent laid-open No. 2016-193869 are cited in the present specification.

On the other hand, with respect to the orientation of cholesterol, it can be achieved by adding a chiral agent to the composition of the present invention, and the direction of cyclotron of the orientation of cholesterol can be controlled according to the direction of chirality thereof.

In addition, the pitch of the cholesteric alignment can be controlled according to the alignment restriction force of the chiral agent.

The content of the orientation-controlling agent when contained is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content in the composition. When the content is within this range, a uniform and highly transparent cured product can be obtained which realizes a desired alignment state and which is free from precipitation, phase separation, alignment defects, and the like.

These orientation control agents can also impart a polymerizable functional group, particularly a polymerizable functional group capable of polymerizing with the compound (I) contained in the composition of the present invention.

[ other Components ]

The polymerizable composition of the present invention may further contain components other than the above components, and examples thereof include a surfactant, a tilt angle controlling agent, an orientation assistant, a plasticizer, a crosslinking agent, and the like.

[ cured product ]

The cured product of the present invention is a cured product obtained by curing the polymerizable composition of the present invention.

Here, when the polymerizable composition of the present invention contains a polymerizable liquid crystal compound different from the compound (I) together with the compound (I), for example, the polymerizable composition of the present invention is polymerized, whereby an optically anisotropic layer can be formed as a cured product.

Examples of the method for forming a cured product include a method in which the polymerizable composition of the present invention is used to form a desired alignment state, and then the composition is fixed by polymerization.

The polymerization conditions are not particularly limited, but in polymerization by light irradiation, ultraviolet rays are preferably used. The irradiation dose is preferably 10mJ/cm²～50J/cm²More preferably 20mJ/cm²～5J/cm²More preferably 30mJ/cm²～3J/cm²Particularly preferably 50 to 1000mJ/cm². Further, the polymerization reaction may be carried out under heating to promote the polymerization reaction.

In the present invention, the cured product can be formed on an arbitrary support in the optical film of the present invention described later, or on a polarizer in the polarizing plate of the present invention described later.

The cured product of the present invention is preferably an optically anisotropic layer satisfying the following formula (II).

0.50＜Re(450)/Re(550)＜1.00……(II)

In the formula (II), Re (450) represents an in-plane retardation of the optically anisotropic layer at a wavelength of 450nm, and Re (550) represents an in-plane retardation of the optically anisotropic layer at a wavelength of 550 nm. In the present specification, when the measurement wavelength of retardation is not specified, the measurement wavelength is 550 nm.

The values of the in-plane retardation and the retardation in the thickness direction are values measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Opto Science, inc.).

Specifically, the average refractive index ((Nx + Ny + Nz)/3) and the film thickness (d (. mu.m)) were inputted to Axoscan OPMF-1, and calculated therefrom

Slow axis direction (°)

Re(λ)＝R0(λ)

Rth(λ)＝((nx+ny)/2-nz)×d。

R0 (. lamda.) is a numerical value calculated by Axoscan OPMF-1, but refers to Re (. lamda.).

Also, such an optically anisotropic layer is preferably a positive a plate or a positive C plate, more preferably a positive a plate.

Here, positive a plate (positive a plate) and positive C plate (positive C plate) are defined as follows.

When the refractive index in the slow axis direction (direction in which the in-plane refractive index is largest) in the film plane is nx, the refractive index in the direction orthogonal to the in-plane slow axis is ny, and the refractive index in the thickness direction is nz, the positive a plate satisfies the relationship of expression (a1), and the positive C plate satisfies the relationship of expression (C1). In addition, Rth of the positive a plate indicates a positive value, and Rth of the positive C plate indicates a negative value.

Formula (A1) nx > ny ≈ nz

Formula (C1) nz > nx ≈ ny

The term "substantially" as used herein includes not only the case where both are completely identical but also the case where both are substantially identical.

The term "substantially the same" means that, in the positive A plate, for example, it is included in "ny ≈ nz" even when (ny-nz). times.d (where d is the thickness of the thin film) is-10 to 10nm, preferably-5 to 5nm, and is included in "nx ≈ nz" even when (nx-nz). times.d is-10 to 10nm, preferably-5 to 5 nm. Also, in the positive C plate, for example, even in the case of (nx-ny) × d (wherein d is the thickness of the thin film) of 0 to 10nm, preferably 0 to 5nm, is included in "nx ≈ ny".

When the optically anisotropic layer is a positive A plate, Re (550) is preferably 100 to 180nm, more preferably 120 to 160nm, further preferably 130 to 150nm, and particularly preferably 130 to 140nm, from the viewpoint of functioning as a lambda/4 plate.

Here, the "λ/4 plate" refers to a plate having a λ/4 function, and specifically, refers to a plate having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).

[ optical film ]

The optical film of the present invention is an optical film having the cured product of the present invention.

Fig. 1A, 1B, and 1C (hereinafter, simply referred to as "fig. 1" without particularly distinguishing between these figures) are schematic cross-sectional views each showing an example of the optical film of the present invention.

Fig. 1 is a schematic view, and the relationship of the thicknesses, positional relationship, and the like of the respective layers do not necessarily coincide with reality, and the support, alignment film, and hard coat layer shown in fig. 1 are all arbitrary constituent members.

The optical film 10 shown in fig. 1 includes a support 16, an alignment film 14, and an optically anisotropic layer 12 as a cured product in this order.

Also, as shown in fig. 1B, the optical film 10 may have a hard coat layer 18 on the side of the support 16 opposite to the side on which the alignment film 14 is provided, and as shown in fig. 1C, may have a hard coat layer 18 on the side of the optically anisotropic layer 12 opposite to the side on which the alignment film 14 is provided.

Hereinafter, various members used in the optical film of the present invention will be described in detail.

[ cured product ]

The cured product of the optical film of the present invention is the cured product of the present invention.

In the optical film of the present invention, the thickness of the cured product is not particularly limited, but when the cured product is used as an optically anisotropic layer, the thickness is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[ support body ]

As described above, the optical film of the present invention may have a support as a base material for forming a cured product.

Such a support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.

Examples of such a support include a glass substrate and a polymer film, and examples of a material of the polymer film include a cellulose-based polymer; acrylic polymers having an acrylate polymer such as polymethyl methacrylate and polymers containing a lactone ring; a thermoplastic norbornene-based polymer; a polycarbonate-series polymer; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene polymers such AS polystyrene and acrylonitrile-styrene copolymer (AS resin); polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; a vinyl chloride polymer; amide polymers such as nylon and aromatic polyamide; an imide polymer; a sulfone-based polymer; a polyether sulfone-based polymer; a polyether ether ketone polymer; polyphenylene sulfide-based polymer; a vinylidene chloride polymer; a vinyl alcohol polymer; a vinyl butyral polymer; an aryl ester polymer; a polyoxymethylene polymer; an epoxy polymer; or a polymer obtained by mixing these polymers.

Further, a polarizer described later may also serve as the support.

In the present invention, the thickness of the support is not particularly limited, but is preferably 5 to 60 μm, and more preferably 5 to 30 μm.

[ alignment film ]

When the optical film of the present invention has any of the above-mentioned supports, it is preferable to have an alignment film between the support and the cured product. In addition, the above-described embodiment may be adopted in which the support also serves as an alignment film.

The alignment film generally has a polymer as a main component. As a polymer material for an alignment film, there are many documents describing that a plurality of commercial products can be obtained.

Preferably, the polymeric material utilized in the present invention is polyvinyl alcohol or polyimide and derivatives thereof. Especially preferred are modified and unmodified polyvinyl alcohols.

Examples of the alignment film that can be used in the present invention include the alignment films described in international publication No. 01/88574, page 43, line 24 to page 49, line 8; modified polyvinyl alcohols described in paragraphs [0071] to [0095] of Japanese patent No. 3907735; a liquid crystal alignment film formed by a liquid crystal alignment agent as described in Japanese patent laid-open publication No. 2012-155308.

In the present invention, it is also preferable to use a photo-alignment film as the alignment film, because the photo-alignment film does not contact the surface of the alignment film when the alignment film is formed, and thus deterioration of the surface morphology can be prevented.

The photo-alignment film is not particularly limited, but a polymer material such as a polyamide compound or a polyimide compound described in paragraphs [0024] to [0043] of international publication No. 2005/096041; a liquid crystal alignment film formed by a liquid crystal alignment agent having a photo-alignment group as described in Japanese patent laid-open No. 2012-155308; trade name LPP-JP265CP manufactured by the company of Rolic Technologies, and the like.

In the present invention, the thickness of the alignment film is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm, from the viewpoint of reducing surface irregularities that can be present on the support and forming an optically anisotropic layer having a uniform thickness.

[ hard coating ]

In order to impart physical strength to the film, it is preferable that the optical film of the present invention has a hard coat layer. Specifically, the support may have a hard coat layer on the side opposite to the side on which the alignment film is provided (see fig. 1B), or may have a hard coat layer on the side opposite to the side on which the alignment film is provided of the optically anisotropic layer (see fig. 1C).

As the hard coat layer, the hard coat layers described in paragraphs [0190] to [0196] of Japanese patent laid-open No. 2009-98658 can be used.

[ ultraviolet light absorber ]

The optical film of the present invention preferably includes an Ultraviolet (UV) absorber in consideration of the influence of external light, particularly, ultraviolet rays.

The ultraviolet absorber may be contained in the cured product of the present invention, or may be contained in a member other than the cured product constituting the optical film of the present invention. The cured product is preferably cured by curing the cured product.

As the ultraviolet absorber, any conventionally known ultraviolet absorber that can exhibit ultraviolet absorbability can be used. Among such ultraviolet absorbers, benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorbers are preferably used from the viewpoint of high ultraviolet absorptivity and obtaining ultraviolet absorbing ability (ultraviolet cut-off ability) used in image display devices.

In addition, in order to widen the absorption width of ultraviolet rays, 2 or more kinds of ultraviolet absorbers having different maximum absorption wavelengths can be used simultaneously.

Specific examples of the ultraviolet absorber include compounds described in paragraphs [0258] to [0259] of Japanese patent laid-open No. 2012 and 18395, and compounds described in paragraphs [0055] to [0105] of Japanese patent laid-open No. 2007 and 72163.

Examples of commercially available products include Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, and Tinuvin1577 (both manufactured by BASF corporation).

[ polarizing plate ]

The polarizing plate of the present invention has the optical film of the present invention and a polarizer described above.

When the optically anisotropic layer of the cured product of the present invention is a λ/4 plate (positive a plate), the polarizing plate of the present invention can be used as a circular polarizing plate.

In the polarizing plate of the present invention, when the optically anisotropic layer as a cured product of the present invention is a λ/4 plate (positive a plate), an angle formed by a slow axis of the λ/4 plate and an absorption axis of a polarizer described later is preferably 30 to 60 °, more preferably 40 to 50 °, even more preferably 42 to 48 °, and particularly preferably 45 °.

Here, the "slow axis" of the λ/4 plate means a direction in which the refractive index becomes maximum in the plane of the λ/4 plate, and the "absorption axis" of the polarizer means a direction in which the absorbance is highest.

[ polarizer ]

The polarizer included in the polarizing plate of the present invention is not particularly limited as long as it has a function of converting light into specific linearly polarized light, and conventionally known absorption polarizers and reflection polarizers can be used.

As the absorption type polarizer, an iodine type polarizer, a dye type polarizer using a dichroic dye, a polyene type polarizer, and the like can be used. The iodine-based polarizer and the dye-based polarizer can be used as both a coated polarizer and a stretched polarizer, but a polarizer produced by adsorbing iodine or a dichroic dye onto polyvinyl alcohol and stretching the adsorbed iodine or dichroic dye is preferable.

Further, as a method for obtaining a polarizer by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a substrate, there can be mentioned japanese patent No. 5048120, japanese patent No. 5143918, japanese patent No. 4691205, japanese patent No. 4751481, and japanese patent No. 4751486, and known techniques related to polarizers can be preferably used.

As the reflective polarizer, a polarizer obtained by laminating thin films having different birefringence, a wire grid polarizer, a polarizer obtained by combining a cholesteric liquid crystal having a selective reflection region and an 1/4 wavelength plate, and the like can be used.

Among them, from the viewpoint of more excellent adhesion, it is preferable to contain a polyvinyl alcohol resin (containing-CH)₂-CHOH-as a polymer of repeating units. In particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymer).

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 30 μm, and still more preferably 5 μm to 15 μm.

[ adhesive layer ]

In the polarizing plate of the present invention, an adhesive layer may be disposed between the cured product and the polarizer in the optical film of the present invention.

The pressure-sensitive adhesive layer for laminating a cured product and a polarizer includes, for example, a material having a ratio (tan δ ═ G "/G ') of storage modulus G' to loss elastic modulus G ″ measured by a dynamic viscoelasticity measuring apparatus of 0.001 to 1.5, and includes a so-called pressure-sensitive adhesive, a material that is easily subject to creep, and the like. Examples of the binder that can be used in the present invention include, but are not limited to, a polyvinyl alcohol-based binder.

[ image display apparatus ]

The image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.

The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter, abbreviated as "EL") display panel, and a plasma display panel.

Among these, a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, as the image display device of the present invention, a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element are preferable, and a liquid crystal display device is more preferable.

[ liquid Crystal display device ]

A liquid crystal display device as an example of the image display device of the present invention is a liquid crystal display device having the polarizing plate and the liquid crystal cell of the present invention described above.

In the present invention, among the polarizing plates provided on both sides of the liquid crystal cell, the polarizing plate of the present invention is preferably used as the front polarizing plate, and more preferably used as the front and rear polarizing plates.

Hereinafter, a liquid crystal cell constituting the liquid crystal display device will be described in detail.

< liquid crystal cell >

The liquid crystal cell used In the liquid crystal display device is preferably a VA (Vertical Alignment: Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode, but is not limited thereto.

In a TN mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially horizontally when no voltage is applied, and further twisted to 60 to 120 degrees. TN mode liquid crystal cells are most commonly used as color TFT liquid crystal display devices and are described in various documents.

In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. The VA mode liquid crystal cell includes (1) a narrow VA mode liquid crystal cell (described in japanese patent application laid-open No. 2-176625) in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and are aligned substantially horizontally when a voltage is applied, and further includes (2) a liquid crystal cell (SID97, described in Digest of tech. papers 28 (1997)) 845) in which the VA mode is multi-domain (MVA mode) in order to enlarge a viewing angle, (3) a liquid crystal cell (n-ASM mode) in which the rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and are twisted in multi-domain alignment when a voltage is applied (described in proceedings 58 to 59 (1998)) of japan liquid crystal association), and (4) a liquid crystal cell (LCD International 98) in a surveyal mode. Further, any of a PVA (Patterned Vertical Alignment) type, a photo-Alignment (Optical Alignment) type, and a PSA (Polymer-stabilized Alignment) type may be used. The details of these modes are described in detail in Japanese patent laid-open Nos. 2006-215326 and 2008-538819.

In the IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in plane by applying an electric field parallel to the substrate surface. In the IPS mode, black display is performed in a state where no electric field is applied, and absorption axes of the upper and lower pair of polarizing plates are orthogonal to each other. Methods of reducing light leakage in black display in an oblique direction and improving a viewing angle using an optical compensation sheet are disclosed in japanese patent application laid-open nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[ organic EL display device ]

As an example of the image display device of the present invention, an organic EL display device is preferably provided with a polarizer, a λ/4 plate (positive a plate) composed of the optically anisotropic layer of the present invention, and an organic EL display panel in this order from the viewing side.

The organic EL display panel is a display panel including organic EL elements in which an organic light-emitting layer (organic electroluminescent layer) is interposed between electrodes (between a cathode and an anode). The structure of the organic EL display panel is not particularly limited, and a known structure can be employed.

Examples

The present invention will be described in further detail below based on examples. The materials, amounts, ratios, processing contents, processing steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed restrictively by the examples shown below.

[ example 1]

According to the following synthesis scheme, compound A-1 represented by the following formula A-1 was synthesized.

[ chemical formula 18]

(1) Synthesis of Compound 1

2-hydroxyethyl acrylate (50.0g, 0.431mol) and dibutylhydroxytoluene (190mg, 0.862mmol) were dissolved in ethyl acetate (250mL), and triethylamine (51.0g, 0.504mol) and methanesulfonic acid chloride (50.4g, 0.440mol) were added under ice cooling, followed by stirring at room temperature for 5 hours. Water (125mL) was added to the reaction solution, and extraction was performed with ethyl acetate. The organic layer obtained by extraction was washed with saturated brine, and sodium sulfate was added. After the obtained organic layer was filtered and the filtrate was recovered, dibutylhydroxytoluene (190mg, 0.862mmol) was added, and the solvent was distilled under reduced pressure, whereby compound 1(80.9g) was obtained.

(2) Synthesis of Compound 2

Compound 1(75.6g, 0.354mol) and dibutylhydroxytoluene (0.78g, 3.5mmol) were dissolved in a mixed solvent of toluene (180mL) and dimethylacetamide (200mL), dicyclohexyl-1, 1' -dicarboxylic acid (90.0g, 0.354mol) and triethylamine (71.6g, 0.708mol) were added at room temperature, and the mixture was stirred at 90 ℃ for 5 hours. After the reaction solution was cooled to room temperature, a mixed solution of concentrated hydrochloric acid (23.4g) and water (130mL) was added, followed by warming to 45 ℃ to remove the aqueous layer. The obtained organic layer was washed with a mixed solution of sodium hydrogencarbonate (13.5g) and water (260mL) and a mixed solution of sodium hydrogencarbonate (2.7g) and water (270mL) in this order, and magnesium sulfate was added. After the obtained organic layer was subjected to celite filtration and a filtrate was recovered, dibutylhydroxytoluene (0.78g, 3.5mmol) was added, and the solvent was distilled from the filtrate under reduced pressure. The obtained residue was dissolved in toluene (360mL), and hexane (830mL) was added at 40 ℃. The solution was cooled to 5 ℃ while stirring and stirred for 30 minutes. The resulting crystals were filtered and washed with hexane, whereby compound 2(25.0g) was obtained.

(3) Synthesis of Compound A-1

Phenol (1.00g, 10.6mmol) and compound 2(4.68g, 13.3mmol) were dissolved in chloroform (10mL), and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.75g, 14.3mmol) and dimethylaminopyridine (64.9mg, 0.531mmol) were added thereto at room temperature, followed by stirring at room temperature for 4 hours. The reaction solution was purified by flash column chromatography to obtain a white solid. The obtained white solid was dissolved in ethyl acetate (10mL), and hexane (100mL) was added. The solution was cooled to 0 ℃ while stirring, and stirred for 1 hour. The resulting crystals were filtered, and washed with hexane, whereby Compound A-1(0.80g) was obtained.

The following shows the preparation of the obtained Compound A-1¹H-NMR (Nuclear Magnetic Resonance).

¹H-NMR(CDCl₃)：δ＝7.36(t、2H)、7.23(t、1H)、7.04(d、2H)、6.43(dd、1H)、6.13(dd、1H)、5.88(dd、1H)、4.28-4.38(m、4H)、2.41-2.52(m、1H)、2.13-2.30(m、3H)、1.97-2.06(m、2H)、1.77-1.90(m、4H)、1.33-1.66(m、4H)、0.98-1.20(m、6H)。

[ example 2]

According to the following synthesis scheme, compound A-2 represented by the following formula A-2 was synthesized.

[ chemical formula 19]

(1) Synthesis of Compound 3

Hydroxypropyl acrylate (50.0g, 0.384mol) and dibutylhydroxytoluene (1.69g, 7.67mmol) were dissolved in ethyl acetate (250mL), and triethylamine (45.5g, 0.450mol) and methanesulfonic acid chloride (46.7g, 0.407mol) were added under ice-cooling, followed by stirring at room temperature for 2 hours. Water (125mL) was added to the reaction solution, and extraction was performed with ethyl acetate. The organic layer obtained by extraction was washed with saturated brine, and sodium sulfate was added. After the obtained organic layer was filtered and the filtrate was recovered, dibutylhydroxytoluene (0.34g, 1.54mmol) was added, and the solvent was distilled under reduced pressure, whereby compound 3(79.3g) was obtained.

(2) Synthesis of Compound 4

Compound 3(76.6g, 0.368mol) and dibutylhydroxytoluene (0.74g, 3.4mmol) were dissolved in a mixed solvent of toluene (170mL) and dimethylacetamide (190mL), dicyclohexyl-1, 1' -dicarboxylic acid (85.0g, 0.334mol) and triethylamine (67.6g, 0.668mol) were added at room temperature, and the mixture was stirred at 90 ℃ for 5 hours. After the reaction solution was cooled to room temperature, a mixed solution of concentrated hydrochloric acid (22.1g) and water (120mL) was added, followed by warming to 45 ℃ to remove the aqueous layer. The obtained organic layer was washed with a mixed solution of sodium hydrogencarbonate (12.7g) and water (240mL), sodium hydrogencarbonate (2.5g) and a mixed solution of sodium chloride (10g) and water (350mL) in this order, and magnesium sulfate was added. After the obtained organic layer was subjected to celite filtration and a filtrate was recovered, dibutylhydroxytoluene (95.7mg, 0.434mmmol) was added, and the solvent was distilled from the filtrate under reduced pressure. The obtained residue was dissolved in toluene (340mL), and hexane (630mL) was added at 40 ℃. The solution was cooled to 5 ℃ while stirring and stirred for 30 minutes. The resulting crystals were filtered and washed with hexane, whereby compound 4(31.3g) was obtained.

(3) Synthesis of Compound A-2

Phenol (1.00g, 10.6mmol) and compound 4(4.87g, 13.3mmol) were dissolved in chloroform (10mL), and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.75g, 14.3mmol) and dimethylaminopyridine (64.9mg, 0.531mmol) were added thereto at room temperature, followed by stirring at room temperature for 4 hours. Compound 4(4.87g, 13.3mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.75g, 14.3mmol) and dimethylaminopyridine (64.9mg, 0.531mmol) were added to the reaction solution at room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was purified by flash column chromatography to obtain a white solid. The obtained white solid was dissolved in chloroform (5mL), and methanol (150mL) was added. The solution was cooled to 0 ℃ while stirring, and stirred for 1 hour. The resulting crystals were filtered, and washed with methanol, whereby Compound A-2(3.23g) was obtained.

The following shows the obtained Compound A-2¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.37(t、2H)、7.23(t、1H)、7.04(d、2H)、6.41(dd、1H)、6.12(dd、1H)、5.86(dd、1H)、5.15-5.28(m、1H)、4.10-4.23(m、2H)、2.46(tt、1H)、2.13-2.29(m、3H)、1.95-2.07(m、2H)、1.22-1.61(m、7H)、0.96-1.19(m、6H)。

[ example 3]

Compound A-3 was obtained as a white solid, represented by the following formula A-3, in the same manner as in example 1, except that 2-methoxyphenol was used instead of phenol.

[ chemical formula 20]

The following shows the obtained Compound A-3¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.18(dt、1H)、6.90-7.02(m、3H)、6.44(d、1H)、6.14(dd、1H)、5.88(dd、1H)、4.28-4.39(m、4H)、3.81(s、3H)、2.51(tt、1H)、2.12-2.31(m、3H)、1.95-2.07(m、2H)、1.77-1.92(m、4H)、1.34-1.63(m、4H)、0.97-1.20(m、6H)。

[ example 4]

Compound A-4 was obtained as a white solid, which was represented by the following formula A-4, in accordance with the same procedures as in example 1, except that 2-ethoxyphenol was used instead of phenol.

[ chemical formula 21]

The following shows the obtained Compound A-4¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.14(dt、1H)、7.01(dd、1H)、6.87-6.95(m、2H)、6.44(dd、1H)、6.14(dd、1H)、5.87(dd、1H)、4.28-4.39(m、4H)、4.02(q、2H)、2.50(tt、1H)、2.15-2.31(m、3H)、1.96-2.07(m、2H)、1.68-1.90(m、4H)、1.32-1.63(m、7H)、0.97-1.18(m、6H)。

[ example 5]

According to the following synthetic scheme, compound A-5 represented by the following formula A-5 was synthesized.

[ chemical formula 22]

(1) Synthesis of Compound 5

2-hydroxybenzoic acid (5.01g, 36.3mmol), Compound 1(7.25g, 37.3mmol), dibutylhydroxytoluene (0.16g, 0.73mmol), and potassium iodide (0.30g, 1.8mmol) were dissolved in dimethylacetamide (25mL), and triethylamine (4.05g, 40.0mmol) was added thereto at room temperature, followed by stirring at 60 ℃ for 2 hours. After the reaction solution was cooled to ice-cooling, 0.5N hydrochloric acid (100mL) was added, and extraction was performed with ethyl acetate. The obtained organic layer was washed with water (25mL), 1N hydrochloric acid (25mL), a saturated aqueous solution of sodium hydrogencarbonate (25mL) and saturated brine (25mL) in this order, and sodium sulfate was added thereto. After the obtained organic layer was filtered and the filtrate was recovered, dibutylhydroxytoluene (0.16g, 0.73mmol) was added, and the solvent was distilled from the filtrate under reduced pressure. The obtained residue was purified by flash column chromatography, whereby compound 5(6.55g) was obtained.

(2) Synthesis of Compound A-5

Compound 5(1.00g, 4.23mmol) and compound 1(4.68g, 5.28mmol) were dissolved in chloroform (10mL), and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (1.10g, 5.74mmol) and dimethylaminopyridine (25.2mg, 0.206mmol) were added thereto at room temperature, followed by stirring at room temperature for 3 hours. Compound 1(2.34g, 2.64mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (0.55g, 2.9mmol) and dimethylaminopyridine (12.6mg, 0.103mmol) were added to the reaction solution at room temperature, and the mixture was stirred at room temperature for 3 hours. The reaction solution was purified by flash column chromatography to obtain a white solid. The obtained white solid was dissolved in ethyl acetate (2mL), and hexane (40mL) was added. The solution was cooled to 0 ℃ while stirring, and stirred for 1 hour. The resulting crystals were filtered and washed with hexane, whereby Compound A-5(1.31g) was obtained.

The following shows the obtained Compound A-5¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.99(dd、1H)、7.53(dt、1H)、7.33(t、1H)、7.04(d、1H)、6.43(dd、1H)、6.42(dd、1H)、6.14(dd、1H)、6.13(dd、1H)、5.89(dd、2H)、4.42-4.52(m、4H)、4.28-4.38(m、4H)、2.53(t、1H)、2.17-2.31(m、3H)、1.96-2.07(m、2H)、1.76-1.90(m、4H)、1.33-1.66(m、4H)、0.98-1.20(m、6H)。

[ example 6]

Compound a-6 represented by the following formula a-6 was obtained as a white solid in the same manner as in example 1 except that 3-methoxyphenol was used instead of phenol.

[ chemical formula 23]

The following shows the obtained Compound A-6¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.26(t、1H)、6.78(dd、1H)、6.60-6.68(m、2H)、6.43(dd、1H)、6.16(dd、1H)、5.87(dd、1H)、4.29-4.39(m、4H)、3.78(s、3H)、2.46(tt、1H)、2.12-2.31(m、3H)、1.96-2.07(m、2H)、1.77-1.91(m、4H)、1.35-1.61(m、4H)、0.96-1.19(m、6H)。

[ example 7]

According to the following synthesis scheme, compound A-7 represented by the following formula A-7 was synthesized.

[ chemical formula 24]

(1) Synthesis of Compound 6

4-hydroxybutylacrylate (50.0g, 0.347mol) and dibutylhydroxytoluene (190mg, 0.862mmol) were dissolved in ethyl acetate (250mL), and triethylamine (41.1g, 0.406mol) and methanesulfonic acid chloride (41.1g, 0.406mol) were added under ice cooling, followed by stirring at room temperature for 5 hours. Water (125mL) was added to the reaction solution, and extraction was performed with ethyl acetate. The organic layer obtained by extraction was washed with saturated brine, and sodium sulfate was added. After the obtained organic layer was filtered and the filtrate was recovered, dibutylhydroxytoluene (190mg, 0.862mmol) was added, and the solvent was distilled under reduced pressure, whereby compound 1(73.7g) was obtained.

(2) Synthesis of Compound 7

Compound 6(86.5g, 0.389mol) and dibutylhydroxytoluene (0.78g, 3.5mmol) were dissolved in a mixed solvent of toluene (180mL) and dimethylacetamide (200mL), dicyclohexyl-1, 1' -dicarboxylic acid (90.0g, 0.354mol) and triethylamine (71.6g, 0.708mol) were added at room temperature, and the mixture was stirred at 90 ℃ for 5 hours. After the reaction solution was cooled to room temperature, a mixed solution of concentrated hydrochloric acid (23.4g) and water (130mL) was added, followed by warming to 45 ℃ to remove the aqueous layer. The obtained organic layer was washed with a mixed solution of sodium hydrogencarbonate (13.5g) and water (260mL) and a mixed solution of sodium hydrogencarbonate (2.7g) and water (270mL) in this order, and magnesium sulfate was added. After the obtained organic layer was subjected to celite filtration and a filtrate was recovered, dibutylhydroxytoluene (0.78g, 3.5mmol) was added, and the solvent was distilled from the filtrate under reduced pressure. The obtained residue was dissolved in toluene (360mL), and hexane (830mL) was added at 40 ℃. The solution was cooled to 5 ℃ while stirring and stirred for 30 minutes. The resulting crystals were filtered and washed with hexane, whereby compound 7(28.4g) was obtained.

(3) Synthesis of Compound A-7

Phenol (1.00g, 10.6mmol) and compound 6(5.06g, 13.3mmol) were dissolved in chloroform (10mL), and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.75g, 14.3mmol) and dimethylaminopyridine (64.9mg, 0.531mmol) were added thereto at room temperature, followed by stirring at room temperature for 4 hours. The reaction solution was purified by flash column chromatography to obtain a white solid. The obtained white solid was dissolved in ethyl acetate (10mL), and hexane (100mL) was added. The solution was cooled to 0 ℃ while stirring, and stirred for 1 hour. The resulting crystals were filtered, and washed with hexane, whereby Compound A-1(3.48g) was obtained.

The following shows the obtained Compound A-7¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.36(t、2H)、7.24(t、1H)、7.06(d、2H)、6.42(dd、1H)、6.12(dd、1H)、5.83(dd、1H)、4.14(dt、4H)、2.44(tt、1H)、2.12-2.29(m、3H)、1.95-2.06(m、2H)、1.63-1.92(m、8H)、1.25-1.64(m、4H)、0.97-1.21(m、6H)。

[ example 8]

Compound a-8 was obtained as a white solid represented by the following formula a-8 in accordance with the same procedure as in example 7, except that compound 5 was used instead of phenol.

[ chemical formula 25]

The following shows the obtained Compound A-8¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.99(dd、1H)、7.65(dt、1H)、7.33(dt、2H)、7.09(dd、1H)、6.44(dd、1H)、6.43(dd、1H)、6.16(dd、1H)、6.15(dd、1H)、5.87(dd、1H)、5.86(dd、1H)、4.44-4.52(m、4H)、4.14(dt、4H)、2.53(tt、1H)、2.17-2.29(m、3H)、1.96-2.06(m、2H)、1.69-1.92(m、8H)、1.25-1.64(m、4H)、0.96-1.20(m、6H)。

[ example 9]

Compound A-9 was obtained as a white solid, which was represented by the following formula A-9, in the same manner as in example 7 except that 1-naphthol was used instead of phenol.

[ chemical formula 26]

The following shows the obtained Compound A-9¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.81-7.89(m、2H)、7.72(d、1H)、7.42-7.53(m、3H)、7.22(dd、1H)、6.42(dd、1H)、6.12(dd、1H)、5.83(dd、1H)、4.05-4.24(m、4H)、2.65(tt、1H)、2.14-2.38(m、3H)、1.59-2.04(m、10H)、1.28-1.50(m、4H)、0.93-1.28(m、6H)。

[ example 10]

According to the following synthetic scheme, compound A-10 represented by the following formula A-10 was synthesized.

[ chemical formula 27]

(1) Synthesis of Compound 8

1, 4-Cyclohexyldicarboxylic acid dichloride (31.4g, 0.150mol) and dibutylhydroxytoluene (1.1g, 5.0mmol) were dissolved in ethyl acetate (160mL), and triethylamine (12.1g, 0.120mol) and 2-hydroxyethyl acrylate (11.6g, 0.100mol) were added under ice cooling, followed by stirring at room temperature for 3 hours. A mixed solution of sodium hydrogencarbonate (12.2g) and water (120mL) and 1-methylimidazole (8.0g, 0.098mol) were added to the reaction solution, and after stirring at 40 ℃ for 1 hour, the aqueous layer was removed. The obtained organic layer was washed with 0.1N hydrochloric acid (160mL) and 5% saline (160mL) in this order, and magnesium sulfate was added. After the obtained organic layer was subjected to celite filtration and a filtrate was recovered, dibutylhydroxytoluene (1.1g, 5.0mmol) was added, and the solvent was distilled from the filtrate under reduced pressure. The obtained residue was dissolved in acetonitrile (310mL), and tert-butylamine (5.78g, 0.079mol) was added under ice-cooling. The solution was stirred for 1 hour, and the formed crystals were filtered and washed with acetonitrile.

Then, toluene (25mL) and water (20mL) were added to 10.0g of the crystals obtained, and a mixed solution of concentrated hydrochloric acid (3.3g) and water (0.3mL) was added under ice cooling, and after stirring at room temperature for 30 minutes, the aqueous layer was removed. The obtained organic layer was washed with water (50mL), and magnesium sulfate was added. After the obtained organic layer was subjected to celite filtration and a filtrate was recovered, dibutylhydroxytoluene (111mg, 0.504mmol) was added, and the solvent was distilled under reduced pressure from the filtrate, whereby compound 8(7.25g) was obtained.

(2) Synthesis of A-10

4-phenylphenol (1.34g, 7.87mmol) and Compound 8(2.66g, 9.85mmol) were dissolved in chloroform (10mL), and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.05g, 10.7mmol) and dimethylaminopyridine (48.1mg, 0.394mmol) were added thereto at room temperature, followed by stirring at room temperature for 4 hours. The reaction solution was purified by flash column chromatography to obtain a white solid. The obtained white solid was dissolved in ethyl acetate (4mL), and hexane (80mL) was added. The solution was cooled to 0 ℃ while stirring, and stirred for 1 hour. The resulting crystals were filtered, and washed with hexane, whereby Compound A-10(0.66g) was obtained.

The following shows the obtained Compound A-10¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.56(t、4H)、7.43(t、2H)、7.31-7.38(m、1H)、7.13(d、2H)、6.44(dd、1H)、6.15(dd、1H)、5.88(dd、1H)、4.33-4.41(m、4H)、2.56(tt、1H)、2.38(tt、1H)、2.10-2.30(m、4H)、1.48-1.61(m、4H)。

[ example 11]

Compound A-11 was obtained as a white solid, which was represented by the following formula A-11, in accordance with the same procedures as in example 10, except that 4-cyclohexylphenol was used instead of 4-phenylphenol.

[ chemical formula 28]

The following shows the preparation of the obtained Compound A-11¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.19(d、2H)、6.96(d、2H)、6.42(dd、1H)、6.13(dd、1H)、5.83(dd、1H)、4.08-4.25(m、4H)、2.43-2.59(m、2H)、2.03-2.40(m、6H)、1.15-1.92(m、13H)。

[ example 12]

A compound A-12 represented by the following formula A-12 was obtained as a white solid in the same manner as in example 7 except that 4-phenylphenol was used instead of phenol.

[ chemical formula 29]

The following shows the obtained Compound A-12¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.52-7.62(m、4H)、7.43(t、2H)、7.34(tt、1H)、7.13(d、2H)、6.41(dd、1H)、6.12(dd、1H)、5.82(dd、1H)、4.13(dt、4H)、2.48(tt、1H)、2.13-2.39(m、3H)、1.93-2.07(m、2H)、1.66-1.92(m、8H)、1.28-1.63(m、4H)、0.97-1.20(m、6H)。

[ example 13]

According to the following synthetic scheme, compound A-13 represented by the following formula A-13 was synthesized.

[ chemical formula 30]

(1) Synthesis of Compound 9

2-hydroxyethyl methacrylate (50.0g, 0.384mol) and dibutylhydroxytoluene (1.69g, 7.67mmol) were dissolved in ethyl acetate (250mL), and triethylamine (45.5g, 0.450mol) and methanesulfonic acid chloride (46.7g, 0.407mol) were added under ice cooling, followed by stirring at room temperature for 5 hours. Water (125mL) was added to the reaction solution, and extraction was performed with ethyl acetate. The organic layer obtained by extraction was washed with saturated brine, and sodium sulfate was added. After the obtained organic layer was filtered and the filtrate was recovered, dibutylhydroxytoluene (0.34g, 1.54mmol) was added, and the solvent was distilled under reduced pressure, whereby compound 9(82.6g) was obtained.

(2) Synthesis of Compound 10

Compound 9(76.6g, 0.368mol) and dibutylhydroxytoluene (0.74g, 3.4mmol) were dissolved in a mixed solvent of toluene (170mL) and dimethylacetamide (190mL), dicyclohexyl-1, 1' -dicarboxylic acid (85.0g, 0.334mol) and triethylamine (67.6g, 0.668mol) were added at room temperature, and the mixture was stirred at 90 ℃ for 5 hours. After the reaction solution was cooled to room temperature, a mixed solution of concentrated hydrochloric acid (22.1g) and water (120mL) was added, followed by warming to 45 ℃ to remove the aqueous layer. The obtained organic layer was washed with a mixed solution of sodium hydrogencarbonate (12.7g) and water (240mL) and a mixed solution of sodium hydrogencarbonate (2.5g) and water (250mL) in this order, and magnesium sulfate was added. After the obtained organic layer was subjected to celite filtration and a filtrate was recovered, dibutylhydroxytoluene (95.7g, 0.434mmol) was added, and the solvent was distilled from the filtrate under reduced pressure. The obtained residue was dissolved in toluene (340mL), and hexane (630mL) was added at 40 ℃. The solution was cooled to 5 ℃ while stirring and stirred for 30 minutes. The resulting crystals were filtered and washed with hexane, whereby compound 10(26.7g) was obtained.

(3) Synthesis of Compound A-13

Phenol (1.00g, 10.6mmol) and compound 10(4.87g, 13.3mmol) were dissolved in chloroform (10mL), and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.75g, 14.3mmol) and dimethylaminopyridine (64.9mg, 0.531mmol) were added thereto at room temperature, followed by stirring at room temperature for 4 hours. The reaction solution was purified by flash column chromatography to obtain a white solid. The obtained white solid was dissolved in chloroform (5mL), and methanol (100mL) was added. The solution was cooled to 0 ℃ while stirring, and stirred for 1 hour. The resulting crystals were filtered and washed with methanol, whereby Compound A-13(3.71g) was obtained.

The following shows the obtained Compound A-13¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.37(t、2H)、7.23(t、1H)、7.04(d、2H)、6.11(s、1H)、5.59(s、1H)、4.27-4.39(m、4H)、2.43(tt、1H)、2.12-2.31(m、3H)、1.93-2.06(m、5H)、1.76-1.90(m、4H)、1.22-1.61(m、4H)、0.93-1.20(m、6H)。

[ example 14]

Compound A-14 represented by the following formula A-14 was obtained as a white solid in the same manner as in example 10 except that 2-hydroxyethyl methacrylate was used in place of 2-hydroxyethyl acrylate.

[ chemical formula 31]

The following shows the obtained Compound A-14¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.52-7.62(m、4H)、7.43(t、2H)、7.33(t、1H)、7.13(d、2H)、6.12(s、1H)、5.59(s、1H)、4.33(br s、4H)、2.52(tt、1H)、2.33(tt、1H)、2.09-2.28(m、4H)、1.95(s、3H)、1.46-1.69(m、4H)。

[ example 15]

[ Synthesis example (1 thereof) ]

According to the following synthetic scheme, compound A-15 represented by the following formula A-15 was synthesized.

[ chemical formula 32]

(1) Synthesis of Compound 11

Was dissolved in 2- (4-hydroxyphenyl) ethanol (50.0g, 0.362mol) and dimethylacetamide (340mL), and acryloyl chloride (36.0g, 0.398mol) was added under ice-cooling, followed by stirring at room temperature for 4 hours. After the reaction solution was diluted with ethyl acetate (400mL), 1N hydrochloric acid (250mL) was added, and extraction was performed with ethyl acetate. The organic layer obtained by the extraction was washed with a saturated aqueous sodium bicarbonate solution and a saturated brine in this order, and magnesium sulfate was added. After the obtained organic layer was filtered and the filtrate was recovered, dibutylhydroxytoluene (0.14g, 0.64mmol) was added, and the solvent was distilled under reduced pressure, whereby compound 10(69.6g) was obtained.

(2) Synthesis of Compound 12

1, 4-Cyclohexyldicarboxylic acid (55.0g, 0.319mol) was suspended in tetrahydrofuran (550mL), and methanesulfonyl chloride (20.2g, 0.176mol) and triethylamine (19.4g, 0.192mol) were added under ice-cooling, followed by stirring at room temperature for 1 hour. After dibutylhydroxytoluene (0.18g, 0.82mmol), dimethylaminopyridine (1.95g, 16.0mmol) and compound 11(30.7g, 0.160mol) were added to the reaction solution, triethylamine (19.4g, 0.192mol) was added thereto under ice cooling, and the mixture was stirred at room temperature for 2 hours. The reaction solution was filtered through celite, diluted with ethyl acetate (300mL), and 1N hydrochloric acid (100mL) was added to conduct extraction with ethyl acetate. The obtained organic layer was washed with a saturated aqueous sodium bicarbonate solution and a saturated saline solution in this order, and magnesium sulfate was added thereto. After the obtained organic layer was filtered and the filtrate was recovered, dibutylhydroxytoluene (0.14g, 0.64mmol) was added, and the solvent was distilled under reduced pressure. The obtained residue was dissolved in chloroform (130mL), and hexane (260mL) was added. The solution was stirred for 1 hour, and the formed crystals were filtered and washed with hexane, whereby compound 11(29.8g) was obtained.

(3) Synthesis of Compound A-15

Phenol (0.94g, 10mmol) and compound 11(3.46g, 9.99mmol) were dissolved in chloroform (15mL), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.30g, 12.0mmol) and dimethylaminopyridine (0.06g, 0.5mmol) were added at room temperature, and the mixture was stirred at room temperature for 2 hours. The reaction solution was purified by flash column chromatography to obtain a white solid. The obtained white solid was dissolved in ethyl acetate (15mL), and methanol (50mL) was added. The solution was stirred for 1 hour, and the formed crystals were filtered and washed with methanol, whereby compound a-15(2.60g) was obtained.

The following shows the obtained Compound A-15¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.38(t、2H)、7.21-7.24(m、3H)、7.08(d、2H)、7.02(d、2H)、6.39(d、1H)、6.12(dd、1H)、5.81(d、1H)、4.36(t、2H)、2.98(t、2H)、2.68-2.50(m、2H)、2.18-2.37(m、4H)、1.58-1.78(m、4H)。

[ Synthesis example (2) ]

According to the following synthetic scheme, compound A-15 represented by the following formula A-15 was synthesized.

[ chemical formula 33]

(1) Synthesis of Compound 11

2- (4-hydroxyphenyl) ethanol (19.3g, 0.14mol) was dissolved in toluene (80mL) and dimethylacetamide (24mL), the temperature was raised to 60 ℃, 3-chloropropionyl chloride (17.8g, 0.14mol) was added dropwise, and the reaction was carried out at 60-70 ℃ for 2 hours. After 2, 6-di-t-butyl-p-cresol (0.15g) was added thereto, triethylamine (42.5g, 0.42mol) was added dropwise and reacted at 60 to 70 ℃ for 2 hours. After completion of the reaction, the internal temperature was lowered to 25 ℃ or lower, and water (51mL) and concentrated hydrochloric acid (16g) were added to conduct a liquid separation operation. Water (68mL) was added to the organic layer obtained by the extraction, and a liquid separation operation was performed again to obtain an organic layer. 2, 6-di-t-butyl-p-cresol (0.3g) was added thereto, and toluene was distilled under reduced pressure. Further, toluene (42g) was added thereto, and distillation under reduced pressure was further carried out to obtain compound 11(23 g).

(2) Synthesis of Compound 12A

1, 4-Cyclohexyldicarboxylic acid dichloride (79.9g, 0.38mol) was dissolved in ethyl acetate (89mL) and tetrahydrofuran (194mL), the external temperature was set to 5 ℃ and the mixture was cooled, and a 67% THF solution of phenol (27.7g, 0.294mol) was added. Triethylamine (35.7g, 0.35mol) was added dropwise thereto, and the mixture was reacted at an internal temperature of 5 to 15 ℃ for 0.5 hour. After completion of the reaction, water (29mL) was added dropwise, and a mixture of water (76mL) and a 40% aqueous solution of sodium hydroxide (62g) was added dropwise. Then, after the reaction was carried out at an internal temperature of 15 to 25 ℃ for 0.5 hour, N-methylimidazole (18g) was added dropwise thereto, and the reaction was further carried out at an internal temperature of 35 to 40 ℃ for 1 hour. Then, acetic acid (2.7g) was added dropwise thereto to conduct a liquid separation operation. Subsequently, water (58mL) and concentrated hydrochloric acid (17.7g) were added to the organic layer to conduct a liquid separation operation. Finally, water (133mL) and common salt (2.9g) were added thereto to conduct a liquid separation operation, thereby extracting an organic layer. Toluene (70mL) was added to the organic layer and distillation was performed under reduced pressure, and toluene (70mL) was further added and distillation was performed again under reduced pressure. Toluene (388mL) was added thereto, and the mixture was filtered under reduced pressure, washed with a mixed solution of cyclohexane (29mL) and isopropanol (7.5mL), and dried overnight at room temperature to obtain Compound 12A (33 g).

(3) Synthesis of Compound A-15

Compound 12A (28.4g, 0.114mol) was dissolved in toluene (59mL) and dimethylformamide (22mL), and thionyl chloride (15.1g, 0.127mol) was added dropwise so that the internal temperature became 20 to 40 ℃ to react at 30 to 40 ℃ for 1 hour. After standing to remove the bottom layer, ethyl acetate (91mL) was added and the internal temperature was cooled to 5 ℃. N-methylimidazole (1.9g) was added dropwise thereto, and 2, 6-di-tert-butyl-p-cresol (0.25g) was added. To the reaction mixture was added dropwise a solution of compound 11(39.5g, 0.104mol) in ethyl acetate (30mL), followed by dropwise addition of triethylamine (21.1g, 0.21mol), and the reaction was carried out at an internal temperature of 30 to 40 ℃ for 2 hours. Thereafter, methanol (5.7mL) was added dropwise thereto, the mixture was stirred for 15 to 30 minutes, and water (34mL) and ethyl acetate (28mL) were further added thereto, followed by dust removal and filtration. Water (165mL) and concentrated hydrochloric acid (1.4g) were added thereto to conduct a liquid separation operation. Subsequently, water (180mL) and common salt (20g) were added to the extracted organic layer to conduct a liquid separation operation, thereby extracting the organic layer. A mixed solution of methanol (400mL) and water (140mL) was added dropwise to the obtained organic layer, and the internal temperature was cooled to 5 ℃ and stirred for 0.5 hour, followed by filtration under reduced pressure to obtain compound A-15(35 g).

[ example 16]

Compound a-16 represented by the following formula a-16 was obtained as a white solid in the same manner as in example 15, except that methacryloyl chloride was used instead of acryloyl chloride.

[ chemical formula 34]

The following shows the obtained Compound A-16¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.4(t、2H)、7.2-7.3(m、3H)、7.1(d、2H)、7.0(d、2H)、6.1(s、1H)、5.55(s、1H)、4.3(t、2H)、3.0(t、2H)、2.5-2.65(m、2H)、2.3(m、4H)、1.9(s、3H)、1.6-1.7(m、4H)。

[ example 17]

Except that o-methoxyphenol was used instead of phenol, compound a-17 was obtained as a white solid, as represented by the following formula a-17, in accordance with the same procedure as in example 15.

[ chemical formula 35]

The following shows the obtained Compound A-17¹H-NMR。

¹H-NMR(CDCl₃)：δ＝7.2-7.3(m、3H)、6.9-7.1(m、5H)、6.4(d、1H)、6.1(dd、1H)、5.80(d、1H)、4.35(t、2H)、3.8(s、3H)、3.0(t、3H)、2.5-2.7(m、2H)、2.2-2.4(m、4H)、1.6-1.8(m、4H)。

Comparative example 1

According to the disclosure of Japanese patent application laid-open No. 2010-100609, a compound B-1 represented by the following formula B-1 was synthesized.

[ chemical formula 36]

Comparative example 2

According to the disclosure of Japanese patent application laid-open No. 2011-246365, a compound B-2 represented by the following formula B-2 is synthesized.

[ chemical formula 37]

Comparative example 3

A compound B-3 represented by the following formula B-3 was synthesized as described in Japanese patent application laid-open No. 2018-77465.

[ chemical formula 38]

Comparative example 4

Compound B-4 represented by the following formula B-4 was synthesized as described in International publication No. 2012/002140.

[ chemical formula 39]

Comparative example 5

According to the disclosure of Japanese patent laid-open publication No. 2015-166887, a compound B-5 represented by the following formula B-5 was synthesized.

[ chemical formula 40]

Comparative example 6

A compound B-6 represented by the following formula B-6 was synthesized as described in Japanese patent application laid-open No. 2013-152439.

[ chemical formula 41]

Comparative example 7

A compound B-7 represented by the following formula B-7 was synthesized in accordance with the disclosure of Japanese patent application laid-open No. 2016-126941.

[ chemical formula 42]

[ production of optical film ]

< production of substrate with alignment film >

The following coating liquid for forming an alignment film was applied to a cleaned glass substrate using a #5 bar coater, and the glass substrate was dried with warm air at 100 ℃ for 120 seconds and then subjected to rubbing treatment, thereby producing a substrate with an alignment film.

< formation of Positive A plate >

The following composition was applied to a substrate with an alignment film by spin coating. The coating film formed on the substrate with the alignment film was heated at 150 ℃ with warm air, and then cooled to 105 ℃ and irradiated with 10mJ/cm of light having a wavelength of 365nm using a high-pressure mercury lamp under a nitrogen atmosphere²Then irradiating the coating film with 500mJ/cm of ultraviolet light while heating to 120 ℃²Thereby fixing the alignment of the liquid crystal compound, and an optical film including a positive a plate was produced.

Polymerizable liquid Crystal Compound L-1[ chemical formula 43]

Polymerizable liquid Crystal Compound L-2[ chemical formula 44]

Polymerizable liquid Crystal Compound L-3[ chemical formula 45]

Polymerization initiator PI-1

[ chemical formula 46]

Flatting agent T-1

[ chemical formula 47]

[ evaluation ]

< Damp-heat resistance >

The Re change rate was evaluated by bonding a glass plate to the coated surface of the prepared positive a plate using a pressure sensitive adhesive (SK-2057, Soken Chemical & Engineering co., ltd.), peeling the substrate with the alignment film from the glass plate, transferring only the positive a plate onto the glass plate, and comparing the result with the same sample which was not exposed to high temperature and high humidity after 136 hours at 100 ℃ and 95% humidity. In table 4 below, "a" indicates a change rate of Re of less than 5%, "B" indicates a change rate of Re of 5% or more and less than 10%, and "C" indicates 10% or more.

< determination of the Tilt Angle >

The tilt angle is a value obtained by directly measuring the positive a plate on the substrate with the alignment film prepared by using AxoScan OPMF-1 (manufactured by Opto Science, inc.) and light having a wavelength of 550 nm. In table 4 below, "a" indicates an inclination angle of less than 7.0 °, "B" indicates an inclination angle of 7.0 ° or more and less than 9.3 °, "C" indicates an inclination angle of 9.3 ° or more and less than 10.0 °, and "D" indicates an inclination angle of 10.0 ° or more.

[ Table 4]

From the results shown in Table 4, it is understood that when the compounds B-1 to B-7 not corresponding to the above formula (I) are used, the tilt angle of the liquid crystal molecules becomes 10 ° or more (comparative examples 1 to 7).

In contrast, it was found that when the compounds A-1 to A-14 which do not correspond to the formula (I) were used, the tilt angles of the liquid crystal molecules became small (examples 1 to 17).

In particular, from the comparison results of examples 1 and 3 to 6 and the comparison results of examples 7 and 8, it is clear that A in the above formula (I)²In the case of an aromatic ring having a substituent R, the moist heat resistance is improved when the substituent R is a substituent represented by-Z-Sp-P.

It is also found that when Sp in the formula (I) is a linear or branched alkylene group having 1 to 3 carbon atoms or m in the formula (I) is 0, the tilt angle of the liquid crystal molecules becomes smaller.

Further, as is clear from a comparison between example 10 and example 14, when the compound (I) and the polymerizable liquid crystal compound have different polymerizable groups, the tilt angle of the liquid crystal molecules becomes smaller.

[ examples 18 and 19]

[ production of optical film ]

< production of substrate with alignment film >

The following coating liquid for forming an alignment film was applied to a cleaned glass substrate using a #5 bar coater, and the glass substrate was dried with warm air at 100 ℃ for 120 seconds and then subjected to rubbing treatment, thereby producing a substrate with an alignment film.

< formation of Positive A plate >

The following composition was applied to a substrate with an alignment film by spin coating. The coating film formed on the substrate with the alignment film was heated at 150 ℃ with warm air, and then cooled to 105 ℃ and irradiated with 10mJ/cm of light having a wavelength of 365nm using a high-pressure mercury lamp under a nitrogen atmosphere²Then irradiating the coating film with 500mJ/cm of ultraviolet light while heating to 120 ℃²Thereby immobilizing the orientation of the liquid crystal compound, thereby producing a packageOptical film comprising a positive a plate.

Polymerizable liquid Crystal Compound L-1

[ chemical formula 48]

Polymerizable liquid Crystal Compound L-2

[ chemical formula 49]

Polymerizable liquid Crystal Compound L-13

[ chemical formula 50]

The tilt angle of the positive a plate on the substrate with the alignment film was measured for the optical films produced in examples 18 and 19 by the method described above. The results are shown in table 5 below. In table 5 below, "a" indicates that the tilt angle is less than 7.0 °.

[ Table 5]

[ examples 20 and 21]

An optical film including a front a plate was produced in the same manner as in example 18, except that the method for forming a front a plate was changed to the method and composition described below.

< formation of Positive A plate >

The following composition was applied to a substrate with an alignment film by spin coating. The coating film formed on the substrate with the alignment film was heated at 150 ℃ with warm air, and then cooled to 105 ℃ and irradiated with 10mJ/cm of light having a wavelength of 365nm using a high-pressure mercury lamp under a nitrogen atmosphere²Then irradiating the coating film with 500mJ/cm of ultraviolet light while heating to 120 ℃²Thereby fixing the alignment of the liquid crystal compound, and an optical film including a positive a plate was produced.

Polymerizable liquid Crystal Compound L-14

[ chemical formula 51]

Polymerizable liquid Crystal Compound L-15

[ chemical formula 52]

The tilt angle of the positive a plate on the substrate with the alignment film was measured for the optical films produced in examples 20 and 21 by the method described above. The results are shown in table 6 below. In table 6 below, "a" indicates that the tilt angle is less than 7.0 °.

[ Table 6]

Examples 22 to 26 and comparative examples 8 to 9

An optical film including a front a plate was produced in the same manner as in example 18, except that the method for forming a front a plate was changed to the method and composition described below.

< formation of Positive A plate >

The following composition was applied to a substrate with an alignment film by spin coating. The coating film formed on the substrate with the alignment film was heated at 150 ℃ with warm air, and then cooled to 60 ℃ and irradiated with 10mJ/cm of light having a wavelength of 365nm using a high-pressure mercury lamp under a nitrogen atmosphere²Then irradiating the coating film with 500mJ/cm of ultraviolet light while heating to 120 ℃²Thereby fixing the alignment of the liquid crystal compound, and an optical film including a positive a plate was produced.

In the structural formulae of the polymerizable liquid crystal compound L-4 and the polymerizable liquid crystal compound L-5 shown below, a group adjacent to an acryloyloxy group represents a propylene group (a group in which a methyl group is substituted with an ethylene group), and the polymerizable liquid crystal compounds L-4 and L-5 represent a mixture of positional isomers in which the positions of the methyl groups are different.

Polymerizable liquid Crystal Compound L-4

[ chemical formula 53]

Polymerizable liquid Crystal Compound L-5

[ chemical formula 54]

The tilt angles of the positive a plate on the substrate with the alignment film were measured for the optical films produced in examples 22 to 26 and comparative examples 8 to 9 by the above-described method. The results are shown in table 7 below. In table 7 below, "a" indicates an inclination angle of less than 7.0 °, "B" indicates an inclination angle of 7.0 ° or more and less than 9.3 °, and "D" indicates an inclination angle of 10.0 ° or more.

[ Table 7]

In Table 7, the structures of the compound A-1 and the like are shown in example 1 and the like, and the structure of the compound O-3 is shown below.

[ chemical formula 55]

Examples 27 to 61 and comparative examples 10 to 16

An optical film including a front a plate was produced in the same manner as in example 18, except that the method for forming a front a plate was changed to the method and composition described below.

< formation of Positive A plate >

Optical films including a front a plate were produced in the same manner as in example 22, except that the coating film was irradiated with ultraviolet rays at a temperature 35 ℃ lower than the phase transition temperature between the smectic phase and the nematic phase of the polymerizable liquid crystal compound shown in table 8.

The tilt angles of the positive a plate on the substrate with the alignment film were measured for the optical films produced in examples 27 to 61 and comparative examples 10 to 16 by the above-described method. The results are shown in table 8 below. In table 8 below, "a" indicates an inclination angle of less than 7.0 °, "B" indicates an inclination angle of 7.0 ° or more and less than 9.3 °, "C" indicates an inclination angle of 9.3 ° or more and less than 10.0 °, and "D" indicates an inclination angle of 10.0 ° or more.

[ Table 8]

In Table 8, the structures of the compound A-1 and the like are shown in example 1 and the like, and the structures of the polymerizable liquid crystal compound and the compounds O-3 and O-5 are shown below.

Polymerizable liquid Crystal Compound L-6

[ chemical formula 56]

Polymerizable liquid Crystal Compound L-7[ chemical formula 57]

Polymerizable liquid Crystal Compound L-8[ chemical formula 58]

Polymerizable liquid Crystal Compound L-9[ chemical formula 59]

Polymerizable liquid Crystal Compound L-10[ chemical formula 60]

Polymerizable liquid Crystal Compound L-11

[ chemical formula 61]

Polymerizable liquid Crystal Compound L-12

[ chemical formula 62]

Compound O-3

[ chemical formula 63]

Compound O-5

[ chemical formula 64]

Description of the symbols

10-optical film, 12-optically anisotropic layer, 14-oriented film, 16-support, 18-hard coat layer.