KR102477376B1 - Composition, optical film, and methods of producing the composition and the optical film - Google Patents

Abstract

[Problem] In a conventional composition (coating solution) obtained by dissolving a polymerizable liquid crystal compound used in the production of optical films included in polarizing plates, retardation plates, etc. in a solvent, the problem that precipitation of the polymerizable liquid crystal compound occurs in the coating solution there was
[Solution] A composition containing a polymerizable liquid crystal compound represented by formulas (2-1) and (2-2) and a solvent. m and n: an integer greater than or equal to 1; B: -CO-O- etc. E: -CO-O- etc. G: A divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms. A: A divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. F: An alkanediyl group having 1 to 12 carbon atoms. P: A hydrogen atom or a polymerizable group. W: A divalent aliphatic hydrocarbon group of 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group of 3 to 13 carbon atoms, a divalent aromatic hydrocarbon group of 6 to 20 carbon atoms, and the like. X: A divalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a divalent aromatic heterocyclic group having 3 to 20 carbon atoms.

Description

Composition and optical film and method for producing composition and optical film

The present invention relates to compositions and optical films and methods of making the compositions and optical films.

The display device includes members using optical films such as polarizing plates and retardation plates. As an optical film, for example, an optical film obtained by dissolving a polymerizable compound (trade name: LC242, manufactured by BASF) represented by the following formula in a solvent, applying a solution obtained by applying to a substrate, and then polymerizing the optical film is known.

[Non-Patent Literature]

[Non-Patent Document 1] Cordula Mock-Knoblauch, Olivier S. Enger, Ulrich D. Schalkowsky, "L-7 Novel Polymerisable Liquid Crystalline Acrylates for the Manufacturing of Ultrathin Optical Films", SID Symposium Digest of Technical Papers, 2006, 37 Vol, p. 1673

[Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2011-207765

In the conventional composition (coating solution) obtained by dissolving a polymerizable liquid crystal compound used in the production of optical films included in polarizing plates, retardation plates, etc. in a solvent, there was a problem that the polymerizable liquid crystal compound precipitated in the coating solution. It has been desired to improve the solubility of polymerizable liquid crystal compounds in solvents.

The present invention provides the following [1] to [10].

[1] A composition containing a polymerizable liquid crystal compound represented by formula (2-1), a polymerizable liquid crystal compound represented by formula (2-2), and a solvent.

[In formulas (2-1) and (2-2),

m11, m12, m21, m22 and n each independently represents an integer of 1 or greater.

B ¹¹ , B ¹² , B ²¹ and B ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

E ¹¹ , E ¹² , E ²¹ and E ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond.

G ¹¹ , G ¹² , G ²¹ and G ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, -R ³ , -OR ³ , It may be substituted with a cyano group or a nitro group, and -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. R ³ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

A ¹¹ , A ¹² , A ²¹ and A ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The contained hydrogen atom may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group, or a nitro group.

F ¹¹ , F ¹² , F ²¹ , and F ²² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with -OR ³ or a halogen atom; -CH ₂ - contained in the alkanediyl group may be substituted with -O- or -CO-.

P ¹¹ , P ¹² , P ²¹ and P ²² each independently represent a hydrogen atom or a polymerizable group. However, at least one of P ¹¹ and P ¹² is a polymerizable group, and at least one of P ²¹ and P ²² is a polymerizable group.

W each independently represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent aliphatic group having 1 to 13 carbon atoms At least two groups selected from the group consisting of a hydrocarbon group, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms are connected by a linking group, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group And the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group, or a nitro group.

X ¹¹ , X ²¹ and X ²² each independently represent a divalent aromatic group which may have a substituent.]

[2] The liquid crystal composition according to [1], wherein X ¹¹ , X ²¹ , and X ²² are each independently a divalent aromatic group having 10 to 30 π electrons, which may have a substituent.

[ ³ ] [ ¹ ] or [ ¹ ] or [ The composition described in 2].

[4] The composition according to any one of [1] to [3], wherein X ¹¹ , X ²¹ , and X ²² are divalent aromatic groups each independently having an aromatic heterocyclic group as a substituent and which may have a substituent.

[5] The composition according to any one of [1] to [3], wherein X ¹¹ , X ²¹ and X ²² are divalent aromatic heterocyclic groups which may each independently have a substituent.

[6] The composition according to [3] or [4], wherein the aromatic heterocyclic group is a benzothiazole group.

[7] The composition according to any one of [1] to [6], wherein G ¹¹ , G ¹² , G ²¹ and G ²² are trans-cyclohexane-1,4-diyl groups.

[8] W is a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 1 to 5 carbon atoms At least two groups selected from the group consisting of 13 divalent aliphatic hydrocarbon groups, 1 to 5 divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and 1 to 5 divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O- , -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S- CH ₂ -, -CH ₂ -S- or a group linked through an imide bond, and the hydrogen atoms included in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are halogen atoms, -R ³ , -OR The composition according to any one of [1] to [7], which may be substituted with ³ , a cyano group or a nitro group.

[9] The area value of the compound represented by formula (2-2) measured by high-performance liquid chromatography (HPLC) is the ratio of the compound represented by formula (2-1) and the compound represented by formula (2-2). The composition according to any one of [1] to [8], which is 0.01% or more and 50% or less with respect to the total area value.

[10] The composition according to any one of [1] to [9] further containing a polymerization initiator.

[11] An optical film formed from the composition according to any one of [1] to [10].

[12] An optical film containing a polymer of a polymerizable liquid crystal compound represented by formula (2-1) and a polymer of a polymerizable liquid crystal compound represented by formula (2-2).

[In formulas (2-1) and (2-2),

m11, m12, m21, m22 and n each independently represents an integer of 1 or greater.

B ¹¹ , B ¹² , B ²¹ and B ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

E ¹¹ , E ¹² , E ²¹ and E ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond.

G ¹¹ , G ¹² , G ²¹ and G ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, -R ³ , -OR ³ , It may be substituted with a cyano group or a nitro group, and -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. R ³ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

A ¹¹ , A ¹² , A ²¹ and A ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The contained hydrogen atom may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group, or a nitro group.

F ¹¹ , F ¹² , F ²¹ and F ²² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with -OR ³ or a halogen atom, and -CH ₂ - contained in the candiyl group may be substituted with -O- or -CO-.

P ¹¹ , P ¹² , P ²¹ and P ²² each independently represent a hydrogen atom or a polymerizable group. However, at least one of P ¹¹ and P ¹² is a polymerizable group, and at least one of P ²¹ and P ²² is a polymerizable group.

Each W independently represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent hydrocarbon group having 1 to 13 carbon atoms. At least two groups selected from the group consisting of an aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms are connected by a linking group, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group The hydrogen atom contained in the group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group, or a nitro group.

X ¹¹ , X ²¹ and X ²² each independently represent a divalent aromatic group which may have a substituent.]

[13] A color filter comprising the optical film according to [11] or [12].

[14] A polarizing plate comprising the optical film according to [11] or [12].

[15] A liquid crystal display device comprising the color filter according to [13] or the polarizing plate according to [14].

According to the composition of the present invention, a composition having improved solubility of a polymerizable liquid crystal compound in a solvent can be obtained. In addition, by controlling the content of the polymerizable liquid crystal compound included in the composition, the wavelength dispersion characteristics of the optical film obtained by polymerizing the composition can be arbitrarily adjusted.

1 is a schematic diagram showing an example of a color filter.
2 is a schematic diagram showing an example of a liquid crystal display device according to the present invention.
3 is a schematic diagram showing an example of a polarizing plate according to the present invention.

The composition of the present invention (hereinafter sometimes referred to as composition (1)) is a compound represented by formula (2-1) and a compound represented by formula (2-2) (hereinafter, respectively, compound (2-1) , sometimes referred to as compound (2-2)) and a solvent. Since the composition of the present invention contains the polymerizable liquid crystal compound represented by the formula (2-2) in addition to the polymerizable liquid crystal compound represented by the formula (2-1), the formula (2-1) for the solvent ) It becomes possible to increase the solubility of the polymerizable liquid crystal compound represented by.

[In formulas (2-1) and (2-2),

m11, m12, m21, m22 and n each independently represents an integer of 1 or greater.

B ¹¹ , B ¹² , B ²¹ and B ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

E ¹¹ , E ¹² , E ²¹ and E ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond.

G ¹¹ , G ¹² , G ²¹ and G ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, -R ³ , -OR ³ , It may be substituted with a cyano group or a nitro group, and -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. R ³ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

A ¹¹ , A ¹² , A ²¹ and A ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The contained hydrogen atom may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group, or a nitro group.

F ¹¹ , F ¹² , F ²¹ and F ²² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with -OR ³ or a halogen atom, and -CH ₂ - contained in the candiyl group may be substituted with -O- or -CO-.

P ¹¹ , P ¹² , P ²¹ and P ²² each independently represent a hydrogen atom or a polymerizable group. However, at least one of P ¹¹ and P ¹² is a polymerizable group, and at least one of P ²¹ and P ²² is a polymerizable group.

Each W independently represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent hydrocarbon group having 1 to 13 carbon atoms. At least two groups selected from the group consisting of an aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms are connected by a linking group, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group The hydrogen atom contained in the group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group, or a nitro group.

X ¹¹ , X ²¹ and X ²² each independently represent a divalent aromatic group which may have a substituent.]

From the viewpoint of easy synthesis of compound (2-1), m11 and m12 are preferably the same number, and from the viewpoint of easy synthesis of compound (2-2), m21 and m22 are preferably the same number. It is more preferable that all of m11, m12, m21, and m22 are the same number from the point that composition (1) can be manufactured by fewer steps.

In view of the excellent liquid crystallinity of compounds (2-1) and (2-2), m11, m12, m21 and m22 are preferably 0 to 2, more preferably 1.

In view of the excellent liquid crystallinity of the compound (2-2), n is preferably 1 to 2, and more preferably 1.

Also, the sum of m11 and m12 is preferably 1 to 6, and the sum of m21, m22 and n is preferably 1 to 6.

B ¹¹ , B ¹² , B ²¹ and B ²² are each independently -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹ -, -NR ² -CO-, - CH ₂ -O-, -O-CH ₂ -, -CH ₂ -S-, -S-CH ₂ - or preferably a single bond, more preferably -O-CO- or -CO-O- .

From the viewpoint of easy synthesis of compound (2-1), when a plurality of B ¹¹ and B ¹² are present, the plurality of B ^11s are preferably the same group, and the plurality of B ^12s are preferably the same group. Similarly, from the standpoint of easy synthesis of compound (2-2), when a plurality of B ²¹ and B ²² are present, the plurality of B ^21s are preferably the same group, and the plurality of B ^22s are preferably the same group. Further, B ¹¹ and B ¹² are more preferably the same group, and B ²¹ and B ²² are more preferably the same group. It is particularly preferable that all of B ¹¹ , B ¹² , B ²¹ and B ²² are the same group from the point that the composition (1) can be manufactured by fewer steps.

Examples of the C1-C4 alkyl group represented by R ¹ , R ² and R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a tert-butyl group. A C1-C2 alkyl group is preferable, and a methyl group is more preferable.

E ¹¹ , E ¹² , E ²¹ and E ²² are each independently -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹ -, -NR ² -CO-, - CH ₂ -O-, -O-CH ₂ -, -CH ₂ -S-, -S-CH ₂ - or preferably a single bond, more preferably -O-CO- or -CO-O- .

In terms of easy synthesis of compound (2-1), E ¹¹ and E ¹² are preferably the same group. From the viewpoint of easy synthesis of compound (2-2), it is preferable that E ²¹ and E ²² are the same group. It is more preferable that all of E ¹¹ , E ¹² , E ²¹ and E ²² are the same group from the point that the composition (1) can be manufactured by fewer steps.

The divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms represented by G ¹¹ , G ¹² , G ²¹ and G ²² each independently includes a hetero atom represented by any of formulas (g-1) to (g-10), A divalent alicyclic hydrocarbon group is preferable, and an alicyclic hydrocarbon group having a 5-membered ring or a 6-membered ring represented by any of formulas (g-1) to (g-4) is more preferable, and the formula (g-1) ) is more preferred, a cyclohexane-1,4-diyl group is particularly preferred, and a trans-cyclohexane-1,4-diyl group is particularly preferred.

[The hydrogen atom in the group represented by the formulas (g-1) to (g-10) is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group; alkoxy groups having 1 to 4 carbon atoms, such as a methoxy group and an ethoxy group; C1-C4 fluoroalkyl groups, such as a trifluoromethyl group; a fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; cyano group; nitro group; It may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.]

From the viewpoint of facilitating synthesis of compound (2-1), G ¹¹ and G ¹² are preferably the same group. From the viewpoint of facilitating synthesis of compound (2-2), G ²¹ and G ²² are preferably the same group. It is more preferable that all of G ¹¹ , G ¹² , G ²¹ and G ²² are the same group from the point that the composition (1) can be manufactured by fewer steps.

The divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms represented by A ¹¹ , A ¹² , A ²¹ and A ²² is preferably a group independently represented by any one of formulas (g-1) to (g-10), It is more preferably an alicyclic hydrocarbon group having a 5-membered ring or a 6-membered ring represented by any of formulas (g-1) to (g-4), more preferably a group represented by formula (g-1), and cyclohexane A -1,4-diyl group is particularly preferred, and a trans-cyclohexane-1,4-diyl group is particularly preferred.

The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A ¹¹ , A ¹² , A ²¹ and A ²² is preferably a group independently represented by any of the following formulas (a-1) to (a-8), and The group represented by (a-1) is preferable, and p-phenylene group is more preferable.

[Some of the hydrogen atoms of the groups represented by the formulas (a-1) to (a-8) are alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, and tert-butyl groups; alkoxy groups having 1 to 4 carbon atoms, such as a methoxy group and an ethoxy group; trifluoromethyl group; trifluoromethyloxy group; cyano group; nitro group; It may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.]

From the viewpoint of easy synthesis of compound (2-1), when a plurality of A ¹¹ and A ¹² are present, the plurality of A ¹¹ groups are preferably the same group, and the plurality of A ¹² groups are preferably the same group. Similarly, from the viewpoint of easy synthesis of compound (2-2), when a plurality of A ²¹ and A ²² are present, the plurality of A ^21s are preferably the same group, and the plurality of A ^22s are preferably the same group. Further, A ¹¹ and A ¹² are more preferably the same group, and A ²¹ and A ²² are more preferably the same group. It is particularly preferable that all of A ¹¹ , A ¹² , A ²¹ and A ²² are the same group from the point that the composition (1) can be manufactured by fewer steps.

Alkanediyl groups having 1 to 12 carbon atoms represented by F ¹¹ , F ¹² , F ²¹ and F ²² are each independently -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₇ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₉ -, -(CH ₂ ) ₁₀ -, -(CF ₂ ) ₄ -, -( CF ₂ ) ₆ - and -(CF ₂ ) ₈ - are preferable, and -(CH ₂ ) ₄ - or -(CH ₂ ) ₆ - are more preferable.

From the viewpoint of facilitating synthesis of compound (2-1), F ¹¹ and F ¹² are preferably the same group. From the point that the synthesis|combination of compound (2-2) is easy, it is preferable that F<^21> and F< ²² > are the same group. It is more preferable that all of F ¹¹ , F ¹² , F ²¹ and F ²² are the same group from the point that the composition (1) can be manufactured by fewer steps.

P ¹¹ , P ¹² , P ²¹ and P ²² each independently represent a hydrogen atom or a polymerizable group, at least one of P ¹¹ and P ¹² is a polymerizable group, and at least one of P ²¹ and P ²² is a polymerizable group, the composition It is preferable that all of P11, ^P12 , ^P21 , and ^P22 are polymeric groups from the point that the film hardness of the optical film obtained from ( ¹ ) is excellent. It is more preferable that all of P ¹¹ , P ¹² , P ²¹ and P ²² are the same polymerizable group.

The polymerizable group may be a group capable of participating in the polymerization reaction of the polymerizable liquid crystal compound included in the composition (1) of the present invention, and is a vinyl group, a vinyloxy group, a styryl group, or a p-(2-phenylethenyl)phenyl group. , acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxy group, acetyl group, hydroxyl group, carbamoyl group, N-alkylamino group having 1 to 4 carbon atoms, amino group, oxiranyl group, oxeta A nyl group, a formyl group, an isocyanato group, an isothiocyanato group, etc. are mentioned. P ¹¹ , P ¹² , P ²¹ and P ²² are preferably groups bonded to F ¹¹ , F ¹² , F ²¹ and F ²² via an ether bond or an ester bond, respectively. In view of being suitable for photopolymerization, a radical polymerizable group or a cationic polymerizable group is preferable. Among them, from the viewpoint of easy handling and easy production of compounds (2-1) and (2-2), P ¹¹ , P ¹² , P ²¹ and P ²² each independently represent an acryloyloxy group or a meta A acryloyloxy group is preferable, and an acryloyloxy group is more preferable.

W, when a plurality of W exists, are each independently a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 1 to 13 carbon atoms. 2 selected from the group consisting of 5 divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms, 1 to 5 divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and 1 to 5 divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms A group in which the above groups are linked via a linking group is preferable. The linking group is -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(= S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ¹ -CO-, -O-CH ₂ -, -CH ₂ -O -, -S-CH ₂ -, -CH ₂ -S-, or an imide bond is preferable, and -O-, -CO-O-, or -O-CO- is more preferable. A hydrogen atom contained in a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms is a halogen atom, -R ³ , -OR ³ , It may be substituted with a cyano group or a nitro group.

1 to 5 divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms, 1 to 5 divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and 1 to 5 divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms The number of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups in which two or more groups are linked via a linking group is preferably 2 or more and 10 or less in total, and more preferably 2 or more and 6 or less.

The divalent aliphatic hydrocarbon group of 1 to 13 carbon atoms and the divalent alicyclic hydrocarbon group of 3 to 13 carbon atoms of W are preferably groups represented by formulas (W-1) to (W-19). The divalent aromatic hydrocarbon group of 6 to 20 carbon atoms of W is preferably a group represented by any one of formulas (W-20) to (W-25).

Among them, W preferably has a group represented by formula (W-4) or formula (W-20), more preferably has a cyclohexane-1,4-diyl group, trans-cyclohexane-1, Those having a 4-diyl group are more preferred. From the viewpoint that the synthesis of compound (2-2) is easy, when a plurality of W's are present, it is preferable that the plurality of W's are the same group.

X ¹¹ , X ²¹ and X ²² each independently represent a divalent aromatic group which may have a substituent. In view of the ease of synthesis of compound (2-2), when a plurality of X ^21s are present, the plurality of X ^21s are preferably the same group, and more preferably, X ²¹ and X ²² are the same group.

In view of the excellent liquid crystallinity of compounds (2-1) and (2-2), it is preferable that X ¹¹ , X ²¹ and X ²² each independently represent an aromatic group having 10 to 30 π electrons. X ¹¹ , X ²¹ and X ²² may each independently have a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. It is preferable that it is one or more, and, as for the number of hetero atoms, it is more preferable that it is two or more. Usually, the number of heteroatoms is 4 or less. When X ¹¹ , X ²¹ and X ²² have a hetero atom, X ¹¹ , X ²¹ and X ²² may be a divalent aromatic heterocyclic group which may have a substituent or a divalent aromatic group having an aromatic heterocyclic group. It is preferable that the said aromatic heterocyclic group is a benzothiazole group.

Here, the aromatic group is a divalent group derived from an aromatic heterocyclic compound, and may be a group having a structure in which an aromatic ring is condensed with a 1,4-phenylene group, and the aromatic ring may be a 5- or 6-membered ring.

When X ¹¹ , X ²¹ and X ²² are divalent aromatic heterocyclic groups which may have substituents, the number of π electrons contained in X ¹¹ , X ²¹ and X ²² is preferably 8 or more, respectively, and preferably 16 or more, respectively. More preferably, it is 22 or less normally respectively. X ¹¹ , X ²¹ and X ²² may be a divalent group represented by formula (X-1).

[In Formula (X-1), Z ¹ and Z ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Q ¹ represents -CR ⁴ R ⁵ -, -S-, -NR ⁴ -, -CO- or -O-.

Q ² represents -CR ⁴ = or -N=.

R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Y ¹ represents a monovalent aromatic hydrocarbon group or monovalent aromatic heterocyclic group which may have a substituent.

* indicates the number of bonds.]

In view of the excellent liquid crystallinity of compounds (2-1) and (2-2), at least one of the alkyl groups of 1 to 6 carbon atoms represented by Z ¹ and Z ² is a branched chain alkyl group of 3 to 6 carbon atoms. preferred, and a tert-butyl group is more preferred. As a C1-C6 alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, tert- butyl group etc. are mentioned. More preferably, Z ¹ is a branched chain alkyl group of 3 to 6 carbon atoms, and Z ² is a hydrogen atom, or Z ² is a branched chain alkyl group of 3 to 6 carbon atoms, and Z ¹ is a hydrogen atom.

In view of the excellent liquid crystallinity of compound (2-1) and compound (2-2), Q ¹ is each independently -S-, -NH-, -N(CH ₃ )-, or -O-. desirable. Q ² is preferably -N=. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ and R ⁵ in Q ¹ and Q ² include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a tert-butyl group.

From the viewpoint that the optical properties of the optical film formed from the composition (1) are excellent, Y ¹ is preferably any of the groups represented by the following formulas (Y ³ -1) to (Y ³ -3), and the formula ( A group represented by Y ³ -3) is more preferable.

[In formula (Y ³ -1) to (Y ³ -3),

Each of Z ³ independently represents a hydrogen atom, a halogen atom, -R ⁸ , a cyano group, a nitro group, -SO ₂ R ⁶ , -SOR ⁶ , -SR ⁶ , -OR ⁶ , a carboxy group, or -NR ⁴ R ⁷ . Each Z ³ may be the same or different.

R ⁶ represents an alkyl group having 1 to 6 carbon atoms.

R ⁷ represents an alkyl group having 1 to 4 carbon atoms.

R ⁸ represents an alkyl group having 1 to 6 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

J ³ represents -CR ¹ R ² -, -S-, -NR ² -, -CO- or -O-.

R ¹ , R ² and R ⁴ each have the same meaning as described above.

* indicates the number of bonds.]

Examples of the C1-C6 alkyl group represented by R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group and a tert-butyl group. Examples of the C1-C4 alkyl group represented by R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a tert-butyl group. As a C1-C6 alkyl group represented by ^R8 , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a tert-butyl group, etc. are mentioned.

Examples of the substituent that Y ¹ may have include a halogen atom, -R ⁶ , a cyano group, a nitro group, -SO ₂ R ⁴ , -SOR ⁴ , -SR ⁴ , -OR ⁴ , a carboxy group, or -NR ¹ R ⁵ have.

When X ¹¹ , X ²¹ and X ²² are divalent aromatic groups having aromatic heterocyclic groups as substituents, the aromatic groups may be divalent groups derived from the above-mentioned aromatic groups or aromatic heterocyclic compounds containing heteroatoms. In this case, the aromatic heterocyclic group serves as a substituent for the divalent aromatic group. The aromatic heterocyclic group more preferably has one or more hetero atoms such as a nitrogen atom, an oxygen atom, and a sulfur atom, and still more preferably has two or more. Usually, the number of heteroatoms is 7 or less. The aromatic heterocyclic group is preferably a group represented by the following formula (X-2), and is preferably a benzothiazole group.

[In Formula (X-2), Z ³ and Z ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Q ³ represents -CR ⁴ R ⁵ -, -S-, -NR ⁴ -, -CO- or -O-.

Q ⁴ represents -CR ⁴ = or -N=.

Y ² represents -S-, -NR ⁶ -, -NR ⁶ -N=CR ⁴ - or -O-.

R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A carbon atom constituting the alkyl group may be substituted with a secondary amino group, an oxygen atom, or a sulfur atom, and a hydrogen atom constituting the alkyl group may be substituted with -O-(C ₂ H ₄ O) _n -R ⁷ . n represents an integer of 0 to 4, and R ⁷ represents an alkyl group having 1 to 10 carbon atoms.

* indicates the number of bonds.]

In composition (1), since the solubility of compound (2-1) in a solvent is further improved, the area value of compound (2-2) measured by high performance liquid chromatography (HPLC) is It is preferably 0.01% or more and 50% or less, more preferably 0.01% or more and 30% or less, and still more preferably 0.01% or more and 20% or less with respect to the sum of the area values of 1) and compound (2-2). In the present specification, as the method of HPLC, the method described in the Examples described later can be exemplified.

According to the present invention, when compounds (2-1) and (2-2) are dissolved in N-methylpyrrolidone at, for example, 25°C, compared to the case where only compound (2-1) is dissolved, Compound (2-1) dissolves 1.05 times or more.

*-O-CO-G ¹¹ -E ¹¹ -(A ¹¹ -B ¹¹ ) _m11 -F ¹¹ -P ¹¹ , *-O-CO-G in formulas (2-1) and (2-2) ¹² -E ¹² -(A ¹² -B ¹² ) _m12 -F ¹² -P ¹² , *-O-CO-G ²¹ -E ²¹ -(A ²¹ -B ²¹ ) _m21 -F ²¹ -P ²¹ , *-O Specific examples of -CO-G ²² -E ²² -(A ²² -B ²² ) _m22 -F ²² -P ²² include groups represented by formulas (R-1) to (R-104). * (asterisk) indicates the number of bonds to X ¹¹ , X ²¹ , or X ²² . n in Formulas (R-1) to (R-104) represents an integer of 2 to 12. The cyclohexane ring may be either trans or cis, but is preferably trans.

Among the specific examples, (R-1) to (R -40) is preferred, and a group represented by any of (R-1) to (R-36) is more preferred.

When E ¹¹ is -O-CO- and E ¹² is -CO-O-, compound (2-1) can also be represented by the following formula (2-1)'. That is, B' represents *-O-(A ¹¹ -B ¹¹ ) _m11 -F ¹¹ -P ¹¹ and *-O-(A ¹² -B ¹² ) _m12 -F ¹² -P ¹² , and C' represents *- CO-G ¹¹ -CO-OX ¹¹ -O-CO-G ¹² -CO-*. B' and C' include structures represented by any of formulas (B-1) to (B-8) and formulas (C-1) to (C-200) described below, respectively. * represents a connecting portion, and for example, compound (2-1)' represented by a combination of formula (B-1) and formula (C-1) is a compound represented by the following formula (2-1-1).

Below, the structures of Formulas (B-1) to (B-8) are shown.

Below, the structures of Formulas (C-1) to (C-200) are shown.

The manufacturing method of composition (1) is demonstrated.

Compound (2-1) and compound (2-2) contained in composition (1) are known organic synthesis reactions described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lecture, etc. (e.g., condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buch Wald-Hartwig reaction, Friedel-Crafts reaction, Heck reaction, Aldol reaction, etc.) can be prepared by appropriately combining them according to the structures of compounds (2-1) and (2-2).

In particular, P ¹¹ , P ¹² , P ²¹ and P ²² are the same group (P), F ¹¹ , F ¹² , F ²¹ and F ²² are the same group (F), and B ¹¹ , B ¹² , B ²¹ and B ²² are the same group (B), A ¹¹ , A ¹² , A ²¹ and A ²² are the same group (A), E ¹¹ , E ¹² , E ²¹ and E ²² are the same group (E), and G ¹¹ , G ¹² , G ²¹ and G ²² are the same group (G), X ¹¹ , X ²¹ and X ²² are the same group (X), and m11, m12, m21 and m22 are the same number (m), the composition (1 The compound (2-1) and compound (2-2) contained in ) are compounds represented by the following formula (1-1) (hereinafter sometimes referred to as compound (1-1)) and formula (1- Reaction of the compound represented by 2) (hereinafter sometimes referred to as compound (1-2)) and the compound represented by formula (1-3) (hereinafter sometimes referred to as compound (1-3)) can be obtained easily by

In the formulas (1-1), (1-2) and (1-3), B, E, G, A, F, m, P, W, and X each have the same meaning as above.

The amount of compound (1-2) used in the reaction to obtain compound (2-1) and compound (2-2) contained in composition (1) is 0.01 parts by mass per 100 parts by mass of compound (1-1). It is preferably 30 parts by mass or more and more preferably 0.1 part by mass or more and 10 parts by mass or less. The amount of compound (1-3) used to obtain composition (1) is preferably 1 part by mass or more and 70 parts by mass or less, and 10 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of compound (1-1). it is more preferable

The reaction of compounds (1-1) to (1-3) is preferably carried out in the presence of a condensing agent.

As the condensing agent, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide-metho-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) )carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (some water soluble carbodiimides; commercially available as WSC), bis(2,6-diisopropylphenyl)carbodiimide , carbodiimides such as bis(trimethylsilyl)carbodiimide, N,N'-diisopropylcarbodiimide, 2-methyl-6-nitrobenzoic acid anhydride, 2,2'-carbonylbis-1H-imide dazole, 1,1'-oxalyldiimidazole, diphenylphosphorylazide, 1(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazol-1-yloxy Citripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N -Succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzoxysuccinimide, O- (6- Chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N' , N'-tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3 -Dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para - Toluenesulfonate, trichloroacetic acid pentachlorophenyl ester, etc. are mentioned.

In terms of reactivity, cost, and the number of solvent options that can be used, condensing agents include dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 1-ethyl-3-( 3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, N,N'-diisopropylcarbodiimide, 2,2 '-Carbonylbis-1H-imidazole is preferred.

[solvent]

Composition (1) contains a solvent. The solvent may be any solvent capable of dissolving the solid content in the composition (1) and inactive to the polymerization reaction, such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, etc. of alcohol solvent; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents, such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; non-chlorinated aromatic hydrocarbon solvents such as toluene, xylene and phenol; nitrile solvents such as acetonitrile; ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran, and dimethoxyethane; chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; phenol; Amide solvents, such as N-methylpyrrolidone, etc. are mentioned. A solvent may be used individually or may be used combining plurality. Since the composition (1) has excellent compatibility and is soluble in alcohol solvents, ester solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon solvents, and non-chlorinated aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents such as chloroform are not used, You can unveil.

The content of the solvent is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass, based on the total amount of the composition (1).

Conversely, the concentration of the solid content in the composition of the present invention is preferably 2 to 50 parts by mass, more preferably 5 to 50 parts by mass, based on the total amount of the composition (1). It is preferable that the concentration of the solid content is 2 parts by mass or more in that the optical film obtained from the composition (1) does not become too thin and an optical film having birefringence necessary for optical compensation of a liquid crystal panel can be easily obtained. Moreover, it is preferable that the concentration of solid content is 50 parts by mass or less from the point that the viscosity of the composition does not become too small and unevenness in the film thickness of the optical film becomes difficult to occur. On the other hand, the solid content means the amount excluding the solvent from the composition (1).

From the point of making it difficult for the nonuniformity of the film thickness of an optical film to occur, the viscosity of the composition (1) is preferably 0.1 to 10 mPa·s, and more preferably 0.1 to 7 mPa·s. It is preferable to select the type and amount of the solvent so as to be within this range.

[liquid crystal compound (A)]

Composition (1) is a liquid crystal compound other than compound (1-1) and compound (1-2) (hereinafter referred to as “liquid crystal compound (A)) in that it is easy to adjust the optical properties of an optical film obtained from composition (1). ”) is preferably contained.

As specific examples of such a liquid crystal compound (A), Chapter 3 of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editing Committee, Maruzen Co., Ltd., issued on October 30, 2000), Chapter 3 molecular structure and liquid crystal, 3.2 non-chiral rod-shaped liquid crystal molecules, 3.3 Compounds described in chiral rod-shaped liquid crystal molecules, compounds described in Japanese Unexamined Patent Publication No. 2010-31223, and the like are exemplified. Especially, the liquid crystal compound which has a polymeric group is preferable. The liquid crystal compound (A) may be used alone or in combination of two or more. As for compound (A), the following compounds are preferable.

When the composition (1) contains the liquid crystal compound (A), the content of the liquid crystal compound (A) is, for example, 0.01 to 90 parts by mass, preferably 0.01 to 70 parts by mass, based on 100 parts by mass of the solid content in the composition (1). It is a mass part, More preferably, it is 0.01-40 mass parts.

In this specification, compound (2-1), compound (2-2), and liquid crystal compound (A) may be collectively referred to as a liquid crystal compound component.

[Polymerization initiator]

The composition (1) preferably contains a polymerization initiator. The polymerization initiator preferably contains a photopolymerization initiator, and as the photopolymerization initiator, a photopolymerization initiator that generates radicals upon irradiation with light is preferable.

Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts and sulfonium salts.

Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether etc. are mentioned as a benzoin compound.

Examples of the benzophenone compound include benzophenone, o-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxy carbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As the alkylphenone compound, α,α-diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxy-1-eta Non, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl- Oligomers of 1-[4-(1-methylvinyl)phenyl]propan-1-one; etc. are mentioned.

Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

As a triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4 -bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) tenyl] -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. can be heard

As the photopolymerization initiator, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (above, all manufactured by Chiba Japan Co., Ltd.), Say Quol BZ, SeiQuol Z, SeiQuol BEE (above, all manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nihon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Corporation) ), Adeka Optoma SP-152 or Adeka Optoma SP-170 (above, all manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, manufactured by Nippon Siever Hegna Co., Ltd.), TAZ-104 (Sanwa Chemical) commercially available photopolymerization initiators such as) can also be used.

An alkylphenone compound is preferable as the photopolymerization initiator from the viewpoint of increasing the heat resistance and heat-and-moisture resistance of the obtained optical film. Among them, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one is more preferable.

When the composition (1) contains a polymerization initiator, the content of the polymerization initiator in the composition (1) is 0.1 part by mass to 30 parts by mass, preferably 0.5 part by mass to 10 parts by mass, based on 100 parts by mass of the solid content. is the mass part.

[Photosensitizer]

Composition (1) may contain a photosensitizer. As the photosensitizer, xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.), anthracene compounds having substituents such as anthracene or alkoxy group, etc. compounds (for example, dibutoxy anthracene, etc.), phenothiazine, or rubrene; and the like.

When the composition (1) contains a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound component contained in the composition (1) is carried out with high sensitivity, or the stability over time of the optical film obtained by polymerization is improved. can do. Moreover, when composition (1) contains a photosensitizer, as content of a photosensitizer, it is 0.1 mass part - 30 mass parts with respect to 100 mass parts of solid content, Preferably they are 0.5 mass part - 10 mass parts.

[Polymerization inhibitor]

The composition (1) may contain a polymerization inhibitor. As the polymerization inhibitor, hydroquinone compounds having substituents such as hydroquinone or alkoxy groups, catechol compounds having substituents such as alkyl groups such as butylcatechol, pyrogallol compounds, 2,2,6,6-tetramethyl-1-pipe radical supplements such as lidinyloxy radicals, thiophenol compounds, β-naphthylamine compounds, and β-naphthol compounds; and the like.

When the polymerization inhibitor is included, polymerization of the polymerizable liquid crystal compound component included in the composition (1) can be easily controlled. When composition (1) contains a polymerization inhibitor, content of a polymerization inhibitor is 0.1 mass part - 30 mass parts with respect to 100 mass parts of solid content, Preferably they are 0.5 mass part - 10 mass parts.

[Leveling agent]

The composition (1) may contain a leveling agent. As the leveling agent, additives for radiation curing paints (manufactured by Big Chemie Japan: BYK-352, BYK-353, BYK-361 N), paint additives (manufactured by Toray Dow Corning Co., Ltd.: SH28PA, DC11PA, ST80PA), paints additives (manufactured by Shin-Etsu Kasei Kogyo Co., Ltd.: KP321, KP323, X22-161 A, KF6001), fluorine-based additives (manufactured by DIC Kabuki Kaishiya: F-445, F-470, F-479); and the like.

When a leveling agent is included, a smoother optical film can be obtained. In addition, in the manufacturing process of an optical film, the fluidity|liquidity of composition (1) can be controlled, or the crosslinking density in the obtained optical film can be adjusted. When the composition (1) contains a leveling agent, the content of the leveling agent is, for example, 0.01 part by mass to 30 parts by mass, preferably 0.05 part by mass to 10 parts by mass, more preferably based on 100 parts by mass of the solid content. It is preferably 0.05 to 1 part by mass.

The optical film of the present invention refers to a film formed from composition (1), that is, a film containing a polymer of compound (2-1) and a polymer of compound (2-2), and having an optical function. The optical function means refraction, birefringence, and the like. A retardation film, which is a type of optical film, is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or vice versa.

The optical film of the present invention has structural units derived from compound (2-1) and compound (2-2), and the wavelength dispersion characteristics of the optical film can be adjusted by appropriately changing the ratio of the structural units. Among all structural units included in the optical film, when the ratio of structural units derived from compound (2-1) and compound (2-2) increases, birefringence increases as the wavelength increases (so-called reverse wavelength dispersion characteristic). It tends to be easy.

When the desired reverse wavelength dispersion characteristic is imparted to the optical film, the compound (2-1) and the compound (2-2) in the composition (1) are prepared according to the procedures shown in (a) to (e) below. You just need to determine the content. Since the composition (1) of the present invention has improved solubility in solvents, the range of selectable reverse wavelength dispersion characteristics has widened.

(a) About 2 to 5 types of compositions (1) with different contents of compound (2-1) and compound (2-2) are prepared.

(b) Regarding each prepared composition (1), an optical film is manufactured with the same film thickness.

(c) The retardation value of the optical film obtained in (b) is obtained.

(d) Based on the retardation values obtained in (c), a correlation between the content of structural units derived from compounds (2-1) and (2-2) and the retardation values of the optical film is determined.

(e) Based on the correlation obtained in (d), the content of structural units derived from compounds (2-1) and (2-2) necessary for imparting a desired retardation value to the optical film at the above film thickness is determined. do.

The value obtained by dividing the phase difference value Re(λ) at a certain wavelength λ by the phase difference value Re(550) at 550 nm (Re(λ)/Re(550)) is a wavelength region close to 1, or [Re(450) )/Re(550)]<1 and in the wavelength region exhibiting reverse wavelength dispersion of [Re(650)/Re(550)]>1, the same polarization conversion is possible.

The optical film of the present invention is obtained by polymerizing the liquid crystal compound component contained in the composition (1) by applying the composition (1) to a substrate, drying, light irradiation and/or heating. When the composition (1) is applied and the dried film exhibits a liquid crystal phase such as a nematic phase, the resulting optical film exhibits birefringence due to monodomain orientation.

The film thickness of the optical film can be prepared by appropriately adjusting the content of the compounds (2-1) and (2-2) contained in the composition (1) or the amount of application of the composition (1) on the substrate. When the ratio of compound (2-1) and compound (2-2) is constant, the retardation value (retardation value, Re(λ)) of the obtained optical film is expressed by formula (7)

Re(λ)=d×Δn(λ) (7)

(In the formula, Re(λ) represents a phase difference value at a wavelength of λ nm, d represents a film thickness, and Δn(λ) represents a birefringence at a wavelength of λ nm.)

Since it is determined by , in order to obtain the desired Re(λ), the film thickness d and Δn(λ) may be adjusted.

Examples of the method for applying the composition (1) to the substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Further, a method of applying by a coater such as a dip coater, a bar coater, or a spin coater, and the like are exemplified.

As said base material, glass, a plastic sheet, a plastic film translucent film, etc. are mentioned. On the other hand, as the translucent film, polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylic acid ester films, polyacrylic acid ester films, cellulose ester films, polyethylene naphthalate A film, a polycarbonate film, a polysulfone film, a polyethersulfone film, a polyether ketone film, a polyphenylene sulfide film, a polyphenylene oxide film, etc. are mentioned.

The optical film of the present invention can be easily handled without tearing or the like by using the base material even in processes requiring strength of the optical film, such as a bonding process, a transportation process, and a storage process of the optical film.

When manufacturing the optical film of the present invention, it is preferable to apply the composition (1) on the orientation film after forming the alignment film on the substrate. The alignment film is preferably an alignment film having solvent resistance that does not dissolve in the composition (1) when the composition (1) is applied. Moreover, it is more preferable that the alignment film is an alignment film having heat resistance in removal of the solvent or heat treatment for alignment of the liquid crystal. It is more preferable that it is an alignment film in which peeling by friction etc. does not occur at the time of rubbing. As such an orientation film, it is preferable to consist of an orientation polymer or a composition containing an orientation polymer.

Examples of the orienting polymer include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule, and polyamic acid as a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and polyoxa. and polymers such as sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. These polymers may be used alone, or two or more kinds may be mixed or copolymerized. These polymers can be easily obtained by polycondensation by dehydration or deamination, chain polymerization such as radical polymerization, anionic polymerization or cationic polymerization, coordination polymerization or ring-opening polymerization.

In addition, these orientation polymers are usually dissolved in a solvent and used as a solution. As a solvent, it is water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, and ethylene glycol butyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents, such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran, and dimethoxyethane; chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; etc. can be mentioned. A solvent may be used individually or may be used combining plurality.

The alignment film may be formed using a commercially available alignment film material as it is. Examples of commercially available alignment film materials include Saneva (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optima (registered trademark, manufactured by JSR Corporation). When the commercially available alignment film is used, the in-plane variation of birefringence is reduced because there is no need to control the refractive index by stretching. Therefore, it is possible to provide a large optical film capable of responding to an increase in the size of a display device on a base material.

As a method of forming an alignment film on a substrate, for example, a method of applying a commercially available alignment film material or a compound to be an alignment film material as a solution onto the substrate, followed by annealing.

The thickness of the alignment film is usually 10 nm to 10000 nm, preferably 10 nm to 1000 nm. Within the above range, the polymerizable liquid crystal compound component can be aligned at a desired angle on the alignment layer.

If necessary, the alignment film may be subjected to a rubbing treatment or polarized UV irradiation may be applied to the alignment film, and the liquid crystal compound component can be aligned in a desired direction by such treatment. That is, the shape or inclination of the refractive index ellipsoid representing the birefringence state of the manufactured optical film can be adjusted. As a method of rubbing the alignment film, for example, a method in which a rubbing cloth is wound and a rotating rubbing roll is brought into contact with the alignment film conveyed on a stage is exemplified.

Methods, such as natural drying, ventilation drying, and vacuum drying, are mentioned as a method of removing a solvent. The drying temperature is preferably 0 to 250°C, more preferably 0 to 200°C, and still more preferably 30 to 190°C. Moreover, as drying time, 10 second - 60 minutes are preferable, and 30 second - 30 minutes are more preferable. If the drying temperature and drying time are within the above ranges, a substrate that does not necessarily have sufficient heat resistance can be used as the substrate.

After drying, by polymerizing the compound (2-1) and the compound (2-2) contained in the composition (1), an optical film having a fixed orientation of the polymerizable liquid crystal compound can be obtained. Since the orientation of the optical film of the present invention is fixed, it is not easily affected by birefringence by heat.

A method of polymerizing compound (2-1) and compound (2-2) contained in composition (1) may be appropriately determined depending on the types of compound (2-1) and compound (2-2). If the polymerizable groups of the compounds (2-1) and (2-2) are photopolymerizable, photopolymerization is applied, and if the polymerizable groups are thermally polymerizable, thermal polymerization is applied. The photopolymerization method is preferable in that an unpolymerized film can be polymerized at a low temperature, the selection range of heat resistance of the base material is widened, and the manufacturing process is industrially easy. Photopolymerization is performed by irradiating an unpolymerized film with visible light, ultraviolet light, or the like. From the viewpoint of ease of handling, ultraviolet light is preferred. Light irradiation is preferably carried out at a temperature at which compounds (2-1) and (2-2) take a liquid crystal phase. A patterned optical film can also be obtained by performing light irradiation after masking.

The birefringence Δn(λ) can be adjusted so as to impart a desired phase difference by appropriately adjusting the exposure amount, heating temperature, and heating time during polymerization.

When an optical film is formed on the alignment film of a substrate having an alignment film, a laminated film of the alignment film and the optical film of the present invention can be obtained by peeling the substrate. Alternatively, the alignment film may be peeled off to obtain a film composed only of the optical film of the present invention.

The optical film obtained in this way is excellent in transparency and is suitably used as a film for various display devices. As described above, the thickness of the optical film varies depending on the retardation value of the optical film, but is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and 0.5 to 3 μm from the viewpoint of reducing photoelasticity. μm is particularly preferred. Thus, the film thickness of the optical film of the present invention can be made thinner than that of a stretched film in which a phase difference is imparted by stretching a polymer.

The retardation value of the optical film exhibiting birefringence is 50 to 500 nm, preferably 100 to 300 nm.

In this way, the optical film of the present invention capable of uniform polarization conversion in a wider wavelength range as a thin film can be used as an optical compensation film in a display device such as a liquid crystal panel or an organic EL panel.

The optical film of the present invention can be used as a broadband λ/4 plate or λ/2 plate. When used as a broadband λ/4 plate or λ/2 plate, the content of structural units derived from compounds (2-1) and (2-2) in the optical film is adjusted by the above method to reduce the film thickness. good to regulate When used for a λ/4 plate, Re (550) of the optical film is usually 113 to 163 nm, preferably 135 to 140 nm, and particularly preferably 137.5 nm. When used for a λ/2 plate, Re (550) of the optical film is usually 250 to 300 nm, preferably 273 to 277 nm, and particularly preferably 275 nm.

The optical film of the present invention can also be used as an optical film for VA (Vertical Alignment) mode. What is necessary is just to select content of the structural unit derived from the compound of this invention suitably, when using it as an optical film for VA mode. What is necessary is just to adjust the film thickness so that Re(550) of the optical film obtained may become preferably 40-100 nm, more preferably 60-80 nm.

The optical film of the present invention is also used in antireflection films such as anti-reflection (AR) films, polarizing films, retardation films, elliptically polarizing films, broadband circular polarizing films, viewing angle expansion films, and optical compensation films for viewing angle compensation of transmissive liquid crystal displays. can be used

Although the optical film of the present invention exhibits excellent optical properties even when used alone, a plurality of optical films may be laminated and used, or may be used in combination with other films. Specific examples in combination with other films include an elliptically polarizing plate in which the optical film of the present invention is bonded to a polarizing film, and a broadband circular polarizing plate in which the optical film of the present invention is bonded to a polarizing film as a broadband λ/4 plate.

Since the optical film of the present invention can be formed by coating and polymerization on a substrate or an alignment film, as shown in FIG. can form

Fig. 1 is a schematic diagram showing a color filter 1 according to the present invention.

The color filter 1 is a color filter formed by forming the optical film 2 of the present invention on the color filter layer 4 via the orientation film 3 .

An example of a method for manufacturing such a color filter 1 will be described. First, an orientation polymer is laminated on the color filter layer 4, and a rubbing treatment is performed to form an orientation film 3. Then, the composition (1) is applied on the obtained orientation film (3) to form an optical film (2).

In particular, α, which is the ratio of optically measured front retardation values [Re(450)/Re(550)] of the optical film, is obtained when only compound (2-1) is used, that is, when compound (2-2) is not included. In comparison, the case of using the composition (1) is lower by 0.001 or more.

By using such a color filter 1, it becomes possible to manufacture a thinner liquid crystal display device. As an example thereof, a schematic diagram showing a liquid crystal display device 5 according to the present invention is shown in FIG. 2 .

2 is a schematic diagram showing a liquid crystal display device according to the present invention.

In the liquid crystal display device 5 shown in FIG. 2 , a substrate 7 such as a glass substrate facing the backlight is fixed on the polarizing plate 6 with an adhesive. An optical film 2' is formed on the color filter layer 4' formed on the substrate 7 via an orientation film 3'. Further, a counter electrode 8 is formed on the optical film 2', and a liquid crystal layer 9 is formed on the counter electrode 8. In the configuration on the backlight side, a substrate 11 such as a glass substrate is fixed to the polarizing plate 10 with an adhesive, and a thin film transistor (TFT) for actively driving the liquid crystal layer 9 is attached to the substrate 11, and An insulating layer 12 is formed, and a transparent electrode and/or a reflective electrode 13 made of Ag, Al or ITO (Indium Tin Oxide) is formed on the TFT. The structure of the liquid crystal display device 5 shown in FIG. 2 is a structure with few optical films compared with the conventional liquid crystal display device, and manufacture of a thinner liquid crystal display device is attained.

The polarizing plate of the present invention is obtained by laminating the optical film of the present invention and a film having a polarizing function (polarizing film). Specifically, it is obtained by bonding the optical film of the present invention to one side or both sides of a polarizing film directly or using an adhesive agent. Such a polarizing plate can also be incorporated suitably into a liquid crystal display device. In this specification, an adhesive agent layer means both an adhesive bond layer and an adhesive layer, and what is necessary is just to select the preferable one suitably. Hereinafter, with reference to FIG. 3, the polarizing plate of this invention is demonstrated.

3(a) to 3(e) are schematic views showing an example of a polarizing plate according to the present invention.

In the polarizing plate 30a of the present invention shown in FIG. 3(a), the laminate 14 and the polarizing film 15 are directly bonded, and the laminate 14 includes the substrate 16, the alignment film ( 17) and the optical film 18 of the present invention. In the polarizing plate 30a, the substrate 16, the alignment film 17, the optical film 18 of the present invention, and the polarizing film 15 are laminated in this order.

In the polarizing plate 30b of the present invention shown in FIG. 3(b), the layered product 14 and the polarizing film 15 are bonded via the adhesive agent layer 19.

In the polarizing plate 30c of the present invention shown in Fig. 3(c), the laminate 14 and the laminate 14' are directly bonded, and the laminate 14' and the polarizing film 15 are directly bonded. are joined The layered product 14' consists of a substrate 16', an alignment film 17', and an optical film 18' of the present invention.

In the polarizing plate 30d of the present invention shown in FIG. 3(d), the laminate 14 and the laminate 14' are bonded via the adhesive layer 19, and the laminate 14' is The polarizing film 15 is directly bonded to it.

In the polarizing plate 30e of the present invention shown in FIG. 3(e), the laminate 14 and the laminate 14' are bonded via the adhesive layer 19, and the laminate 14' and the laminate 14' are bonded together. A configuration in which the polarizing film 15 is bonded through the adhesive agent layer 19' is shown.

The polarizing film 15 may be any film having a polarizing function, for example, a film obtained by adsorbing iodine or a dichroic dye to a polyvinyl alcohol-based film and then stretched, or a film obtained by stretching a polyvinyl alcohol-based film and adsorbing iodine or a dichroic dye. A film etc. are mentioned.

Example

Hereinafter, the present invention will be described in more detail with reference to examples.

"%" and "part" in the example are mass % and mass part unless otherwise indicated.

<HPLC measurement>

The HPLC measurement may be performed under any conditions as long as peaks derived from compounds (2-1) and (2-2) can be separated. An example of HPLC measurement conditions is shown below.

HPLC analysis was performed under the following measurement conditions by HPLC LC-10AT manufactured by Shimadzu Corporation equipped with a column (L-Column ODS, inner diameter: 3.0 mm, length: 150 mm, particle size: 3 µm).

(Measuring conditions)

Temperature: 40℃

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

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

Gradient: 0 min 70%-B

30 min 100%-B

60 min 100%-B

60.01 min 70%-B

75 min 70%-B

Flow rate: 0.5 mL/min

Injection volume: 5 μL

Detection wavelength: 254 nm

<Synthesis example of composition (1)>

(Example 1)

Composition (1) was prepared according to the following scheme. On the other hand, the compound represented by formula (1-1-1) (hereinafter sometimes referred to as compound (1-1-1)) is an example of compound (1-1), and formula (1-2-1) The compound represented by (hereinafter sometimes referred to as compound (1-2-1)) is an example of compound (1-2), and the compound represented by formula (1-3-1) (hereinafter, compound (1-2-1) -3-1) is an example of compound (1-3), and the compound represented by formula (2-1-2) (hereinafter sometimes referred to as compound (2-1-2)) ) is an example of compound (2-1), and the compound represented by formula (2-2-1) (hereinafter sometimes referred to as compound (2-2-1)) is an example of compound (2-2) to be.

79.6 g (190 mmol) of compound (1-1-1), 0.41 g (2.38 mmol) of compound (1-2-1), and 429 g of chloroform were mixed. The resulting liquid mixture was stirred at 60°C for 1 hour under a nitrogen atmosphere to dissolve compound (1-2-1). After that, the liquid mixture was cooled to 0°C.

30.0 g (96.4 mmol) of compound (1-3-1), 0.12 g (0.96 mmol) of N,N-dimethyl-4-aminopyridine, and 1.49 g (6.74 mmol) of dibutylhydroxytoluene were added to the mixture. 30.4 g (241 mmol) of diisopropylcarbodiimide was added dropwise to the liquid mixture while stirring at 0°C, and the mixture was kept warm at 0°C for 3 hours. The mixture was heated to 25°C, and 2.02 g (4.82 mmol) of compound (1-1-1) was added.

After spreading 5.34 g of silica gel on a filter, the liquid mixture was filtered to remove insoluble components. The obtained liquid mixture was added dropwise to normal heptane at a weight six times greater than the weight of chloroform contained in the liquid mixture, and kept warm at 25°C for 1 hour or more. Subsequently, after filtration was performed to remove the precipitated solid, drying was performed at 45°C to obtain 104.1 g of a composition (1-1). As a result of HPLC measurement, compound (2-2-1) was 3.45% in the obtained composition (1-1) with respect to the sum of the area values of compound (2-1-2) and compound (2-2-1). found to be included.

(Example 2)

79.6 g (190 mmol) of compound (1-1-1), 0.65 g (3.78 mmol) of compound (1-2-1), and 643 g of chloroform were mixed. The resulting liquid mixture was stirred at 60°C under a nitrogen atmosphere to dissolve compound (1-2-1). After that, the liquid mixture was cooled to 30°C. The liquid mixture was concentrated under reduced pressure, and 214 g of the solvent was distilled off. The obtained liquid mixture was cooled to 0°C.

30.0 g (96.4 mmol) of compound (1-3-1), 0.12 g (0.96 mmol) of N,N-dimethyl-4-aminopyridine, and 1.49 g (6.74 mmol) of dibutylhydroxytoluene were added to the mixture and mixed. did. 30.4 g (241 mmol) of diisopropyl carbodiimide was added dropwise to the liquid mixture while stirring at 0°C, and kept warm at 0°C for 3 hours. The mixture was heated to 25°C, and 2.02 g (4.82 mmol) of compound (1-1-1) was added.

After 5.34 g of silica gel was spread on a filter, the liquid mixture was filtered to remove insoluble components. The obtained liquid mixture was added dropwise to normal heptane at a weight six times greater than the weight of chloroform contained in the liquid mixture, and kept warm at 25°C for 1 hour or longer. Subsequently, after filtration was performed to remove the precipitated solid, drying was performed at 45°C to obtain 104.3 g of a composition (1-2). As a result of HPLC measurement, compound (2-2-1) was 6.48% in the obtained composition (1-2) with respect to the sum of the area values of compound (2-1-2) and compound (2-2-1). found to be included.

(Example 3)

Composition (1) was prepared according to the following scheme. On the other hand, the compound represented by formula (1-2-2) (hereinafter sometimes referred to as compound (1-2-2)) is an example of compound (1-2), and formula (2-2-2) The compound represented by (hereinafter sometimes referred to as compound (2-2-2)) is an example of compound (2-2).

13.0 g (31.2 mmol) of compound (1-1-1), 0.39 g (0.63 mmol) of compound (1-2-2), and 64.3 g of chloroform were mixed. The obtained liquid mixture was stirred at 60 degreeC for 1 hour in nitrogen atmosphere. After that, the liquid mixture was cooled to 0°C.

5.00 g (16.1 mmol) of compound (1-3-1), 0.020 g (0.16 mmol) of N,N-dimethyl-4-aminopyridine, and 0.25 g (1.12 mmol) of dibutylhydroxytoluene were added to the mixture. 5.07 g (40.1 mmol) of diisopropylcarbodiimide was added dropwise to the liquid mixture while stirring at 0°C, and kept warm at 0°C for 3 hours. The mixed solution was heated to 25°C, and 1.01 g (2.41 mmol) of compound (1-1-1) was added to the mixed solution.

After spreading 0.80 g of silica gel on a filter, the liquid mixture was filtered to remove insoluble components. The obtained liquid mixture was added dropwise to normal heptane at a weight six times greater than the weight of chloroform to contain, and kept warm at 25°C for 1 hour or more. Subsequently, after filtration was performed to remove the precipitated solid, drying was performed at 45°C to obtain 17.1 g of a composition (1-3). As a result of HPLC measurement, the compound (2-2-2) was 1.26% in the obtained composition (1-3) with respect to the sum of the area values of the compound (2-1-2) and the compound (2-2-2). found to be included.

(Example 4)

Composition (1) was prepared according to the following scheme. The compound represented by formula (1-2-3) (hereinafter sometimes referred to as compound (1-2-3)) is an example of compound (1-2), represented by formula (2-2-3), The losing compound (hereinafter sometimes referred to as compound (2-2-3)) is an example of compound (2-2).

13.0 g (31.2 mmol) of compound (1-1-1), 0.32 g (0.63 mmol) of compound (1-2-3), and 64.3 g of chloroform were mixed. The resulting liquid mixture was stirred at 60°C under a nitrogen atmosphere to dissolve compound (1-2-3). After that, the liquid mixture was cooled to 0°C.

5.00 g (16.1 mmol) of compound (1-3-1), 0.020 g (0.16 mmol) of N,N-dimethyl-4-aminopyridine, and 0.25 g (1.12 mmol) of dibutylhydroxytoluene were added to the mixture and mixed. did. Furthermore, 5.07 g (40.1 mmol) of diisopropylcarbodiimide was added dropwise to the liquid mixture while stirring at 0°C, and kept warm at 0°C for 3 hours. The mixed solution was heated to 25°C, and 1.01 g (2.41 mmol) of compound (1-1-1) was added to the mixed solution.

After 0.80 g of silica gel was spread on the filter, the mixture was filtered to remove insoluble components. The obtained liquid mixture was added dropwise to normal heptane at a weight six times greater than the weight of chloroform contained in the liquid mixture, and kept warm at 25°C for 1 hour or more. Subsequently, after filtration was performed to remove the precipitated solid, drying was performed at 45°C to obtain 17.3 g of a composition (1-4). As a result of HPLC measurement, compound (2-2-3) was 5.93% in the obtained composition (1-4) with respect to the sum of the area values of compound (2-1-2) and compound (2-2-3). found to be included.

(Example 5)

13.0 g (31.2 mmol) of compound (1-1-1), 0.83 g (1.60 mmol) of compound (1-2-3), and 64.3 g of chloroform were mixed. The resulting liquid mixture was stirred at 60°C under a nitrogen atmosphere to dissolve the compound represented by compound (1-2-3). After that, the liquid mixture was cooled to 0°C.

5.00 g (16.1 mmol) of compound (1-3-1), 0.020 g (0.16 mmol) of N,N-dimethyl-4-aminopyridine, and 0.25 g (1.12 mmol) of dibutylhydroxytoluene were added to the mixture and mixed. did. Furthermore, 5.07 g (40.1 mmol) of diisopropylcarbodiimide was added dropwise to the liquid mixture while stirring at 0°C, and kept warm at 0°C for 3 hours. The mixed solution was heated to 25°C, and 1.01 g (2.41 mmol) of compound (1-1-1) was added to the mixed solution.

After 0.80 g of silica gel was spread on the filter, the mixture was filtered to remove insoluble components. The obtained liquid mixture was added dropwise to normal heptane at a weight six times greater than the weight of chloroform contained in the liquid mixture, and kept warm at 25°C for 1 hour or longer. Subsequently, after filtration was performed to remove the precipitated solid, drying was performed at 45°C to obtain 17.2 g of a composition (1-5). As a result of the HPLC measurement, with respect to the sum of the area values of compound (2-1-2) and compound (2-2-3), the obtained composition (1-5) is represented by compound (2-2-3). It was found that 17.0% of the compound was included.

<Measurement of solubility of compound (2-1-2))>

Composition (1-1) was added to N-methylpyrrolidone cooled to 0°C until it was suspended, and stirred for 1 hour. Thereafter, the suspension was heated to 25°C and kept warm for 1 hour or more.

The supernatant of the suspension was subjected to HPLC measurement, the content of compound (2-1-2) in the supernatant was calculated, and the solubility of compound (2-1-2) in N-methylpyrrolidone was calculated. Solubility of compound (2-1-2) in N-methylpyrrolidone and compound (2-1-2), compound (2-2-1), compound (2-2) contained in composition (1-1) 2-2) and the relationship between the content ratio of the compound (2-2-3) is shown in Table 1.

In the same manner for composition (1-2) to composition (1-5) and composition (1-0) in which the ratio of compound (2-1-2) is 100%, the compound to N-methylpyrrolidone ( 2-1-2) was calculated. Solubility of compound (2-1-2) in N-methylpyrrolidone and compounds (2-1-2), compound (2-2-1) and compound (2-2-2) contained in each composition Table 1 shows the relationship with the content ratio of compound (2-2-3).

The solubility of compound (2-1-2) in N-methylpyrrolidone is a compound containing compound (2-2-1), compound (2-2-2), or compound (2-2-3). composition is higher. Although the groups represented by W in compound (2-2-1), compound (2-2-2) and compound (2-2-3) differ greatly in structure, in any case, compound (2-1 The solubility of -2) was improved. In addition, the solubility of compound (2-1-2) increases, so that the composition contains a large amount of compound (2-2-1) and compound (2-2-3).

(Example 6)

[Preparation of Composition for Forming Alignment Film]

The composition for alignment film formation (1) was obtained by mixing the following components and stirring the obtained mixture at 80 degreeC for 1 hour. The following photo-alignment material was synthesized by the method described in Japanese Unexamined Patent Publication No. 2013-33248.

Photo-Orientable Material (5 parts):

Solvent (95 parts): cyclopentanone

<Manufacture example of optical film>

A cycloolefin polymer film (COP) (ZF-14, manufactured by Nippon Zeon Co., Ltd.) was prepared by a corona treatment device (AGF-B10, manufactured by Kasuga Denki Co., Ltd.) at an output of 0.3 kW and a processing speed of 3 m/min. It was treated once under the condition of On the corona-treated surface, the alignment film-forming composition (1) is applied with a bar coater, dried at 80°C for 1 minute, and then placed in a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.). Then, polarized UV exposure was performed with a cumulative light amount of 100 mJ/cm ² . It was 100 nm when the film thickness of the obtained alignment film was measured with the laser microscope (LEXT, Olympus Corporation make). Subsequently, a composition (1-1-1) obtained by mixing the components shown in Table 2 was applied on the alignment film using a bar coater, dried at 120°C for 1 minute, and then dried by a high-pressure mercury lamp (Unicure VB-15201BY-A, An optical film was produced by irradiating ultraviolet rays (under a nitrogen atmosphere, wavelength: 365 nm, integrated light amount at a wavelength of 365 nm: 1000 mJ/cm ² ) by Ushio Denki Co., Ltd.).

(Example 7)

An optical film was produced in the same manner as in Example 6, except that the composition applied on the alignment film was the composition (1-2-1) shown in Table 2.

(Comparative Example 2)

An optical film was produced in the same manner as in Example 6, except that the composition applied on the alignment film was the composition (1-0-1) shown in Table 2.

LC242: Polymerizable liquid crystal manufactured by BASF, represented by the following formula

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

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

Additive: Polyfunctional isocyanate compound (Laromer LR9000; manufactured by BASF)

Solvent: N-methylpyrrolidone (NMP)

<Measurement of optical characteristics>

The front retardation value of the optical film was measured with a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). In addition, since the glass substrate used for the base material does not have birefringence, the front phase difference value of the optical film produced on the glass substrate can be obtained by measuring the film provided with the glass substrate with a measuring instrument. The obtained optical measurement front retardation values were measured at wavelengths of 450 nm, 550 nm and 627 nm, respectively, [Re (450) / Re (550)] (referred to as α) and [Re (627) / Re (550) ] (referred to as β) was calculated. In addition, the film thickness d (μm) of the optical film was measured with a laser microscope (LEXT, manufactured by Olympus). The results are shown in Table 3.

Since α of the obtained optical film was 1 or less and the value of β was 1 or more, it was confirmed that the refractive index showed reverse wavelength dispersion. From this, it can be seen that the optical film formed from the composition of the present invention is capable of uniform polarization conversion in a wide wavelength range. In addition, α of the obtained optical film is lower in the composition containing the compound (2-2-1), and α of the optical film is lower in the composition with higher content of the compound (2-2-1).

According to the composition of the present invention, a composition having improved solubility of a polymerizable liquid crystal compound in a solvent can be obtained. In addition, by controlling the content of the polymerizable liquid crystal compound included in the composition, the wavelength dispersion characteristics of the optical film obtained by polymerizing the composition can be arbitrarily adjusted.

1, 1' : color filter
2, 2', 18, 18': optical film
3, 3', 17, 17': alignment layer
4, 4': color filter layer
5: liquid crystal display
6, 10: polarizer
7, 11: substrate
8: counter electrode
9: liquid crystal phase
12: insulating layer
13: transparent electrode and/or reflective electrode
14, 14': laminate
15: polarizing film
16, 16': description
19, 19': adhesive layer
30a, 30b, 30c, 30d, 30e: polarizer

Claims (21)

A polymerizable liquid crystal compound represented by formula (2-1), a polymerizable liquid crystal compound represented by formula (2-2), and a solvent are included,
The area value of the compound represented by formula (2-2) measured by high performance liquid chromatography (HPLC) is the sum of the area values of the compound represented by formula (2-1) and the compound represented by formula (2-2). 0.01% or more and 20% or less relative to the composition:

[In formulas (2-1) and (2-2),
m11, m12, m21, m22 and n each independently represents an integer of 1 or greater.
B ¹¹ , B ¹² , B ²¹ and B ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
E ¹¹ , E ¹² , E ²¹ and E ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond.
G ¹¹ , G ¹² , G ²¹ and G ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and hydrogen atoms contained in the alicyclic hydrocarbon group are halogen atoms, -R ³ , -OR ³ , and cyano It may be substituted with a furnace group or a nitro group, and -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
A ¹¹ , A ¹² , A ²¹ and A ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The contained hydrogen atom may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group, or a nitro group.
F ¹¹ , F ¹² , F ²¹ and F ²² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with -OR ³ or a halogen atom, and the alkanediyl group may be substituted with -OR 3 or a halogen atom. -CH ₂ - contained in diary may be substituted with -O- or -CO-.
P ¹¹ , P ¹² , P ²¹ and P ²² each independently represent a hydrogen atom or a polymerizable group. However, at least one of P ¹¹ and P ¹² is a polymerizable group, and at least one of P ²¹ and P ²² is a polymerizable group.
W is each independently a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 1 to 5 carbon atoms and 1 to 13 carbon atoms. At least two groups selected from the group consisting of a divalent aliphatic hydrocarbon group, 1 to 5 divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and 1 to 5 divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, - OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a group connected through an imide bond, and the hydrogen atoms included in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are halogen atoms, -R ³ , -OR ³ , and cyano It may be substituted with a no group or a nitro group.
X ¹¹ , X ²¹ and X ²² each independently represent a divalent aromatic group which may have a substituent.] The composition according to claim 1, wherein X ¹¹ , X ²¹ and X ²² are each independently a divalent aromatic group having 10 to 30 π electrons, which may have a substituent. The composition according to claim 1, wherein X ¹¹ , X ²¹ and X ²² are each independently a divalent aromatic group having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may have a substituent. The composition according to claim 1, wherein X ¹¹ , X ²¹ and X ²² are each independently a divalent aromatic group which has an aromatic heterocyclic group as a substituent and which may have a substituent. The composition according to claim 1, wherein X ¹¹ , X ²¹ and X ²² are each independently a divalent aromatic heterocyclic group which may have a substituent. 5. The composition according to claim 4, wherein the aromatic heterocyclic group is a benzothiazole group. 6. The composition according to claim 5, wherein the aromatic heterocyclic group is a benzothiazole group. The composition according to claim 1, wherein G ¹¹ , G ¹² , G ²¹ and G ²² are trans-cyclohexane-1,4-diyl groups. delete delete The composition according to claim 1, further comprising a polymerization initiator. An optical film formed from the composition according to any one of claims 1 to 8 and 11. A polymer of a polymerizable liquid crystal compound represented by formula (2-1) and a polymer of a polymerizable liquid crystal compound represented by formula (2-2) are included,
The area value of the compound represented by formula (2-2) measured by high performance liquid chromatography (HPLC) is the sum of the area values of the compound represented by formula (2-1) and the compound represented by formula (2-2). 0.01% or more and 20% or less relative to the optical film:

[In formulas (2-1) and (2-2),
m11, m12, m21, m22 and n each independently represents an integer of 1 or greater.
B ¹¹ , B ¹² , B ²¹ and B ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
E ¹¹ , E ¹² , E ²¹ and E ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond.
G ¹¹ , G ¹² , G ²¹ and G ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and hydrogen atoms contained in the alicyclic hydrocarbon group are halogen atoms, -R ³ , -OR ³ , and cyano It may be substituted with a furnace group or a nitro group, and -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
A ¹¹ , A ¹² , A ²¹ and A ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The contained hydrogen atom may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group, or a nitro group.
F ¹¹ , F ¹² , F ²¹ and F ²² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with -OR ³ or a halogen atom, and the alkanediyl group may be substituted with -OR 3 or a halogen atom. -CH ₂ - contained in diary may be substituted with -O- or -CO-.
P ¹¹ , P ¹² , P ²¹ and P ²² each independently represent a hydrogen atom or a polymerizable group. However, at least one of P ¹¹ and P ¹² is a polymerizable group, and at least one of P ²¹ and P ²² is a polymerizable group.
W is each independently a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 1 to 5 carbon atoms and 1 to 13 carbon atoms. At least two groups selected from the group consisting of a divalent aliphatic hydrocarbon group, 1 to 5 divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and 1 to 5 divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, - OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a group linked through an imide bond, and the hydrogen atoms included in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are halogen atoms, -R ³ , -OR ³ , cyano It may be substituted with a no group or a nitro group.
X ¹¹ , X ²¹ and X ²² each independently represent a divalent aromatic group which may have a substituent.] A color filter comprising the optical film according to claim 12. A color filter comprising the optical film according to claim 13. A polarizing plate comprising the optical film according to claim 12. A polarizing plate comprising the optical film according to claim 13. A liquid crystal display device comprising the color filter according to claim 14. A liquid crystal display device comprising the color filter according to claim 15. A liquid crystal display device comprising the polarizing plate according to claim 16. A liquid crystal display device comprising the polarizing plate according to claim 17.

Images