JP2013120350A - Optical anisotropic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical anisotropic film that has optical anisotropy, and excellent reliability by having heat resistance and light resistance.SOLUTION: An optical anisotropic film is obtained by processing a liquid crystalline composition layer formed by using a liquid crystalline composition including a liquid crystalline polymer compound having a crosslinkable functional group so that the crosslinkable functional group can be fully crosslinked while the liquid crystalline polymer compound is oriented. The density of a crosslinking point in the optical anisotropic film is 4×10to 1×10/g.

Description

  The present invention relates to an optically anisotropic film having high reliability.

  2. Description of the Related Art Conventionally, technical development relating to an optical anisotropic film used for an optical element such as a wave plate of an optical pickup has been performed. In recent years, higher output and longer life of optical pickups have progressed, and a highly reliable optically anisotropic film excellent in heat resistance and light resistance that can sufficiently cope with this has been produced with a sufficient level of orientation. The technology to do is demanded.

  In response to such demands, a technique for producing a liquid crystal material for forming an optically anisotropic film so as to achieve both high reliability and orientation has been developed. On the other hand, as a technique that pays attention to the alignment method of liquid crystal materials, for example, a technique that stabilizes alignment by applying a DC voltage to a mixed system in which a low-molecular liquid crystal is mixed with a side chain liquid crystalline polymer is known. (See Patent Document 1).

  Patent Document 2 discloses a polymer liquid crystal that continuously reduces the temperature from a temperature range showing an isotropic phase to a temperature range showing a liquid crystal phase while applying shear stress to the polymer liquid crystal laminated on the substrate. Techniques relating to the alignment method are described.

  However, even if the alignment method of the polymer liquid crystal described in Patent Document 1 or Patent Document 2 is used, the alignment is sufficient depending on the type of the polymer liquid crystal, for example, the type of the polymer liquid crystal to have light resistance and heat resistance. In some cases, it is not always possible to achieve both high reliability and orientation.

JP-A 63-243165 JP-A-2-123331

  The present invention has been made in view of the above circumstances, and an object thereof is to provide an optically anisotropic film excellent in reliability by having optical anisotropy, heat resistance, light resistance, and the like.

The present invention is an optically anisotropic film having the following configurations [1] to [7].
[1] A liquid crystalline composition layer formed by using a liquid crystalline composition containing a liquid crystalline polymer compound having a crosslinkable functional group, the crosslinkable functional group being in a state where the liquid crystalline polymer compound is aligned. An optically anisotropic film obtained by processing so as to completely crosslink, wherein the density of crosslinking points in the optically anisotropic film is 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g.
An optically anisotropic film.
[2] A pressure of 1000 Pa or less without applying pressure in the vertical direction to the liquid crystalline composition layer at a temperature that is higher than the glass transition temperature of the liquid crystalline composition and less than the clearing point. The optically anisotropic film according to [1], which is performed by applying a shearing force in the horizontal direction while adding.
[3] The optically anisotropic film according to [1] or [2], wherein the liquid crystalline polymer compound is a compound having a fluorine atom bonded to main chain carbon.
[4] The optically anisotropic film according to any one of [1] to [3], wherein the crosslinkable functional group is a photocrosslinkable functional group.
[5] The optically anisotropic film according to [4], wherein the photocrosslinking is crosslinking by cationic polymerization or radical polymerization.
[6] The optically anisotropic film according to [5], wherein the photocrosslinking is crosslinking by cationic polymerization, and the crosslinkable functional group is a cyclic ether group.
[7] The optically anisotropic film according to [6], wherein the cyclic ether group is an epoxy group or an oxetane group.

  ADVANTAGE OF THE INVENTION According to this invention, while having optical anisotropy, it can provide the optically anisotropic film excellent in reliability by having heat resistance, light resistance, etc.

It is a figure which shows roughly an example of the method of manufacturing the optically anisotropic film of this invention. It is a figure which shows roughly an example of the apparatus which manufactures the optically anisotropic film of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. Terms used in the description of the present specification should be interpreted as follows. In addition, the compound represented by the formula is also expressed as a compound given the number of the formula. For example, the compound represented by the formula (a1) is also expressed as the compound (a1).

  “Liquid crystal compound” means “a compound capable of exhibiting a liquid crystal phase alone”, and “polymerizable liquid crystal compound” means “a compound capable of exhibiting a polymer liquid crystal phase alone” To do. The “polymerizable liquid crystal composition” means “a composition having a polymerizability and capable of exhibiting a liquid crystal phase”. The “liquid crystalline composition” means “containing at least one liquid crystalline compound and each of the liquid crystalline compounds can independently exhibit a liquid crystal phase, or contains a composition containing the liquid crystalline compound. It means “a composition in which a reaction product obtained by reacting various components can exhibit a liquid crystal phase”. The mesogen refers to a rigid molecular chain portion such as a rod-like or plate-like molecular chain (including an alicyclic ring and an aromatic ring).

“Ph” represents a 1,4-phenylene group, which may include a hydrogen atom bonded to a carbon atom in the group substituted by a fluorine atom, a chlorine atom, or a methyl group. “Cy” represents a trans-1,4-cyclohexylene group, and “Dhn” represents a trans-2,6-decahydronaphthalenyl group. The hydrogen atom bonded to the carbon atom in these groups may be substituted with a fluorine atom, a chlorine atom, or a methyl group.
“Δn” is an abbreviation for “refractive index anisotropy”. In addition, the value of the wavelength in the following description may include the range of description value +/- 2nm.

The notation "(meth) acryl ..." is used as a generic term that means both "acryl ..." and "methacryl ...". For example, “(meth) acryloyl group” means both “acryloyl group” and “methacryloyl group”. In the chemical formula, —COO— represents —C (═O) O—, and —OCO— represents —OC (═O) —.
The “oxetane group” refers to a group having a structure in which a hydrogen atom at the 3-position of oxetane is replaced with a bond. Furthermore, the “oxetane group” is used as a term including those in which the hydrogen atom remaining at the 3-position is substituted with an alkyl group having 1 to 5 carbon atoms.
The crosslinkable functional group is a functional group having crosslinkability, and is hereinafter also referred to as “crosslinkable group”.

The optically anisotropic film of the present invention comprises a liquid crystalline composition layer formed using a liquid crystalline composition containing a liquid crystalline polymer compound having a crosslinkable group in a state where the liquid crystalline polymer compound is aligned. An optically anisotropic film obtained by processing so that the crosslinkable group is completely crosslinked, and the density of crosslinking points in the optically anisotropic film is 4 × 10 ⁻⁴ to 1 × 10 ^−2. / G.

Here, the “density of cross-linking points in the optically anisotropic film” used in this specification refers to the crosslinkage that the solid content of the liquid crystalline composition used for the production of the optically anisotropic film contains per unit mass (1 g). It is a value calculated from the number of sex groups as follows according to the type of crosslinking.
When the cross-linking reaction is based on two types of cross-linkable groups, for example, in the case of a thermal cross-linking reaction with a hydroxyl group and an isocyanate group, the number of cross-linkable groups contained in 1 g of the solid content is small as “optical”. The density of crosslinking points in the anisotropic film ”.
When the crosslinking reaction is based on one type of crosslinkable group, for example, in the case of a photocrosslinking reaction between (meth) acryloyl groups or between oxetane groups, the value obtained by dividing the number of all crosslinkable groups contained per gram of solid content by 2 “Density of crosslinking points in optically anisotropic film”.
In the case of photocrosslinking, whether it is cationic polymerization or radical polymerization, the crosslinking point is not necessarily constituted by the crosslinking of two crosslinking groups. The cross-linking points in the case of photo-crosslinking were similarly defined on the basis that one of each of the two types of cross-linkable groups constitutes a cross-linking point.

  Conventionally, when an optically anisotropic film is formed of a liquid crystalline polymer compound, it has been difficult to achieve both crosslinking and orientation, but in the present invention, in an optically anisotropic film using a liquid crystalline polymer compound, High crosslink density and sufficient orientation were realized. With such a configuration, the optically anisotropic film of the present invention has high reliability in long-term use with improved heat resistance and light resistance.

[Liquid crystal composition]
The liquid crystalline composition used for production of the optically anisotropic film of the present invention contains a liquid crystalline polymer compound having a crosslinkable group. The liquid crystalline polymer compound having a crosslinkable group is a polymer compound comprising a polymer unit having a group containing a mesogen skeleton in the side chain and a polymer unit having a crosslinkable group in the side chain, wherein the liquid crystal composition In the case where only the liquid crystalline polymer compound is blended, only the liquid crystalline polymer compound, and when blended together with the crosslinking agent described later, the liquid crystallinity calculated by the above method in relation to the crosslinking agent. The liquid crystal polymer compound is not particularly limited as long as the density of the crosslinkable group in the composition falls within the above range.

  Examples of the crosslinkable group possessed by the liquid crystalline polymer compound include a hydroxyl group, a thiol group, a carboxyl group, an iodine atom, a silyl group, an amino group, an epoxy group, a nitrile group, an oxetane group, and a vinyl group. In addition, it is preferable that a vinyl group is contained in a liquid crystalline polymer compound as a (meth) acryloyl group.

  The optically anisotropic film of the present invention is such that the liquid crystalline polymer compound having a crosslinkable group is cross-linked through the crosslinkable group and the alignment state is fixed in a state where the liquid crystalline composition is aligned. High reliability. Crosslinking through a crosslinkable group is classified into thermal crosslinking and photocrosslinking. Photocrosslinking can be further divided into photocrosslinking by cationic polymerization and photocrosslinking by radical polymerization.

  These classifications in crosslinking depend on the type of crosslinkable group. Among the crosslinkable groups exemplified above, examples of the crosslinkable group that is crosslinked by thermal crosslinking include a hydroxyl group, a thiol group, a carboxyl group, an iodine atom, a silyl group, an amino group, an epoxy group, a nitrile group, and an oxetane group. . Of these, a hydroxyl group is preferred. Moreover, as a crosslinkable group that is crosslinked by photocrosslinking by radical polymerization among photocrosslinks, a vinyl group, preferably a (meth) acryloyl group can be mentioned. Examples of the crosslinkable group that is cross-linked by photocrosslinking by cationic polymerization among the photocrosslinks include an epoxy group and an oxetane group.

  In the present invention, the crosslinking is preferably carried out by photocrosslinking, and therefore the crosslinkable group is preferably a (meth) acryloyl group, an epoxy group or an oxetane group. Furthermore, the photocrosslinking is preferably performed by cationic polymerization, and the crosslinkable group is preferably an epoxy group or an oxetane group.

In the case of thermal crosslinking, crosslinking is performed using a crosslinking agent having a functional group that reacts with the crosslinking group of the liquid crystalline polymer compound. When the crosslinking is performed by photocrosslinking, the crosslinking is performed by reaction between the crosslinkable groups using only the liquid crystalline polymer compound having a crosslinkable group. Moreover, even when the crosslinking is performed by photocrosslinking, as in the case of thermal crosslinking, the crosslinking may be performed using a crosslinking agent having a functional group that reacts with the crosslinking group of the liquid crystalline polymer compound. Good.
In the present specification, the crosslinking agent refers to a low molecular weight compound having a molecular weight of approximately 2,000 or less among compounds having a functional group that reacts with the crosslinkable group of the liquid crystalline polymer compound.

Here, the liquid crystal polymer compound having a crosslinkable group contained in the liquid crystal composition usually copolymerizes a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a monomer having a crosslinkable group. Can be obtained. However, when the crosslinkable group in the side chain of the liquid crystalline polymer compound is a radical polymerizable group such as a vinyl group, preferably a (meth) acryloyl group, a functional group reactive with the polymerizable liquid crystalline compound. After copolymerizing a polymerizable liquid crystal composition containing a monomer having a group, a radical such as a functional group reactive with the functional group and a vinyl group, preferably a (meth) acryloyl group is added to the copolymer. A liquid crystalline polymer compound having a crosslinkable group can be obtained by reacting a compound having a polymerizable group.
In addition, it is preferable that the position of the crosslinkable group in the liquid crystalline polymer compound having a crosslinkable group is at a position where it can easily react with the functional group having reactivity with the crosslinkable group of the crosslinking agent.

  As the polymerizable liquid crystal compound, a polymerizable liquid crystal compound having at least one mesogen skeleton and a radical polymerizable group is used. These may be used alone or in combination of two or more. Specific examples of the radical polymerizable group include a vinyl group optionally substituted with a fluorine atom or an alkyl group.

Specifically, as the polymerizable liquid crystalline compound, a vinyl ether compound or (meth) acrylic compound having at least one mesogenic skeleton, or a cyclopolymerizable diene compound having at least one mesogenic skeleton in the side chain Etc.
When a vinyl ether compound is used as the polymerizable liquid crystal compound, the vinyl ether compound is also preferred for the monomer having a crosslinkable group. Similarly, a monomer having a crosslinkable group used in combination with a (meth) acrylic compound or a diene compound can be cyclopolymerized with a (meth) acrylic compound having a crosslinkable group and a crosslinkable group, respectively. Diene compounds are preferred.

  The liquid crystalline polymer compound having a crosslinkable group preferably has a fluorine atom bonded to the main chain carbon from the viewpoint of light resistance to blue light. Such a constitution in which the polymer compound has a fluorine atom bonded to the carbon of the main chain is hereinafter referred to as “having a fluorine atom in the main chain”. In order to make the liquid crystalline polymer compound have a fluorine atom in the main chain, a fluorine atom may be introduced into the polymerizable liquid crystalline compound or the polymerizable group of the monomer having a crosslinkable group. Alternatively, when copolymerizing the polymerizable liquid crystalline compound and the monomer having a crosslinkable group, for example, a fluoroolefin such as tetrafluoroethylene may be copolymerized therewith.

  Hereinafter, the liquid crystalline polymer compound having a crosslinkable group is a vinyl ether liquid crystalline polymer compound (A) obtained mainly using a vinyl ether compound, and a diene liquid crystalline polymer obtained mainly using a diene compound. When the liquid crystal composition is a molecular compound (B) or a (meth) acrylic liquid crystalline polymer compound (C) obtained mainly using a (meth) acrylic compound, the crosslinking is performed by thermal crosslinking. The composition will be described separately and the composition in the case of photocrosslinking. However, these are examples, and the liquid crystalline polymer compound and the liquid crystalline composition used in the present invention are not limited to these. Hereinafter, for each liquid crystalline composition, the composition when crosslinking is performed by thermal crosslinking is referred to as “thermal crosslinking liquid crystalline composition”, and the composition when crosslinking is performed by photocrosslinking is referred to as “photocrosslinkable liquid crystalline composition”. It is called "thing".

(1) Liquid crystalline composition containing a vinyl ether liquid crystalline polymer compound (A) (1-1) Thermally crosslinkable liquid crystalline composition A liquid crystalline composition containing a vinyl ether liquid crystalline polymer compound (A) is heated. In the case of crosslinkability, the liquid crystalline composition is a vinyl ether liquid crystalline polymer compound (Aa) having a thermally crosslinkable group (hereinafter also referred to as “thermally crosslinkable group”) as exemplified above. ) (Hereinafter also referred to simply as “liquid crystalline polymer compound (Aa)”) and a crosslinking agent having a functional group having reactivity with the thermally crosslinkable group of liquid crystalline polymer compound (Aa) To do.

(Liquid crystal polymer compound (Aa))
Examples of the liquid crystalline polymer compound (Aa) include a vinyl ether polymerizable liquid crystal compound (A1), a vinyl ether compound (A2) having a thermally crosslinkable group, and any other polymerizable compound (A3). And a liquid crystalline polymer compound obtained by copolymerization of In order to make the vinyl ether liquid crystalline polymer compound (Aa) have a fluorine atom in the main chain from the viewpoint of blue light resistance, a fluorine atom is present in the polymerizable group as the other polymerizable compound (A3). A bonded fluoroolefin or the like may be used.

Examples of the vinyl ether-based polymerizable liquid crystal compound (A1) include a vinyl ether-based compound represented by the following formula (a1).
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -OW 11 - (E 11) h1 -W 12 - (E 12) j1 - (E 13) k1 -E 14 -R ¹² …… (a1)

However, the symbols in formula (a1) are as follows.
R ¹¹ : a group represented by an alkylene group having 1 to 12 carbon atoms, a polyfluoroalkylene group having 1 to 12 carbon atoms, or —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ — (x is 1 to 6) Integer).
R ¹² : an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a trifluoromethyl group, or a cyano group.
E ^{11 is a} 1,4-phenylene group, and a hydrogen atom bonded to a carbon atom in the group may be substituted with a fluorine atom, a chlorine atom, or a methyl group.
E ¹² , E ¹³ , E ¹⁴ : each independently a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or a trans-2,6-decahydronaphthalenyl group, The hydrogen atom bonded to the carbon atom may be substituted with a fluorine atom, a chlorine atom, or a methyl group.
m1 is an integer from 0 to 3.
n: An integer from 0 to 3.
h1, j1, k1: each independently 0 or 1, and 1 ≦ h1 + j1 + k1 holds.
W ¹¹ and W ¹² : each independently a carbonyl group or a single bond.

The compound (a1) with a plurality of 6-membered ring in crystalline framework (formula (a1) ^- represented by _{^{- (E 11) h1 -W 12}} - (E 12) j1 - (E 13) k1 -E 14 ) Containing vinyl ether compounds, which have both polymerizability and liquid crystallinity. Some compounds (a1) alone do not exhibit a liquid crystal phase, but such a compound may also exhibit a liquid crystal phase when a copolymer obtained by copolymerization with another polymerizable compound. It can be used as a constituent component of a copolymer.

Compound (a1) has an alkylene group, a polyfluoroalkylene group, a polyfluoroalkylene group on the spacer portion of the molecule (indicated by — (CH ₂ ) _m1 —R ¹¹ — (CH ₂ ) _n1 — in formula (a1)). It has at least one group selected from oxide groups. By the action of this group, the compound (a1) can ensure compatibility with other polymerization components during polymerization.

In the polymerization, in order not to lower the compatibility with the component containing no fluorine atom in the polymerization solution, in the compound (a1), when R ¹¹ in the formula (a1) is an alkylene group or a polyfluoroalkylene group, those groups The carbon number of 1-12. When R ¹¹ is a polyfluoroalkylene oxide group represented by —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ —, x is an integer of 1 to 6.
The alkylene group preferably has 2 to 8 carbon atoms, the polyfluoroalkylene oxide group x preferably has an integer of 1 to 4, and the polyfluoroalkylene group preferably has 2 to 8 carbon atoms. Moreover, as for carbon number of an alkylene group, 2, 4, and 6 are preferable so that non-crystallinity may be shown. The number of carbon atoms of the polyfluoroalkylene group is particularly preferably 2, 4, or 6. Furthermore, in the case of a polyfluoroalkylene group, it is preferable that one or more fluorine atoms are bonded to the terminal carbon atom, and a perfluoroalkylene group is more preferable. The polyfluoroalkylene group has better liquid crystallinity than the polyfluoroalkylene oxide group.

Examples of the polyfluoroalkylene group include the following groups.
_{- (CF 2) 2 -,} - (CF 2) 4 -, - (CF 2) 6 -, - (CF 2) 8 -, - (CF 2) 10 -, - (CF 2) 12 -, - CF _{2 CHF -, - CF 2 CHF} (CF 2) 2 -, - CF 2 CHF (CF 2) 4 -, - CF 2 CHF (CF 2) 2 CHFCF 2 -, - CF 2 CHF (CF 2) 4 CHF- _{, -CF 2 CH 2 (CF 2} ) CH 2 CF 2 -, - CF 2 CHF (CF 2) 4 CHFCF 2 -, - CHF (CF 2) 6 CHF -, - CF 2 CH (CF 2 CF 3) ( CF _{2) 2} CH ₂ -.

Examples of the alkylene group include the following groups.
_{- (CH 2) 2 -,} - (CH 2) 4 -, - (CH 2) 6 -, - (CH 2) 8 -, - (CH 2) 10 -, - (CH 2) 12 -.

The compound (a1) has an alkyl group, an alkoxy group, a fluorine atom, a trifluoromethyl group, or a cyano group as R ¹² , and thereby a liquid crystalline polymer compound (Aa) having a polymer unit based on the compound (a1) Expands the temperature range in which the liquid crystallinity is exhibited. When R ¹² is an alkyl group or an alkoxy group, the number of carbon atoms is preferably 2 to 6, and more preferably 3 to 5. When R ¹² has a linear structure, it is particularly preferable because the temperature range in which the liquid crystalline polymer compound (Aa) exhibits liquid crystallinity can be widened. m1 and n1 are each an integer of 0 to 3, and 1 or 2 is preferable. From the viewpoint of ease of production of the compound (a1), m1 and n1 are preferably the same value. h1, j1, and k1 are each 0 or 1. However, at least one of h1, j1, and k1 is 1, and 1 ≦ h1 + j1 + k1 holds. W ¹¹ and W ¹² are a carbonyl group (—CO—) or a single bond.

Preferable specific examples of the compound (a1) include the following compounds (1A) to (1J).
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-Ph-Ph-R 12 (1A)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-Ph-Cy-Ph-R 12 (1B)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-Ph-Cy-Ph-Ph-R 12 (1C)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-Cy-Cy-R 12 (1D)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-CO-Cy-Cy-R 12 (1E)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-Cy-Cy-Cy-R 12 (1F)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-CO-Dhn-Cy-R 12 (1G)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-CO-Dhn-Cy-Cy-R 12 (1H)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-Dhn-Cy-R 12 (1I)
_{CH 2 = CH-O- (CH} 2) m1 -R 11 - (CH 2) n1 -O-CO-Cy-Cy-Cy-R 12 (1J)

However, the symbols R ¹¹ , R ¹² , m1 and n1 in the formulas (1A) to (1J) are independent for each formula and are the same as the above-mentioned definition. Ph, Cy and Dhn are also the same as defined above independently for each formula, and a plurality of Ph and Cy in one molecule are also independently substituted or unsubstituted phenylene groups and substituted Or it may represent an unsubstituted cyclohexylene group.

  More specific examples include the following compounds. However, the expressions Ph, Cy, and Dhn in the following formulas are the same as the above definition independently for each formula. The symbol r1 represents an integer of 1 to 8 independently for each formula.

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Ph-CN (1A0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Ph-CN (1A0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Ph-CN (1A0c)
_{CH 2 = CH-O- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Ph-CN (1A0j)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A0l)
CH ₂ = CH-O- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A0ba)
CH ₂ = CH-O- (CH ₂ ) ₄ -O-Ph-Ph-CN (1A0bb)
CH ₂ = CH-O- (CH ₂ ) ₆ -O-Ph-Ph-CN (1A0bc)
CH ₂ = CH-O- (CH ₂ ) ₈ -O-Ph-Ph-CN (1A0bd)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0c)
_{CH 2 = CH-O- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Cy-Ph- (CH 2) r1 H (1B0j)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0l)
CH ₂ = CH-O- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0ba)
CH ₂ = CH-O- (CH ₂ ) ₄ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0bb)
CH ₂ = CH-O- (CH ₂ ) ₆ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0bc)
CH ₂ = CH-O- (CH ₂ ) ₈ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B0bd)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0c)
_{CH 2 = CH-O- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Cy-Ph-Ph- (CH 2) r1 H (1C0j)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0l)
CH ₂ = CH-O- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0ba)
CH ₂ = CH-O- (CH ₂ ) ₄ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0bb)
CH ₂ = CH-O- (CH ₂ ) ₆ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0bc)
CH ₂ = CH-O- (CH ₂ ) ₈ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C0bd)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Cy-Cy- (CH ₂ ) _r1 H (1D0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Cy-Cy- (CH ₂ ) _r1 H (1D0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Cy-Cy- (CH ₂ ) _r1 H (1D0c)
_{CH 2 = CH-O- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Cy-Cy- (CH 2) r1 H (1D0j)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Cy-Cy- (CH ₂ ) _r1 H (1D0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Cy-Cy- (CH ₂ ) _r1 H (1D0l)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0c)
_{CH 2 = CH-O- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-CO-Cy-Cy- (CH 2) r1 H (1E0j)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0l)
CH ₂ = CH-O- (CH ₂ ) ₂ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0ba)
CH ₂ = CH-O- (CH ₂ ) ₄ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0bb)
CH ₂ = CH-O- (CH ₂ ) ₆ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0bc)
CH ₂ = CH-O- (CH ₂ ) ₈ -O-CO-Cy-Cy- (CH ₂ ) _r1 H (1E0bd)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Cy-Cy-Cy- (CH ₂ ) _r1 H (1F0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Cy-Cy-Cy- (CH ₂ ) _r1 H (1F0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Cy-Cy-Cy- (CH ₂ ) _r1 H (1F0c)
_{CH 2 = CH-O- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Cy-Cy-Cy- (CH 2) r1 H (1F0j)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Cy-Cy-Cy- (CH ₂ ) _r1 H (1F0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Cy-Cy-Cy- (CH ₂ ) _r1 H (1F0l)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0c)
_{CH 2 = CH-O- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-CO-Dhn-Cy- (CH 2) r1 H (1G0j)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0l)
CH ₂ = CH-O- (CH ₂ ) ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0ba)
CH ₂ = CH-O- (CH ₂ ) ₄ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0bb)
CH ₂ = CH-O- (CH ₂ ) ₆ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0bc)
CH ₂ = CH-O- (CH ₂ ) ₈ -O-CO-Dhn-Cy- (CH ₂ ) _r1 H (1G0bd)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0c)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0l)
CH ₂ = CH-O- (CH ₂ ) ₂ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0ba)
CH ₂ = CH-O- (CH ₂ ) ₄ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0bb)
CH ₂ = CH-O- (CH ₂ ) ₆ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0bc)
CH ₂ = CH-O- (CH ₂ ) ₈ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r1 H (1H0bd)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Dhn-Cy- (CH ₂ ) _r1 H (1I0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Dhn-Cy- (CH ₂ ) _r1 H (1I0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Dhn-Cy- (CH ₂ ) _r1 H (1I0c)

CH ₂ = CH-O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0a)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0b)
CH ₂ = CH-O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0c)
_{CH 2 = CH-O- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-CO-Cy-Cy-Cy- (CH 2) r1 H (1J0j)
CH ₂ = CH-O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0k)
CH ₂ = CH-O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0l)
CH ₂ = CH-O- (CH ₂ ) ₂ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0ba)
CH ₂ = CH-O- (CH ₂ ) ₄ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0bb)
CH ₂ = CH-O- (CH ₂ ) ₆ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0bc)
CH ₂ = CH-O- (CH ₂ ) ₈ -O-CO-Cy-Cy-Cy- (CH ₂ ) _r1 H (1J0bd)

CH ₂ = CH-O-CH ₂ -CF ₂ -OCF ₂ CF ₂ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5a)
CH ₂ = CH-O-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5b)
CH ₂ = CH-O-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5c)
CH ₂ = CH-O- (CH ₂ ) ₂ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A5g)
CH ₂ = CH-O- (CH ₂ ) ₃ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A5h)
CH ₂ = CH-O- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A5i)
CH ₂ = CH-O- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A5j)

CH ₂ = CH-O-CH ₂ -CF ₂ -OCF ₂ CF ₂ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B5a)
CH ₂ = CH-O-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B5b)
CH ₂ = CH-O-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B5c)
CH ₂ = CH-O- (CH ₂ ) ₂ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B5g)
CH ₂ = CH-O- (CH ₂ ) ₃ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B5h)
CH ₂ = CH-O- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B5i)
CH ₂ = CH-O- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r1 H (1B5j)

CH ₂ = CH-O-CH ₂ -CF ₂ -OCF ₂ CF ₂ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C5a)
CH ₂ = CH-O-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C5b)
CH ₂ = CH-O-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C5c)
CH ₂ = CH-O- (CH ₂ ) ₂ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C5g)
CH ₂ = CH-O- (CH ₂ ) ₃ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H (1C5h)
CH ₂ = CH-O- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H ( 1C5i)
CH ₂ = CH-O- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r1 H ( 1C5j)

  In the above compound, r1 is preferably an integer of 2 to 6, and more preferably an integer of 3 to 5. Ph is an unsubstituted 1,4-phenylene group or a 1,4-phenylene group substituted by a methyl group, Cy is an unsubstituted trans-1,4-cyclohexylene group, and Dhn is a non-substituted group. A substituted trans-2,6-decahydronaphthalenyl group is preferred.

  Among these, more preferred compounds include (1E0bb), (1G0bb), (1G0c), (1J0bb), and the like.

Next, a method for synthesizing the vinyl ether compound (a1) will be described with specific examples.
In the above formula (a1), the synthesis method is (11) when W ¹¹ is a carbonyl group (—CO—) (in the above preferred compounds, the compound (1E), the compound (1G), the compound (1H), the compound ( Equivalent to 1J)) and (12) when W ¹¹ is a single bond (in the above preferred compounds, equivalent to compound (1A) to compound (1D), compound (1F), compound (1I)) .

Further, in each of the above (11) and (12), when (A) R ¹¹ is a polyfluoroalkylene group or a polyfluoroalkylene oxide group (in the above-mentioned more specific compound, the compounds (1... A) to ( 1 ... c), corresponding to compounds (1 ... g) to (1 ... l)) and (B) when R ¹¹ is an alkylene group (in the more specific compounds described above, compounds (1 ... ba) to ( 1 ... bd)).

(A-11) In the formula (a1), when R ¹¹ is a polyfluoroalkylene group or a polyfluoroalkylene oxide group and W ¹¹ is a carbonyl group (—CO—), it is classified as (A-11). As a method for synthesizing the compound, the method shown in the following reaction formula (F-1) can be given by taking the compound (1E0b) as an example. In addition, the symbol in a formula shows the same meaning as the above.

First, the compound (01b) and 3,4-dihydrofuran are reacted in dichloromethane in the presence of p-toluenesulfonic acid to obtain the compound (01b-2). Next, this compound (01b-2), trans-4- (trans-4-alkylcyclohexyl) cyclohexanecarboxylic acid (HO—CO—Cy—Cy— (CH ₂ ) _r1 H: compound (21AA)), dicyclohexyl Carbodiimide and 4- (N, N-dimethylamino) pyridine are reacted in chloroform to obtain compound (01b-3). Further, this compound is reacted with p-toluenesulfonic acid to obtain the above compound (01b-4). Next, this compound (1E0b) is obtained by reacting this compound with vinyl acetate in toluene in the presence of chloro (1,5-cyclooctadiene) iridium (I) and sodium carbonate.

  In the reaction for converting the compound (01b-4) to the compound (1E0b), as a catalyst, in addition to the chloro (1,5-cyclooctadiene) iridium (I), mercury (II) acetate, biz Benzonitrile palladium (II), bizacetonitrile palladium (II) and the like can be used. In the above reaction, in addition to sodium carbonate, potassium carbonate, monopotassium phosphate, dipotassium phosphate, or the like may or may not be used. As the solvent, aprotic solvents such as ether, toluene and hexane are preferable, and toluene is particularly preferable. In addition to vinyl acetate, vinyl ether compounds such as ethyl vinyl ether, butyl vinyl ether, vinyl propionate, and vinyl pivaloate can be used. The reaction temperature is preferably in the range of room temperature to 200 ° C, particularly preferably in the range of 30 ° C to 150 ° C. The reaction time is preferably 0.5 hours to 200 hours, particularly preferably 1 hour to 10 hours. The reaction pressure is preferably 1 MPa.

In the reaction shown in the above reaction formula (F-1), in place of the compound (01b), a divalent group sandwiched by the hydroxyl group ^{_{- (CH 2) m1 -R 11}} - (CH 2) n1 - ( a compound R ¹¹ is polyfluoroalkylene group or a polyfluoro alkylene oxide group) and were, in place of the compound (21 AA), the -Cy-Cy-, -Dhn-Cy - , - Dhn-Cy-Cy-, or , -Cy-Cy-Cy- and the like can be used to synthesize other compounds classified as (A-11).

(B-11) In the formula (a1), when R ¹¹ is an alkylene group and W ¹¹ is a carbonyl group (—CO—), the method for synthesizing the compound classified as (B-11) is the above compound Taking (1E0bb) as an example, the method shown in the following reaction formula (F-2) can be mentioned. In addition, the symbol in a formula shows the same meaning as the above.

Further, in the reaction shown in the above reaction formula (F-2), in place of the compound (61b), a divalent group sandwiched by the vinyloxy group and a hydroxyl group ^{_{- (CH 2) m1 -R 11}} - (CH ^{(compound of R 11} is an alkylene group), in place of the compound (21A), the -Cy-Cy-, -Dhn-Cy - - 2) n1, - Dhn-Cy-Cy-, or, -Cy By using a compound such as -Cy-Cy- or the like, another compound classified as (B-11) can be synthesized.

(A-12) In the formula (a1), when R ¹¹ is a polyfluoroalkylene group or a polyfluoroalkylene oxide group and W ¹¹ is a single bond, the method for synthesizing the compound classified as (A-12) is Taking the above compound (1A0b) as an example, the method shown in the following reaction formula (F-3) can be mentioned. In addition, the symbol in a formula shows the same meaning as the above.

  First, compound (01b-2) is obtained in the same manner as in the synthesis method of compound (1E0b). This compound (01b-2) and 4-hydroxy- (4′-cyano) -biphenyl (HO—Ph—Ph—CN: Compound (13A)) were reacted with triphenylphosphine and diethyl azodicarboxylate. Reaction in tetrahydrofuran gives compound (01b-5). Further, this compound (01b-6) is obtained in the same manner as in the synthesis method of the above compound (1E0b). Next, compound (1A0b) is obtained from compound (01b-6) in the same manner as in the method for synthesizing compound (1E0b).

In the reaction represented by the above reaction formula (F-3), in place of the compound (01b), a divalent group sandwiched between hydroxyl groups is represented by — (CH ₂ ) _m1 —R ¹¹ — (CH ₂ ) _n1 — ( Instead of the compound (13A), a group in which R ¹¹ is a polyfluoroalkylene group or a polyfluoroalkylene oxide group) is a group in which a hydroxyl group is removed, -Ph-Cy-Ph- (CH ₂ ) _r1 H,- _{Ph-Cy-Ph-Ph- (} CH 2) r1 H, -Cy-Cy- (CH 2) r1 H, -Ph-Cy-Cy-Cy- (CH 2) r1 H or,, -Dhn-Cy- By using each of the compounds such as (CH ₂ ) _r1 H, other compounds classified as (A-12) can be synthesized.

(B-12) In the formula (a1), when R ¹¹ is an alkylene group and W ¹¹ is a single bond, the method for synthesizing the compound classified as (B-12) is exemplified by the above compound (1C0bb). Then, the method shown to the following reaction formula (F-4) is mentioned. In addition, the symbol in a formula shows the same meaning as the above.

Further, in the reaction represented by the reaction formula (F-4), instead of the compound (13C), a group excluding the hydroxyl group is replaced with -Ph-Ph-CN, -Ph-Cy-Ph- (CH ₂ ). _{r1 H, -Cy-Cy- (CH} 2) r1 H, -Ph-Cy-Cy-Cy- (CH 2) r1 H, or a -Dhn-Cy- _{(CH 2)} compound with _r1 H, etc., in place of compound (71b), the Br and sandwiched by a divalent radical with a hydroxyl group _- using ^{(R 11} is an alkylene group) of the compound, respectively ^{_{- (CH 2) m1 -R 11}} - (CH 2) n1 Thus, other compounds classified as (B-12) can be synthesized.

  Heretofore, the vinyl ether compound represented by the above formula (a1) that becomes a polymerization unit constituting the vinyl ether-based liquid crystalline polymer compound (Aa) having a thermally crosslinkable group by polymerization has been described.

  In producing the liquid crystalline polymer compound (Aa) used in the present invention, a vinyl ether-based polymerizable liquid crystalline compound (A1), preferably a compound (a1), and a vinyl ether-based compound having a thermally crosslinkable group used in combination ( A2) is not particularly limited as long as it is a compound (A2) having a thermally crosslinkable group and a vinyloxy group. The compound (A2) having a thermally crosslinkable group and a vinyloxy group is preferably a compound having a thermally crosslinkable group and a vinyloxy group at opposite ends in the molecule.

  When such a vinyl ether compound (A2) is used, when the compound (A1) or the other monomer (A3) is copolymerized to obtain a liquid crystalline polymer compound (Aa), the compound (A2) The polymerized unit based has a structure in which a carbon chain derived from a vinyl group forms a part of the main chain, and a thermally crosslinkable group is located at the end of the side chain bonded to the main chain. The liquid crystalline polymer compound (Aa) is blended in the liquid crystalline composition, and finally, this thermally crosslinkable group reacts with the thermally crosslinkable group of the crosslinking agent contained in the liquid crystalline composition. It reacts with the group and crosslinks. Considering this crosslinking reaction, the type and length of the side chain, that is, the linking group between the thermally crosslinkable group and the vinyloxy group in the compound (A2) is appropriately adjusted.

Examples of the vinyl ether compound (A2) having such a thermally crosslinkable group include a vinyl ether compound represented by the following formula (a2).
CH ₂ = CH—O—R ¹ —L ¹ (a2)
R ¹ represents an alkylene group having 1 to 10 carbon atoms (however, a hydrogen atom bonded to a carbon atom in the alkylene group may be substituted with a fluorine atom, and an etheric oxygen atom, an ester is bonded between the carbon-carbon bonds) A bond or a urethane bond).
L ¹ represents a hydroxyl group, a thiol group, a carboxyl group, an iodine atom, a silyl group, an amino group, an epoxy group, a nitrile group, or an oxetane group. L ¹ is preferably a hydroxyl group or an oxetane group, and particularly preferably a hydroxyl group, from the viewpoint of absorption characteristics and ease of synthesis.
The compound having a hydroxyl group as L ¹ (a2), for example, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether is preferred.

As the other monomer (A3) optionally used as a raw material monomer of the liquid crystalline polymer compound (Aa), a fluoroolefin is preferable. The fluoroolefin is not particularly limited as long as it is a compound having a fluorine atom and an ethylenic double bond. As the fluoroolefin, a fluoroethylene having 2 carbon atoms represented by the following formula (a3) is preferably used. In the formula (a3), X ¹¹ , Y ¹¹ , and Z ¹¹ each independently represent a hydrogen atom, a fluorine atom, or a chlorine atom.
CFX ¹¹ = CY ¹¹ Z ¹¹ (a3)

  The fluoroethylene represented by the formula (a3) is preferably a fluoroolefin having 3 or 4 fluorine atoms, and specific examples thereof include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and the like.

  In the raw material monomer of the liquid crystalline polymer compound (Aa), as the other monomer (A3), a polymerizable compound having an ethylenic double bond other than the above may be included as necessary. . As such a monomer, specifically, it does not have a functional group reactive with the thermally crosslinkable group of the vinyl ether compound (A2), preferably has no functional group, vinyl ether, allyl ether, non-functional group. Examples thereof include fluorine-based ethylenic monomers.

  The liquid crystalline polymer compound (Aa) is preferably a liquid crystalline compound obtained by using a vinyl ether polymerizable liquid crystal compound (A1), a vinyl ether compound (A2) having a thermally crosslinkable group, and a fluoroolefin as a raw material monomer. The polymer compound (Aa1) is preferable.

  In such a liquid crystal polymer compound (Aa1), the content (ratio) of the polymer units based on the vinyl ether-based polymerizable liquid crystal compound (A1), preferably the compound (a1), is from the viewpoint of liquid crystallinity and light resistance. From 30 to 50 mol% is preferable. 30-45 mol% is more preferable. When the content of the polymerization unit based on the compound (A1) is 30 mol% or more, a thin film having excellent liquid crystallinity and uniaxial alignment can be obtained. When the content of polymerized units based on the compound (A1) is 50 mol% or less, sufficient light resistance can be obtained.

  The content (ratio) of the polymer units based on the fluoroolefin, preferably the compound (a3), in the liquid crystalline polymer compound (Aa1) is preferably 45 to 55 mol%. From the point of light resistance and liquid crystallinity, 47 to 52 mol% is more preferable. When the content of the polymerized units based on fluoroolefin is 45 mol% or more, sufficient light resistance is obtained, and when it is 55 mol% or less, a thin film having excellent liquid crystallinity and uniaxial alignment is obtained.

  The content (ratio) of the polymer units based on the vinyl ether compound (A2) having a thermally crosslinkable group in the liquid crystalline polymer compound (Aa1), preferably the compound (a2), is preferably 1 to 20 mol%, 10 mol% is more preferable. When the content of the polymerized unit based on the compound (A2) is 1 mol% or more, the light resistance and alignment stability are excellent, and when it is 20 mol% or less, a liquid crystal property is excellent and a uniaxially oriented thin film is obtained. .

  In addition, the liquid crystalline polymer (Aa1) is polymerized based on a vinyl ether-based polymerizable liquid crystalline compound (A1), a polymer unit based on a fluoroolefin, a polymer unit based on a fluoroolefin, and a vinyl ether compound (A2) having a thermally crosslinkable group. When a polymer unit is included in addition to the unit, the upper limit of the content is preferably 1 mol%. In the case of 1 mol% or less, liquid crystallinity, light resistance, and orientation are sufficiently obtained.

  Specific examples of the polymer compound that is more preferably used as the liquid crystalline polymer compound (Aa) used in the present invention include a polymer compound represented by the following formula (Aa11) having an average composition structure. The liquid crystalline polymer compound (Aa11) is composed only of a polymer unit based on the compound (a1), a polymer unit based on the compound (a3), and a polymer unit based on the compound (a2), and each content thereof is Polymer compound in which polymerized units based on compound (a1) are 30 to 50 mol%, polymerized units based on compound (a3) are 45 to 55 mol%, and polymerized units based on compound (a2) are 1 to 20 mol% It is. In the case where the polymer compound is composed only of a polymer unit based on the compound (a1), a polymer unit based on the compound (a3), and a polymer unit based on the compound (a2), the compound (a1) which is a vinyl ether compound In addition, the polymer units based on the compound (a2) and the polymer units based on the compound (a3), which is a fluoroethylene, are almost alternately bonded.

  In addition, the content rate of each above-mentioned polymerization unit is a rate based on the preparation amount of each compound (monomer) used as a raw material. Moreover, x1 and y1 which are the composition ratios of the respective polymerization units in the following formula (Aa11) also indicate the ratio of the charged amount of the raw material monomer. Furthermore, also in the following description of this specification, what shows the content rate of a polymerization unit and the composition ratio of a polymerization unit is shown in the ratio based on the preparation amount of a raw material monomer.

In the formula (aa11), ^{Q 1} is in the formula _{(a1) - (CH 2)} m1 -R 11 - (CH 2) n1 -OW 11 - (E 11) h1 -W 12 - (E 12) j1 -(E ¹³ ) _k1 -E ¹⁴ -R ¹² , and the other symbols have the same meanings as the symbols in the above formula (a1), the above formula (a3), and the above formula (a2). X1 is a positive number from 60 to 99, and y1 is a positive number from 1 to 40, and x1 + y1 = 100. The value of x1: y1 corresponds to the content of polymerized units based on the compound (a1): the content of polymerized units based on the compound (a2) in the polymer compound (Aa11).

The number average molecular weight (Mn) of the liquid crystalline polymer compound (Aa) used in the present invention is preferably in the range of 2,000 to 20,000, more preferably in the range of 3,000 to 10,000. The molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) is preferably in the range of 1.0 to 3.0, and more preferably in the range of 1.0 to 2.0.
If the number average molecular weight (Mn) and the molecular weight distribution are in this range, the orientation in a liquid crystal composition containing the molecular weight and the light resistance when used as an optically anisotropic material will be good. In the present specification, the mass average molecular weight (Mw) and the number average molecular weight (Mn) are those measured by a gel permeation chromatography (GPC) method using polystyrene as a standard.

  The liquid crystalline polymer compound (Aa) in the present invention can be synthesized, for example, by the method described in JP-A No. 58-136662, and is incorporated herein. For example, in order to obtain a liquid crystal polymer compound (Aa11), a vinyl ether compound (a1) which is a polymerizable liquid crystal compound, a vinyl ether compound (a2) having a thermally crosslinkable group, and a compound which is a fluoroethylenes A method of polymerizing by adding a polymerization initiator to a mixture obtained by mixing (a3) at a predetermined ratio is adopted. As the polymerization method, a polymerization method used for usual radical polymerization such as bulk polymerization, emulsion polymerization, solution polymerization, suspension polymerization and the like can be used without particular limitation, and solution polymerization is preferable from the viewpoint of easy control of molecular weight.

  Polymerization solvents include saturated hydrocarbons such as heptane, saturated halogenated hydrocarbons containing one or more fluorine atoms, ketones such as acetone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate. Kind is used. Moreover, alcohols, such as t-butanol and ethanol, can be used as a chain transfer agent for molecular weight adjustment.

A normal radical polymerization initiator can be used as the polymerization initiator. Specific examples include peroxides such as diisopropyl peroxybiscarbonate and dilauroyl peroxide, and azo compounds such as azobisisobutyronitrile. As a commercial product, V40 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) or the like may be used.
The usage-amount of a polymerization initiator can be changed suitably, Usually, about 0.05-1 mass part is preferably employ | adopted per 100 mass parts of polymeric compounds. These polymerization initiators may be added all at once, but may be added in portions as necessary.

  In order to keep the polymerization reaction system on the alkali side during the polymerization, the polymerization reaction is preferably performed in the presence of a basic compound. The basic compound can be selected from a wide range of organic basic compounds and inorganic basic compounds. Of the organic basic compounds, alkylamines such as triethylamine and alkylphosphines such as triethylphosphine are preferable. Among the inorganic basic compounds, carbonates, hydroxides or oxides of alkali metals or alkaline earth metals such as potassium carbonate, potassium hydroxide, sodium hydroxide and magnesium oxide are preferable.

The reaction temperature of the polymerization reaction is preferably 40 ° C to 70 ° C. The reaction pressure is preferably 0.2 to 2.0 MPa, more preferably 0.2 to 1.0 MPa.
The liquid crystalline polymer compound (Aa) thus obtained is blended into a thermally crosslinkable liquid crystalline composition after obtaining a purification treatment such as removal of unreacted raw material compounds and polymerization solvent.

(Crosslinking agent)
In the thermally crosslinkable liquid crystalline composition containing the vinyl ether liquid crystalline polymer compound (Aa) having a thermally crosslinkable group, specifically, as a crosslinking agent used in combination with the liquid crystalline polymer compound (Aa), A crosslinking agent (Da) having a thermal functional group and a reactive functional group of the liquid crystalline polymer compound (Aa) is used.

  When the thermally crosslinkable group possessed by the liquid crystalline polymer compound (Aa) is a hydroxyl group, for example, a crosslinking agent having a functional group such as an isocyanate group, a carboxyl group, or an acyl chloride group can be used. More specifically, as a crosslinking agent, a polyisocyanate compound having two or more isocyanate groups in one molecule, a melamine resin such as methylated melamine, methylolated melamine, and butyrolated melamine, methylated urea, butylated urea, etc. A urea resin etc. are mentioned. Of these, polyisocyanate compounds are preferred.

Similarly, when the thermally crosslinkable group is a thiol group, a crosslinking agent having a functional group such as a vinyl group can be used. When the thermally crosslinkable group is a carboxyl group, a crosslinking agent having a functional group such as a hydroxyl group or an epoxy group can be used. When the thermally crosslinkable group is a silyl group, a crosslinking agent having a functional group such as a hydroxyl group or a carboxyl group can be used.
When the thermally crosslinkable group is an amino group, a crosslinking agent having a functional group such as a carboxyl group or an epoxy group can be used. When the thermally crosslinkable group is an epoxy group, a crosslinking agent having a functional group such as a carboxyl group or an amino group can be used.
When the thermally crosslinkable group is an oxetane group, a crosslinking agent having a functional group such as a carboxyl group or an amino group can be used.

  Further, as a crosslinking agent used in combination with the liquid crystalline polymer compound (Aa), in addition to the crosslinking agent (Da) having a functional group that reacts with a thermally crosslinkable group, the thermal crosslinking possessed by the liquid crystalline polymer compound (Aa). A crosslinking agent having the same thermally crosslinkable group as the functional group may be used. As such a crosslinking agent, a crosslinking agent having the thermally crosslinkable group at the end of the molecular chain is preferable. The number of thermally crosslinkable groups is preferably 1 or more per molecule of the crosslinking agent, and more preferably a bifunctional structure having one each of the thermally crosslinkable groups at both ends of the linear molecular chain. In particular, when it is desired to efficiently increase the number of thermally crosslinkable groups per gram of the liquid crystalline composition, it is preferable to use a bifunctional compound. Moreover, as a crosslinking agent which has this heat crosslinkable group, a low molecular weight liquid crystalline compound (henceforth a liquid crystalline low molecular compound) (Db) is preferable.

As described above, the liquid crystalline polymer compound (Aa) is a polymer compound having a relatively bulky liquid crystal skeleton in the side chain. The molecules of (Aa) tend to be obstructed and the orientation is not promoted. In the present invention, the low molecular weight liquid crystal compound (Db) is used in combination with the liquid crystal polymer compound (Aa), thereby increasing the degree of freedom of the compound (Aa) during the alignment and improving the alignment. Furthermore, since the compound (Db) is also liquid crystalline, it is aligned with the compound (Aa) to obtain uniform uniaxial alignment as the whole liquid crystalline composition.
The molecular weight of the liquid crystalline low molecular compound (Db) used in the present invention is preferably in the range of 100 to 2,000, more preferably in the range of 200 to 1,000, from the viewpoint of the orientation. .

(Other ingredients)
The thermally crosslinkable liquid crystalline composition containing the vinyl ether liquid crystalline polymer compound (Aa) having a thermally crosslinkable group contains various additives in addition to the liquid crystalline polymer compound (Aa) and the crosslinking agent. May be. Specific examples include a catalyst that promotes a crosslinking reaction between the liquid crystalline polymer compound (Aa) and a crosslinking agent, an ultraviolet absorber, an antioxidant, and a light stabilizer.

(The number of thermally crosslinkable groups per gram of solid content of the liquid crystalline composition)
Here, in order to make the density of the cross-linking points in the optically anisotropic film within the above range, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g, the liquid crystalline composition used for producing the same The number of thermally crosslinkable groups per gram of solid content of the product is adjusted as follows.
For example, a liquid crystalline polymer compound (Aa) having a thermally crosslinkable group, a crosslinking agent (Da) having a functional group that reacts with the thermally crosslinkable group, a catalyst added as necessary, and other crosslinking involved In the case where the liquid crystalline composition is composed of optional components that are not, the number of thermally crosslinkable groups possessed by the liquid crystalline polymer compound (Aa) per 1 g of the liquid crystalline composition solid content, N _Aa [pieces / g] And the number of functional groups of the cross-linking agent (Da) per 1 g of the liquid crystalline composition solid content, N _Da [pieces / g], are adjusted so that the smaller number falls within the above range. .

Further, a liquid crystalline polymer compound (Aa) having a thermally crosslinkable group, a crosslinking agent (Da) having a functional group that reacts with the thermally crosslinkable group, and a liquid crystal having the same thermally crosslinkable group as the thermally crosslinkable group In the case where the liquid crystalline composition is composed of the low molecular weight compound (Db), the catalyst added as necessary, and other optional components not involved in crosslinking, the liquid crystalline polymer compound (Aa) has Number per 1 g of liquid crystalline composition solid content of thermally crosslinkable group, Number per 1 g of liquid crystalline composition solid content of liquid crystalline low molecular compound (Db) in N _Aa [number / g], Comparison of N _Aa + N _Db [pieces / g] to which N _Db [pieces / g] is added and the number N _Da [pieces / g] of the functional group of the crosslinking agent (Da) per 1 g of the liquid crystal composition solid content Thus, the smaller number is adjusted to be within the above range.

  Here, in the optically anisotropic film, it is assumed that the higher the number of cross-linking points in the film, the higher the structural stability is obtained. However, the liquid crystalline compound contained in the liquid crystalline composition as the constituent raw material is oriented. However, there are limits to crosslinking at many points on the molecule. That is, when the number of cross-linking points is increased, the orientation of the liquid crystal compound is not sufficient. The optically anisotropic film of the present invention is an optically anisotropic film that is sufficiently oriented while having a crosslinking point in the above-mentioned range at a level that cannot be achieved by conventional techniques. This was made possible by performing the above alignment.

Regarding the thermally crosslinkable liquid crystalline composition containing the vinyl ether liquid crystalline polymer compound (Aa) having a thermally crosslinkable group, the following liquid crystalline composition in which the thermally crosslinkable group is a hydroxyl group is exemplified (hereinafter referred to as “No. This will be described in detail by “example 1”).
<First example>
The liquid crystal composition of the first example is a liquid crystal polymer compound (Aa11) represented by the above formula (Aa11) as the liquid crystal polymer compound (Aa), and a polymer unit based on the compound (a2) is A crosslinker (Da) containing a liquid crystalline polymer compound (Aa-1) represented by the following formula (Aa-1) in which the thermally crosslinkable group (L ¹ ) is a hydroxyl group and having a functional group reactive with the hydroxyl group ) As a liquid crystal composition containing a polyisocyanate compound (Da-1) having an isocyanate group. In addition, in this liquid crystalline composition, the liquid crystalline low molecular weight compound (Db-1) which has a hydroxyl group may be contained as another type of crosslinking agent.

ただし、式（Ａａ−１)中の記号は、上記式（Ａａ１１）の記号と同じ意味を示す。

However, the symbols in formula (Aa-1) have the same meaning as the symbols in formula (Aa11).

  A polyisocyanate compound is mentioned as a compound which has an isocyanate group used for the liquid crystalline composition of a 1st example. As the polyisocyanate compound, any compound having two or more isocyanate groups in one molecule can be used without particular limitation. Specifically, a known or well-known polyisocyanate compound or a modified product thereof can be employed.

  Examples of such polyisocyanate compounds include aliphatic polyisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; m- or p-phenylene diisocyanate, m-xylylene diisocyanate (XDI), 2,4- or 2, Aromatic polyisocyanate compounds such as 6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), naphthalene-1,5-diisocyanate, 4,4′-diisocyanate-3,3′-dimethyldiphenyl; isophorone diisocyanate , Cycloaliphatic polyisocyanate compounds such as hydrogenated xylylene diisocyanate (hydrogenated XDI) and dicyclohexylmethane 4,4′-diisocyanate (hydrogenated MDI); Down diisocyanate, crude polyisocyanate compounds such as crude diphenylmethane diisocyanate; carbodiimide-modified diphenylmethane diisocyanate, polyol-modified diphenylmethane diisocyanate, modified polyisocyanate compounds such as polyol-modified hexamethylene diisocyanate.

  These polyisocyanate compounds are dimer or trimer by burette type, isocyanurate ring type, uretdione type, etc., or block type polyisocyanate compounds obtained by reacting isocyanate groups with blocking agents. Good.

  Examples of the blocking agent include alcohols, phenols, caprolactams, oximes, and active methylene compounds. A polyisocyanate compound may be used individually by 1 type, or may use 2 or more types together.

  When a block type polyisocyanate compound is used as a crosslinking agent in the liquid crystalline composition, the hydroxyl group of the liquid crystalline polymer compound as described above usually does not react unless it is generally 140 ° C. or higher. In the case of reaction / crosslinking, it is preferable to use a non-blocked polyisocyanate compound which is not blocked.

  In the liquid crystalline composition of the first example, the crosslinking reaction between the liquid crystalline polymer compound (Aa-1) having a hydroxyl group and the polyisocyanate compound (Da-1) is a liquid crystalline polymer compound in the liquid crystalline composition. (Aa-1) is performed in an aligned state, that is, in a state showing a liquid crystal phase. Moreover, when this liquid crystalline composition contains the liquid crystalline low molecular compound (Db-1) which further has a hydroxyl group, in a liquid crystalline composition, a liquid crystalline high molecular compound (Aa-1) and a liquid crystalline low molecular compound ( The crosslinking reaction is performed in a state where Db-1) is aligned, that is, in a state showing a liquid crystal phase.

  As will be described later, the atmospheric temperature for maintaining the liquid crystal composition in a liquid crystal phase is less than the nematic phase-isotropic phase transition temperature, that is, less than the clearing point (Tc) and above the glass transition temperature (Tg). Since it is preferably (Tc-10) ° C. or lower (Tc-30) ° C. or higher, when selecting the polyisocyanate compound (Da-1), the compound (Aa-1) and the compound (Da-1) And a reaction temperature at least lower than the Tc is selected. From such a viewpoint, in the present invention, a non-blocking polyisocyanate compound is preferably used as the polyisocyanate compound (Da-1).

  On the other hand, in a state where the liquid crystalline polymer compound (Aa-1) having a hydroxyl group and the liquid crystalline low molecular compound (Db-1) having a hydroxyl group optionally contained are not aligned at all, or the alignment is not sufficient, In order to avoid cross-linking by reacting with the polyisocyanate compound (Da-1), the reaction temperature is preferably room temperature or higher. Select a combination of liquid crystalline polymer compound (Aa-1), liquid crystalline low molecular compound (Db-1) and polyisocyanate compound (Da-1) having a reaction temperature in the range of room temperature to (Tc-10) ° C. By doing so, it can be adjusted such that the orientation and crosslinking are performed simultaneously, or the orientation and crosslinking are performed stepwise in that order.

  In addition, from the viewpoint of light resistance of the optically anisotropic film formed from the liquid crystalline composition, the polyisocyanate compound (Da-1) used in the first example is the aliphatic polyisocyanate compound or alicyclic compound. Polyisocyanate compounds are preferred. Examples of such a polyisocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated MDI, trimethylhexamethylene diisocyanate, hydrogenated XDI, or their isocyanurate-modified, trimethylol-modified, trisburette, etc. An amine derivative etc. are mentioned.

  Further, in consideration of the orientation of the liquid crystalline composition, the polyisocyanate compound (Da-1) is the above liquid crystalline polymer compound (Aa-1) having a hydroxyl group or a liquid crystalline low molecular compound having a hydroxyl group optionally contained. A structure that does not hinder the uniaxial orientation of (Db-1) is preferable. In the case of a polyisocyanate compound having two isocyanate groups in one molecule, a polyisocyanate compound having a linear structure or a molecular structure close to a straight chain is preferable. In the case of a polyisocyanate compound having 3 or more isocyanate groups in one molecule, a polyisocyanate compound having a small molecular weight is preferred.

  Specifically, in the case of a polyisocyanate compound having an isocyanurate structure, a trimer consisting of three molecules of a diisocyanate monomer is preferable, and in the case of having a biuret structure, 1- (6-cyanatohexyl) -3- (6 Biuret isocyanate compounds having a hexamethylene structure such as -isocyanatohexyl) -1-((6-isocyanatohexyl) carbamoyl) urea are preferred.

  Among the polyisocyanate compounds exemplified as the preferred polyisocyanate compound (Da-1) from the viewpoint of light resistance, the polyisocyanate compound (Da-1) having a preferred structure considering the orientation of the liquid crystalline composition is given as hexa Examples thereof include methylene diisocyanate, hydrogenated MDI or their isocyanurate-modified products, trimethylol-modified products, and trifunctional amine derivatives.

  Such a polyisocyanate compound (Da-1) can be produced by a conventionally known method, and a commercially available product containing this composition may be used. As a commercially available product, for example, in the case of a polyisocyanate compound having an isocyanurate structure, “Desmodule (trade name, manufactured by Bayer)” or the like, in the case of having a biuret structure, “Duranate (trade name, manufactured by Asahi Kasei Co., Ltd.)”, etc. Therefore, a product that meets the above conditions can be selected as appropriate. Specifically, Death Module N3300, TLA-100, etc. are preferably mentioned, respectively.

  The blending amount of the polyisocyanate compound (Da-1) in the first example includes the hydroxyl group of the liquid crystalline polymer compound (Aa-1) contained in the liquid crystalline composition, and optionally described below. The compounding quantity which the molar equivalent of the isocyanate group which a polyisocyanate compound (Da-1) has is 1.0-2.0 times with respect to the total molar equivalent of the hydroxyl group which a liquid crystalline low molecular compound (Db-1) has. Preferably, the blending amount is 1.0 to 1.5 times. When the molar equivalent of the isocyanate group with respect to the total molar equivalent of the hydroxyl group is 1.0 times or more, the crosslinking is sufficiently performed and stable orientation can be maintained. can get.

  In the first example, as the liquid crystalline low molecular weight compound (Db-1) having a hydroxyl group that can be used as a crosslinking agent, specifically, a compound having one hydroxyl group per molecule represented by the following formula (4) (Monofunctional compound) or a compound (bifunctional compound) having two hydroxyl groups per molecule represented by formula (5). As described above, when it is desired to efficiently increase the number of thermally crosslinkable groups per gram of the liquid crystalline composition, it is more preferable to use a bifunctional compound.

(Monofunctional compound)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -W 31 - (E 31) h3 -W 32 - (E 32) j3 - (E 33) k3 -E 34 -R 32 ...... (4 )
However, the symbol in Formula (4) is as follows.
R ³¹ : a group having 1 to 12 carbon atoms, a polyfluoroalkylene group having 1 to 12 carbon atoms, or a group represented by —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ — (x is 1 to 6 Integer).
R ^{32 is} an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a trifluoromethyl group, or a cyano group, and the hydrogen atom bonded to the carbon atom in the group is a fluorine atom. May be substituted.

E ³¹ , E ³² , E ³³ , E ³⁴ : each independently a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or a trans-2,6-decahydronaphthalenyl group, and these A hydrogen atom bonded to a carbon atom in the group may be substituted with a fluorine atom, a chlorine atom, or a methyl group.
m3: An integer from 0 to 3.
n3: An integer from 0 to 3.
h3, j3, k3: each independently 0 or 1, and 1 ≦ h3 + j3 + k3 holds.
W ³¹ : ether group (—O—), ester group (—CO—O—, —O—CO—) or a single bond.
W ³² : ether group (—O—), ester group (—CO—O—, —O—CO—), —CF ₂ —O—, —O—CF ₂ — or a single bond.

(Bifunctional _{compound) HO- (CH 2) m4 -R} 41 - (CH 2) n4 -W 41 - (E 41) h4 -W 42 - (E 42) j4 - (E 43) k4 -E 44 - ^{_{W 43 - (CH 2) 04}} -R 42 - (CH 2) p4 -OH ... (5)
However, the symbol in Formula (5) is as follows.
R ⁴¹ and R ^{42 are} each independently represented by an alkylene group having 1 to 12 carbon atoms, a polyfluoroalkylene group having 1 to 12 carbon atoms, or —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ —. Group (x is an integer of 1-6).
E ⁴¹ , E ⁴² , E ⁴³ , E ⁴⁴ : each independently a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or a trans-2,6-decahydronaphthalenyl group, and A hydrogen atom bonded to a carbon atom in the group may be substituted with a fluorine atom, a chlorine atom, or a methyl group.

m4: An integer from 0 to 3.
n4: An integer from 0 to 3.
o4: An integer from 0 to 3.
p4: An integer from 0 to 3.
h4, j4, k4: each independently 0 or 1, and 1 ≦ h4 + j4 + k4 holds.
W ⁴¹ : an ether group (—O—), an ester group (—CO—O—, —O—CO—) or a single bond.
W ⁴² , W ⁴³ : each independently an ether group (—O—), an ester group (—CO—O—, —O—CO—), —CF ₂ —O—, —O—CF ₂ — or a single bond .

The compound (4) and the compound (5) have a liquid crystalline skeleton having a plurality of 6-membered rings (in the above formula (4), (E ³¹ ) _{h 3} -W ^32- (E ³² ) _{j 3-} (E ³³ ) _{k 3-} in E ^34, in the formula _{^{(5), (E 41)}} h4 -W 42 - (E 42) j4 - a compound containing indicated _{(E 43)} respectively k4 ^{-E 44),} reactive (crosslinking Property) and liquid crystal properties.

Compound (4) and the compound (5) is in the spacer portion of the molecule (the formula ^{_{(4), - (CH 2}} ) m3 -R 31 - (CH 2) n3 - a, in the formula (5), - ( CH ₂ ) _{m 4} —R ⁴¹ — (CH ₂ ) _{n 4} — and — (CH ₂ ) ₀₄ —R ⁴² — (CH ₂ ) _{p 4} — respectively), an alkylene group, a polyfluoroalkylene group, a polyfluoroalkylene oxide It has at least one group selected from the group.

In the compound (4) and the compound (5), R ³¹ in the formula (4) and R ⁴¹ in the formula (5) are used so as not to lower the compatibility with the component not containing a fluorine atom in the liquid crystal composition. When is an alkylene group or a polyfluoroalkylene group, the number of carbons in these groups is 1-12. When R ³¹ and R ⁴¹ are polyfluoroalkylene oxide groups represented by —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ —, x is an integer of 1 to 6. From the relationship between leveling properties and compatibility, the alkylene group preferably has 2 to 8 carbon atoms, the polyfluoroalkylene oxide group x preferably has an integer of 1 to 4, and the polyfluoroalkylene group has 2 to 8 carbon atoms. Is preferred. Moreover, as for carbon number of an alkylene group, 2, 4, and 6 are preferable so that non-crystallinity may be shown. The number of carbon atoms of the polyfluoroalkylene group is particularly preferably 2, 4, or 6. Furthermore, in the case of a polyfluoroalkylene group, it is preferable that one or more fluorine atoms are bonded to the terminal carbon atom, and a perfluoroalkylene group is more preferable. The polyfluoroalkylene group has better liquid crystallinity than the polyfluoroalkylene oxide group.

Examples of the polyfluoroalkylene group include the following groups.
_{- (CF 2) 2 -,} - (CF 2) 4 -, - (CF 2) 6 -, - (CF 2) 8 -, - (CF 2) 10 -, - (CF 2) 12 -, - CF _{2 CHF -, - CF 2 CHF} (CF 2) 2 -, - CF 2 CHF (CF 2) 4 -, - CF 2 CHF (CF 2) 2 CHFCF 2 -, - CF 2 CHF (CF 2) 4 CHF- _{, -CF 2 CH 2 (CF 2} ) CH 2 CF 2 -, - CF 2 CHF (CF 2) 4 CHFCF 2 -, - CHF (CF 2) 6 CHF -, - CF 2 CH (CF 2 CF 3) ( CF _{2) 2} CH ₂ -.

Examples of the alkylene group include the following groups.
_{- (CH 2) 2 -,} - (CH 2) 4 -, - (CH 2) 6 -, - (CH 2) 8 -, - (CH 2) 10 -, - (CH 2) 12 -.

The compound (4) and the compound (5) have an alkyl group, an alkoxy group, a fluorine atom, a trifluoromethyl group, or a cyano group as R ³² and R ⁴² , whereby the compound (4) and the compound (5) The temperature range which shows the liquid crystallinity of the liquid crystalline composition containing becomes wide. When R ³² and R ⁴² are an alkyl group or an alkoxy group, the number of carbon atoms is preferably 2 to 6, and more preferably 3 to 5. When R ³² and R ⁴² have a straight chain structure, the compound (4) and the compound (5) are particularly preferable because the temperature range in which liquid crystallinity is exhibited can be widened. m3, m4, n3, n4, o4 and p4 are each an integer of 0 to 3, preferably 1 or 2. Further, from the viewpoint of ease of production of the compound (5), m4 and p4, and n4 and o4 are preferably the same value. h3, h4, j3, j4, k3, and k4 are each 0 or 1. However, at least one of h3, j3, and k3 is 1, and 1 ≦ h3 + j3 + k3 holds. In addition, at least one of h4, j4, and k4 is 1, and 1 ≦ h4 + j4 + k4 holds.

W ³¹ is an ether group (—O—), an ester group (—CO—O—, —O—CO—) or a single bond, and W ³² is an ether group (—O—), an ester group (—CO -O-, -O-CO-), -CF ₂ -O-, -O-CF ₂ -or a single bond. W ⁴¹ is an ether group (—O—), an ester group (—CO—O—, —O—CO—) or a single bond, and W ⁴² is an ether group (—O—), an ester group ( -CO-O-, -O-CO-), -CF ₂ -O-, -O-CF ₂ -or a single bond. W ^{43 is} also an ether group (—O—), an ester group (—CO—O—, —O—CO—), —CF ₂ —O—, —O—CF ₂ — or a single bond.

Preferable specific examples of compound (4) include the following compounds (4A) to (4J).
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-Ph-Ph-R 32 (4A)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-Ph-Cy-Ph-R 32 (4B)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-Ph-Cy-Ph-Ph-R 32 (4C)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-Cy-Cy-R 32 (4D)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-CO-Cy-Cy-R 32 (4E)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-Cy-Cy-Cy-R 32 (4F)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-CO-Dhn-Cy-R 32 (4G)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-CO-Dhn-Cy-Cy-R 32 (4H)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-Dhn-Cy-R 32 (4I)
^{_{HO- (CH 2) m3 -R 31}} - (CH 2) n3 -O-CO-Cy-Cy-Cy-R 32 (4J)

However, the symbols R ³¹ , R ³² , m3 and n3 in the formulas (4A) to (4J) are independent for each formula, and are the same as the above-mentioned definition. Ph, Cy and Dhn are also the same as defined above independently for each formula, and a plurality of Ph and Cy in one molecule are also independently substituted or unsubstituted phenylene groups and substituted Or it may represent an unsubstituted cyclohexylene group.

Preferable specific examples of compound (5) include the following compounds (5A) to (5N).
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-Ph-Ph-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5A)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-Ph-Cy-Ph-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5B)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-Ph-Cy-Ph-Ph-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5C)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-Cy-Cy-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5D)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-CO-Cy-Cy-CO-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5E)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-Cy-Cy-Cy-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5F)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-CO-Dhn-Cy-CO-0- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5G)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-CO-Dhn-Cy-Cy-CO-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5H)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-Dhn-Cy-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5I)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -O-CO-Cy-Cy-Cy-CO-O- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5J)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -CO-O-Cy-Cy-O-CO- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5K)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -CO-O-Dhn-Cy-O-CO- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5L)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -CO-O-Dhn-Cy-Cy-O-CO- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5M)
^{_{HO- (CH 2) m4 -R 41}} - (CH 2) n4 -CO-O-Cy-Cy-Cy-O-CO- (CH 2) 04 -R 42 - (CH 2) p4 -OH (5N)

However, the symbols R ⁴¹ , R ⁴² , m4, n4, o4, and p4 in the formulas (5A) to (5N) are independent for each formula and are the same as the above-mentioned definition. Ph, Cy and Dhn are also the same as defined above independently for each formula, and a plurality of Ph and Cy in one molecule are also independently substituted or unsubstituted phenylene groups and substituted Or it is an unsubstituted cyclohexylene group.

In the synthesis method of the monofunctional compound (4), when (41) W ³¹ is a carbonyl group (—CO—) in the above formula (4) (in the preferred compound, the compound (4E), the compound (4G ), Compound (4H) and compound (4J)) and (42) when W ³¹ is a single bond (in the above preferred compounds, compound (4A) to compound (4D), compound (4F), compound ( This can be explained in the same way as 4I).

In the above formula (4), when (41) W ³¹ is a carbonyl group (—CO—), for example, the compound (4E) is represented by the reaction formula (F-1) of the method for synthesizing the vinyl ether compound (a1). , (1E0b) can be produced in the same manner as the intermediate substance (01b-4) obtained. In addition, the compound (4G), the compound (4H), and the compound (4J) are the same as the compound (21AA: trans-4- (trans-4-alkylcyclohexyl) cyclohexanecarboxylic acid (HO—CO—Cy—) used above. In place of Cy- (CH ₂ ) _r H)), a compound in which -Cy-Cy- is replaced with -Dhn-Cy-, -Dhn-Cy-Cy-, or -Cy-Cy-Cy-, respectively It can be manufactured by using. Note that in the reaction formula (F-1) of the synthesis method, a divalent group sandwiched between hydroxyl groups is represented by — (CH ₂ ) _{m 3} —R ³¹ — (CH ₂ ) _n3 instead of the starting material (01b). - ^{(m3, R 31,} n3 is suitably selected in the above range) by using the compounds were, in the compound ^{(4), W 31} is capable of producing various compounds a carbonyl group (-CO-).

In the above formula (4), when (42) W ³¹ is a single bond, for example, the compound (4A) is obtained by changing (1A0b) in the reaction formula (F-3) of the synthesis method of the vinyl ether compound (a1). It can be produced in the same manner as the intermediate substance (01b-6) during production. Alternatively, the compound (4C) can be produced in the same manner as the intermediate substance (81b) for producing (1C0bb) in the reaction formula (F-4) of the synthesis method of the vinyl ether compound (a1).

In addition, the compound (4B), the compound (4D), the compound (4F) and the compound (4I) are groups in which the hydroxyl group is removed instead of the compound (13A) and the compound (13C) used above, respectively. -Ph-Cy-Ph-R ³² , -Cy-Cy-R ³² , -Cy-Cy-Cy-R ³² or -Dhn-Cy-R ³² can be used for production. As described above, in the reaction formula (F-3) of the synthesis method, instead of the starting material (01b) or in the reaction formula (F-4) of the synthesis method, instead of the compound (71b), A divalent group sandwiched between two hydroxyl groups or between a hydroxyl group and Br is represented by — (CH ₂ ) _{m 3} —R ³¹ — (CH ₂ ) _{n 3} — (m 3, R ³¹ and n 3 are appropriately selected within the above range) In the compound (4), various compounds in which W ³¹ is a single bond can be produced.

When the bifunctional compound (5) is (51) W ⁴¹ is (—CO—O—) and W ⁴³ is (—O—CO—) by the bonding method of W ⁴¹ and W ⁴³ (preferably above) Compound (corresponding to compound (5K) to compound (5N)), (52) when W ⁴¹ is (—O—CO—), and W ⁴³ is (—CO—O—) (in the above preferred compounds, the compound (5E), compound (5G), compound (5H), equivalent to compound (5J)), (53) when W ⁴¹ and W ⁴³ are (—O—) (in the above preferred compounds, compounds (5A) to Compound (5D), compound (5F), and compound (5I)).

As a synthesis method of the compound (5), when the compound (5) is classified into the above (51) (W ⁴¹ : (— CO—O—), W ⁴³ : (— O—CO—)) Taking the compound (5K) as an example, a method shown in the following reaction formula (B-1) can be mentioned. In addition, the symbol in a formula shows the same meaning as the above. In addition, a compound that is one type of the compound (5K) obtained by the following reaction formula (B-1) is referred to as a compound (5K-1).

  First, bi (cyclohexane) -4,4′-diol (compound (4a)) and 4-pentenoic acid (compound (4b)) are added in the presence of dicyclohexylcarbodiimide and 4- (N, N-dimethylamino) pyridine. The compound (4c) is obtained by reaction in chloroform. Further, compound (4c) is reacted with 9-borabicyclo [3.3.1] nonane (9-BBN) in tetrahydrofuran and further reacted with sodium hydroxide in the presence of hydrogen peroxide to give compound (5K -1) is obtained.

In the above reaction, in place of the compound (4a), a divalent group -Cy-Cy- sandwiched between hydroxyl groups is replaced with -Dhn-Cy-, -Dhn-Cy-Cy-, or -Cy-Cy-. If each of the compounds represented by Cy- is used, a compound classified as compound (5L), compound (5M), or compound (5N) can be synthesized. Further, by using an unsaturated carboxylic acid in which the carbon number of the unsaturated hydrocarbon group in 4-pentenoic acid (H ₂ C═CH (CH ₂ ) ₂ OOH: compound (4b)) is changed, — (CH ₂ ) ^{_{m4 -R 41 - (CH 2)}} n4 - and ^{_{- (CH 2) 04 -R 42}} - (CH 2) p4 - number of carbon atoms of the divalent group is different from the compound (5) can be synthesized represented by.

When the compound (5) is classified into the above (52) (W ⁴¹ : (—O—CO—), W ⁴³ : (—CO—O—)), the compound (5E) is taken as an example and the following The method shown to Reaction formula (B-2) is mentioned. In addition, the symbol in a formula shows the same meaning as the above. In addition, a compound that is one type of the compound (5E) obtained by the following reaction formula (B-2) is referred to as a compound (5E-1).

  Compound (4e) is synthesized from compound (4d) by the same reaction as that for obtaining compound (01b-2) from starting material (01b) in reaction formula (F-1) of the synthesis method. The obtained compound (4e) is reacted with 4,4′-bicyclohexyldicarboxylic acid (compound (4f)) in chloroform in the presence of dicyclohexylcarbodiimide and 4- (N, N-dimethylamino) pyridine. To obtain the compound (4 g). Further, this compound (4 g) is reacted with p-toluenesulfonic acid to obtain the above compound (5E-1).

In the above reaction, instead of the compound (4f), a divalent group -Cy-Cy- sandwiched between carboxyl groups is replaced with -Dhn-Cy-, -Dhn-Cy-Cy-, or -Cy-Cy. If each of the compounds represented by -Cy- is used, a compound classified as compound (5G), compound (5H), or compound (5J) can be synthesized. In addition, a divalent group sandwiched between hydroxyl groups in the compound (4d) (HO (CH ₂ ) ₆ OH) is represented by — (CH ₂ ) _{m 4} —R ⁴¹ — (CH ₂ ) _{n 4} — (— (CH ₂ )). ^{_{04 -R 42 - (CH 2)}} p4 - with divalent group represented by), a compound that differ carbon number of the spacer portion (5) can be synthesized.

When the compound (5) is classified into the above (53) (W ⁴¹ : (— O—), W ⁴³ : (— O—)), the following reaction formula (B The method shown to -3) is mentioned. In addition, the symbol in a formula shows the same meaning as the above. In addition, a compound that is one type of compound (5D) obtained by the following reaction formula (B-3) is referred to as compound (5D-1).

In the above reaction, in place of the compound (4a), a divalent group -Cy-Cy- sandwiched between hydroxyl groups is changed to -Ph-Ph-, -Ph-Cy-Ph-, -Ph-Cy-Ph-. When the compounds represented by Ph-, -Cy-Cy-Cy-, or -Dhn-Cy- are used, the compound (5A), the compound (5B), the compound (5C), the compound (5F) or the compound (5I ) Can be synthesized. In the Br (CH ₂ ) ₅ OH, a divalent group sandwiched between Br and a hydroxyl group is represented by — (CH ₂ ) _{m 4} —R ⁴¹ — (CH ₂ ) _{n 4} — (— (CH ₂ ) ₀₄ —R. ^{By using a} divalent group represented by _42- (CH ₂ ) _p4- ), a compound (5) having a different carbon number in the spacer portion can be synthesized.

  In the liquid crystalline composition of the first example, the blending amount of the liquid crystalline low molecular weight compound (Db-1) (crosslinking agent) having a hydroxyl group, which is preferably blended as a crosslinking agent, is the above liquid crystalline polymer compound (Aa). 1-30 parts by mass is preferable with respect to 100 parts by mass of 1), and 1-20 parts by mass is more preferable. If the compounding amount of the liquid crystalline low molecular compound (Db-1) is 1 part by mass or more with respect to 100 parts by mass of the liquid crystalline polymer compound (Aa-1), a sufficient effect of improving the orientation can be obtained. If it is at most part by mass, the light resistance of the optically anisotropic film obtained can be sufficiently maintained.

  In addition, when the compounding quantity of the said liquid crystalline low molecular compound (Db-1) which has the said hydroxyl group in the liquid crystalline composition of a 1st example is shown with a molar ratio with a liquid crystalline polymer compound (Aa-1), it will be liquid crystal. The compounding amount is preferably 1.0 to 2.0 mol, more preferably 1.0 to 1.5 mol based on 1 mol of the conductive polymer compound (Aa-1).

  Here, the blending amount of the polyisocyanate compound (Da-1) in the first example is preferably a hydroxyl group of the liquid crystalline polymer compound (Aa-1) contained in the liquid crystalline composition, and optionally The molar equivalent of the isocyanate group of the polyisocyanate compound (Da-1) is 1.0 to 2.0 times the total molar equivalent of the hydroxyl group of the liquid crystalline low molecular compound (Db-1) to be blended. It is a blending amount. Therefore, the density of crosslinking points in the optically anisotropic film obtained using the liquid crystalline composition in the first example is the same as the number of hydroxyl groups per 1 g of the liquid crystalline composition solid content.

Therefore, in the liquid crystalline composition of the first example, the number of hydroxyl groups of the liquid crystalline polymer compound (Aa-1) per 1 g of the liquid crystalline composition solid content, N _Aa-1 [pieces / g], Or when liquid crystalline low molecular weight compound (Db-1) is contained, the number per 1g of liquid crystalline composition solid content of the liquid crystalline low molecular weight compound (Db-1), N _Db-1 [ N _Aa-1 + N _Db-1 [pieces / g] is added within the range of the present invention, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g. After the amount is adjusted, the blending ratio of each compound is further adjusted as described above.

  The liquid crystal composition of the first example includes the above liquid crystal polymer compound (Aa-1) having a hydroxyl group, a polyisocyanate compound (Da-1) as a crosslinking agent, and a liquid crystal low molecular compound (Db optionally having a hydroxyl group). -1), but may contain various additives in addition to these. Specifically, a catalyst for promoting a crosslinking reaction by the above three components, an ultraviolet absorber, an antioxidant, a light stabilizer and the like can be mentioned.

  Examples of the catalyst include tin compounds such as conventionally known dibutyltin laurate (DBTDL) that catalyzes the reaction between a hydroxyl group and an isocyanate group, other metal chelate compounds such as aluminum chelate, organic acid systems such as p-toluenesulfonic acid, hydrochloric acid, and the like. Inorganic acid type and amino type catalysts can be used. The amount of the catalyst added is preferably 0 to 1000 ppm, more preferably 10 to 100 ppm, based on 100 parts by mass of the total mass of the three components, although it depends on the type of catalyst used.

  When the liquid crystalline composition of the first example contains an ultraviolet absorber, an antioxidant, a light stabilizer, etc. as other components, the content of these components is based on the total amount of the liquid crystalline composition. 5 mass% or less is preferable and 2 mass% or less is especially preferable.

  The liquid crystalline composition of the first example is obtained by mixing the above essential components so that each component is uniform by adding an additive as necessary, so as to have a predetermined blending ratio. . Moreover, after processing so that each compounding component may be uniformly mixed and dissolved using an appropriate solvent as required, the solvent may be removed by vacuum drying or the like to obtain a liquid crystalline composition.

  As described above, as specific examples of the thermally crosslinkable liquid crystalline composition containing the vinyl ether liquid crystalline polymer compound (A), a liquid crystalline polymer compound (Aa-1) having a hydroxyl group and a polyisocyanate compound (Da as a crosslinking agent). Although the example using the liquid crystalline low molecular weight compound (Db-1) having -1) and optionally a hydroxyl group has been described, the thermally crosslinkable liquid crystalline composition is not limited thereto.

(1-2) Photocrosslinkable liquid crystalline composition When the liquid crystalline composition containing the vinyl ether-based liquid crystalline polymer compound (A) is photocrosslinkable, the liquid crystalline composition has a photocrosslinkable crosslinkable group ( Hereinafter, it contains a vinyl ether liquid crystalline polymer compound (Ab) having a “photocrosslinkable group” (hereinafter also simply referred to as “liquid crystalline polymer compound (Ab)”).

(Liquid crystal polymer compound (Ab))
Of the liquid crystalline polymer compound (Ab), when the photocrosslinkable group is a cyclic ether group that is a photocrosslinkable group corresponding to cationic polymerization, for example, an epoxy group or an oxetane group, The liquid crystalline polymer compound (Ab) can be produced by the same method as the above (1-1) liquid crystalline polymer compound (Aa).

However, when used as a liquid crystalline polymer compound (Ab), in order to make the crosslinking point within the scope of the present invention, for example, a vinyl ether-based polymerizable liquid crystalline compound (A1) and an epoxy group or oxetane group It is necessary to adjust the ratio of the compound (A2) in the copolymer of the vinyl ether type compound (A2) having the above and any other polymerizable compound (A3). For example, the liquid crystalline polymer compound of the above formula (aa11), the ^{L 1} is an epoxy group and an oxetane group, x1 to 60-99, by changing y1 to 1-40, liquid crystalline polymer compound ( Aa11) can be used as the liquid crystalline polymer compound (Ab).

Of the liquid crystalline polymer compound (Ab), a photocrosslinkable group is a photocrosslinkable group corresponding to radical polymerization, such as a vinyl group or a group containing a vinyl group (hereinafter referred to as “vinyl group etc.”), preferably (meta ) In the case of an acryloyl group, the introduction of the vinyl group or the like is, for example, via a thermally crosslinkable group of a polymer unit based on the compound (a2) of the liquid crystalline polymer compound (Aa11) obtained as described above. Done. As a method for introducing a vinyl group or the like into the liquid crystalline polymer compound (Aa11), specifically, a thermal crosslinkable group (L ¹ ) and a reactive group of a polymerization unit based on the compound (a2) are provided at one terminal. And a compound having a vinyl group or the like at the other end is reacted with the liquid crystalline polymer compound (Aa11) under predetermined conditions.

  The group introduced into the terminal of the side chain of the liquid crystalline polymer compound, for example, the liquid crystalline polymer compound (Aa11) is preferably a vinyl group, and a (meth) acryloyl group is introduced as a group having a vinyl group. Is particularly preferred. In addition, an epoxy group or an oxetane group, which is a cationically polymerizable photocrosslinkable group, is introduced into the end of the side chain of a liquid crystalline polymer compound, for example, a liquid crystalline polymer compound (Aa11), in the same manner as the vinyl group. And it is good also as a photocrosslinkable liquid crystalline polymer compound.

Here, as a liquid crystalline polymer compound (Aa11) into which a photocrosslinkable group is introduced, a compound in which the ratio of x1 and y1 is adjusted according to the number of photocrosslinkable groups to be introduced is prepared. For example, when one photocrosslinkable group is introduced at a ratio of 1 to one of the thermally crosslinkable groups (L ¹ ) of the liquid crystalline polymer compound (Aa11), x1 is 60 to 99, y1 Is preferably adjusted to a range of 1 to 40. Moreover, when a photocrosslinkable group is introduce | transduced in the ratio of 2 with respect to ¹ of the heat crosslinkable group (L1) of a liquid crystalline polymer compound (Aa11), x1 is 50-98, y1 is set. A range of 2-50 is preferred.

Hereinafter, taking as an example a liquid crystal polymer compound in which a (meth) acryloyl group is introduced at the end via a thermally crosslinkable group (L ¹ ) in the liquid crystal polymer compound (Aa11), this is referred to as a liquid crystal polymer compound. It will be described as (Ab1). The (meth) acryloyl group is introduced into the end of the side chain through the thermally crosslinkable group (L ¹ ) of the polymer unit based on the compound (a2) in the liquid crystalline polymer compound (Aa11). At the time of introduction, a compound having a reactive functional group in the thermally crosslinkable group (L ¹ ) at one end and a (meth) acryloyl group at the other end is used. The number of (meth) acryloyl groups at the end of the compound is preferably 1 or 2. When it is desired to efficiently increase the number of crosslinkable groups per gram of the liquid crystal composition solid content, 2 Is preferred.

  Here, the adjustment of the number of photocrosslinkable groups per gram of the liquid crystalline composition solid content is also performed by adjusting the ratio of x1 and y1 in the liquid crystalline polymer compound (Aa11) as described above. In the present invention, the liquid crystalline polymer compound to be blended so that the number of photocrosslinkable groups per gram of the liquid crystalline composition solid content in the finally obtained liquid crystalline composition satisfies the above-mentioned conditions of the present invention. In combination with these requirements, each component contained in the liquid crystal composition is designed in consideration of a combination with a crosslinking agent described later.

The liquid crystalline polymer compound (Aa11) is not particularly limited as long as the thermally crosslinkable group (L ¹ ) is selected from the functional groups exemplified above, and among these, as the thermally crosslinkable group (L ¹ ) A liquid crystalline polymer compound (Aa-1) having a hydroxyl group is preferably used. As the group reactive to the hydroxyl group of the compound for introducing a (meth) acryloyl group, a carboxyl group, an isocyanate group and the like are preferable, and an isocyanate group is particularly preferable. That is, a (meth) acryloyl group is introduced at the end of the side chain by a urethane bond between the hydroxyl group of the liquid crystalline polymer compound (Aa-1) and the isocyanate group of the compound used for introducing the (meth) acryloyl group. The liquid crystalline polymer compound (Ab1) is preferred.

  Examples of the isocyanate compound having a (meth) acryloyl group include 1,1-bis (acryloyloxymethyl) ethyl isocyanate and 2-methacryloyloxyethyl isocyanate. For example, dibutyltin laurate (DBTDL) is used as the terminal isocyanate group of these compounds as a conventionally known catalyst for catalyzing the reaction between a hydroxyl group and an isocyanate group, and a liquid crystalline polymer compound (Aa-1) is used. ), The (meth) acryloyl group can be introduced into the side chain.

  Moreover, (meth) acrylic acid chloride, (meth) acrylic acid, etc. were ester-reacted with the hydroxyl group which liquid crystalline polymer compound (Aa-1) has, and the (meth) acryloyl group was introduce | transduced into the terminal of the side chain. A liquid crystalline polymer compound (Ab1) can also be obtained. The reaction may be performed at room temperature, for example, by adding triethylamine, N, N-dimethyl-4-aminopyridine or the like to the raw material components.

  As a specific example, it can be obtained by reacting 1,1-bis (acryloyloxymethyl) ethyl isocyanate with x1 and y1 adjusted to x2 and y2, respectively, in the liquid crystalline polymer compound (Aa-1). The obtained liquid crystalline polymer compound is represented by the following formula (Ab-1). The symbols in formula (Ab-1) all have the same meaning as the symbols in formula (Aa-1) except for x2 and y2. Moreover, x2 shows 60-99 and y2 shows the positive number of 1-40, respectively, and is x2 + y2 = 100.

The number average molecular weight (Mn) of the liquid crystalline polymer compound (Ab) used in the present invention is preferably in the range of 2,000 to 20,000, more preferably in the range of 3,000 to 10,000. The molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) is preferably in the range of 1.0 to 3.0, and more preferably in the range of 1.0 to 2.0.
If the number average molecular weight (Mn) and the molecular weight distribution are in this range, the orientation in a liquid crystal composition containing the molecular weight and the light resistance when used as an optically anisotropic material will be good.
The liquid crystalline polymer compound (Ab) obtained in this manner is subjected to a purification treatment such as removal of unreacted raw material compounds and reaction solvent, and is blended into the photocrosslinkable liquid crystalline composition.

  The liquid crystalline polymer compound (Ab) having a photocrosslinkable group forms a liquid crystalline composition that is a raw material for producing the optically anisotropic film of the present invention only with this and a photopolymerization initiator blended as necessary. Yes. The photocrosslinkable liquid crystalline composition may optionally contain a crosslinking agent.

(Crosslinking agent)
As a crosslinking agent that may optionally be contained in the photocrosslinkable liquid crystalline composition containing the vinyl ether liquid crystalline polymer compound (Ab) having a photocrosslinkable group, the liquid crystalline polymer compound (Ab) has. The crosslinking agent which has the same photocrosslinkable group as a photocrosslinkable group is mentioned. In addition, when the photocrosslinkable group is an acryloyl group and a methacryloyl group, since they have a vinyl group in common, a combination thereof is also possible. Therefore, the acryloyl group and the methacryloyl group are treated as the same photocrosslinkable group.
As such a crosslinking agent, a crosslinking agent having the photocrosslinkable group at the end of the molecular chain is preferable. The number of photocrosslinkable groups is preferably one or more per molecule of the crosslinker, and more preferably a bifunctional structure having one photocrosslinkable group at each end of a linear molecular chain. In particular, when it is desired to efficiently increase the number of photocrosslinkable groups per gram of the liquid crystalline composition, it is preferable to use a bifunctional compound. Moreover, as a crosslinking agent which has this photocrosslinkable group, a liquid crystalline low molecular weight compound (Dbb) is preferable.

As described above, the photocrosslinkable liquid crystalline polymer compound (Ab) is a polymer compound having a relatively bulky liquid crystal skeleton in the side chain, like the above-mentioned thermally crosslinked liquid crystalline polymer compound (Ab). In the case of aligning in a uniaxial method from a state in which R is present at random, the molecules of the compound (Ab) tend to become obstacles and not promoted in a high density state. In the present invention, as in the case of the thermally crosslinkable liquid crystalline composition, the liquid crystalline low molecular weight compound (Dbb) is replaced with the liquid crystalline polymer compound (Ab) in the case of the photocrosslinkable liquid crystalline composition. In combination, the degree of freedom of the compound (Ab) is increased and the orientation is improved, and the compound (Dbb) is also liquid crystalline. Uniform uniaxial orientation was obtained as a whole of the composition.
In addition, 100-2,000 are preferable from the viewpoint of the said orientation, and, as for the molecular weight of the liquid crystalline low molecular compound (Dbb) used for this invention, 200-1,000 are more preferable.

(Other ingredients)
Moreover, the photocrosslinkable liquid crystalline composition containing the vinyl ether type liquid crystalline polymer compound (Ab) having a photocrosslinkable group is various in addition to the liquid crystalline polymer compound (Ab) and a crosslinking agent optionally blended. An additive may be contained. Specifically, a catalyst such as a photopolymerization initiator that promotes a crosslinking reaction by a photocrosslinkable group possessed by a crosslinking agent optionally blended with the liquid crystalline polymer compound (Ab), an ultraviolet absorber, an antioxidant, light A stabilizer etc. are mentioned.

(Number of photocrosslinkable groups per gram of solid content of liquid crystal composition)
Here, in order to make the density of the cross-linking points in the optically anisotropic film within the above range, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g, the liquid crystalline composition used for producing the same The number of photocrosslinkable groups per gram of the product is adjusted as follows.
For example, in the case where the liquid crystalline composition is composed of a liquid crystalline polymer compound (Ab) having a photocrosslinkable group, a photopolymerization initiator added as necessary, and other optional components not involved in crosslinking Is the number of photocrosslinkable groups possessed by the liquid crystalline polymer compound (Ab) per gram of the liquid crystalline composition solids, N _Ab [pieces / g] divided by 2, N _Ab / 2 [pieces / g ] To be within the above range.

In addition, a liquid crystalline polymer compound (Ab) having a photocrosslinkable group, a liquid crystalline low molecular compound (Dbb) having the same photocrosslinkable group as the photocrosslinkable group, and photopolymerization added as necessary When the liquid crystalline composition is composed of an initiator and other optional components not involved in crosslinking, the number of photocrosslinkable groups of the liquid crystalline polymer compound (Ab) per 1 g of the liquid crystalline composition solid content. , _{N Ab} [pieces / g] to the number of the liquid crystal composition solids per 1g of photocrosslinkable groups having liquid crystal low molecular compound (Dbb) _{is, N Dbb} [pieces / g] a _N Ab _{+ N Dbb} plus [ The value obtained by dividing [piece / g] by 2 is adjusted so that (N _Ab + N _Dbb ) / 2 [piece / g] is within the above range.

  In the optically anisotropic film, it is assumed that the higher the number of cross-linking points in the film, the higher the structural stability can be obtained. There is a limit to crosslinking at many points on the molecule in a state where the liquid crystal compound contained in the liquid crystal composition as a raw material is aligned. That is, when the number of cross-linking points is increased, the orientation of the liquid crystal compound is not sufficient. The optically anisotropic film of the present invention has a well-oriented optical system at a level that cannot be achieved by conventional techniques while having a crosslinking point in the above range, whether in the case of thermal crosslinking or photocrosslinking. This is an anisotropic film, and in the present invention, this is made possible by performing orientation by orientation using shearing force described later.

For the photocrosslinkable liquid crystalline composition containing the vinyl ether liquid crystalline polymer compound (Ab) having a photocrosslinkable group, the following liquid crystalline composition in which the photocrosslinkable group is a (meth) acryloyl group is exemplified ( Hereinafter, this will be described in more detail in “second example”.
<Second example>
The liquid crystalline composition of the second example contains a liquid crystalline polymer compound (Ab-1) having two acryloyl groups per polymerization unit at the end of the side chain represented by the above formula (Ab-1), Furthermore, the photocrosslinkable liquid crystal containing the liquid crystalline low molecular compound (Dbb-1) in which the photocrosslinkable group of the liquid crystalline low molecular compound (Dbb) having a photocrosslinkable group as a crosslinking agent is a (meth) acryloyl group. Composition.

The liquid crystalline polymer compound (Ab-1) is as described above.
As the liquid crystalline low molecular weight compound (Dbb-1) having a (meth) acryloyl group used as a crosslinking agent, a compound (monofunctional) having one (meth) acryloyl group represented by the following formula (6) per molecule Compound) or a compound having two (meth) acryloyl groups represented by the formula (7) per molecule (bifunctional compound). As described above, when it is desired to efficiently increase the number of photocrosslinkable groups per gram of the liquid crystalline composition solid content, it is more preferable to use a bifunctional compound.

(Monofunctional compound)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -W 31 - (E 31) h3 -W 32 - (E 32) j3 - (E 33) k3 -E ³⁴ -R ³² (6)
However, the symbol in Formula (6) is as follows.
R ²¹ : a hydrogen atom or a methyl group.
R ³¹ , R ³² , E ³¹ , E ³² , E ³³ , E ³⁴ , W ³¹ and W ³² are the same as the symbols in the above-described formula (4). Further, m3, n3, h3, j3, and k3 are also the same as the symbols in the aforementioned equation (4).

(Bifunctional ^{_{compound) CH 2 = CR 22 -CO-}} O- (CH 2) m4 -R 41 - (CH 2) n4 -W 41 - (E 41) h4 -W 42 - (E 42) j4 - ( _{^{E 43) k4 -E 44 -W 43}} - (CH 2) 04 -R 42 - (CH 2) p4 -O-CO-CR 23 = CH 2 ... (7)
However, the symbol in Formula (7) is as follows.
R ²² and R ^{23 are} each independently a hydrogen atom or a methyl group.
R ⁴¹ , R ⁴² , E ⁴¹ , E ⁴² , E ⁴³ , E ⁴⁴ , W ⁴¹ , W ⁴² and W ⁴³ are the same as the symbols in the above-described formula (5). Further, m4, n4, o4, p4, h4, j4, and k4 are the same as the symbols in the above-described formula (5).

  The compound (6) and the compound (7) are compounds containing a liquid crystalline skeleton composed of a plurality of 6-membered rings, and have both reactivity (crosslinkability) and liquid crystallinity.

  Compound (6) and Compound (7) have at least one group selected from an alkylene group, a polyfluoroalkylene group, and a polyfluoroalkylene oxide group in the spacer portion of the molecule.

In order not to lower the compatibility with the component not containing a fluorine atom in the liquid crystal composition, in the compound (6) and the compound (7), R ³¹ in the formula (6) and R ⁴¹ in the (7) In the case of an alkylene group or a polyfluoroalkylene group, the carbon number of these groups is 1-12. When R ³¹ and R ⁴¹ are polyfluoroalkylene oxide groups represented by —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ —, x is an integer of 1 to 6. From the relationship between leveling properties and compatibility, the alkylene group preferably has 2 to 8 carbon atoms, the polyfluoroalkylene oxide group x preferably has an integer of 1 to 4, and the polyfluoroalkylene group has 2 to 8 carbon atoms. Is preferred. Moreover, as for carbon number of an alkylene group, 2, 4, and 6 are preferable so that non-crystallinity may be shown. The number of carbon atoms of the polyfluoroalkylene group is particularly preferably 2, 4, or 6. Furthermore, in the case of a polyfluoroalkylene group, it is preferable that one or more fluorine atoms are bonded to the terminal carbon atom, and a perfluoroalkylene group is more preferable. The polyfluoroalkylene group has better liquid crystallinity than the polyfluoroalkylene oxide group.

Examples of the polyfluoroalkylene group include the following groups.
_{- (CF 2) 2 -,} - (CF 2) 4 -, - (CF 2) 6 -, - (CF 2) 8 -, - (CF 2) 10 -, - (CF 2) 12 -, - CF _{2 CHF -, - CF 2 CHF} (CF 2) 2 -, - CF 2 CHF (CF 2) 4 -, - CF 2 CHF (CF 2) 2 CHFCF 2 -, - CF 2 CHF (CF 2) 4 CHF- _{, -CF 2 CH 2 (CF 2} ) CH 2 CF 2 -, - CF 2 CHF (CF 2) 4 CHFCF 2 -, - CHF (CF 2) 6 CHF -, - CF 2 CH (CF 2 CF 3) ( CF _{2) 2} CH ₂ -.

Examples of the alkylene group include the following groups.
_{- (CH 2) 2 -,} - (CH 2) 4 -, - (CH 2) 6 -, - (CH 2) 8 -, - (CH 2) 10 -, - (CH 2) 12 -.

The compound (6) and the compound (7) have an alkyl group, an alkoxy group, a fluorine atom, a trifluoromethyl group, or a cyano group as R ³² and R ⁴² , whereby the compound (6) and the compound (7) The temperature range which shows the liquid crystallinity of the liquid crystalline composition containing becomes wide. When R ³² and R ⁴² are an alkyl group or an alkoxy group, the number of carbon atoms is preferably 2 to 6, and more preferably 3 to 5. In the case where R ³² and R ⁴² have a linear structure, the compound (6) and the compound (7) are particularly preferable because the temperature range in which liquid crystallinity is exhibited can be widened. m3, m4, n3, n4, o4 and p4 are each an integer of 0 to 3, preferably 1 or 2. Moreover, it is preferable that m4 and p4 and n4 and o4 are the same value from a viewpoint of the manufacture ease of a compound (7). h3, h4, j3, j4, k3, and k4 are each 0 or 1. However, at least one of h3, j3, and k3 is 1, and 1 ≦ h3 + j3 + k3 holds. In addition, at least one of h4, j4, and k4 is 1, and 1 ≦ h4 + j4 + k4 holds.

W ³¹ is an ether group (—O—), an ester group (—CO—O—, —O—CO—) or a single bond, and W ³² is an ether group (—O—), an ester group (—CO -O -, - O-CO - ), - CF 2 -O -, - O-CF 2 - or a single bond. W ⁴¹ is an ether group (—O—), an ester group (—CO—O—, —O—CO—) or a single bond, and W ⁴² is an ether group (—O—), an ester group ( -CO-O -, - O- CO -), - CF 2 -O -, - O-CF 2 - or a single bond. W ^{43 is} also an ether group (—O—), an ester group (—CO—O—, —O—CO—), —CF ₂ —O—, —O—CF ₂ — or a single bond.

Preferable specific examples of compound (6) include the following compounds (6A) to (6J).
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-Ph-Ph-R 32 (6A)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-Ph-Cy-Ph-R 32 (6B)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-Ph-Cy-Ph-Ph-R 32 (6C)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-Cy-Cy-R 32 (6D)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-CO-Cy-Cy-R 32 (6E)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-Cy-Cy-Cy-R 32 (6F)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-CO-Dhn-Cy-R 32 (6G)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-CO-Dhn-Cy-Cy-R 32 (6H)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-Dhn-Cy-R 32 (6I)
^{_{CH 2 = CR 21 -CO-O-}} (CH 2) m3 -R 31 - (CH 2) n3 -O-CO-Cy-Cy-Cy-R 32 (6J)

However, the symbols R ²¹ , R ³¹ , R ³² , m3, and n3 in the formulas (6A) to (6J) are independent for each formula and are the same as the above-mentioned definition. Further, Ph, Cy and Dhn are the same as defined above independently for each formula. Plural Ph and Cy in one molecule are also independently a substituted or unsubstituted phenylene group and a substituted or unsubstituted cyclohexylene group.

Preferable specific examples of the compound (7) include the following compounds (7A) to (7N).
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-Ph-Ph-O- (CH 2) 04 -R 42 - (CH 2) p4 -O- CO-CR ²³ = CH ₂ (7A)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-Ph-Cy-Ph-O- (CH 2) 04 -R 42 - (CH 2) p4 - O-CO-CR ²³ = CH ₂ (7B)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-Ph-Cy-Ph-Ph-O- (CH 2) 04 -R 42 - (CH 2) _p4 -O-CO-CR ²³ = CH ₂ (7C)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-Cy-Cy-O- (CH 2) 04 -R 42 - (CH 2) p4 -O- CO-CR ²³ = CH ₂ (7D)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-CO-Cy-Cy-CO-O- (CH 2) 04 -R 42 - (CH 2) _p4 -O-CO-CR ²³ = CH ₂ (7E)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-Cy-Cy-Cy-O- (CH 2) 04 -R 42 - (CH 2) p4 - O-CO-CR ²³ = CH ₂ (7F)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-CO-Dhn-Cy-CO-0- (CH 2) 04 -R 42 - (CH 2) _p4 -O-CO-CR ²³ = CH ₂ (7G)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-CO-Dhn-Cy-Cy-CO-O- (CH 2) 04 -R 42 - (CH ₂ ) _p4 -O-CO-CR ²³ = CH ₂ (7H)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-Dhn-Cy-O- (CH 2) 04 -R 42 - (CH 2) p4 -O- CO-C R ²³ = CH ₂ (7I)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -O-CO-Cy-Cy-Cy-CO-O- (CH 2) 04 -R 42 - (CH ₂ ) _p4 -O-CO-CR ²³ = CH ₂ (7J)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -CO-O-Cy-Cy-O-CO- (CH 2) 04 -R 42 - (CH 2) _p4 -O-CO-CR ²³ = CH ₂ (7K)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -CO-O-Dhn-Cy-O-CO- (CH 2) 04 -R 42 - (CH 2) _p4 -O-CO-CR ²³ = CH ₂ (7L)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -CO-O-Dhn-Cy-Cy-O-CO- (CH 2) 04 -R 42 - (CH ₂ ) _p4 -O-CO-CR ²³ = CH ₂ (7M)
^{_{CH 2 = CR 22 -CO-O-}} (CH 2) m4 -R 41 - (CH 2) n4 -CO-O-Cy-Cy-Cy-O-CO- (CH 2) 04 -R 42 - (CH ₂ ) _p4 -O-CO-CR ²³ = CH ₂ (7N)

However, the symbols R ²² , R ²³ , R ⁴¹ , R ⁴² , m4, n4, o4, and p4 in the formulas (7A) to (7N) are independent for each formula and are the same as the above definition. . Also, Ph, Cy and Dhn are the same as defined above independently for each formula, and a plurality of Ph and Cy in one molecule are also independently substituted or unsubstituted phenylene groups and substituted Or it is an unsubstituted cyclohexylene group.

In the synthesis method of the monofunctional compound (6), in the above formula (6), when (61) W ³¹ is a carbonyl group (—CO—) (in the preferred compound, the compound (6E), the compound (6G ), Compound (6H), equivalent to compound (6J)) and (62) when W ³¹ is a single bond (in the above preferred compounds, compound (6A) to compound (6D), compound (6F), compound ( This can be explained in terms of 6I).

In the above formula (6), when (61) W ³¹ is a carbonyl group (—CO—), for example, the compound (6E) is represented by the reaction formula (F-1) of the method for synthesizing the vinyl ether compound (a1). After producing a hydroxyl group-containing compound in the same manner as the intermediate substance (01b-4) obtained when producing (1E0b), the obtained compound is reacted with a compound containing a carboxylic acid group and having a mesogen in the main skeleton. Thus, the terminal hydroxyl group can be converted to a (meth) acryloyloxy group. The mesogen means a rigid molecular chain portion such as a rod-like or plate-like molecular chain (including a cyclo ring and an aromatic ring).

In addition, the compound (6G), the compound (6H), and the compound (6J) are the same as the compound (21AA: trans-4- (trans-4-alkylcyclohexyl) cyclohexanecarboxylic acid (HO—CO—Cy—) used above. In place of Cy- (CH ₂ ) _r H)), a compound in which -Cy-Cy- is replaced with -Dhn-Cy-, -Dhn-Cy-Cy-, or -Cy-Cy-Cy-, respectively Can be used. Note that in the reaction formula (F-1) of the synthesis method, a divalent group sandwiched between hydroxyl groups is represented by — (CH ₂ ) _{m 3} —R ³¹ — (CH ₂ ) _n3 instead of the starting material (01b). Various compounds in which W ³¹ is a carbonyl group (—CO—) in the compound (6) can be produced by using a compound in which — (m3, R ³¹ and n3 are appropriately selected within the above range).

In the above formula (6), if it is ^{(62) W 31} is a single bond, for example, compound (6A), in the reaction formula of the synthesis method of the vinyl ether compound (a1) (F-3), the (1A0b) After the production of a hydroxyl group-containing compound in the same manner as the intermediate substance (01b-6), the resulting compound is reacted with an alcohol-containing mesogen to convert the terminal hydroxyl group to a (meth) acryloyloxy group. Can be manufactured. Alternatively, as the compound (6C), a hydroxyl group-containing compound was produced in the same manner as the intermediate substance (81b) for producing (1C0bb) in the reaction formula (F-4) of the synthesis method of the vinyl ether compound (a1). Then, it can manufacture by making the obtained compound react with the mesogen containing a halogen, and converting the terminal hydroxyl group into a (meth) acryloyloxy group.

The compound (6B), the compound (6D), the compound (6F) and the compound (6I) are each obtained by replacing the group (13A) or the compound (13C) used above with a group except for the hydroxyl group thereof with -Ph. ^{-Cy-Ph-R 32, -Cy} -Cy-R 32, -Cy-Cy-Cy-R 32 or, ^{-Dhn-Cy-R 32} and the compounds can be prepared by using respectively. As described above, in the reaction formula (F-3) of the synthesis method, instead of the starting material (01b) or in the reaction formula (F-4) of the synthesis method, instead of the compound (71b), A divalent group sandwiched between two hydroxyl groups or a hydroxyl group and Br is represented by — (CH ₂ ) _{m 3} —R ³¹ — (CH ₂ ) _{n 3} — (m 3, R ³¹ and n 3 are appropriately selected within the above range) By using the compound, it is possible to produce various compounds in which W ³¹ is a single bond in the compound (6).

The bifunctional compound (7) is preferably (71) when W ⁴¹ is (—CO—O—) and W ⁴³ is (—O—CO—) by the bonding method of W ⁴¹ and W ⁴³ (preferably above). In the compound (corresponding to the compound (7K) to the compound (7N)), (72) when W ⁴¹ is (—O—CO—) and W ⁴³ is (—CO—O—) (in the above preferred compounds, the compound (7E), Compound (7G), Compound (7H), Corresponding to Compound (7J)), (73) In the case where W ⁴¹ and W ⁴³ are (—O—) (in the above preferred compounds, the compounds (7A) to Compound (7D), compound (7F), and compound (7I)).

As a synthesis method of the compound (7), when the compound (7) is classified into the above (71) (W ⁴¹ : (—CO—O—), W ⁴³ : (—O—CO—)). Taking the compound (7L) as an example, a method shown in the following reaction formula (C-1) can be mentioned. In addition, the symbol in a formula shows the same meaning as the above. In addition, the symbol in a formula shows the same meaning as the above. In addition, a compound that is one type of the compound (7L) obtained by the following reaction formula (C-1) is referred to as compound (7L-1).

  6- (4-Hydroxycyclohexyl) decahydronaphthalen-2-ol (4La) and 3-acryloyloxybutanoic acid are reacted in dichloromethane in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine to give compound (7L-1) Get.

  The compound (7K), the compound (7M), and the compound (7N) each represent a group sandwiched between two hydroxyl groups instead of the compound (4La) used above, -Cy-Cy-, -Dhn- It can manufacture by using the compound made into Cy-Cy- or -Cy-Cy-Cy-, respectively.

When the compound (7) is classified into the above (72) (W ⁴¹ : (— O—CO—), W ⁴³ : (— CO—O—)), the compound is one of the compounds (7E) The production method will be described using (7E-1) as an example. The hydroxyl group-containing compound (5E-1) is produced by the method shown in the reaction formula (B-2).

  That is, compound (4e) is synthesized from compound (4d) by a reaction similar to that obtained from compound (01b-2) from starting material (01b) in reaction formula (F-1) of the synthesis method. The obtained compound (4e) is reacted with 4,4′-bicyclohexyldicarboxylic acid (compound (4f)) in chloroform in the presence of dicyclohexylcarbodiimide and 4- (N, N-dimethylamino) pyridine. To obtain the compound (4 g). Further, this compound (4 g) is reacted with p-toluenesulfonic acid to obtain the above compound (5E-1).

  Next, the compound (7E-1) can be produced by reacting the hydroxyl group-containing compound (5E-1) with (meth) acryloyl chloride and converting the terminal hydroxyl group to a (meth) acryloyloxy group.

In the above reaction, instead of the compound (4f), a divalent group -Cy-Cy- sandwiched between carboxyl groups is replaced with -Dhn-Cy-, -Dhn-Cy-Cy-, or -Cy-Cy. If each of the compounds represented by -Cy- is used, a compound classified as compound (7G), compound (7H), or compound (7J) can be synthesized. In addition, a divalent group sandwiched between hydroxyl groups in the compound (4d) (HO (CH ₂ ) ₆ OH) is represented by — (CH ₂ ) _{m 4} —R ⁴¹ — (CH ₂ ) _{n 4} — (— (CH ₂ )). ^{_{04 -R 42 - (CH 2)}} p4 - with divalent group represented by), a compound that differ carbon number of the spacer portion (7) can be synthesized.

When the compound (7) is classified into the above (73) (W ⁴¹ : (— O—), W ⁴³ : (— O—)), the compound (7D-1) which is one of the compounds (7D) ) As an example, a hydroxyl group-containing compound (5D-1) is first produced by the method shown in the reaction formula (B-3).

  Next, the compound (7D-1) can be produced by reacting the hydroxyl group-containing compound (5D-1) with (meth) acryloyl chloride and converting the terminal hydroxyl group to a (meth) acryloyloxy group.

In the above reaction, in place of the compound (4a), a divalent group -Cy-Cy- sandwiched between hydroxyl groups is changed to -Ph-Ph-, -Ph-Cy-Ph-, -Ph-Cy-Ph-. When the compound represented by Ph-, -Cy-Cy-Cy-, or -Dhn-Cy- is used, the compound (7A), the compound (7B), the compound (7C), the compound (7F) or the compound (7I ) Can be synthesized. In the Br (CH ₂ ) ₅ OH, a divalent group sandwiched between Br and a hydroxyl group is represented by — (CH ₂ ) _{m 4} —R ⁴¹ — (CH ₂ ) _{n 4} — (— (CH ₂ ) ₀₄ —R. ^{By using a} divalent group represented by _42- (CH ₂ ) _p4- ), a compound (7) having a different carbon number in the spacer portion can be synthesized.

  In the liquid crystal composition of the second example, the blending amount of the liquid crystalline low molecular compound (Dbb-1) (crosslinking agent) having the (meth) acryloyl group is the liquid crystalline polymer compound (Ab having the acryloyl group). 1-30 parts by mass is preferable with respect to 100 parts by mass of 1), and 1-20 parts by mass is more preferable. If the blending amount of the liquid crystalline low molecular compound (Dbb-1) is 1 part by mass or more with respect to 100 parts by mass of the liquid crystalline polymer compound (Ab-1) having an acryloyl group, the effect of sufficient alignment improvement is achieved. If it is 30 parts by mass or less, the light resistance of the obtained optically anisotropic film can be sufficiently maintained.

  In addition, the compounding quantity of the said liquid crystalline low molecular compound (Dbb-1) which has the said (meth) acryloyl group in the liquid crystalline composition of a 2nd example is set with the liquid crystalline polymer compound (Ab-1) which has an acryloyl group. The molar amount of the liquid crystalline polymer compound (Ab-1) having an acryloyl group is preferably 1.0 to 2.0 mol, and preferably 1.0 to 1.5 mol. The blending amount is more preferable.

Here, in the liquid crystalline composition of the second example, the number of acryloyl groups of the liquid crystalline polymer compound (Ab-1) per 1 g of liquid crystalline composition solids, N _Ab-1 [pieces / g] The value obtained by dividing the value obtained by adding the number of (meth) acryloyl groups of the liquid crystalline low molecular weight compound (Dbb-1) per 1 g of the liquid crystalline composition solid content and N _Dbb-1 [pieces / g]. , (N _Ab-1 + N _Dbb-1 ) / 2 [pieces / g] is within the scope of the present invention, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g. In addition, the blending ratio of each compound is adjusted as described above. In the case where the photocrosslinkable liquid crystalline composition contains only the liquid crystalline polymer compound (Ab-1) as a component having a photocrosslinkable group, N _Ab-1 / 2 [pieces / g] The value only needs to be within the scope of the present invention.

  The liquid crystalline composition of the second example contains various additives in addition to the liquid crystalline low molecular compound (Dbb-1) having the (meth) acryloyl group and the liquid crystalline polymer compound (Ab-1) having an acryloyl group. You may contain. Specifically, a catalyst, an ultraviolet absorber, an antioxidant, a light stabilizer and the like that promote the photocrosslinking reaction by the two components can be mentioned.

  The liquid crystalline composition of the second example is a radically polymerizable photocrosslinkable liquid crystalline composition, and a photopolymerization initiator for radical polymerization is used as a catalyst. As the photopolymerization initiator for radical polymerization, one or two selected as appropriate from acetophenones, benzophenones, benzoins, benzyls, Michler ketones, benzoin alkyl ethers, benzyldimethyl ketals, thioxanthones, and the like More than seeds can be used. As commercial products, trade name Irgacure 184, trade name Irgacure 754: both manufactured by Ciba Specialty Chemicals, Inc. may be used. Content of a photoinitiator is 100 mass parts of total amounts of the liquid crystalline low molecular compound (Dbb-1) which has a (meth) acryloyl group, and the liquid crystalline polymer compound (Ab-1) which has an acryloyl group. 0.1-5 mass parts is preferable and 0.3-2 mass parts is especially preferable.

  In addition, when the photocrosslinkable group of the liquid crystalline polymer compound (Ab) contained in the photocrosslinkable liquid crystalline composition is a cationic polymerizable photocrosslinkable group such as an epoxy group or an oxetane group, A photopolymerization initiator for cationic polymerization is used. Examples of the photopolymerization initiator for cationic polymerization include ionic photoacid generators, for example, onium salts such as sulfonium salts and iodonium salts, and nonionic photoacid generators. As a commercial item, you may use brand name Adeka optomer SP-172, the product made by ADEKA, etc. The content of the photopolymerization initiator can be the same as that of the photopolymerization initiator for radical polymerization.

  When the liquid crystalline composition of the second example uses an ultraviolet absorber, an antioxidant, a light stabilizer, etc. as other components, the content of these components is based on the total amount of the liquid crystalline composition. 5 mass% or less is preferable and 2 mass% or less is especially preferable.

  The liquid crystalline composition of the second example is obtained by mixing each of the above essential components so as to have a predetermined blending ratio and, if necessary, adding an additive so that the respective components are uniform. It is done. Moreover, after processing so that each compounding component may be uniformly mixed and dissolved using an appropriate solvent as required, the solvent may be removed by vacuum drying or the like to obtain a liquid crystalline composition.

  As mentioned above, as a specific example of a photocrosslinkable liquid crystalline composition containing a vinyl ether liquid crystalline polymer compound (A), a liquid crystalline polymer compound (Ab-1) having an acryloyl group and (meth) acryloyl as a crosslinking agent Although the example using the liquid crystalline low molecular compound (Dbb-1) having a group has been described, the photocrosslinkable liquid crystalline composition is not limited thereto.

(2) Liquid crystalline composition containing diene liquid crystalline polymer compound (B) (2-1) Thermally crosslinkable liquid crystalline composition The liquid crystalline composition containing diene liquid crystalline polymer compound (B) is heated. In the case of crosslinkability, the liquid crystalline composition is a diene liquid crystalline polymer compound (Ba) having a thermally crosslinkable group as exemplified above (hereinafter also simply referred to as “liquid crystalline polymer compound (Ba)”). And a crosslinking agent having a functional group having reactivity with the thermally crosslinkable group of the liquid crystalline polymer compound (Ba).

(Liquid Crystalline Polymer Compound (Ba))
Examples of the liquid crystal polymer compound (Ba) include a diene polymerizable liquid crystal compound (B1), a diene compound (B2) having a thermally crosslinkable group, and any other polymerizable compound (B3). And a liquid crystalline polymer compound obtained by copolymerization of In order to make the diene liquid crystalline polymer compound (Ba) have a fluorine atom in the main chain from the viewpoint of blue light resistance, at least one of the two ethylenic double bonds of the diene compound is used. A fluorine-containing diene-based polymerizable liquid crystal compound (B1) in which fluorine atoms are introduced may be used. Alternatively, a fluoroolefin having a fluorine atom bonded to a polymerizable group may be used as the other polymerizable compound (B3).

  As the diene polymerizable liquid crystalline compound (B1), a fluorine-containing diene polymerizable liquid crystalline compound (B1) in which a fluorine atom is introduced into at least one of ethylenic double bonds is preferable. For example, a fluorine-containing diene-based polymerizable liquid crystal compound represented by the following formula (b1) can be given.

The fluorine-containing diene compound represented by the following formula (b1) is a polymerizable liquid crystal compound, and the fluorine-containing liquid crystal polymer compound (b1) has liquid crystallinity by having a polymer unit based on the compound (b1). .
_{CF 2 = CFCXYCH (CZ-OW} 21 - (CH 2) m2 -R 21 - (CH 2) n2 - (O) i2 -W 22 - (E 21) h2 -W 23 - (E 22) j2 - (E ²³ ) _k2 -E ²⁴ -R ²² ) CH ₂ CH = CH ₂ ……… (b1)

However, the symbols in the formula (b1) are as follows.
R ²¹ : a single bond, an alkylene group having 1 to 12 carbon atoms, or a polyfluoroalkylene group having 1 to 12 carbon atoms.
R ²² : an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a trifluoromethyl group, or a cyano group.
E ^{21 is a} 1,4-phenylene group, and a hydrogen atom bonded to a carbon atom in the group may be substituted with a fluorine atom, a chlorine atom, or a methyl group.
E ²² , E ²³ , E ²⁴ : each independently a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or a trans-2,6-decahydronaphthalenyl group, The hydrogen atom bonded to the carbon atom may be substituted with a fluorine atom, a chlorine atom, or a methyl group.
m2: An integer from 0 to 3.
n2: An integer from 0 to 3.
h2, j2, k2: each independently 0 or 1, and 1 ≦ h2 + j2 + k2.
i2: 0 or 1.
W ²¹ , W ²² , W ²³ : each independently a carbonyl group or a single bond.
X: A fluorine atom or a hydrogen atom.
Y: A fluorine atom or a hydrogen atom.
Z: -O- which forms a carbonyl group with CZ, or two hydrogen atoms which form a methylene group with CZ.

The compound (b1) is in crystalline framework by a plurality of 6-membered ring (wherein _{^{(b1), - (E 21}} ) h2 -W 23 - (E 22) j2 - (E 23) k2 -E 24 - at the indicated A fluorine-containing diene compound having both polymerizability and liquid crystallinity. Some compounds (b1) do not exhibit a liquid crystal phase by themselves, but such compounds can also exhibit a liquid crystal state in a mixed state with other components, and a liquid crystalline composition exhibiting a liquid crystal phase. It can be used as a component of a product.

Compound (b1) is in the spacer portion of the molecule (formula ^{(b1), -CX 21 Y 21} CH (CZ 21 -OW 21 - (CH 2) m2 -R 21 - in represented by) - (CH _{2) n2} The compound (b1) has a structure having an alkylene group or a polyfluoroalkylene group, and the compatibility of the compound (b1) with other polymerization components can be ensured during the polymerization.

In the polymerization, in order not to lower the compatibility with the component containing no fluorine atom in the polymerization solution, in the compound (b1), when R ²¹ in the formula (b1) is an alkylene group or a polyfluoroalkylene group, those groups The carbon number of 1-12. The alkylene group preferably has 2 to 8 carbon atoms, and the polyfluoroalkylene group preferably has 2 to 8 carbon atoms. In addition, in view of non-crystallinity, the alkylene group preferably has 2, 4, or 6 carbon atoms. The number of carbon atoms of the polyfluoroalkylene group is particularly preferably 2, 4, or 6. Furthermore, in the case of a polyfluoroalkylene group, it is preferable that one or more fluorine atoms are bonded to the terminal carbon atom, and a perfluoroalkylene group is more preferable.

Specific examples of the polyfluoroalkylene group include the following groups.
_{- (CF 2) 2 -,} - (CF 2) 4 -, - (CF 2) 6 -, - (CF 2) 8 -, - (CF 2) 10 -, - (CF 2) 12 -, - CF _{2 CHF -, - CF 2 CHF} (CF 2) 2 -, - CF 2 CHF (CF 2) 4 -, - CF 2 CHF (CF 2) 2 CHFCF 2 -, - CF 2 CHF (CF 2) 4 CHF- _{, -CF 2 CH 2 (CF 2} ) CH 2 CF 2 -, - CF 2 CHF (CF 2) 4 CHFCF 2 -, - CHF (CF 2) 6 CHF-,
_{-CF 2 CH (CF 2 CF 3} ) (CF 2) 2 CH 2 -.

In the formula (b1), m2 and n2 are each an integer of 0 to 3, and 1 or 2 is preferable. From the viewpoint of ease of production of the compound (b1), m2 and n2 are preferably the same value. h2, i2, j2, and k2 are each 0 or 1. However, 1 ≦ h2 + j2 + k2, and at least one of h2, j2, and k2 is 1. W ²¹ , W ²² and W ²³ are a carbonyl group (—CO—) or a single bond, and X and Y are a fluorine atom or a hydrogen atom. Z is -O- which forms a carbonyl group with CZ, or two hydrogen atoms which form a methylene group with CZ. That is, CZ is a carbonyl group or a methylene group.

Preferable specific examples of the compound (b1) include the following compounds (2A) to (2M).
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-Ph-Ph-R 22) CH 2 CH = CH 2 (2A)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-Ph-Cy-Ph-R 22) CH 2 CH = CH 2 (2B)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-Ph-Cy-Ph-Ph-R 22) CH 2 CH = CH 2 (2C)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-Cy-Cy-R 22) CH 2 CH = CH 2 (2D)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-CO-Cy-Cy-R 22) CH 2 CH = CH 2 (2E)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-Cy-Cy-Cy-R 22) CH 2 CH = CH 2 (2F)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-CO-Dhn-Cy-R 22) CH 2 CH = CH 2 (2G)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-CO-Dhn-Cy-Cy-R 22) CH 2 CH = CH 2 (2H)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-Dhn-Cy-R 22) CH 2 CH = CH 2 (2I)
_{CF 2 = CFCH 2 CH (CH} 2 -O-CO- (CH 2) m2 -R 21 - (CH 2) n2 -O-CO-Dhn-Cy-R 22) CH 2 CH = CH 2 (2J)
_{CF 2 = CFCF 2 CH (CH} 2 -O-CO- (CH 2) m2 -R 21 - (CH 2) n2 -O-CO-Dhn-Cy-R 22) CH 2 CH = CH 2 (2K)
_{CF 2 = CFCF 2 CH (CO} -O- (CH 2) m2 -R 21 - (CH 2) n2 -O-CO-Dhn-Cy-R 22) CH 2 CH = CH 2 (2L)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) m2 -R 21 - (CH 2) n2 -CO-Dhn-Cy-R 22) CH 2 CH = CH 2 (2M)

The symbols R ²¹ , R ²² , m2, and n2 in the formulas (2A) to (2M) are independent for each formula and are as described above. Ph, Cy and Dhn are also as described above independently for each formula. A plurality of Ph and Cy in one molecule can also independently represent a substituted or unsubstituted 1,4-phenylene group and 1,4-cyclohexylene group.

  More specific examples include the following compounds. However, r2 in a following formula shows the integer of 1-8 independently for every formula.

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Ph-CN) CH ₂ CH = CH ₂ (2AOa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Ph-CN) CH ₂ CH = CH ₂ (21AOb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Ph-CN) CH ₂ CH = CH ₂ (2AOc)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Ph-CN) CH 2 CH = CH 2 (2AOj)
CF ₂ = CFCH ₂ CH (CH ₂ -O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Ph-CN) CH ₂ CH = CH ₂ (2AOk)
CF ₂ = CFCH ₂ CH (CH ₂ -O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Ph-CN) CH ₂ CH = CH ₂ (2AOl)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2BOa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2BOb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2BOc)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Cy-Ph- (CH 2) r2 H) CH 2 CH = CH ₂ (2BOj)
CF ₂ = CFCH ₂ CH (CH ₂ -O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2BOk)
CF ₂ = CFCH ₂ CH (CH ₂ -O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2BOl)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2COa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2COb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2COc)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Cy-Ph-Ph- (CH 2) r2 H) CH 2 CH = CH ₂ (2COj)
CF ₂ = CFCH ₂ CH (CH ₂ -O- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2COk)
CF ₂ = CFCH ₂ CH (CH ₂ -O- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2COl)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2DOa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2DOb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2DOc)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Cy-Cy- (CH 2) r2 H) CH 2 CH = CH 2 ( 2DOj)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-CO-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2EOa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-CO-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2EOb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-CO-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2EOc)
CF ₂ = CFCH ₂ CH (CH ₂ -O- (CH ₂ ) ₄ -O-CO-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2EOd)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Cy-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2FOa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Cy-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2FOb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Cy-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2FOc)
_{CF 2 = CFCH 2 CH (CH} 2 -O- (CH 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Cy-Cy-Cy- (CH 2) r2 H) CH 2 CH = CH ₂ (2FOj)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2GOa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2GOb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2GOc)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2HOa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2HOb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-CO-Dhn-Cy-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2HOc)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2IOa)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2IOb)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2IOc)

CF ₂ = CFCH ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₃ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2JOx3)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₄ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2JOx4)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₅ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2JOx5)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₆ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2JOx6)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₇ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2JOx7)

CF ₂ = CFCF ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₃ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2KOx3)
CF ₂ = CFCF ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₄ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2KOx4)
CF ₂ = CFCF ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₅ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2KOx5)
CF ₂ = CFCF ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₆ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2KOx6)
CF ₂ = CFCF ₂ CH (CH ₂ -O-CO- (CH ₂ ) ₇ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2KOx7)
CF ₂ = CFCH ₂ CH (CH ₂ -O-CO-Dhn-Cy- (CH ₂ ) _r2 H) CH ₂ CH = CH ₂ (2MOx0)

  In the above compound, r2 is preferably an integer of 2 to 6, and more preferably 3 to 5. Ph is an unsubstituted 1,4-phenylene group or a 1,4-phenylene group substituted with a methyl group, Cy is an unsubstituted trans-1,4-cyclohexyl group, and Dhn is unsubstituted. The trans-2,6-decahydronaphthalenyl group is preferred.

  Among these, more preferred compounds include (2EOd), (2GOc), (2MOx0) and the like.

Next, a method for synthesizing the fluorine-containing diene compound (b1) will be described with specific examples.
First, in the formula ^{_{(b1), -W 21 - (}} CH 2) m2 -R 21 - (CH 2) n2 - (O) i2 - is a single ^{bond, W 22} is a carbonyl group (-CO-) As a method for synthesizing the above compound (2MOx0), the method shown in the following reaction formula (20) can be mentioned. In addition, the symbol in Formula (20) shows the same meaning as the above.

  For example, the compound (22A) synthesized by the method described in WO2002 / 065212 and the compound (Gr3) ((2R, 4aR, 6S, 8aS) -6-((1r, 4R) -4-propylcyclohexyl) Compound (2MOx0) is obtained by reacting () decahydronaphthalene-2-carboxylic acid) with a dehydrating condensing agent in the presence or absence of a solvent.

  A strong acid can be used as the dehydrating condensing agent, but amide condensing agents such as dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and its hydrochloride are preferable, and 1-ethyl-3- ( Preference is given to using 3-dimethylaminopropyl) carbodiimide and its hydrochloride. Further, 4-dimethylaminopyridine or the like may be added as a base. The reaction may be solventless, but as the reaction solvent, an aprotic solvent such as toluene, hexane, cyclohexane, xylene, dichloromethane, dichloroethane, chloroform, or a fluorine solvent such as pentafluorodichloropropane may be used.

  The reaction temperature is preferably in the range of 0 ° C to 200 ° C, particularly preferably in the range of 10 ° C to 150 ° C. The reaction time is preferably in the range of 0.5 hour to 100 hours, particularly preferably in the range of 1 hour to 20 hours. The reaction pressure is preferably 1 MPa.

Next, when the formula (b1) is (21) when W ²¹ is a single bond and W ²² is a carbonyl group (—CO—) (in the above preferred compounds, the compound (2E), the compound (2G), the compound ( 2H), compound (2L), equivalent to compound (2M)), (22) When W ²¹ and W ²² are both single bonds (in the above preferred compounds, compound (2A) to compound (2D), compound (2F) ), Equivalent to compound (2I)) and (23) when W ²¹ and W ²² are both carbonyl groups (—CO—) (in the above preferred compounds, equivalent to compound (2J) and compound (2K)) The synthesis method will be described.

(21) In the formula (b1), when W ²¹ is a single bond and W ²² is a carbonyl group (—CO—) As a method for synthesizing the compound classified as (21), the above compound (2GOc) is taken as an example. Then, the method shown in the following reaction formula (D-1) may be mentioned. In addition, the symbol in a formula shows the same meaning as the above.

  First, the above compound (01c) and 3,4-dihydrofuran are reacted in an aprotic solvent such as dichloromethane in the presence of p-toluenesulfonic acid to produce the above compound (01c-2). The reaction temperature is preferably 0 ° C to 100 ° C, particularly preferably 0 ° C to 50 ° C. The reaction time is preferably 0.5 hours to 100 hours, particularly preferably 1 hour to 20 hours. The reaction pressure is preferably 1 MPa.

Next, the obtained compound (01c-2) was treated with a reagent prepared from n-BuLi-Ph ₂ PCl, and then reacted with a quinone such as dimethylquinone or tetrafluoroquinone and the compound (22A). To obtain the above compound (O1c-3). In addition, by treating with amide condensing agents such as dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and its hydrochloride, tributylphosphine, triphenylphosphine, and their solid bead carriers. To obtain the above compound (O1c-3).

  Furthermore, the hydroxyl group of either compound (01c-2) or compound (22A) is converted to an iodine atom, bromine atom, chlorine atom, trifluoromethanesulfonyl group, or methanesulfonyl group, and the remaining hydroxyl group is converted to sodium or Compound (O1c-3) may be synthesized under the conditions of Williamson etherification in which it is converted to a potassium salt and reacted.

  The reaction temperature is preferably 0 ° C to 200 ° C, particularly preferably 10 ° C to 150 ° C. The reaction time is preferably 0.5 hours to 100 hours, particularly preferably 1 hour to 20 hours. The reaction pressure is preferably 1 MPa.

  Subsequently, the obtained compound (O1c-3) was mixed with hydrochloric acid, sulfuric acid, p-toluene in a protic solvent such as methanol, ethanol, propanol, isopropyl alcohol, or a mixed solvent of these protic solvents and water. Reaction with sulfonic acid or the like gives a compound (O1c-4) in which the tetrahydropyranyl protecting group is deprotected.

  The reaction temperature is preferably 0 ° C to 150 ° C, particularly preferably 0 ° C to 100 ° C. The reaction time is preferably in the range of 0.5 hour to 100 hours, particularly preferably in the range of 1 hour to 20 hours. The reaction pressure is preferably 1 MPa.

  Next, the compound (O1c-4) and the compound (Gr3) are reacted under the same conditions as in the synthesis of the compound (2MOx0) in the method shown in the above reaction formula (20) (hereinafter referred to as the method (20)). Thus, a compound (2GOc) is obtained.

In the reaction shown in the reaction formula (D-1), in place of the compound (01c), a divalent group sandwiched by the hydroxyl group ^{_{- (CH 2) m2 -R 21}} - (CH 2) n2 (m2, R ²¹ and n2 are appropriately selected within the above range), instead of the compound (Gr3), the -Dhn-Cy- is replaced by -Cy-Cy-, -Dhn-Cy-Cy-, or -Cy By using a compound such as -Cy-Cy- or the like, another compound classified as (21) can be synthesized.

(22) In the formula (b1), when W ²¹ and W ²² are both single bonds As a method for synthesizing the compound classified as (22), the above compound (2COc) is taken as an example. The method shown to Formula (D-2) is mentioned. In addition, the symbol in a formula shows the same meaning as the above.

  That is, first, in the synthesis of compound (2GOc) described above (method (21)), compound (01c-2) is obtained in the same manner as compound (01c-2) is obtained from compound (01c) (above Not shown in the formula). Next, the compound (01c-2) and the compound (Cr3) are reacted by the same method as that obtained by converting the compound (01c-2) to the compound (O1c-3) by the method 21, whereby the compound ( 01c-7) is obtained. Next, the hydroxyl-protecting group of this compound (01c-7) is deprotected under the same conditions as the reaction conditions led from the compound (01c-3) to the compound (01c-4) by the method (21), Compound (01c-8) is obtained. Next, the obtained compound (01c-8) and compound (22A) are reacted by the same method as that obtained by converting the compound (01c-2) to the compound (O1c-3) by the method (21). 2COc) is obtained.

In the method of synthesizing the above compound (2COc), first, in place of the compound (01c) in the method (21), a divalent group sandwiched between the hydroxyl groups is represented by — (CH ₂ ) _{m 2} —R ²¹ — (CH ₂ ) In the reaction shown in the above reaction formula (D-2), a compound obtained using a compound of _n2 (m2, R ²¹ and n2 are appropriately selected within the above range) is used instead of compound (01c-2). used, further, in place of the compound (Cr3), a group obtained by removing the hydroxyl _{group, -Ph-Ph-CN, -Ph} -Cy-Ph- (CH 2) r2 H, -Cy-Cy- (CH 2) _{r2 H, -Ph-Cy-Cy} -Cy- (CH 2) r2 H, -Dhn-Cy-Cy- (CH 2) r2 H _{or,, -Dhn-Cy- (CH 2} ) compound with _r2 H, etc. Synthesize other compounds classified as (22) Kill.

(23) In the formula (b1), when W ²¹ and W ²² are both carbonyl groups (—CO—) As a method for synthesizing the compound classified as (23), the above compound (2JOx5) is taken as an example. And the method shown in the following reaction formula (D-3). In addition, the symbol in a formula shows the same meaning as the above.

  That is, the compound (12o-1) and the compound (22A) are reacted under the same conditions as those obtained by dehydration condensation of the compound (01c-4) and the compound (Gr3) by the method (21). Get (12o-2). Next, the protecting group for the hydroxyl group of the obtained compound (12o-2) is deprotected under the same conditions as the reaction conditions led from the compound (01c-3) to the compound (01c-4) by the method (21). To obtain the above compound (12o-3). Next, the obtained compound (12o-3) and compound (Gr3) are subjected to dehydration condensation under the same conditions as described above to obtain compound (2JOx5).

In the reaction shown in the reaction formula (D-3), in place of the compound (12o), a divalent group sandwiched by the hydroxyl group and a carboxyl group ^{_{- (CH 2) m2 -R 21}} - (CH 2) n21 (M2, R ²¹ , n2 are appropriately selected within the above range), instead of the compound (Gr3), the -Dhn-Cy- is replaced with -Cy-Cy-, -Dhn-Cy-Cy-, or , -Cy-Cy-Cy- and the like can be used to synthesize other compounds classified as (23).

  Heretofore, the fluorine-containing diene compound represented by the above formula (b1), which is a polymerization unit constituting the diene liquid crystalline polymer compound (Ba) having a thermally crosslinkable group, has been described.

Here, the fluorinated diene compound (b1) undergoes cyclopolymerization under relatively mild conditions. As a form of the polymerized unit obtained by cyclopolymerizing the compound (b1), polymerized units represented by the following formulas (b11) to (b13) can be considered, and hereinafter, represented by the following formula (b13). The polymer unit is used as a polymer unit based on the fluorinated diene compound (b1) including all the forms of the polymer units (b11) to (b13). In the following formulas (b11) ~ (b13), Q 2 moiety, -W ²¹ in the formula _{(b1) - (CH 2)} m2 -R 21 - (CH 2) n2 - (O) i2 -W 22 - _{^{(E 21) h2 -W 23 -}} (E 22) j2 - is representative of the _{^{(E 23) k2 -E 24 -R}} 22. Other symbols have the same meaning as in formula (b1).

  In preparing the liquid crystalline polymer compound (Ba) used in the present invention, it has a heat-crosslinkable group used in combination with a diene polymerizable liquid crystal compound (B1), preferably a fluorinated diene compound (b1). The diene compound (B2) is not particularly limited as long as it is a diene compound (B2) having a thermally crosslinkable group in the side chain. The diene compound (B2) having a thermally crosslinkable group in the side chain is preferably a cyclopolymerizable diene compound having a thermally crosslinkable group at the end of the side chain.

  When a diene compound (B2) having a thermally crosslinkable group in such a side chain is used, it is copolymerized with the compound (B1) or other monomer (B3) to obtain a liquid crystalline polymer compound (Ba). In the polymerization unit based on the compound (B2), the carbon chain having cyclopolymerization preferably constitutes a part of the main chain, and the thermally crosslinkable group is located at the end of the side chain bonded to the main chain. It becomes the composition to do. The liquid crystalline polymer compound (Ba) is blended in the liquid crystalline composition, and finally, the thermally crosslinkable group reacts with the thermally crosslinkable group of the crosslinking agent contained in the liquid crystalline composition. It reacts with the group and crosslinks. Considering this crosslinking reaction, the type and length of the side chain, that is, the side chain having a thermally crosslinkable group in the compound (B2) is appropriately adjusted.

As the diene compound (B2) having a thermally crosslinkable group, a 5-membered ring or a 6-membered ring is incorporated into the main chain by cyclopolymerization as in the fluorine-containing diene compound (b1). A fluorine-containing diene compound represented by the following formula (b2) that can form a structure having a fluorine atom is more preferred.
_{^{CF 2 = CFCX 22 Y 22 CH}} (R 2 -L 2) CH 2 CH = CH 2 ......... (b2)
However, in formula (b2), X ²² and Y ²² are each independently a fluorine atom or a hydrogen atom, and R ² represents an alkylene group having 1 to 3 carbon atoms. L ² represents a hydroxyl group, a thiol group, a carboxyl group, an iodine atom, a silyl group, an amino group, an epoxy group, a nitrile group, or an oxetane group. L ² is preferably a hydroxyl group or an oxetane group from the viewpoint of absorption characteristics and ease of synthesis, and particularly preferably a hydroxyl group.

  The fluorinated diene compound (b2) having the thermally crosslinkable group undergoes cyclopolymerization under relatively mild conditions, like the fluorinated diene compound (b1). As a form of the polymerized unit obtained by cyclopolymerizing the compound (b2), polymerized units represented by the following formulas (b21) to (b23) are considered. Hereinafter, polymerization represented by the following formula (b23) is considered. The unit is used as a polymerized unit based on the fluorinated diene compound (b2) containing all the forms of the polymerized units (b21) to (b23). The symbols in the following formulas (b21) to (b23) have the same meaning as in the formula (b2).

  The liquid crystal polymer compound (Ba) is a diene-based polymerizable liquid crystal compound (B1), preferably a polymer unit based on the compound (b1), and a diene compound (B2) having a thermally crosslinkable group, preferably In addition to the polymerized units based on the compound (b2), polymerized units (B3) based on a polymerizable compound having an ethylenic double bond may be included as necessary. Specific examples of such polymer units include vinyl ethers, allyl ethers, non-fluorine groups that do not have a functional group that is reactive with the thermally crosslinkable group of the diene compound (B2), and preferably have no functional group. And polymerized units based on ethylene-based monomers.

  The content (ratio) of polymerized units based on the diene-based polymerizable liquid crystal compound (B1), preferably the compound (b1), in the liquid crystal polymer compound (Ba) is 50 from the viewpoint of liquid crystallinity and light resistance. -98 mol% is preferable and 70-95 mol% is more preferable. When the content of the polymerization unit based on the compound (B1) is 50 mol% or more, the liquid crystallinity is good and a uniaxially oriented thin film is obtained. When the content of polymerized units based on the compound (B1) is 98 mol% or less, sufficient light resistance can be obtained.

  In the liquid crystalline polymer compound (Ba), the content (ratio) of the polymer units based on the diene compound (B2) having a thermally crosslinkable group, preferably the compound (b2), is preferably 2 to 50 mol%. -30 mol% is more preferable. When the content of the polymer unit based on the compound (B2) is 2 mol% or more, the light resistance and the alignment stability are good, and when it is 50 mol% or less, the liquid crystallinity is good and the alignment is uniaxial. A thin film is obtained.

  The liquid crystalline polymer compound (Ba) is a polymer unit other than a polymer unit based on a diene-based polymerizable liquid crystal compound (B1) and a polymer unit based on a diene compound (B2) having a thermally crosslinkable group. When it contains, it is preferable that the upper limit of the content shall be 1 mol%. In the case of 1 mol% or more, liquid crystallinity, light resistance, and orientation are sufficiently obtained.

  Specific examples of the polymer compound that is more preferably used as the liquid crystalline polymer compound (Ba) used in the present invention include a polymer compound represented by the following formula (Ba1) having an average composition structure. The liquid crystalline polymer compound (Ba1) is composed only of polymerized units based on the compound (b1) and polymerized units based on the compound (b2), and each content is 50 polymerized units based on the compound (b1). It is a high molecular compound of -98 mol% and the polymerization unit based on a compound (b2) is 2-50 mol%.

In the formula (Ba1), Q ² is the -W ²¹ in the formula _{(b1) - (CH 2)} m2 -R 21 - (CH 2) n2 - (O) i2 -W 22 - (E 21) h2 -W ²³ - represents the _{^{(E 23) k2 -E 24 -R}} 22 - (E 22) j2. Other symbols have the same meaning as the symbols in formula (b1) and formula (b2). Moreover, x3 shows 50-98, y3 shows 2-50 positive number, respectively, and is x3 + y3 = 100. The value of x3: y3 corresponds to the content of polymerized units based on the compound (b1): the content of polymerized units based on the compound (b2) in the polymer compound (Ba1).

The number average molecular weight (Mn) of the liquid crystalline polymer compound (Ba) used in the present invention is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, and 3,000 to 20,000. Most preferred. The molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0.
If the number average molecular weight (Mn) and the molecular weight distribution are in this range, the orientation in a liquid crystal composition containing the molecular weight and the light resistance when used as an optically anisotropic material will be good.

  The liquid crystalline polymer compound (Ba) in the present invention is, for example, a diene polymerizable liquid crystalline compound (B1), preferably a compound (b1), a diene compound (B2) having a thermally crosslinkable group, by the following method. ), Preferably by subjecting raw material monomers such as the compound (b2) and other monomers (B3) to radical polymerization.

As the polymerization initiator, diene-based polymerizable liquid crystal compound (B1), preferably compound (b1), diene-based compound (B2) having a thermally crosslinkable group, preferably compound (b2) and other monomers The polymerization reaction is not limited as long as the polymerization reaction such as (B3) proceeds radically, and examples thereof include a radical generator, light, and ionizing radiation. As the polymerization initiator, a radical generator is particularly preferable. Examples of the radical generator include peroxides, azo compounds, persulfates and the like. Of these radical generators, peroxides are preferred. Specific examples of the peroxide include the following compounds. Incidentally, in the following formula, _-C 6 _{H 5} is a phenyl group, _-C 6 _{F 5} group is pentafluorophenyl _group, -C _{6 H 10} - represents a cyclohexylene group.

C ₆ H ₅ -C (O) O-OC (O) -C ₆ H ₅
C ₆ F ₅ −C (O) O−OC (O) −C ₆ F ₅
C ₃ F ₇ −C (O) O−OC (O) −C ₃ F ₇
(CH ₃ ) ₃ C-C (O) O-OC (O) -C (CH ₃ ) ₃
(CH ₃ ) ₂ CH-C (O) O-OC (O) -CH (CH ₃ ) ₂
(CH ₃ ) ₃ C-C ₆ H ₁₀ -C (O) O-OC (O) -C ₆ H ₁₀ -C (CH ₃ ) ₃
(CH ₃ ) ₃ C-O-C (O) O-OC (O) -O-C (CH ₃ ) ₃
(CH ₃ ) ₂ CH-O-C (O) O-OC (O) -O-CH (CH ₃ ) ₂
(CH ₃ ) ₃ C-C ₆ H ₁₀ -O-C (O) O-OC (O) -O-C ₆ H ₁₀ -C (CH ₃ ) ₃

  Also, the polymerization method is not limited, and the diene polymerizable liquid crystal compound (B1), preferably the compound (b1), the diene compound (B2) having a thermally crosslinkable group, preferably the compound (b2) and others. So-called bulk polymerization in which the raw material monomer such as the monomer (B3) is directly subjected to polymerization, fluorinated hydrocarbon, chlorinated hydrocarbon, fluorinated chlorohydrocarbon, alcohol capable of dissolving or dispersing the raw material monomer , Solution polymerization by polymerization in hydrocarbons and other organic solvents, suspension polymerization by polymerization in the presence or absence of a suitable organic solvent in an aqueous medium, and emulsification by adding an emulsifier to the aqueous medium Examples include polymerization.

The temperature and pressure at which the polymerization is carried out are not particularly limited, and are preferably set appropriately in consideration of various factors such as the boiling point of the raw material monomer, the heating source and the removal of the polymerization heat. For example, the polymerization temperature can be set to a suitable temperature between 0 ° C. and 200 ° C., and if it is about room temperature to 100 ° C., a practically preferable temperature can be set. The polymerization pressure may be reduced or increased. Practically, suitable polymerization can be carried out at a pressure of about normal pressure to about 10 MPa, and further about normal pressure to about 1 MPa.
The liquid crystalline polymer compound (Ba) thus obtained is blended in the liquid crystalline composition of the present invention after obtaining purification treatment such as removal of unreacted raw material compounds and polymerization solvent.

(Crosslinking agent)
In the thermally crosslinkable liquid crystalline composition containing the diene liquid crystalline polymer compound (Ba) having a thermally crosslinkable group, as a crosslinking agent used in combination with the liquid crystalline polymer compound (Ba), specifically, A crosslinking agent (Da ′) having a thermally crosslinkable group and a reactive functional group of the liquid crystalline polymer compound (Ba) is used.

  Here, the thermally crosslinkable group possessed by the liquid crystalline polymer compound (Ba) is the same as the thermally crosslinkable group possessed by the thermally crosslinkable vinyl ether-based liquid crystalline polymer compound (Aa). As the crosslinking agent (Da ′) used for the diene liquid crystalline composition, the same crosslinking agent as the crosslinking agent (Da) used for the thermally crosslinkable vinyl ether liquid crystalline composition described above can be used.

  Further, as a crosslinking agent used in combination with the liquid crystalline polymer compound (Ba), in addition to the crosslinking agent (Da ′) having a functional group that reacts with a thermally crosslinkable group, the heat possessed by the liquid crystalline polymer compound (Ba). A crosslinking agent having the same thermally crosslinkable group as the crosslinkable group may be used. As such a crosslinking agent, a liquid crystalline low molecular weight compound (Db ') is preferable. As the liquid crystalline low molecular weight compound (Db ′), the same compounds as the liquid crystalline low molecular weight compound (Db) used in the thermally crosslinkable vinyl ether liquid crystalline composition described above can be used.

(Other ingredients)
The thermally crosslinkable liquid crystalline composition containing the diene liquid crystalline polymer compound (Ba) having a thermally crosslinkable group contains various additives in addition to the liquid crystalline polymer compound (Ba) and the crosslinking agent. May be. Specific examples include a catalyst that promotes a crosslinking reaction between the liquid crystalline polymer compound (Ba) and a crosslinking agent, an ultraviolet absorber, an antioxidant, and a light stabilizer. As these other components, those similar to the thermally crosslinkable vinyl ether liquid crystal composition described above can be used.

(The number of thermally crosslinkable groups per gram of solid content of the liquid crystalline composition)
In addition, in order to make the density of the cross-linking points in the optically anisotropic film within the range of the present invention, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g, the liquid crystal used for producing this is used. It is necessary to adjust the number of thermally crosslinkable groups per gram of the solid content of the composition. This adjustment method can be the same as that of the thermally crosslinkable vinyl ether liquid crystal composition described above.

More specific examples of the thermally crosslinkable liquid crystalline composition containing the diene liquid crystalline polymer compound (Ba) include the liquid crystalline composition of the following third example.
<Third example>
The liquid crystalline composition of the third example is represented by the following formula (Ba-1) in which the thermally crosslinkable group (L ² ) of the liquid crystalline polymer compound (Ba1) is a hydroxyl group as the liquid crystalline polymer compound (Ba). The polyisocyanate compound (Da-1) which has an isocyanate group is contained as a crosslinking agent (Da ') which contains the liquid crystalline polymer compound (Ba-1) shown and has a functional group reactive with a hydroxyl group. However, the symbols in formula (Ba-1) have the same meaning as the symbols in formula (Ba1).

In addition, in this liquid crystalline composition, the liquid crystalline low molecular weight compound (Db-1) which has a hydroxyl group may be contained as another type of crosslinking agent. Furthermore, you may contain a catalyst, a ultraviolet absorber, antioxidant, a light stabilizer etc. as another component.
Regarding the polyisocyanate compound (Da-1), the liquid crystalline low molecular weight compound (Db-1) having a hydroxyl group, and other components, the thermally crosslinkable vinyl ether liquid crystalline composition described above and preferred embodiments are included. It is the same. The blending ratio of each component is the same as that of the thermally crosslinkable vinyl ether-based liquid crystalline composition, including preferred embodiments.

  Here, also in the diene liquid crystalline composition in which the thermally crosslinkable group is a hydroxyl group, the amount of hydroxyl groups in the composition is the same as that of the isocyanate group, as in the vinyl ether liquid crystalline composition in which the thermally crosslinkable group is a hydroxyl group. Less than the amount is preferred. Therefore, in this preferred embodiment, the density of crosslinking points in the optically anisotropic film obtained by using the liquid crystalline composition is the same as the number of hydroxyl groups per 1 g of the solid content of the liquid crystalline composition.

Therefore, in the thermally crosslinkable diene liquid crystal composition, the number of hydroxyl groups of the liquid crystal polymer compound (Ba-1) per 1 g of the liquid crystal composition solid content, N _Ba-1 [piece / g] Or when the liquid crystalline low molecular compound (Db-1) is contained, the number of hydroxyl groups of the liquid crystalline low molecular compound (Db-1) per 1 g of the liquid crystalline composition solid content, N _{Db- 1} plus the number _{/ g], N Ba-1} + N Db-1 [ number / g] is within the scope of the present invention, i.e., so as to be 4 × ¹⁰ -4 ~1 × ^{10 -2} cells / g In addition, the amount of each component is adjusted.

  The liquid crystalline composition of the third example is obtained by mixing the above-mentioned essential components so as to have a predetermined blending ratio and further adding additives as necessary to make the components uniform. . Moreover, after processing so that each compounding component may be uniformly mixed and dissolved using an appropriate solvent as required, the solvent may be removed by vacuum drying or the like to obtain a liquid crystalline composition.

(2-2) Photocrosslinkable liquid crystalline composition When the liquid crystalline composition containing the diene liquid crystalline polymer compound (B) is photocrosslinkable, the liquid crystalline composition has a diene type having a photocrosslinkable group. Contains a liquid crystalline polymer compound (Bb) (hereinafter sometimes simply referred to as “liquid crystalline polymer compound (Bb)”).

(Liquid Crystalline Polymer Compound (Bb))
Of the liquid crystalline polymer compound (Bb), when the photocrosslinkable group is a cyclic ether group that is a photocrosslinkable group corresponding to cationic polymerization, for example, an epoxy group or an oxetane group, The liquid crystalline polymer compound (Bb) can be produced by the same method as the liquid crystalline polymer compound (Ba) of (2-1) above.

However, when used as the liquid crystalline polymer compound (Bb), in order to make the crosslinking point within the scope of the present invention, for example, a diene-based polymerizable liquid crystalline compound (B1) and an epoxy group or oxetane group. It is necessary to adjust the ratio of the compound (B2) in the copolymer of the diene compound (B2) having a side chain with any other polymerizable compound (B3). For example, in the liquid crystalline polymer compound represented by the formula (Ba1), by changing the thermally crosslinkable group (L ² ) to an epoxy group or an oxetane group, x3 is changed to 50 to 98, and y3 is changed to 2 to 50. The liquid crystalline polymer compound (Ba1) can be used as the liquid crystalline polymer compound (Bb).

Among the liquid crystalline polymer compound (Bb), a photocrosslinkable group is a photocrosslinkable group corresponding to radical polymerization, such as a vinyl group or a group containing a vinyl group (hereinafter referred to as “vinyl group etc.”), preferably (meta ) In the case of an acryloyl group, introduction of the vinyl group or the like is, for example, a thermally crosslinkable group (L ² ) of a polymer unit based on the compound (b2) of the liquid crystalline polymer compound (Ba1) obtained as described above. ) Is done through. As a method for introducing a vinyl group or the like into the liquid crystalline polymer compound (Ba1), specifically, a thermal crosslinkable group (L ² ) and a reactive group of a polymerization unit based on the compound (b2) are provided at one terminal. And a compound having a vinyl group or the like at the other end is reacted with the liquid crystalline polymer compound (Ba1) under predetermined conditions.

  The group introduced into the terminal of the side chain of the liquid crystalline polymer compound, for example, the liquid crystalline polymer compound (Ba1) is preferably a vinyl group, and a (meth) acryloyl group is introduced as a group having a vinyl group. Is particularly preferred. An epoxy group or an oxetane group, which is a cationically polymerizable photocrosslinkable group, is introduced into the end of the side chain of a liquid crystal polymer compound, for example, a liquid crystal polymer compound (Ba1), in the same manner as the vinyl group or the like. And it is good also as a photocrosslinkable liquid crystalline polymer compound.

Here, as the liquid crystalline polymer compound (Ba1) into which the photocrosslinkable group is introduced, a compound in which the ratio of x3 and y3 is adjusted according to the number of photocrosslinkable groups to be introduced is prepared. For example, when the photocrosslinkable group is introduced at a ratio of one to one of the thermally crosslinkable groups (L ² ) of the liquid crystalline polymer compound (Ba1), x3 is 50 to 98, y3 Is preferably adjusted to 2-50. When the photocrosslinkable group is introduced at a ratio of two to one of the thermally crosslinkable groups (L ² ) of the liquid crystalline polymer compound (Ba1), x3 is 50 to 98, and y3 is 2 ~ 50 is preferred.

Hereinafter, taking as an example a liquid crystalline polymer compound in which a (meth) acryloyl group is introduced at the end via a thermally crosslinkable group (L ² ) in the liquid crystalline polymer compound (Ba1), this is referred to as a liquid crystalline polymer compound. It will be described as (Bb1). The (meth) acryloyl group is introduced into the end of the side chain via the thermally crosslinkable group (L ² ) of the polymer unit based on the compound (b2) in the liquid crystalline polymer compound (Ba1). In the introduction, a compound having a reactive functional group in the thermally crosslinkable group (L ² ) at one end and a (meth) acryloyl group at the other end is used. In addition, the number of (meth) acryloyl groups possessed by the compound at the end is preferably 1 or 2, and when it is desired to efficiently increase the number of crosslinkable groups per gram of the liquid crystal composition solid content, 2 Preferably.

  Here, the adjustment of the number of photocrosslinkable groups per gram of the liquid crystalline composition solid content is also performed by adjusting the ratio of x3 and y3 in the liquid crystalline polymer compound (Ba1) as described above. In the present invention, the liquid crystalline polymer compound to be blended so that the number of photocrosslinkable groups per gram of the liquid crystalline composition solid content in the finally obtained liquid crystalline composition satisfies the above-mentioned conditions of the present invention. In combination with these requirements, each component contained in the liquid crystal composition is designed in consideration of a combination with a crosslinking agent described later.

The liquid crystalline polymer compound (Ba1) is not particularly limited as long as the thermally crosslinkable group (L ² ) is selected from the functional groups exemplified above, and among these, as the thermally crosslinkable group (L ² ) A liquid crystalline polymer compound (Ba-1) having a hydroxyl group is preferably used. As the group reactive to the hydroxyl group of the compound for introducing a (meth) acryloyl group, a carboxyl group, an isocyanate group and the like are preferable, and an isocyanate group is particularly preferable. That is, a (meth) acryloyl group is introduced at the end of the side chain by a urethane bond between the hydroxyl group of the liquid crystalline polymer compound (Ba-1) and the isocyanate group of the compound used for introducing the (meth) acryloyl group. The liquid crystalline polymer compound (Bb1) is preferred.

  Examples of the isocyanate compound having a (meth) acryloyl group include 1,1-bis (acryloyloxymethyl) ethyl isocyanate and 2-methacryloyloxyethyl isocyanate. For example, dibutyltin laurate (DBTDL) is used as the terminal isocyanate group of these compounds as a conventionally known catalyst that catalyzes the reaction between a hydroxyl group and an isocyanate group. ), The (meth) acryloyl group can be introduced into the side chain.

  Moreover, (meth) acrylic acid chloride, (meth) acrylic acid, etc. were ester-reacted with the hydroxyl group which liquid crystalline polymer compound (Ba-1) has, and the (meth) acryloyl group was introduce | transduced into the terminal of the side chain. A liquid crystalline polymer compound (Bb1) can also be obtained. The reaction may be performed at room temperature, for example, by adding triethylamine, N, N-dimethyl-4-aminopyridine or the like to the raw material components.

  As a specific example, by reacting 1,3-bis (acryloyloxymethyl) ethyl isocyanate with x3 and y3 of the liquid crystalline polymer compound (Ba-1) adjusted to x4 and y4, respectively. The obtained liquid crystalline polymer compound is represented by the following formula (Bb-1). The symbols in formula (Bb-1) all have the same meaning as the symbols in formula (Ba-1) except for x4 and y4. Further, x3 is a positive number from 50 to 98, y3 is a positive number from 2 to 50, and x4 + y4 = 100.

The number average molecular weight (Mn) of the liquid crystalline polymer compound (Bb) used in the present invention is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, and 3,000 to 20,000. Most preferred. The molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0.
If the number average molecular weight (Mn) and the molecular weight distribution are in this range, the orientation in a liquid crystal composition containing the molecular weight and the light resistance when used as an optically anisotropic material will be good.
The liquid crystalline polymer compound (Bb) thus obtained is blended with the photocrosslinkable liquid crystalline composition after obtaining a purification treatment such as removal of unreacted raw material compounds and reaction solvent.

The liquid crystalline polymer compound (Bb) having a photocrosslinkable group forms a liquid crystalline composition that is a raw material for producing the optically anisotropic film of the present invention only with this and a photopolymerization initiator blended as necessary. Yes. The photocrosslinkable liquid crystalline composition may optionally contain a crosslinking agent.
(Crosslinking agent)
As a crosslinking agent that the photocrosslinkable liquid crystalline composition containing the diene liquid crystalline polymer compound (Bb) having a photocrosslinkable group may optionally contain, the liquid crystalline polymer compound (Bb) has. The crosslinking agent which has the same photocrosslinkable group as a photocrosslinkable group is mentioned. As such a crosslinking agent, a liquid crystalline low molecular weight compound (Dbb ′) is preferable. As the liquid crystalline low molecular weight compound (Dbb ′), the same compounds as the liquid crystalline low molecular weight compound (Dbb) used in the photocrosslinkable vinyl ether liquid crystalline composition described above can be used.

(Other ingredients)
The photocrosslinkable liquid crystalline composition containing the diene liquid crystalline polymer compound (Bb) having a photocrosslinkable group contains various additives in addition to the liquid crystalline polymer compound (Bb) and the crosslinking agent. May be. Specifically, a catalyst such as a photopolymerization initiator that promotes a crosslinking reaction by a photocrosslinkable group possessed by a crosslinking agent optionally blended with the liquid crystalline polymer compound (Bb), an ultraviolet absorber, an antioxidant, light A stabilizer etc. are mentioned. As these other components, those similar to the photocrosslinkable vinyl ether liquid crystal composition described above can be used.

(The number of thermally crosslinkable groups per gram of solid content of the liquid crystalline composition)
In addition, in order to make the density of the cross-linking points in the optically anisotropic film within the range of the present invention, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g, the liquid crystal used for producing this is used. It is necessary to adjust the number of photocrosslinkable groups per gram of the solid content of the composition. This adjustment method can also be the same as in the case of the photocrosslinkable vinyl ether liquid crystal composition described above.

More specifically, examples of the photocrosslinkable liquid crystalline composition containing the diene liquid crystalline polymer compound (Bb) include the liquid crystalline composition of the following fourth example.
<Fourth example>
The liquid crystalline composition of the fourth example contains a liquid crystalline polymer compound (Bb-1) having an acryloyl group as the liquid crystalline polymer compound (Bb) having a photocrosslinkable group, and (meta ) It contains a liquid crystalline low molecular compound (Dbb-1) having an acryloyl group. Furthermore, you may contain the catalyst (photoinitiator etc.) which accelerates | stimulates the photocrosslinking reaction by said 2 component, a ultraviolet absorber, antioxidant, a light stabilizer etc. as another component.

  The liquid crystalline low molecular weight compound (Dbb-1) having a (meth) acryloyl group and other components are the same as those described above, including the photocrosslinkable vinyl ether liquid crystalline composition described above and preferred embodiments. The blending ratio of each component is the same as that of the photocrosslinkable vinyl ether liquid crystal composition, including preferred embodiments.

In the liquid crystal composition of the fourth example, the number of acryloyl groups of the liquid crystal polymer compound (Bb-1) per 1 g of the liquid crystal composition solid content, N _Bb-1 [pieces / g], Value obtained by dividing the number of (meth) acryloyl groups of the low molecular weight compound (Dbb-1) per 1 g of the liquid crystalline composition solid content, the value obtained by adding N _Dbb-1 [pieces / g], by (N _Bb-1 + N _Dbb-1 ) / 2 [pieces / g] is within the range of the present invention, that is, the blending amount is adjusted to be 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g. Thus, the blending ratio of each compound is adjusted as described above. In the case where the photocrosslinkable liquid crystalline composition contains only the liquid crystalline polymer compound (Bb-1) as a component having a photocrosslinkable group, N _Bb-1 / 2 [pieces / g] The value only needs to be within the scope of the present invention.

  The liquid crystalline composition of the fourth example is obtained by mixing the above essential components so that each component is uniform by adding an additive as necessary so as to have a predetermined blending ratio. . Moreover, after processing so that each compounding component may be uniformly mixed and dissolved using an appropriate solvent as required, the solvent may be removed by vacuum drying or the like to obtain a liquid crystalline composition.

(3) Liquid crystalline composition containing (meth) acrylic liquid crystalline polymer compound (C) (3-1) Thermally crosslinkable liquid crystalline composition (Meth) containing acrylic liquid crystalline polymer compound (C) When the liquid crystalline composition is thermally crosslinkable, the liquid crystalline composition is a (meth) acrylic liquid crystalline polymer compound (Ca) having a thermally crosslinkable group as exemplified above (hereinafter simply referred to as “liquid crystalline high Molecular compound (Ca) ") and a crosslinking agent having a functional group having reactivity with the thermally crosslinkable group of the liquid crystalline polymer compound (Ca).

(Liquid crystal polymer compound (Ca))
As the liquid crystalline polymer compound (Ca), for example, a (meth) acrylic polymerizable liquid crystalline compound (C1), a (meth) acrylic compound (C2) having a thermally crosslinkable group, and any other arbitrary Examples thereof include liquid crystalline polymer compounds obtained by copolymerizing a polymerizable compound (C3).

Examples of the (meth) acrylic polymerizable liquid crystalline compound (C1) include compounds having a (meth) acryloyl group represented by the following formula (c1).
CH ₂ = CR ⁵¹ -COO-R ⁵² -E ⁵¹ -W ⁵¹ -E ⁵² -E ⁵³ -E ⁵⁴ -R ⁵³ ...... (c1)
Each symbol in the formula (c1) has the following meaning.
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents a single bond or an alkylene group having 1 to 15 carbon atoms, and in the case of an alkylene group, each independently has an ether bond at the end of the bond between the carbon-carbon bond of the alkylene group or the ring group. It may have an oxygen atom, or may have a carboxyl group at the end bonded to the cyclic group, and a part or all of the hydrogen atoms bonded to carbon atoms in this alkylene group are fluorine atoms. May be substituted.

R ⁵³ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyloxy group having 1 to 12 carbon atoms, a fluorine atom or a cyano group, and an alkyl group, an alkoxy group or In the case of alkylcarbonyloxy groups, some or all of the hydrogen atoms bonded to carbon atoms in these groups may be substituted with fluorine atoms.
W ⁵¹ represents a single bond or —COO—.

E ⁵¹ , E ⁵² , E ⁵³ and E ⁵⁴ each independently represent a single bond, a trans-1,4-cyclohexylene group or a 1,4-phenylene group. However, one of E ⁵¹ , E ⁵² and E ⁵³ is a naphthalene-1,4-diyl group, a naphthalene-1,5-diyl group, a naphthalene-2,6-diyl group or a trans-2,6-deca group. It may be a hydronaphthalene group. In the combination of E ⁵¹ , E ⁵² , E ⁵³ and E ⁵⁴ , each independently has 2 or less single bonds, and 3 1,4-phenylene groups do not continue. In addition, a part or all of hydrogen atoms of the trans-1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-diyl group or trans-2,6-decahydronaphthalene group may be fluorine atoms or methyl groups. May be substituted.

The (meth) acrylic polymerizable liquid crystal compound (C1), preferably the compound (c1) and the (meth) acrylic compound (C2) having a thermally crosslinkable group used in combination include a thermally crosslinkable group and The compound which has a radically polymerizable group is mentioned, Preferably, the compound which has a (meth) acryloyl group shown by following formula (c2) is mentioned.
_{^{CH 2 = CR 61 -COO-R}} 3 -L 3 ...... (c2)

Each symbol in the formula (c2) has the following meaning.
R ⁶¹ represents a hydrogen atom or a methyl group.
R ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms and optionally having a 1,4-phenylene group between the terminals or the carbon-carbon bond. - ends etheric oxygen atom bonded carbon-carbon bonds or with functional groups L ^1, an ester bond, and may have a urethane bond. Furthermore, some or all of the hydrogen atoms bonded to the carbon atom in the alkylene group containing the 1,4-phenylene group may be substituted with a fluorine atom.
L ³ represents a hydroxyl group, a thiol group, a carboxyl group, an iodine atom, a silyl group, an amino group, an epoxy group, a nitrile group, or an oxetane group. L ³ is preferably a hydroxyl group or an oxetane group.

  The other monomer (C3) optionally used as a raw material monomer for the liquid crystalline polymer compound (Ca) includes (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl ether, etc. ) Acrylic polymerizable liquid crystalline compound (C1) and (meth) acrylic compounds other than the (meth) acrylic compound (C2) having a thermally crosslinkable group.

  The liquid crystalline polymer compound (Ca) is converted into a (meth) acrylic polymerizable liquid crystalline compound (C1), preferably a compound (c1), and a (meth) acrylic compound (C2) having a thermally crosslinkable group, Preferably, the content ratio of the polymerized units based on each monomer in the liquid crystalline polymer compound (Ca) in the case of using the compound (c2) and, if necessary, the other monomer (C3) is as follows: The range of is preferable. Although it depends on the kind of the crosslinking agent used in combination, by setting it in such a range, the density of the crosslinkable group in the liquid crystalline composition calculated by the above method can be set in the above range.

  The (meth) acrylic polymerizable liquid crystal compound (C1) in the liquid crystal polymer compound (Ca), preferably the content (ratio) of polymerized units based on the compound (c1) is from the viewpoint of liquid crystallinity. 50-99 mol% is preferable and 60-95 mol% is more preferable. When the content of the polymerized units based on the compound (c1) is 50 mol% or more, a liquid crystal property is good and a uniaxially oriented thin film is obtained. When the content of the polymerization unit based on the compound (c1) is 99 mol% or more, sufficient heat resistance is obtained.

  The (meth) acrylic compound (C2) having a thermally crosslinkable group in the liquid crystalline polymer compound (Ca), preferably the content (ratio) of polymerized units based on the compound (c2) is 1 to 50 mol%. Preferably, 5-40 mol% is more preferable. When the content of the polymerization unit based on the (meth) acrylic compound having a thermally crosslinkable group is 1 mol% or more, light resistance and alignment stability are good, and when it is 50 mol% or less, liquid crystallinity is obtained. Is obtained, and a uniaxially oriented thin film is obtained.

  Moreover, when a liquid crystalline polymer compound (Ca) contains another monomer (C3), the upper limit of the content of the polymerized units based on the other monomer (C3) is preferably 1 mol%. In the case of 1 mol% or less, liquid crystallinity, light resistance, and orientation are sufficiently obtained.

  In the liquid crystalline polymer compound (Ca), the content ratio of each polymerization unit described above is a ratio based on the charged amount of each compound (monomer) used as a raw material. The liquid crystalline polymer compound (Ca) is obtained by a method in which a polymerization initiator is added to a mixture obtained by mixing the above raw material compounds (monomers) at a predetermined ratio. As the polymerization method, a polymerization method used for usual radical polymerization such as bulk polymerization, emulsion polymerization, solution polymerization, suspension polymerization and the like can be used without particular limitation, and solution polymerization is preferable from the viewpoint of easy control of molecular weight.

Examples of the polymerization solvent include dimethylformamide (DMF), dioxane, toluene and the like. Moreover, alcohols, such as t-butanol and ethanol, and a thiol can be used as a chain transfer agent for molecular weight adjustment.
A normal radical polymerization initiator can be used as the polymerization initiator. Specific examples include peroxides such as diisopropyl peroxybiscarbonate and dilauroyl peroxide, azo compounds such as azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), and the like. The usage-amount of a polymerization initiator can be changed suitably, Usually, about 0.05-1 mass part is preferably employ | adopted per 100 mass parts of polymeric compounds. Moreover, these polymerization initiators may be added all at once or may be added in portions as necessary.

The reaction temperature of the polymerization reaction is preferably 40 ° C to 100 ° C. The reaction pressure is preferably 0.2 to 2.0 MPa, more preferably 0.2 to 1.0 MPa.
The liquid crystalline polymer compound (Ca) thus obtained is blended in the liquid crystalline composition of the present invention after obtaining a purification treatment such as removal of unreacted raw material compounds and polymerization solvent.

The number average molecular weight (Mn) of the liquid crystalline polymer compound (Ca) is preferably 2,000 to 20,000, and more preferably 3,000 to 15,000. The molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0.
If the number average molecular weight (Mn) and the molecular weight distribution are in this range, the orientation in a liquid crystal composition containing the molecular weight and the light resistance when used as an optically anisotropic material will be good.

(Crosslinking agent)
As a crosslinking agent used in combination with a liquid crystalline polymer compound (Ca) in a thermally crosslinkable liquid crystalline composition containing a (meth) acrylic liquid crystalline polymer compound (Ca) having a thermally crosslinkable group, For the liquid crystal polymer compound (Ca), a crosslinking agent (Da ″) having a thermally crosslinkable group and a reactive functional group is used.

  Here, the thermally crosslinkable group possessed by the liquid crystalline polymer compound (Ca) is the same as the thermally crosslinkable group possessed by the above-mentioned thermally crosslinkable vinyl ether liquid crystalline polymer compound (Aa). As the crosslinking agent (Da ″) used for the (meth) acrylic liquid crystalline composition, the same crosslinking agent as the crosslinking agent (Da) used for the thermally crosslinkable vinyl ether liquid crystalline composition described above can be used. .

  Further, as a crosslinking agent used in combination with the liquid crystalline polymer compound (Ca), in addition to the crosslinking agent (Da ″) having a functional group that reacts with the thermally crosslinkable group, the heat possessed by the liquid crystalline polymer compound (Ca). A crosslinking agent having the same thermally crosslinkable group as the crosslinkable group may be used. As such a crosslinking agent, a liquid crystalline low molecular weight compound (Db ″) is preferable. As the liquid crystalline low molecular weight compound (Db ″), the same compounds as the liquid crystalline low molecular weight compound (Db) used in the thermally crosslinkable vinyl ether liquid crystalline composition described above can be used.

(Other ingredients)
Moreover, the thermally crosslinkable liquid crystalline composition containing the (meth) acrylic liquid crystalline polymer compound (Ca) having a thermally crosslinkable group includes various additives in addition to the liquid crystalline polymer compound (Ca) and the crosslinking agent. It may contain. Specific examples include a catalyst that promotes a crosslinking reaction between the liquid crystalline polymer compound (Ca) and a crosslinking agent, an ultraviolet absorber, an antioxidant, and a light stabilizer. As these other components, those similar to the thermally crosslinkable vinyl ether liquid crystal composition described above can be used.

(The number of thermally crosslinkable groups per gram of solid content of the liquid crystalline composition)
In addition, in order to make the density of the cross-linking points in the optically anisotropic film within the range of the present invention, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g, the liquid crystal used for producing this is used. It is necessary to adjust the number of thermally crosslinkable groups per gram of the solid content of the composition. This adjustment method can be the same as that of the thermally crosslinkable vinyl ether liquid crystal composition described above.

More specific examples of the thermally crosslinkable liquid crystalline composition containing the (meth) acrylic liquid crystalline polymer compound (Ca) include the liquid crystalline composition of the following fifth example.
<Fifth example>
The liquid crystal composition of the fifth example is a liquid crystal polymer compound (Ca) having a structure having an average composition represented by the following formula (Ca-1) in which the thermally crosslinkable group is a hydroxyl group. And a polyisocyanate compound (Da-1) having an isocyanate group as a crosslinking agent (Da ″) having a functional group reactive with a hydroxyl group. The liquid crystalline polymer compound (Ca-1) is (meth) Thermally crosslinkable group (L ³ ) in a copolymer consisting only of an acrylic polymerizable liquid crystalline compound (c1) and a (meth) acrylic compound (c2) having a thermally crosslinkable group (L ³ ) The polymer unit content based on each monomer is 50 to 99 mol% of the polymer units based on the compound (c1) and the polymer unit based on the compound (c2). It is in the range of 1 to 50 mol%.

However, in the formula (Ca-1), the Q ³ portion represents -R ⁵² -E ⁵¹ -W ⁵¹ -E ⁵² -E ⁵³ -E ⁵⁴ -R ⁵³ in the above formula (c1). Other symbols have the same meaning as the symbols in formula (c1) and formula (c2). X5 is a positive number from 50 to 99, and y5 is a positive number from 1 to 50, and x5 + y5 = 100. The value of x5: y5 corresponds to the content of polymerized units based on the compound (c1): the content of polymerized units based on the compound (c2) in the polymer compound (Ca).

In addition, in this liquid crystalline composition, the liquid crystalline low molecular weight compound (Db-1) which has a hydroxyl group may be contained as another type of crosslinking agent. Furthermore, you may contain a catalyst, a ultraviolet absorber, antioxidant, a light stabilizer etc. as another component.
Regarding the polyisocyanate compound (Da-1), the liquid crystalline low molecular weight compound (Db-1) having a hydroxyl group, and other components, the thermally crosslinkable vinyl ether liquid crystalline composition described above and preferred embodiments are included. It is the same. The blending ratio of each component is the same as that of the thermally crosslinkable vinyl ether-based liquid crystalline composition, including preferred embodiments.

  Here, in the (meth) acrylic liquid crystalline composition in which the thermally crosslinkable group is a hydroxyl group, the amount of the hydroxyl group in the composition is the same as the vinyl ether liquid crystalline composition in which the thermally crosslinkable group is a hydroxyl group. It is preferable to make it below the amount of isocyanate groups. Therefore, in this preferred embodiment, the density of crosslinking points in the optically anisotropic film obtained by using the liquid crystalline composition is the same as the number of hydroxyl groups per 1 g of the solid content of the liquid crystalline composition.

Therefore, in the thermally crosslinkable (meth) acrylic liquid crystalline composition, the number of hydroxyl groups contained in the liquid crystalline polymer compound (Ca-1) per 1 g of liquid crystalline composition solids, N _Ca-1 [pieces] / G] or when the liquid crystalline low molecular weight compound (Db-1) is contained, the number of hydroxyl groups of the liquid crystalline low molecular weight compound (Db-1) per 1 g of solid content of the liquid crystalline composition, N _Db-1 plus the number _{/ g], N Ca-1} + N Db-1 [ number / g] is within the scope of the present invention, ^{i.e., 4 × 10 -4 ~1 × 10} -2 cells / g Thus, the blending amount of each component is adjusted.

  The liquid crystalline composition of the fifth example is obtained by mixing each of the above essential components so as to have a predetermined blending ratio, and if necessary, adding an additive so that the respective components are uniform. . Moreover, after processing so that each compounding component may be uniformly mixed and dissolved using an appropriate solvent as required, the solvent may be removed by vacuum drying or the like to obtain a liquid crystalline composition.

(3-2) Photocrosslinkable liquid crystalline composition When the liquid crystalline composition containing the (meth) acrylic liquid crystalline polymer compound (C) is photocrosslinkable, the liquid crystalline composition contains a photocrosslinkable group. (Meth) acrylic liquid crystalline polymer compound (Cb) (hereinafter sometimes simply referred to as “liquid crystalline polymer compound (Cb)”).

(Liquid crystal polymer compound (Cb))
In the liquid crystalline polymer compound (Cb), when the photocrosslinkable group is a cyclic ether group that is a photocrosslinkable group corresponding to cationic polymerization, for example, an epoxy group or an oxetane group, The liquid crystalline polymer compound (Cb) can be produced by the same method as the liquid crystalline polymer compound (Ca) of (3-1) above.

  However, when used as the liquid crystalline polymer compound (Cb), in order to make the crosslinking point within the scope of the present invention, for example, a (meth) acrylic polymerizable liquid crystalline compound (C1) and an epoxy group It is necessary to adjust the ratio of the compound (C2) in the copolymer of the (meth) acrylic compound (C2) having an oxetane group in the side chain and any other polymerizable compound (C3). For example, in the liquid crystalline polymer compound represented by the above formula (Ca-1), by changing the hydroxyl group to an epoxy group or oxetane group, and changing x5 to 50 to 99 and y5 to 1 to 50, the liquid crystalline polymer compound (Ca-1) can be used as the liquid crystalline polymer compound (Cb).

Of the liquid crystalline polymer compound (Cb), the photocrosslinkable group is a photocrosslinkable group corresponding to radical polymerization, such as a vinyl group or a group containing a vinyl group (hereinafter referred to as “vinyl group etc.”), preferably (meta ) In the case of an acryloyl group, the vinyl group or the like is introduced, for example, by a thermally crosslinkable group (L ³ ) of a polymer unit based on the compound (c2) of the liquid crystalline polymer compound (Ca) obtained as described above. ) Is done through. As a method for introducing a vinyl group or the like into the liquid crystalline polymer compound (Ca), specifically, a thermal crosslinkable group (L ³ ) and a reactive group of a polymerization unit based on the compound (c2) are provided at one terminal. And a compound having a vinyl group or the like at the other end is reacted with the liquid crystalline polymer compound (Ca) under predetermined conditions.

  The group introduced into the terminal of the side chain of the liquid crystalline polymer compound, for example, the liquid crystalline polymer compound (Ca) is preferably a vinyl group, and a (meth) acryloyl group is introduced as a group having a vinyl group. Is particularly preferred. In addition, an epoxy group or an oxetane group, which is a cationically polymerizable photocrosslinkable group, is introduced into the end of the side chain of a liquid crystal polymer compound, for example, a liquid crystal polymer compound (Ca), in the same manner as the vinyl group. And it is good also as a photocrosslinkable liquid crystalline polymer compound.

  Here, the case where the liquid crystalline polymer compound (Ca-1) is used as the liquid crystalline polymer compound (Ca) into which the photocrosslinkable group is introduced will be described as an example. As the liquid crystalline polymer compound (Ca-1), a compound in which the ratio of x5 and y5 is adjusted in accordance with the number of photocrosslinkable groups to be introduced is prepared. For example, when a photocrosslinkable group is introduced at a ratio of one to one hydroxyl group of the liquid crystalline polymer compound (Ca-1), x5 is 50 to 99 and y5 is 1 to 50. It is preferable to adjust. Moreover, when a photocrosslinkable group is introduce | transduced in the ratio of two with respect to one of the hydroxyl groups of a liquid crystalline polymer compound (Ca-1), x5 is 50-99 and y5 is preferable 1-50. .

  Hereinafter, taking as an example a liquid crystalline polymer compound in which a (meth) acryloyl group is introduced via a hydroxyl group in the liquid crystalline polymer compound (Ca-1), this is referred to as a liquid crystalline polymer compound (Cb1). I will explain. In the liquid crystalline polymer compound (Ca-1), the (meth) acryloyl group is introduced into the end of the side chain via the hydroxyl group of the polymer unit based on the compound (c2). In the introduction, a compound having a functional group reactive to a hydroxyl group at one end and a (meth) acryloyl group at the other end is used. In addition, the number of (meth) acryloyl groups possessed by the compound at the end is preferably 1 or 2, and when it is desired to efficiently increase the number of crosslinkable groups per gram of the liquid crystal composition solid content, 2 Preferably.

  Here, the adjustment of the number of photocrosslinkable groups per gram of the liquid crystalline composition solid content is also performed by adjusting the ratio of x5 and y5 in the liquid crystalline polymer compound (Ca-1) as described above. . In the present invention, the liquid crystalline polymer compound to be blended so that the number of photocrosslinkable groups per gram of the liquid crystalline composition solid content in the finally obtained liquid crystalline composition satisfies the above-mentioned conditions of the present invention. In combination with these requirements, each component contained in the liquid crystal composition is designed in consideration of a combination with a crosslinking agent described later.

  As the functional group reactive to the hydroxyl group of the liquid crystalline polymer compound (Ca-1), which the compound for introducing the (meth) acryloyl group has, a carboxyl group, an isocyanate group, and the like are preferable, and an isocyanate group is particularly preferable. . That is, a (meth) acryloyl group is introduced at the end of the side chain by a urethane bond between the hydroxyl group of the liquid crystalline polymer compound (Ca-1) and the isocyanate group of the compound used for introducing the (meth) acryloyl group. The liquid crystalline polymer compound (Cb1) is preferred.

  Examples of the isocyanate compound having a (meth) acryloyl group include 1,1-bis (acryloyloxymethyl) ethyl isocyanate and 2-methacryloyloxyethyl isocyanate. By using dibutyltin laurate (DBTDL) or the like exemplified above as a conventionally known catalyst for catalyzing the reaction between a hydroxyl group and an isocyanate group, the terminal isocyanate group of these compounds is used for the liquid crystalline polymer compound (Ca-1). By reacting with a hydroxyl group on the side chain, a (meth) acryloyl group can be introduced into the side chain.

  Moreover, (meth) acrylic acid chloride, (meth) acrylic acid, etc. were ester-reacted with the hydroxyl group which liquid crystalline polymer compound (Ca-1) has, and the (meth) acryloyl group was introduce | transduced into the terminal of the side chain. A liquid crystalline polymer compound (Cb1) can also be obtained. The reaction may be performed at room temperature, for example, by adding triethylamine, N, N-dimethyl-4-aminopyridine or the like to the raw material components.

  As a specific example, by reacting 1,5-bis (acryloyloxymethyl) ethyl isocyanate with x5 and y5 of the liquid crystalline polymer compound (Ca-1) adjusted to x6 and y6, respectively. The obtained liquid crystalline polymer compound is represented by the following formula (Cb-1). The symbols in formula (Cb-1) all have the same meaning as the symbols in formula (Ca-1) except for x6 and y6. X6 is a positive number from 50 to 99, and y6 is a positive number from 1 to 50, and x6 + y6 = 100.

The number average molecular weight (Mn) of the liquid crystalline polymer compound (Cb) used in the present invention is preferably 2,000 to 30,000, more preferably 3,000 to 20,000, and more preferably 3,000 to 15,000. Particularly preferred.
Further, the molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0.
If the number average molecular weight (Mn) and the molecular weight distribution are in this range, the orientation in a liquid crystal composition containing the molecular weight and the light resistance when used as an optically anisotropic material will be good.
The liquid crystalline polymer compound (Cb) thus obtained is blended with the photocrosslinkable liquid crystalline composition after obtaining a purification treatment such as removal of the unreacted raw material compound and the reaction solvent.

  The liquid crystalline polymer compound (Cb) having a photocrosslinkable group forms a liquid crystalline composition which is a raw material for producing the optically anisotropic film of the present invention only with this and a photopolymerization initiator blended as necessary. Yes. The photocrosslinkable liquid crystalline composition may optionally contain a crosslinking agent.

(Crosslinking agent)
As a crosslinking agent that the photocrosslinkable liquid crystalline composition containing the (meth) acrylic liquid crystalline polymer compound (Cb) having a photocrosslinkable group may optionally contain, a liquid crystalline polymer compound (Cb The crosslinking agent which has the same photocrosslinkable group as the photocrosslinkable group which) has. As such a crosslinking agent, a liquid crystalline low molecular weight compound (Dbb ″) is preferable. As for the liquid crystalline low molecular weight compound (Dbb ″), the liquid crystallinity used in the photocrosslinkable vinyl ether liquid crystalline composition described above. A compound similar to the low molecular compound (Dbb) can be used.

(Other ingredients)
In addition, the photocrosslinkable liquid crystalline composition containing the (meth) acrylic liquid crystalline polymer compound (Cb) having a photocrosslinkable group includes various additives in addition to the liquid crystalline polymer compound (Cb) and the crosslinking agent. It may contain. Specifically, a catalyst such as a photopolymerization initiator that promotes a crosslinking reaction by a photocrosslinkable group possessed by a crosslinking agent that is optionally blended with the liquid crystalline polymer compound (Cb), an ultraviolet absorber, an antioxidant, light A stabilizer etc. are mentioned. As these other components, those similar to the photocrosslinkable vinyl ether liquid crystal composition described above can be used.

(The number of thermally crosslinkable groups per gram of solid content of the liquid crystalline composition)
In addition, in order to make the density of the cross-linking points in the optically anisotropic film within the range of the present invention, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g, the liquid crystal used for producing the same It is necessary to adjust the number of photocrosslinkable groups per gram of the solid content of the composition. This adjustment method can also be the same as in the case of the photocrosslinkable vinyl ether liquid crystal composition described above.

More specifically, the liquid crystalline composition of the following sixth example can be exemplified as the photocrosslinkable liquid crystalline composition containing the (meth) acrylic liquid crystalline polymer compound (Cb).
<Sixth example>
The liquid crystalline composition of the sixth example contains a liquid crystalline polymer compound having an oxetane group represented by the following formula (Cb-2) as the liquid crystalline polymer compound (Cb) having a photocrosslinkable group, A crosslinking agent is not particularly contained. The symbols in formula (Cb-2) all have the same meaning as the symbols in formula (Ca-1) except for x6 and y6. X6 is a positive number from 50 to 99, and y6 is a positive number from 1 to 50, and x6 + y6 = 100.

Furthermore, as other components, a catalyst (photopolymerization initiator or the like) that promotes a photocrosslinking reaction with the liquid crystalline polymer compound (Cb-2), an ultraviolet absorber, an antioxidant, a light stabilizer, or the like may be contained. Good.
A photopolymerization initiator for cationic polymerization is used as a catalyst (photopolymerization initiator or the like) that accelerates the photocrosslinking reaction with the liquid crystalline polymer compound (Cb-2). Examples of the photopolymerization initiator for cationic polymerization include ionic photoacid generators, for example, onium salts such as sulfonium salts and iodonium salts, and nonionic photoacid generators. As a commercial item, you may use brand name Adeka optomer SP-172, the product made by ADEKA, etc. The content of the photopolymerization initiator is preferably 0.1 to 5 parts by mass, particularly preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the liquid crystalline polymer compound (Cb-2) having an oxetane group. .

  When the liquid crystal composition of the sixth example uses an ultraviolet absorber, an antioxidant, a light stabilizer, etc. as other components, the content of these components is based on the total amount of the liquid crystal composition. 5 mass% or less is preferable and 2 mass% or less is especially preferable.

In the liquid crystal composition of the sixth example, the number of oxetane groups of the liquid crystal polymer compound (Cb-2) per 1 g of the liquid crystal composition solid content, N _Cb-2 [pieces / g] is 2. The divided value, N _Cb-2 [pieces / g] / 2 [pieces / g] is adjusted to be within the range of the present invention, that is, 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g. The
Note that a liquid crystalline composition obtained by adding a liquid crystalline low molecular compound (Dbb) having an oxetane group to the liquid crystalline composition of the sixth example may be used. In that case, the liquid crystalline low molecular weight having an oxetane group may be used. The number of oxetane groups of the compound (Dbb) per 1 g of the liquid crystalline composition solid content, N _Dbb [pieces / g], is the oxetane group liquid crystalline composition solids of the liquid crystalline polymer compound (Cb-2). The number per minute per gram, the value added to N _Cb-2 [pieces / g] divided by 2, and (N _Cb-2 + N _Dbb ) / 2 [pieces / g] are within the scope of the present invention, ie The blending amount is adjusted to be 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g.

  The liquid crystalline composition of the sixth example is obtained by mixing the above essential components so that each component becomes uniform by adding an additive as necessary, so as to have a predetermined blending ratio. . Moreover, after processing so that each compounding component may be uniformly mixed and dissolved using an appropriate solvent as required, the solvent may be removed by vacuum drying or the like to obtain a liquid crystalline composition.

[Optically anisotropic film and optical element]
The optically anisotropic film of the present invention is a state in which a liquid crystal composition layer formed using a liquid crystal composition containing a liquid crystal polymer compound having a crosslinkable functional group is aligned with the liquid crystal polymer compound. In the optically anisotropic film obtained by treating the crosslinkable functional group so as to be completely crosslinked, the density of crosslinking points in the optically anisotropic film is 4 × 10 ⁻⁴ to 1 × 10 ^−. It is characterized by ² / g.

The liquid crystalline composition containing the liquid crystalline polymer compound having a crosslinkable functional group is as described above. By using such a crosslinkable liquid crystalline composition and crosslinking it in an aligned state, the density of crosslinking points in the film is in the range of 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g. The optically anisotropic film of the present invention is obtained. The density of crosslinking points in the optically anisotropic film is preferably 4 × 10 ⁻⁴ to 1 × 10 ⁻³ pieces / g, and more preferably 5 × 10 ^{−4 to} 11 × 10 ⁻⁴ pieces / g. Since the density of crosslinking points in the film is in the above range, the optically anisotropic film of the present invention has optical anisotropy and is excellent in heat resistance, light resistance and the like with high reliability. Become a film.

Hereinafter, embodiments of the optically anisotropic film of the present invention and an optical element having the same will be described with reference to the drawings.
The optically anisotropic film of the present invention includes the above-described crosslinkable liquid crystalline composition in a state where the liquid crystalline composition exhibits a liquid crystal phase, and the liquid crystalline polymer compound or liquid crystal in the liquid crystalline composition. Obtained by cross-linking liquid crystalline compounds with each other or by reaction with a cross-linking agent in a state in which liquid crystalline compounds such as low molecular weight compounds are uniaxially aligned (for example, aligned in a horizontal direction parallel to the surface of the substrate described later). It is done.

  Further, since the optically anisotropic film of the present invention is usually formed on a support that supports the optically anisotropic film, the optical element having the optically anisotropic film of the present invention and the support is usually optically anisotropic. It is produced simultaneously with the formation of the conductive film. The support may have an alignment film on the surface in contact with the film, if necessary.

  In preparing the optically anisotropic film, in order to keep the liquid crystalline composition in a state in which the composition exhibits a liquid crystal phase, the atmospheric temperature is set to be equal to or higher than the glass transition point (Tg) of the liquid crystalline composition and the liquid crystal. The nematic phase-isotropic phase transition temperature (Tc, hereinafter also referred to as “clearing point”) of the conductive composition may be used. Note that since the Δn value of the liquid crystal composition is extremely small at a temperature close to Tc, the ambient temperature is preferably set to (Tc−10) ° C. or lower. In order to obtain sufficient orientation, the ambient temperature is preferably adjusted to (Tc-30) ° C. or higher.

  Moreover, when the crosslinking reaction performed in the state in which the liquid crystalline composition is oriented is a thermal crosslinking reaction, this crosslinking reaction is usually performed under heating conditions. In the thermally crosslinkable liquid crystalline composition used in the present invention described above, the temperature of the crosslinking reaction is designed to be in the range of room temperature or higher and (Tc-10) ° C. or lower. It may be performed simultaneously, or may be performed stepwise in the order of orientation and crosslinking reaction.

  In order to produce an optically anisotropic film as described above, the liquid crystalline compound in the liquid crystalline composition needs to be aligned. The alignment state of the liquid crystal compound is, for example, preferably by arranging a liquid crystal composition containing the same on a substrate that has been subjected to an alignment treatment, and applying a shearing force to the liquid crystal composition layer by the following method. Can be obtained. In addition, the board | substrate with which the said orientation processing used for preparation of an optical anisotropic film | membrane was performed can be used as a support plate of an optical element as it is.

  A flat plate is preferable as the shape of the substrate. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, ethylene / tetrafluoroethylene copolymer, Examples include polyethylene, polypropylene, polyarylate, polysulfone, triacetyl cellulose, cellulose, polyether ether ketone, and the like. Examples of the inorganic material include silicon, glass, calcite, and the like.

When the surface of the substrate is subjected to an alignment treatment, specifically, a method of rubbing the surface of the substrate with fibers such as cotton, wool, nylon, polyester, or the like can be given. Alternatively, an alignment film formed by rubbing with a cloth after forming an organic thin film or an inorganic thin film on the surface of the substrate may be provided. The alignment film only needs to have a function of aligning liquid crystals. For example, a thin film made of an organic material such as polyimide, polyamide, polyvinyl alcohol, polyvinyl cinnamate and polystyrene, or an inorganic material such as SiO ₂ and Al ₂ O ₃ is used. The liquid crystal compound is formed on the substrate surface and rubbed in one direction with a rubbing cloth such as nylon or rayon so that the liquid crystal compound is aligned in that direction. An alignment film subjected to alignment treatment by a method other than the rubbing method, for example, an alignment film obtained by obliquely depositing SiO ₂ , an alignment film by an ion beam method or a photo-alignment film can be used.

  The substrate may be separated from the optically anisotropic film after the liquid crystalline compound in the liquid crystalline composition is in an oriented state and an optically anisotropic film is formed by the crosslinking reaction. In that case, a mold release process may be performed in advance on the surface of the substrate, or in the case where the substrate is subjected to an alignment process, on the alignment process surface. Examples of the release treatment include a method of treating the orientation-treated surface of the substrate with a release agent such as a fluorosilane-based or fluorine-containing polymer having a fluorine-containing aliphatic ring structure.

  Using such an arbitrarily aligned substrate and a crosslinkable liquid crystalline composition, using shear stress to align and crosslink the liquid crystalline composition to produce an optically anisotropic film As a method for producing an optical element having this, for example, the following method can be used.

  FIG. 1 is a diagram schematically showing an example of a method for producing an optically anisotropic film of the present invention. FIGS. 1A, 1B, 1C, and 1D are diagrams illustrating steps in an example of a method for manufacturing an optical element according to the present invention.

First, FIG. 1A to FIG. 1C show liquid crystallinity whose orientation is controlled by providing a layer 102 of a liquid crystalline composition before orientation control on a first substrate 101 and applying a shearing force at a predetermined temperature. The process of obtaining the layer 106 of a composition is shown. In FIG. 1D, the layer 106 of the liquid crystal composition whose orientation is controlled is treated under a crosslinking condition such as heating or light irradiation, and the density of crosslinking points in the film is 4 × 10 ⁻⁴ to 1 × 10 ^{−. The} process of obtaining the optical anisotropic film 107 of the present invention in the range of ² / g and the optical element 108 including the same is shown.
Each step will be described below.

First, as shown in FIG. 1A, a layer 102 of a liquid crystalline composition before orientation control is provided on a first substrate 101. As the liquid crystal composition, the crosslinkable liquid crystal composition described above is used. This crosslinkable liquid crystalline composition is perpendicular to the liquid crystalline composition layer composed of the liquid crystalline composition at a temperature not lower than the glass transition temperature (Tg) and lower than the clearing point (Tc). The liquid crystal composition layer is prepared such that a shearing force can be applied in the horizontal direction without applying pressure in the direction or while applying a pressure of 1000 Pa or less.
Even in this case, as described above, since the Δn value of the liquid crystalline composition is extremely small at a temperature close to Tc, the ambient temperature when applying the shearing force is preferably (Tc−10) ° C. or lower. In order to obtain sufficient orientation, the ambient temperature is preferably adjusted to (Tc-30) ° C. or higher.

  Specifically, in order for the liquid crystalline composition layer to enable application of shearing force, the number average molecular weight (Mn) of the liquid crystalline polymer compound contained in the crosslinkable liquid crystalline composition is preferably 2,000 to 50,000, more preferably 3,000 to 20,000, the liquid crystalline polymer contained in the crosslinkable liquid crystalline composition described above as described above The molecular weight of the compound is within this range. When the number average molecular weight of the liquid crystalline polymer compound is 2,000 or more, a shearing force can be effectively applied to the layer 102 of the liquid crystalline composition before orientation control. When it is 50,000 or less, a shearing force can be easily applied to the layer 102 of the liquid crystal composition before orientation control.

  Here, the first substrate 101 is adsorbed by the first stage 103 that can adsorb the first substrate 101. The stage 103 is a stage capable of adjusting the temperature. Furthermore, the stage 103 is a stage that can be moved in the directions of three axes orthogonal to each other, that is, in the directions of the X, Y, and Z axes shown in FIG. The Z-axis direction is a direction orthogonal to the main surface of the layer 102 of the liquid crystalline composition before alignment control formed on the first substrate 101, and the X-axis direction and the Y-axis direction are the liquid crystal properties. The direction parallel to the major surface of the layer 102 of the composition.

  Further, as described above, the first substrate 101 is preferably subjected to an alignment treatment for aligning the liquid crystalline composition on the side of the liquid crystalline composition layer 102 before the alignment control. In this case, as described later, after controlling the orientation of the liquid crystalline composition in the layer 102 of the liquid crystalline composition before orientation control, the liquid crystalline composition in the layer 106 of the liquid crystalline composition after orientation control is controlled. The controlled orientation can be further stabilized.

  On the other hand, a second substrate 104 is further provided on the layer 102 of the liquid crystalline composition before alignment control provided on the first substrate 101. Here, the liquid crystalline composition before alignment control provided on the first substrate 101 on the stage 3 before the second substrate 104 is disposed on the layer 102 of liquid crystalline composition before alignment control. For the purpose of deaeration, the product layer 102 may be melted at a temperature equal to or higher than the clearing point (Tc) of the liquid crystalline composition and kept for a predetermined time, and then cooled to room temperature.

  Similar to the first substrate 101, the second substrate 104 is adsorbed to the second stage 105 that can adsorb the second substrate 104. Similarly to the stage 103, the stage 105 is a stage capable of adjusting the temperature. Furthermore, the stage 105 is a stage that can be moved in the directions of the X, Y, and Z axes shown in FIG.

  Since the stage 103 and the stage 105 are configured to be movable in the X, Y, and Z axis directions, for example, the thickness of the layer 102 of the liquid crystalline composition before alignment control is adjusted by movement in the Z axis direction. And pressurization in the vertical direction to the layer is possible. Also, either stage is moved in the X-axis direction or Y-axis direction, or both stages are moved in directions opposite to each other in the X-axis direction, or moved in directions opposite to each other in the Y-axis direction. By doing so, a shearing force can be applied in the horizontal direction of the layer 102 of the liquid crystalline composition before orientation control.

  Similar to the first substrate 101, the second substrate 104 is preferably subjected to an alignment treatment for aligning the liquid crystalline composition on the side of the layer 102 of the liquid crystalline composition before alignment control. . In this case, as described later, after controlling the orientation of the liquid crystalline composition in the layer 102 of the liquid crystalline composition before orientation control, the liquid crystalline composition in the layer 106 of the liquid crystalline composition after orientation control is controlled. The controlled orientation can be further stabilized.

  Note that, as shown in FIGS. 1A, 1B, and 1C, the first stage 103 and the second stage 105 have a temperature of the first stage 103 and a temperature of the second stage 105, respectively. Since the temperature can be adjusted, the temperature of the liquid crystal polymer layer 102 before the alignment control sandwiched between the first substrate 101 and the second substrate 104 can be controlled better.

  Next, the interval between the first substrate 101 and the second substrate 104 is controlled by adjusting the interval between the first stage 103 and the second stage 105. In FIG. 1A, by adjusting the relative position between the first stage 103 and the second stage 105 in the Z-axis direction, the distance between the first stage 103 and the second stage 105 is adjusted. Adjust the interval. Thereby, the pressure applied in the vertical direction to the layer 102 of the liquid crystalline composition before orientation control can be adjusted. Here, the first substrate 101 is configured such that no pressure is applied to the liquid crystalline composition layer 102 before the alignment control, or a pressure of 1000 Pa or less is applied to the liquid crystalline composition layer 102 before the alignment control. And the interval between the second substrates 104 is controlled.

  Next, the first temperature is set so that the temperature of the layer 102 of the liquid crystalline composition before orientation control is not lower than the glass transition temperature (Tg) of the liquid crystalline composition and lower than the clearing point (Tc) of the liquid crystalline composition. The temperature of the stage 103 and the temperature of the second stage 105 are controlled. When the temperature of the liquid crystalline composition layer 102 before the orientation control is equal to or higher than the glass transition temperature (Tg) of the liquid crystalline composition, the liquid crystalline composition in the layer 102 of the liquid crystalline composition before the orientation control. The orientation can be controlled more easily. In addition, when the temperature of the layer 102 of the liquid crystalline composition before the alignment control is a temperature lower than the clearing point (Tc) of the liquid crystalline composition, the liquid crystallinity in the layer 106 of the liquid crystalline composition after the alignment control. The orientation of the composition can be better stabilized.

Here, the temperature above the glass transition temperature (Tg) of the liquid crystalline composition and below the clearing point (Tc) of the liquid crystalline composition is preferably the viscosity of the layer 102 of the liquid crystalline composition before orientation control. , 1N · s · ^{m -2} or more 1,000N · s · ^{m -2} or less, more preferably, 5N · s · ^{m -2} or 500N · s · ^{m -2} or less, the temperature is. When the viscosity of the layer 102 of the liquid crystalline composition before alignment control is 1 N · s · m ⁻² or more, a shearing force can be effectively applied to the layer 102 of the liquid crystalline composition before alignment control. it can. Further, when the viscosity of the layer 102 of the liquid crystalline composition before orientation control is 1,000 N · s · m ⁻² or less, the optical force that applies a shearing force to the layer 102 of the liquid crystalline composition before orientation control. The load on the device for manufacturing the element can be reduced, and aggregation or breakage of the layer 106 of the liquid crystalline composition after orientation control can be reduced.

  The liquid crystalline composition before orientation control until the pressure applied to the layer 102 of liquid crystalline composition before orientation control and the temperature of the layer 102 of liquid crystalline composition before orientation control have their respective desired values. The adjustment of the pressure applied to the layer 102 and the temperature of the layer 102 of the liquid crystal composition before orientation control is repeated.

  Next, the first stage 101 adsorbed on the first stage 103 is adsorbed by the second stage 105 so as to apply a shearing force in the horizontal direction to the layer 102 of the liquid crystalline composition before orientation control. The second substrate 104 is moved relatively. In FIG. 1A, the first substrate 101 adsorbed on the first stage 103 is stopped, while the second substrate 104 adsorbed on the second stage 105 is moved in the X-axis direction. Yes. By applying a shearing force in a horizontal direction to the layer 102 of the liquid crystalline composition before alignment control sandwiched between the first substrate 101 and the second substrate 104, the liquid crystal in the layer 102 of liquid crystalline composition before alignment control is applied. The orientation of the composition can be controlled.

Here, the shear force, the shear stress generated in the layer 102 of the liquid crystal composition before the orientation control is preferably, 100 N · ^{m -2} or more 1,000,000N · ^{m -2} or less, more preferably, 1000 N · m ^-2 or more 100000N · ^{m -2} or less, as a, applied to the layer 102 of the liquid crystal composition before the orientation control. The shear stress generated in the layer 102 of the liquid crystalline composition before the orientation control is determined by the shear rate (1 / s) of the shearing force applied to the layer 102 of the liquid crystalline composition before the orientation control and the liquid crystalline composition before the orientation control. It is represented by the product of the viscosity (N · s · m ⁻² ) of the object layer 102. When the shear stress generated in the layer 102 of the liquid crystalline composition before the alignment control is 100 N · m ⁻² or more, the shearing force can be effectively applied to the layer 102 of the liquid crystalline composition before the alignment control. It becomes possible. When the shear stress generated in the layer 102 of the liquid crystalline composition before the orientation control is 1,000,000 N · m ⁻² or less, the optical force that applies a shearing force to the layer 102 of the liquid crystalline composition before the orientation control The load on the device for manufacturing the element can be reduced, and aggregation or destruction of the liquid crystal polymer layer 106 after the orientation control can be reduced.

Further, the shear velocity of the shear force applied horizontally to the layer 102 of the liquid crystal composition before the orientation control is preferably, ^{10s -1} or 10,000 s ^-1 or less, more preferably, ^{50s -1} or 5, 000 s ⁻¹ or less. Note that the shear rate of the shearing force applied to the layer 102 of the liquid crystalline composition before orientation control is the relative movement speed of the second substrate 104 with respect to the first substrate 101 / liquid crystalline composition before orientation control. Of the first layer 102 (the distance between the first substrate 101 and the second substrate 104). When the shear rate of the shearing force applied to the layer 102 of the liquid crystalline composition before orientation control is 10 s ⁻¹ or more, the shearing force is effectively applied to the layer 102 of the liquid crystalline composition before orientation control. be able to. When the shear rate of the shearing force applied to the layer 102 of the liquid crystalline composition before orientation control is 10,000 s ⁻¹ or less, the optical force that applies the shearing force to the layer 102 of the liquid crystalline composition before orientation control. The load on the device for manufacturing the element can be reduced, and aggregation or breakage of the layer 106 of the liquid crystalline composition after orientation control can be reduced.

  Furthermore, the time for applying a shearing force to the layer 102 of the liquid crystalline composition before orientation control is preferably 0.1 second or more and 5.0 seconds or less, more preferably 0.2 second or more and 1.0 second or less. is there. When the time for applying the shearing force to the layer 102 of the liquid crystalline composition before the alignment control is 0.1 seconds or more, the uneven alignment of the liquid crystalline composition in the layer 106 of the liquid crystalline composition after the alignment control. Can be reduced. When the time for applying the shearing force to the layer 102 of the liquid crystalline composition before the alignment control is 5.0 seconds or less, the aggregation or destruction of the layer 106 of the liquid crystalline composition after the alignment control can be reduced.

  As a result, as shown in FIG. 1B, the alignment-controlled liquid crystal between the first substrate 101 adsorbed on the first stage 103 and the second substrate 104 adsorbed on the second stage 105. A layer 106 of the functional composition is obtained.

  Further, as shown in FIG. 1C, the second substrate 104 is detached from the second stage 105. Then, for example, as shown in FIG. 1C, the liquid crystal composition layer 106 after the alignment control is cooled by a cooling unit that blows a cooling gas such as air onto the second substrate 104. That is, after applying a shearing force to the layer 102 of the liquid crystalline composition before orientation control, it is preferable to cool the layer 106 of the liquid crystalline composition after orientation control using, for example, a cooling means. In this case, the alignment of the liquid crystal composition in the layer 106 of the liquid crystal composition after the alignment control can be more satisfactorily stabilized.

Here, the layer 106 of the liquid crystal composition after orientation control is preferably cooled to a temperature at which the viscosity of the layer 106 of the liquid crystal composition after orientation control is 20 N · s · m ⁻² or more. In this case, the alignment of the liquid crystal composition in the layer 106 of the liquid crystal composition after the alignment control can be more satisfactorily stabilized. Moreover, the layer 106 of the liquid crystalline composition after the alignment control is more preferably cooled to a temperature lower than the glass transition temperature (Tg) of the liquid crystalline composition. In this case, the orientation of the liquid crystalline composition in the layer 106 of the liquid crystalline composition after the orientation control can be further stabilized.

  When at least one of the first substrate 101 and the second substrate 104 has an alignment film, the alignment of the liquid crystalline composition in the layer 106 of the liquid crystalline composition after the alignment control is stabilized by the alignment film. May be. In this case, the step of cooling the liquid crystal composition layer 106 after orientation control with a cooling gas such as air as shown in FIG. 1C can be omitted.

  In this manner, as shown in FIG. 1C, a layer 106 of the liquid crystalline composition after alignment control in which the alignment is stabilized by cooling is obtained. Next, as shown in FIG. 1D, the liquid crystal composition layer 106 after alignment control sandwiched between the cooled first substrate 101 and second substrate 104 is thermally cross-linked. If it is, the liquid crystalline composition is heated to a condition for crosslinking, and the state is maintained until the crosslinking is completely performed.

  For example, when the liquid crystalline composition of the first example is used as the thermally crosslinkable liquid crystalline composition, a liquid crystalline polymer compound having a crosslinking reaction temperature in the range of room temperature to (Tc-10) ° C. ( Aa-1), a combination of a liquid crystalline low molecular compound (Db-1) and a polyisocyanate compound (Da-1) is selected. Accordingly, the crosslinking conditions are set in accordance with the crosslinking temperature of the liquid crystalline composition used for the production of the optically anisotropic film.

When the liquid crystalline composition is photocrosslinkable, as shown in FIG. 1 (d), the liquid crystallinity after alignment control sandwiched between the first substrate 101 and the second substrate 104 after cooling. The composition layer 106 is irradiated with light under conditions that allow the liquid crystalline composition to crosslink, and the light irradiation is continued until crosslinking is complete. For example, when the photocrosslinkable liquid crystalline composition by radical polymerization of the fourth example is used as the photocrosslinkable liquid crystalline composition, the light irradiation condition is 10 to 500 mW / cm using a mercury lamp as the light source. irradiation condition of about 2 to 10 minutes at ² illuminance thereof.

Moreover, also when the photocrosslinkable liquid crystalline composition by cationic polymerization of the sixth example is used, the light irradiation condition is ² to 10 at an illuminance of 10 to 500 mW / cm ² using a mercury lamp as a light source. An irradiation condition of about min.
In addition, light irradiation may be performed under a heating of about 80 to 150 ° C. as necessary. Further, after that, it is preferable to perform annealing treatment at 50 ° C. to 200 ° C. for about 1 to 24 hours as necessary.

The layer 106 of the liquid crystal composition after alignment control in which the alignment is stabilized in this way is subjected to a crosslinking treatment such that the crosslinkable group of the liquid crystal composition is completely crosslinked, thereby crosslinking in the film. The optical anisotropic film 107 of the present invention having a dot density in the range of 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g is obtained. As a result, an optical element 108 in which such an optically anisotropic film 107 is sandwiched between the first substrate 101 and the second substrate 104 is obtained. That is, the optical element 108 as shown in FIG. 1 (d) is manufactured by the method of manufacturing the optically anisotropic film of the present invention as shown in FIGS. 1 (a) to 1 (d). The application of the optical element 108 is not particularly limited, and the optical element 108 can be used, for example, as a wavelength plate in an optical disc apparatus.
Further, the first substrate 101 or the second substrate 104 can be separated as necessary, so that an optical element having a substrate as a support only on one side of the optical anisotropic film can be obtained. If necessary, the optical element can have a configuration in which an electrode is further provided for the purpose of controlling optical characteristics, or a configuration in which a reflective film is provided for the purpose of use as a reflective element.

  The degree of alignment of the liquid crystalline composition in the optically anisotropic film can be confirmed by, for example, crossed Nicol observation with a polarizing microscope.

  FIG. 2 is a diagram schematically illustrating an example of an apparatus for manufacturing an optical element including the optically anisotropic film of the present invention. FIG. 2 shows an apparatus 200 for manufacturing an optical element including an optical anisotropic film provided on the first substrate 201. The optically anisotropic film of the present invention is usually produced as a part of an optical element, for example, using such an apparatus.

  First, the configuration of an apparatus 200 for manufacturing an optical element will be described with reference to FIG. The apparatus 200 for manufacturing an optical element may include means for providing a first substrate 201 not shown and means for providing a second substrate 202 not shown. When an optical element is manufactured using the apparatus 200 for manufacturing an optical element, a layer of the liquid crystalline composition before alignment control is provided on the first substrate 201, and the layer of the liquid crystalline composition before alignment control is provided. A second substrate 202 is provided. That is, the liquid crystal composition layer before orientation control is sandwiched between the first substrate 201 and the second substrate 202. Note that at least one of the first substrate 201 and the second substrate 202 has an alignment film for aligning the liquid crystalline composition on the layer side of the liquid crystalline composition before alignment control or an alignment treatment is performed. Sometimes.

  The optical element manufacturing apparatus 200 includes means for sucking the first substrate 201 and means for sucking the second substrate 202. That is, the first substrate 201 and the second substrate 202 are adsorbed by means for adsorbing the first substrate 201 and means for adsorbing the second substrate 202, respectively.

  Here, the means for adsorbing the first substrate 201 includes the first hollow body 203. At least a portion of the wall of the first hollow body 203 includes a first porous member 204. Examples of the material of the first porous member 204 include a ceramic material and a sintered metal. The first porous member 204 includes a first heater 205 for heating the layer of the liquid crystalline composition before orientation control through the first substrate 201. Further, a first thermometer 206 for measuring the temperature of the first porous member 204 is provided in the first porous member 204. In addition, the means for adsorbing the first substrate 201 includes means for exhausting the inside of the first hollow body 203. The means for exhausting the inside of the first hollow body 203 includes a vacuum pump 207 that sucks the gas inside the first hollow body 203 and a first vacuum that controls the exhaust of the gas inside the first hollow body 203. A valve 208 is included.

  On the other hand, the means for adsorbing the second substrate 202 includes a second hollow body 209. At least a portion of the wall of the second hollow body 209 includes a second porous member 210. Examples of the material of the second porous member 210 include a ceramic material and a sintered metal. Further, the second porous member 210 includes a second heater 211 for heating the layer of the liquid crystalline composition before orientation control through the second substrate 202. Further, a second thermometer 212 for measuring the temperature of the second porous member 210 is provided on the second porous member 210. In addition, the means for adsorbing the second substrate 202 includes means for exhausting the inside of the second hollow body 209. The means for exhausting the inside of the second hollow body 209 is a vacuum for sucking the gas inside the second hollow body 209 that is common to the vacuum pump 207 that sucks the gas inside the first hollow body 203. The pump 207 and the 2nd vacuum valve 213 which controls exhaust_gas | exhaustion of the inside of the 2nd hollow body 209 are included.

  The apparatus 200 for manufacturing an optical element also has a means for moving the first substrate 201 adsorbed by the means for adsorbing the first substrate 201 relative to the second substrate 202 or the second substrate 202. Means for moving the second substrate 202 adsorbed by the means for adsorbing relative to the first substrate 201. The apparatus 200 for manufacturing the optical element shown in FIG. 2 has means for moving the first substrate 201 adsorbed by the means for adsorbing the first substrate 201 relative to the second substrate 202. The means for moving the first substrate 201 adsorbed by the means for adsorbing the first substrate 201 relative to the second substrate 202 has three axes orthogonal to each other, ie, X shown in FIG. Means for moving the means for adsorbing the first substrate 201 in the Y and Z axis directions is provided. For example, as shown in FIG. 2, an XY stage 214 as means for moving the means for sucking the first substrate 201 in the X and Y axis directions and means for sucking the first substrate 201 in the Z axis direction are provided. A Z stage 215 as means for moving is included. Note that the directions of the X, Y, and Z axes referred to here are the same as those described with reference to FIG.

  Furthermore, the apparatus 200 for manufacturing an optical element includes a load cell 216 as a means for measuring the pressure applied to the liquid crystalline composition layer provided between the first substrate 201 and the second substrate 202.

  In addition, the apparatus 200 for manufacturing an optical element further includes means for cooling the layer of the liquid crystalline composition before and after alignment control. The means (cooling means) for cooling the liquid crystal composition layer before and after the alignment control is supplied from means 217 for supplying a cooling gas such as an air cylinder or a liquid nitrogen cylinder, and means 217 for supplying a cooling gas. Pressure adjusting valve 218 for adjusting the pressure of the cooling gas to be supplied, first supply valve 219 for controlling the supply of the cooling gas to the inside of the first hollow body 203, and the inside of the second hollow body 209 A second supply valve 220 for controlling the supply of the cooling gas to the. Examples of the cooling gas include air or nitrogen.

  Next, operation | movement of the apparatus 200 which manufactures an optical element is demonstrated using FIG. Using the apparatus 200 for manufacturing an optical element as shown in FIG. 2, a method for manufacturing an optical element having the optical anisotropic film of the present invention as shown in FIGS. Thus, a highly reliable optical element having excellent heat resistance and light resistance can be obtained. First, the first vacuum valve 208, the second vacuum valve 213, the first supply valve 219, and the second supply valve 220 are all closed.

  First, the first substrate 201 is provided to the first porous member 204 of the first hollow body 203 by means for providing the first substrate 201 (not shown). The first substrate 201 has a size that covers the first porous member 204. Next, the inside of the first hollow body 203 is exhausted by operating the vacuum pump 207 and opening the first vacuum valve 208. At this time, the first substrate 201 is adsorbed and fixed to the first porous member 204 of the first hollow body 203.

  Next, on the first substrate 201, a layer of the liquid crystalline composition before alignment control, which is composed of the above-described crosslinkable liquid crystalline composition is provided. Here, the first heater 205 included in the first porous member 204 and the first thermometer 206 provided in the first porous member 204 are used to pass through the first substrate 201. You may heat the layer of the liquid crystalline composition before orientation control.

  Next, the 2nd board | substrate 202 is provided in the layer of the liquid crystalline composition before orientation control by the means which provides the 2nd board | substrate 202 which is not illustrated. The second substrate 202 has a size that covers the second porous member 210. In this manner, the layer of the liquid crystalline composition before orientation control is sandwiched between the first substrate 201 and the second substrate 202. Next, by using the Z stage 215, the first hollow body 203 and the first substrate 201 are moved in the Z direction, whereby the second porous member 210 of the second hollow body 209 is moved to the second stage. Contact the substrate 202. Next, the second vacuum valve 213 is opened while the vacuum pump 207 is operated. At this time, the second substrate 202 is adsorbed and fixed to the second porous member 210 of the second hollow body 209.

  Next, the distance between the first substrate 201 and the second substrate 202 is adjusted by moving the first hollow body 203 and the first substrate 201 in the Z direction using the Z stage 215. At this time, the load cell 216 is used to measure the pressure applied to the layer of the liquid crystalline composition before alignment control sandwiched between the first substrate 201 and the second substrate 202. Then, pressure is not applied to the layer of the liquid crystalline composition before alignment control sandwiched between the first substrate 201 and the second substrate 202, or the first substrate 201 and the second substrate 202. The interval between the first substrate 201 and the second substrate 202 is adjusted so that the pressure applied to the layer of the liquid crystalline composition before alignment control sandwiched between the layers is 1000 Pa or less.

  Next, orientation control is performed via the second substrate 202 using the second heater 211 included in the second porous 210 and the second thermometer 212 provided in the second porous member 210. The previous layer of liquid crystalline composition is heated.

  If necessary, the pressure of the cooling gas supplied from the means 217 for supplying the cooling gas is adjusted using the pressure adjusting valve 218, and the first supply valve 219 and / or the second supply valve are adjusted. By opening 220, the cooling gas is supplied into the first hollow body 203 and / or the second hollow body 209. In this case, the cooling gas supplied to the first hollow body 203 and / or the second hollow body 209 causes the first porous member 204 and / or the second porous member 210 to pass through. Thus, the first substrate 201 and / or the second substrate 202 is cooled. As a result, the layer of the liquid crystalline composition before alignment control sandwiched between the first substrate 201 and the second substrate 202 can be cooled.

  At this time, the temperature of the first substrate 201 and the temperature of the second substrate 202 are the same, that is, before the orientation control sandwiched between the first substrate 201 and the second substrate 202. Heating of the first substrate 201 by the first heater 205, heating of the second substrate 202 by the second heater 212, and cooling gas so that the temperature distribution in the liquid crystal composition layer is uniform. The cooling of the first substrate 201 and / or the second substrate 202 is adjusted.

  And the temperature of the layer of the liquid crystalline composition before alignment control sandwiched between the first substrate 201 and the second substrate 202 is equal to or higher than the glass transition temperature (Tg) of the liquid crystalline composition. The temperatures of the first substrate 201 and the second substrate 202 are adjusted so that the temperature is lower than the clearing point (Tc). Thereby, the viscosity of the layer of the liquid crystalline composition before the alignment control is adjusted.

  Note that no pressure is applied to the liquid crystalline composition layer before orientation control or the pressure applied in the vertical direction to the liquid crystalline composition layer before orientation control is 1000 Pa or less and the liquid crystalline composition layer before orientation control. Is a temperature not lower than the glass transition temperature (Tg) of the liquid crystalline composition and lower than the clearing point (Tc) of the liquid crystalline composition (the viscosity of the layer of the liquid crystalline composition before the orientation control is a desired viscosity). Until this is realized, the adjustment of the distance between the first substrate 201 and the second substrate 202 and the adjustment of the temperature of the first substrate 201 and the second substrate 202 are repeated in the manner described above.

  Next, no pressure is applied to the layer of the liquid crystalline composition before the alignment control, or the pressure applied in the vertical direction to the layer of the liquid crystalline composition before the alignment control is 1000 Pa or less and the liquid crystalline composition before the alignment control The shearing force in the horizontal direction is applied to the layer of the liquid crystalline composition before orientation control under the condition that the temperature of the layer is not lower than the glass transition temperature (Tg) of the liquid crystalline composition and lower than the clearing point (Tc) of the liquid crystalline composition. Add

  In the apparatus 200 for manufacturing an optical element as shown in FIG. 2, the first substrate 201 is moved in at least one of the X and Y axis directions by the XY stage 214, for example, in the X axis direction as shown in FIG. The means for adsorbing is moved. That is, using the XY stage 214, the Z stage 215 provided on the XY stage 214, the first hollow body 203 provided on the Z stage 215, and the first hollow body 203 in the X-axis direction. The first substrate 201 adsorbed and fixed to the porous member 204 is moved relative to the second substrate 202. Thereby, in at least one of the X and Y axis directions, for example, as shown in FIG. 2, in the X axis direction, it is possible to apply a shear force in the horizontal direction to the layer of the liquid crystalline composition before orientation control. Become. Shear rate of shearing force applied to the layer of liquid crystalline composition before orientation control, time for applying shearing force to the layer of liquid crystalline composition before orientation control, and shear generated in the layer of liquid crystalline composition before orientation control The stress is adjusted by the speed of movement of the first substrate 201 caused by the XY stage 214.

  In this way, after applying a shearing force to the layer of liquid crystalline composition before orientation control (a layer of liquid crystalline composition after orientation control is obtained), cooling is performed using a pressure adjusting valve 218 as necessary. By adjusting the pressure of the cooling gas supplied from the gas supply means 217 and opening the first supply valve 219 and / or the second supply valve 220, the inside of the first hollow body 203 and A cooling gas is supplied into the second hollow body 209. In this case, the cooling gas supplied to the first hollow body 203 and / or the second hollow body 209 causes the first porous member 204 and / or the second porous member 210 to pass through. Thus, the first substrate 201 and / or the second substrate 202 is cooled. As a result, the layer of the liquid crystalline composition after alignment control sandwiched between the first substrate 201 and the second substrate 202 can be cooled.

  Preferably, after applying a shearing force to the layer of the liquid crystalline composition before orientation control, the pressure of the cooling gas supplied from the cooling gas supply means 217 is adjusted using the pressure adjusting valve 218, and By opening the second supply valve 220, the cooling gas is supplied into the second hollow body 209. In this case, by supplying the cooling gas to the second hollow body 209, the second substrate 202 adsorbed and fixed to the second porous member 210 of the second hollow body 209 is removed. The second substrate 202 can be rapidly cooled by desorbing from the second porous member 210 and ejecting a cooling gas from the second porous member 210. As a result, the layer of the liquid crystalline composition after alignment control sandwiched between the first substrate 201 and the second substrate 202 can be rapidly cooled. In this way, a layer of a liquid crystalline composition in which the alignment is stabilized is obtained.

  Thereafter, as shown in FIG. 1 (d), the liquid crystal composition layer after the alignment control sandwiched between the cooled first substrate 201 and the second substrate 202 is formed. The composition is subjected to heat treatment or light irradiation treatment under the condition that the crosslinkable group of the composition is completely crosslinked.

In this way, the cross-linking treatment in which the cross-linkable group of the liquid crystal composition is completely cross-linked is performed on the layer of the liquid crystal composition after the alignment control in which the orientation is stabilized, thereby cross-linking in the film. An optical element having the optically anisotropic film of the present invention having a dot density in the range of 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g between the first substrate 201 and the second substrate 202. can get.
The degree of alignment of the liquid crystalline composition in the optically anisotropic film can be confirmed by, for example, crossed Nicol observation with a polarizing microscope.

Examples of the present invention will be described below, but the present invention is not limited to these examples. Examples 1 and 2 are examples, and examples 3 to 5 are comparative examples.
The number average molecular weight (Mn) and molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) were measured using a GPC apparatus (HLC8220, manufactured by Tosoh Corporation) using tetrahydrofuran (THF) as a solvent. . The copolymer composition ratio was measured using ¹ H-NMR (AL300, manufactured by JEOL Ltd.) using deuterated chloroform as a solvent. Furthermore, the glass transition point (Tg) and the nematic phase-isotropic phase transition temperature (Tc) were measured using a differential scanning calorimeter (DSC8000, manufactured by PerkinElmer). Furthermore, the horizontal orientation was confirmed by measuring the incidence angle dependency of retardation using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).

First, a liquid crystalline polymer compound and a liquid crystalline low molecular compound to be blended in a crosslinkable liquid crystalline composition used for production of an optically anisotropic film were synthesized.
[Synthesis Example 1] Synthesis of Liquid Crystalline Polymer Compound (Cb-21) Liquid Crystalline Polymer Compound (Formula below) classified into (meth) acrylic liquid crystalline polymer compound (Cb-2) having the oxetane group. (Cb-21) shows the structure of the average composition) as follows.
(Synthesis of monomer (c2-1))
In a 1 L four-necked flask equipped with a reflux apparatus and a stirrer, 14.3 g of 4- (6- (acryloyloxy) hexyloxy) benzoic acid, 5 g of 3-methyloxetan-3-methanol, 13.6 g of dicyclohexylcarbodiimide, dimethylamino 2.3 g of pyridine and 350 ml of dichloromethane were added and the reaction was allowed to stir at room temperature for 24 hours.

  After completion of the reaction, water and dichloromethane were added for liquid separation, and the organic layer was recovered. The collected organic layer was washed with a saturated aqueous sodium chloride solution (400 mL) and then washed with water, and the organic layer was collected again. Subsequently, after drying the obtained organic layer with anhydrous magnesium sulfate, the anhydrous magnesium sulfate was removed by filtration under reduced pressure. By concentrating the filtrate, powder crystals were obtained. A mixed solvent of ethyl acetate and hexane was added to the powder crystal and purified by silica gel chromatography to obtain 5.6 g of a compound represented by the following formula (c2-1). The yield was 33% by mass.

(Synthesis of polymer (Cb-21))
2792 mg of liquid crystalline monomer (P6OCB: 6- (4′-cyanobiphenyl-4-yloxy) hexyl acrylate), 752 mg of the monomer (c2-1) obtained above, 35 mg of polymerization initiator in a 10 mL screw-cap test tube (Trade name “V40” manufactured by Wako Pure Chemical Industries, Ltd.) and 4.16 g of N, N-dimethylformamide were charged, and the air in the screw-mouth test tube was replaced with nitrogen, and then the screw-mouth test tube was sealed. The screw mouth test tube was stirred and shaken in an 80 ° C. constant temperature bath for 18 hours, and the above-mentioned raw material monomers were copolymerized.

  After the product was washed in methanol to remove unreacted raw material monomers, the product was dissolved in tetrahydrofuran, and the resulting solution was dropped into methanol to purify the product by reprecipitation. Thereafter, the product was dried in a vacuum dryer at 40 ° C. for 2 hours, and 3190 mg (yield 90%) of white, an average composition is shown in the following formula (Cb-21) having an oxetane group as a crosslinking group. A liquid crystalline polymer compound was obtained. The number average molecular weight (Mn) of the liquid crystalline polymer compound (Cb-21) is 18,000, the glass transition point (Tg) is 33 ° C., and the phase transition temperature (Tc) from the nematic phase to the isotropic phase is 141. C. and purity was> 99%. The raw material monomer charge ratio was 70/30 (molar ratio) in terms of (P6OCB / (c2-1)).

[Synthesis Example 2] Synthesis of Bifunctional (Hydroxyl) Liquid Crystalline Low Molecular Compound (5L-1) In the above bifunctional (hydroxyl) liquid crystalline low molecular compound (5L), a compound in which the spacer portion is a butylene group (the following The structural formula (shown in 5L-1) was prepared as shown in the following reaction formula.
To a 1 L four-necked flask equipped with a reflux apparatus and a stirrer was added 6- (4-hydroxycyclohexyl) decahydronaphthalen-2-ol (in formula (4h ), 2.0 g of 4-pentenoic acid, and 0.08 g of dimethylaminopyridine were added, and 100 ml of dichloromethane was added thereto and cooled to 0 ° C. A solution prepared by dissolving 3.92 g of dicyclohexylcarbodiimide in 100 ml of dichloromethane was added dropwise thereto over 5 minutes, and the mixture was reacted at room temperature for 24 hours.

  After completion of the reaction, the reaction solution was filtered, and water and ethyl acetate were added for liquid separation, and the organic layer was recovered. The collected organic layer was washed with a saturated aqueous sodium chloride solution (400 mL) and then washed with water, and the organic layer was collected again. Subsequently, after drying the obtained organic layer with anhydrous magnesium sulfate, the anhydrous magnesium sulfate was removed by filtration under reduced pressure. A powder was obtained by concentrating the filtrate. A mixed solvent (1: 4) of ethyl acetate and hexane was added to the powder, and the mixture was purified by silica gel chromatography. The compound represented by the following reaction formula (4i) (6- (4- (pent-4-enoyloxy) ) cyclohexyl) decahydronaphthalen-2-yl pent-4-enoate) 3 g. The yield was 91% by mass.

  To a 1 L four-necked flask equipped with a reflux apparatus and a stirrer, the compound (4i) 6- (4- (pent-4-enoyloxy) cyclohexyl) decahydronaphthalen-2-yl pent-4-enoate obtained above was added. 2.85 g was dissolved in 30 ml of tetrahydrofuran, charged, cooled to 0 ° C., 30 ml of a THF solution containing 9-BBN at 0.5 M was added dropwise over 15 minutes, and stirred at room temperature for 2 hours. The reaction solution was cooled again to 0 ° C., 5 ml of 3M aqueous sodium hydroxide solution and 5 ml of 30% aqueous hydrogen peroxide were successively added dropwise, and the mixture was stirred at room temperature for 2 hours.

  After completion of the reaction, a saturated aqueous sodium chloride solution and ethyl acetate were added for liquid separation, and the organic layer was recovered. Further, the organic layer was washed successively with aqueous ammonium chloride and saturated aqueous sodium chloride solution. Subsequently, after drying the obtained organic layer with anhydrous magnesium sulfate, the anhydrous magnesium sulfate was removed by filtration under reduced pressure. A powder was obtained by concentrating the filtrate. To this powder, a mixed solvent of ethyl acetate and methanol (50: 1) was added and purified by silica gel chromatography. One hydroxyl group was present at both ends represented by (5L-1) in the reaction formula. As a result, 2.24 g of a liquid crystalline low molecular compound having a molecular weight of 452.3 was obtained. The yield was 72% by mass.

[Synthesis Example 3] Synthesis of a bifunctional (acryloyl group) liquid crystalline low molecular compound (7L-1) In the above bifunctional ((meth) acryloyl group) liquid crystalline low molecular compound (7L), the functional group is an acryloyl group. Thus, a compound having a propylene group in the spacer portion (shown in the following structural formula (7L-1)) was produced.
In a 1 L four-necked flask equipped with a reflux apparatus and a stirrer, 50 g of 6- (4-hydroxycyclohexyl) decahydronaphthalen-2-ol, 75 g of 3-acryloyloxybutanoic acid, 40 g of dicyclohexylcarbodiimide, dimethylamino 4.2 g of pyridine and 500 ml of dichloromethane were added and reacted by stirring at room temperature for 20 hours.

  After completion of the reaction, water and diethyl ether were added for liquid separation, and the organic layer was recovered. The collected organic layer was washed with a saturated aqueous sodium chloride solution (400 mL) and then washed with water, and the organic layer was collected again. Subsequently, after drying the obtained organic layer with anhydrous magnesium sulfate, the anhydrous magnesium sulfate was removed by filtration under reduced pressure. By concentrating the filtrate, powder crystals were obtained. To this powder crystal, a mixed solvent of ethyl acetate and hexane was added and purified by silica gel chromatography to obtain 78 g of a compound having a molecular weight of 532.3 represented by the formula (7L-1). The yield was 63% by mass.

[Synthesis Example 4] Synthesis of Liquid Crystalline Polymer Compound (Aa-11) Liquid crystal polymer compounds classified into vinyl ether liquid crystal polymer compounds (Aa-1) having the above hydroxyl groups (the following formula (Aa-11) The structure of the average composition is shown in FIG.
(Synthesis of vinyl ether compound (1G0bb-1))
First, the vinyl ether polymerizable liquid crystal compound (a1) was classified as a vinyl ether compound (1G0bb), and a compound having r1 of 3 (shown in the following structural formula (1G0bb-1)) was produced.
4-hydroxyvinyl ether (8.2 g, 70.2 mmol) and (trans-6- (trans-4-propylcyclohexyl) -trans-decahydronaphthalene-2-carboxylic acid (16.6 g, 54.2 mmol) were mixed with chloroform ( 1200 ml), dicyclohexylcarbodiimide (12.1 g, 58.6 mmol) and 4- (N, N-dimethylamino) pyridine (1.16 g, 9.49 mmol) were added, and the mixture was stirred at room temperature for 13 hours. After removing the white precipitate by filtration, the filtrate was washed with 0.5 M hydrochloric acid and saturated aqueous sodium bicarbonate, dried, and then the solvent was removed to obtain a crude product.Silica gel column chromatography (silica gel: Asahi Glass S-Tech Co., Ltd.) MS-GEL D50-60-A (N) 1,200 g, eluent: hexane / ethyl acetate = 6 / 1) and a vinyl ether compound (1G0bb-1) having the structure shown below: trans-6- (trans-4-propylcyclohexyl) -trans-decahydronaphthalene-2-carboxylic acid-4- (vinyloxy ) Butyl (17.9 g, 72% yield) was obtained.

The NMR spectrum data of the obtained compound (1G0bb-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.65-2.00 (m, 40H), 2.48 (m, 1H), 3.96 (t , J = 13.5 Hz, 2H), 4.26 (dd, J = 2.5 Hz, 14.0 Hz, 2H), 4.08 (t, J = 13.8 Hz, 2H), 6.47 (dd, J = 6.5 Hz, 14.0 Hz, 1H).

(Synthesis of Liquid Crystalline Polymer Compound (Aa-11))
In an autoclave with a stainless steel stirrer with an internal volume of 30 mL, 0.066 g of potassium carbonate, 21.9 g of the compound (1G0bb-1) obtained above, 0.26 g of 4-hydroxybutyl vinyl ether (HBVE), heptane 11.0 g and 0.15 g of perbutyl PV (trade name of peroxide polymerization initiator: manufactured by NOF Corporation) were added, and the autoclave was closed.

  Next, the autoclave was cooled with liquid nitrogen to solidify the liquid phase, and then degassed under reduced pressure. Thereafter, 1.1 g of tetrafluoroethylene (TFE) was introduced into the autoclave, and the liquid phase solidified by heating was melted, and then stirring was started. When the temperature was further raised and the temperature in the autoclave was 65 ° C., the pressure became 0.27 MPa. After stirring at that temperature for 3.5 hours, the reaction was stopped by putting in an ice bath, the autoclave was opened, and the slurry containing the fluorine-containing copolymer was recovered.

  Next, 200 mL of toluene and 400 mL of saturated saline were added to the slurry containing the fluorinated copolymer, and an extraction operation was performed using a separatory funnel to recover the organic layer. The recovered organic layer was poured into 2 L of methanol, and the resulting white precipitate was collected by filtration under reduced pressure, dried under reduced pressure at 40 ° C. for 8 hours, and 7.8 g of liquid crystalline polymer compound (Aa-11) (recovery). 52%).

  The number average molecular weight (Mn) of the obtained liquid crystalline polymer compound (Aa-11) is 12,000, the molecular weight distribution (Mw / Mn) is 2.09, and the copolymer composition ratio ((1G0bb-1) / HBVE / TFE) was 36/14/50 (molar ratio). The raw material monomer charge ratio was 45/5/50 (molar ratio) in terms of ((1G0bb-1) / HBVE / TFE). Moreover, Tg was 42 degreeC and Tc was 170 degreeC.

[Synthesis Example 5] Synthesis of Liquid Crystalline Polymer Compound (Ab-11) Liquid crystal polymer compounds classified into vinyl ether liquid crystal polymer compounds (Ab-1) having an acryloyl group (the following formula (Ab- The structure of the average composition is shown in 11).
In a 500 ml three-necked flask equipped with a reflux device and a stirring device, 2.0 g of the liquid crystalline polymer compound (Aa-11) obtained in Synthesis Example 4, 1,1-bis (acryloyloxymethyl) ethyl isocyanate ( (Product name: Karenz BEI, Showa Denko Co., Ltd.) 0.64 g, DBTDL 0.2 g, and toluene 200 ml were added and stirred at 60 ° C. for 12 hours. The reaction solution was poured into 2 L of methanol, and the resulting white precipitate was collected by filtration under reduced pressure and dried under reduced pressure at 40 ° C. for 8 hours.

  Thus, 1.8 g (yield 78%) of a liquid crystalline polymer compound (Ab-11) having an acryloyl group in the side chain was obtained. The reaction rate of the hydroxyl group in the polymer compound (Aa-11) is 100%, and the number average molecular weight (Mn) of the obtained liquid crystalline polymer compound (Ab-11) is 12,000, and the molecular weight distribution (Mw / Mn) was 2.09. Moreover, Tg was 41 degreeC and Tc was 172 degreeC.

[Synthesis Example 6] Synthesis of Liquid Crystalline Polymer Compound (Ba-11) Liquid crystal polymer compounds classified into the diene-based liquid crystal polymer compound (Ba-1) having a hydroxyl group (the following formula (Ba-11) The structure of the average composition is shown in FIG.
(Synthesis of fluorine diene compound (2MOx0))
In a 2 L four-necked flask equipped with a reflux apparatus and a stirrer, 35 g of the compound represented by the following formula (22A) synthesized by the method described in WO2002 / 065212 and the above formula (Gr3) Of the compound ((2R, 4aR, 6S, 8aS) -6-((1r, 4R) -4-propylcyclohexyl) decahydronaphthalene-2-carboxylic acid), THF 1000 mL, 1-ethyl-3- (3 -Dimethylaminopropyl) carbodiimide hydrochloride (36 g) and dimethylaminopyridine (2.4 g) were added, and the mixture was stirred at room temperature for 17 hours to be reacted.

  After completion of the reaction, water and diethyl ether were added for liquid separation, and the organic layer was recovered. The recovered organic layer was washed with a saturated aqueous sodium chloride solution (400 mL) and then with water, and the organic layer was recovered again. Subsequently, after drying the obtained organic layer with anhydrous magnesium sulfate, the anhydrous magnesium sulfate was removed by filtration under reduced pressure. By concentrating the filtrate, powder crystals were obtained. To this powder crystal, a mixed solvent of ethyl acetate and hexane was added and purified by silica gel chromatography to obtain 77 g of a compound represented by the following formula (2MOx0). The yield was 84% by mass.

(Synthesis of fluorinated liquid crystalline polymer compound (Ba-11))
Polymerization is carried out by the following method using the fluorine-containing diene compound (2MOx0) obtained above and the fluorine-containing diene compound represented by the above formula (22A) as a raw material monomer, and a liquid crystalline polymer compound having a hydroxyl group (Ba- 11) was produced.
That is, after introducing nitrogen into a 20-ml test tube, 41 mg of the compound represented by the above formula (22A) synthesized by the method described in WO2002 / 065212 and the fluorinated diene obtained in Synthesis Example 1 959 mg of the compound (2MOx0), 1250 mg of dioxane, and 50 mg of V40 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) which is a thermal polymerization initiator were added, and the mixture was reacted by stirring at 80 ° C. for 72 hours under nitrogen. Polymer compound (Ba-11) (yield 64%) was obtained.

  The number average molecular weight (Mn) of the obtained liquid crystalline polymer compound (Ba-11) is 6,000, the molecular weight distribution (Mw / Mn) is 1.64, and the copolymer composition ratio (2MOx0) / (22A) Was 87/13 (molar ratio). The raw material monomer charge ratio was 90/10 (molar ratio) of (2MOx0) / (22A). Moreover, Tg was 90 degreeC and Tc was 138 degreeC.

[Synthesis Example 7] Synthesis of Liquid Crystalline Polymer Compound (Ba-12) Using the fluorinated diene compound (2MOx0) obtained in Synthesis Example 6 and the fluorinated diene compound represented by the above formula (22A) as raw material monomers Polymerization is performed by the following method, and the structure of the average composition is shown in the liquid crystal polymer compound (the following formula (Ba-12), which is classified into the diene liquid crystal polymer compound (Ba-1) having a hydroxyl group. ) Was prepared as follows.

  That is, after introducing nitrogen into a 20 ml test tube, 142 mg of the compound represented by the above formula (22A) synthesized by the method described in WO2002 / 065212 and the fluorinated diene obtained in Synthesis Example 1 859 mg of the compound (2MOx0), 1250 mg of dioxane, and 50 mg of V40 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal polymerization initiator were added, and the mixture was reacted by stirring at 80 ° C. for 72 hours under nitrogen. Molecular compound (Ba-12) (yield 65%) was obtained.

  The number average molecular weight (Mn) of the obtained liquid crystalline polymer compound (Ba-12) is 3,400, the molecular weight distribution (Mw / Mn) is 2.05, and the copolymer composition ratio (2MOx0) / ( 22A) was 69/31 (molar ratio). The raw material monomer charge ratio was (2MOx0) / (22A) and was 70/30 (molar ratio). Moreover, Tg was 88 degreeC and Tc was 110 degreeC.

[Synthesis Example 8] (Synthesis of fluorinated liquid crystalline polymer compound (Bb-11))
The liquid crystalline polymer compound (the structure of the average composition is shown in the following formula (Bb-11)) classified into the diene liquid crystalline polymer compound (Bb-1) having the acryloyl group was prepared as follows. .
After introducing nitrogen into a 50 ml flask equipped with a reflux apparatus and a stirring apparatus, 1000 mg of the liquid crystalline polymer compound (Ba-11) obtained in Synthesis Example 6 and 1,1-bis (acryloyloxymethyl) ethyl isocyanate 110 mg of Nart (trade name: Karenz BEI, manufactured by Showa Denko KK), 20 mg of DBTDL, and 20 g of dichloromethane were added and stirred at room temperature for 24 hours. The reaction solution was concentrated to 3 g and poured into 50 ml of methanol, and the resulting white precipitate was collected by centrifugation and dried under reduced pressure at room temperature for 8 hours.

  Thus, 980 mg (yield 88) of a liquid crystalline polymer compound (fluorinated liquid crystalline polymer compound) having an acryloyl group in the side chain, in which the composition ratio of the raw material monomers is represented by the following formula (Bb-11). %)Obtained. The reaction rate of the hydroxyl group in the polymer compound (Ba-11) is 100%, and the number average molecular weight (Mn) of the obtained liquid crystal polymer compound (Bb-11) is 3,900, and the molecular weight distribution (Mw / Mn) was 1.68. Moreover, Tg was 85 degreeC and Tc was 127 degreeC.

A liquid crystalline composition is prepared using the liquid crystalline polymer compound and the liquid crystalline low molecular compound obtained in each of the above synthesis examples, and the following optical examples are prepared using the optical element manufacturing apparatus shown in FIG. An isotropic film was produced and an optical element having the same was obtained.
[Example 1]
(1) Preparation of liquid crystalline composition A The liquid crystalline polymer compound (Cb-21) obtained in Synthesis Example 1 and Adekaoptomer SP-172 (trade name, manufactured by ADEKA) as a polymerization initiator were 100 A liquid crystalline composition A was obtained by mixing at a mass ratio of 1: 1. The obtained liquid crystalline composition A exhibited a nematic phase at 31 ° C. (Tg = 31 ° C.). The phase transition temperature (Tc) from the nematic phase to the isotropic phase was 139 ° C.

(2) Preparation of sample precursor A glass substrate (10 cm long, 10 cm wide, 0.7 mm thick) was heated to 137 ° C., and the liquid crystalline composition A was placed on the glass substrate and melted. . The liquid crystalline composition A was degassed by holding in this state for 3 minutes, and then cooled to room temperature to prepare a sample precursor A.

(3) Production of optical element having optically different constituent film The sample precursor A was placed on the lower stage (first porous member 204) of the apparatus 200 for producing an optical element, heated to 137 ° C. The glass substrate was fixed to the lower stage by suction. Thereafter, one glass substrate having the same size as that described above was adsorbed and fixed to the upper stage (second porous member 210).

  The lower stage was raised and held for 10 minutes when the gap between the substrates reached 10 μm. The indication of the pressure of the load cell 216 at this time was 5.0 N, and the pressure applied to the layer of the liquid crystalline composition A formed to the same thickness (10 μm) as the gap between the glass substrates was equivalent to 500 Pa.

After cooling the temperature of the upper and lower stages to 109 ° C., only the lower stage is moved in the X-axis direction at a speed of 10 mm / s for 0.5 seconds, and a shear stress of 100,000 (N / m ^{2) is applied} to the liquid crystalline composition layer. ) ((Shear rate 1,000 (1 / s) × shear viscosity of liquid crystal composition layer 100 (N · s / m ² ))) was applied, and then the lower stage was lowered to move the upper glass substrate. Cold air was blown from right above to cool to 25 ° C.

The liquid crystal composition layer thus subjected to the alignment treatment was heated to 90 ° C. on the lower stage while the lower stage was lowered, and the mercury lamp was passed through the upper glass substrate from directly above. Irradiates with light at an illuminance of 260 mW / cm ² for 5 minutes and further anneals at 90 ° C. for 12 hours to carry out a crosslinking reaction, and has an optically different film between the two glass substrates. Optical element A was obtained.

(4) Evaluation of optical element A (4-1) Density of cross-linking points When the density of cross-linking points of the optical anisotropic film of optical element A obtained above was calculated, 4.2 × 10 ⁻⁴ pieces were obtained. / G.

(4-2) Orientation It was found that the obtained optical element A was horizontally oriented in the shear direction by measuring the incidence angle dependency of retardation. Optical element A was transparent in the visible light range, and no scattering was observed. The evaluation of orientation was performed according to the following criteria from the results obtained by this method.

(Evaluation criteria for orientation)
○: Transparent in the visible light range and no scattering observed.
Δ: Transparent in the visible light range, but scattering is observed.
X: It is opaque in the visible light range, and scattering is recognized.

(4-3) Heat resistance (Reliability 1)
Next, the temperature dependence measurement of the retardation of the optical element A obtained above was performed. The measurement wavelength was 400 nm. The temperature at which the retardation before crosslinking (sample precursor A) was reduced by 20% was 93 ° C., whereas the temperature at which the retardation after crosslinking (optical element A) was reduced by 20% was 130 ° C. The temperature dependence of the retardation was measured by mounting the sample on the center of the temperature control part of the heating stage of FP82HT manufactured by METTLER and incorporating it into a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.). It was confirmed that the optical element A was excellent in reliability. Reliability was determined on the basis of the results obtained by this method as follows.

(Reliability 1 evaluation criteria)
○: Temperature rise due to crosslinking at a temperature at which retardation at room temperature is reduced by 20% is 30 ° C. or more.
Δ: Temperature rise due to crosslinking at a temperature at which the retardation at room temperature is reduced by 20% is 10 ° C. or more and less than 30 ° C. x: Temperature rise due to crosslinking at a temperature at which the retardation at room temperature is reduced by 20% is 10 ° C. Is less than

[Example 2]
(1) Preparation of liquid crystalline composition B Liquid crystalline polymer compound (Ba-12) obtained in Synthesis Example 7 above, polyfunctional isocyanate (trade name: Desmodur N3300; manufactured by Bayer), and polymerization initiation DBTDL as an agent was mixed at a mass ratio of 100: 7.8: 0.0003 to obtain a liquid crystal composition B. The obtained liquid crystal composition B exhibited a nematic phase at 70 ° C. (Tg = 70 ° C.). The phase transition temperature (Tc) from the nematic phase to the isotropic phase was 120 ° C.

(2) Preparation of sample precursor A glass substrate (length 10 cm, width 10 cm, thickness 0.7 mm) was heated to 110 ° C., and the liquid crystalline composition B was placed on the glass substrate and melted. . The liquid crystalline composition B was deaerated by holding in this state for 3 minutes, and then cooled to room temperature to prepare a sample precursor B.

(3) Production of optical element having optically different constituent film The sample precursor B was placed on the lower stage (first porous member 204) of the apparatus 200 for producing an optical element, heated to 110 ° C. The glass substrate was fixed to the lower stage by suction. Thereafter, one glass substrate having the same size as that described above was adsorbed and fixed to the upper stage (second porous member 210).

  The lower stage was raised and held for 10 minutes when the gap between the glass substrates reached 10 μm. The indication of the pressure of the load cell 216 at this time was 5.0 N, and the pressure applied to the layer of the liquid crystalline composition B formed to the same thickness (10 μm) as the gap between the glass substrates was equivalent to 500 Pa.

After cooling the temperature of the upper and lower stages to 100 ° C., only the lower stage is moved in the X-axis direction at a speed of 10 mm / s for 0.5 seconds, and a shear stress of 100,000 (N / m ^{2) is applied} to the liquid crystalline composition layer. ) ((Shear rate 1,000 (1 / s) × shear viscosity of liquid crystal composition layer 100 (N · s / m ² ))) was applied, and then the lower stage was lowered to move the upper glass substrate. Cold air was blown from right above to cool to 25 ° C.

  The liquid crystalline composition layer thus subjected to the alignment treatment is subjected to a crosslinking reaction by annealing at 100 ° C. for 12 hours on the lower stage while the lower stage is lowered, and two glasses An optical element B having an optically different constituent film between the substrates was obtained.

(4) Evaluation of optical element B (4-1) Density of cross-linking points When the density of cross-linking points of the optical anisotropic film of optical element B obtained above was calculated, 7.3 × 10 ⁻⁴ pieces were obtained. / G.

(4-2) Orientation It was found that the obtained optical element B was horizontally oriented in the shear direction by measuring the dependency of retardation on the incident angle. Optical element B was transparent in the visible light range, and no scattering was observed. The evaluation of orientation was performed according to the following criteria from the results obtained by this method.

(Evaluation criteria for orientation)
○: Transparent in the visible light range and no scattering observed.
Δ: Transparent in the visible light range, but scattering is observed.
X: It is opaque in the visible light range, and scattering is recognized.

(4-3) Light resistance (Reliability 2)
Next, the optical element B obtained above was irradiated with a Kr laser (wavelength 407 nm, multimode of 413 nm), and a blue laser light exposure acceleration test was performed. The irradiation conditions were a temperature of 80 ° C. and an integrated exposure energy of 700 W · h / mm ² . Since the decrease in transmittance after the test with respect to the transmittance before the acceleration test was less than 2%, it was confirmed that the optical element B was excellent in durability against blue laser light. From the results obtained by this method, the light resistance was determined based on the rate of decrease in transmittance after the test with respect to the transmittance before the accelerated test shown below.

(Reliability 2 evaluation criteria)
○: The decrease in transmittance is less than 2%.
(Triangle | delta): The fall of the transmittance | permeability is 2% or more and less than 5%.
X: The decrease in transmittance is 10% or more.

[Example 3]
(1) Preparation of liquid crystalline composition C Liquid crystalline polymer compound (Ba-11) obtained in Synthesis Example 6 above, polyfunctional isocyanate (trade name: Desmodur N3300; manufactured by Bayer), and polymerization initiation DBTDL as an agent was mixed at a mass ratio of 100: 2.6: 0.0001 to obtain a liquid crystal composition C. The obtained liquid crystal composition C exhibited a nematic phase at 90 ° C. (Tg = 90 ° C.). The phase transition temperature (Tc) from the nematic phase to the isotropic phase was 135 ° C.
(2) Production of optical element Except that the liquid crystal composition C was used in place of the liquid crystal composition B in Example 2 and the temperature of the glass substrate when the liquid crystal composition C was melted on the glass substrate was 130 ° C. Produced a sample precursor C in the same manner.
Further, in Example 2, the sample precursor C is used instead of the sample precursor B, the heating temperature of the lower stage when the sample precursor C is placed on the optical element manufacturing apparatus is set to 130 ° C., and shear stress is applied. Optical element C was produced in the same manner except that the temperature of the upper and lower stages at that time was 115 ° C.
(4) Evaluation of optical element C The obtained optical element C was evaluated in the same manner as in Example 2.

[Example 4]
(1) Preparation of liquid crystalline composition D The liquid crystalline polymer compound (Bb-11) obtained in Synthesis Example 8 above and Irgacure 754 (trade name: manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator. , 100: 0.1 mass ratio was mixed to obtain liquid crystal composition D. The obtained liquid crystal composition D exhibited a nematic phase at 83 ° C. (Tg = 83 ° C.). The phase transition temperature (Tc) from the nematic phase to the isotropic phase was 125 ° C.
(2) Production of optical element In Example 1, instead of the liquid crystalline composition A, the liquid crystalline composition D was used, except that the temperature of the glass substrate when the liquid crystalline composition D was melted on the glass substrate was 120 ° C. Produced a sample precursor D in the same manner.
Further, in Example 1, the sample precursor D is used instead of the sample precursor A, the heating temperature of the lower stage when the sample precursor D is placed on the optical element manufacturing apparatus is 120 ° C., and shear stress is applied. Optical element D was produced in the same manner except that the temperature of the upper and lower stages was changed to 105 ° C.
(3) Evaluation of optical element D The obtained optical element D was evaluated in the same manner as in Example 2.

[Example 5]
Optical element E was produced in the same manner as in Example 2 except that the operation for applying the shear stress was not performed. When the orientation was evaluated by the method (4-2) above, the result was “x”.
Table 1 shows the evaluation results obtained for the optical elements A to E obtained in Examples 1 to 5 together with the liquid crystalline composition and the production method used for the production.

101, 201 ... first substrate, 102 ... layer of liquid crystalline composition before orientation control, 103 ... first stage, 104, 202 ... second substrate, 105 ... second stage, 106 ... after orientation control Layer of liquid crystal composition 107, optical anisotropic film 108, optical element 200, device for manufacturing liquid crystal element, 203, first hollow body, 204, first porous member, 205, first. One heater, 206 ... first thermometer, 207 ... vacuum pump, 208 ... first vacuum valve, 209 ... second hollow body, 210 ... second porous member, 211 ... second heater, 212 ... second thermometer, 213 ... second vacuum valve, 214 ... XY stage, 215 ... Z stage, 216 ... load cell, 217 ... means for supplying cooling gas, 218 ... pressure adjusting valve, 219 ... first Supply valve, 220 The second supply valve

Claims (7)

A liquid crystalline composition layer formed using a liquid crystalline composition containing a liquid crystalline polymer compound having a crosslinkable functional group is completely crosslinked with the crosslinkable functional group in a state where the liquid crystalline polymer compound is oriented. An optical anisotropy film obtained by processing so that the density of cross-linking points in the optical anisotropy film is 4 × 10 ⁻⁴ to 1 × 10 ⁻² pieces / g. film.   While the orientation is not lower than the glass transition temperature of the liquid crystalline composition and less than the clearing point, while applying a pressure of 1000 Pa or less to the liquid crystalline composition layer without applying pressure in the vertical direction. The optically anisotropic film according to claim 1, which is performed by applying a shearing force in the horizontal direction.   The optically anisotropic film according to claim 1 or 2, wherein the liquid crystalline polymer compound is a compound having a fluorine atom bonded to main chain carbon.   The optically anisotropic film according to claim 1, wherein the crosslinkable functional group is a photocrosslinkable functional group.   The optically anisotropic film according to claim 4, wherein the photocrosslinking is crosslinking by cationic polymerization or radical polymerization.   The optically anisotropic film according to claim 5, wherein the photocrosslinking is crosslinking by cationic polymerization, and the crosslinkable functional group is a cyclic ether group.   The optically anisotropic film according to claim 6, wherein the cyclic ether group is an epoxy group or an oxetane group.

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