JP2003055661A - Polymerizable liquid crystal composition and optically anisotropic body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal composition which contains a polymerizable liquid-crystalline compound excellent in compatibility with another polymerizable liquid-crystalline compound used together and exhibits a nematic phase in a wide temperature range, even at 25 deg.C or lower. SOLUTION: This polymerizable liquid crystal composition contains a compound which has a liquid-crystalline skeleton having at least two cyclic structures and has a partial structure represented by the formula: P<1> -(S<1> -S<2> )m -S<3> - A<1> -D<1> -E<1> [wherein P<1> is an ethylene or propylene group; S<2> is an ester or ether bond; m is 1 or 2; S<3> is a linking chain represented by -(CH2 )V-, -(CH2 )V-O-C(= O)- or the like (wherein v is 1-20); A<1> and E<1> are each a hydrocarbon ring or a hetero ring provided E<1> is a ring contained in a liquid-crystalline skeleton; and D<1> is a linking chain represented by -C(=O)-O-(CH2 )w -O-, -O(CH2 )w -O-C(= O)- or the like]. An optically anisotropic body using the composition is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optical film, a retardation plate, a polarizing plate, a polarizing prism, an optical anisotropic body such as various optical filters, an optical waveguide, a piezoelectric element, a non-linear optical element, and a selective reflection of a cholesteric liquid crystal phase. Liquid crystal pigment using
Liquid crystal-resin composite display, holographic liquid crystal display, polymer-stabilized liquid crystal (ferroelectric liquid crystal, antiferroelectric liquid crystal) display, polymerization containing a liquid crystalline compound having a polymerizable property useful as a coating agent for optical fibers, etc. Liquid crystal composition.

[0002]

2. Description of the Related Art A liquid crystal compound having a polymerizable functional group (hereinafter referred to as a polymerizable liquid crystal compound) or a polymerizable liquid crystal composition containing such a compound is aligned in a liquid crystal state and then in that state. Irradiation with active energy rays such as ultraviolet rays makes it possible to produce a polymer in which the alignment structure of liquid crystal molecules is fixed. The polymer thus obtained is
Since it has anisotropy of physical properties such as a refractive index, a dielectric constant, a magnetic susceptibility, an elastic modulus, and a thermal expansion coefficient, for example, a retardation plate, a polarizing plate, a polarizing prism, a waveguide, a piezoelectric element, a nonlinear It can be applied as an optical element, various optical filters, a pigment utilizing selective reflection of a cholesteric liquid crystal phase, and a coating agent for optical fibers.

As a polymerizable liquid crystal composition used for such an application, JP-A-8-3111 discloses a polymerizable liquid crystal composition containing a liquid crystal compound having one (meth) acryl group in one molecule. Is disclosed. Although the polymerizable liquid crystal composition disclosed in the publication has a characteristic that it exhibits liquid crystallinity at room temperature, it is a monofunctional compound and therefore, when polymerized, it may form a network structure like a polyfunctional compound. This is not possible and the strength of the obtained polymer is poor. Further, the molecular chain of the monofunctional compound grows due to the polymerization, but the growth often stops just at a size that easily becomes a light scattering source. Therefore, there is a problem that the obtained polymer has insufficient mechanical strength and transparency.

On the other hand, Japanese Laid-Open Patent Publication No. 6-507987 (US Pat. No. 5,871,665) and Japanese Laid-Open Publication No. 8-277.
No. 247, Japanese Patent Laid-Open No. 10-310612 (European Patent Publication No. 869112), and Japanese Patent Laid-Open No. 10-509.
No. 726, Japanese Patent Publication No. 11-513360 (US Pat. No. 5,833,880), German Published Patent No. 4226994, British Published Patent 2306.
470 and International Patent Application Publication No. 98/23580.
The specification and the like disclose a liquid crystal compound having two polymerizable functional groups such as a (meth) acrylic group in one molecule and a polymerizable liquid crystal composition containing such a compound. In the compounds described in these publications, at least one polymerizable functional group is bonded to the ring A in the linking chain via a linking chain such as an alkyleneoxy group, and this ring A is directly or in the form of an ether bond or a thioether. Bond, alkylene group,
A ring in another mesogen via an oxyalkylene group, an alkyleneoxy group, a carbonyl group, an ester bond, a thioester bond, a vinyl group, a vinylcarbonyloxy group, a vinylarylene group, an alkylenevinyl group, a methylimino group, an azo group or an amide group. It has a partial structure bonded to E.

Among them, compounds having no substituent on the ring are
Although the lower limit temperature showing a nematic phase is 100 degrees or more,
Among compounds having a substituent such as a fluorine atom, a methyl group, a methoxy group or a methylcarbonyl group in the ring, those in which the lower limit of the temperature at which a nematic phase is exhibited is around 60 degrees are disclosed.

Generally, a polymerizable liquid crystal composition is prepared by uniformly aligning liquid crystal molecules and then photopolymerizing by irradiating an energy ray such as ultraviolet rays while maintaining the liquid crystal state to semi-permanently maintain a uniform alignment state. Fix it. Therefore, if the lower limit temperature indicating the nematic phase is higher than room temperature, it is necessary to heat to obtain a uniform alignment while maintaining the liquid crystal state. Due to this heating, not only photopolymerization by energy rays, There is a problem that unintended thermal polymerization is also induced, the uniform alignment state of liquid crystal molecules is lost, and a non-uniform alignment state different from the desired alignment state is fixed.
Therefore, in order to prepare a polymerizable liquid crystal composition exhibiting a nematic phase at a temperature range from room temperature to 40 degrees, which is excellent in workability and has a temperature range in which thermal polymerization is not induced, many materials can be prepared using these materials. There is a problem in that different kinds of liquid crystal compounds must be used together.

Further, JP-A-9-40585 (US Pat. No. 5,800,733) and JP-A-9-52.
In Japanese Patent No. 857 (European Patent No. 755915),
A compound having a structure in which two crosslinkable intermediate phase (liquid crystal phase) forming residues are bonded to the 1,2-position of a 6-membered ring is disclosed. Here, a compound showing only a smectic A phase without showing a nematic phase is disclosed, but the smectic A phase has a problem of high viscosity and poor orientation. Furthermore, "Liquid Crystals" (24th
Vol. 3, No. 3, pp. 375-379, 1998),
As impurities produced when 2- (alkenyloxyphenyloxy) -5- (hydrothioalkyleneoxyphenyloxy) toluene was synthesized at the end of the molecule that is the target compound, the hydrothio group of this compound and 4-hydrothioalkyleneoxy Compounds having a structure in which benzoic acid is bound are described. However, in this document,
It only discloses that it is specified as an impurity, and the possibility of using the compound specified as an impurity in a polymerizable liquid crystal composition is not discussed at all.

[0008]

The problem to be solved by the present invention is that the temperature range in which a nematic phase is exhibited is wide, and the nematic phase is exhibited even in a temperature range of 25 ° C. or lower, and it has other polymerizability in combination. Another object of the present invention is to provide a polymerizable liquid crystal composition containing a liquid crystal compound having polymerizability and having excellent compatibility with the liquid crystal compound.

In order to solve the above-mentioned problems, the present invention provides (A) a liquid crystalline skeleton having two or more ring structures and a general formula:

[0009]

[Chemical 5] [In the formula, P ¹ represents a polymerizable functional group. S ¹ represents an ethylene group or a propylene group, S ² represents an ester bond or an ether bond, m represents 1 or 2, and S ³ represents −.
_{(CH 2) V -, -} (CH 2) V O -, - (CH 2) V -O
-C (= O) - or _{- (CH 2) V -C (} = O) -O-
(V represents an integer of 1 to 20), and A ¹ and E ¹ each independently represent a hydrocarbon ring or a heterocycle. However, E ¹ is a ring contained in the liquid crystal skeleton. D ¹ is -C (= O) -O- (C
_{H 2) W -O -, -} O (CH 2) W -O-C (= O) -,
-O- (CH _{2) W} -O- or -O-C (= O) - (C
H ₂ ) _W- C (= O) -O- (w represents an integer of 1 to 15) represents a linking chain. ] The polymeric liquid crystal composition containing the compound (c1) which has a partial structure represented by this is provided.

The present invention also provides an optically anisotropic body composed of the polymer of the polymerizable liquid crystal composition described in (A) above.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (c1) used in the polymerizable liquid crystal composition of the present invention is preferably a compound represented by the general formula (c2).

[0012]

[Chemical 6]

[Wherein P²And P³Are each independent
A (meth) acryloyloxy group, (meth) acrylic
Amide group, vinyl group, epoxy group, mercapto group, vinyl
Group selected from the group consisting of ruoxy group and maleimide group
Represents a compatible functional group. S^FourAnd S ⁹Are each independent
Represents an ethylene group or a propylene group, and S⁵And S⁸Is
Represents an ester bond or an ether bond, and m and n are 0 to
Represents an integer of 2, and m + n represents an integer of 1 to 4. S
⁶And S⁷Is-(CH₂)_V-,-(CH₂)_VO-,-
(CH₂)_V-OC (= O)-or-(CH₂)_V-C
(= O) -O- (V represents an integer of 1 to 20)
Represents a connecting chain represented by A², A³, E², F¹And G¹
Each independently,

[0014]

[Chemical 7] (In the formula, p represents an integer of 1 to 4) and represents a ring structure selected from the group consisting of: D ² and D ³ are each independently —C (═O) —O— (CH ₂ ) _m —O—, —O (C
_{H 2) m -O-C (} = O) -, - O- (CH 2) m -O, -
O-C (= O) - (CH 2) m -C (= O) -O- (m
Represents an integer of 1 to 15. ) Represents a connecting chain selected from the group consisting of: Y ¹ and Y ² are each independently
Single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -
, -C (= O) O-, -OC (= O)-, -C≡C
-, - CH = CH -, - CF = CF -, - (CH 2)
_{4 -, - CH 2 CH 2} CH 2 O-, -OCH 2 CH 2 CH 2
-, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH
= CH-, -CH = CH-C (= O) O- and -OC
It represents a linking group selected from the group consisting of (= O) -CH = CH-. r represents an integer of 0 to 3, q is 0 or 1
Represents ]

In the compound (c1) and the compound represented by the general formula (c2) used in the polymerizable liquid crystal composition having liquid crystallinity of the present invention, the polymerizable functional group is a radical polymerization, cationic polymerization or anionic polymerization. There is no particular limitation as long as it can react, but ultraviolet rays, electron rays, α rays, β
Particularly preferred are functional groups which polymerize upon irradiation with ionizing radiation such as rays and gamma rays, and active energy rays such as microwaves and high frequency actinic rays.

Examples of the polymerizable functional group include (meth)
Acryloyloxy group, (meth) acrylamide group, vinyl group, epoxy group, ethynyl group, mercapto group, vinyloxy group, maleimide group, vinyl ketone group and the like, and among these, (meth) acryloyloxy group, vinyl group, Epoxy group, mercapto group or vinyloxy group is preferable, (meth) acryloyloxy group,
A vinyl group, an epoxy group and a vinyloxy group are particularly preferable, and a (meth) acryloyloxy group is further preferable.

S in compound (c1)^Three, General formula (c2)
S in the compound represented by⁶And S ⁷Is the above
Represents a connecting chain defined in, but v is in the range of 2 to 18
Are preferred, and those in the range of 4 to 10 are particularly preferred.

In the compound (c1), A ¹ and E ¹ are
Each independently represents a hydrocarbon ring such as an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, or a hetero ring such as a hetero ring. These rings are preferably 6-membered rings or condensed rings of 6-membered rings. Also, the hydrogen atom on the ring is
It may be substituted with a substituent such as a halogen atom such as a fluorine atom and a chlorine atom, a lower alkyl group such as a methyl group, and a lower alkoxyl group such as a methoxy group. Also, E1
Is a ring contained in the liquid crystal skeleton. Further, the liquid crystal skeleton in the compound (c1) has two or more, preferably 2 to 6 ring structures such as a hydrocarbon ring and / or a hetero ring. Such crystalline framework, the general formula -E ² in the general formula ^{(c2) - (Y 1 -F} 1)
_r -Y ² -G ¹ - crystalline framework represented by are preferred.

In the compound (c1), A ¹ and E ¹ are
Above all,

[0020]

[Chemical 8] (In the formula, p represents an integer of 1 to 4.) It is preferably a ring structure selected from the group consisting of:

A ¹ and E ¹ in the compound (c1),
A ² , A ³ , E ² , F ¹ and G ¹ in the compound represented by the general formula (c2), which represents the ring structure defined above, include

[0022]

[Chemical 9] Is particularly preferable.

D in compound (c1)¹Or the general formula (c
D in the compound represented by 2)²And D ³Is defined above
And a connecting chain represented by the formula
H₂)_m-O- or -O- (CH₂)_m-OC (= O)-
Is particularly preferable. In addition, m is preferably in the range of 2 to 12.
The range of 4 to 10 is particularly preferable.

A general formula -E ² -which is an example of a liquid crystal skeleton
Examples of the structure represented by (Y ¹ -F ¹ ) _r —Y ² —G ¹ — include structures represented by the following formulas (a1) to (a447).

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

[0035]

[Chemical 20]

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

[0038]

[Chemical formula 23]

[0039]

[Chemical formula 24]

[0040]

[Chemical 25]

[0041]

[Chemical formula 26]

[0042]

[Chemical 27]

[0043]

[Chemical 28]

[0044]

[Chemical 29]

[0045]

[Chemical 30]

[0046]

[Chemical 31]

[0047]

[Chemical 32]

[0048]

[Chemical 33]

[0049]

[Chemical 34]

[0050]

[Chemical 35]

[0051]

[Chemical 36]

[0052]

[Chemical 37]

[0053]

[Chemical 38]

[0054]

[Chemical Formula 39]

[0055]

[Chemical 40]

[0056]

[Chemical 41]

[0057]

[Chemical 42]

(The aromatic ring in the formulas (a1) to (a447),
The alicyclic ring, heterocyclic ring and condensed ring are a cyano group, a halogen atom,
It may be substituted with one or more substituents selected from the group consisting of alkyl groups having 1 to 7 carbon atoms, alkoxy groups and alkanoyl groups. )

Among the compounds represented by the general formula (c2), the general formula (c3)

[Chemical 43]

(In the formula, X represents a hydrogen atom or a methyl group, d represents an integer of 2 or 3, and f represents 1 to 20.
Represents an integer of 1, and q represents an integer of 1 to 15. In addition, each 1,4-phenylene group is, independently, one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. May be replaced with. ), A polymerizable liquid crystal compound represented by the general formula (c4)

[0061]

[Chemical 44]

(In the formula, X represents a hydrogen atom or a methyl group, d represents an integer of 2 or 3, and f represents 1 to 20.
Represents an integer of 1, and q represents an integer of 1 to 15. In addition, each 1,4-phenylene group is, independently, one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. May be replaced with. ), A polymerizable liquid crystal compound represented by the general formula (c5)

[0063]

[Chemical formula 45]

(Wherein X represents a hydrogen atom or a methyl group, d represents an integer of 2 or 3, and f represents 1 to 20).
Represents an integer of 1, and q represents an integer of 1 to 15. In addition, each 1,4-phenylene group is, independently, one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. May be replaced with. ), A polymerizable liquid crystal compound represented by the general formula (c6)

[0065]

[Chemical formula 46]

(In the formula, X represents a hydrogen atom or a methyl group, d represents an integer of 2 or 3, and f represents 1 to 20.
Represents an integer of 1, and q represents an integer of 1 to 15. In addition, each 1,4-phenylene group is, independently, one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. May be replaced with. The polymerizable liquid crystal compound represented by the formula (1) is particularly preferable.

Although a (meth) acrylate compound has been mentioned as a preferred example of the compound of the present invention, a compound having an epoxy group or a vinyloxy group as a reactive group is also preferable. Examples of such compounds include compounds represented by the following general formula (c7) or (c8).

[0068]

[Chemical 47]

(In the formula, d represents an integer of 2 or 3,
f represents an integer of 1 to 20, and q represents an integer of 1 to 15. Further, each 1,4-phenylene group is
Each of them may be independently substituted with one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. )

[0070]

[Chemical 48]

(In the formula, d represents an integer of 2 or 3,
f represents an integer of 1 to 20, and q represents an integer of 1 to 15. Further, each 1,4-phenylene group is
Each of them may be independently substituted with one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. Although preferred examples of the compound of the present invention have been described above, the compound represented by the general formula (c3) can be synthesized, for example, by the following method.

[0072]

[Chemical 49]

(In the formula, X, d, f and q are represented by the general formula (c
It has the same contents as in 3). DCC represents dicyclohexylcarbodiimide. That is, the alcohol derivative represented by the general formula (c9) and 2 equivalents of the carboxylic acid derivative represented by the general formula (c10) are esterified by using a condensing agent such as DCC (dicyclohexylcarbodiimide). As a result, the desired compound represented by the general formula (c3) can be synthesized.

The alcohol derivative represented by the general formula (c9), which is a raw material for synthesizing the compound represented by the general formula (c3), can be synthesized, for example, by the following method.

[0075]

[Chemical 50]

(In the formula, q represents the same content as in the above general formula (c3), and Ph represents a phenyl group.), That is, 4-bromo-phenol represented by the formula (c9-1). After protecting the hydroxyl group with tetrapyranyl ether to obtain the compound represented by the formula (c9-2), 2-methyl-3-butyne-2- is obtained in the presence of a palladium catalyst.
Reaction with oar gives a compound of formula (c9-3). Subsequently, the t-butyl alcohol group is eliminated to obtain the acetylene derivative represented by the general formula (c9-4). The acetylene derivative represented by the general formula (c9-4) and 4-iodophenol are subjected to a coupling reaction in the presence of a palladium catalyst to give the general formula (c9-5).
A compound represented by After reacting the compound represented by the general formula (c9-5) with the bromine-containing alcohol derivative represented by the general formula (c9-6), an acid catalyst is added,
By deprotecting, the intended alcohol derivative represented by the general formula (c9) can be obtained.

The carboxylic acid derivative represented by the general formula (c10), which is a raw material for synthesizing the compound represented by the general formula (c3), can be synthesized, for example, by the following method.

[0078]

[Chemical 51]

(In the formula, X, d and q are represented by the general formula (c3))
Represents the same content as. ) That is, 4-hydroxybenzoic acid represented by the formula (c10-1) and the general formula (c10-
The compound represented by the general formula (c10-3) is obtained by reacting with an alcohol derivative having a bromine group represented by 2). By reacting this compound with a carboxylic acid derivative represented by the general formula (c10-4) in the presence of an acid catalyst while distilling off water, the desired general formula (c1
A carboxylic acid derivative represented by 0) can be obtained.

Next, general formula (c4) and general formula (c5)
The compound represented by will be described. General formula (c4)
And the compound represented by the general formula (c5) include, for example, a carboxylic acid derivative represented by the general formula (c10),
Using the carboxylic acid derivative represented by the general formula (c11),

[0081]

[Chemical 52] It can be synthesized in the same manner as in the method for synthesizing the compound represented by the general formula (c3). The carboxylic acid derivative represented by the general formula (c11), which is a raw material for synthesizing the compounds represented by the general formulas (c4) and (c5), can be synthesized, for example, by the following method.

[0082]

[Chemical 53]

By reacting the compound of the alcohol derivative represented by the general formula (c10-3) with (meth) acrylic acid in the presence of an acid catalyst while distilling off water, the desired general formula (c11) is obtained. A carboxylic acid derivative represented by can be obtained.

Next, the compound represented by formula (c6) will be described. The compound represented by the general formula (c6) can be synthesized, for example, by the following method.

[0085]

[Chemical 54] (In the formula, X, d, f and q have the same meanings as in the case of the general formula (c6), and DCC represents dicyclohexylcarbodiimide.)

That is, the alcohol derivative represented by the general formula (c12) and 2 equivalents of the alcohol derivative represented by the general formula (c10)
The carboxylic acid derivative represented by the formula (c) is subjected to an esterification reaction by using a condensing agent such as DCC (dicyclohexylcarbodiimide).
The compound represented by 6) can be synthesized.

The alcohol derivative represented by the general formula (c12), which is a starting material for synthesizing the compound represented by the general formula (c6), can be synthesized, for example, by the following method.

[0088]

[Chemical 55]

(In the formula, q has the same meaning as in the general formula (c6), DMF represents dimethylformamide, and PTS represents paratoluenesulfonic acid).
1,4-dihydroquinone and 2.0 equivalents of 4-
Hydroxybenzoic acid under paratoluene sulfonic acid catalyst,
The compound (c12-
1) is synthesized. Subsequently, the phenol derivative represented by the general formula (c12-1) and the halogen derivative represented by the general formula (c9-6) in an amount of 2.0 equivalents thereof are subjected to a substitution reaction in the presence of potassium carbonate in a DMF solvent. As a result, the desired compound represented by the general formula (c12) can be synthesized.

Next, the epoxy compound represented by the general formula (c7) will be described. The compound represented by the general formula (c7) can be synthesized, for example, by the following method.

[0091]

[Chemical 56]

(In the formula, d, f and q are represented by the general formula (c7)
The same content as in the case of. Further, DMF represents dimethylformamide. ) A phenol derivative represented by the general formula (c14) and 3.0 equivalents of the halogen derivative represented by the general formula (c13) in the presence of potassium carbonate in a DMF solvent,
By the substitution reaction, the desired general formula (c7)
The compound represented by can be synthesized.

Next, the vinyl ether compound represented by the general formula (c8) will be described. The compound represented by the general formula (c8) can be synthesized, for example, by the following method.

[0094]

[Chemical 57]

(In the formula, d, f and q are represented by the general formula (c8)
The same content as in the case of. DCC represents dicyclohexylcarbodiimide. ) That is, the general formula (c
The alcohol derivative represented by 12) and 2
Esterifying an equivalent amount of the carboxylic acid derivative represented by the general formula (c15) by using a condensing agent such as DCC (dicyclohexylcarbodiimide) to synthesize the desired compound represented by the general formula (c8). You can

The composition of the polymerizable liquid crystal compound used in the present invention can be prepared by itself, but it is also possible to prepare a composition by mixing a known polymerizable liquid crystal compound. Examples of the known polymerizable liquid crystal compound include a polymerizable liquid crystal compound having a skeleton generally recognized as a liquid crystal ring skeleton in this technical field and a polymerizable functional group in the molecule. The liquid crystal ring skeleton particularly preferably has at least two or three 6-membered rings. Examples of the polymerizable functional group include an acryloyloxy group, a methacryloyloxy group, an epoxy group, a vinyloxy group, a cinnamoyl group, a vinyl group, an ethynyl group, and a maleimide.

In the case of a compound having a plurality of polymerizable functional groups in one molecule, the kinds of polymerizable functional groups may be different. For example, in the case of a compound having two polymerizable functional groups, one may be a methacryloyl group and the other a vinyloxy group.

The polymerizable liquid crystal composition of the present invention may be any composition which exhibits a phase generally recognized as a liquid crystal phase in this technical field. Among such compositions, the liquid crystal phase includes a nematic phase, a smectic A phase, and a (chiral) smectic C.
Those expressing a phase and a cholesteric phase are preferable. Among them, the nematic phase is particularly preferable because it has good orientation. Further, in the case of exhibiting a (chiral) smectic C phase, a smectic A phase is present in a temperature range higher than the temperature range of the (chiral) smectic C phase, and a nematic phase is presented in a temperature range higher than the temperature range of the smectic A phase. Liquid crystal compositions that exhibit the respective properties are preferable because they tend to obtain good alignment properties.

Examples of the compound that can be contained in the polymerizable liquid crystal composition of the present invention include liquid crystal (meth) acrylate compounds represented by the general formula (c16).

[0100]

[Chemical 58]

(Wherein, X represents a hydrogen atom or a methyl group, and R ¹ represents an alkyl group having 1 to 10 carbon atoms), or a compound represented by the general formula (c17).

[0102]

[Chemical 59]

A compound represented by the formula (wherein X represents a hydrogen atom or a methyl group, and R ¹ represents an alkyl group having 1 to 10 carbon atoms) is preferable. These compounds represented by general formula (c16) and compounds represented by general formula (c17) may be used alone or in combination. When used in combination, the general formula (c
It is preferable that the concentrations of the compound represented by 16) and the compound represented by the general formula (c17) are equal. However, the compounds that can be used in the polymerizable liquid crystal composition of the present invention are not limited to these compounds.

In addition to the (meth) acrylate compounds represented by the general formulas (c16) and (c17), the polymerizable liquid crystal composition of the present invention may contain other monofunctional (meth) functional compounds.
An acrylate compound can also be included. Specific examples of the compounds represented by formulas (c16) and (c17) and other monofunctional (meth) acrylate compounds include compounds represented by formulas (a-1) to (a-25). To be In addition, the exemplified formulas (a-1) to (a-2
The phase transition temperature is shown below the structural formula of the compound represented by 5). (In the formula, the cyclohexane ring represents a transcyclohexane ring, and the numbers represent phase transition temperatures,
C is a crystalline phase, N is a nematic phase, S is a smectic phase,
Each I represents an isotropic liquid phase. )

[0105]

[Chemical 60]

[0106]

[Chemical formula 61]

[0107]

[Chemical formula 62]

[0108]

[Chemical formula 63]

Further, the polymerizable liquid crystal composition of the present invention may contain a (meth) acrylate compound having a liquid crystal ring skeleton in a side chain. Further, a liquid crystal compound having no polymerizable functional group may be added to the polymerizable liquid crystal composition of the present invention depending on the application. However, from the viewpoint of ensuring the heat resistance of the polymer produced using the liquid crystal composition, the addition amount thereof is preferably 80% by weight or less, more preferably 30% by weight or less, and particularly preferably 10% by weight or less. Further, to the polymerizable liquid crystal composition of the present invention, a compound having a polymerizable functional group, which does not exhibit liquid crystallinity, can be added. Such compounds include:
Generally, any polymer recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation.

The polymerizable liquid crystal composition of the present invention is intended to polymerize the polymerizable compound in the composition by irradiating with active energy rays in the temperature range of the liquid crystal phase. Therefore,
In order to avoid undesired induction of thermal polymerization in the active energy ray irradiation step and produce a polymer having excellent uniformity, the polymerizable liquid crystal composition of the present invention has a room temperature (typically 2%).
(5 degrees) or those exhibiting liquid crystallinity around room temperature are preferable. For example, in the (chiral) smectic C phase, when the polymerizable liquid crystal composition of the present invention is irradiated with an active energy ray to polymerize the polymerizable compound in the composition, the (chiral) smectic C phase is obtained at or near room temperature. What expresses is preferable.

A chiral (optically active) compound may be added to the polymerizable liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of a liquid crystal skeleton therein. The chiral compound used for such a purpose does not need to exhibit liquid crystallinity by itself, and may or may not have a polymerizable functional group. Further, the direction of the helix of the chiral compound can be appropriately selected depending on the intended use of the polymer.

Examples of such chiral compounds include those manufactured by BDH (BDH, England) having cholesterol pelargonate having a cholesteryl group as a chiral group, cholesterol stearate, and 2-methylbutyl group having a chiral group. "CB-15", "C
-15 "," S-1082 "manufactured by Merck GmbH (Germany),
Chisso's "CM-19", "CM-20", "CM";
"S-811" manufactured by Merck & Co. having a 1-methylheptyl group as a chiral group, "CM-21" and "C" manufactured by Chisso Co.
M-22 ”, and the like.

The preferred addition amount of the chiral compound depends on the use of the liquid crystal composition, but is a value obtained by dividing the thickness (d) of the polymer obtained by polymerization by the helical pitch (P) in the polymer. The amount that (d / P) is in the range of 0.1 to 100 is preferable, and the amount that is in the range of 0.1 to 20 is more preferable.

Further, to the polymerizable liquid crystal composition of the present invention, a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator may be added for the purpose of improving the polymerization reactivity. Examples of the thermal polymerization initiator include benzoyl peroxide and bisazobutyronitrile. Further, as the photopolymerization initiator, for example, benzoin ethers,
Examples thereof include benzophenones, acetophenones, benzyl ketals and the like. The addition amount of the thermal polymerization initiator or the photopolymerization initiator is 1 with respect to the liquid crystal composition.
It is preferably 0% by weight or less, particularly preferably 5% by weight or less, further preferably 0.5 to 1.5% by weight.

A polymerization inhibitor may be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of usable polymerization inhibitors include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines,
β-naphthols and the like can be mentioned. When the polymerization inhibitor is used, the addition amount thereof is preferably 1% by weight or less, and particularly preferably 0.5% by weight or less based on the liquid crystal composition.

As described above, in the polymerizable liquid crystal composition of the present invention, in addition to the polymerizable compound represented by the general formula (c1) or the general formula (c2), a liquid crystal compound having a polymerizable functional group and a polymerizable liquid crystal compound A liquid crystal compound having no functional group, a polymerizable compound having no liquid crystallinity, a polymerization initiator, and a polymerization inhibitor may be appropriately combined and added, but at least liquid crystallinity of the obtained liquid crystal composition is not lost. It is necessary to adjust the addition amount of each component.

When the polymerizable liquid crystal composition of the present invention is used as a raw material for a polarizing film or an alignment film, or as a printing ink and paint, a protective film, etc., a metal or a metal complex may be used depending on the purpose. , Dyes, pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents,
It is also possible to add a polysaccharide, an ultraviolet absorber, an infrared absorber, an antioxidant, an ion exchange resin, a metal oxide such as titanium oxide, and the like.

The polymerizable liquid crystal composition of the present invention is polymerized into a polymer to obtain a retardation plate, a polarizing plate, a polarizing prism, a waveguide, a piezoelectric element, a non-linear optical element, various optical filters, a cholesteric liquid crystal phase, etc. For various applications such as liquid crystal pigments utilizing selective reflection of liquid crystal, liquid crystal-resin composite display, holographic liquid crystal display, polymer stabilized liquid crystal (ferroelectric liquid crystal, antiferroelectric liquid crystal) display, coating agent for optical fiber, etc. It can be applied. Among them, a polymer obtained by polymerizing the polymerizable liquid crystal composition of the present invention in an oriented state is useful because it has anisotropy in physical properties. Such a polymer is, for example, a substrate obtained by rubbing the surface of the polymerizable liquid crystal composition of the present invention with a cloth or the like, a substrate obtained by rubbing the surface of a substrate on which an organic thin film is formed with a cloth or the like, or SiO ₂ It can be produced by coating on a substrate having an orientated film obliquely vapor-deposited or sandwiched between the substrates and then polymerizing a polymerizable compound.

The method of applying the polymerizable liquid crystal composition of the present invention onto a substrate is, for example, spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping,
Printing method, etc. In addition, an organic solvent may be added to the polymerizable liquid crystal composition during coating. Examples of the organic solvent that can be used for such a purpose include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolves, and the like. To be These organic solvents may be used alone or in combination of two or more, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. The amount of organic solvent added is
90% by weight or less of the coating material is preferred. When it is 90% by weight or more, the obtained film thickness tends to be thin, which is not preferable.

As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, and reduced pressure heat drying can be used. In order to further improve the coatability of the polymerizable liquid crystal composition, a method of providing an intermediate layer such as a polyimide thin film on the substrate or a method of adding a leveling agent to the polymerizable liquid crystal composition is also effective. In particular, the method of providing an intermediate layer such as a polyimide thin film on the substrate is also effective as a means for improving the adhesiveness when the adhesiveness between the polymer obtained by polymerizing the polymerizable liquid crystal composition and the substrate is not good. is there.

As a method for sandwiching the polymerizable liquid crystal composition of the present invention between substrates, an injection method utilizing a capillary phenomenon can be mentioned. It is also effective to reduce the pressure of the space formed between the substrates and then inject the polymerizable liquid crystal composition.

Examples of the alignment treatment other than the rubbing treatment or the SiO ₂ oblique vapor deposition include a method utilizing the flow orientation of the liquid crystal material and a method utilizing an electric field or a magnetic field. These orientation means can be used alone or in combination of two or more methods.

Further, a photo-alignment method can be used as an alignment treatment method instead of rubbing. This method, for example, an organic thin film having a functional group that undergoes a photodimerization reaction in the molecule such as polyvinyl cinnamate, an organic thin film having a functional group that is isomerized by light or an organic thin film such as polyimide, polarized light, preferably The alignment film is formed by irradiating polarized ultraviolet rays. By applying a photomask to this photo-alignment method, alignment patterning can be easily achieved, so that the molecular alignment inside the polymer can also be precisely controlled.

The shape of the substrate may be a flat plate or a curved surface. The material forming the substrate may be an organic material or an inorganic material. Examples of the organic material for the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethylmethacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone,
Triacetyl cellulose, cellulose, polyether ether ketone and the like can be mentioned, and as the inorganic material,
Examples include silicon, glass, calcite and the like.

When proper orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the surface of the substrate according to a known method, and this is wiped with a cloth or the like. You can rub it. In addition, the usual twisted nematic (T
N) element or super twisted nematic (S)
The polyimide thin film used in the TN) device for providing a pretilt angle is particularly preferable because the molecular orientation structure inside the polymer can be controlled more precisely. Also,
When controlling the orientation state by an electric field, a substrate having an electrode layer is used. In this case, it is preferable to form an organic thin film such as the above-mentioned polyimide thin film on the electrode.

The alignment state of the liquid crystal composition may be various alignment states generally known in the technical field of liquid crystals,
For example, there may be mentioned a homogeneous (horizontal) orientation, a tilted homogeneous orientation, a homeotropic (vertical) orientation, a tilted homeotropic orientation, a hybrid orientation, a twisted nematic orientation, and a super twisted nematic orientation state. Further, a pattern may be formed by combining these orientations or changing the orientation state for each place.

In the case of tilted homogeneous alignment and tilted homeotropic alignment, in both cases, it means that the angle between the substrate surface and the long axis of the liquid crystal molecule is not 0 or 90 degrees. The angle between the substrate surface and the long axis of the liquid crystal molecule may be selected depending on the use and function of the polymer to be obtained. When the angle between the substrate surface and the long axis of the liquid crystal molecule is set in the range of 10 to 80 degrees, more preferably 20 to 70 degrees, the obtained polymer is an optical member for improving the viewing angle of a liquid crystal display. Can be used as

Also, when the alignment state of the liquid crystal composition is hybrid alignment, the obtained polymer can be used as an optical member for widely improving the viewing angle of a liquid crystal display. When the angle between the substrate surface and the long axis of the liquid crystal molecule is set to 30 to 60 degrees, more preferably 40 to 50 degrees, and particularly preferably 45 degrees, the obtained polymer has
The polarized light separating ability can be efficiently imparted. Such a polymer is useful as a polarization separation element or an optical low pass filter. Further, even when the liquid crystal composition has an alignment state of hybrid alignment, the obtained polymer is useful as a polarizing optical element or an optical low pass filter.

On the other hand, an oriented structure having a helical structure represented by twisted nematic orientation, super twisted nematic orientation and cholesteric orientation is also useful. When the twist angle is set to 60 to 270 degrees, the resulting polymer is useful for optical compensation of liquid crystal display devices. Further, when the helical pitch is adjusted and set so as to selectively reflect a specific wavelength region, the obtained polymer is useful as a notch filter or a reflective color filter.

When the wavelength range of the light that is selectively reflected is set to the infrared range, the polymer obtained is useful as a heat ray cut filter. Further, in the case of a homogeneous orientation or a homeotropic orientation state, the obtained polymer has a larger anisotropy in refractive index than that obtained by stretching the plastic, and therefore exhibits the same anisotropy in refractive index. Has the advantage that it can be designed thin. Also,
There is a possibility that an optical compensator can be built inside the liquid crystal cell. When used for optical compensation of a reflection type liquid crystal display element, this characteristic is important, and particularly useful as a quarter wavelength plate.

As a method of polymerizing the polymerizable liquid crystal composition of the present invention, a method of polymerizing by irradiating with active energy rays such as ultraviolet rays or electron rays is preferable from the viewpoint of rapid polymerization. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerizable liquid crystal composition is polymerized in a state of being sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to active energy rays. . Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing the conditions such as electric field, magnetic field or temperature, and further irradiation with active energy rays is performed. It is also possible to use a means of polymerizing the polymer. The temperature during irradiation is preferably within the temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the present invention is maintained. In particular, in the case of producing a polymer by photopolymerization, a temperature close to room temperature, that is, as far as possible from the viewpoint of avoiding unintended induction of thermal polymerization, that is,
Polymerization is typically preferred at a temperature of 25 degrees. The intensity of active energy rays is 0.1 mW / cm ² ~ 2
A range of W / cm ² is preferred. If the strength is less than 0.1 mW / cm ² , a large amount of time is required to complete the photopolymerization, and the productivity tends to deteriorate. If the strength exceeds ² W / cm ² , the polymerizable liquid crystal composition is Is likely to deteriorate, which is not preferable.

After irradiating the polymerizable liquid crystal composition of the present invention with an actinic ray, a heat treatment may be carried out for the purpose of reducing changes in initial characteristics of the obtained polymer and achieving stable characteristics. . The heat treatment temperature is preferably in the range of 50 to 250 degrees, and the heat treatment time is preferably in the range of 30 seconds to 12 hours.
The polymer comprising the polymerizable liquid crystal composition of the present invention produced by such a method can be peeled from the substrate and used alone, or can be used as it is without being peeled from the substrate. In addition, the polymer comprising the polymerizable liquid crystal composition of the present invention can be used by laminating two or more or by laminating it on another substrate.

[0133]

EXAMPLES The present invention will be described in more detail with reference to examples. However, the invention is not limited to these examples.

<Synthesis Example 1> [Synthesis of Liquid Crystalline Acrylate Compound] To a solution of 48.0 g of 4-bromo-2-fluorophenol and 250 m of dichloromethane, 6.3 g of pyridinium p-toluenesulfonic acid was added, and then, in an ice bath. A solution of 42.0 g of dihydropyran and 75 ml of dichloromethane was gradually added dropwise from the dropping funnel over about 1 hour. After completion of dropping, the reaction temperature was brought to room temperature and the mixture was stirred for about 4 hours. After confirming the completion of the reaction by gas chromatography, the mixture was washed once with 250 ml of saturated aqueous sodium hydrogen carbonate solution and once with 250 ml of saturated saline. After the organic layer was dehydrated from anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain the compound of formula (S1).

[0135]

[Chemical 64] 67.0 g of the compound represented by

¹ H-NMR (300 MHz, CDC
l ₃ ); Chemical shift = 1.50 to 2.08 (m, 6
H), 3.56 to 3.63 (m, 1H), 3.84 to
3.92 (m, 1H), 5.38-5.40 (m, 1
H), 7.00 to 7.32 (m, 3H)

(S1) Compound 3 obtained by the above synthesis
4.4 g, trimethylsilylacetylene 14.7 g, dimethylformimide 120 ml and triethylamine 4
1.73 g of tetrakistriphenylphosphine palladium and 0.57 g of copper iodide were added to a 5 ml solution, and the mixture was heated at 80 ° C. for 8 hours while stirring. Thin layer chromatography (developing solvent; hexane: dichloromethane = 2:
After confirming the completion of the reaction in 1), the reaction solution was diluted with 300 ml of ethyl acetate. Wash once with 200 ml of saturated ammonium chloride solution, saturated saline solution 2
It was washed twice with 00 ml. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was subjected to column chromatography (hexane: dichloromethane =
2: 1) and purified by the formula (S2)

[0138]

[Chemical 65] 32.8 g of the compound represented by

A solution of 34.5 g of 75% tetra-n-butylammonium fluoride and 60 ml of dichloromethane was cooled in an ice bath, and then a solution of 30.7 g of the compound represented by the above formula (S2) and 60 ml of dichloromethane was added dropwise to the dropping funnel. Then, the solution was gradually added dropwise over about 1 hour. After completion of dropping, the reaction temperature was raised to room temperature and the mixture was stirred for about 3 hours. After confirming the completion of the reaction by thin layer chromatography (developing solvent: toluene), the reaction mixture was washed twice with 150 ml of saturated saline. The organic layer was dehydrated from anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (toluene) to obtain the compound of formula (S3).

[0140]

[Chemical formula 66] 22.1 g of the compound represented by

¹ H-NMR (300 MHz, CDC
l ₃ ); chemical shift = 1.50 to 2.09 (m, 6
H), 3.01 (s, 1H), 3.60 to 3.65.
(M, 1H), 3.85 to 3.93 (m, 1H), 5.
46-5.48 (m, 1H), 7.10-7.35
(M, 3H)

(S3) Compound 2 obtained by the above synthesis
2.5 g, 4-iodophenol 25.3 g, dimethylformimide 120 ml and triethylamine 35 ml
1.25 g of tetrakistriphenylphosphine palladium and 0.41 g of copper iodide were added to the above solution, and the mixture was stirred at 30 degrees for 8
Stir for hours. After confirming the completion of the reaction by thin layer chromatography (toluene: ethyl acetate = 10: 1), the reaction solution was diluted with 200 ml of ethyl acetate. It was washed once with 150 ml of a saturated aqueous solution of ammonium chloride and twice with 150 ml of saturated saline. The organic layer was dehydrated from anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was subjected to column chromatography (developing solvent;
Purified from toluene: ethyl acetate = 10: 1, the formula (S
4)

[0143]

[Chemical formula 67] 22.5 g of the compound represented by

¹ H-NMR (300 MHz, CDC
l ₃ ); Chemical shift = 1.60 to 2.06 (m, 6
H), 3.62 to 3.66 (m, 1H), 3.90 to
3.98 (m, 1H), 5.11 (s, 1H), 5.4
7 to 5.49 (m, 1H), 6.70 to 7.41 (m,
7H)

(S4) Compound 1 obtained by the above synthesis
1 g of potassium carbonate was added to a solution of 4.4 g, 16.7 g of 6-bromohexanol and 140 ml of dimethylformimide.
2.7 g was added and the mixture was heated with stirring at 85 ° C. for about 4 hours. Thin layer chromatography (developing solvent; toluene:
After confirming the completion of the reaction with ethyl acetate = 4: 1), the reaction solution was diluted with 200 ml of ethyl acetate. It was washed 3 times with 100 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was subjected to column chromatography (toluene:
Separated by ethyl acetate = 4: 1). After distilling off the solvent under reduced pressure, recrystallization (chloroform: hexane = 1: 3)
More refined formula (S5)

[0146]

[Chemical 68] 17.0 g of the compound represented by

White crystal, melting point: 96.5-97.0 ° C. ¹ H-NMR (300 MHz, CDCl ₃ ); Chemical shift = 1.32-2.12 (m, 14H), 3.61-
3.69 (m, 3H), 3.88 to 3.99 (m, 3
H), 5.46-5.48 (m, 1H), 6.84-
7.45 (m, 7H)

Compound (S5) obtained by the above synthesis 7.
To a solution of 6 g and 70 ml of tetrahydrofuran was added 35 ml of a 10% hydrochloric acid aqueous solution, and the mixture was stirred and reacted at room temperature for about 4 hours. Thin layer chromatography (developing solvent;
After confirming the completion of the reaction with toluene: ethyl acetate = 4: 1), the reaction solution was diluted with 200 ml of ethyl acetate. It was washed twice with 100 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was purified by recrystallization (chloroform) to obtain the compound of formula (S6).

[0149]

[Chemical 69] 5.5 g of the compound represented by

White crystals, melting point: 127.0-128.0
Degree ¹ H-NMR (300 MHz, CDCl ₃ ); chemical shift = 1.42 to 1.83 (m, 8H), 3.00 (b
r. s, 1H) 3.56 (t, 2H), 4.02 (t,
2H), 6.92 to 7.45 (m, 7H)

4-hydroxybenzoic acid 138.1 g, 6
A mixture of 136.1 g of -chloro-1-hexanol, 84.0 g of sodium hydroxide, 25.0 g of potassium iodide, 440 ml of ethanol and 440 ml of water was stirred and heated at 80 ° C for 32 hours. After cooling the obtained reaction solution to room temperature, 1000 ml of saturated saline was added to the reaction solution, and dilute hydrochloric acid was added until the aqueous layer of the reaction solution became weakly acidic.
The reaction product was extracted by adding 1000 ml of ethyl acetate to the reaction solution. After washing the organic layer with water, the extraction solvent was evaporated under reduced pressure, and the residue was air-dried to obtain the compound of formula (S7)

[0152]

[Chemical 70] 223.9 g of the compound represented by

Compound represented by formula (S7) 110.0
g, acrylic acid 133.1 g, p-toluenesulfonic acid 27.0 g, hydroquinone 6.0 g, toluene 420 m
l, n-hexane 180 ml and tetrahydrofuran 26
The mixture consisting of 0 ml was stirred with heating and refluxed for 6 hours while distilling off the produced water. After cooling the reaction solution to room temperature, the reaction solution was mixed with 1000 ml of saturated saline and 8% of ethyl acetate.
The reaction product was extracted by adding 00 ml. After washing the organic layer with water, the organic solvent was distilled off under reduced pressure to obtain 231.4 g of a crude product. Next, the crude product is recrystallized from a mixture of 400 ml of n-hexane and 100 ml of toluene twice to obtain a compound of formula (S8).

[0154]

[Chemical 71] 114.7 g of the compound represented by

¹ H-NMR (300 MHz, CDC
l ₃ ); Chemical shift = 1.40 to 1.87 (m, 8)
H), 4.03 (t, 2H), 4.16 (t, 2H),
5.80 (d, 1H), 6.14 (d, 1H), 6.4
4 (d, 1H), 6.93 (d, 2H), 8.07
(D, 2H)

Compound 110.0 represented by formula (S7)
g, acrylic acid dimer (M-5600, manufactured by Toagosei Co., Ltd.) 266.2 g, p-toluenesulfonic acid 27.
A mixture consisting of 0 g, 6.0 g of hydroquinone and 900 ml of toluene was heated and stirred, and refluxed for 8 hours while distilling off the produced water. After cooling the reaction solution to room temperature, 1000 ml of saturated saline and 800 ml of ethyl acetate were added to the reaction solution to extract the reaction product. After washing the organic layer with water, the organic solvent was distilled off under reduced pressure to obtain 231.4 g of a crude product. next,
This crude product was mixed with 400 ml of n-hexane and 40 ml of toluene.
By repeating the operation of recrystallizing from 0 ml of the mixture, the compound of formula (S9)

[0157]

[Chemical 72] 50.4 g of the compound represented by

¹ H-NMR (300 MHz, CDC
l ₃ ); Chemical shift = 1.40 to 1.87 (m, 8)
H), 2.70 (t, 2H), 4.03 (t, 2H),
4.16 (t, 2H), 4.42 (t, 2H), 5.8
0 (d, 1H), 6.14 (d, 1H), 6.44
(D, 1H), 6.93 (d, 2H), 8.07 (d,
2H)

(S6) Compound 1 obtained by the above synthesis
6.4 g, 15.3 g of 4- (6-acryloyloxyhexyloxy) benzoic acid of the (S7) compound, 19.1 g of the (S8) compound and 700 ml of methylene chloride were added to 1 solution.
20.1 g of -ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 12.8 g of 4-dimethylaminipyridine were added and reacted at room temperature for about 2 days while stirring. After confirming the completion of the reaction by thin layer chromatography (developing solvent; toluene: ethyl acetate = 10: 1), the reaction solution was diluted with 200 ml of ethyl acetate. It was washed twice with 100 ml of saturated saline.
The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was separated by column chromatography (developing solvent; toluene: ethyl acetate = 10: 1) to obtain the compound of formula (S10).

[0160]

[Chemical formula 73]

19.0 g of a polymerizable liquid crystal composition as a mixture of the two isomers represented by was obtained. The two isomers obtained were not separated further due to difficulty in separation. Regarding the phase transition temperature of the polymerizable liquid crystal composition of the formula (S10) at the time of heating, the crystal phase-nematic phase was 2 degrees, the nematic phase-isotropic liquid phase was 56 degrees, and the nematic phase was exhibited in a wide range. .

¹ H-NMR (300 MHz, CDC
l ₃ ); Chemical shift = 1.44 to 1.83 (m, 2
4H), 2.70 (t, 2H), 3.96 to 4.33.
(M, 12H), 4.45 (t, 2H), 5.80
(M, 2H), 6.13 (m, 2H), 6.43 (m,
2H), 6.85 to 7.46 (m, 11H), 8.00
(D, 2H), 8.14 (d, 2H)

<Example 1> [Preparation of liquid crystal composition (1)] Formula (a-1)

[0164]

[Chemical 74] 50 parts by weight of a liquid crystal acrylate compound represented by formula (a-4)

[0165]

[Chemical 75]

A composition (A) comprising 50 parts by weight of a liquid crystal acrylate represented by the formula (A) was prepared. The composition (A) is
It exhibited a nematic liquid crystal phase at room temperature (25 degrees). The nematic phase-isotropic liquid phase transition temperature was 46 degrees. Also,
N _e (refractive index of extraordinary light) measured at 589 nm is 1.6.
In 62, n _o (refractive index of ordinary light) was 1.510 and birefringence was 0.152.

10 parts by weight of the liquid crystal acrylate compound represented by the formula (S10) obtained in Synthesis Example 1 and the composition (A)
A composition (B) consisting of 90 parts by weight was prepared. The composition (B) exhibited a nematic liquid crystal phase from 13 degrees. The nematic phase-isotropic liquid phase transition temperature was 51 degrees.

<Example 2> [Preparation of liquid crystal composition (2)] A composition comprising 30 parts by weight of the liquid crystal acrylate compound represented by the formula (S10) obtained in Example 1 and 70 parts by weight of the composition (A). The thing (C) was prepared. The composition (C) is -3.
It exhibited a nematic liquid crystal phase from 8 degrees. The nematic phase-isotropic liquid phase transition temperature was 60 degrees.

<Example 3> [Preparation (3) of liquid crystal composition] A composition comprising 50 parts by weight of the liquid crystal acrylate compound represented by the formula (S10) obtained in Example 1 and 50 parts by weight of the composition (A). The thing (D) was prepared. The composition (D) is -3.
It exhibited a nematic liquid crystal phase from 8 degrees. The nematic phase-isotropic liquid phase transition temperature was 56 degrees. <Example 4> [Preparation (4) of liquid crystal composition] A composition (E) comprising 70 parts by weight of the liquid crystal acrylate compound represented by the formula (S10) obtained in Example 1 and 30 parts by weight of the composition (A). ) Was prepared. The composition (E) exhibited a nematic liquid crystal phase from twice. The nematic phase-isotropic liquid phase transition temperature was 64 degrees. As shown in Examples 2 to 5 above, the polymerizable liquid crystal compound represented by the formula (S10) obtained in Synthesis Example 1 showed good compatibility with the composition (A) up to 70 parts by weight or more. It was In addition, these compositions exhibited a nematic liquid crystal phase in a wide range from -38 degrees to 60 degrees and exhibited excellent liquid crystallinity.

<Example 5> [Preparation of optical anisotropic body (1)] 99 parts by weight of the composition (B) prepared in Example 2 and a photopolymerization initiator "Irgacure 651" (manufactured by Ciba Geigy) 1
A composition (F) consisting of parts by weight was prepared. Anti-parallel alignment liquid crystal glass cell with a cell gap of 50 microns (glass cell that has been subjected to alignment treatment so that liquid crystal is uniaxially aligned)
Then, the composition (F) was injected at room temperature. After the injection, it could be confirmed that uniform uniaxial orientation was obtained.
Then, at room temperature (25 ° C.), UVGL of 1 mW / cm ² was irradiated for 10 minutes using UVGL-25 manufactured by UVP to polymerize the composition (F) to obtain a polymer. It was confirmed that the obtained polymer had a different refractive index depending on the direction, and functioned as an optically anisotropic body.

Example 6 [Preparation of Optically Anisotropic Body (2)] 99 parts by weight of the composition (C) prepared in Example 3 and a photopolymerization initiator "Irgacure 651" (manufactured by Ciba Geigy) 1
A composition (G) consisting of parts by weight was prepared. Anti-parallel alignment liquid crystal glass cell with a cell gap of 50 microns (glass cell that has been subjected to alignment treatment so that liquid crystal is uniaxially aligned)
Then, the composition (G) was injected at room temperature. After the injection, it could be confirmed that uniform uniaxial orientation was obtained.
Then, at room temperature (25 ° C.), UVGL at 1 mW / cm ² was irradiated for 10 minutes using UVGL-25 manufactured by UVP to polymerize the composition (G) to obtain a polymer. It was confirmed that the obtained polymer had a different refractive index depending on the direction, and functioned as an optically anisotropic body.

Example 7 [Preparation of Optically Anisotropic Body (3)] 99 parts by weight of the composition (D) prepared in Example 4 and a photopolymerization initiator "Irgacure 651" (manufactured by Ciba Geigy) 1
A composition (H) consisting of parts by weight was prepared. Anti-parallel alignment liquid crystal glass cell with a cell gap of 50 microns (glass cell that has been subjected to alignment treatment so that liquid crystal is uniaxially aligned)
Then, the composition (H) was injected at room temperature. After the injection, it could be confirmed that uniform uniaxial orientation was obtained.
Then, at room temperature (25 ° C.), UVGL of 1 mW / cm ² was irradiated for 10 minutes using UVGL-25 manufactured by UVP to polymerize the composition (H) to obtain a polymer. It was confirmed that the obtained polymer had a different refractive index depending on the direction, and functioned as an optically anisotropic body.

<Example 8> [Preparation of optical anisotropic body (4)] 99 parts by weight of the composition (E) prepared in Example 5 and a photopolymerization initiator "Irgacure 651" (manufactured by Ciba Geigy) 1
A composition (I) consisting of parts by weight was prepared. Anti-parallel alignment liquid crystal glass cell with a cell gap of 50 microns (glass cell that has been subjected to alignment treatment so that liquid crystal is uniaxially aligned)
Then, the composition (I) was injected at room temperature. After the injection, it could be confirmed that uniform uniaxial orientation was obtained.
Then, at room temperature (25 degrees), UVGL of UVP Co., Ltd. was used to irradiate 1 mW / cm ² of ultraviolet rays for 10 minutes to polymerize the composition (I) to obtain a polymer. It was confirmed that the obtained polymer had a different refractive index depending on the direction, and functioned as an optically anisotropic body.

Example 9 A composition (J) consisting of 50 parts by weight of the composition (G) prepared in Example 7 and 50 parts by weight of ethyl acetate was prepared. Next, a polyimide thin film having a film thickness of about 100 nanometers was formed on the surface of a 5 cm square glass substrate using a polyimide aligning agent “AL1051” (manufactured by JSR), and the surface of the polyimide thin film was rubbed. Composition (J) was coated on the rubbing-treated surface so that the dry film thickness was 10 μm. The composition did not flow significantly while the ethyl acetate was air-dried, and good film thickness uniformity was maintained. After the ethyl acetate was naturally dried, 2 m was obtained using UVGL-25 manufactured by UVP under a nitrogen stream.
The composition was polymerized by irradiating it with UV light of W / cm ² for 5 minutes. The refractive index of the obtained polymer was different depending on the direction, and it could be confirmed that it functions as an optically anisotropic body. The film thickness unevenness was small.

Comparative Example 1 The composition (A) 99 prepared in Example 1 was used instead of the composition (G) in Example 6.
Coating was performed in the same manner as in Example 9 except that the composition (K) consisting of 1 part by weight of the photopolymerization initiator "Irgacure 651" (manufactured by Ciba Geigy) was used, and the composition was dried during natural drying. The substance was liable to flow and the film thickness uniformity was impaired. After the ethyl acetate was naturally dried, UVGL of ² mW / cm ² was irradiated for 5 minutes using UVGL-25 manufactured by UVP under a nitrogen stream to polymerize the composition. The obtained polymer had a different refractive index depending on the direction, and it could be confirmed that the polymer functions as an optically anisotropic substance, but film thickness unevenness was also observed.

From Example 9 and Comparative Example 1, it can be seen that the viscosity of the polymerizable liquid crystal composition of the present invention is adjusted to a viscosity suitable for coating. The compound of the general formula (1) used in the present invention is also useful as a viscosity modifier.

[0177]

The polymerizable liquid crystal compound used in the present invention is
It has a wide temperature range showing a nematic phase, exhibits a nematic phase even in a temperature range of 25 ° C. or less, and has excellent compatibility with other liquid crystal compounds. Further, the polymerizable liquid crystal composition of the present invention containing the compound can be adjusted to have a viscosity suitable for coating. Therefore, the polymerizable liquid crystal composition of the present invention is, for example, an optically anisotropic substance such as a retardation plate, a polarizing plate, a polarizing prism, an optical waveguide, a piezoelectric element, a non-linear optical element, various optical filters, selective reflection of a cholesteric liquid crystal phase, etc. It is extremely useful for application to coating materials for pigments, optical fibers, etc.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 19/30 C09K 19/30 19/32 19/32 19/34 19/34 19/38 19/38 G02B 5/30 G02B 5/30 G02F 1/13 500 G02F 1/13 500 505 505 F term (reference) 2H049 BA02 BA05 BA06 BA42 BC04 BC05 2H088 EA45 EA47 EA48 HA16 HA18 HA23 JA14 JA17 JA20 MA20 4H027 BA01 BA11 BD05 CM02 CB02 CH02 CB02 4J036 AC01 JA15 4J100 AE76P AL66P AL74P AM23P AM54P BA02P BA15P BB07P BC04P BC07P BC12P BC23P BC43P BC49P BC58P BC69P BC73P CA01 JA32

Claims (6)

[Claims] 1. A liquid crystalline skeleton having two or more ring structures,
General formula [Chemical formula 1] [In the formula, P ¹ represents a polymerizable functional group. S ¹ represents an ethylene group or a propylene group, S ² represents an ester bond or an ether bond, m represents 1 or 2, and S ³ represents −.
_{(CH 2) V -, -} (CH 2) V O -, - (CH 2) V -O
-C (= O) - or _{- (CH 2) V -C (} = O) -O-
(V represents an integer of 1 to 20), and A ¹ and E ¹ each independently represent a hydrocarbon ring or a heterocycle. However, E ¹ is a ring contained in the liquid crystal skeleton. D ¹ is -C (= O) -O- (C
_{H 2) W -O -, -} O (CH 2) W -O-C (= O) -,
-O- (CH _{2) W} -O- or -O-C (= O) - (C
H ₂ ) _W- C (= O) -O- (w represents an integer of 1 to 15) represents a linking chain. ] The polymerizable liquid crystal composition containing the compound (c1) which has a partial structure represented by these. 2. The compound (c1) has the general formula (c2): [Wherein P ² and P ³ are each independently a polymerizable functional group selected from the group consisting of (meth) acryloyloxy group, (meth) acrylamide group, vinyl group, epoxy group, vinyloxy group and maleimide group. Represents S ⁴ and S ⁹ each independently represent an ethylene group or a propylene group, S ⁵ and S ⁸ represent an ester bond or an ether bond, m and n represent an integer of 0 to 2, and m + n is 1 to Represents an integer of 4. S ⁶ and ^{S 7} is - (CH _{2) V} -,
_{- (CH 2) V O -} , - (CH 2) V -O-C (= O) -
Or _{- (CH 2) V -C (} = O) -O- (V is 1-2
Represents an integer of 0. ) Represents a connecting chain represented by
A ² , A ³ , E ² , F ¹ and G ¹ are each independently: (In the formula, p represents an integer of 1 to 4) and represents a ring structure selected from the group consisting of: D ² and D ³ are each independently —C (═O) —O— (CH ₂ ) _m —O—, —O (C
_{H 2) m -O-C (} = O) -, - O- (CH 2) m -O, -
O-C (= O) - (CH 2) m -C (= O) -O- (m
Represents an integer of 1 to 15. ) Represents a connecting chain selected from the group consisting of: Y ¹ and Y ² are each independently
Single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -
, -C (= O) O-, -OC (= O)-, -C≡C
-, - CH = CH -, - CF = CF -, - (CH 2)
_{4 -, - CH 2 CH 2} CH 2 O-, -OCH 2 CH 2 CH 2
-, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH
= CH-, -CH = CH-C (= O) O- and -OC
It represents a linking group selected from the group consisting of (= O) -CH = CH-. r represents an integer of 0 to 3, q is 0 or 1
Represents ] The polymerizable liquid crystal composition according to claim 1, which is a compound represented by the formula: 3. A compound represented by the general formula (c2) is
A ² , A ³ , E ² , F ¹ and G ¹ are And the connecting chain D ² and the connecting chain D ³ are —C (=
_{O) -O- (CH 2) m} -O- or -O (CH _{2) m} -O-
The polymerizable liquid crystal composition according to claim 2, which is C (= O)-(m represents an integer of 1 to 15). 4. A compound represented by the general formula (c2):
Linking chain ^{S 6} and connecting chain ^{S 7} is _{- (CH 2) V O- (} V is
It represents an integer of 1 to 20. ) The polymerizable liquid crystal composition according to claim 2. 5. The polymerizable liquid crystal composition according to claim 2, wherein both P ² and P ³ are (meth) acryloyloxy groups. 6. An optical anisotropic body composed of the polymer of the polymerizable liquid crystal composition according to claim 1.