JP2003321430A - Polymerizable compound, liquid crystalline composition containing the same and its polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound capable of forming a film excellent in mechanical properties such as film strength and scratch resistance without changing properties such as optical properties when the polymer is used at a high temperature. <P>SOLUTION: The polymerizable compound is represented by general formula (I), e.g. a compound represented by the formula No.4-1, No.4-2 or No.4-3. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a compound having photopolymerization crosslinkability, a liquid crystal composition containing the compound, and a polymer thereof, and particularly to an optical component in a crosslinked state and a patterned structure. Or a liquid crystal composition that can be used as a constituent component of an electronic material.

[0002]

2. Description of the Related Art Liquid crystal compounds are used not only in liquid crystal display devices but also in retardation films, waveguides, diffractive gratings, optical filters, which utilize their optical, mechanical strength and electrical anisotropy. It is also actively researched as a constituent material such as high-strength fiber and conductive anisotropic material. In the case of the latter application, the fluidity of the liquid crystal becomes a problem for that application, and therefore, attempts have been made to solidify it. For example, JP-A-5-61
For 039, a method in which a polymer liquid crystal is used to heat above the glass transition temperature to perform orientation aging in a temperature range showing a liquid crystal phase, and then to be rapidly cooled into a glass state to fix the orientation of liquid crystal molecules Is listed. Also, "liquid crystal", <3
(1)>, 34 (1999),
A method of fixing alignment by photopolymerizing a liquid crystal monomer or a diacrylate monomer is also known.

However, since the film or structure immobilized by these methods has a relatively low glass transition temperature, the orientation is disturbed when used at a high temperature, and the properties such as optical anisotropy are generated. It changes a lot. Further, there are drawbacks that not only the film strength is low, but also the film is easily damaged and the resistance to chemicals such as a solvent is low. In addition, JP-A-8-1048
JP-A-70 discloses a polymerizable liquid crystal compound having a trifunctional polymerizable group. However, there is a problem that this polymerizable liquid crystal compound has low miscibility with the bifunctional liquid crystal compound. Further, in Japanese Patent Laid-Open No. 7-278060, 2
A tetrafunctional polymerizable liquid crystal compound is shown in the form of linked functional polymerizable liquid crystal compounds. However, this polymerizable liquid crystal compound also has a drawback that the anisotropy of the refractive index becomes small.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and a first object of the present invention is not to change the characteristics such as optical properties of a polymer when it is used at high temperature. Another object is to provide a polymerizable compound capable of forming a film having excellent mechanical properties such as film strength and scratch resistance.

[0005]

The above-mentioned problems can be solved by providing the following polymerizable compound of the present invention, a liquid crystal composition using the same, and a polymer thereof. That is,
The present invention <1> is a polymerizable compound represented by the following general formula (I).

[Chemical 3] [In the general formula (I), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, P ³ —L ³ —X ³ —, R ²
A hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, P ⁴ -L ⁴ -X ⁴ - represents, R ¹ and R at least one of the ² P ³ -L ³ -X ³ -, or P ⁴ -L ⁴ -X ⁴ - represents a. P ^{1 to} P ⁴ each independently represent a polymerizable group. L ¹ ~
L ⁴ is independently an alkylene group, an alkenylene group,
Represents an aralkylene group, a single bond. X ^{1 to} X ⁴ are each independently a single bond, —O—, —COO—, —O.CO—, —C.
Represents ONH- and -NHCO-. Z ^{1 to} Z ³ are each independently a single bond, —COO—, —O.CO—, —CONH.
-, -NHCO-, -CH = CH-, -C≡C-, -C
_{H 2 CH 2 -, - CH} 2 O -, - OCH 2 -, - CF = CF
-, -CH = CH-COO-, -O.CO-CH = CH
Represents-. n represents an integer of 0 or 1, and when n = 0, Z ² or Z ³ represents -CONH- or -NHCO-,
When n = 1, any one of Z ^{1 to} Z ³ is -CONH.
-Or-NHCO- is represented. The 6-membered rings A and D are each independently a benzene ring, a benzene ring in which one or two non-adjacent CHs are substituted with nitrogen atoms, a cyclohexane ring, 1
Or two non-adjacent CH ₂ represent a cyclohexane ring substituted with an oxygen atom or a sulfur atom, and the hydrogen atoms of the 6-membered rings A and D may be further substituted with a halogen atom, an alkyl group or an alkoxy group. Good. 6-membered rings B and C are each independently a 1,4-phenylene group, a 1,4-phenylene group in which one or two non-adjacent CH are substituted with nitrogen atoms, a 1,4-cyclohexylene group, one Or 1,4 in which two non-adjacent CHs are replaced by oxygen or sulfur atoms
A cyclohexylene group, a naphthalene-2,6-diyl group, a cyclohexene-1,4-diyl group, wherein the hydrogen atoms of the 6-membered rings B and C are further substituted with a halogen atom, an alkyl group or an alkoxy group. Good. <2> A polymerizable compound represented by the following general formula (II).

[Chemical 4] [In the general formula (II), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or P ² —L ² —X ² —. P ¹
And P ² each independently represent a polymerizable group. L ¹ and L ²
Each independently represents an alkylene group, an alkenylene group, an aralkylene group, or a single bond. X ¹ and X ² are each independently a single bond, —O—, —COO—, —O.CO—, —CO.
Represents NH- and -NHCO-. Z ⁴ is a single bond, -COO
-, -O-CO-, -CH = CH-, -C≡C-, -C
_{H 2 CH 2 -, - CH} 2 O -, - OCH 2 -, - CF = CF
-, -CH = CH-COO-, -O.CO-CH = CH
Represents-. Z ⁵ represents -CONH- or -NHCO-. n represents an integer of 0 or 1. 6-membered ring A is a benzene ring, substituted with one or nonadjacent two CH benzene ring substituted with a nitrogen atom, a cyclohexane ring, one or nonadjacent two CH ₂ oxygen atom or a sulfur atom It represents a cyclohexane ring, and the hydrogen atom of the 6-membered ring A may be further substituted with a halogen atom, an alkyl group or an alkoxy group. The 6-membered ring B is a 1,4-phenylene group or 1,4-wherein one or two non-adjacent CHs are substituted with a nitrogen atom.
Phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CHs are substituted with oxygen atom or sulfur atom, naphthalene-2,6
Represents a -diyl group or a cyclohexene-1,4-diyl group, and the hydrogen atom of the 6-membered ring B may be further substituted with a halogen atom, an alkyl group or an alkoxy group. The 6-membered ring C ′ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group, and the hydrogen atom of the 6-membered ring C ′ may be further substituted with a halogen atom, an alkyl group or an alkoxy group. . <3> A liquid crystal composition containing at least the polymerizable compound according to <1> above. <4> A liquid crystal composition containing at least the polymerizable compound according to <1> above and an optically active compound. <5> A liquid crystal composition containing at least the polymerizable compound according to the above <1> and a liquid crystal compound having one or two polymerizable groups in the molecule. <6> A polymer obtained by polymerizing and curing the liquid crystalline composition according to the above items <3> to <5>.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (Polymerizable Compound of General Formula (I))
First, the polymerizable compound of the present invention represented by the following general formula (I) will be described in detail.

[Chemical 5]

In the general formula (I), P ^{1 to} P ⁴ each independently represent a polymerizable group. Examples of the polymerizable group represented by P ^{1 to} P ⁴ include the following polymerizable groups.

[Chemical 6] The alkyl group represented by R ⁴ in the above formula may have a substituent, is preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 12 carbon atoms.

Among these polymerizable groups, addition-polymerizable polymerizable groups are preferable, and the following polymerizable groups are particularly preferable.

[Chemical 7] Further, the polymerizable groups represented by P ^{1 to} P ⁴ are preferably the same polymerizable group.

In the general formula (I), L ^{1 to} L ⁴ each independently represent an alkylene group, an alkenylene group, an aralkylene group or a single bond. The alkylene group represented by L ^{1 to} L ⁴ may have a substituent and has 1 to 20 carbon atoms.
Is preferable, and an alkylene group having 2 to 12 carbon atoms is particularly preferable. As the substituent, a halogen atom, an alkoxy group, an aryl group, an alkenyl group and the like are preferable. Further, one carbon atom in the alkylene chain or two or more non-adjacent carbon atoms may be replaced with an oxygen atom or a sulfur atom. Specific examples of the alkylene group, an ethylene group, butylene group, 1-methyl - ethylene _{group, - (CH 2) 2 O} (CH 2) 2 - and the like.

The alkenylene group represented by L ^{1 to} L ⁴ may have a substituent and is preferably an alkenylene group having 2 to 20 carbon atoms, and particularly preferably an alkenylene group having 2 to 12 carbon atoms. preferable. The substituent is preferably a halogen atom, an alkoxy group or an aryl group. Specific examples of the alkenylene group, -CH ₂ CH = CHCH
_{2 -, - CH 2 CH 2} CH = CHCH 2 - , and the like.

The aralkylene group represented by L ^{1 to} L ⁴ may have a substituent and is preferably an aralkylene group having 8 to 30 carbon atoms, and particularly preferably an aralkylene group having 8 to 20 carbon atoms. preferable. The substituent is preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group or an alkenyl group. Specific examples of the above aralkylene group include the following aralkylene groups.

[Chemical 8]

Above, L¹~ L^FourAmong the groups represented by
Is preferably an alkylene group, and L ¹~ L^FourGroup represented by
Are preferably the same group.

In the general formula (I), X ^{1 to} X ⁴ are each independently a single bond, --O--, --COO--, --O.CO--,
Represents -CONH- and -NHCO-. Among these groups, -O-, -COO-, and -O.CO- are preferable, and -O- is particularly preferable.

In the general formula (I), Z¹~ Z³Is that
Independently, a single bond, -COO-, -O.CO-, -CON
H-, -NHCO-, -CH = CH-, -C≡C-,-
CH ₂CH₂-, -CH₂O-, -OCH₂-, -CF = C
F-, -CH = CH-COO-, -O.CO-CH = C
Represents H-. Among these groups, a single bond, -COO-,
-O-CO-, -CONH-, -NHCO-, -C≡C
-Is preferable, and particularly -COO-, -O.CO-, -CO
NH- and -NHCO- are preferred.

In the general formula (I), n represents an integer of 0 or 1. Here, when n = 0, the above Z ² or Z ³ represents —CONH— or —NHCO—, and when n = 1,
Any ^{one of the} above Z ^{1 to} Z ³ is -CONH- or-.
Represents NHCO-.

In the general formula (I), R ¹ is a hydrogen atom,
Halogen atom, an alkyl group, an alkoxy group, P ³ -L ³ -
X ³ −, R ² represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, P ⁴ —L ⁴ —X ⁴ —, R ¹ and R
^At least one of ² is P ³ -L ³ -X ^3- , or P ⁴ -L ⁴
-X ⁴ - represents a.

The halogen atom represented by R ¹ and R ² is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom or a bromine atom.

The alkyl group represented by R ¹ and R ² may have a substituent and is preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms. preferable. The substituent is preferably a halogen atom, an alkoxy group or an alkenyl group. Specific examples of the alkyl group include a methyl group, an isobutyl group, a trifluoromethyl group and the like.

The alkoxy group represented by R ¹ and R ² may have a substituent and is preferably an alkoxy group having 1 to 20 carbon atoms, and particularly preferably an alkoxy group having 1 to 8 carbon atoms. preferable. The substituent is preferably a halogen atom or an alkenyl group. Specific examples of the alkoxy group include a methoxy group, a butyloxy group and a benzyloxy group.

As mentioned above, among the groups represented by R ¹ and R ² ,
A hydrogen atom, a halogen ^{atom, P 3 -L 3 -X 3 -} , or P ⁴ -
L ⁴ —X ⁴ — is preferred, and particularly hydrogen atom, P ³ —L ³ —X ³
-, or P ⁴ -L ⁴ -X ⁴ - are preferred.

In the general formula (I), the 6-membered rings A and D are each independently a benzene ring, a benzene ring in which one or two non-adjacent CHs are substituted with nitrogen atoms, a cyclohexane ring, one or no adjacent Two CH ₂ 's represent a cyclohexane ring substituted with an oxygen atom or a sulfur atom, and the hydrogen atoms of the 6-membered rings A and D may be further substituted with a halogen atom, an alkyl group or an alkoxy group.

As the above-mentioned 6-membered rings A and D, the following 6-membered rings are preferable.

[Chemical 9]

In the above formula, R represents R ¹ or R ² of the general formula (I). Y ^{1 to} Y ⁶ represent a halogen atom, an alkyl group or an alkoxy group, and a to c represent an integer of 0 to 2. The halogen atom represented by Y ^{1 to} Y ⁶ is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom or a bromine atom. The alkyl group represented by Y ^{1 to} Y ⁶ has 1 to 8 carbon atoms.
Is preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred. The alkoxy group represented by Y ^{1 to} Y ⁶ is
An alkoxy group having 1 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is particularly preferable. 6-membered ring above
Of these, a 6-membered ring is particularly preferable. Also, a to c
Is preferably 0 or 1, and particularly preferably 0.

Specific examples of the divalent aromatic ring, aliphatic ring or heterocyclic group represented by the 6-membered rings A and D are shown below. However, the present invention is not limited to these.

[Chemical 10]

In the general formula (I), the 6-membered rings B and C are each independently a 1,4-phenylene group, a 1,4-phenylene group in which one or two nonadjacent CHs are substituted with nitrogen atoms, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CHs are substituted with oxygen atom or sulfur atom, naphthalene-2,6-diyl group, cyclohexene-1,4- It represents a diyl group, and the hydrogen atoms of the 6-membered rings B and C may be further substituted with a halogen atom, an alkyl group or an alkoxy group.

As the above-mentioned 6-membered rings B and C, the 6-membered rings (circled numbers) 1 to 10 shown below are preferable.

[Chemical 11]

In the above formula, R represents R ¹ or R ² of the general formula (I). Y ⁸ to Y ¹⁷ represents a halogen atom, an alkyl group, an alkoxy group, E～m and o represents an integer of 0 to 3. Y ⁸
The halogen atom represented by Y ¹⁷ is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom or a bromine atom. The alkyl group represented by Y ^{8 to} Y ¹⁷ is preferably an alkyl group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms.
Alkyl groups of are preferred. The alkoxy group represented by Y ^{8 to} Y ¹⁷ is preferably an alkoxy group having 1 to 8 carbon atoms,
Particularly, an alkoxy group having 1 to 4 carbon atoms is preferable. Among the above 6-membered rings (circle numbers 1-10), especially (circle number) 1
Ten 6-membered rings are preferred. Also, e to m and o are 0, 1, 2
Is preferable, and 0 and 1 are particularly preferable.

Specific examples of the divalent aromatic ring, aliphatic ring or heterocyclic group represented by the 6-membered rings B and C are shown below. However, the present invention is not limited to these.

[Chemical 12]

Further, the above X ¹ and X ² and Z ^{1 to} Z ³ are -C.
In the case of representing a bond of ONH- or -NHCO-, in the above-mentioned 6-membered ring to which the nitrogen atom in these bonds is bonded, a halogen atom, an alkyl group, ortho at the ortho position with respect to the nitrogen atom,
Those in which the alkoxy group is substituted are preferred.

Specific examples of the polymerizable compound represented by formula (I) of the present invention are shown below. However, the present invention is not limited to these.

[0031]

[Chemical 13]

[0032]

[Chemical 14]

[0033]

[Chemical 15]

[0034]

[Chemical 16]

[0035]

[Chemical 17]

[0036]

[Chemical 18]

[0037]

[Chemical 19]

[0038]

[Chemical 20]

[0039]

[Chemical 21]

(Production Method of General Formula (I) Compound) The polymerizable compound represented by the general formula (I) of the present invention can be produced, for example, by a method according to the following scheme (1).

[0041]

[Chemical formula 22]

[0042]

[Chemical formula 23]

In the above reaction formula, 6-membered rings A'and D '
Represents a benzene ring, and the hydrogen atom of the benzene ring may be further substituted with a halogen atom, an alkyl group or an alkoxy group. This reaction can be carried out by usual etherification, ester hydrolysis, esterification, acid chloride formation, and amidation reaction.

Further, it can be produced by the method according to the following scheme (2).

[Chemical formula 24]

This reaction can be carried out by usual acid chloride formation and ester / amidation reactions.

Further, it can be produced by a method according to the following scheme (3).

[Chemical 25]

[0047]

[Chemical formula 26]

This reaction is carried out by conventional acid chloride, amidation,
It can be carried out by ester hydrolysis and esterification reaction.

Further, it can be produced by the method according to the following scheme (4).

[Chemical 27]

In this reaction, the acid chloride formation of compound (A-5) and the subsequent esterification reaction with compound (D-1) are as follows:
It can be carried out by a usual method. Compound (D-2)
Hydrolysis of the acetyl group of "Synthesis",
It can be carried out with reference to <438> (1989). The esterification reaction between the compound (D-3) and the compound (A-4) may be carried out by converting the compound (A-4) into an acid chloride and then reacting with the compound (D-3). A-4) and the compound (D-3) may be condensed with a condensing agent such as DCC.

Further, it can be produced by a method according to the following scheme (5).

[Chemical 28]

This reaction can be carried out with reference to the above reaction.

(Polymerizable Compound of General Formula (II)) Next, the polymerizable compound of the present invention represented by the following general formula (II) will be described.

[Chemical 29]

In the general formula (II), R ¹ , P ¹ and P ² , L ¹ and L ² , X ¹ and X ² , the 6-membered ring A, and the 6-membered ring B are the same as those described in the general formula (I). R ¹ , P ¹ and P ² , L ¹ and L ² , X ^{1 in}
And X ² , the 6-membered ring A and the 6-membered ring B have the same meanings and the preferred groups are also the same.

In the general formula (II), Z ⁴ is a single bond,
COO-, -O.CO-, -CH = CH-, -C≡C
_{-, - CH 2 CH 2 -} , - CH 2 O -, - OCH 2 -, - C
F = CF-, -CH = CH-COO-, -O-CO-C
H = CH-, particularly a single bond, -COO-, -O.
CO- and -C≡C- are preferable, and especially -COO- and -O.
-CO- is preferred. Z ⁵ is -CONH- or -NHC
Represents O-, and in particular, when n in the general formula (II) is 0,
CONH- is preferable, and when n is 1, -NHCO- is preferable.

In the general formula (II), the 6-membered ring C'is 1,
It represents a 4-phenylene group or a naphthalene-2,6-diyl group, and the hydrogen atom of the 6-membered ring C ′ may be further substituted with a halogen atom, an alkyl group or an alkoxy group. Among them, the 6-membered ring C'is 1,4-phenylene, or an alkyl group, an alkoxy group, or a halogen atom-substituted 1,
4-phenylene is preferable, and 1,4-phenylene or 1,4-phenylene substituted with a halogen atom is particularly preferable.

The compound represented by the general formula (II) of the present invention is useful as an intermediate in the production of the compound represented by the above general formula (I).

Specific examples of the polymerizable compound represented by formula (II) of the present invention are shown below. However, the present invention is not limited to these.

[0059]

[Chemical 30]

[0060]

[Chemical 31]

[0061]

[Chemical 32]

(Liquid-Crystalline Composition) The polymerizable compound represented by the general formula (I) of the present invention does not necessarily need to exhibit liquid crystallinity itself. A liquid crystal composition can be suitably used by mixing them in a composition ratio that exhibits the property.
Further, it can be applied to applications in which polymer liquid crystals are used.

It is also possible to induce a cholesteric phase or a chiral smectic phase by adding an optically active compound to the liquid crystalline composition containing the polymerizable compound of the general formula (I) of the present invention. In this case, the content of the optically active compound is preferably 0.1 to 20% by mass, and particularly preferably 2 to 15% by mass of the total solid content (mass) of the liquid crystal composition. As such an optically active compound, a known optically active compound can be used. For example, Japanese Unexamined Patent Publication No. 2000-44451 and Japanese Patent Publication No. 10-50972.
No. 6, gazette, WO98 / 00428, special table 2000-50
The optically active compounds described in, for example, Japanese Patent No. 6873, Japanese Patent Publication No. 9-506088, Japanese Patent Application No. 2000-382516 can be used.

When the polymerizable compound of the present invention is used as a mixture with another liquid crystal compound, the liquid crystal compound has a refractive index anisotropy Δn of 0.10 to 0.40. , A polymer liquid crystal compound, and a liquid crystal compound having one or two polymerizable groups can be appropriately selected.
For example, a smectic liquid crystal compound, a nematic liquid crystal compound, etc. can be mentioned, and among them, a nematic liquid crystal compound is preferable. The liquid crystalline compound can be aligned while it is in a liquid crystal state when melted, for example, by using an alignment substrate that has been subjected to an alignment treatment such as a rubbing treatment. Also, when immobilizing the liquid crystal in the solid phase,
Means such as cooling and polymerization can be used.

Specific examples of the liquid crystal compound having one or two polymerizable groups are WO95 / 22586, Japanese Patent Application No. 2
000-51089, Japanese Patent Application No. 2000-68479 and Japanese Patent Application No. 11-91162 can be mentioned. However, the present invention is not limited to these. An example of such a liquid crystal compound is shown below.

[0066]

[Chemical 33]

[0067]

[Chemical 34]

The content of the liquid crystal compound is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass based on the total solid content (mass) of the liquid crystal composition.

(Other Uses) The polymerizable compound of the general formula (I) of the present invention is chloroform, tetrahydrofuran, N-
Since it is well dissolved in an ordinary solvent such as methylpyrrolidone and the viscosity at that time is not so high, the substrate can be easily coated by a method such as spin coating. Furthermore, since the compound of the present invention has photopolymerizability, it can be easily polymerized by irradiation with ultraviolet rays.

When the composition containing the polymerizable compound of the present invention is polymerized at a temperature showing a liquid crystal phase (for example, photopolymerization), the obtained polymer exhibits anisotropy such as optical anisotropy, and Since the polymer is excellent in hardness and strength as compared with the polymer made from the conventional bifunctional polymerizable liquid crystal compound, an optical film having better abrasion resistance than the conventional polymer can be obtained. Further, because of its abrasion resistance, it can be applied not only to optical films, but also to various coating agents that require abrasion resistance.

The polymerizable compound represented by the above general formula (I) of the present invention has a polymerizability, especially a photopolymerizability, and is applicable to the applications generally used as a polymerizable monomer, especially a photopolymerizable monomer. is there. For example, the polymerizable compound of the present invention is
Utilizing its polymerizability (photopolymerizability) for manufacturing printed circuit boards,
It can be applied to microlithography, optical fiber coating, magnetic recording medium paints, inks, adhesives, dental materials, medical materials and the like. At that time, other polymerizable monomers can be appropriately used in combination. Furthermore, the polymerizable compound of the present invention has good compatibility with conventional polymerizable liquid crystal compounds, and the mixture of the two exhibits liquid crystal properties over a wide temperature range. Therefore, when the mixture is polymerized, good results are obtained. Optical anisotropy (birefringence) is obtained.
Further, when the polymerizable compound of the present invention is added to a conventional polymerizable liquid crystal compound and polymerized, mechanical properties such as hardness, strength and scratch resistance of a film obtained are improved.

The present invention also relates to a composition containing the polymerizable compound represented by the general formula (I) and a polymer thereof. In the composition, in addition to the polymerizable compound represented by the general formula (I), other polymerizable monomers, conventional mono- or bifunctional polymerizable liquid crystal compounds, polymer liquid crystals, optically active or cholesteric liquid crystals. A compound, a polymerization initiator, an organic dye, a spectral sensitizer, a surfactant, etc. can be contained. The composition can be used not only for the cholesteric color filter, the retardation film, the overcoat layer and the like, but also for the applications described above for the application of the polymerizable compound of the invention.

From the polymerizable compound of the present invention or the composition containing the same, a color filter, a retardation film, an STN
An optical film such as an optical compensation film for a device or a diffusion film can be produced. The optical film is produced by appropriately adjusting the viscosity of the polymerizable compound of the present invention or the composition containing the same with a solvent, further adding a polymerization catalyst if necessary, and then coating the composition on a substrate for polymerization.

[0074]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In this example, "parts" and "%" all represent "parts by mass" and "% by mass".

Example 1 (Synthesis of Exemplified Compound 6-2) Exemplified Compound (6-2) was synthesized according to the synthetic procedure shown below. 4- (4-acryloyloxybutoxy) benzoic acid 5.6 mmol (1.48 g), a catalytic amount of dimethylformamide, and tetravidrofuran in a mixture of 15 ml, oxalyl chloride 8.4 mmol (0.7 ml)
Was dripped. Then, after stirring at room temperature for 1 hour, the solvent was distilled off. This residue is dissolved in 5 ml of tetrahydrofuran and 4-amino-3-bromophenol 5.6 mmol
(1.06 g) was added dropwise to a solution of 15 ml of dimethylacetamide. After further stirring at room temperature for 30 minutes, the reaction mixture was poured into water and extracted with ethyl acetate. After distilling off the solvent, crystallization from ethyl acetate / n-hexane,
1.71 g of exemplary compound (6-2) was obtained. 71% yield
Met.

The compound obtained above was analyzed by ¹ H-NMR (C
The results of identification by DCl ₃ ) analysis are shown below. δ
(In ppm from TMS); 8.10 (s,
1H), 8.05 (d, 1H), 7.90 (d, 2
H), 7.12 (s, 1H), 6.95 (d, 2H),
6.80 (d, 1H), 6, 48 (s, 1H), 6.4
2 (d, 1H), 6.13 (dd, 1H), 5.85
(D, 1H), 4.35-3.95 (m, 4H), 2.
00-1.80 (m, 4H)

Example 2 (Synthesis of Exemplified Compound 6-11) In Example 1, 4- (4-acryloyloxybutoxy) benzoic acid was converted to 4-acetoxybenzoic acid and 4-amino-3-bromophenol. 4- (4-acetoxybenzoylamino) -3-chlorophenol was obtained in the same manner as in Example 1 except that was changed to 4-amino-3-chlorophenol. Yield 40%. 4- (4-Aryloyloxybutoxy) benzoic acid 17 mmol (4.5
g), a catalytic amount of dimethylformamide and 30 ml of tetrahydrofuran in a mixture of 26 mmo of oxalyl chloride.
1 (2.1 ml) was added dropwise. Then, after stirring at room temperature for 3 hours, the solvent was distilled off.

30 ml of tetrahydrofuran was added to this residue,
After adding 17 mmol (5.0 g) of 4- (4-acetoxybenzoylamino) -3-chlorophenol, 34 mmol (4.5 ml) of triethylamine was added dropwise. After further stirring at room temperature for 1 hour, the reaction mixture was poured into dilute hydrochloric acid and the resulting solid was collected by filtration. This is washed with methanol to give 4- (4-acetoxybenzoylamino).
-3-Chlorophenyl ester was obtained. Yield 96%.
5 mmol (275 g) of the obtained compound, “Syn
thesis ", <438> (1989), p-toluenesulfonic acid supported on silica gel (7.5 g) and water-saturated toluene (20 ml) were mixed, and the mixture was stirred at 80 ° C for 3 hours in an outer bath. Afterwards it was filtered and the filtrate was concentrated. The obtained residue was dispersed with methanol and filtered to obtain 0.95 g of compound (6-11).
Yield 38%.

The obtained compound was analyzed by ¹ H-NMR (CDC
The results identified by l ₃ ) are shown below. δ; 8.60
(D, 1H), 8.40 (s, 1H), 8.10 (d,
2H), 7.80 (d, 2H), 7.40-7.30.
(M, 2H), 7.20 (d, 1H), 7.05-6.
90 (m, 4H), 6.43 (d, 1H), 6.12
(Dd, 1H), 5.83 (d, 1H), 4.35-
4.00 (m, 4H), 2.00-1.85 (m, 4
H)

[Example 3] (Synthesis of Exemplified Compound 1-1) 3,4-dihydroxybenzoic acid ethyl ester 55 mm
ol (10.0 g), potassium carbonate 165 mmol (2
2.7 g), potassium iodide 33 mmol (5.5
g), and a mixture of 100 ml of dimethylformamide in an outer bath heated at 90 ° C. to give 6-chloro-1-hexanol 1
65 mmol (22 ml) was added dropwise. After stirring for 6 hours, the reaction mixture was poured into water and extracted with ethyl acetate. After concentration, purification by column chromatography gave 3,4-di (6-hydroxyhexyloxy) benzoic acid ethyl ester.

The above compound was mixed with 100 ml of methanol, 164 mmol (9.2 g) of potassium hydroxide and 25 ml of water were added, and the mixture was stirred at an external temperature of 80 ° C. for 2 hours. The reaction mixture was dropped in 10% hydrochloric acid, and the obtained solid was collected by filtration. The solid was washed with ethyl acetate to give 3,4-
Di (6-hydroxyhexyloxy) benzoic acid was added to 6.5
6 g were obtained. The yield was 34%.

The above compound 5.6 mmol (2.0
g), 18 mmol of dimethylaniline (2.35 m)
18 mmol (1.5 ml) of acrylic acid chloride was added dropwise to a mixture of 1) and 20 ml of tetrahydrofuran. Then, the mixture was stirred at room temperature for 3 hours and then dropped into 10% hydrochloric acid, and the obtained solid was collected by filtration. This solid was washed with acetonitrile to obtain 1.98 g of 3,4-di (6-acryloyloxyhexyloxy) benzoic acid. The yield is 76%.

1.5 mmol (0.71) of the above compound
g), a catalytic amount of dimethylformamide and 5 ml of tetrahydrofuran in a mixture of oxalyl chloride 2.3 mm
ol (0.18 ml) was added dropwise. Then, after stirring at room temperature for 1 hour, the solvent was distilled off. Tetrahydrofuran 10 ml to the residue, and exemplified compound (6-2) 1.4 mmol
(0.61 g) are mixed and triethylamine 2.8 mm
ol (0.38 ml) was added dropwise. After further stirring at room temperature for 2 hours, the mixture was dropped into 10% hydrochloric acid and extracted with ethyl acetate. After concentrating the solvent, the residue is dispersed in ethanol,
0.82 g of Exemplified Compound (1-1) by filtering
Obtained. Yield 66%.

The melting point of the compound obtained above was 105.degree. The results of identifying the compound by ¹ H-NMR (CDCl ₃ ) are shown below. δ; 8.65-8.60 (m, 1H),
8.37 (s, 1H), 7.95-7.80 (m, 3
H), 7.67 (s, 1H), 7.51 (s, 1H),
7.25-7.20 (m, 2H), 7.05-6.90
(M, 3H), 6.48-5.77 (m, 9H), 4.
32-4.00 (m, 12H), 2.00-1.40
(M, 20H)

Example 4 (Synthesis of Exemplified Compound 1-2) 2.2 mmol (1.0 g) of 3,4-di (6-acryloyloxyhexyl) benzoic acid, a catalytic amount of dimethylformamide, and 5 ml of tetrahydrofuran 3.2 mmol (0.41 ml) of oxalyl chloride was added dropwise to the mixture. Then, after stirring at room temperature for 2 hours, the solvent was distilled off. 10 ml of tetrahydrofuran and 1.1 mmol (0.2 g) of 4-amino-3-glomophenol in the residue.
After addition of 3.3 mmol of triethylamine (0.
3 ml) was added dropwise. After stirring at room temperature for 1 hour,
It was dropped in 10% hydrochloric acid and extracted with ethyl acetate. Purification by column chromatography gave 0.55 g of Exemplified compound (1-2). Yield 47%.

The melting point of the compound obtained above was 95.degree. The results of identifying the compound by ¹ H-NMR (CDCl ₃ ) are shown below. δ; 8.60 (d, 1H), 8.40
(S, 1H), 7.80 (d, 1H), 7.63 (s,
1H), 7.50 (d, 2H), 7.43 (d, 1
H), 7.24 (d, 1H), 6.93 (d, 2H),
6.40 (d, 2H), 6.12 (dd, 2H), 5.
82 (d, 2H), 4.21-4.00 (m, 16)
H), 2.00-1.40 (m, 32H)

Example 5 (Synthesis of Exemplified Compound 3-1) 3,4-Di (6-acryloyloxyhexyloxy)
Benzoic acid 1.7 mmol (0.79 g), catalytic amount of dimethylformamide, and tetrahydrofuran 5 ml were added to a mixture of oxalyl chloride 2.6 mmol (0.22 ml).
Was dripped. Then, after stirring at room temperature for 1 hour, the solvent was distilled off. Tetrahydrofuran 10 ml and Exemplified compound (6-11) 1.7 mmol (0.87 g) were mixed with the residue, and triethylamine 3.4 mmol (0.5 ml) was added dropwise. After further stirring at room temperature for 2 hours, the mixture was dropped into 10% hydrochloric acid and extracted with ethyl acetate. After concentrating the solvent,
The residue was purified by column chromatography, dispersed in methanol, and collected by filtration to give Exemplified Compound (3-1) at 0.
67 g was obtained. Yield 42%.

C 150 ° C. (N 144 ° C.) I The results of identification of the compound by ¹ H-NMR (CDCl ₃ ) are shown below. δ; 8.60 (d, 1H), 8.40
(S, 1H), 8.15 (d, 2H), 8.00 (d,
2H), 7.85 (d, 1H), 7.68 (s, 1
H), 7.45-7.35 (m, 3H), 7.20.
(D, 1H), 7.05-6.90 (m, 4H), 6.
50-5.78 (m, 9H), 4.30-4.00
(M, 12H), 2.00-1.40 (m, 24H)

[Example 6] (Synthesis of Exemplified Compound 3-3) Example 1 was repeated except that 4- (4-acryloyloxyhexyloxy) benzoic acid was changed to 4-acetoxyacetic acid. By the same method, 3.7 g of 4- (4-acetoxybenzoylamino) -3-bromophenol was obtained. To this, 40 ml of methanol, 10 ml of tetrahydrofuran and 10 ml of water were mixed, and 3.2 g of potassium carbonate was added. Then, after stirring at room temperature for 1 hour, the reaction mixture was dropped into 10% hydrochloric acid, and the resulting solid was collected by filtration and washed with acetonitrile to give 4-
2.18 g of (4-hydroxybenzoylamino) -3-bromophenol was obtained. The yield is 68%.

2.1 mmol (1.0 g) of 3,4-di (6-acryloyloxyhexyloxy) benzoic acid, catalytic amount of dimethylformamide and tetrahydrofuran 5
3.2 mmol of oxalyl chloride (0.
27 ml) was added dropwise. Then, after stirring at room temperature for 1 hour, the solvent was distilled off. 10m of tetrahydrofuran on the residue
and 1.05 mmol of 4- (4-hydroxybenzoylamino) -3-bromophenol obtained above
(0.33g) is mixed, triethylamine 4.3mm
ol (0.6 ml) was added dropwise. After further stirring at room temperature for 2 hours, the mixture was dropped into 10% hydrochloric acid and extracted with ethyl acetate. After the solvent was concentrated, the residue was purified by column chromatography, dispersed in ethanol and collected by filtration to obtain 0.53 g of Exemplified compound (3-3). The yield is 41%.

The melting point of the compound obtained above was 104 ° C. The results of identifying the compound by ¹ H-NMR (CDCl ₃ ) are shown below. δ; 8.62 (d, 1H), 8.40
(S, 1H), 8.02 (d, 2H), 7.90-7.
77 (m, 2H), 7.68 (s, 1H), 7.64
(S, 1H), 7.52 (s, 1H), 7.40 (d,
2H), 7.30-7.22 (m, 1H), 6.98-
6.88 (m, 2H), 6.40 (d, 2H), 6.1
2 (dd, 2H), 5.82 (d, 2H), 4.22-
4.02 (m, 16H), 1.95-1.40 (m, 3
2H)

[Example 7] (Synthesis of Exemplified Compound 3-4) Example 1 was the same as Example 1 except that 4-amino-3-bromophenol was changed to 4-amino-3-chlorophenol. An exemplary compound (3-
4) was obtained. The yield is 31%. The melting point of the obtained compound is 1
It was 08 ° C. The results of identifying the compound by ¹ H-NMR (CDCl ₃ ) are shown below. δ; 8.64 (d, 1H), 8.40
(S, 1H), 8.05 to 7.95 (m, 2H), 7.
90-7.78 (m, 2H), 7.69 (s, 1H),
7.66 (s, 1H), 7.47-7.18 (m, 4
H), 7.00-6.88 (m, 2H), 6.40.
(D, 2H), 6.13 (dd, 2H), 5.82
(D, 2H), 4.22-4.02 (m, 16H) 1.
95-1.40 (m, 32H)

[Example 8] (Liquid crystal composition) A liquid crystal composition was prepared according to the formulation shown below.

[Chemical 35]

This solution was added dropwise to a glass substrate on which a polyimide alignment film "LX-1400" manufactured by Hitachi Chemical DuPont Co., Ltd. was formed and rubbed, and the solution was spin-coated at 1000 rpm. Next, this was held at 105 ° C. for 5 minutes and then irradiated with ultraviolet rays using a high pressure mercury lamp to carry out polymerization. This film exhibited optical anisotropy having an optical axis in the rubbing direction. The retardation of this film was 200 nm at a wavelength of 550 nm.

[Example 9] (Cholesteric liquid crystal composition) A coating solution for a photosensitive resin layer prepared according to the following formulation was applied onto the orientation film of the above glass substrate with an orientation film by a spin coater, and the coating solution was applied. A photosensitive resin layer was formed by drying in an oven at 100 ° C. for 2 minutes.

[0096]

[Chemical 36]

Next, when the photosensitive resin layer was developed by holding it on a hot plate at 100 ° C. for 5 minutes so as to make contact with the surface of the glass substrate, blue selective reflection derived from the cholesteric liquid crystal phase was obtained.

Next, the entire surface was exposed with an irradiation energy of 500 mJ / cm ² by an ultra-high pressure mercury lamp while blowing nitrogen gas, and was polymerized and cured. The scratch hardness of this film is JIS-
It was 2H when measured by the method according to K5401. On the other hand, the scratch hardness of the above compound (Z) alone without the exemplified compound (3-1) was 1H, and it was found that the scratch hardness was improved by the coexistence of the polymerizable compound of the present invention.

[0099]

EFFECT OF THE INVENTION Since the polymerizable compound of the present invention is well dissolved in an ordinary solvent and the viscosity at that time is not high, the substrate can be easily coated by a method such as spin coating. The polymer film obtained from the polymerizable compound of the present invention exhibits anisotropy such as optical anisotropy, and the film is excellent in mechanical strength and hardness. Furthermore, the polymerizable compound of the present invention has good compatibility with conventional polymerizable liquid crystal compounds,
Since the mixture of both exhibits liquid crystal properties over a wide temperature range, good optical anisotropy (birefringence) can be obtained when the mixture is polymerized. In addition, when the polymerizable compound of the present invention is added to a conventional polymerizable liquid crystal compound and polymerized, mechanical properties such as strength and scratch resistance of the obtained film are improved.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 239/26 C07D 239/26 4J100 239/34 239/34 239/42 239/42 303/26 303/26 303/27 303/27 319/06 319/06 C08F 12/34 C08F 12/34 20/02 20/02 C08G 59/02 C08G 59/02 C09K 19/38 C09K 19/38 G02F 1/13 500 G02F 1 / 13 500 (72) Inventor Keiichiro Hayashi 200 Onakazato, Fujinomiya-shi, Shizuoka Fuji Photo Film Co., Ltd. F-term (Reference) 4C022 GA15 4C048 AA01 BB11 CC01 CC02 CC03 UU10 XX01 XX04 4H006 AA01 AA03 AB64 BJ50 BM10 BP30 BM30 BT30BT30 BT32 BT36 BV74 4H027 BA13 4J036 AA01 AJ02 AJ08 AJ11 AJ13 AJ14 AJ15 AJ18 JA09 4J100 AB15P AL08P AL66P AL67P BA02P BA04P BA12P BA15P BA34P BA35P BB01P BB03P BC43P BC54P DA66 JA39

Claims (6)

[Claims] 1. A polymerizable compound represented by the following general formula (I). [Chemical 1] [In the general formula (I), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, P ³ —L ³ —X ³ —, R ²
A hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, P ⁴ -L ⁴ -X ⁴ - represents, R ¹ and R at least one of the ² P ³ -L ³ -X ³ -, or P ⁴ -L ⁴ -X ⁴ - represents a. P ^{1 to} P ⁴ each independently represent a polymerizable group. L ¹ ~
L ⁴ is independently an alkylene group, an alkenylene group,
Represents an aralkylene group, a single bond. X ^{1 to} X ⁴ are each independently a single bond, —O—, —COO—, —O.CO—, —C.
Represents ONH- and -NHCO-. Z ^{1 to} Z ³ are each independently a single bond, —COO—, —O.CO—, —CONH.
-, -NHCO-, -CH = CH-, -C≡C-, -C
_{H 2 CH 2 -, - CH} 2 O -, - OCH 2 -, - CF = CF
-, -CH = CH-COO-, -O.CO-CH = CH
Represents-. n represents an integer of 0 or 1, and when n = 0, Z ² or Z ³ represents -CONH- or -NHCO-,
When n = 1, any one of Z ^{1 to} Z ³ is -CONH.
-Or-NHCO- is represented. The 6-membered rings A and D are each independently a benzene ring, a benzene ring in which one or two non-adjacent CHs are substituted with nitrogen atoms, a cyclohexane ring, 1
Or two non-adjacent CH ₂ represent a cyclohexane ring substituted with an oxygen atom or a sulfur atom, and the hydrogen atoms of the 6-membered rings A and D may be further substituted with a halogen atom, an alkyl group or an alkoxy group. Good. 6-membered rings B and C are each independently a 1,4-phenylene group, a 1,4-phenylene group in which one or two non-adjacent CH are substituted with nitrogen atoms, a 1,4-cyclohexylene group, one Or 1,4 in which two non-adjacent CHs are replaced by oxygen or sulfur atoms
A cyclohexylene group, a naphthalene-2,6-diyl group, a cyclohexene-1,4-diyl group, wherein the hydrogen atoms of the 6-membered rings B and C are further substituted with a halogen atom, an alkyl group or an alkoxy group. Good. ] 2. A polymerizable compound represented by the following general formula (II). [Chemical 2] [In the general formula (II), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or P ² —L ² —X ² —. P ¹
And P ² each independently represent a polymerizable group. L ¹ and L ²
Each independently represents an alkylene group, an alkenylene group, an aralkylene group, or a single bond. X ¹ and X ² are each independently a single bond, —O—, —COO—, —O.CO—, —CO.
Represents NH- and -NHCO-. Z ⁴ is a single bond, -COO
-, -O-CO-, -CH = CH-, -C≡C-, -C
_{H 2 CH 2 -, - CH} 2 O -, - OCH 2 -, - CF = CF
-, -CH = CH-COO-, -O.CO-CH = CH
Represents-. Z ⁵ represents -CONH- or -NHCO-. n represents an integer of 0 or 1. 6-membered ring A is a benzene ring, substituted with one or nonadjacent two CH benzene ring substituted with a nitrogen atom, a cyclohexane ring, one or nonadjacent two CH ₂ oxygen atom or a sulfur atom It represents a cyclohexane ring, and the hydrogen atom of the 6-membered ring A may be further substituted with a halogen atom, an alkyl group or an alkoxy group. The 6-membered ring B is a 1,4-phenylene group or 1,4-wherein one or two non-adjacent CHs are substituted with a nitrogen atom.
Phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CHs are substituted with oxygen atom or sulfur atom, naphthalene-2,6
Represents a -diyl group or a cyclohexene-1,4-diyl group, and the hydrogen atom of the 6-membered ring B may be further substituted with a halogen atom, an alkyl group or an alkoxy group. The 6-membered ring C ′ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group, and the hydrogen atom of the 6-membered ring C ′ may be further substituted with a halogen atom, an alkyl group or an alkoxy group. . ] 3. A liquid crystal composition containing at least the polymerizable compound according to claim 1. 4. A liquid crystal composition containing at least the polymerizable compound according to claim 1 and an optically active compound. 5. A liquid crystal composition containing at least the polymerizable compound according to claim 1 and a liquid crystal compound having one or two polymerizable groups in the molecule. 6. A polymer obtained by polymerizing and curing the liquid crystalline composition according to claim 3.