JP2003064032A - Polymerizable compound, liquid crystalline composition and polymer of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable compound of which polymer does not change characteristics such as an optical property on using it at a high temperature and capable of forming a film excellent in mechanical properties such as film strength and scratch resistance. SOLUTION: This polymerizable compound is expressed by the general formula (I) (wherein, P<1> to P<4> are each independently a polymerizable group, H, a halogen atom, hydroxy, -NHR<3> (R<3> is H or an alkyl) and at least one of P<1> to P<4> is a polymerizable group; L<1> to L<4> are each independently an alkylene, an alkenylene, an aralkylene or a single bond; R<1> , R<2> are each independently H, an alkyl or an aryl; X<1> , X<2> are each independently a halogen, an alkyl or an alkoxy; Z<1> , Z<2> are each independently, a single bond, -COO-, -OCO-, -CONH-, -NHCO-, -CH=CH- or -C≡C-; and (a), (b) are each 0, 1 or 2 integer).

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 being 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 the liquid crystal. 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
There is also known a method of fixing the alignment by photopolymerizing a liquid crystalline monomer or a diacrylate monomer as described in (1), 34 (1999).

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. Also, Liquid Crystals 1
988, <3>, 1047-1053 discloses a compound represented by the above general formula (I) in which all of P ^{1 to} P ⁴ are not polymerizable groups. There was a drawback.

[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 composition using the same, and a polymer thereof. That is, the present invention provides <1> a polymerizable compound represented by the following general formula (I).

[Chemical 4] [In formula (I), P ^{1 to} P ⁴ each independently represent a polymerizable group, a hydrogen atom, a halogen atom, a hydroxyl group, —NHR ³ (R ³ represents a hydrogen atom or an alkyl group), and P ^{1 to} P 4 ^At least one of ⁴ represents a polymerizable group. L ^{1 to} L ⁴ each independently represent an alkylene group, an alkenylene group, an aralkylene group, or a single bond. R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. X ¹ and X ² each independently represent a halogen atom, an alkyl group or an alkoxy group. Z ¹ and Z ² are each independently a single bond, —COO—, —O—CO—, —CONH—, —
Represents NHCO-, -CH = CH-, -C≡C-. a and b represent the integer of 0, 1, 2.

[Chemical 5] <2> The polymerizable compound according to <1>, wherein in the general formula (I), P ^{1 to} P ⁴ are all polymerizable groups. <3> The polymerizable compound according to <1> or <2>, wherein the polymerizable group is represented by the following group.

[Chemical 6] <4> A liquid crystal composition containing at least the polymerizable compound described in <1> to <3>. <5> A liquid crystal composition containing at least the polymerizable compound according to the above <1> to <3> and an optically active compound. <6> A liquid crystal composition containing at least the polymerizable compound according to the above <2> or <3> and a liquid crystal compound having one or two polymerizable groups in the molecule. <7> A polymer obtained by polymerizing and curing the liquid crystalline composition according to the above items <4> to <6>.

[0006]

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

[Chemical 7]

In the above general formula (I), P¹~ P^FourIs a husband
Independently polymerizable group, hydrogen atom, halogen atom, hydroxyl group,
-NHR³(R³Represents a hydrogen atom or an alkyl group)
Then P ¹~ P^FourAt least one of them represents a polymerizable group.

Examples of the polymerizable group represented by P ^{1 to} P ⁴ include the following polymerizable groups.

[Chemical 8] 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, a polymerizable group capable of addition polymerization is preferable, and the following polymerizable group is particularly preferable.

[Chemical 9] Further, the polymerizable groups represented by P ^{1 to} P ⁴ are preferably the same polymerizable group.

The halogen atom represented by P ^{1 to} P ⁴ is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom or a bromine atom. Represented by P ^{1 to} P ⁴ −
As NHR ³ , an amino group or an alkyl group (which may have a substituent, preferably has 1 to 20 carbon atoms,
More preferably, the carbon number is 1 to 12. ) And an amino group substituted with. Of these, an amino group is preferred.

Of the groups represented by P ^{1 to} P ⁴ above, a polymerizable group is preferable, and an acrylic acid residue and a methacrylic acid residue are particularly preferable. The number of polymerizable groups is preferably 2 or more, more preferably 3 or more, and most preferably 4 are polymerizable groups.

In the above 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 1 carbon atoms.
20 alkylene groups are preferable, and particularly 2 to 12 carbon atoms.
Is preferred. Examples of the substituent include a halogen atom, an alkoxy group, an aryl group, an alkenyl group and the like. Further, one carbon atom or two or more non-adjacent carbon atoms in the alkylene chain may be replaced with an oxygen atom or a sulfur atom. Examples of such alkylene groups include 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 has 2 to 20 carbon atoms.
Is preferred, and an alkenylene group having 2 to 12 carbon atoms is particularly preferred. Examples of the substituent include a halogen atom, an alkoxy group, an aryl group and the like. Examples of such alkenylene groups, -CH ₂ CH = C
_{HCH 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 has 8 to 30 carbon atoms.
Is preferred, and an aralkylene group having 8 to 20 carbon atoms is particularly preferred. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkenyl group and the like. Examples of such an aralkylene group include the following aralkylene groups.

[Chemical 10]

The 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), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. R
The alkyl group represented by 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 12 carbon atoms.
Examples of the substituent include a halogen atom and an alkoxy group. Examples of such an alkyl group include a methyl group, an isobutyl group, a trifluoromethyl group and the like.

The aryl group represented by R ¹ and R ² may have a substituent and is preferably an aryl group having 6 to 30 carbon atoms, and particularly an aryl group having 6 to 20 carbon atoms. Is preferred. Examples of the substituent include a halogen atom, an alkoxy group, an alkyl group and the like. Examples of such an aryl group include a phenyl group, a 4-chlorophenyl group, a 2-methylphenyl group and the like.

Among the groups represented by R ¹ and R ² above, a hydrogen atom and an alkyl group are preferable, and a hydrogen atom is particularly preferable. Further, the groups represented by R ¹ and R ² are preferably the same groups.

In the above general formula (I), X ¹ and X ² each independently represent a halogen atom, an alkyl group or an alkoxy group. The halogen atom represented by X ¹ and X 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 X ¹ and X ² may have a substituent and is preferably an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms. Is preferred. The alkoxy group represented by X ¹ and X ² may have a substituent and is preferably an alkoxy group having 1 to 12 carbon atoms, and particularly preferably an alkoxy group having 1 to 6 carbon atoms.

Among the groups represented by R ¹ and R ² as described above, a halogen atom and an alkyl group are preferable, and a halogen atom is particularly preferable. Further, the groups represented by R ¹ and R ² are preferably the same groups.

In the above general formula (I), Z ¹ and Z ² are each independently a single bond, —COO—, —O—CO—, —CON.
Represents H-, -NHCO-, -CH = CH-, -C≡C-. Z ¹ and Z ² are -COO-, -O-CO-,-
CONH- and -NHCO- are preferable, and especially -O-CO.
− Is preferable. Further, Z ¹ and Z ² are preferably the same group. In the above divalent linking group, the ring A of the general formula (I) is to be linked by the right hand bond.

In the general formula (I), a and b are 0,
Represents an integer of 1 or 2. 0 and 1 are preferred for a and b, and 0 is particularly preferred.

In the general formula (I), ring A represents a divalent aromatic ring, aliphatic ring or heterocyclic group shown below.

[Chemical 11] [In the above formula, Y ^{1 to} Y ¹⁴ represent a halogen atom, an alkyl group or an alkoxy group, and Z ^{3 to} Z ⁵ are —COO— or —O—CO.
Represents-, -CONH-, and -NHCO-. cp is 0,
Represents an integer of 1 or 2. ]

The above halogen atom, alkyl group and alkoxy group represented by Y ^{1 to} Y ¹⁴ are each represented by X ^{1 of the} general formula (I).
And X ² have the same meaning as the halogen atom, alkyl group and alkoxy group.

Examples of the divalent aromatic ring, aliphatic ring or heterocyclic group represented by ring A include the following:
The divalent aromatic ring group represented by is particularly preferable,
The divalent aromatic ring of is preferred. Z ^{3 to} Z ⁵ are -CONH
-, -NHCO- are preferable. 0 to 1 are preferable, and 0 is particularly preferable for c to p.

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

[Chemical 12] Specific examples of the polymerizable compound represented by the general formula (I) of the present invention are shown below. However, the present invention is not limited to these.

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

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

[0036]

[Chemical 20]

Further, Z ¹ and Z ^{2 in} the general formula (I) are --COO.
When-, -O-CO-, -CONH- or -NHCO- is represented, it can be produced by a method according to the following reaction formula (2).

[0038]

[Chemical 21]

In the above reaction formula (2), R represents R ¹ or R ² , X represents X ¹ or X ² , and r represents a or b. B and E represent a group which is bonded to form the group Z ¹ or Z ² . This reaction can be carried out by a usual esterification or amidation reaction.

The above compound (A) can be produced, for example, by the method according to the following reaction formula (3).

[0041]

[Chemical formula 22]

That is, it is a condensation reaction of the compound (B) and the compound (C), and is preferably carried out by the Knoevenagel reaction. The compound (B) is an aromatic aldehyde or aromatic ketone, and a commercially available product or one synthesized by a known method can be used. The compound (C) is a malonic acid ester derivative and can be obtained by the reaction of malonic acid dichloride and HO-LP.

Further, as shown in the following reaction formula (4), the compound (A) is prepared by once preparing the compound (E) from the compound (B) and the compound (D) and then introducing a polymerizable group and the like. Can be manufactured by.

[0044]

[Chemical formula 23]

In the above reaction formula (4), G and J are -L-
Represents a group in which G and P-J combine to form a group -LP; for example, when P-J represents acrylic acid, G represents a bromine atom, a chlorine atom, an iodine atom, P When -J represents acrylic acid chloride, G represents a hydroxyl group or an amino group.

In the production method according to the above reaction formulas (2) to (4), Z ¹ and Z ² are single bonds, -CH = CH-, -C≡.
Even when C- is represented, it can be similarly applied when the ring A contains Z ^{3 to} Z ⁵ .

(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.

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

The content of the liquid crystalline 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 crystalline 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 a general use as a polymerizable monomer, particularly 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.

Further, from the polymerizable compound of the present invention or a 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.

[0059]

EXAMPLES The present invention will be described in more 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 (1-2) Exemplified Compound (1-2) was synthesized according to the synthetic procedure shown below.

[0061]

[Chemical formula 26]

<Synthesis of Compound (1)> 66.3 ml of 1,4-butanediol, 12.5 g of pyridinium p-toluenesulfonate and 180 ml of THF were mixed, and 42 g of 3,4-dihydro-2H-pyran was added under ice cooling. THF 50m
1 solution was added dropwise over 30 minutes. After stirring for one and a half hours at room temperature, the mixture was poured into an aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. After concentrating the ethyl acetate layer, the residue was purified by column chromatography to give compound (1) 50.8.
g was obtained. The yield was 58%.

<Synthesis of Compound (2)> Above Compound (1) 4
9.5 g, dimethylaniline 37.6 ml and THF3
Mix 00 ml and under ice cooling, 20 g of malonic acid dichloride
30 ml of THF solution was added dropwise. After stirring at room temperature for 1 hour, ethyl acetate and aqueous sodium hydrogen carbonate solution were added to separate the layers, and the ethyl acetate layer was evaporated. The residue was purified by column chromatography, and the compound (2) which was an oily substance was purified by 3
2.4 g was obtained. (55% yield)

<Synthesis of Compound (3)> Compound (2) 3
1.5 g of piperidine was added to a mixture of 2.4 g, 9.5 g of p-hydroxybenzaldehyde and 250 ml of toluene.
1, 0.44 ml of acetic acid were added, and the mixture was refluxed for 1 and a half hours using a Dean Stark trap. The reaction mixture is concentrated,
Purification by column chromatography yielded 34.8 g of compound (3) as a yellow oil. (Yield 8
6%)

<Synthesis of Compound (4)> Compound (3) 3
4.8 g was mixed with 100 ml of DMF, 5.5 g of imidazole and 12 g of t-butyl-dimethylsilyl chloride.
Was added. After stirring for 4 hours and a half at room temperature, brine was added, and the mixture was extracted with ethyl acetate. After concentration, the residue was purified by column chromatography to give compound (4) which was a yellow oily substance to 3
2.6 g were obtained. (Yield 77%)

<Synthesis of Compound (5)> Compound (4) 3
2.6 g of ethanol was mixed with 100 ml of ethanol, 1.3 g of pyridinium p-toluenesulfonate was added, and the mixture was stirred at 60 ° C. for 4 hours. The reaction solvent was concentrated, brine was added, and the mixture was extracted with ethyl acetate. After drying over magnesium sulfate, ethyl acetate was distilled off to obtain compound (5).

<Synthesis of Compound (6)> The whole amount of the compound (5) obtained above and 15.5 ml of dimethylaniline were mixed with THF.
Mix with 100 ml, and under cooling with ice, acrylic acid chloride 1
A solution of 0.0 ml of THF in 10 ml was added dropwise. After stirring at room temperature for 1 hour, the mixture was poured into diluted hydrochloric acid, extracted with ethyl acetate, washed with diluted hydrochloric acid, an aqueous sodium hydrogen carbonate solution and brine in this order, and then the ethyl acetate layer was concentrated to obtain a compound (6).

<Synthesis of Compound (7)> The whole amount of the compound (6) obtained above was mixed with 100 ml of THF and, under ice cooling, a solution of tetrabutylammonium chloride in THF (1M).
46 ml was dropped. After stirring at room temperature for 5 hours, the mixture was poured into diluted hydrochloric acid and extracted with ethyl acetate. After distilling off ethyl acetate, the residue was purified by column chromatography to obtain 21 g of a yellow oily compound (7). The yield based on the compound (4) was 89%.

<Synthesis of Exemplified Compound (1-2)> 5 g of the above compound (7) and 0.1 g of 4-dimethylaminopyridine are added to T
After mixing with 30 ml of HF and adding 1.21 g of 4,4'-biphenylcarboxylic acid chloride, a solution of 2.26 ml of triethylamine in 5 ml of THF was added dropwise. After stirring for one and a half hours at room temperature, diluted hydrochloric acid was added, and the mixture was extracted with ethyl acetate. After concentrating ethyl acetate, the residue was purified by column chromatography, the obtained solid was dispersed in methanol, and collected by filtration to give a white solid exemplary compound (1
2.38 g of -2) was obtained. (Yield 69%)

The results of identifying the compound (1-2) obtained above are shown below. C93 ° C. (N77.3 ° C.) I. ¹ H-NMR (CDCl ₃ ): δ (TMS) 8.30 (4H, d)
7.82 (4H, d) 7.75 (2H, s) 7.55 (4H, d) 7.30 (4H, d) 6.
44-5.80 (12H, m) 4.30-4.12 (16H, m) 1.80-1.65 (16H, m)

Example 2 Synthesis of Exemplified Compound (1-7) 2.68 g of the compound (7) in Example 1
0.7 g of 6-naphthalenedicarboxylic acid chloride in THF
After mixing with 20 ml, 1.5 ml of triethylamine was added dropwise. After stirring for 1 hour at room temperature, the above <exemplified compound (1
Synthesis of -2 >> was performed to obtain 1.44 g of Exemplified compound (1-7) as a white solid. (Yield 47
%)

The results of identifying the compound (1-7) obtained above are shown below. C 55 ° C I. ¹ H-NMR (CDCl ₃ ): δ (TMS) 8.86 (2H, s)
8.30 (2H, d) 8.14 (2H, d) 7.80 (2H, s) 7.56 (4H, d) 7.
32 (4H, d) 6.45-5.80 (12H, m) 4.34-4.15 (16H, m) 1.80-
1.70 (16H, m)

Example 3 Synthesis of Exemplified Compound (1-18) In Example 2, 0.7 g of 2,6-naphthalenedicarboxylic acid chloride was changed to 0.8 g of tolan-4,4′-dicarboxylic acid chloride. The same operation as in Example 2 was carried out except that the above procedure was performed to obtain 1.15 g of the exemplary compound (1-18) in the form of a white solid. (Yield 33%)

The results of identifying the compound (1-18) obtained above are shown below. C 73 ° C N 98.6 ° C I. ¹ H-NMR (CDCl ₃ ): δ (TMS) 8.20 (4H, d)
7.75 (2H, s) 7.70 (4H, d) 7.55 (4H, d) 7.28 (4H, d) 6.
45-5.76 (12H, m) 4.35-4.12 (16H, m) 1.80-1.66 (16H, m)

[Example 4]: Liquid crystal composition The following liquid crystal composition was prepared.

[Chemical 27]

This solution was added dropwise to a glass substrate on which a polyimide alignment film LX-1400 film made by Hitachi Chemical DuPont 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 220 nm at a wavelength of 550 nm.

[Example 5]: Cholesteric liquid crystal composition A coating solution for a photosensitive resin layer prepared according to the following formulation was applied on the orientation film of the above-mentioned glass substrate with an orientation film by a spin coater, and then 100 A photosensitive resin layer was formed by drying in an oven at ℃ for 2 minutes.

[0078]

[Chemical 28]

Next, when the photosensitive resin layer was developed by holding it on a hot plate at 100 ° C. for 5 minutes so that the surface of the glass substrate was in contact with it, 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 3H when measured by the method of K5401. On the other hand, the compound (Z) without using the exemplified compound (1-18)
The scratch hardness in this case was 1H, and it was found that the scratch hardness was improved by the coexistence of the polymerizable compound of the present invention. Further, the hardness of the polymer film was measured using "Micro Surface Material Property Evaluation System MZT-3" manufactured by Akashi Co., Ltd., and the hardness value was 65. on the other hand,
The hardness value of the compound (Z) alone without using the exemplified compound (1-18) was 50, and it was found that the hardness (hardness) of the polymer was improved by the coexistence of the polymerizable compound of the present invention. It was

[0081]

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) G02F 1/13 500 G02F 1/13 500 G03F 7/027 502 G03F 7/027 502 (72) Inventor Keiichiro Hayashi Fujinomiya City, Fujinomiya-shi, 200, F-Term, Fuji Photo Film Co., Ltd. (Reference) 2H025 AB14 BC13 BC44 BC83 4H006 AA01 AA03 AB64 BJ50 BM30 BM73 BT22 BV74 KC30 4H027 BA02 BA11 BD02 BD07 BD14 4J100 AL71 AL74 AL75 AM54 BA02 BC43 BC43

Claims (7)

[Claims] 1. A polymerizable compound represented by the following general formula (I). [Chemical 1] [In formula (I), P ^{1 to} P ⁴ each independently represent a polymerizable group, a hydrogen atom, a halogen atom, a hydroxyl group, —NHR ³ (R ³ represents a hydrogen atom or an alkyl group), and P ^{1 to} P 4 ^At least one of ⁴ represents a polymerizable group. L ^{1 to} L ⁴ each independently represent an alkylene group, an alkenylene group, an aralkylene group, or a single bond. R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. X ¹ and X ² each independently represent a halogen atom, an alkyl group or an alkoxy group. Z ¹ and Z ² are each independently a single bond, —COO—, —O—CO—, —CONH—, —
Represents NHCO-, -CH = CH-, -C≡C-. a and b represent the integer of 0, 1, 2. [Chemical 2] 2. The polymerizable compound according to claim 1, wherein in the general formula (I), P ^{1 to} P ⁴ are all polymerizable groups. 3. The polymerizable compound according to claim 1 or 2, wherein the polymerizable group is represented by the following group. [Chemical 3] 4. A liquid crystal composition containing at least the polymerizable compound according to claim 1. 5. A liquid crystal composition containing at least the polymerizable compound according to claim 1 and an optically active compound. 6. A liquid crystal composition containing at least the polymerizable compound according to claim 2 or 3 and a liquid crystal compound having one or two polymerizable groups in the molecule. 7. A polymer obtained by polymerizing and curing the liquid crystalline composition according to claim 4.