JP4792881B2 - Polymerizable dibenzofuran derivative and polymerizable liquid crystal composition containing the same - Google Patents

Description

  The present invention relates to a compound having a dibenzofuran skeleton, a composition containing the compound, a polymer obtained from the composition, its use, and the like.

When a polymerizable compound has liquid crystallinity, it is known that a polymer having optical anisotropy can be obtained by polymerizing this compound (see Patent Document 1). This is because the orientation of liquid crystal molecules is fixed by polymerization. Therefore, in recent years, such polymerizable liquid crystalline compounds have been used for molded articles having optical anisotropy such as polarizing plates and retardation plates.

As the polymerizable liquid crystalline compound, a liquid crystal compound having —OCOCH═CH ₂ is generally used because of high polymerization reactivity and high transparency of the resulting polymer (see Patent Document 2). ). Further, a liquid crystal compound having a fluorene ring in a skeleton structure is known as a liquid crystal compound that is polymerized at room temperature by irradiation with ultraviolet rays (see Patent Document 3).
JP 2001-055573 A JP 2001-154019 A JP-A-2005-060373

  An object of the present invention is to provide a novel compound having polymerizability and liquid crystallinity. Aspects of this problem include a plurality of properties such as polymerizability at room temperature, photopolymerization, solubility, colorlessness, chemical stability, compatibility with other polymerizable liquid crystal compounds, and wettability to a supporting substrate. It is to provide a polymerizable liquid crystal compound having excellent characteristics and a polymerizable liquid crystal compound having an appropriate balance regarding a plurality of characteristics.

  The subject of the present invention is a polymerizable liquid crystal composition containing such a polymerizable liquid crystal compound and, if necessary, another polymerizable liquid crystal compound, a polymer obtained from the composition, Another object of the present invention is to provide a polymer having an orientation such as homogeneous, homeotropic, hybrid, etc. and having few orientation defects and its use. Aspects of this problem are excellent in multiple characteristics such as colorless transparency, low photoelasticity (small change in refractive index even when bent), adhesion to support substrate, hardness, heat resistance and weather resistance. It is to provide an optically anisotropic film and its use.

  Since the liquid crystal compound containing a dibenzofuran skeleton has an oxygen atom in the condensed ring of the fluorene skeleton, it is expected to improve refractive index anisotropy and heat resistance. Therefore, the present inventors conducted research based on this idea, and obtained better experimental results than expected. Based on these results, the present invention including the following items was completed through repeated studies.

  [1] A compound represented by the following formula (1).

In formula (1), A is independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, Biphenyl-4,4′-diyl, terphenyl-4,4 ″ -diyl, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl, and any hydrogen in the 1,4-phenylene is Chlorine or fluorine may be substituted, and any one or two hydrogens are replaced with cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl or trifluoromethyl Z is independently a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, —OCH _2. —, —CF ₂ O—, —OCF ₂ —, —COO—, —OCO—, —CONH—, —NHCO—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) _2- , -CH = CH-COO- or -OCO-CH = CH-; P is a polymerizable group independently represented by any of the following formulas (P1) to (P8) Q is independently —O—, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O—, — (CH ₂ ) _r —, —O— (CH ₂ ) _r —O—; Or —O— (CH ₂ CH ₂ O) _s —, r is an integer of 1-20, s is an integer of 2-5; x is 0, 1 or 2.

[2] In the formula (1), A is independently 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in the 1,4-phenylene is replaced by chlorine or fluorine. And any one or two hydrogens may be replaced by methyl or trifluoromethyl; Z is independently —CH ₂ O—, —OCH ₂ —, —COO—, — OCO—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO— or —OCO—CH═CH—; and P independently represents the above formula (P1) To (P8); Q is independently —O—, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O—, — (CH ₂ ) _r— or —O— (CH ₂ ) _r —O—, r is an integer from 1 to 15; Or the compound according to [1] above, which is 2.

[3] In the formula (1), A is independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in the 1,4-phenylene are chlorine. Or may be replaced by fluorine; Z is independently —COO—, —OCO—, — (CH
_{2) 2 COO -, - OCO} (CH 2) 2 -, - CH = CH-COO- or -OCO-CH = CH- and is; P is, independently above formula (P1), (P5), ( P6) or (P7) located with a polymerizable group represented by; Q is independently _{-O -, - O- (CH 2} ) r -, - (CH 2) r -O -, - (CH 2 ) _R — or —O— (CH ₂ ) _r —O—, wherein r is an integer of 1 to 15; and x is 1, the compound according to [1] above.

  [4] A compound represented by any one of the following formulas (1-1) to (1-9).

In the above formulas (1-1) to (1-9), Z is independently —COO—, —OCO—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═. CH—COO— or —OCO—CH═CH—; r is independently an integer from 1 to 10; R ¹ , R ² , R ³ and R ⁴ are each hydrogen or fluorine; R ⁵ is hydrogen or methyl.

  [5] The following formulas (1-1-1), (1-1-2), (1-1-3), (1-6-1), (1-6-2), (1-6) 3) A compound represented by (1-7-1), (1-8-1), (1-8-2), (1-9-1) or (1-9-2).

In the above formula, r is an integer of 1 to 10, and R ¹ , R ² , R ³ and R ⁴ are each hydrogen or fluorine.
[6] It is represented by the formula (1-1-1) described in [5], in which R ¹ , R ² , R ³ and R ⁴ are hydrogen, and r is an integer of 2 to 10. A compound characterized by being.

[7] Represented by the formula (1-1-1) described in [5] above, in which R ¹ and R ⁴ are hydrogen, R ² and R ³ are fluorine, and r is 2 to 2 A compound characterized by being an integer of 10.
[8] It is represented by the formula (1-6-1) described in [5], wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen, and r is an integer of 2 to 10. A compound characterized by being.
[9] A polymerizable liquid crystal composition comprising at least one compound according to any one of [1] to [8].

  [10] As the first component, from the group consisting of compounds represented by formula (1-1-1), formula (1-1-2) and formula (1-1-3) according to [5] above And at least one compound selected from the group consisting of compounds represented by the following formulas (M1a) and (M1b) as the second component, and the first component and the second component A polymerizable liquid crystal composition, wherein the content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to the total amount of 100% by weight.

In formulas (M1a) and (M1b), R ⁶ is independently hydrogen, fluorine, trifluoromethyl or methyl; R ⁷ is cyano, trifluoromethoxy, alkyl having 1 to 15 carbons or 1 carbon. It is 15 alkoxy; W ¹ and W ² are independently hydrogen, chlorine or fluorine, W ³ is hydrogen or fluorine; Z ² is a single bond, -COO -, - CH = CH- COO— or —CH ₂ CH ₂ —COO—; A ² represents the following formulas (A-1) to (
A-7) is a group represented by any one of the formulas; m is an integer of 2-8.

  [11] As a first component, from the group consisting of compounds represented by formula (1-1-1), formula (1-1-2) and formula (1-1-3) according to [5] above And (ii) at least one compound represented by the formula (M1a) described in the above [10], and (ii) a formula (described in the above [10]). At least one compound represented by M1b), the content of the first component is 20 to 80% by weight relative to 100% by weight of the total amount of the first component and the second component, and the second component ( A polymerizable liquid crystal composition, wherein the content of i) is 10 to 40% by weight and the content of the second component (ii) is 10 to 40% by weight.

  [12] As the first component, the formula (1-6-1), the formula (1-6-2), the formula (1-6-3) and the formula (1-7-1) described in the above [5] And at least one compound selected from the group consisting of compounds represented by the following formula (M2a), formula (M2b) and formula (M2c) as the second component. Containing one compound, the content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to the total amount of 100% by weight of the first component and the second component A polymerizable liquid crystal composition characterized by the above.

In formulas (M2a) to (M2c), R ⁸ is cyano, fluorine, trifluoromethyl or methyl; W ¹ and W ² are independently hydrogen, chlorine or fluorine, and W ³ is hydrogen or fluorine. Z ² is a single bond, —COO—, —CH═CH—COO— or —CH ₂ CH ₂ —COO—; Z ³ is independently a single bond or —O—; A ² is the above [10
] Is a group represented by any one of formulas (A-1) to (A-7) according to formula; m is an integer of 2 to 8.

  [13] As the first component, the formula (1-6-1), the formula (1-6-2), the formula (1-6-3) and the formula (1-7-1) described in the above [5] And (ii) at least one compound represented by the formula (M2b) according to the above [12], and (ii) And at least one compound represented by the formula (M2c) described in [12] above, wherein the content of the first component is 20 to 80 with respect to 100% by weight of the total amount of the first component and the second component. A polymerizable liquid crystal composition, wherein the content of the second component (i) is 10 to 40% by weight and the content of the second component (ii) is 10 to 40% by weight. .

  [14] As the first component, the formula (1-8-1), the formula (1-8-2), the formula (1-9-1) and the formula (1-9-2) according to the above [5] And at least one compound selected from the group consisting of the compounds represented by the following formulas (M3a) and (M3b) as the second component. The content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to 100% by weight of the total amount of the first component and the second component. A polymerizable liquid crystal composition.

In formulas (M3a) and (M3b), R ⁸ is cyano, fluorine, trifluoromethyl or methyl; R ⁹ is methyl or ethyl; W ¹ and W ² are independently hydrogen, chlorine or fluorine And W ³ is hydrogen or fluorine; Z ² is a single bond, —COO—, —CH═CH—COO— or —CH ₂ CH ₂ —COO—, and A ² is the above-mentioned [10] Or a group represented by any one of formulas (A-1) to (A-7) described above; m is an integer of 2 to 8.

  [15] As the first component, the formula (1-8-1), the formula (1-8-2), the formula (1-9-1) and the formula (1-9-2) according to the above [5] And (ii) at least one compound represented by the formula (M3a) according to the above [14], and (ii) And at least one compound represented by the formula (M3b) described in [14] above, wherein the content of the first component is 20 to 80 with respect to 100% by weight of the total amount of the first component and the second component. A polymerizable liquid crystal composition, wherein the content of the second component (i) is 10 to 40% by weight and the content of the second component (ii) is 10 to 40% by weight. .

[16] The polymerizable liquid crystal composition according to any one of [9] to [15], further including a polymerization initiator.
[17] The polymerizable liquid crystal composition according to any one of [9] to [16], further including a solvent.
[18] A polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of [9] to [17].
[19] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [9] to [17].
[20] A retardation film comprising the optically anisotropic film according to [19].
[21] A liquid crystal display device having the optically anisotropic film according to [19].

  According to the present invention, in properties such as polymerizability at room temperature, photopolymerizability, solubility, colorlessness, chemical stability, compatibility with other polymerizable liquid crystal compounds, and wettability with respect to a supporting substrate, a plurality of Provided is a novel polymerizable liquid crystal compound satisfying properties in a well-balanced manner.

  Moreover, according to the present invention, a polymerizable liquid crystal composition containing such a polymerizable liquid crystal compound and, if necessary, another polymerizable liquid crystal compound, a polymer obtained from the composition, A polymer having an orientation such as homogeneous, homeotropic, hybrid, etc. and having few orientation defects and use thereof are provided.

  An optically anisotropic film made of such a polymer satisfies a plurality of properties in a well-balanced manner in properties such as colorless transparency, low photoelasticity, adhesion to a supporting substrate, hardness, heat resistance, and weather resistance. It can use suitably for a use.

Hereinafter, the compound (polymerizable dibenzofuran derivative) according to the present invention, a polymerizable liquid crystal composition containing the compound, a polymer comprising the composition, and uses thereof will be described in detail.
The terminology used in this specification is as follows. “Liquid crystal (or property) compound” is a generic term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. The “liquid crystal phase” is a nematic phase, a smectic phase, a cholesteric phase, etc., and often means a nematic phase. “Polymerization” means the ability of a monomer to polymerize by means of light, heat, catalyst, etc. to give a polymer. A compound represented by the formula (1), the formula (M1a), or the like may be expressed as “compound (1)”, “compound (M1a)”, or the like.

In the above formula (1), symbols such as A, P, Q, and Z are used. For example, in the formula (1),-(AZ) _x -and -ZA- The meaning of the symbol A may be the same or different. -(A-Z) _x -in formula (1) is when X is 2,
In this case, the meanings of the two symbols A may be the same or different. Such a rule also applies to other symbols such as symbols P, Q, and Z.

First, the compound (1) of this invention is demonstrated.
The compound (1) of the present invention has a dibenzofuran skeleton as shown in the above formula (1). Such a compound having a dibenzofuran ring is expected to have high refractive index anisotropy and high heat resistance since an oxygen atom is present in the ring.

In the above formula (1), A is independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl. , Biphenyl-4,4′-diyl, terphenyl-4,4 ″ -diyl, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl, wherein any hydrogen in the 1,4-phenylene is Any one or two hydrogens can be replaced by cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl or trifluoromethyl. It may be replaced.

  Preferred A is 1,4-cyclohexylene and 1,4-phenylene, and any hydrogen in the 1,4-phenylene may be replaced by chlorine or fluorine, and any one or two One hydrogen may be replaced with methyl or trifluoromethyl.

  More preferable A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-chloro-1,4-phenylene, 2-methyl-1,4-phenylene, 2 -Trifluoromethyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene and 2,6-difluoro-1,4-phenylene. Note that 3-fluoro-1,4-phenylene and the like are not described because they are the same as 2-fluoro-1,4-phenylene and the like.

Particularly preferred A is 1,4-cyclohexylene, 1,4-phenylene and 2-fluoro-1,4-phenylene.
Z is independently a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—.
_{, -OCH 2 -, - CF 2} O -, - OCF 2 -, - COO -, - OCO -, - CONH-,
_{-NHCO -, - (CH 2)} 4 -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - CH = CH-COO- or -OCO-CH = CH- is.

Preferred Z is —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO— and —. OCO-CH = CH-. Further preferred Z is —COO—, —OCO—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO— and —OCO—CH═CH—. Particularly preferred Z is —COO— or —OCO—.

  P is a polymerizable group independently represented by any of the above formulas (P1) to (P8). The names of these groups are acryloyl, methacryloyl, α-trifluoromethacryloyl, α-fluoroacryloyl, 3-ethyl-3-oxetanylmethyl, 3-methyl-3-oxetanylmethyl, 2-oxiranylmethyl and vinyl, respectively. is there.

P is a monovalent group and is bonded to oxygen of Q (excluding — (CH ₂ ) _r —). Only the group (P7) may be bonded to carbon of —O— (CH ₂ ) _r — or — (CH ₂ ) _r —O—. Therefore, the compound having groups (P1) to (P4) is an acrylate or a substituted acrylate.

  Preferred P is the group (P1) among the groups (P1) to (P4) and the groups (P5), (P6) and (P7) among the groups (P5) to (P8). Further, from the viewpoint that the compound (1) can be easily synthesized, it is more preferable that the left and right Ps in the formula (1) are the same.

Q is independently —O—, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O—, — (CH ₂ ) _r —, —O— (CH ₂ ) _r —O— or _{-O- (CH 2 CH 2 O)} s - a and, r is an integer from 1 to 20, s is an integer from 2 to 5.

The oxygen of Q (excluding — (CH ₂ ) _r —) is bonded to the carbon of P. However, as described above, when P is a group (P-7), the carbon of —O— (CH ₂ ) _r — or — (CH ₂ ) _r —O— is bonded to the carbon of P. Also good. When P is a group (P-1) to (P-6) or (P-8), the carbon of P is —O— (CH ₂ ) _r — or — (CH ₂ ) _r —O. It does not bind to the carbon of-.

Preferred Q is —O—, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O— and —O— (CH ₂ ) _r —O—, wherein r is an integer of 1 to 15. is there. More desirable Q is —O— and —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 10.

x is 0, 1 or 2; Preferred x is 1 or 2. Further preferred x is 1.
Preferable examples of the compound (1) of the present invention include compounds represented by the above formulas (1-1) to (1-9).

  The compound (1) of the present invention is symmetric when x is 1 and the meanings of the left and right symbols P, Q, A, and Z are the same in the above formula (1). Symmetric compounds are preferred in that they are cheaper or easier to synthesize than asymmetric compounds. On the other hand, an asymmetric compound is preferable in that the alignment of liquid crystal molecules can be controlled in a wide range as compared with a symmetric compound.

  Since the compound (1) of the present invention has two polymerizable groups, a three-dimensional structure is formed by polymerization to give a hard polymer. Therefore, the compound (1) of this invention is preferable at the point which provides high hardness to a polymer.

  The compound (1) is polymerized at room temperature, easily photopolymerized with a small amount of UV light in the presence of a suitable photopolymerization initiator, chemically stable, colorless, and easily soluble in a solvent. It has characteristics such as good compatibility with other polymerizable compounds and good adhesion to the support substrate.

  Since the compound (1) is easily wetted with respect to the support substrate, a uniform paint film can be obtained. Moreover, since compound (1) is chemically stable, it is excellent in storage stability in a cool and dark place. Furthermore, since the compound (1) has a wide liquid crystal temperature range and good compatibility with other compounds, it is easy to prepare a polymerizable liquid crystal composition. In addition, the characteristic of the said compound (1) is reflected in the characteristic of the composition containing this compound, and the characteristic of this composition is reflected in the characteristic of the polymer obtained.

  The compound (1) is mixed with various polymerizable liquid crystal compounds to give a uniform composition. At this time, the compound (1) can control the alignment of the liquid crystal molecules. This orientation is maintained by polymerization. Therefore, it is possible to obtain a polymer in which the orientation of liquid crystal molecules is controlled by copolymerizing the compound (1) with a polymerizable liquid crystal compound.

  Moreover, if the composition containing the said compound (1) is made into a thin film and is polymerized, the polymer film which has optical anisotropy can be obtained. The compound (1) is particularly useful in that it has an effect of controlling the alignment of liquid crystal molecules. A polymer film having an orientation such as homogeneous, tilt, hybrid, and homeotropic has an effect such as optical compensation.

Next, the polymerizable liquid crystal composition of the present invention will be described.
The polymerizable liquid crystal composition of the present invention contains at least one compound (1). The composition usually means a mixture of a plurality of compounds, but may be referred to as a composition even when it is composed of one polymerizable compound. This is because a polymerization catalyst or the like may be added for polymerization, or diluted with a solvent to form a thin film. The polymerizable liquid crystal composition of the present invention is
A composition containing a plurality of compounds (1) as the first component, or a polymerizable liquid crystal compound other than the compound (1) as the second component, and other polymerizable compounds and additives, etc. It may contain.

The composition of the present invention contains at least one compound (1) as the first component. A preferred first component is at least one compound represented by the above formulas (1-1-1), (1-1-2) and (1-1-3) and having —OCOCH═CH ₂ , (1-6-1), (
1-6-2), (1-6-3) and (1-7-1) represented by at least one compound having an oxetane ring, or the above formulas (1-8-1), (1 -8-2), (1-9-1) and (1-9-2), which are at least one of compounds having an oxirane ring.

The composition of the present invention may contain a polymerizable liquid crystal compound as the second component. A preferred second component is represented by the above formulas (M1a) and (M1b), and at least one of the compounds having —OCOC (R ⁶ ) ═CH ₂ , the above formulas (M2a), (M2b) and (M2c) And at least one of compounds having an oxirane ring, or at least one of compounds having the oxetane ring represented by the above formulas (M3a) and (M3b).

Table 1 shows preferable combinations of the first component and the second component. Table In combination 1 in 1, the first and second components both have a -OCOC (R) = CH _2, in combination 2
3 and 3 are common in that one of the first component and the second component has an oxetane ring and the other has an oxirane ring. Further preferred combinations are shown in Table 2.

  The first component is suitable for adjusting characteristics such as the temperature range of the liquid crystal phase in the composition, the film-forming property of the polymer, the mechanical strength, and the adhesion to the support substrate. On the other hand, the second component is useful for controlling properties such as viscosity, orientation, and coatability of the composition.

  In the composition containing the first component and the second component, the content of the first component is preferably 20 to 80% by weight, more preferably 100 to 80% by weight of the total amount of the first and second components. Preferably it is 40 to 80% by weight, and the content of the second component is preferably 20 to 80% by weight, more preferably 20 to 60% by weight.

  Moreover, when using 2 types of compounds as a 2nd component like the preferable combinations 2, 5, 8, etc. of the said Table 2, in the preferable combination 2, for example, compound (M1a) is 10 to 40 weight%, more It is desirable to contain 10 to 30% by weight and compound (M1b) in the range of 10 to 40% by weight, more preferably 10 to 30% by weight.

  By containing the first component and the second component in the above ranges, the temperature range showing the liquid crystal phase of the composition, the viscosity, the orientation, the coating property, the film forming property of the resulting polymer, the mechanical strength, the support Excellent balance such as adhesion to the substrate.

  Among the compounds (M1a) and (M1b), compounds represented by the following formulas (M1a-1), (M1a-2) and (M1b-1) are particularly preferable. In the following formula, m is an integer of 2 to 8.

  Among the compounds (M2a), (M2b), and (M2c), compounds represented by the following formulas (M2a-1) and (M2b) are particularly preferable. In the following formula, m is an integer of 2 to 8.

Among the compounds (M3a) and (M3b), compounds represented by the following formulas (M3a-1) and (M3b-1) are particularly preferable. In the following formula, W ³ is hydrogen or fluorine, and m is an integer of 2 to 8.

  Particularly preferred compositions in the present invention are shown in Table 3. The composition shown in Table 3 has an advantage that it can be made in a homogeneous orientation, a homeotropic orientation, or a hybrid orientation depending on conditions.

The properties of the preferred composition shown in Table 3 will be described.
1) Homogeneously oriented compositions (A1-1) and (A1-2)
To the composition (A1-1) or (A1-2), 1 to 15% by weight of a photo-radical polymerization catalyst is added to the total weight of the first component and the second component, and this is rubbed and transparent. When applied to a support substrate, the liquid crystal molecules in the composition exhibit homogeneous alignment. As the support substrate, a saponified triacetyl cellulose film or a hydrophilized norbornene resin film can be used. The hydrophilic treatment can be performed by corona treatment or plasma treatment. By irradiating the thus oriented composition with ultraviolet rays in a nitrogen atmosphere, a polymer in which the orientation is maintained can be easily obtained.

2) Homeotropically oriented compositions (A1-1) and (A1-2)
In the composition (A1-1) or (A1-2), 1 to 10% by weight of aminopropyltriethoxysilane is added to the total weight of the first component and the second component, and this is rubbed. When applied to the above support substrate, the liquid crystal molecules in the composition exhibit homeotropic alignment. This orientation is maintained after polymerization as in 1) above.

3) A homogeneously oriented composition (A2-1)
In the composition (A2-1), 1 to 15% by weight of a photocationic polymerization catalyst based on the total weight of the first component and the second component is added to the composition, and this is applied to the rubbing-treated support substrate. Then, the liquid crystal molecules in the composition are homogeneous. By irradiating the thus oriented composition with ultraviolet rays, a polymer in which the orientation is maintained can be easily obtained. The polymerization reaction can be performed in air.

4) Composition with hybrid orientation (A3-1)
In the composition (A3-1), 1 to 15% by weight of a photocationic polymerization catalyst based on the total weight of the first component and the second component is added to the composition, and this is applied to the rubbing-treated support substrate. Then, the liquid crystal molecules in the composition exhibit a hybrid alignment. By irradiating the thus oriented composition with ultraviolet rays, a polymer in which the orientation is maintained can be easily obtained. The polymerization reaction can be performed in air.

The composition of the present invention may further contain other polymerizable compounds and additives as necessary, and may contain a solvent for diluting the composition. Examples of the additive for adjusting the physical properties of the polymer include a silane coupling agent, a surfactant, an antioxidant, an ultraviolet absorber, and fine particles. Examples of the additive for polymerizing the monomer include a polymerization initiator (for example, a photo radical polymerization initiator and a photo cationic polymerization initiator), a photosensitizer, and the like.

  In the composition of the present invention, the content of the other polymerizable compound (non-liquid crystalline polymerizable compound) is preferably less than 20% by weight based on the total amount of the first component and the second component. Preferably it is less than 10% by weight. Examples of non-liquid crystalline polymerizable compounds that can be used in the composition of the present invention are shown below.

The first example is a compound suitable for radical polymerization. Examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl acrylate, vinyl chloride, Vinyl fluoride, vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, 2-ethyl 2-methylbutanoic acid vinyl, N-vinylacetamide, p-t-butylvinylbenzoate, N, N-dimethylaminovinylbenzoate, vinylbenzoate, styrene, o-, m- or p-chloromethylstyrene, α -Methylstyrene, tetrafluoroethylene, hex Such as fluoro-propene, and the like. These compounds are suitable for adjusting the viscosity of the composition. These compounds are suitable for compositions based on compounds having a -OCOCH = CH _2.

  The second example is a polyfunctional acrylate suitable for radical polymerization. Preferred polyfunctional acrylates include, for example, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene Glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO addition triacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, bisphenol A EO addition diacrylate, bisphenol A glycidyl diacrylate (Osaka Organic Chemical Co., Ltd. “Biscoat 700”), polyethylene glycol di Acrylate and the like. These compounds are suitable for further enhancing the film-forming ability of the polymer.

  The third example is a polymerizable compound suitable for cationic polymerization. Examples of such compounds include ethyl vinyl ether, hydroxybutyl monovinyl ether, t-amyl vinyl ether, cyclohexanedimethanol methyl vinyl ether, 3-ethyl-3-hydroxymethyl oxetane, 3-methyl-3-hydroxymethyl oxetane, di ( 3-ethyl-oxeta-3-ylmethyl), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and the like. These compounds are suitable for adjusting the viscosity of the composition. Moreover, these compounds are suitable for the composition which has as a main component the compound which has an oxetane ring or an oxirane ring.

Next, the example of the additive which can be added to the composition of this invention is shown below.
Examples of the silane coupling agent include vinyl trialkoxysilane, 3-aminopropyltrialkoxysilane, N (2-aminoethyl) 3aminopropyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3- Examples include chlorotrialkoxysilane and 3-methacryloxypropyltrialkoxysilane. In these compounds, dialkoxymethylsilane in which one of alkoxy groups (three) is replaced with methyl is also included. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

  Examples of the surfactant include quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl Examples thereof include substituted aromatic sulfonates, alkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl trimethyl ammonium salts. The surfactant has effects such as facilitating application of the composition to a support substrate or the like. The addition amount of the surfactant varies depending on the kind of the surfactant, the composition ratio of the composition, etc., but is 100 ppm to 5% by weight based on the total amount of the first component and the second component used as necessary. More preferably, it is in the range of 0.1 to 1% by weight.

  Examples of the antioxidant include hydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, triphenyl phosphite, and trialkyl phosphite. Examples of commercially available products include “Irganox 245, Irganox 1035” manufactured by Ciba Specialties.

  Examples of the ultraviolet absorber include “TINUVIN PS, TINUVIN 292, TINUVIN 109, TINUVIN 328, TINUVIN 384-2, TINUVIN 123, TINUVIN 400, and TINUVIN 400L” manufactured by Ciba Specialty Chemicals.

  Examples of the material of the fine particles include inorganic substances, organic substances, metals, and the like. The particle diameter of the fine particles is 0.001 to 0.1 μm, more preferably 0.001 to 0.05 μm. Depending on the material, the fine particles preferably have a small particle size in order to prevent the agglomeration phenomenon, and a sharp particle size distribution is preferred. Such fine particles are useful when adjusting the optical anisotropy or increasing the strength of the polymer. The addition amount of the fine particles is 0.1 to 30% by weight with respect to the total amount of the first component and the second component used as necessary, and a small proportion is preferable as long as the purpose of addition is achieved.

Examples of the inorganic substance include ceramics, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, saponite, stevensite, montmorillonite, beidellite, kaolinite, frypontite, ZnO, TiO ₂ , _{CeO 2, Al 2 O 3,} Fe 2 O 3, ZrO 2, MgF 2, SiO 2, S
rCO ₃ , Ba (OH) ₂ , Ca (OH) ₂ , Ga (OH) ₃ , Al (OH) ₃ , Mg (OH
) ₂ , Zr (OH) _{4 and the} like. Fine particles such as calcium carbonate needle-like crystals have optical anisotropy. Such fine particles can adjust the optical anisotropy of the polymer. Examples of the organic substance include carbon nanotubes, fullerenes, dendrimers, polyvinyl alcohol, polymethacrylates, and polyimides.

The photo radical polymerization initiator may be a general-purpose product. Examples of such general-purpose initiators include DAROCUR1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one), IRGACURE184 (from Ciba Specialty Chemicals). 1-hydroxycyclohexyl phenyl ketone), IRGACURE651 (2,2-dimethoxy-1,2-diphenylethane-1-one), IRGACURE500, IRGACURE2959, IRGACURE907, IRGACURE369, IRGACURE1300, IRGACURE819, IRGACURE4URU, IRGACURE1UUR Is mentioned. Such an initiator is suitable for a composition based on a compound having —OCOCH═CH ₂ .

  Examples of other radical photopolymerization initiators include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadi. Azole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one , Benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanol Such as amine mixtures. It is.

  Examples of the photocationic polymerization initiator include diaryliodonium salts and triarylsulfonium salts. Such an initiator is suitable for a composition mainly composed of a compound having an oxetane ring or an oxirane ring.

  Examples of commercially available photo-cationic polymerization initiators include “DTS-102” manufactured by Midori Chemical Co., Ltd., “Syracure UVI-6990, Syracure UVI-6974, Syracure UVI-6922” manufactured by UCC, Asahi Denka ( "Adekaoptomer SP-150, SP-152, SP-170, SP-172", Rhodia "PHOTOINITITOR 2074", Ciba Specialty "IRGACURE250", GE Silicones "UV-9380C", etc. Is mentioned.

  Next, examples of the solvent that can be used in the composition of the present invention include benzene, toluene, xylene, mesitylene, butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, and diethylene glycol. Dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone, 2-pyrrolidone, N -Methyl-2-pyrrolidone, dimethylformamide, chloroform, dichloromethane, carbon tetrachloride, Examples include chloroethane, tetrachloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, and butyl cellosolve. . The said solvent may be used individually by 1 type, or may mix and use 2 or more types.

Next, the polymer of the present invention will be described.
The polymer of the present invention is obtained by polymerizing the above composition, and has a plurality of characteristics such as colorless transparency, photoelasticity, adhesion to a support substrate, hardness, heat resistance, weather resistance and the like. Satisfy balance. The polymer of the present invention is also excellent in properties such as impact resistance, workability, electrical properties, and solvent resistance. Important properties for the polymer film are high adhesion to the support substrate, sufficient hardness, high heat resistance, and the like.

The type of the polymerization reaction is radical polymerization, anion polymerization, cationic polymerization, coordination polymerization, living polymerization, and the like, and can be appropriately selected depending on the type of polymerizable group possessed by the polymerizable compound constituting the composition. For example, when the polymerizable group of the compound (1) is (P1), (P2), (P3) or (P4), the preferred reaction is radical polymerization, and the polymerizable group is (P5), (P6), In the case of (P7) or (P8), the preferred reaction is cationic polymerization. When obtaining a polymer with excellent orientation, polymerization using a photopolymerization catalyst is preferable to thermal polymerization. This is because it is easy to perform polymerization under the condition that the composition exhibits a liquid crystal phase.

  Preferred types of light used for photopolymerization are ultraviolet rays, visible rays, infrared rays, and the like, and electromagnetic waves such as electron beams and X-rays may be used. Usually, ultraviolet rays or visible rays are used. The wavelength range is 150 to 500 nm, preferably 250 to 450 nm, particularly preferably 300 to 400 nm. Light sources include low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short arc discharge lamps (super-high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. Among them, an ultrahigh pressure mercury lamp is preferable.

The light from the light source may be irradiated to the composition as it is, or the composition may be irradiated with a specific wavelength (or a specific wavelength region) selected by a filter. Irradiation energy density 2~5000mJ / cm ^2, preferably in the range 10~3000mJ / cm ^2, particularly preferably of 100 to 2000 mJ / cm ^2. The illuminance is in the range of 0.1 to 5000 mW / cm ² , preferably 1 to 2000 mW / cm ² .

  The temperature for light irradiation may be set so that the composition has a liquid crystal phase, but is preferably 100 ° C. or lower. When the temperature exceeds 100 ° C., polymerization due to heat may occur, and good alignment may not be obtained.

  The shape of the polymer is a film or a plate. The polymer may be molded. In order to obtain a film-like polymer, a support substrate is generally used. A film having optical anisotropy is obtained by applying the composition onto a support substrate and polymerizing a paint film having a liquid crystal phase. The preferred polymer thickness varies depending on the value of the optical anisotropy of the polymer and the application, and therefore the range cannot be determined strictly. For example, the thickness is 0.05 to 50 μm, preferably 0. It is 1-20 micrometers, More preferably, it is the range of 0.5-10 micrometers. The haze value (haze value) of such a film-like polymer is usually 1.5% or less, and the transmittance is usually 80% or more in the visible light region. Therefore, the film polymer is suitable as an optically anisotropic thin film used for a liquid crystal display element.

  As the support substrate, a uniaxially stretched film or a biaxially stretched film can be used. Examples of the material for such a support substrate include triacetyl cellulose, polyvinyl alcohol, polyimide, polyester, polyarylate, polyether imide, polyethylene terephthalate, and polyethylene naphthalate. Examples of commercially available products include “Arton” manufactured by JSR Corporation, “Zeonex” manufactured by Nippon Zeon Co., Ltd., “Zeonor”, “Appel” manufactured by Mitsui Chemicals, Inc., and the like. A preferred support substrate is a triacetyl cellulose (TAC) film. The TAC film may be used as it is without being pretreated, and may be subjected to surface treatment such as saponification treatment, corona discharge treatment, UV-ozone treatment as necessary. As another supporting substrate other than the above, for example, a supporting substrate made of metal such as aluminum, iron or copper, or a supporting substrate made of glass such as alkali glass, borosilicate glass or flint glass may be used.

  The coating film may be formed by directly applying the composition of the present invention on a supporting substrate, or may be formed by dissolving the composition in a suitable solvent and then removing the solvent. Examples of the coating method include spin coating, roll coating, caten coating, flow coating, printing, micro gravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating, and cast film formation.

Factors that determine the alignment of the liquid crystal composition include (1) the chemical structure of the compound constituting the composition, (2) the type of the support substrate, and (3) the method of alignment treatment. The factor (1) depends on the types of the compound (1), polymerizable liquid crystal compound, silane coupling agent and the like. The factor (2) depends on the material of the support substrate such as a polymer, glass, metal or the like. Examples of the orientation treatment method in factor (3) include a method of rubbing in one direction with a rayon cloth (rubbing), a method of obliquely depositing silicon oxide, and a method of etching into a slit. As the rubbing treatment, the support substrate may be directly rubbed, or the support substrate may be coated with a thin film such as polyimide or polyvinyl alcohol, and the thin film may be rubbed. A special thin film that gives good orientation without performing such rubbing treatment is also known. Further, a side substrate type liquid crystal polymer may be coated on the support substrate.

Examples of the orientation classification in the liquid crystal molecule include homogeneous (parallel), homeotropic (vertical), hybrid, and the like. Homogeneous means a state in which the orientation vector is parallel to the substrate and in one direction. Homeotropic means a state in which the orientation vector is perpendicular to the substrate. Hybrid refers to a state in which the orientation vector rises from parallel to vertical as the distance from the substrate increases. These orientations are observed in a composition having a nematic phase or the like.

Next, the use of the polymer of the present invention will be described.
The polymer of the present invention can be used as a molded product having optical anisotropy. Applications of such a molded body are, for example, optical films such as retardation plates (1/2 wavelength plates, 1/4 wavelength plates, etc.), antireflection films, selective reflection films, and viewing angle compensation films. Polymers having an orientation such as homogeneous, hybrid, and homeotropic can be used for retardation plates, polarizing elements, liquid crystal alignment films, antireflection films, selective reflection films, viewing angle compensation films, and the like. Thus, the polymer of the present invention can be used for a retardation plate of a liquid crystal display element, a viewing angle compensation film, and the like for the purpose of optical compensation. An example of an important industrial application is viewing angle compensation in liquid crystal display elements such as VA mode, IPS mode, TN mode, and MVA mode. The polymer of the present invention can also be used for highly heat-conductive epoxy resins, adhesives, synthetic polymers having mechanical anisotropy, cosmetics, decorations, nonlinear optical materials, information storage materials, and the like.

  A retardation plate, which is an example of a polymer application, has a function of converting the state of polarization. For example, a half-wave function plate has a function of rotating the vibration direction of linearly polarized light by 90 degrees. In order to obtain such a half-wave functional plate, first, a composition is applied on a support substrate so as to satisfy the formula d = λ / (2 × Δn). Here, d is the thickness of the composition, λ is the wavelength, and Δn is the optical anisotropy. Next, the thus coated composition is oriented and then photopolymerized to obtain a ½ wavelength functional plate. On the other hand, the quarter wavelength functional plate has a function of converting linearly polarized light into circularly polarized light or converting circularly polarized light into linearly polarized light. In order to obtain this 1/4 wavelength functional plate, the coating film of the composition may be prepared so as to satisfy the condition of d = λ / (4 × Δn).

  The thickness (d) of the polymer is adjusted as follows. In the method of applying the composition on a support substrate after diluting the composition with a solvent, a coating film having a desired thickness can be obtained by appropriately selecting the concentration of the composition, the application method, the application conditions, and the like. Can do. A method using a liquid crystal cell is also preferable. The liquid crystal cell is convenient because it has an alignment film such as polyimide. When injecting the composition into the liquid crystal cell, the thickness of the coating film can be adjusted by the interval of the liquid crystal cell.

Next, a method for synthesizing the compound used in the present invention is described.
Compounds used in the present invention include Houben Wyle (Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart), Organic Reactions (Organic Reactions, John Wily & Sons Inc.), Organic Synths (Organic).
Synthes, John Wily & Sons, Inc.), Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen), etc. Can be synthesized.

Compound (1) of the present invention is synthesized as follows. A benzoic acid derivative represented by the following formulas (AC1) to (AC3) having —OCOC (R ⁵ ) ═CH ₂ is described in Polymer Journal, Vol. 35, No. 2, pp160-166 (2003). Synthesize according to method. The following formulas (AC4) to (AC7)
In the synthesis of a benzoic acid derivative having an oxetane ring represented by the formula, 3-alkyl-3-oxetanemethanol can be used as a starting material. In addition, 3-ethyl-3-oxetanemethanol and 3-methyl-3-oxetanemethanol are commercially available. According to the method of literature (Macromolecules, 24, 4531-4537 (1991), WO 02/28985),
By reacting these compounds with α, ω-dibromomethylene such as 1,2-dibromoethane, 1,4-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, the carbon chain length Can be extended.

The synthesis scheme of compound (1) will be exemplified and described.
After reacting 2,4-dimethoxybromobenzene [a], Grignard reagent prepared from metal magnesium and trimethyl borate, 2,4-dimethoxybenzeneboronic acid [b] is obtained by hydrolysis. 2,4,2 ′, 4′-tetramethoxybiphenyl [c] can be synthesized by cross-coupling compound [b] and 2,4-dimethoxybromobenzene [a] in the presence of a palladium catalyst. . The compound [c] is reacted with a Lewis acid such as boron tribromide to obtain 2,4,2 ′, 4′-hydroxybiphenyl [d]. 3,7-dihydroxybenzofuran [e] can be synthesized by dehydrating the compound [d] with a catalyst such as zeolite.

Next, by esterifying the obtained 3,7-dihydroxybenzofuran [e] and 2 equivalents of one carboxylic acid derivative selected from the above-mentioned compounds (AC1) to (AC7), R ¹ = R ⁴ , R Compounds (1-1-1) to (1-1-3), (1-6-1) to (1-6-3), and (1-7-1) in which ² = R ³ can be synthesized. For the esterification, a condensing agent such as dicyclohexylcarbodiimide (DCC) can be suitably used.

Compounds (1-8-1), (1-8-2), (1-9-1), and (1-9-2) in which R ¹ = R ⁴ and R ² = R ³ are 3, 7 -After esterifying dihydroxybenzofuran [e] and one equivalent of a benzoic acid derivative selected from the compounds represented by the following formulas (AC8) to (AC11), a peroxide such as m-chloroperbenzoic acid It can be synthesized by oxidizing with A synthesis scheme is shown below.

Next, in the above formula (1-2), Z represents —COO—, —OCO—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO— or —OCO. A synthesis scheme of compounds in which —CH═CH— and different terminal polymerizable groups are shown below. Y in the synthesis scheme is a single bond, — (CH ₂ ) ₂ —, or —CH═CH—.

  First, after synthesizing monoester [f] by esterifying 3,7-dihydroxybenzofuran [e] and one equivalent of one benzoic acid derivative selected from the above-mentioned compounds (AC1) to (AC3), It can be synthesized by esterifying with 1 equivalent of the benzoic acid derivative selected from the above-mentioned compounds (AC4) to (AC6). The above compound (1-3) can also be synthesized by the same method.

  As examples of the compound (1) that can be synthesized by the above method, the following compound No. 1-No. 40.

  Next, specific examples of the polymerizable liquid crystal compound that can be used as the second component in the composition of the present invention are shown below.

The compounds (MLC1) and (MLC2) can be synthesized by the method described in Japanese Patent Application No. 2005-169337. The above compounds (MLC3) and (MLC4) can be synthesized according to the method described in Macromolecules, 26, 6132-6134 (1993). The compound (MLC5) can be synthesized according to the method described in JP-A-2005-60373. The above compound (MLC6) is described in Macromolecules, 26, 1244-1247 (1993).
It can be synthesized according to the method described in 1. The compounds (MLC7) and (MLC8) can be synthesized according to the method described in JP-A-2005-60373. The compounds (MLC9) and (MLC10) can be synthesized according to the method described in Japanese Patent Application No. 2004-353822.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In addition, the measuring methods, such as a physical property, are as follows.

<Phase transition temperature>
A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, heated at a rate of 1 ° C./min, and the temperature at which the liquid crystal phase transitioned to another liquid crystal phase was measured. C is a crystal, N is a nematic phase, SA is a smectic A phase, and I is an isotropic liquid. The NI point is the upper limit temperature of the nematic phase or the transition temperature from the nematic phase to the isotropic liquid. For example, “C50N63I” indicates that the crystal transitioned to a nematic phase at 50 ° C. and the nematic phase to an isotropic liquid at 63 ° C.

<Cellotape (registered trademark) peel test>
The test method of JIS standard “JIS-K-5400, 8.5, adhesion (8.5.2, cross-cut tape method)” was followed. That is, the result was evaluated by the number of squares that did not peel out of 100 squares.

<Pencil hardness>
The method of JIS standard “JIS-K-5400, 8.4, pencil scratch test” was followed. The result was expressed by the hardness of the pencil lead.

<Heat resistance test>
A heat resistance test was conducted at 100 ° C. for 500 hours, and the result was evaluated by the variation of retardation. Specifically, first, polyamic acid (“PIA5310” manufactured by Chisso Corporation) was applied to a glass substrate, and then heated at 210 ° C. for 30 minutes to obtain a support substrate. The surface of the polyimide produced by heating was rubbed with a rayon cloth. The composition of the sample was diluted with a mixed solvent of toluene and cyclopentanone (2: 1 by weight) to prepare a 30% by weight solution. This solution was applied to a support substrate with a spin coater and heated at 70 ° C. for 3 minutes, and then the produced coating film was irradiated with ultraviolet rays at 60 ° C. for 10 seconds using an ultrahigh pressure mercury lamp (250 W / cm). The retardation of the obtained polymer was measured at 25 ° C. Then, after heating the polymer at 100 ° C. for 500 hours, the retardation was measured again at 25 ° C. The heat resistance was evaluated by comparing the values before and after heating. Retardation was measured at a wavelength of 550 nm using a Senarmont compensator according to the method of literature (Hiroshi Hiroya, “Introduction to Polarizing Microscope of Polymer Materials”, p. 94, published by Agne Technology Center, 2001). .

<Optical anisotropy (Δn)>
The retardation value (25 ° C.) of the polymer film was measured according to the heat resistance test method, and the thickness (d) of the polymer film was also measured. Since retardation is Δn × d, the value of optical anisotropy was calculated from this relationship.

<Alignment of liquid crystal molecules>
A polymer film (liquid crystal alignment film) was formed on the saponified TAC film. The orientation of the polymer was determined by two methods of visual observation and analysis by a measuring device based on the angle dependency of the transmitted light intensity.

(1) Visual observation—A polymer film was sandwiched between two polarizing plates arranged in crossed Nicols, and light was irradiated from the direction perpendicular to the film surface (the tilt angle was 0 degree). The change in transmitted light was observed while increasing the tilt angle of irradiation from 0 degrees to, for example, 50 degrees. The direction of tilting the irradiation was made to coincide with the major axis direction of the liquid crystal molecules. When the transmitted light from the vertical direction was the maximum, the orientation was judged to be a homogeneous orientation. This is because in homogeneous alignment, the alignment vector of liquid crystal molecules is parallel to the TAC film. On the other hand, when the transmitted light from the vertical direction is minimum and the transmitted light increases as the tilt angle is increased, the orientation is determined to be homeotropic orientation. This is because in homeotropic alignment, the alignment vector of liquid crystal molecules is perpendicular to the TAC film.

  (2) Measurement by ellipsometer-An OPTIPRO ellipsometer manufactured by Shintech Co., Ltd. was used. The polymer film was irradiated with light having a wavelength of 550 nm. The retardation (Δn × d) was measured while decreasing the incident angle of this light from 90 degrees with respect to the film surface.

[Example 1] Synthesis of compound (No. 6) 4- [6- (acryloyloxy) hexyloxy] benzoic acid represented by the following formula (AK1) was synthesized from literature (Makromol. Chem., 190, 2255-2268). Page, 1989).

(First stage)
A solution prepared by dissolving 25 g of 2,4-dimethoxybromobenzene in 100 mL of tetrahydrofuran was added to a 500 mL container and heated so that 2.9 g of magnesium was immersed therein. After confirming that magnesium was dissolved and reacted, the remaining solution was added dropwise. After completion of the dropwise addition, the mixture was refluxed for 1 hour to prepare a Grignard reagent. The Grignard reagent solution was cooled to −30 ° C., 65 g of triisopropyl borate was added dropwise thereto, and the mixture was stirred for 1 hour. 50 mL of 3% hydrochloric acid was added dropwise to complete the reaction. Extraction with diethyl ether was performed, and the diethyl ether layer was washed with water, saturated aqueous sodium carbonate, and water in this order. The residue obtained by distilling off the solvent was recrystallized from heptane to obtain 8.3 g of 2,4-dimethoxybenzeneboronic acid. The melting point was 125-128 ° C.

(Second stage)
The obtained 2,4-dimethoxybenzeneboronic acid 17.6 g, 2,4-dimethoxybromobenzene 21 g, tetrakis palladium 1.1 g, sodium carbonate 20.5 g and water 120 mL were added to diethylene glycol dimethyl ether 500 mL and refluxed for 6 hours. Water was added, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was recrystallized with ethanol to obtain 14.7 g of 2,4,2 ′, 4′-tetramethoxybiphenyl. The melting point was 92.3-93.1 ° C.

(3rd stage)
14 g of the obtained 2,4,2 ′, 4′-tetramethoxybiphenyl was dissolved in 300 mL of methylene chloride and cooled to −60 ° C. using a dry ice acetone bath. Thereto, 60 g of boron tribromide was added dropwise. Then, the dry ice acetone bath was removed and the mixture was stirred for 12 hours. Water was added, extracted with diethyl ether, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 9.3 g of 2,4,2 ′, 4′-tetrahydroxybiphenyl. The melting point was 223-226 ° C.

(Fourth stage)
14 g of 2,4,2 ′, 4′-tetrahydroxybiphenyl obtained and 15 g of a zeolite catalyst (“Zeolite HSZ-360HUA” manufactured by Tosoh Corporation) were added to 100 mL of 1,2-dichlorobenzene and refluxed for 4 hours. The reaction solution was filtered and reduced in pressure to distill off 1,2-dichlorobenzene. The residue was purified by silica gel column chromatography to obtain 5.5 g of 3,7-dihydroxybenzofuran. The melting point was 244 ° C.

(5th stage)
To a solution obtained by adding 1.0 g of 3,7-dihydroxybenzofuran obtained, 3.1 g of 4- [6- (acryloyloxy) hexyloxy] benzoic acid (AK1) and 0.1 g of dimethylaminopyridine to 50 mL of methylene chloride, 2.1 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added, and the mixture was stirred at room temperature for 12 hours. 50 mL of water was added, and the obtained organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography to obtain 0.7 g of compound (No. 6). The melting point was 115 ° C., and the NI point could not be confirmed because it was polymerized by heating.

The structure was confirmed by measuring proton NMR. ¹ H-NMR (CDCl ₃ ): δ 1.45 to 1.58 (8H, m), 1.70 to 1.76 (4H, m), 1.83 to 1.88 (4H, m), 4. 06 (2H, t, J = 5 Hz), 4.19 (2H, t, J = 5 Hz), 5.83 (2H, d, J = 10 Hz), 6.13 (2H, dd), 6.40 ( 2H, d, J = 15 Hz), 6.99 (4H, d, J = 8.7 Hz), 7.22 (2H, dd), 7.47 (2H, d, J = 1.9 Hz), 7. 94 (2H, d, J = 8.3 Hz), 8.18 (4
H, d, J = 8.7 Hz)

Example 2 Synthesis of Compound (No. 9) 2-Fluoro-4- [6- (acryloyloxy) hexyloxy] benzoic acid represented by the following formula (AK3) was converted to 2-fluoro-4-hydroxybenzoic acid. Synthesis was carried out using ethyl acid as a starting material and the method described in the literature (Makromol. Chem., 190, 2255-2268, 1989). The melting point of the compound (AK3) was 98 to 99 ° C.

  Next, 1.0 g of 3,7-dihydroxybenzofuran, 3.2 g of 2-fluoro-4- [6- (acryloyloxy) hexyloxy] benzoic acid (AK3) and 0.1 g of dimethylaminopyridine were added to 50 mL of methylene chloride. To the solution, 1 g of dicyclohexylcarbodiimide was added and stirred at room temperature for 12 hours. 50 mL of water was added, and the obtained organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography to obtain 1.2 g of compound (No. 9). The melting point was 90 ° C., and the NI point could not be confirmed because it was polymerized by heating.

The structure was confirmed by measuring proton NMR. ¹ H-NMR (CDCl ₃ ): δ 1.45 to 1.58 (8H, m), 1.70 to 1.76 (4H, m), 1.83 to 1.88 (4H, m), 4. 04 (2H, t, J = 5 Hz), 4.19 (2H, t, J = 5 Hz), 5.83 (2H, d, J = 10 Hz), 6.13 (2H, dd), 6.41 ( 2H, d, J = 15 Hz), 6.71 (2H, dd, J = 12.5 and 2 Hz), 6.79 (2H, dd, J = 8.5 and 2.5 Hz), 7.22 (2H , Dd), 7.47 (2H, d, J = 1.9 Hz), 7.94 (2H, d, J = 8.3 Hz), 8.08 (2H, dd, J = 8.5 and 8.). 5Hz)

Example 3 Synthesis of Compound (No. 26) (First Step)
4- [6- (3-Ethyloxetane-3-ylmethoxy) hexyloxy] benzoic acid represented by the following formula (OX2) was synthesized by the method described in JP-A-2005-60373. The melting point was 58.5 ° C.

  Next, 1.1 g of 3,7-dihydroxybenzofuran, 3.9 g of 4- [6- (3-ethyloxetane-3-ylmethoxy) hexyloxy] benzoic acid (OX2) and 0.1 g of dimethylaminopyridine were added to 50 mL of methylene chloride. To the added solution, 2.3 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred at room temperature for 12 hours. 50 mL of water was added, and the obtained organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography to obtain 1.8 g of compound (No. 26). The phase transition temperature was C 96 N 138 I.

The structure was confirmed by measuring proton NMR. ¹ H-NMR (CDCl ₃ ): δ 0.89 (6H, t, J = 7.5 Hz, 1.45 to 1.58 (8H, m), 1.70 to 1.76 (4H, m), 1 .75 (4H, q, J = 7.5 Hz), 1.83 to 1.88 (4H, m), 3.48 (4H, t, J = 6.4 Hz), 3.53 (4H, s) 4.06 (4H, t, J = 6.4 Hz), 4.39 (4H, d, J = 5.7 Hz), 4.47 (4H, d, J = 5.7 Hz), 6.99 ( 4H, d, J = 8.7 Hz), 7.22 (2H, dd), 7.47 (2H, d, J = 1.9 Hz), 7.94 (2H, d, J = 8.3 Hz), 8.18 (4H, d, J = 8.7Hz)

[Example 4] Preparation of composition (PLC-1) Composition (MIX1) comprising 60% by weight of compound (No. 9), 20% by weight of compound (MLC1) and 20% by weight of compound (MLC4) shown below Was prepared. Compound (No. 9) showed good compatibility without phase separation. Further, the composition (MIX1) was not immediately crystallized even at room temperature.

  Next, 3 parts by weight of a polymerization initiator (“IRGACURE 907” manufactured by Ciba Specialty Chemicals) is added to 100 parts by weight of the composition (MIX1), and then a cyclopentanone is added to prepare a 25% by weight solution. A composition (PLC-1) was obtained.

[Example 5] Preparation of composition (PLC-2) Composition (MIX2) comprising 60% by weight of compound (No. 9), 20% by weight of compound (MLC2) and 20% by weight of compound (MLC4) shown below Was prepared. Compound (No. 9) showed good compatibility without phase separation. Further, the composition (MIX2) was not immediately crystallized even at room temperature.

  Next, 3 parts by weight of a polymerization initiator (“IRGACURE 907” manufactured by Ciba Specialty Chemicals) was added to 100 parts by weight of the composition (MIX2), and then cyclopentanone was added to prepare a 25% by weight solution. A composition (PLC-2) was obtained.

[Example 6] Preparation of composition (PLC-3) In the composition (PLC-1) described in Example 4, the compound represented by the following formula (5) with respect to 100 parts by weight of the composition (MIX1) 10 parts by weight (“Sila Ace S-330” manufactured by Chisso Corporation) was added to obtain a composition (PLC-3).

[Example 7] Preparation of composition (PLC-4) A composition (MIX3) consisting of 70% by weight of compound (No. 26) and 30% by weight of compound (MLC9) shown below was prepared. Compound (No. 26) showed good compatibility without phase separation. Further, the composition (MIX3) did not immediately crystallize even at room temperature.

  Next, 3 parts by weight of a polymerization initiator (“DTS-102” manufactured by Midori Chemical Co., Ltd.) is added to 100 parts by weight of the composition (MIX3), and then cyclopentanone is added to prepare a 25% by weight solution. A composition (PLC-4) was obtained.

[Example 8] Evaluation of polymer film (F1) The composition (PLC-1) obtained in Example 4 was applied to a support substrate obtained by rubbing the surface of a saponified TAC film with a rayon cloth. Was applied to a TAC film. After the application, the solution was heat-treated in an oven set at 70 ° C. for 5 minutes to remove the solvent and align the liquid crystal layer. Subsequently, the polymer film (F1) was obtained by irradiating the coating film with ultraviolet rays (30 mW / cm ² ; 365 nm) using an ultrahigh pressure mercury lamp (250 W) at 25 ° C. for 30 seconds in a nitrogen atmosphere.

  The orientation of the obtained film (F1) was homogeneous by visual observation, and was also homogeneous by the measurement result by the apparatus. The surface hardness of the film (F1) was H of pencil hardness. In the cellophane (registered trademark) peel test, no peeling occurred, and all the residue remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the optically anisotropic film (F1) was difficult to peel off from the support substrate and had sufficient hardness.

[Example 9] Evaluation of polymer film (F2) A polymer film (F2) was obtained in the same manner as in Example 8 except that the composition (PLC-2) obtained in Example 5 was used. . The orientation of the obtained film (F2) was homogeneous by visual observation and coincided with the measurement result by the apparatus. The surface hardness of the film (F2) was H of pencil hardness. In the cellophane (registered trademark) peel test, no peeling occurred, and all the residue remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the optically anisotropic film (F2) was hardly peeled off from the support substrate and had sufficient hardness.

[Example 10] Evaluation of polymer film (F3) A polymer film (F3) was obtained in the same manner as in Example 8 except that the composition (PLC-3) obtained in Example 6 was used. . The orientation of the obtained film (F3) was homeotropic by visual observation and coincided with the measurement result obtained by the apparatus. The surface hardness of the film (F3) was H of pencil hardness. In the cellophane (registered trademark) peel test, no peeling occurred, and all the residue remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the optically anisotropic film (F3) was not easily peeled from the support substrate and had sufficient hardness.

[Example 11] Evaluation of polymer film (F4) The composition (PLC-4) obtained in Example 7 was applied to a TAC film (no rubbing treatment) subjected to saponification treatment as a support substrate using a bar coater. Applied. After the application, the solution was heat-treated in an oven set at 70 ° C. for 5 minutes to remove the solvent and align the liquid crystal layer. Subsequently, ultraviolet rays (30 mW / cm ² ; 365 n) were used for the coating film using an ultrahigh pressure mercury lamp (250 W).
The polymer film (F4) was obtained by irradiating m) for 30 seconds at 25 ° C. under air release.

  The orientation of the obtained film (F4) was a hybrid orientation by visual observation and coincided with the measurement result obtained by the apparatus. The surface hardness of the film (F4) was H of pencil hardness. In the cellophane (registered trademark) peel test, no peeling occurred, and all the residue remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the optically anisotropic film (F4) was difficult to peel off from the support substrate and had sufficient hardness.

Claims (20)

A compound represented by the following formula (1).

[In Formula (1),
A is a xylene or 1,4-phenylene independently 1,4-cyclohexylene,
Any hydrogen in the 1,4-phenylene may be replaced by chlorine or fluorine, also, any one or two hydrogen, main switch luma other may be replaced by trifluoromethyl;
Z is independently _{- CH 2 O -, - OCH} 2 -, - COO -, - OCO-, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - CH = CH-COO- Or -OCO-CH = CH-;
P is independently a polymerizable group represented by any of the following formulas (P1) , (P2), (P5) to (P8);
Q is independently —O—, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O—, — (CH ₂ ) _r — or —O— (CH ₂ ) _r —O —. There, r is Ri integer der from 1 15;
x is 1 . ]

In the formula (1),
A is independently 1,4-cyclohexylene or 1,4-phenylene;
Any one or two hydrogens in the 1,4-phenylene may be replaced by chlorine or fluorine;
Z is independently —COO—, —OCO—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO— or —OCO—CH═CH—;
P is independently a polymerizable group represented by the above formula (P1), (P5), (P6) or (P7);
Q is independently —O—, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O—, — (CH ₂ ) _r — or —O— (CH ₂ ) _r —O—. And r is an integer from 1 to 15;
The compound according to claim 1, wherein x is 1. The compound represented by either of following formula (1-1)-(1-9).

[In the above formulas (1-1) to (1-9),
Z is independently —COO—, —OCO—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO— or —OCO—CH═CH—;
r is independently an integer from 1 to 10;
R ¹ , R ² , R ³ and R ⁴ are each hydrogen or fluorine;
R ⁵ is hydrogen or methyl. ] The following formulas (1-1-1), (1-1-2), (1-1-3), (1-6-1), (1-6-2), (1-6-3), The compound represented by (1-7-1), (1-8-1), (1-8-2), (1-9-1) or (1-9-2).

[Wherein, r is an integer of 1 to 10, and R ¹ , R ² , R ³ and R ⁴ are each hydrogen or fluorine. ] It is represented by the formula (1-1-1) according to claim 4 , wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen, and r is an integer of 2 to 10. A compound. It is represented by the formula (1-1-1) according to claim 4 , wherein R ¹ and R ⁴ are hydrogen, R ² and R ³ are fluorine, and r is an integer of 2 to 10. A compound characterized by being. It is represented by the formula (1-6-1) according to claim 4 , wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen, and r is an integer of 2 to 10. A compound. The polymerizable liquid crystal composition characterized by containing at least one compound according to any one of claims 1-7. As a 1st component, at least 1 chosen from the group which consists of a compound represented by Formula (1-1-1) of Claim 4 , Formula (1-1-2), and Formula (1-1-3). Containing two compounds
As the second component, including at least one compound selected from the group consisting of compounds represented by the following formulas (M1a) and (M1b),
The content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to 100% by weight of the total amount of the first component and the second component. A polymerizable liquid crystal composition.

[In the formulas (M1a) and (M1b),
R ⁶ is independently hydrogen, fluorine, trifluoromethyl or methyl;
R ⁷ is cyano, trifluoromethoxy, alkyl having 1 to 15 carbons or alkoxy having 1 to 15 carbons;
W ¹ and W ² are independently hydrogen, chlorine or fluorine;
W ³ is hydrogen or fluorine;
Z ² is a single bond, —COO—, —CH═CH—COO— or —CH ₂ CH ₂ —COO—;
A ² is a group represented by any of the following formulas (A-1) to (A-7);
m is an integer of 2-8. ]

As a 1st component, at least 1 chosen from the group which consists of a compound represented by Formula (1-1-1) of Claim 4 , Formula (1-1-2), and Formula (1-1-3). Containing two compounds
As a second component, at least one compound represented by (i) the formula of claim 9 (M1a), and at least one compound represented by the formula (M1b) according to (ii) according to claim 9 Including
The content of the first component is 20 to 80% by weight and the content of the second component (i) is 10 to 40% by weight with respect to 100% by weight of the total amount of the first component and the second component, A polymerizable liquid crystal composition, wherein the content of the second component (ii) is 10 to 40% by weight. The first component is represented by the formula (1-6-1), the formula (1-6-2), the formula (1-6-3), and the formula (1-7-1) according to claim 4. Including at least one compound selected from the group consisting of compounds;
The second component includes at least one compound selected from the group consisting of compounds represented by the following formula (M2a), formula (M2b) and formula (M2c),
The content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to 100% by weight of the total amount of the first component and the second component. A polymerizable liquid crystal composition.

[In the formulas (M2a) to (M2c),
R ⁸ is cyano, fluorine, trifluoromethyl or methyl;
W ¹ and W ² are independently hydrogen, chlorine or fluorine;
W ³ is hydrogen or fluorine;
Z ² is a single bond, —COO—, —CH═CH—COO— or —CH ₂ CH ₂ —COO—;
Z ³ is independently a single bond or —O—;
A ² is a group represented by any one of formulas (A-1) to (A-7) according to claim 9 ;
m is an integer of 2-8. ] The first component is represented by the formula (1-6-1), the formula (1-6-2), the formula (1-6-3), and the formula (1-7-1) according to claim 4. Including at least one compound selected from the group consisting of compounds;
As a second component, at least one compound represented by formula (M2b) according to (i) according to claim 11, and at least one compound of formula (M2c) according to (ii) according to claim 11 Including
The content of the first component is 20 to 80% by weight and the content of the second component (i) is 10 to 40% by weight with respect to 100% by weight of the total amount of the first component and the second component, A polymerizable liquid crystal composition, wherein the content of the second component (ii) is 10 to 40% by weight. The first component is represented by the formula (1-8-1), the formula (1-8-2), the formula (1-9-1), and the formula (1-9-2) according to claim 4. Including at least one compound selected from the group consisting of compounds;
As the second component, including at least one compound selected from the group consisting of compounds represented by the following formula (M3a) and formula (M3b),
The content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to 100% by weight of the total amount of the first component and the second component. A polymerizable liquid crystal composition.

[In the formulas (M3a) and (M3b),
R ⁸ is cyano, fluorine, trifluoromethyl or methyl;
R ⁹ is methyl or ethyl;
W ¹ and W ² are independently hydrogen, chlorine or fluorine;
W ³ is hydrogen or fluorine;
Z ² is a single bond, —COO—, —CH═CH—COO— or —CH ₂ CH ₂ —COO—;
A ² is a group represented by any one of formulas (A-1) to (A-7) according to claim 9 ;
m is an integer of 2-8. ] The first component is represented by the formula (1-8-1), the formula (1-8-2), the formula (1-9-1), and the formula (1-9-2) according to claim 4. Including at least one compound selected from the group consisting of compounds;
As a second component, at least one compound represented by (i) the formula of claim 13 (M3a), at least one compound represented by formula (M 3 b) according to (ii) according to claim 13 Including
The content of the first component is 20 to 80% by weight and the content of the second component (i) is 10 to 40% by weight with respect to 100% by weight of the total amount of the first component and the second component, A polymerizable liquid crystal composition, wherein the content of the second component (ii) is 10 to 40% by weight. The polymerizable liquid crystal composition according to any one of claims 8 to 14, characterized in that it contains a further polymerization initiator. The polymerizable liquid crystal composition according to any one of claims 8 to 15 , further comprising a solvent. A polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 8 to 16 . An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 8 to 16 . A retardation film comprising the optically anisotropic film according to claim 18 . A liquid crystal display device comprising the optically anisotropic film according to claim 18 .