JP2004231638A - Polymerizable compound and its polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal compound having a broad temperature range of a liquid crystal phase, excellent compatibility with other compounds, and furthermore necessary properties such as optical anisotropy, a polymer excellent in many properties such as transparency, mechanical strengths, coating properties, solubility, crystallinity, shrinkage, water permeability, water absorption, a melting point, a glass transition temperature, a clear point, and chemical resistance, a molded product having optical anisotropy from this polymer, and a liquid crystal display device containing this polymer. <P>SOLUTION: The compound is represented by formula (1): R<SP>a</SP>-Z-(A-Z)<SB>m</SB>-R<SP>b</SP>or formula (2): R<SP>a</SP>-Z-(A-Z)<SB>m</SB>-R<SP>a</SP>. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a compound having polymerizability and liquid crystallinity, a polymer thereof, and a use of the polymer. This polymer can be used for molded articles having optical anisotropy, liquid crystal display devices, and the like.

  In recent years, polymerizable liquid crystalline compounds have been used for molded articles having optical anisotropy such as polarizing plates and retardation plates. This is because the compound has optical anisotropy in a liquid crystal state, and the arrangement of the compound is fixed by polymerization. Since the optical properties required for a molded article having optical anisotropy differ depending on the purpose, a compound having properties suitable for the purpose is required. In general, this compound is polymerized into a polymer, which is then molded and used. For the compound used for such a purpose, in addition to the above-described anisotropy, properties relating to a polymer are also important. These characteristics include compound polymerization rate, polymer transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, chemical resistance, etc. It is.

  Acrylates are used for such purposes because they have high polymerization reactivity and the resulting polymers have high transparency (see, for example, Patent Documents 1, 2, 3, and 4).

JP-A-7-17910 JP-A-8-3111 (US Pat. No. 5,863,457) JP-A-9-316032 U.S. Pat. No. 5,622,648

  A first object of the present invention is to provide a polymerizable liquid crystal having a wide temperature range of a liquid crystal phase, having excellent compatibility with other compounds, and further having necessary properties such as optical anisotropy. An object of the present invention is to provide a compound and a liquid crystal composition containing the compound. The second purpose is excellent in many properties such as transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, chemical resistance And a molded article having optical anisotropy produced from the polymer. A third object is to provide a liquid crystal display device containing the polymer.

  The means for achieving the above object are as follows.

式中、Ｒ^ａは、式（３−１）〜（３−５）の重合性基のいずれか１つであり；Ｒ^ｂは水素、ハロゲン、−ＣＮ、−ＮＣＯ、−ＮＣＳ、または炭素数１〜２０のアルキルであり、このアルキルにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンまたは−ＣＮで置き換えられてもよく；Ａは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイル、ビシクロ［２．２．２］オクト−１，４−ジイル、またはビシクロ［３．１．０］ヘキス−３，６−ジイルであり、これらの環において任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよく、これらの環において任意の水素はハロゲン、炭素数１〜５のアルキルまたは炭素数１〜５のハロゲン化アルキルで置き換えられてもよく、これらの置換基が隣接しているときには、互いに結合して環の炭素−炭素結合と共に環を形成してもよいが、少なくとも１つのＡは式（４−１）または式（４−２）で表される置換された１，４−フェニレンであり、；Ｚは、単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；Ｒ^ｃは水素、ハロゲン、−ＣＦ₃、または炭素数１〜５のアルキルであり；ｍは１〜６の整数であり、ｑは０または１である。 [1] A compound represented by the following formula (1) or formula (2).
_{^{R a -Z- (A-Z)}} m -R b (1)
_{^{R a -Z- (A-Z)}} m -R a (2)

In the formula, R ^a is any one of the polymerizable groups of the formulas (3-1) to (3-5); R ^b is hydrogen, halogen, —CN, —NCO, —NCS, or carbon number. 1-20 alkyl, wherein any -CH ₂ -is -O-, -S-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C- And any hydrogen may be replaced by halogen or -CN; A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2 , 6-Diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3 , 6-diyl, any of these rings -CH ₂ - may be replaced by -O-, arbitrary -CH = may be replaced by -N =, arbitrary hydrogen in these rings are halogen, alkyl having 1 to 5 carbon atoms or It may be substituted by an alkyl halide having 1 to 5 carbon atoms, and when these substituents are adjacent to each other, they may be bonded to each other to form a ring together with the carbon-carbon bond of the ring, A is a substituted 1,4-phenylene represented by the formula (4-1) or (4-2); Z is a single bond or an alkylene having 1 to 20 carbon atoms. arbitrary -CH ₂ - -O -, - S -, - COO -, - OCO -, - CH = CH -, - CF = CF- or -C≡C-, and any Hydrogen may be replaced by halogen; ^c is hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons; m is an integer of 1 to 6, and q is 0 or 1.

[2] formula (1) and ^{R a} has the formula (2) (3-1) or (3-5) at a [1] A compound according to claim.
[3] In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), and other than the ring represented by the formula (4-1) or the formula (4-2). A is 1,4-cyclohexylene, 1,4-cyclohexylene in which any hydrogen is replaced by halogen, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by halogen [ 1] The compound according to the above.
[4] In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), and other than the ring represented by the formula (4-1) or the formula (4-2). A is 1,4-cyclohexylene, 1,4-cyclohexylene in which any hydrogen is replaced by halogen, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by halogen, Z is a single _{bond, - (CH 2) a -} , - O (CH 2) a -, - (CH 2) a O -, - O (CH 2) a O -, - CH = CH -, - C ≡C -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - OCF 2 - , or _-CF 2 is a O-, a is an integer from 1 to 20 [1] a compound according to claim.

[5] Formula (1) and (2) ^{R a} is any one of formulas (3-2) to (3-4) in [1] A compound according to claim.
[6] In Formulas (1) and (2), ^Ra is any one of Formulas (3-2) to (3-4), and is represented by Formula (4-1) or Formula (4-2). A other than the ring to be formed is 1,4-cyclohexylene, 1,4-cyclohexylene in which any hydrogen is replaced by halogen, 1,4-phenylene, or 1,4 in which any hydrogen is replaced by halogen -The compound according to item [1], which is phenylene.
[7] In Formulas (1) and (2), ^Ra is any one of Formulas (3-2) to (3-4), and is represented by Formula (4-1) or Formula (4-2). A other than the ring to be formed is 1,4-cyclohexylene, 1,4-cyclohexylene in which any hydrogen is replaced by halogen, 1,4-phenylene, or 1,4 in which any hydrogen is replaced by halogen - phenylene, Z is a single _{bond, - (CH 2) a -} , - O (CH 2) a -, - (CH 2) a O -, - O (CH 2) a O -, - CH = CH -, - C≡C -, - COO -, - OCO -, - OCF 2 -, or _-CF 2 is a O-, a is an integer from 1 to 20 [1] a compound according to claim.

[8] The compound according to item [1], wherein m is 2 in the formulas (1) and (2).
[9] The compound according to item [1], wherein m is 3 in the formulas (1) and (2).
[10] The compound according to item [1], wherein m in the formulas (1) and (2) is 4.

[11] In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), one of A is the formula (4-1), and the other A is 1 , 4-cyclohexylene, 1,4-phenylene or arbitrary hydrogen is replaced by halogen 1,4-phenylene, Z is a single bond, -COO -, - OCO -, - (CH 2) a - _{, -CH = CH-COO -,} - OCO-CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} is O-, a is an integer from 1 to 20 [1] a compound according to claim.
[12] In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), one of A is the formula (4-2), and the other A is 1 , 4-cyclohexylene, 1,4-phenylene or arbitrary hydrogen is replaced by halogen 1,4-phenylene, Z is a single bond, -COO -, - OCO -, - (CH 2) a - , —O (CH ₂ ) _a —, — (CH ₂ ) _a O—, or —O (CH ₂ ) _a O—, wherein a is an integer of 1 to 20.
[13] In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), one of A is the formula (4-1), and the other A is 1 , 4-phenylene, Z is -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} The compound according to item [1], wherein O- and a is an integer of 1 to 20.

[14] In formulas (1) and (2), ^Ra is any one of formulas (3-2) to (3-4), one of A is formula (4-1), and A is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which arbitrary hydrogen is replaced by halogen, and Z is a single bond, -COO-, -OCO-,-( _{CH 2) a -, - O} (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} a O-, a is an integer from 1 to 20 [1] to claim A compound as described.
[15] In the formulas (1) and (2), ^Ra is any one of the formulas (3-2) to (3-4), one of A is the formula (4-2), A is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which arbitrary hydrogen is replaced by halogen, and Z is a single bond, -COO-, -OCO-,-( _{CH 2) a -, - O} (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} a O-, a is an integer from 1 to 20 [1] to claim A compound as described.
[16] In formulas (1) and (2), ^Ra is any one of formulas (3-2) to (3-4), one of A is formula (4-1), and a is 1,4-phenylene, Z is -COO the -, - OCO -, - ( CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O The compound according to item [1], wherein (CH ₂ ) _a O—, wherein a is an integer of 1 to 20.

式中、Ｒ^ａは、式（３−１）〜（３−５）の重合性基のいずれか１つであり；Ｒ^ｂは水素、ハロゲン、−ＣＮ、−ＮＣＯ、−ＮＣＳ、または炭素数１〜２０のアルキルであり、このアルキルにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンまたは−ＣＮで置き換えられてもよく；Ａは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイル、ビシクロ［２．２．２］オクト−１，４−ジイル、またはビシクロ［３．１．０］ヘキス−３，６−ジイルであり、これらの環において任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよく、これらの環において任意の水素はハロゲン、炭素数１〜５のアルキルまたは炭素数１〜５のハロゲン化アルキルで置き換えられてもよく、これらの置換基が隣接しているときには、互いに結合して環の炭素−炭素結合と共に環を形成してもよく；Ｂは式（４−１）または式（４−２）で表される置換された１，４−フェニレンであり；Ｚは、単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；Ｒ^ｃは水素、ハロゲン、−ＣＦ₃、または炭素数１〜５のアルキルであり；ｑは０または１である。 [17] A compound represented by any one of the following formulas (a) to (r).
^Ra- ZB- ^Ra (a)
^{R a -Z-B-Z-} A-R a (b)
^{R a -Z-B-Z-} A-Z-A-R a (c)
R ^a -ZA-Z-B-Z-A-R ^a (d)
^{R a -Z-B-Z-} A-Z-A-Z-A-R a (e)
R ^a -ZA-Z-B-Z-A-Z-A-A-R ^a (f)
^{R a -Z-B-Z-} A-Z-A-Z-A-Z-A-R a (g)
R ^a -ZA-Z-B-Z-A-Z-A-Z-A-A-R ^a (h)
^{R a -Z-A-Z-} A-Z-B-Z-A-Z-A-R a (i)
^{R a -Z-B-Z-} R a (j)
^{R a -Z-B-Z-} A-Z-R a (k)
^{R a -Z-B-Z-} A-Z-A-Z-R a (l)
^{R a -Z-A-Z-} B-Z-A-Z-R a (m)
^{R a -Z-B-Z-} A-Z-A-Z-A-Z-R a (n)
R ^a -ZA-Z-B-Z-A-Z-A-Z-Z-R ^a (o)
^{R a -Z-B-Z-} A-Z-A-Z-A-Z-A-Z-R a (p)
R ^a -ZA-Z-B-Z-A-Z-A-Z-A-Z-Z-R ^a (q)
^{R a -Z-A-Z-} A-Z-B-Z-A-Z-A-Z-R a (r)

In the formula, R ^a is any one of the polymerizable groups of the formulas (3-1) to (3-5); R ^b is hydrogen, halogen, —CN, —NCO, —NCS, or carbon number. 1-20 alkyl, wherein any -CH ₂ -is -O-, -S-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C- And any hydrogen may be replaced by halogen or -CN; A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2 , 6-Diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3 , 6-diyl, any of these rings -CH ₂ - may be replaced by -O-, arbitrary -CH = may be replaced by -N =, arbitrary hydrogen in these rings are halogen, alkyl having 1 to 5 carbon atoms or B may be replaced by an alkyl halide having 1 to 5 carbon atoms, and when these substituents are adjacent to each other, they may combine with each other to form a ring together with the carbon-carbon bond of the ring; 4-1) or a substituted 1,4-phenylene represented by the formula (4-2); Z is a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, any -CH ₂ -May be replaced by -O-, -S-, -COO-, -OCO-, -CH = CH-, -CF = CF- or -C≡C-, and any hydrogen is replaced by halogen. R ^c is hydrogen, halogen, —CF ₃ or alkyl having 1 to 5 carbons; q is 0 or 1.

[18] In the formulas (a) to (r), A is 1,4-cyclohexylene or 1,4-phenylene, and in these rings, any hydrogen may be replaced by halogen; bond, -CH = CH -, - C≡C -, - COO -, - OCO -, - (CF 2) 2 -, - CF = CF -, - OCF 2 -, - CF 2 O -, - (CH _{2) a -, - CH =} CH-COO -, - OCO-CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - O (CH 2) a -, - ( The compound according to item [17], which is CH ₂ ) _a O— or —O (CH ₂ ) _a O—, wherein a is an integer of 1 to 20.
[19] In the formulas (a) to (i), A is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which arbitrary hydrogen is replaced by halogen, and Z is a single bond , -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} a O-, a is 1 The compound according to item [17], which is an integer of from 20 to 20.

式中、Ｒ^ｄは水素、メチル、エチルまたはプロピルであり；Ｒ^ｅは−ＣＮ、炭素数１〜２０のアルキルまたは炭素数１〜２０のアルコキシであり；環Ａ^ａ、Ａ^ｂおよびＡ^ｃは独立して、１，４−シクロヘキシレン、１，４−フェニレンまたは任意の水素がフッ素で置き換えられた１，４−フェニレンであり；環Ａ^ｄは、１，４−フェニレン、または２−メチル−１，４−フェニレンであり；Ｚ^ａおよびＺ^ｂは独立して、単結合、−（ＣＨ₂）₂−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；αは、０〜２０の整数であり；ｓは０または１である。 [20] A liquid crystal composition comprising at least two polymerizable compounds, wherein at least one polymerizable compound is the compound according to any one of [1] to [19].
[21] The liquid crystal composition according to item [20], wherein all of the polymerizable compounds are the compound according to any one of items [1] to [19].
[22] The liquid crystal composition according to the item [20], comprising at least one of the compounds according to any one of the items [1] to [19] and at least one polymerizable compound other than the compound.
[23] At least one of the compounds according to any one of [1] to [19] and a compound selected from the group consisting of compounds represented by formulas (A), (B) and (C). Liquid crystal composition according to item [20], containing at least one polymerizable compound.

Wherein R ^d is hydrogen, methyl, ethyl or propyl; R ^e is —CN, alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons; rings A ^a , ^Ab and ^Ac are Independently, 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which any hydrogen has been replaced by fluorine; ring ^Ad is 1,4-phenylene, or 2-methyl- be a 1,4-phenylene; ^{Z a} and ^{Z b} are independently a single _{bond, - (CH 2) 2 -} , - CH = CH-COO -, - OCO-CH = CH -, - CH 2 CH 2 —COO—, —OCO—CH ₂ CH ₂ —, —COO—, or —OCO—; α is an integer of 0 to 20; s is 0 or 1.

[24] The liquid crystal composition according to any one of [20] to [23], wherein the liquid crystal composition further contains an optically active compound.

[25] A polymer obtained by polymerizing at least one of the compounds according to any one of [1] to [19].
[26] A polymer obtained by homopolymerizing one of the compounds according to any one of [1] to [19].
[27] A polymer obtained by polymerizing the composition according to any one of [20] to [24].
[28] The polymer according to item [25], having a weight average molecular weight of 500 to 100,000.
[29] The polymer according to item [25], having a weight average molecular weight of 1,000 to 50,000.
[30] The polymer according to any one of the items [25] to [27], wherein the polymer is optically active.

[31] A film obtained from the polymer according to any one of [25] to [30].
[32] A molded article having optical anisotropy, comprising the polymer according to any one of [25] to [30].
[33] A retardation film containing the polymer according to any one of [25] to [30].
[34] A liquid crystal alignment film containing the polymer according to any one of [25] to [30].
[35] An antireflection film containing the polymer according to any one of [25] to [30].
[36] A viewing angle compensation film containing the polymer according to any one of [25] to [30].
[37] A polarizing element containing the polymer according to any one of [25] to [30].
[38] A film having a selective reflection function, comprising the polymer according to any one of [25] to [30].
[39] The film according to item [31], the molded article having optical anisotropy according to item [32], the retardation film according to item [33], the liquid crystal alignment film according to item [34], From the group of the antireflection film according to the item [35], the viewing angle compensation film according to the item [36], the polarizing element according to the item [37], and the film having a selective reflection function according to the item [38]. A liquid crystal display device containing at least one selected.
[40] A liquid crystal display device comprising the composition according to any one of [20] to [24].

Here, the meaning of the phrase “any —CH ₂ — in these rings may be replaced by —O—” is shown as an example. -C ₄ H ₈ - some groups replaced with _{-O-, -C 3 H 6 O -} - any -CH ₂ - _{in, - CH 2 -O- (CH 2} ) 2 - and -CH ₂ —O—CH ₂ —O—. Thus, “arbitrary” means “at least one selected without distinction”. In consideration of the stability of the compound, -CH ₂ -O-CH ₂ -O- in which oxygen and oxygen are not adjacent to each other is better than -CH ₂ -O-O-CH ₂ -in which oxygen and oxygen are adjacent. Is preferred.
"Arbitrary -CH 2 in these rings _- may be replaced by -O-, arbitrary -CH = may be replaced by -N =, optionally hydrogen in these rings halogen, carbon atoms in may "be replaced by 1-5 alkyl or halogenated alkyl of 1 to 5 carbon atoms, the latter" these ring ", any -CH 2 _-. ring is replaced by -O-, And -CH = is replaced by -N = to include a ring.

Preferred ^{R b} is hydrogen, _{halogen, -CN, -CF 3, -CF 2} H, -CFH 2, -OCF 3, -OCF 2 H, alkyl having 1 to 20 carbon atoms, 1 to 19 carbon atoms alkoxy, And alkenyl having 2 to 21 carbon atoms. Particularly preferred ^Rb is -CN, alkyl having 1 to 20 carbons and alkoxy having 1 to 19 carbons. In these groups, alkyl and alkenyl are preferably straight-chain rather than branched.

  At least one of the independent A is a substituted 1,4-phenylene represented by the formula (4-1) or (4-2), and preferred other A is 1,4-cyclohexylene; 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4- Phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, naphthalene -2,6-diyl, tetrahydronaphthalene-2,6-diyl, and fluorene-2,7-diyl. Other particularly preferred A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1 , 4-phenylene and 2,6-difluoro-1,4-phenylene. For 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl, trans is preferable to cis. Since 2-fluoro-1,4-phenylene is structurally identical to 3-fluoro-1,4-phenylene, the latter was not illustrated. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.

  Compounds having a large optical anisotropy are those wherein A other than the substituted 1,4-phenylene represented by the formula (4-1) or (4-2) is obtained by replacing any hydrogen with a halogen. 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, Alternatively, it is preferably fluorene-2,7-diyl. In the compound having a small optical anisotropy, A is preferably 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,3-dioxane-2,5-diyl.

Preferred Z is a single _{bond, - (CH 2) a -} , - O (CH 2) a -, - (CH 2) a O -, - O (CH 2) a O -, - CH = CH -, - C ≡C—, —COO—, —OCO—, — (CF ₂ ) ₂ —, —CH ＝ CH—COO—, —OCO—CH ＝ CH—, —CH ₂ CH ₂ —COO—, —OCO—CH ₂ CH ₂ —, —C≡C—COO—, —OCO—C≡C—, —CH ＝ CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH ＝ CH—, —CF ＝ CF—, —C≡C—HC ＝ CH—, —CH ＝ CH—C≡C—, —OCF ₂ —, or —CF ₂ O—, and a is an integer of 1 to 20.

More preferred Z is a single _{bond, - (CH 2) 2 -} , - (CH 2) 4 -, - OCH 2 -, - O (CH 2) 3 -, - CH 2 O -, - (CH 2) 3 _{O -, - O (CH 2} ) 2 O -, - CH = CH -, - C≡C -, - COO -, - OCO -, - (CF 2) 2 -, - CF = CF -, - CH = _{CH-COO -, - OCO-} CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - OCF 2 -, or _-CF 2 is O-. Particularly preferred Z is a single _{bond, - (CH 2) 2 -} , - OCH 2 -, - CH 2 O -, - O (CH 2) 2 O -, - CH = CH -, - (CH 2) 4 - , -CF = CF -, - CH = CH-COO -, - OCO-CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - OCF 2 -, or -CF ₂ O-. Compounds having a small viscosity, Z is a single _{bond, - (CH 2) 2 -} , - CH = CH -, - CF = CF -, - OCF 2 -, or is preferably _-CF 2 O-in which. In these linking groups, the double bond is more preferably trans than cis.

In Z adjacent to ^Ra or ^Rb , the number of carbon atoms of the alkylene is preferably 1 to 9, more preferably 3 to 7, and particularly preferably 2 to 6. Preferred examples of the alkylene ^{is (Z 1 -1) ~ (Z} 1 -7) and ^{(Z 5 -1) ~ (Z} 5 -7).

In ^{(Z 1 -1) ~ (Z} 1 -7), r is an integer of 2-6, s and t are independently 1 or 2. In ^{(Z 5 -1) ~ (Z} 5 -7), u is an integer of 2-6, v and w are independently 1 or 2. However, s + t ≦ 8 and v + w ≦ 8.

Preferred R ^c are hydrogen, halogen and methyl. Particularly preferred R ^c are hydrogen, fluorine and methyl.

m is an integer of 1 to 6. Desirable m is an integer of 2 to 4. The compound of the present invention is a bicyclic compound having two rings such as a six-membered ring when m is 2. When m is 3 or 4, the compound is a tricyclic or tetracyclic compound, respectively. When m is 1, the two Zs may be the same or different. When m is 2, the three Z (or the two A) may be the same or different. The same applies when m is 3 to 6. The same applies to the group R ^a and ^{R c.} When it is desired to set the temperature range of the liquid crystal phase on the low temperature side, a bicyclic compound may be selected, and when it is desired to set the liquid crystal phase at a relatively high temperature side, a tricyclic or tetracyclic compound may be selected. When it is desired to set the temperature range of the liquid crystal phase on the higher temperature side, a compound in which m is 4, 5, or 6 may be selected.

  The compound of the present invention has a wide temperature range of the liquid crystal phase, has excellent compatibility with other compounds, and further has a polymerizable liquid crystal compound having necessary properties such as optical anisotropy and the like. It can be used for a liquid crystal composition containing a compound. The polymer of the present invention has many properties such as transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, and chemical resistance. Excellent, a molded article having optical anisotropy can be produced from this polymer, and a liquid crystal display device containing this polymer can be produced.

  The usage of terms in this specification is as follows. The term "liquid crystal compound" is used as a generic term for compounds having a liquid crystal phase and compounds having no liquid crystal phase but useful as components of a liquid crystal composition. The term polymerizable in the art refers to the ability to polymerize by light, heat, catalysis and the like to give a polymer. The terms liquid crystal compound and liquid crystal composition may be referred to as a compound and a composition, respectively. The compounds represented by Formula (1) and Formula (2) may be referred to as Compound (1) and Compound (2), respectively. Polymers obtained from compound (1) and compound (2) may be referred to as polymer (1) and polymer (2), respectively. Acrylate and methacrylate are sometimes referred to as (meth) acrylate.

Compounds (1) and (2) and their polymers have the following characteristics.
(1) Compounds (1) and (2) have one to six rings, and have polymerizability and liquid crystallinity.
(2) Compounds (1) and (2) are extremely stable physically and chemically under the conditions usually used, and have good compatibility with other compounds.
(3) By appropriately selecting the ring, bonding group or side chain constituting the compounds (1) and (2), large dielectric anisotropy, small dielectric anisotropy, large optical anisotropy, small optical anisotropy Physical properties such as anisotropy and small viscosity can be adjusted.
(4) By appropriately selecting the structures of the compounds (1) and (2), the polymer can have optimal transparency, mechanical strength, coatability, solubility, crystallinity, shrinkage, water permeability, water absorption. It has properties such as temperature, melting point, glass transition point, clearing point, and chemical resistance. These characteristics can be determined according to a measurement method defined in JIS or the like.

Physical properties of compounds (1) and (2) are as follows.
Bicyclic and tricyclic compounds (1) and (2) have low viscosities. Compounds (1) and (2) having three or more rings have a high clearing point (liquid crystal phase-isotropic liquid phase transition temperature). Even when the compounds (1) and (2) are compounds having three or more rings, they have good wettability when dissolved in a solvent, which is advantageous in the preparation of a composition, coating on a substrate, and thinning. Compounds (1) and (2) having three or more rings have a very wide temperature range of the liquid crystal phase. In particular, since the compounds (1) and (2) having three or more rings have a liquid crystal phase in a high temperature range, by mixing with the compound (1) or (2) having two rings, the liquid crystal phase is reduced to a low temperature range. A liquid crystal composition covered in a temperature range can be prepared.

  Compounds (1) and (2) having at least two cyclohexane rings have a high clearing point, a small optical anisotropy and a small viscosity. The compounds (1) and (2) having at least two benzene rings have relatively large optical anisotropy and large liquid crystal alignment order parameter. The compounds (1) and (2) having at least three benzene rings have particularly large optical anisotropy, a wide temperature range of a liquid crystal phase, and high chemical stability.

  The compounds (1) and (2) in which the 2-position or the 3,5-position of 1,4-phenylene is fluorine are chemically stable and have a particularly large dielectric anisotropy. Compounds (1) and (2) in which A is 2,3-difluoro-1,4-phenylene are chemically stable and have a negative dielectric anisotropy.

Compounds (1) and (2) in which R ^c is hydrogen, halogen or alkyl having 1 to 5 carbon atoms are preferable because of high polymerizability. Compounds (1) and (2) in which R ^c is hydrogen or fluorine have the highest polymerizability. In the compounds (1) and (2) in which R ^c is alkyl having 1 to 5 carbon atoms, the polymerizability decreases as the number of carbon atoms increases. Therefore, when R ^c is alkyl, methyl is preferred.

Compounds (1) and (2) in which all of Z is a single bond have a particularly high clearing point. Compounds (1) and (2) in which the bonding group has a double bond have a wide temperature range of the liquid crystal phase. Compounds (1) and (2) in which the bonding group has a triple bond have particularly large optical anisotropy.
From these, compounds (1) and (2) having desired physical properties can be obtained by appropriately selecting a ring, a side chain and a bonding group. Even if the atoms constituting the compounds (1) and (2) are isotopes, they exhibit the same characteristics and can be preferably used.

  Preferred examples of the central group "-Z- (AZ)-" of the compounds in the compounds (1) and (2) are the central groups (1-1) to (1-78). In these compounds, Z has the same meaning as in formulas (1) and (2), and a plurality of Zs may be the same or different. Further, ring C (2) represents any of the substituted 1,4-phenylenes represented by the formula (4-1) or the formula (4-2). 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, naphthalene-2,6-diyl in the central groups (1-1) to (1-78) , Tetrahydronaphthalene-2,6-diyl, and fluoren-2,7-diyl may be substituted with fluorine or methyl as represented by the following formula.

  More preferred examples of the compounds (1) and (2) include a central group (1-2) to (1-3), a central group (1-13) to (1-16), and a central group (1-23) to (1-37), central group (1-44), central group (1-45), central group (1-48), central group (1-63), central group (1-65), central group (1 -69) or a compound having a central group (1-70).

Next, a method for producing the compounds (1) and (2) will be described.
Compounds (1) and (2) were obtained from Houben Wyle (Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart), Organic Reactions (John Wily & Sons Inc.), Organic Synthesis (Organic Synthesis). Syntheses, John Wily & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Laboratory Chemistry Course (Maruzen), etc. Can be manufactured.

  The ring structure represented by the formula (4-1) can be constructed by the following method. After the compound (a) and 1,1,1,4,4,4-hexafluoro-2-butyne (b) are converted into a compound (c) by a Diels-Alder reaction, ring opening and deprotection are performed under acidic conditions. By performing protection, compound (4-1-a) can be produced. By reacting compound (4-1-a) with halogen (chlorine, bromine, iodine) in the presence of triphenylphosphine, compound (4-1-b) having a hydroxyl group converted to halogen can be produced. When conversion to the compound (4-1-b) is difficult, tosylate or triflate can be used as an equivalent of the compound (4-1-b). The compound (a) can be synthesized by a known method (Gui-Ding Zhu, et al, Organic Letters, 2 (21), 3345 [2000]).

  The ring structure represented by the formula (4-2) can be constructed by the following method. The compound (d) is reacted with normal butyl lithium, then triisopropyl borate, and then oxidized with hydrogen peroxide to obtain a compound (e). Compound (f) is obtained by reacting compound (e) with dihydropyran in the presence of pyridium p-toluenesulfonate. The compound (4-2-a) can be produced by allowing normal butyl lithium to act on this, then allowing triisopropyl borate to act, and then oxidizing with hydrogen peroxide. Then, a compound (4-2-b) in which a hydroxyl group is converted into a halogen by reacting a halogen (chlorine, bromine, iodine) on the compound (4-2-a) in the presence of triphenylphosphine can be produced. As described above, tosylate or triflate can be used as an equivalent of the compound (4-2-b).

The main skeleton (liquid crystal residue) of compounds (1) and (2) can be constructed by the following method or by appropriately combining them. That is, with respect to an example of a method for producing the bonding group Z, a scheme is shown first, and then a method for producing the scheme is described. In this scheme, MSG ¹ or MSG ² is a monovalent organic group having at least one ring. A plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1K) correspond to compounds (1) and (2).

(I) Formation of Single Bond The boric acid derivative (5) is reacted with a halide (6) synthesized by a known method in the presence of an aqueous carbonate solution in the presence of a catalyst such as tetrakis (triphenylphosphine) palladium. Compound (1A) is synthesized. This compound (1A) is prepared by reacting compound (7), which is synthesized by a known method, with n-butyllithium and then with zinc chloride in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Can also be synthesized. The boric acid derivative (5) can be produced by deriving the compound (7) with a Grignard reagent or a lithium reagent and reacting with a trialkyl borate.

(II) Formation of —COO— and —OCO— Compound (7) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain carboxylic acid (8). Carboxylic acid (8) and phenol (9) synthesized by a known method are dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to have -COO-. Compound (1B) is synthesized. A compound having -OCO- can also be synthesized by this method.

(III) Formation of —CF ₂ O— and —OCF ₂ — The compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain a compound (10). The compound (10) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize a compound (1C) having —CF ₂ O—. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) is also synthesized by fluorinating compound (10) with (diethylamino) sulfur trifluoride. See William H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. -OCF ₂ by this method - compounds having also synthesized.

(IV) Formation of —CH ＝ CH— The compound (6) is treated with n-butyllithium and then reacted with a formamide such as N, N-dimethylformamide to obtain an aldehyde (11). Compound (1D) is synthesized by reacting phosphoiridium (12), which is synthesized by a known method, with a base such as potassium t-butoxide and generating phosphorus ylide with aldehyde (11). Since a cis form is generated depending on the reaction conditions, the cis form is isomerized to a trans form by a known method as necessary.

(V) Formation of — (CH ₂ ) ₂ — Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium on carbon.

(VI) Formation of — (CH ₂ ) ₄ — A compound having — (CH ₂ ) ₂ —CH ＝ CH— according to the method of item (IV) using a phosphonium salt (13) instead of the phosphonium salt (12). obtain. This is catalytically hydrogenated to synthesize compound (1F).

(VII) Formation of —C≡C— After reacting compound (7) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, the compound was reacted under basic conditions. Deprotection gives compound (14). Compound (14) is reacted with compound (6) in the presence of a catalyst of dichlorobistriphenylphosphine palladium and copper halide to synthesize compound (1G).

(VIII) Formation of —CF ＝ CF— The compound (7) is treated with n-butyllithium, and then reacted with tetrafluoroethylene to obtain a compound (15). Compound (15) is treated with n-butyllithium, and then reacted with compound (6) to synthesize compound (1H).

(IX) Formation of —CH ₂ O— or —OCH ₂ — The compound (11) is reduced with a reducing agent such as sodium borohydride to obtain a compound (16). This is halogenated with hydrobromic acid or the like to obtain a compound (17). Compound (1J) is synthesized by reacting compound (17) with compound (9) in the presence of potassium carbonate or the like.

Formation of (X) — (CH ₂ ) ₃ O— or —O (CH ₂ ) ₃ — Compound (1K) is synthesized according to the method of section (IX) using compound (18) instead of compound (11). I do.

_{(XI) - (CF 2)} 2 - generation of
... J. Am Chem Soc, 2001, 123, according to the method described in 5414. in the presence of a hydrogen fluoride catalyst diketone (21), and fluorinated with sulfur tetrafluoride - (CF _{2) 2} - (1 L) having the formula

  A first composition of the present invention is a composition containing at least one of the compounds (1) and (2) and a non-polymerizable liquid crystal compound. In the following description, “a non-polymerizable liquid crystal compound” is referred to as “non-polymerizable liquid crystal”. Compounds (1) and (2) have high properties as a liquid crystal, such as an appropriate temperature range of a liquid crystal phase and suitable compatibility with other liquid crystal compounds. Therefore, a liquid crystal composition containing the compound (1) or (2) and a non-polymerizable liquid crystal can be used as a composition to be enclosed when a liquid crystal display device is manufactured. By subjecting such a composition to appropriate polymerization conditions, the compound (1) or (2) in the composition is polymerized to form a network structure by polymerization. Thus, the first of this composition can be used as a material for PDLC and PNLC.

  When the compound (1) or (2) is optically active, it is useful for adjusting the helical pitch of the composition. This liquid crystal composition can also be used as a raw material for obtaining the polymer of the present invention. In that case, a composite of the polymer of the present invention and a liquid crystal compound may be used. Examples of the non-polymerizable liquid crystal are liquid crystal compounds described in a liquid crystal compound database LiqCryst (registered trademark) (LCI Publisher GmbH (Hamburg, Germany)). The liquid crystal composition may further contain an additive such as a dichroic dye.

  A second composition of the present invention is a composition containing at least one of the compound (1) or (2) and a polymerizable compound other than the compound (1) or (2). In the following description, “a polymerizable compound other than the compound (1) or (2)” is referred to as “another polymerizable compound”, and “at least one of the compound (1) or (2) and the other polymerizable compound” The “containing composition” is referred to as a “polymerizable composition”. The polymerizable composition preferably has a liquid crystal phase, but may not have a liquid crystal phase depending on the purpose. The description of the polymerizable composition is included in the following description of the polymer.

The polymer of the present invention is a polymer obtained by polymerizing at least one of the compounds (1) and (2). The polymer (1) and the polymer (2) can be produced by polymerizing the compound (1) and the compound (2), respectively. The first of the polymers of the present invention is a homopolymer obtained by homopolymerizing one of the compounds (1) and (2). The second of the polymers of the present invention is a copolymer obtained by copolymerizing at least two of the compounds (1) and (2). The third of the polymer of the present invention is a composition containing at least one compound (1) or (2) and another polymerizable compound, that is, a copolymer obtained by copolymerizing a polymerizable composition. is there. All of these polymers have structural units (3-1-p) to (3-5-p) derived from the polymerizable groups (3-1) to (3-5).

  The compound (1) having a polymerizable group (3-1) has high radical polymerizability. Polymerization is possible in the presence of a radical polymerization initiator such as azobisisobutyronitrile. The polymer (1) having the structural unit (3-1-p) has high transparency.

  The compound (1) having a polymerizable group (3-2) and the compound (1) having a polymerizable group (3-4) have high radical polymerizability. These compounds (1) have particularly high radical polymerizability by ultraviolet rays. When the polymer (1) having the structural unit (3-2-p) or the structural unit (3-4-p) is produced by photopolymerization, the mechanical strength is high and the surface hardness is high.

  The compound (1) having a polymerizable group (3-3) and the compound (1) having a polymerizable group (3-5) have high cationic polymerizability. Polymerization can be performed even in the presence of a substance (eg, oxygen) that inhibits the polymerization reaction. The polymer (1) having the structural unit (3-5-p) has excellent adhesion to various substrate materials. Since the curing shrinkage is small, it can be suitably used for various optically functional thin films.

  Compound (1) has one polymerizable group. Compound (2) has two polymerizable groups. Essentially, compound (2) has the same basic characteristics as compound (1) having a corresponding polymerizable group. In addition, compound (2) has higher polymerizability than compound (1). Compound (2) has a high polymerization rate and is completed in a short time. Compound (2) gives a polymer with a high degree of polymerization. The obtained polymer (2) has high heat resistance, low water permeability, water absorption and gas permeability, and mechanical strength (particularly Young's modulus, tensile strength, tear strength, bending strength, flexural modulus, impact strength) Excellent in strength, hardness, chemical stability (chemical resistance), etc.

  When at least two of the compounds (1) and (2) or the polymerizable composition is polymerized, a copolymer is obtained. By appropriately selecting at least two of the compounds (1) and (2) or the composition of the polymerizable composition, the polymer (1) or the polymer (2) having desired properties can be produced. . For example, when a compound (2) having a polymerizable group (3-1) and a compound (2) having a polymerizable group (3-2) are polymerized, mechanical strength, surface hardness, heat resistance, and transparency are improved. An excellent polymer (2) is obtained. This has the properties of each polymer (2) obtained by homopolymerizing the compound (2) having the polymerizable group (3-1) and the compound (2) having the polymerizable group (3-2). It shows that a copolymer is obtained.

  A thermoplastic resin can be produced using the compound (1) or the compound (2). The preferred weight average molecular weight of the thermoplastic resin is from 500 to 100,000, more preferably from 1,000 to 50,000, and even more preferably from 2,000 to 10,000. When producing a thermoplastic resin, it is necessary not to increase the degree of polymerization or to adjust the weight average molecular weight to the above range. Compound (1) having one polymerizable group is advantageous.

  Thermosetting resins can be produced using the compounds of the present invention. The thermosetting polymers (1) and (2) have a three-dimensional crosslinked structure, become insoluble and infusible, and the molecular weight cannot be measured. When producing a thermosetting resin, the compound (2) having two polymerizable groups having a large polymerization rate is advantageous.

  Other polymerizable compounds contained in the polymerizable composition are used for optimizing thin film forming property, mechanical strength and thermal strength, and can be copolymerized with the compound (1) or (2). There is no particular limitation as long as it is present, and it need not have liquid crystallinity. Examples of the polymerizable compound having no liquid crystallinity include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, and itaconic acid derivatives.

  Preferred vinyl derivatives are vinyl chloride, vinyl fluoride, vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, and vinyl propionate. , Vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, N-vinylacetamide, vinyl pt-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, ethyl vinyl ether, hydroxybutyl monovinyl ether , T-amyl vinyl ether, cyclohexane dimethanol methyl vinyl ether, α, β-vinylnaphthalene, methyl vinyl ketone, isobutyl vinyl ketone and the like. Preferred styrene derivatives are styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, α-methylstyrene and the like.

  Preferred (meth) acrylic acid derivatives are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, 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, trimethylol Propane triacrylate, trimethylol EO added triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, bis Phenol A EO addition diacrylate, bisphenol A glycidyl Jijiru diacrylate (trade name: Osaka Organic Chemical Co., Ltd. Viscoat 700) is polyethylene glycol diacrylate dimethyl itaconate.

  Preferred sorbic acid derivatives are sodium sorbate, potassium sorbate, lithium sorbate, 1-naphthylmethyl ammonium sorbate, benzyl ammonium sorbate, dodecyl ammonium sorbate, octadecyl ammonium sorbate, methyl sorbate, ethyl sorbate, sorbin Propyl acid, isopropyl sorbate, butyl sorbate, t-butyl sorbate, hexyl sorbate, octyl sorbate, octadecyl sorbate, cyclopentyl sorbate, cyclohexyl sorbate, vinyl sorbate, allyl sorbate, propargyl sorbate, etc. is there.

  Preferred fumaric acid derivatives are dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclopentyl fumarate, dicyclohexyl fumarate and the like. Preferred itaconic acid derivatives are diethyl itaconate, dibutyl itaconate, diisopropyl itaconate and the like. In addition, butadiene, isoprene and the like can be used. The polymerizable compound that does not exhibit liquid crystallinity is not limited by the above examples.

  The other polymerizable compound having liquid crystallinity is a liquid crystal compound having, as a functional group, an acryloyloxy group, a methacryloyloxy group, a fumaroyloxy group, a maleimidyl group, an oxirane ring, or an oxetane ring, and the compound (1) or ( Examples that are not 2) can be given. Among them, the liquid crystalline acrylic acid derivative is preferable because it gives a transparent polymer having high mechanical strength. This compound can also be used to adjust the temperature range of the liquid crystal phase of the polymerizable composition.

In addition, among the other polymerizable compounds having the above liquid crystallinity, compounds other than the liquid crystalline acrylic acid derivative may require a longer time for polymerization than the acrylic acid derivative. However, these polymerizable compounds are useful because they suppress the formation of by-products and improve the mechanical strength and thermal stability of the polymer. In order to maintain the characteristics of the polymer of the present invention and to remarkably exhibit the characteristics of such a copolymer, structural units other than those represented by formulas (3-1-p) to (3-5-p) must be used. It is necessary that the content is preferably 5 to 95 mol%, more preferably 60 to 95 mol%. Among the structural units other than the structural units represented by formulas (3-1-p) to (3-5-p), the structural units having liquid crystallinity and the structural units having no liquid crystallinity are within this range. Can be freely changed, as long as their total amount is within the above-mentioned range. Alternatively, only one of them may be used.
Examples of the polymerizable compound other than the compound (1) or (2) having a liquid crystal property include, for example, formulas (BRM-1) to (BRM-16).

In the formulas (BRM-1) to (BRM-16), P ⁰ is a polymerizable group having an acryloyloxy group, a methacryloyloxy group, a fumaroyloxy group, a maleimidyl group, an oxirane ring, or an oxetane ring; the number 2 to 15 are alkylene, [delta] is 0 or 1, ^{X 0} represents an alkoxy alkyl or 1 to 15 carbon atoms of 1 to 15 carbon atoms, halogen, halogenated alkyl or C 1 to 3 carbon atoms A halogenated alkoxy having the formulas 1 to 3, -CN, or -O (CH ₂ ) _γP ⁰ , wherein L ¹ , L ² , L ³ and L ⁴ are each independently hydrogen, a halogen, a C ¹ to C 15 alkyl, alkoxy having 1 to 15 carbon atoms, a halogenated alkyl of 1 to 3 carbon atoms, is a halogenated alkoxy having 1 to 3 carbon ^{atoms, L} 3 = L ⁴ = trifluoromethyl And ^{L 3} = is not hydrogen and ^{L 4} = trifluoromethyl.

  Among them, particularly suitable polymerizable compounds other than the compound (1) or (2) having liquid crystallinity are represented by the following formulas (BRM-a-1) to (BRM-a-11) and formula (BRM-b-1). To (BRM-b-11). Any liquid crystal compound having similar physical properties can be suitably used, and this exemplification does not limit the constitution of the composition of the present invention.

  The polymer of the present invention is a polymerizable polymer containing one of compound (1) or (2), at least two of compound (1) or (2), or at least one of compound (1) or (2). The composition can be obtained by adding an initiator, a catalyst, a solvent, and the like, if necessary, and polymerizing the composition. The copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer and the like. The arrangement repeating unit may be any of isotactic, syndiotactic, and atactic.

  In order to obtain the polymer of the present invention from the compound (1) or (2), various polymerization reaction types can be used. Available polymerization reaction types include free radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization. In order to produce the polymer of the present invention, it is preferable to select a polymerization method suitable for the use. For example, in order to produce an optically anisotropic film such as a retardation film or a polarizing element, it is necessary to rapidly polymerize while maintaining a liquid crystal phase. Therefore, a polymerization method of irradiating ultraviolet rays or an electron beam is preferable. . At that time, the compound (1) or (2) and another polymerizable compound as an optional component are polymerized in the presence of a photo-radical polymerization initiator, if necessary.

  Examples of the initiator of the photoradical polymerization method include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocure 1173), 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184), 2,2-Dimethoxy-1,2-diphenylethan-1-one (trade name: Irgacure 651), Irgacure 500 (trade name), Irgacure 2959 (trade name), Irgacure 907 (trade name), Irgah Cure 369 (trade name), Irgacure 1300 (trade name), Irgacure 819 (trade name), Irgacure 1700 (trade name), Irgacure 1800 (trade name), Irgacure 1850 (trade name), Darocure 4265 (trade name) (Trade name), Irgacure 784 (trade name), p-methoxyph Nyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethylketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2,4-diethylxanthone / p-dimethyl And methyl aminobenzoate mixtures.

  A polymer obtained by a thermal polymerization method or a photopolymerization method can be applied to various protective films, liquid crystal alignment films, viewing angle compensation films, and the like. In the photopolymerization method, by using polarized light, particularly polarized UV light, the polymerizable molecules can be polymerized in a state where they are aligned in the direction of polarized light. Therefore, the polymer obtained by the photopolymerization method can be applied to various protective films, liquid crystal alignment films, and other alignment films that do not require rubbing. Since the polymer of the present invention has optical anisotropy, used alone as a retardation film or in combination with another retardation film, a polarizing element, a circularly polarizing element, an elliptically polarizing element, an antireflection film, It can be applied to a color compensator, a selective reflection film, a viewing angle compensator and the like.

  A composition containing an appropriate amount of the optically active compound (1) or (2) or a composition obtained by adding an appropriate amount of the optically active compound to the compound (1) or (2) having no optical activity is oriented. A phase difference film exhibiting a helical structure (twist structure) can be obtained by applying the composition on the treated substrate and polymerizing it. This helical structure is fixed by polymerization of the compound (1) or (2). The properties of the obtained molded article having optical anisotropy depend on the helical pitch of the obtained helical structure. The helical pitch length can be adjusted by the type and the amount of the optically active compound added. One optically active compound may be added, but a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the helical pitch. In addition to the compound (1) or (2) and the optically active compound, a polymerizable compound other than the compound (1) or (2) may be included in the composition.

  In the selective reflection of visible light, which is a characteristic of the molded article having optical anisotropy, a helical structure acts on incident light to reflect circularly polarized light or elliptically polarized light. Since the selective reflection characteristic is represented by λ = n · Pitch (where λ is the central wavelength of selective reflection, n is the average refractive index, and Pitch is a helical pitch), λ and its band (Δλ) are appropriately adjusted by n and Pitch. be able to. Δλ may be reduced to improve color purity, and Δλ may be increased when broadband reflection is desired. Further, this selective reflection is greatly affected by the cell thickness. In order to maintain color purity, the cell thickness must not be too small. In order to maintain the uniformity of the orientation, the cell thickness must not be too large. Therefore, an appropriate adjustment of the cell thickness is required, and the thickness is preferably 0.5 to 25 μm, more preferably 0.5 to 5 μm.

By making the helical pitch shorter than visible light, a negative-type c-plate (c-plate) described in WH de Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980) can be prepared. The helical pitch can be shortened by using an optically active compound having a large twisting power (HTP: helical twisting power) and further increasing the amount thereof.
Specifically, a negative c-plate can be prepared by setting λ to 350 nm or less, preferably 200 nm or less. This negative c-plate serves as an optical compensation film suitable for a display device such as a VAN type, a VAC type, and an OCB type among liquid crystal display devices.

  As the optically active compound to be added, any optically active compound may be used as long as it induces a helical structure and can be appropriately mixed with the polymerizable composition as a base. For example, the following optically active compounds (Op-1) to (Op-13) are suitable.

式中、Ｒｆは炭素数１〜１０のアルキルであり、＊が付与された炭素は不斉炭素である。

In the formula, Rf is alkyl having 1 to 10 carbons, and the carbon given * is an asymmetric carbon.

The optically active compound to be added may be either a polymerizable compound or a non-polymerizable compound. Can be optimized according to purpose. In consideration of heat resistance and solvent resistance, a polymerizable compound is more preferable. Further, it is preferable that the added optically active compound has a large torsional force (HTP: helical twisting power) to shorten the helical pitch. A representative example of a compound having a large torsional force is disclosed in DE 10221751. Particularly preferred compounds are the following (Op-14) to (Op-19).
(Op-14) to (Op-16) are polymerizable compounds, and (Op-17) to (Op-19) are non-polymerizable compounds. Here, if introducing a polymerizable group into _-C 3 _{H 7} of the ends of the compound (Op-17) ~ (Op -19), the optically active compound with a useful polymerizable.

  In order to produce an alignment film, an antireflection film, a viewing angle compensation film, and the like, a thermal polymerization method is preferable. In the thermal polymerization, the compound (1) or (2) and another polymerizable compound as an optional component are polymerized in the presence of a radical polymerization initiator. Preferred initiators for radical polymerization by heat are benzoyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxide (DTBPO). ), T-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), and the like. The polymerization is generally carried out at a reaction temperature of 0 to 150 ° C. for 1 to 100 hours.

Preferred initiators for anionic polymerization and coordination polymerization _{method, n-C 4 H 9 Li} , alkali metal alkyl such as _{t-C 4 H 9 Li-} R 3 Al, an aluminum compound, a transition metal compound and the like.

  At least one of the compounds (1) and (2), or the polymerizable composition containing them, can also be polymerized by cationic polymerization. Cationic polymerization can be initiated by light irradiation or heating. A cationic polymerization initiator can be added to shorten the reaction time and increase the degree of polymerization. As the photocation, a Bronsted acid, a metal halide compound, and an onium salt can be suitably used. For specific examples, see Makromolekulare Chemie, VCH Verlag, Weinheim and An Introduction to Polymer Science, VCH Verlag, Weinheim.

The polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, but polymerization in air is also possible by optimizing the structures of the initiator and the compound.
When the polymerizable group is represented by the formula (3-5), the compound (1) or (2) reacts with a nucleophile such as phenol or amine to generate a secondary alcohol. By using a polyfunctional nucleophile, a polymer can be produced.

  In the polymerization, a solvent may be added to at least two of the compounds (1) and (2) or the polymerizable composition in addition to the initiator and the catalyst. Preferred solvents are, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone, cyclohexanone , PGMEA and their mixed solvents. When manufacturing an alignment film, an antireflection film, a viewing angle compensation film, etc. by photopolymerization, a solution of the composition is applied on a substrate by a spin coating method, and after removing the solvent, irradiation with light is performed to polymerize. You may. A known coater (doctor blade, coating apparatus, etc.) may be used for coating the composition on the substrate. It is not meaningful to limit the ratio of the solvent used during the polymerization. It may be determined for each individual case in consideration of polymerization efficiency, solvent cost, energy cost, and the like.

  The isolated polymer can be formed by dissolving in a solvent. Preferred solvents are N-methylpyrrolidone, dimethylsulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylacetamidodimethylacetal, tetrahydrofuran, chloroform, 1,4-dioxane, bis (methoxyethyl) Ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, cyclohexane, methylcyclohexane, cyclopentanone, cyclohexanone, PGMEA, and the like. However, the solvent is not limited to these, and may be a mixture with common organic solvents such as acetone, benzene, toluene, heptane, and methylene chloride. It should be noted that it is not very meaningful to limit the proportion of the solvent used during molding, as in the case of polymerization. It may be determined for each case in consideration of the thickness of the thin film to be manufactured, the vapor pressure of the solvent in the manufacturing environment, and the like. Depending on the application, at least two of the polymers of the present invention can be used as a mixture, or can be used by laminating. In the case of using a laminated structure, a thin film may be directly formed by photopolymerization without isolating the polymer.

  Since the polymer of the present invention has optical anisotropy, it can be used alone for a retardation film. By combining this polymer with another retardation film, it can be used for a polarizing plate, a circularly polarizing plate, an elliptically polarizing plate, an antireflection film, a color compensating plate, a viewing angle compensating plate and the like. The compounds of the present invention can also be used as adhesives, synthetic polymers having mechanical anisotropy, cosmetics, decorative articles, non-linear optical materials and information storage materials.

The polymer of the present invention has a refractive index of about 1.35 to 1.60. The refractive index can be optimized by selecting the structures of the compounds (1) and (2). That is, a large refractive index can be obtained by increasing unsaturated bonds, and a small refractive index can be obtained by reducing unsaturated bonds and introducing halogen. The refractive index can also be adjusted by adding inorganic fine particles. By adding the fine particles, the refractive index can be increased to about 2.50, and at the same time, the adhesion and the mechanical strength are improved. Fine particles such as TiO ₂ , SiO ₂ , SnO ₂ having a particle diameter of about 10 nm to 1 μm can be used for this purpose.

  Since the compound (2) has a polymerizable group at both ends, a polymer having a large degree of polymerization and a large molecular weight can be easily prepared. In a composition containing the compound (2) and a compound other than the compound (2), when the compound other than the compound (2) contains many compounds having one polymerizable group, the molecular weight of the obtained polymer is small, Low glass transition point and low melting point and excellent workability such as moldability. The preferred molecular weight range for applications requiring such properties is 500 to 100,000 in terms of weight average molecular weight. When a compound other than the compound (2) is polyfunctional, the resulting polymer has a large molecular weight and is excellent in chemical resistance and heat resistance. For applications requiring such properties, the preferred range of molecular weight is 100,000 or more in terms of weight average molecular weight. When the composition of the present invention is coated and polymerized on a substrate to obtain the optical anisotropy by fixing the molecular orientation, the size of the molecular weight does not matter because no further processing is performed. What is necessary is just to satisfy the conditions in the use environment.

  To further increase the molecular weight, a crosslinking agent can be added to the composition of the present invention. This composition can provide a polymer having an infinite molecular weight. The resulting polymer is extremely excellent in chemical resistance and heat resistance. As the crosslinking agent, any one can be used as long as it is known to those skilled in the art. For example, tri (3-methylmercaptopropionate) can be used.

  The compounds and compositions of the present invention have high polymerizability. Stabilizers can be added to facilitate handling. As the stabilizer, any one known to those skilled in the art can be used, and examples thereof include hydroquinone, 4-ethoxyphenol and 3,5-di-t-butyl-4-hydroxytoluene (BHT). .

  When forming an optically anisotropic thin film, any substrate can be suitably used as long as it is known to those skilled in the art. For example, glass, polyester such as polyethylene terephthalate (PET), polyvinyl alcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC), and ZEONOR (registered trademark: manufactured by Nippon Zeon Co., Ltd.) and ZEONEX (registered trademark) : Manufactured by Zeon Corporation) and Arton (registered trademark: manufactured by JSR Corporation). The polymer of the present invention has excellent adhesion to these substrates and is suitable.

  The orientation of the compound of the present invention on the substrate can be obtained by subjecting the alignment film applied on the substrate to a rubbing treatment and applying the composition of the present invention thereon. As long as the orientation can be controlled, the object can be achieved using any of the orientation films known to those skilled in the art, but polyimide, polyamide and polyvinyl alcohol-based orientation films are preferred. Alternatively, the orientation can also be obtained by rubbing the substrate itself with a rubbing cloth or the like and directly applying the composition of the present invention. The composition containing the oriented compound of the present invention is industrially advantageous since it is polymerized by light irradiation or the like to give a molded article having optical anisotropy.

The compounds, compositions and polymers of the present invention can also be used in liquid crystal display devices such as color filters, holographic devices, PDLC (Polymer Dispersed Liquid Crystal), and PSCT (Polymer Stabilized Cholesteric Texture).
The compounds (1) and (2) are suitably used particularly for an alignment-controlled polymer liquid crystal thin film. Those skilled in the art can easily apply these to liquid crystal display elements.
Further, the compound (1) or (2) is mixed with a ferroelectric liquid crystal or an antiferroelectric liquid crystal and polymerized to form a ferroelectric liquid crystal display element or an antiferroelectric liquid crystal stabilized by polymerization. A liquid crystal display element can be formed. The specific method of constructing the display element itself is known in the literature (J. of Photopoly. Sci. Technol., 2000, 13 (2), 295-300).

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The structure of the compound was confirmed by a nuclear magnetic resonance spectrum, a mass spectrum and the like. The unit of the phase transition temperature is ° C., C represents a crystal, N represents a nematic phase, Iso represents an isotropic liquid phase, and parentheses represent a monotropic liquid crystal phase. For example, the notation “C 100.0 N” indicates that the phase transition temperature from the crystal to the nematic phase is 100.0 ° C. The phase transition temperature was observed using a DSC and a polarizing microscope.

  For the measurement of the weight average molecular weight and the number average molecular weight, Shimadzu LC-9A type gel permeation chromatography (GPC) manufactured by Shimadzu Corporation and column Shodex GF-7M HQ manufactured by Showa Denko KK (developing solvent is DMF) Or THF) was used. The pencil hardness was determined according to the method of JIS standard "JIS-K-5400 8.4 Pencil scratch test". Note that the unit symbol L represents liter.

Example 1
Production of 2,3-bistrifluoromethyl-1,4-di (4- (6-acryloyloxyhexyloxy) benzoyloxy) benzene (compound (1-13-7)) Compound (1-13- 7) was manufactured.

2,3-bistrifluoromethylhydroquinone (g) (1.46 g), 4- (6-acryloyloxyhexyloxy) benzoic acid (h) (4.66 g), 4-dimethylaminopyridine (1.83 g), and A mixture of THF (70 mL) was cooled in an ice bath. To this was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (4.50 g) at the same temperature, and the mixture was stirred overnight. Distilled water was added and the reaction mixture was extracted with methylene chloride. The organic layers were combined, washed with 2M hydrochloric acid and a saturated aqueous solution of sodium hydrogen carbonate, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain the desired product (3.36 g, yield: 56.7%) as colorless crystals having a nematic phase.
Phase transition temperature (° C.): C 90.3 (N 91.3) Iso.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.14 (d, 4H), 7.56 (s, 2H), 6.99 (d, 4H), 6.41 (dd, 2H), 6. 13 (dd, 2H), 5.82 (dd, 2H), 4.19 (t, 4H), 4.07 (t, 4H), 1.88-1.83 (m, 4H), 1.76 -1.71 (m, 4H), 1.58-1.45 (m, 8H).

Example 2
Production of 5,8-di (4- (6-acryloyloxyhexyloxy) benzoyloxy) -2,2-difluoro-1,3-benzodioxole (compound (1-23-7)) Compound (1-23-7) was produced.

5,8-dihydroxy-2,2-difluoro-1,3-benzodioxole (i) (3.02 g), 4- (6-acryloyloxyhexyloxy) benzoic acid (h) (9.24 g), A mixture of 4-dimethylaminopyridine (3.84 g) and THF (180 mL) was cooled in an ice bath. 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide (9.06 g) was added thereto at the same temperature, and the mixture was stirred overnight. Distilled water was added and the reaction mixture was extracted with methylene chloride. The organic layers were combined, washed with 2M hydrochloric acid and a saturated aqueous solution of sodium hydrogen carbonate, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain the desired product (7.66 g, yield 65.7%) as a colorless liquid.
_{^{1 H-NMR (CDCl 3;}} δ ppm): 8.01 (d, 4H), 7.02 (dd, 2H), 6.86 (d, 4H), 6.39 (dd, 2H), 6. 12 (dd, 2H), 5.81 (dd, 2H), 4.17 (t, 4H), 3.98 (t, 4H), 1.83-1.78 (m, 4H), 1.74 -1.70 (m, 4H), 1.56-1.42 (m, 8H).

Compounds (1-11-1) to (1-34-6) are produced according to the methods of Examples 1 and 2.

化合物（Ｂ）

Example 3
27 parts by weight of the compound (1-13-7) produced in Example 1, 40 parts by weight of the compound (A), 30 parts by weight of the compound (B), and a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals) ) 3 parts by weight were mixed to prepare a polymerizable liquid crystal composition (C). The resulting composition had a nematic phase in the temperature range from 52C to 100C.
Compound (A)

Compound (B)

Example 4
Two glass substrates with a polyimide alignment film having been subjected to rubbing treatment were opposed to each other at an interval of 5 μm so that the rubbing directions would make an angle of 180 °, thereby producing a cell. On a hot plate heated to 60 ° C., the polymerizable liquid crystal composition (C) obtained in Example 3 was injected into this cell. When observed in this state using a polarizing microscope, it was confirmed that there was no defect and the film was homogeneously aligned. When retardation was measured using a Berek compensator, a value of 890 nm was obtained. Further, this was placed on a hot plate heated to 60 ° C., and irradiated with ultraviolet rays of 365 nm at an intensity of 30 mW / cm ² for 10 seconds using an ultra-high pressure mercury lamp of 250 W as a light source to obtain composition (C). Was polymerized. When the obtained polymer was observed using a polarizing microscope, it was found that there was no defect and the homogeneous orientation was uniformly maintained. Further, when the retardation was measured using a Berek compensator, it was confirmed that the retardation did not change from that before polymerization, and that the retardation hardly changed even when left at 150 ° C. for 10 minutes.

Example 5
The polymerizable liquid crystal composition (C) obtained in Example 3 was dissolved in 200 parts by weight of cyclopentanone to prepare a solution having a concentration of about 33% by weight. This solution was applied to a glass substrate with a polyimide alignment film having been subjected to a rubbing alignment treatment using a bar coater capable of obtaining a wet film thickness of about 12 μm. This was placed on a hot plate heated to 70 ° C. for 120 seconds to perform solvent drying and liquid crystal alignment. Further, light with an intensity of 30 mW / cm ² (center wavelength: 365 nm) was irradiated for 20 seconds at room temperature using an ultra-high pressure mercury lamp of 250 W / cm to polymerize in a nitrogen atmosphere. Observation of the optical thin film thus obtained with a polarizing microscope confirmed that uniform liquid crystal alignment without alignment defects was obtained. When the retardation was determined using a Berek compensator, a value of 212 nm was obtained. Furthermore, the optical thin film was sandwiched between crossed Nicols polarizers so that the angle between the rubbing direction and the absorption axis of the polarizer was 45 °, and the state of light transmission on a backlight was observed. When observing the state of light transmission while tilting in the rubbing direction, it was confirmed that the change was symmetrical in the left and right directions with the front as the center. This suggests that the orientation vector of the liquid crystal skeleton in this optical thin film is horizontal to the glass substrate, that is, it is homogeneously oriented.

Example 6
Photopolymerization initiator Irga was added to a polymerizable composition comprising 25 parts by weight of compound (1-3-7), 35 parts by weight of compound (A), 25 parts by weight of compound (B), and 12 parts by weight of compound (OP-15). 3 parts by weight of Cure 907 (manufactured by Ciba Specialty Chemicals) are added. The polymerizable composition containing this photopolymerization initiator was dissolved in 200 parts by weight of cyclopentanone to prepare a solution having a concentration of about 33% by weight. This solution was applied to a glass substrate with a polyimide alignment film having been subjected to a rubbing alignment treatment using a bar coater capable of obtaining a wet film thickness of about 12 μm. This was placed on a hot plate heated to 70 ° C. for 120 seconds to perform solvent drying and liquid crystal alignment. Further, while being heated to 70 ° C. on a hot plate, light with an intensity of 30 mW / cm ² (central wavelength: 365 nm) was irradiated for 20 seconds using a 250 W ultra-high pressure mercury lamp to polymerize in a nitrogen atmosphere. As a result, an optical thin film exhibiting red selective reflection was obtained.

Example 7
The compound (1-13-7) (10 mg) produced in Example 1, azobiscyclohexanecarbonitrile (0.1 mg) and benzene (100 μL) were put in a glass ampoule. This was cooled to −60 ° C., sufficiently degassed with a vacuum pump, and then sealed. The ampoule was heated in a 70 ° C. water bath for 24 hours. The obtained reaction mixture was reprecipitated three times from methanol (15 mL) to obtain a polymer (8.1 mg). The weight average molecular weight (Mw) measured by GPC was 30,000. The polydispersity (Mw / Mn) was 1.99. The polymer (1.025 mg) was immersed in pure water (1 mL) and left at 50 ° C. for 10 days. The polymer was taken out, dried sufficiently, and weighed to find that it was 1.028 mg. It can be seen that the water absorption of this polymer is small.

Example 8
5 parts by weight of the polymer produced in Example 7 was dissolved in 100 parts by weight of NMP (N-methylpyrrolidone). This solution was applied to two glass substrates that had been sufficiently washed in advance using a spin coater. These glass substrates were heated at 200 ° C. for 3 hours, and the solvent was removed to form a polymer thin film on the glass substrate. The surface of the polymer thin film formed on these glass substrates was rubbed in one direction with a roller equipped with a rubbing cloth to perform a rubbing treatment. The two glass substrates were bonded so that the rubbing directions were the same with a 10 μm-thick spacer interposed therebetween in a direction in which the thin film of the polymer was opposed. A liquid crystal composition ZLI-1132 manufactured by Merck was injected into the cell at room temperature. The liquid crystal composition in the liquid crystal cell showed uniform homogeneous alignment.

Example 9
Preferred examples of the composition that can be prepared using the compound of the present invention are shown as Composition Examples 1 to 6. Each of them is polymerized by irradiation with UV light to give a molded article having optical anisotropy. In the following, (%) represents% by weight.

Composition Example 1

Composition Example 2

Composition Example 3

Composition Example 4

Composition Example 5

Composition Example 6

化合物（Ｂ）

Comparative Example 1
A polymerizable liquid crystal composition (E) is prepared by mixing 61 parts by weight of the compound (A), 26 parts by weight of the compound (B), and 3 parts by weight of a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals). did. When the obtained composition was gradually heated, crystals started to melt at around 85 ° C., and the whole showed a nematic phase at around 95 ° C. The melting point of the polymerizable liquid crystal composition (E) was much higher than that of the polymerizable liquid crystal composition (C) of Example 3, and the effect of lowering the melting point of the compound (1) of the present application was proved.
Compound (A)

Compound (B)

Claims (40)

A compound represented by the following formula (1) or (2).
_{^{R a -Z- (A-Z)}} m -R b (1)
_{^{R a -Z- (A-Z)}} m -R a (2)

In the formula, R ^a is any one of the polymerizable groups of the formulas (3-1) to (3-5); R ^b is hydrogen, halogen, —CN, —NCO, —NCS, or carbon number. 1-20 alkyl, wherein any -CH ₂ -is -O-, -S-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C- And any hydrogen may be replaced by halogen or -CN; A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2 , 6-Diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3 , 6-diyl, any of these rings -CH ₂ - may be replaced by -O-, arbitrary -CH = may be replaced by -N =, arbitrary hydrogen in these rings are halogen, alkyl having 1 to 5 carbon atoms or It may be substituted by an alkyl halide having 1 to 5 carbon atoms, and when these substituents are adjacent to each other, they may be bonded to each other to form a ring together with the carbon-carbon bond of the ring, A is a substituted 1,4-phenylene represented by the formula (4-1) or (4-2); Z is a single bond or an alkylene having 1 to 20 carbon atoms. arbitrary -CH ₂ - -O -, - S -, - COO -, - OCO -, - CH = CH -, - CF = CF- or -C≡C-, and any Hydrogen may be replaced by halogen; ^c is hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons; m is an integer of 1 to 6, and q is 0 or 1. A compound according to claim 1 ^{R a} is Formula (3-1) or (3-5) In the formula (1) and (2). In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), and A other than the ring represented by the formula (4-1) or the formula (4-2) is The compound according to claim 1, which is 1,4-cyclohexylene, 1,4-cyclohexylene in which any hydrogen is replaced by halogen, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by halogen. A compound as described. In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), and A other than the ring represented by the formula (4-1) or the formula (4-2) is 1,4-cyclohexylene, 1,4-cyclohexylene in which any hydrogen is replaced by halogen, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by halogen, wherein Z is single _{bond, - (CH 2) a -} , - O (CH 2) a -, - (CH 2) a O -, - O (CH 2) a O -, - CH = CH -, - C≡C- , -COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - OCF 2 -, or - CF ₂ is O-, a compound according to claim 1 a is an integer of from 1 to 20. Equation (1) and ^{R a} has the formula (2) (3-2) - A compound according to claim 1 is any one of (3-4). In formulas (1) and (2), ^Ra is any one of formulas (3-2) to (3-4), and a ring represented by formula (4-1) or formula (4-2). A other than 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced by halogen, 1,4-phenylene, or 1,4-phenylene in which arbitrary hydrogen is replaced by halogen A compound according to claim 1. In formulas (1) and (2), ^Ra is any one of formulas (3-2) to (3-4), and a ring represented by formula (4-1) or formula (4-2). A other than 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced by halogen, 1,4-phenylene, or 1,4-phenylene in which arbitrary hydrogen is replaced by halogen There, Z is a single _{bond, - (CH 2) a -} , - O (CH 2) a -, - (CH 2) a O -, - O (CH 2) a O -, - CH = CH-, -C≡C -, - COO -, - OCO -, - OCF 2 -, or _-CF 2 is O-, a compound according to claim 1 a is an integer of from 1 to 20.   The compound according to claim 1, wherein m is 2 in the formulas (1) and (2).   The compound according to claim 1, wherein m is 3 in the formulas (1) and (2).   The compound according to claim 1, wherein m is 4 in the formulas (1) and (2). In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), one of A is the formula (4-1), and the other A is 1,4- cyclohexylene, 1,4-phenylene or arbitrary hydrogen is replaced by halogen 1,4-phenylene, Z is a single bond, -COO -, - OCO -, - (CH 2) a -, - CH _{= CH-COO -, - OCO} -CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} is O-, a compound according to claim 1 a is an integer of from 1 to 20. In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), one of A is the formula (4-2), and the other A is 1,4- cyclohexylene, 1,4-phenylene or arbitrary hydrogen is replaced by halogen 1,4-phenylene, Z is a single bond, -COO -, - OCO -, - (CH 2) a -, - O _{(CH 2) a -, -} (CH 2) a O- or -O (CH _{2) a} is O-, a compound according to claim 1 a is an integer of from 1 to 20. In the formulas (1) and (2), ^Ra is the formula (3-1) or (3-5), one of A is the formula (4-1), and the other A is 1,4- phenylene, Z is -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} O- in The compound according to claim 1, wherein a is an integer of 1 to 20. In Formulas (1) and (2), ^Ra is any one of Formulas (3-2) to (3-4), one of A is Formula (4-1), and the other A is , 1,4-cyclohexylene, 1,4-phenylene or arbitrary hydrogen is replaced by halogen 1,4-phenylene, Z is a single bond, -COO -, - OCO -, - (CH 2) _{a -, - O (CH 2} ) a -, - (CH 2) a O- or -O (CH _{2) a} is O-, a compound according to claim 1 a is an integer of from 1 to 20. In Formulas (1) and (2), ^Ra is any one of Formulas (3-2) to (3-4), one of A is Formula (4-2), and the other A is , 1,4-cyclohexylene, 1,4-phenylene or arbitrary hydrogen is replaced by halogen 1,4-phenylene, Z is a single bond, -COO -, - OCO -, - (CH 2) _{a -, - O (CH 2} ) a -, - (CH 2) a O- or -O (CH _{2) a} is O-, a compound according to claim 1 a is an integer of from 1 to 20. In Formulas (1) and (2), ^Ra is any one of Formulas (3-2) to (3-4), one of A is Formula (4-1), and the other A is , 1,4-phenylene, Z is -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH ₂ ) _a is O-, a compound according to claim 1 a is an integer of from 1 to 20. A compound represented by any one of the following formulas (a) to (r).
^Ra- ZB- ^Ra (a)
^{R a -Z-B-Z-} A-R a (b)
^{R a -Z-B-Z-} A-Z-A-R a (c)
R ^a -ZA-Z-B-Z-A-R ^a (d)
^{R a -Z-B-Z-} A-Z-A-Z-A-R a (e)
R ^a -ZA-Z-B-Z-A-Z-A-A-R ^a (f)
^{R a -Z-B-Z-} A-Z-A-Z-A-Z-A-R a (g)
R ^a -ZA-Z-B-Z-A-Z-A-Z-A-A-R ^a (h)
^{R a -Z-A-Z-} A-Z-B-Z-A-Z-A-R a (i)
^{R a -Z-B-Z-} R a (j)
^{R a -Z-B-Z-} A-Z-R a (k)
^{R a -Z-B-Z-} A-Z-A-Z-R a (l)
^{R a -Z-A-Z-} B-Z-A-Z-R a (m)
^{R a -Z-B-Z-} A-Z-A-Z-A-Z-R a (n)
R ^a -ZA-Z-B-Z-A-Z-A-Z-Z-R ^a (o)
^{R a -Z-B-Z-} A-Z-A-Z-A-Z-A-Z-R a (p)
R ^a -ZA-Z-B-Z-A-Z-A-Z-A-Z-Z-R ^a (q)
^{R a -Z-A-Z-} A-Z-B-Z-A-Z-A-Z-R a (r)

In the formula, R ^a is any one of the polymerizable groups of the formulas (3-1) to (3-5); R ^b is hydrogen, halogen, —CN, —NCO, —NCS, or carbon number. 1-20 alkyl, wherein any -CH ₂ -is -O-, -S-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C- And any hydrogen may be replaced by halogen or -CN; A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2 , 6-Diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3 , 6-diyl, any of these rings -CH ₂ - may be replaced by -O-, arbitrary -CH = may be replaced by -N =, arbitrary hydrogen in these rings are halogen, alkyl having 1 to 5 carbon atoms or B may be replaced by an alkyl halide having 1 to 5 carbon atoms, and when these substituents are adjacent to each other, they may combine with each other to form a ring together with the carbon-carbon bond of the ring; 4-1) or a substituted 1,4-phenylene represented by the formula (4-2); Z is a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, any -CH ₂ -May be replaced by -O-, -S-, -COO-, -OCO-, -CH = CH-, -CF = CF- or -C≡C-, and any hydrogen is replaced by halogen. R ^c is hydrogen, halogen, —CF ₃ or alkyl having 1 to 5 carbons; q is 0 or 1. In the formulas (a) to (r), A is 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in these rings may be replaced by halogen; Z is a single bond,- CH = CH -, - C≡C - , - COO -, - OCO -, - (CF 2) 2 -, - CF = CF -, - OCF 2 -, - CF 2 O -, - (CH 2) a -, - CH = CH-COO -, - OCO-CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - O (CH 2) a -, - (CH 2) _a O- or -O (CH _{2) a} is O-, a compound according to claim 17 a is an integer from 1 to 20. In the formulas (a) to (i), A is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which arbitrary hydrogen is replaced by halogen, and Z is a single bond, -COO -, - OCO -, - ( CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} a O-, a is from 1 to 20 18. The compound according to claim 17, which is an integer.   A liquid crystal composition comprising at least two polymerizable compounds, wherein at least one polymerizable compound is the compound according to any one of claims 1 to 19.   The liquid crystal composition according to claim 20, wherein all of the polymerizable compounds are the compounds according to any one of claims 1 to 19.   The liquid crystal composition according to claim 20, comprising at least one compound according to any one of claims 1 to 19 and at least one polymerizable compound other than the compound. 20. At least one compound according to any one of claims 1 to 19 and at least one polymerization selected from the group of compounds represented by formulas (A), (B) and (C). 21. The liquid crystal composition according to claim 20, comprising a hydrophilic compound.

Wherein R ^d is hydrogen, methyl, ethyl or propyl; R ^e is —CN, alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons; rings A ^a , ^Ab and ^Ac are Independently, 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which any hydrogen has been replaced by fluorine; ring ^Ad is 1,4-phenylene, or 2-methyl- be a 1,4-phenylene; ^{Z a} and ^{Z b} are independently a single _{bond, - (CH 2) 2 -} , - CH = CH-COO -, - OCO-CH = CH -, - CH 2 CH 2 —COO—, —OCO—CH ₂ CH ₂ —, —COO—, or —OCO—; α is an integer of 0 to 20; s is 0 or 1.   The liquid crystal composition according to any one of claims 20 to 23, wherein the liquid crystal composition further contains an optically active compound.   A polymer obtained by polymerizing at least one of the compounds according to claim 1.   A polymer obtained by homopolymerizing one of the compounds according to claim 1.   A polymer obtained by polymerizing the composition according to any one of claims 20 to 24.   The polymer according to claim 25, wherein the weight average molecular weight is from 500 to 100,000.   The polymer according to claim 25, wherein the weight average molecular weight is 1,000 to 50,000.   The polymer according to any one of claims 25 to 27, wherein the polymer is optically active.   A film obtained from the polymer according to any one of claims 25 to 30.   A molded article having optical anisotropy, comprising the polymer according to any one of claims 25 to 30.   A retardation film containing the polymer according to any one of claims 25 to 30.   A liquid crystal alignment film containing the polymer according to any one of claims 25 to 30.   An antireflection film containing the polymer according to any one of claims 25 to 30.   A viewing angle compensation film containing the polymer according to any one of claims 25 to 30.   A polarizing element containing the polymer according to any one of claims 25 to 30.   A film having a selective reflection function, comprising the polymer according to any one of claims 25 to 30.   The film according to claim 31, the molded article having optical anisotropy according to claim 32, the retardation film according to claim 33, the liquid crystal alignment film according to claim 34, and the reflection according to claim 35 A liquid crystal display comprising at least one selected from the group consisting of an anti-reflection film, a viewing angle compensation film according to claim 36, a polarizing element according to claim 37, and a film having a selective reflection function according to claim 38. element.   A liquid crystal display device comprising the composition according to claim 20.