JP2003342239A - Cyclopropane compound and polymer thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid crystal compound having polymerizable functional groups as a raw material for optically anisotropic polymers having sufficient properties in terms of heat resistance and mechanical strengths. <P>SOLUTION: The liquid crystal compound is a cyclopropane compound of formula (1) (wherein, R<SP>1</SP>and R<SP>2</SP>are each H, a polymerizable group, a halogen atom, CN, CF<SB>3</SB>, CF<SB>2</SB>H, CFH<SB>2</SB>, OCF<SB>3</SB>, OCF<SB>2</SB>H, NCO, NCS or a 1-20C alkyl, at least one of them being a polymerizable group; B<SP>1</SP>is a bivalent group of formula (2), formula (3) or formula (4); A is a single bond, the same as B<SP>1</SP>, 1,4- cyclohexylene group, 1,4-cyclohexenylene group, 1,4-phenylene group, naphthalen-2,6-diyl group or tetrahydronaphthalen-2,6-diyl group; Z is a single bond or a 1-20C alkylene group; (m) and (n) are each an integer of 0-10, totaling 0-10). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystalline cyclopropane compound having a polymerizable functional group, a composition containing this compound, a polymer thereof and uses thereof. The composition and the polymer are a liquid crystal composition which is a component of a liquid crystal display device, a retardation film, a reflective film, a polarizing element,
It can be used as a liquid crystal alignment film, an antireflection film, a viewing angle compensation film and the like.

Terms used in the present invention will be described.
“Liquid crystallinity” is not limited to the meaning that the compound has a liquid crystal phase. This term is also used for a compound which does not have a liquid crystal phase itself but can be used as a component of a liquid crystal composition when mixed with another liquid crystal compound. The term "arbitrary" used to indicate a specific group in a chemical formula means that the number as well as the position of the group is arbitrary. For example, any-in alkyl
When expressing that CH ₂ — may be replaced by —O— or —CH═CH—, each of a plurality of —CH ₂ — may be replaced by different groups. Examples of such cases are alkyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl and the like. “Alkyl” and “alkylene” include both straight-chain and branched groups unless otherwise specified. “(Meth) acryloyloxy” means “acryloyloxy or methacryloyloxy”.
“(Meth) acrylate” means “acrylate or methacrylate”. "(Meth) acrylic acid"
Means "acrylic acid or methacrylic acid".

[0003]

It is disclosed in Patent Document 1 that when a polymerizable liquid crystal compound is photopolymerized in an aligned state, a polymer having optical anisotropy is obtained by fixing a uniform aligned state. ing. As the polymerizable liquid crystal compound, an acrylate derivative is generally used because of its high reactivity and transparency of the resulting polymer (Patent Documents 2 and 3). Examples of preferable liquid crystal acrylate derivatives are compounds such as (a) to (c) below.

[0004]

[Patent Document 1] JP-A-8-3111

[Patent Document 2] JP-A-7-17910

[Patent Document 3] Japanese Unexamined Patent Publication No. 9-316032

[0005]

However, an optically anisotropic substance using a polymer of a known acrylate derivative is
It did not have sufficient characteristics in heat resistance and mechanical strength. An object of the present invention is to solve the problems of this prior art.

[0006]

As a result of research to solve the above-mentioned problems, the present inventors have found that cyclopropane-1,2-
It was found that the polymerizable liquid crystal compound having a diyl skeleton has excellent properties such as an appropriate temperature range of the liquid crystal phase and suitable compatibility with other liquid crystal compounds. Then, they found that the polymer was excellent in heat resistance and mechanical strength. The present invention has the following configurations.

[1] A cyclopropane compound represented by the formula (1). In formula (1), R ¹ and R ² are independently a polymerizable group, hydrogen, halogen, —CN, —CF ₃ , —CF.
_{2 H, -CFH 2, -OCF 3} , -OCF 2 H, -NC
O, —NCS, or alkyl having 1 to 20 carbons, at least one of R ¹ and R ² is a polymerizable group, and in this alkyl having 1 to 20 carbons, any —
CH ₂ - is -O -, - S -, - CO -, - COO -, -
OCO-, -NH-, -CH = CH-, -CF = CF-
Or it may be replaced by -C≡C- and any hydrogen may be replaced by halogen or -CN; B ¹
Is any one of the following divalent groups, any hydrogen in these groups may be replaced by halogen; A's are independently a single bond, B ¹ , 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, or tetrahydronaphthalene-2,6. - diyl, any -CH ₂ - in these rings - may be replaced by -O-, arbitrary -CH = may be replaced by -N =,
And in all the rings, any hydrogen may be replaced by halogen; Zs are independently a single bond or alkylene having 1 to 20 carbons, and in this alkylene, any —CH ₂ — is -O-, -CO-, -C
OO-, -OCO-, -CH = CH-, -CF = CF
_{-, - CF 2 O -,} - OCF 2 - or -C≡C-, arbitrary hydrogen may be replaced by halogen; m and n an integer independently 0 Yes, the sum of these is 0-10.

[2] The polymerizable group is a group represented by the formula (2), a group represented by the formula (3), or a group represented by the formula (4). Cyclopropane compounds. In these formulas, R ³ , R ⁴ and R ⁵ are independently hydrogen or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — is —O—, —CO.
May be replaced by O-, -OCO- or -CH = CH- and any hydrogen may be replaced by halogen; k is an integer from 0 to 20, h and j are independently 0 or a is ;-( CH _{2) k} 1 - in any -
CH ₂ — may be replaced by —O—.

[3] The cyclopropane compound according to the item [1] or [2], wherein the compound represented by the formula (1) is optically active.

[4] Only ^one of R ¹ and R ² is a group represented by formula (2), a group represented by formula (3) or a group represented by formula (4), [2] The cyclopropane compound according to the item.

[5] R ¹ and R ² are independently a group represented by formula (2), a group represented by formula (3) or a group represented by formula (4), [2 ] The cyclopropane compound as described in the above item.

[6] Only ^one of R ¹ and R ² is a group represented by the formula (2), a group represented by the formula (3) or a group represented by the formula (4), and R ³ , R ⁴ and R ⁵ are independently hydrogen, alkyl having 1 to 10 carbons, and 2-1 carbons.
The cyclopropane compound according to the item [2], which is an alkoxycarbonyl having 0 or an alkoxycarbonylalkyl having 3 to 10 carbon atoms.

[7] R ¹ and R ² are independently a group represented by the formula (2), a group represented by the formula (3) or a group represented by the formula (4), and R ³ , R ⁴ and R ⁵ are independently hydrogen, alkyl having 1 to 10 carbons, and 2-1 carbons.
The cyclopropane compound according to the item [2], which is an alkoxycarbonyl having 0 or an alkoxycarbonylalkyl having 3 to 10 carbon atoms.

[8] The cyclopropane compound according to item [1], which is represented by any one of formulas (G-1) to (G-11). R ¹ , B ¹ , R ² , A and Z in these formulas are
It is defined similarly to these symbols in equation (1).

[9] The cyclopropane compound according to the item [8], which is represented by any one of the formulas (G-1) to (G-6).

[10] A composition containing at least one of the cyclopropane compounds according to any one of [1] to [9].

[11] At least one of the cyclopropane compounds according to any one of [1] to [3],
A composition containing a polymerizable compound other than the cyclopropane compound according to the item [1].

[12] At least one compound selected from the group consisting of the cyclopropane compounds described in [4] and [5], and a polymerizable compound other than the cyclopropane compound described in [1]. A composition containing and.

[13] At least one compound selected from the group consisting of the cyclopropane compounds described in [6] and [7], and a polymerizable compound other than the cyclopropane compound described in [1]. A composition containing and.

[14] A composition containing at least one cyclopropane compound according to item [8] and a polymerizable compound other than the cyclopropane compound according to item [1].

[15] A composition containing at least one cyclopropane compound according to item [9] and a polymerizable compound other than the cyclopropane compound according to item [1].

[16] A composition containing at least one cyclopropane compound according to any one of [1] to [3] and a non-polymerizable liquid crystal compound.

[17] A composition containing at least one compound selected from the group consisting of the cyclopropane compounds described in each of the items [4] and [5], and a non-polymerizable liquid crystal compound.

[18] A composition containing at least one compound selected from the group consisting of the cyclopropane compounds described in [6] and [7] and a non-polymerizable liquid crystal compound.

[19] A composition containing at least one of the cyclopropane compounds described in the item [8] and a non-polymerizable liquid crystal compound.

[20] A composition containing at least one of the cyclopropane compounds described in [9] and a non-polymerizable liquid crystal compound.

[21] A polymer obtained from the cyclopropane compound according to any one of [1] to [9].

[22] A polymer obtained by hydrogenating the polymer according to the item [21].

[23] Any one of [10] to [15]
A polymer obtained from the composition according to the item.

[24] A polymer obtained by hydrogenating the polymer described in the item [23].

[25] The polymer is optically active, [2]
The polymer according to any one of 1] to [24]. [2
6] An optical anisotropic body containing the polymer according to any one of [21] to [25].

[27] Any one of [21] to [25]
A retardation film containing the polymer according to the item.

[28] Any one of [21] to [25]
A liquid crystal alignment film containing the polymer according to the item.

[29] Any one of [21] to [25]
An antireflection film containing the polymer according to the item.

[30] Any one of [21] to [25]
A viewing angle compensation film containing the polymer according to the item.

[31] Any one of [21] to [25]
A polarizing element containing the polymer according to the item.

[32] The optically anisotropic material as described in [26], the retardation film as described in [27], the liquid crystal alignment film as described in [28], and the antireflection film as described in [29]. Film, the viewing angle compensation film according to the item [30], and [3
[1] A liquid crystal display element containing at least one of the polarizing elements.

[33] Item [10] or [16] to [2]
[0]] A liquid crystal display device containing the composition according to any one of [1] to [4].

[34] The liquid crystal display device according to item [33], which further contains at least one optically active compound.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclopropane compound of the present invention is represented by formula (1). In the following description, the cyclopropane compound represented by the formula (1) may be referred to as the compound (1). B ¹ in the formula (1) is cyclopropane-1,2-diyl, 1,1′-bicyclopropane-3,3′-diyl,
Tercyclopropane-3,3 "-diyl, and these groups in which any hydrogen has been replaced with a halogen.
A preferred example of ^{No. 1} is shown below.

A plurality of A's in the formula (1) are independently a single bond, B ¹ , 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,
6-diyl or tetrahydronaphthalene-2,6-
It's Jeil. Arbitrary -CH ₂ in these rings - it may be replaced by -O-, arbitrary -CH = may -N
It may be replaced with =. Any -CH ₂ - is -O-
Examples replaced with are dioxane and the like. Examples in which any -CH = is replaced by -N = are pyridine, pyridazine, pyrimidine and the like. And in all rings, any hydrogen may be replaced by halogen. Examples of halogen include fluorine and chlorine, with fluorine being preferred.

Preferable examples of A include the above-mentioned B ¹ , 1,4-
Cyclohexylene, 2,2-difluoro-1,4-cyclohexylene, 3,3-difluoro-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4
-Phenylene, 3-fluoro-1,4-phenylene,
2,3-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,
5-diyl, 1,3-dioxane-2,5-diyl and the like. More preferable examples of A include 1,4-cyclohexylene, 2,2-difluoro-1,4-cyclohexylene, 3,3-difluoro-1,4-cyclohexylene,
1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, and 3,5-difluoro-1,4-phenylene Is.

At least one of R ¹ and R ^{2 in} the formula (1) is a polymerizable group. The polymerizable group may be any group as long as it has a polymerizable property. This may be an addition-polymerizable group or a functional group capable of forming a condensation polymer. Examples of the addition-polymerizable group include polyolefin, polystyrene, polydiene, polyacetylene, polyvinyl ester, polyvinyl ether, polyvinyl ketone, poly (meth) acrylate, and polymaleimide, which are polymerized alone or copolymerized with other compounds. It is a group capable of obtaining a polymer. Examples of functional groups capable of forming condensation polymers are:
NH-, -CHO, -COO-, 2-oxapropane-
Group having any one of 1,3-dioyl, -CSO-, -CSS- and epoxy, halogen, -OM
^{1, -SM 1, -COX 1,} -CSX 1, -OCO
X ¹ , —NCO, —SO ₂ X ¹ , —SiR ₂ X ² and the like. Where M ¹ is hydrogen or an alkali metal,
X ¹ is halogen and X ² is hydrogen or halogen.

Preferred examples of the polymerizable group are addition-polymerizable groups represented by the formulas (2), (3) and (4). In these formulas, R ³ , R ⁴ and R ⁵ are independently hydrogen or alkyl having 1 to 20 carbons. In this alkyl, any —CH ₂ — is —O—, —COO
It may be replaced by-, -OCO- or -CH = CH- and any hydrogen may be replaced by halogen. Preferred examples of R ^{3 to} R ⁵ include hydrogen and carbon atoms of 1 to 10.
Alkyl of 2 to 10 carbon atoms,
And alkoxycarbonylalkyl having 3 to 10 carbon atoms. Further preferred examples are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, butoxycarbonyl, and isobutyloxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, isopropyloxycarbonylmethyl, Butoxycarbonylmethyl, isobutyloxycarbonylmethyl and the like. k is an integer of 0 to 20, h and j are independently 0 or 1. And, any —CH ₂ — in — (CH ₂ ) _k — is —O—
May be replaced with.

Examples of the case where R ¹ or R ² in the formula (1) are not polymerizable are hydrogen, halogen, --CN, --CF ₃ ,-.
_{CF 2 H, -CFH 2, -OCF} 3, -OCF 2 H, -
NCO, -NCS, or alkyl having 1 to 20 carbons. Arbitrary -CH ₂ in the alkyl - is, -O
-, -S-, -CO-, -COO-, -OCO-, -N
H-, -CH = CH-, -CF = CF-, or -C≡
It may be replaced with C-. A plurality of --CH _2- ,
O-, -S-, -CO-, -COO-, -OCO-,-
NH-, -CH = CH-, -CF = CF- and -C≡
It may be replaced by two or more groups selected from C-, but adjacent two -CH ₂ - may, -O-O -, - O-
It is not replaced like S- or -S-S-. Any hydrogen in this alkyl may be halogen or-
It may be replaced by CN. The preferred halogen is fluorine. Preferred examples of R ¹ or R ² which is not a polymerizable group are —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —.
OCF ₃ , —OCF ₂ H, linear alkyl having 1 to 10 carbons, linear alkoxy having 1 to 10 carbons, and 2 carbons.
10 is a straight-chain alkoxyalkyl.

Further preferred examples are --CN, --CF ₃ ,-
_{CF 2 H, -CFH 2, -OCF} 3, -OCF 2 H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy,
Ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, methoxymethyl and methoxyethyl. Particularly preferred examples are alkyl and alkoxy among these.

Z in the formula (1) is a bonding group for bonding the rings together. Z's are independently a single bond or an alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in these alkylenes is —O—, —CO—, —CO.
O-, -OCO-, -CH = CH-, -CF = CF-,
It may be replaced by —CF ₂ O—, —OCF ₂ — or —C≡C—, and any hydrogen in these alkylenes may be replaced by halogen. Compound (1) has a bonding group of —COO—, —OCO—, —CF ₂ O—, and —OC.
When F ₂ −, —CH═CH—, or —C≡C—, it has a wide temperature range of a liquid crystal phase. The bonding group is -CF
_{When it is 2} O- or -OCF _2- , it has a relatively low viscosity.

Preferred examples of formulas (2) to (4) are shown below.
R ^{3 in} these formulas is hydrogen, alkyl having 1 to 10 carbons, alkoxycarbonyl having 2 to 10 carbons, or alkoxycarbonylalkyl having 3 to 10 carbons.
R ⁶ is alkyl having 1 to 10 carbons, and any —CH ₂ — in these alkyls is —O— or —CH═.
It may be replaced with CH-. R ⁷ is alkyl having 1 to 9 carbons. And, a is an integer of 1 to 20,
b is an integer of 1 to 10, but the sum of a and b is 2 to 19
Is.

[0049]

[0050]

[0051]

M and n in the formula (1) are independently 0 to
It is an integer of 10, and the sum of m and n is 1 to 10. A preferable example of the compound (1) is also represented by the following formula. R ¹ , B ¹ , R ² , A and Z in these formulas are
It is defined similarly to these symbols in equation (1). Among these formulas, formulas (G1) to (G6) are more preferable.

When attention is paid to the following structures, the compound (1)
Preferred examples of are shown by the following formulas (1-1) to (1-74), respectively.

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

In these formulas, R ¹ , B ¹ and R
The meanings of ² are the same as those in formula (1). The following symbols represent 1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine, and p and q are independently 0 to
It is an integer of 2. _{- (CH 2) r -,} - (CH 2)
_{s -, - (CH 2)} t -, and - _{(CH 2) u} - in, arbitrary -CH ₂ - may be replaced by -O-, but two adjacent -CH ₂ - at the same time It is not replaced by -O-. r, s, t and u are each independently an integer of 0-10. The above-exemplified compounds may or may not be optically active. The configuration of the asymmetric carbon is (R) configuration,
(S) Either body may be used. However, the racemic and meso isomers do not exhibit optical activity even if they have an asymmetric carbon. The site showing optical activity may be any of R ¹ , B ¹ and R ^{2 in} the formula (1), but is preferably B ¹ .

The compound (1) can be synthesized by combining organic synthetic chemistry techniques. A method for introducing a desired end group, ring and linking group into a starting material is described in Houben-Wyle, Methods of Organic Chemistry, G.
eorg Thieme Verlag, Stuttgart), Organic Syntheses, John Wiley & Sons, I
nc.), Organic Reactions (Organic React
ions, John Wiley & Sons Inc.), Comprehensive
Organic Synthesis (Comprehensive Organic Sy
nthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen)
Etc. The method of synthesizing and introducing a cyclopropane-1,2-diyl group is described in, for example, Tetrahedron Le
tt., 2000, 41, 8723, and J. Fluorine Chem., 200
1, 112, 63. A production method using these compounds as raw materials will be specifically described. Either method can be used regardless of the presence or absence of optical activity of the compound.

A cyclopropane compound having CH ₂ as a bonding group can be synthesized by reaction route 1. The symbols in the formulas used in all of the following synthetic routes have the same meanings as the symbols used in formulas (1) to (4), unless otherwise specified. <Reaction path 1>

The compound (102) is obtained by halogenating the compound (101) with carbon tetrabromide or the like. Cross-linking of compound (103) and compound (102) whose hydroxyl groups are protected with THP (tetrahydropyranyl)
Compound (104) is obtained by the coupling reaction.
The protective group for the hydroxyl group may be one commonly used in synthetic organic chemistry, such as THP, but it is necessary to select an optimal protective group for the conditions of the cross coupling reaction. Removal of the protecting group from compound (104) under acidic conditions gives compound (105). Compound (105)
Compound (1-a) is obtained by dehydrating and condensing with various acrylic acid compounds. In the dehydration condensation reaction, a condensing agent such as DCC (dicyclohexylcarbodiimide) can be used. When an acid chloride such as an acrylic acid compound is available, it may be esterified by reacting the compound (105) with the acid chloride under basic conditions. Further, instead of various acrylic acids, ester compounds thereof can be obtained by dehydration condensation with a carboxylic acid compound such as fumaric acid, itaconic acid, sorbic acid and muconic acid. This is
The same applies to all reaction routes shown below.

The cyclopropane compound having —OCO— as the bonding group can be synthesized by the reaction route 2. <Reaction path 2>

The carboxylic acid compound (111) can be obtained by reacting the above compound (101) with an oxidizing agent such as pyridinium dichromate. The obtained compound (111) is dehydrated and condensed with the compound (112) using the method described in the reaction route 1 to obtain the compound (113). Compound (114) is obtained by removing the protecting group of compound (113). Compound (114) is converted to compound (1-b) by reacting with an acrylic acid compound as described above.

The cyclopropane compound having —CO ₂ CH ₂ — as a bonding group can be synthesized by the reaction route 3. <Reaction path 3>

The compound (121) is esterified with the above-mentioned (101) to give a compound (122). After removing the protecting group of the compound (122) to give the compound (123), the compound (1-c) is obtained by dehydration condensation of this and the acrylic acid compound.

The cyclopropane compound having —OCF ₂ — as a bonding group can be synthesized by the reaction route 4. <Reaction path 4>

The above-mentioned carboxylic acid (111) was prepared according to the literature (An.
gew. Chem. Int. Engl., 2001, 40 (8), 1480) to obtain a stable intermediate (131) at room temperature by reacting with 1,3-propanedithiol and trifluoromethanesulfonic acid. To be This is reacted with the above compound (112) under basic conditions. The resulting dithiane compound was converted to DAST ((diethylamino) sulfur
Compound (132) is obtained by reacting with a nucleophilic fluorinating agent such as trifluoride) or HF / triethylamine complex. The compound (133) was prepared by removing the protecting group of this compound, and then the compound (1-d) was dehydrated and condensed with the acrylic acid compound.
Is obtained.

The cyclopropane compound having —OCH ₂ — as the bonding group can be synthesized by the reaction route 5. <Reaction path 5>

The above compound (112) is reacted with the compound (102) under basic conditions to give a compound (141). The compound (141) is converted to the compound (1-e) by dehydration condensation with an acrylic acid compound after removing the protecting group.
Be guided to.

The cyclopropane compound having —CH═CH— as a bonding group can be synthesized by the reaction route 6. <Reaction path 6>

Pyridinium is added to the above compound (101).
By acting an oxidizing agent such as chlorochromate,
An aldehyde compound (151) can be obtained. When the Wittig reaction of the compound (151) and the compound (152) is performed under basic conditions, the compound (153) is obtained. Removal of the protecting group of compound (153) under acidic conditions gives alcohol (154). By dehydration condensation of the compound (154) and an acrylic acid compound, the compound (1-
f) is obtained.

The cyclopropane compound having —C≡C— as a bonding group can be synthesized by the reaction route 7. <Reaction path 7>

When the above compound (151) was reacted with triphenylphosphine and carbon tetrabromide, the compound (16)
1) is obtained. The compound (162) is obtained by treating the compound (161) with a base such as n-BuLi. The compound (162) and the compound (103)
For example, by cross-coupling using the Castro reaction or the Sonogashira reaction, the compound (16
3) is obtained. The protecting group of the compound (163) was removed under acidic conditions, and the resulting compound (164) and an acrylic acid compound were dehydrated and condensed to give the compound (1-g).
Is obtained.

A cyclopropane compound in which R ¹ and R ² are acryloyloxy can be synthesized by Reaction Route 8. <Reaction path 8>

By appropriately applying the reactions described in Reaction Pathways 1 to 7 and other known reactions, the compound (171) can be obtained. The compound (1-h) is obtained by removing the protecting group of this compound under acidic conditions and subjecting the obtained compound (172) and an acrylic acid compound to dehydration condensation.

A cyclopropane compound in which R ¹ is fumaroyloxy, R ² is acryloyloxy, and has CO ₂ CH ₂ and CH ₂ OCO as bonding groups can be synthesized by Reaction Route 9. <Reaction path 9>

The compound (181) is hydrolyzed under basic conditions with sodium hydroxide or the like to give the compound (1).
82). The acrylate compound (183) can be obtained by appropriately applying the reactions described in Reaction Pathways 1 to 8 and other known reactions. This compound is replaced by the compound (18
It is dehydrated and condensed with 2) to give an ester compound (184). The fumarate compound (186) can be prepared by appropriately applying the reactions described in Reaction Pathways 1 to 8 and other known reactions.
Is obtained. The compound (184) is removed from the protective group to give the compound (185), and the compound (186) is dehydrated and condensed to obtain the compound (1-i).

A cyclopropane compound in which R ¹ is maleimide and has CH ₂ as a bonding group can be synthesized by the reaction route 10. <Reaction path 10> The compound (191) can be obtained by appropriately applying the reactions described in Reaction Pathways 1 to 9 and other known reactions. DE
Mitsunobu reaction with compound (191) in the presence of AD (diethyl azodicarboxylate) and triphenylphosphine induces compound (105) to compound (192). Compound (192) was added to the reverse Diels Alder (Di
els-Alder) reaction to give compound (1-j)
Is obtained.

A cyclopropane compound in which R ¹ is vinyl ether and has —CH ₂ — as a bonding group can be synthesized by Reaction Route 11. <Reaction path 11> By reacting the above compound (105) with the compound (201) together with a palladium catalyst, the compound (1-
k) is obtained.

A cyclopropane compound having R ¹ as a vinyl ketone and having CH ₂ as a linking group can be prepared by reaction route 12
Can be synthesized by. <Reaction path 12>

The compound (211) can be obtained by appropriately applying the reactions described in the reaction routes 1 to 11 and other known reactions. Grignard reagent (212) can be prepared by reacting this with magnesium. And (212)
The compound (214) can be obtained by allowing an acid chloride such as (213) to act with a catalyst as appropriate. Compound (1-1) can be obtained by reacting compound (214) with a base such as t-BuOK. Note that in Fe (acac) ₂ in the above route diagram, acac
Means acetylacetonate. The above production methods are all general methods, and the compound (1) is not limited by these production methods.

The composition of the present invention is a composition containing at least one compound (1). A preferred example of the compound (1) having an addition-polymerizable group is a group in which only one of R ¹ and R ² is a group represented by any one of formula (2), formula (3) and formula (4). Propane compound, and R ¹ and R ² are independently formula (2), formula (3) and formula (4)
A cyclopropane compound which is a group represented by any of the above. When two or more such compounds (1) are used in the composition of the present invention, only a compound having a polymerizable functional group at one end can be used. And it is also possible to use only a compound having a polymerizable functional group at both ends.
Further, a compound having a polymerizable functional group at one end and a compound having a polymerizable functional group at both ends can be used in combination. In the case of the compound (1) having a polycondensable group, both R ¹ and R ² are preferably a polycondensable group. At this time, R ¹ and R ² may be groups which react with each other, but it is preferable that both R ¹ and R ² are the same functional group. Then, a polycondensate is obtained from a composition of a compound having at least two functional groups capable of reacting with this group. The partner of the reaction for forming the condensation polymer may be selected from the compound (1).

The compound (1) having an addition-polymerizable group will be described below. The first of the preferred compositions is a composition containing at least one compound (1) and a non-polymerizable liquid crystalline compound. In the following description, “a non-polymerizable liquid crystal compound” is referred to as a “non-polymerizable liquid crystal compound”. The compound (1) exhibits high properties as a liquid crystal such as an appropriate temperature range of liquid crystal phase and a suitable compatibility with other liquid crystal compounds. Therefore, the liquid crystal composition containing the compound (1) and the non-polymerizable liquid crystal compound can be used as a liquid crystal composition enclosed when manufacturing a liquid crystal display device. The optically active compound (1) has a high twist-inducing force, and thus 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. For examples of non-polymerizable liquid crystal compounds, see Liquid Crystal Compound Database LiqC.
Liquid crystal compounds described in ryst (LCI Publisher Gmbh (Hambrug, Germany)) and the like. The liquid crystal composition may further contain an additive such as a dichroic dye.

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

The first of the polymers of the present invention is a homopolymer obtained by polymerizing one of the compounds (1). The second of the polymers of the present invention is a copolymer obtained by polymerizing at least two compounds (1). Third Polymer of the Invention
Is a copolymer obtained by polymerizing the polymerizable composition. Each of these polymers has a structural unit derived from the polymerizable functional group contained in the compound (1). That is, for example,
It has a structural unit derived from at least one of formulas (2) to (4). Then, when the polymerizable functional group of the compound (1) is a conjugated double bond, a polymer having a double bond in the main chain is obtained. The double bond in the main chain can be converted into a saturated bond by a hydrogenation reaction. The polymer of the present invention also preferably includes this hydrogenated polymer. The following are preferred constitutional units contained in the polymer of the present invention.

[0089] The meanings of R ³ , R ⁶ and R ⁷ in these constitutional units are the same as those in the preferred examples of formula (2) to formula (4).

The other polymerizable compound is not particularly limited as long as it does not deteriorate the film forming property and mechanical strength and can be copolymerized with the compound (1), and may not show liquid crystallinity. Examples of other polymerizable compounds are vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives and the like.

Preferred examples of the vinyl derivative having no liquid crystallinity are vinyl chloride, vinyl fluoride, vinyl acetate, vinyl pivalate, 2,2-dimethylbutanoate vinyl and 2,2.
-Vinyl dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate,
Vinyl 2-ethyl-2-methylbutanoate, N-vinylacetamide, vinyl p-t-butylbenzoate, N, N-
Examples thereof include vinyl dimethylaminobenzoate, vinyl benzoate, ethyl vinyl ether, hydroxybutyl monovinyl ether, t-amyl vinyl ether, cyclohexanedimethanol methyl vinyl ether, α, β-vinylnaphthalene, methyl vinyl ketone and isobutyl vinyl ketone. Preferred examples of the styrene derivative that does not exhibit liquid crystallinity are styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene,
Examples include m-chloromethylstyrene, p-chloromethylstyrene, α-methylstyrene and the like.

Preferred examples of the (meth) acrylic acid derivative having no liquid crystallinity are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and 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 addition tri Acrylate, pentaerythritol triacrylate,
Examples include trisacryloyloxyethyl phosphate, bisphenol A EO addition diacrylate, bisphenol A glycidyl diacrylate (trade name: viscoat 700 manufactured by Osaka Organic Chemical Co., Ltd.), and polyethylene glycol diacrylate dimethyl itaconate.

Preferred examples of the sorbic acid derivative having no liquid crystallinity are sodium sorbate, potassium sorbate, lithium sorbate, 1-naphthylmethylammonium sorbate, benzylammonium sorbate, dodecylammonium sorbate and octadecylammonium sorbate. , Methyl sorbate, ethyl sorbate, propyl sorbate, isopropyl sorbate, butyl sorbate, t-butyl sorbate, hexyl sorbate, octyl sorbate, octadecyl sorbate, cyclopentyl sorbate, cyclohexyl sorbate, vinyl sorbate. , Allyl sorbate, propargyl sorbate and the like.

Preferred examples of the fumaric acid derivative having no liquid crystallinity are dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclopentyl fumarate and dicyclohexyl fumarate. Preferred itaconic acid derivatives are diethyl itaconate, dibutyl itaconate, diisopropyl itaconate and the like. In addition, butadiene, isoprene and the like can be used. It should be noted that other polymerizable compounds that do not exhibit liquid crystallinity are not limited to the above examples.

Examples of other polymerizable compounds having liquid crystallinity but not compound (1) are acrylic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, sorbic acid derivatives, esters of these acids, and maleimide. It is a compound having liquid crystallinity. Among these, 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 liquid crystal phase temperature range of the polymerizable composition. Further, among the above-mentioned other polymerizable compounds having liquid crystallinity, in the compounds except the liquid crystalline acrylic acid derivative,
The time required for the polymerization may be longer than that of 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. Examples of acrylic acid derivatives and fumaric acid derivatives are shown below.

The polymer of the present invention is one of the compounds (1),
It is obtained by adding a catalyst or a solvent to at least two of the compounds (1) or the polymerizable composition, 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.

In order to obtain the polymer of the present invention from the compound (1), various polymerization reaction modes can be used. Polymerization reaction types that can be used include a free radical polymerization method, an anionic polymerization method, a cationic polymerization method, and a coordination polymerization method. In order to produce the polymer of the present invention, it is preferable to select a polymerization method suitable for its 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 electron beams is preferable. . In that case, the compound (1) and another polymerizable compound as an optional component are polymerized in the presence of a photoradical polymerization initiator.

Preferred initiators for photoradical polymerization are 2-
Hydroxy-2-methyl-1-phenylpropane-1-
ON (trade name: Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Irgacure 65)
1), Irgacure 500, Irgacure 295
9, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocur 4265, Irgacure 784, p-methoxyphenyl-2,4-bis (trichloromethyl) ) Triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, benzyl dimethyl ketal, 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture and the like.

The polymer obtained by thermal polymerization or photopolymerization can be applied to various protective films, liquid crystal alignment films, viewing angle compensation films and the like. In the photopolymerization, by using polarized light, particularly polarized UV light, it is possible to polymerize the polymerizable molecules in a state of being aligned in the direction of polarized light. Therefore, the polymer obtained by photopolymerization can be applied not only to various protective films and liquid crystal alignment films, but also to alignment films that do not require rubbing. Since the polymer of the present invention has optical anisotropy, it can be 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 compensation plate, a selective reflection film, a viewing angle compensation plate and the like.

The retardation film comprises a composition containing an appropriate amount of the compound (1) having optical activity, or a composition obtained by adding an appropriate amount of another optically active compound to the compound (1) which is not optically active, It is obtained by coating on an oriented substrate and polymerizing. By the addition of the optically active compound, the tissue of the above composition shows a helical structure. This helical structure is fixed by the polymerization of the compound (1) and a retardation film is formed. The properties of the retardation film depend on the obtained helical pitch. This spiral pitch is
It can be adjusted depending on the type and addition amount of the optically active compound.
The amount added is usually 0.01 to 50% by weight, preferably 1 to 30% by weight. The number of optically active compounds added may be one, 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) and the optically active compound, a polymerizable compound other than the compound (1) may be contained. Among other optically active compounds, preferred examples of the non-polymerizable optically active compound are (O
P-1) to (OP-12), and preferred examples of the polymerizable optically active compound are (OP-13) to (OP-19).

[0101]

[0102]

[0103]

[0104]

[0105]

In the selective reflection of visible light, which is a characteristic of this retardation film, a helical structure acts on incident light to reflect circularly polarized light or elliptically polarized light. Selective reflection characteristic is λ = n
Since it is represented by P (λ is the central wavelength of selective reflection, n is the average refractive index, and P is the spiral pitch), λ and its band (Δλ) can be adjusted appropriately by n and P. To improve the color purity, Δλ may be decreased, and when reflection in a wide band is desired, Δλ may be increased. Furthermore, 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 keep the orientation uniformity, the cell thickness must not be too large. Therefore, it is necessary to adjust the cell thickness to an appropriate level.
μm is preferable, and 1 to 10 μm is more preferable.

Thermal polymerization is preferred for producing an alignment film, an antireflection film, a viewing angle compensation film and the like. In the thermal polymerization, the compound (1) and another polymerizable compound as an optional component are polymerized in the presence of a radical polymerization initiator. Preferred initiators of radical polymerization by heat are benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide (DTBPO). ), T-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (A
IBN), azobiscyclohexanecarbonitrile (A
CN) and the like. The polymerization is generally carried out at a reaction temperature of 0 to 150 ° C. for 1 to 100 hours.

Anionic Polymerization, Coordination Polymerization and Living Weight
Preferred initiators are nC_FourH ₉Li, t-C_FourH
₉Li-R_ThreeAlkali metal alkyl such as Al, aluminum
For example, a nickel compound and a transition metal compound.

Upon polymerization, a solvent may be added to the compound (1) or the polymerizable composition in addition to the catalyst.
Preferred solvents are, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, and mixed solvents thereof. When the alignment film, antireflection film, viewing angle compensation film, etc. are produced by photopolymerization,
A solution of the composition may be applied onto a substrate by a spin coating method, the solvent may be removed, and then the composition may be irradiated with light to be polymerized. In addition,
It does not make much sense to limit the proportion of solvent used during polymerization. This is because the required polymer concentration varies depending on the use of the polymer, and this concentration can be adjusted by dilution after the polymerization. The proportion of solvent used during polymerization is
It may be determined for each case in consideration of economic viewpoints such as polymerization efficiency, solvent cost, and energy cost.

The isolated polymer can be molded by dissolving it in a solvent. Preferred solvents are N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide dimethyl acetal, tetrahydrofuran, chloroform, 1,4-dioxane, bis ( Methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, 2-methoxyethyl acetate, methyl ethyl ketone, cyclopentanone, cyclohexanone and the like. However, the solvent is not limited to these, and may be a mixture with a general organic solvent such as acetone, benzene, toluene, heptane, and methylene chloride. It should be noted that limiting the use ratio of the solvent at the time of processing does not have much meaning as in the case of polymerization. Depending on the application, at least two of the polymers of the present invention can be mixed and used, or they can be laminated and used. When used by laminating, a thin film may be directly formed by photopolymerization without isolating the polymer.

The polycondensation reaction may be carried out by mixing two or more compounds or by reacting them in a melt state having a melting point or higher, a method of reacting in a state of being vaporized by heating under reduced pressure, light, super A method of applying energy such as sound waves or plasma from the outside to activate and react is adopted. Usually, a polymerization accelerator such as an acid, an alkali or a metal compound is used for the purpose of accelerating the polymerization reaction.

Since the polymer of the present invention is a polymer having the above-mentioned constitutional units and has optical anisotropy, it can be used alone in the retardation film. By combining this polymer with another retardation film, it can be used as a polarizing plate, a circularly polarizing plate, an elliptically polarizing plate, an antireflection film, a color compensating plate, a viewing angle compensating plate or the like.

[0113]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
In Examples 1 to 3 and Examples 5 to 7, compound (1) was described using the compound numbers described in Example 4. The structure of the compound was confirmed by nuclear magnetic resonance spectrum, mass spectrum and the like. In the nuclear magnetic resonance spectrum, d is a doublet, dd is a double doublet, t is a triplet, sep is a septet, and m is a multiplet. The unit of the phase transition temperature is ° C, C indicates a crystal, and I indicates an isotropic liquid phase. The methods for measuring physical property values are shown below. <Helix pitch> A composition prepared by dissolving 1% by weight of a sample compound in 99% by weight of the following liquid crystal composition (M-1) is used,
The measurement was performed at 25 ° C. according to the wedge method of Cano (Applied Physics, 1974, 43, 125). <Weight average molecular weight and number average molecular weight> Shimadzu LC-9A type gel permeation chromatograph manufactured by Shimadzu, column Shodex GF-7MHQ manufactured by Showa Denko (developing solvent is DM
F) was used. <Pencil hardness> JIS standard “JIS-K-5400 8.
4 Pencil scratch test ”.

Example 1 <No. Production of Compound (1R, 2S, 1 ′S, 2′R) -117> Compound (ex1-1) was obtained according to the method described in Tetrahedron Lett., 2000, 41, 8723. WO 01/53248
Compound (ex 1-2) was obtained by the method described in 1. Compound (ex 1-1) (100 mmol), compound (ex 1-2) (220 mmol), 1-ethyl-3
-(3-Dimethylaminopropyl) carbodiimide hydrochloride (220 mmol) and 4-dimethylaminopyridine (220 mmol) were added to tetrahydrofuran (200 m).
In addition to 1), the mixture was stirred under a nitrogen atmosphere at room temperature for 15 hours.
The deposited precipitate was filtered off, brine (200 ml) was added, the mixture was neutralized with dilute hydrochloric acid, and extracted with toluene (500 ml).
The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate: toluene = 1: 4), and recrystallized from ethanol to obtain the title compound (40 mmol). . Phase transition temperature: C 57.5 I.D. ¹ H-NMR (500 MHz, CDCl ₃ ): δ (pp
m); 0.38-0.53 (m, 4H), 0.90-
1.09 (m, 4H), 1.40-1.86 (m, 16
H), 3.98-4.20 (m, 12H), 5.82.
(Dd, 2H), 6.12 (dd, 2H), 6.40
(Dd, 2H), 6.89 (d, 4H), 7.98
(D, 4H). Helical pitch: 12.1 μm

Example 2 <No. Production of Compound (1R, 2S, 1 ′S, 2′R) -177> On a water bath, the compound (ex 1-1) (100 mm
ol), the above compound (ex 2-1) (240 mmo
l), and 4-dimethylaminopyridine (240 mm
ol) was added to dichloromethane (200 ml), and the mixture was stirred under a nitrogen atmosphere. A dichloromethane (100 ml) solution of 1,3-dicyclohexylcarbodiimide (240 mmol) was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 15 hours. The deposited precipitate was filtered off, and saline (200
ml) was added, and the mixture was extracted with toluene (500 ml). The organic layer was washed with water and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (silica gel, developing solvent: ethyl acetate: toluene =
1: 4) and recrystallized from ethanol to give the title compound (75 mmol). Phase transition temperature: C 49.4 I.D. ¹ H-NMR (500 MHz, CDCl ₃ ): δ (pp
m); 0.35-0.48 (m, 4H), 0.87-
0.99 (m, 4H), 1.30 (d, 12H), 4.
12 (d, 4H), 5.11 (sep, 2H), 6.8
3-6.85 (m, 4H). Helical pitch: 10.3 μm

Example 3 <No. (1R, 2S, 1'S, 2'R, 1 "S, 2" R) -8
Production of compound 7> (1st stage) Compound (ex3-1) was obtained according to the method described in Tetrahedron Lett., 2000, 41, 8723. Compound (ex
3-1) (300 mmol), tetrahydro-2H-
Pyran (600 mmol) and pyridinium p-toluenesulfonate (2 g) were added to methylene chloride (300 m).
l), and the mixture was stirred at room temperature for 6 hours under a nitrogen atmosphere. Water (200 ml) was added, and the mixture was extracted with toluene (800 ml). The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give a crude (ex3-2)
Got

(Second stage) Compound (ex 3-3) (360 mmol) in THF
(300 ml) and cooled to −20 ° C. under a nitrogen atmosphere. T-BuOK (360 mmol) was added there, and it stirred at the same temperature for 1 hour. Next, while maintaining the same temperature,
THF (300 ml) obtained in step (ex 3-2)
The solution was added dropwise. After dropping, after stirring for 2 hours at the same temperature,
The temperature was gradually raised to room temperature. Add water (1000 ml),
It was extracted with toluene (1000 ml). The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate: toluene = 1: 4) to obtain the compound (ex3-4) (250 mol).

(Third stage) Compound (ex 3-4) (25
0 mmol) and pyridinium p-toluenesulfonate (2 g) were added to ethanol (300 ml), and the mixture was stirred at 60 ° C. for 6 hours under a nitrogen atmosphere. Water (200m
1) was added, and the mixture was extracted with ethyl acetate (800 ml). The organic layer was washed with water and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure to obtain crude (ex3-5).

(Fourth step) The crude compound (ex
3-5), acrylic acid (300 ml) and 4-dimethylaminopyridine (300 mmol) were added to dichloromethane (300 ml), and the mixture was stirred under a nitrogen atmosphere. There, 1,3-dicyclohexylcarbodiimide (300
A solution of (mmol) in dichloromethane (200 ml) was added dropwise. After the dropping, the mixture was stirred at room temperature for 10 hours. The deposited precipitate was separated by filtration, brine (300 ml) was added, and the mixture was extracted with toluene (800 ml). The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure,
The residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate: toluene = 1: 4),
Recrystallize from ethanol to give the title compound (120 mmo
l) was obtained.

Example 4 According to the method of Examples 1 to 3, compound No. 1 to compound No. 216 is manufactured. These compounds are summarized in the table. In this table, the bonding order of the groups described in the respective columns of R ¹ , the ring structure group and R ² is in accordance with the formula (1). The skeleton described as an example of B ¹ indicates that any of the different configurations, where present, may be present. It may be a mixture thereof. However, the racemic and meso isomers do not exhibit optical activity even if they have an asymmetric carbon.

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

Example 5 Compound No. 1 prepared in Example 1 (1R, 2S, 1'S,
2'R) -117 (100 mg) and a photopolymerization initiator (Irgacure 1 manufactured by Ciba Specialty Chemicals)
84; 4 mg) to prepare a polymerizable composition. The composition was irradiated for 30 minutes at 30 ° C. using a 4 W UV lamp with a wavelength of 365 nm. The weight average molecular weight (Mw) of the obtained polymer by GPC was 25,000,
The polydispersity index (Mw / Mn) was 1.40. Melting point (T
m) was 200 ° C. or higher and was excellent in heat resistance. The pencil hardness of the film was 3H.

Example 6 Compound No. produced in Example 1 (1R, 2S, 1'S,
2'R) -117 (5% by weight) and the liquid crystal composition (M-1) (95% by weight) (100 m)
g) and a photopolymerization initiator (Irgacure 184; 4 mg manufactured by Ciba Specialty Chemicals) are mixed,
A polymerizable composition was prepared. Two glass substrates were stuck together to produce a cell with a gap of 5 μm. The resulting composition was injected into the cell at 40 ° C. When injected into the cell, this composition could be injected faster than the conventional composition. This indicates that the composition has a low viscosity. When the cell was observed with a polarizing microscope, the texture of the cholesteric phase was observed. Irradiation was performed at 40 ° C. for 3 minutes using a 4 W ultraviolet lamp having a wavelength of 365 nm. The cell was returned to room temperature, and the formed optically anisotropic film was peeled off from the glass substrate. The weight average molecular weight (Mw) by GPC is 22,000.
0, the polydispersity (Mw / Mn) was 1.37. The melting point (Tm) was 200 ° C. or higher, and the heat resistance was excellent.
The pencil hardness of the film was 3H.

Example 7 Compound No. prepared in Example 2 (1R, 2S, 1'S,
2′R) -177 (0.2 g), azobiscyclohexanecarbonitrile (ACN; 0.01 g), and benzene (1 mL) were placed in a glass ampoule. This-
After cooling to 60 ° C. and sufficiently degassing with a vacuum pump, the tube was sealed. The ampoule was heated in a 70 ° C. water bath for 24 hours. The obtained reaction mixture was treated with methanol (150 mL)
Was reprecipitated 3 times to obtain a polymer. The weight average molecular weight measured by GPC _{(M W)} was 14,000.

Example 8 Compound No. produced in Example 1 (1R, 2S, 1 '
S, 2′R) -117 (20 mg), compound (ex 7
-1) (50 mg), compound (ex 7-2) (50 m
g) and a photopolymerization initiator (Irgacure 184; 4 mg manufactured by Ciba Specialty Chemicals) were mixed to prepare a polymerizable composition. The composition was observed with a polarizing microscope and confirmed to exhibit a cholesteric phase at room temperature. A glass substrate that had been subjected to orientation treatment and a glass plate that had not been subjected to orientation treatment were attached to each other to produce cells having a gap of 7 μm. The above composition was injected into this cell at room temperature. This composition could be quickly injected into the cell. This fact indicates that the composition has a low viscosity. Cell 3
When heat-treated at 0 ° C. for 5 minutes and observed with a polarizing microscope, uniform cholesteric orientation was observed. It was also confirmed that the cell exhibits selective reflection in the visible light range. Using a 4W UV lamp with a wavelength of 365 nm, 30 at 30 ℃
Ultraviolet rays were irradiated for a minute to polymerize the injected composition. Observation of the cell with a polarizing microscope showed that a uniform cholesteric orientation was maintained. Then, the transmission spectrum of the cell is measured, and the central wavelength is 555 nm and the wavelength range 525 to 5
It was confirmed that selective reflection was exhibited in the region of 85 nm. From the above, it was confirmed that it can be used as a circularly polarized light selective reflection functional element. The produced optically anisotropic substance was peeled off from the glass substrate. The weight average molecular weight (Mw) by GPC was 13,000, and the polydispersity (Mw / Mn) was 1.60. The melting point (Tm) was 130 ° C. or higher, and the heat resistance was excellent. The pencil hardness of the film was 3H.

[0147]

INDUSTRIAL APPLICABILITY The cyclopropane compound of the present invention exhibits an appropriate liquid crystal phase temperature range and has excellent compatibility with other compounds. By polymerizing a polymerizable composition containing this compound, a polymer having excellent properties such as polymerization rate, transparency of the polymer, mechanical strength and coatability can be obtained.
This polymer can be used as an optically anisotropic substance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 22/10 C08F 22/10 C09K 19/14 C09K 19/14 19/20 19/20 19/30 19 / 30 19/32 19/32 19/38 19/38 G02F 1/1335 G02F 1/1335 1/13363 1/13363 1/1337 520 1/1337 520 F Term (reference) 2H090 HB11Y HD15 2H091 FA11 FA37 FB02 LA02 LA04 4H006 AA01 AA03 AB46 AB64.

Claims (34)

[Claims] 1. A cyclopropane compound represented by the formula (1). In formula (1), R ¹ and R ² are independently a polymerizable group, hydrogen, halogen, —CN, —CF ₃ , —CF.
_{2 H, -CFH 2, -OCF 3} , -OCF 2 H, -NC
O, —NCS, or alkyl having 1 to 20 carbons, at least one of R ¹ and R ² is a polymerizable group, and in this alkyl having 1 to 20 carbons, any —
CH ₂ - is -O -, - S -, - CO -, - COO -, -
OCO-, -NH-, -CH = CH-, -CF = CF-
Or it may be replaced by -C≡C- and any hydrogen may be replaced by halogen or -CN; B ¹
Is any one of the following divalent groups, any hydrogen in these groups may be replaced by halogen; A's are independently a single bond, B ¹ , 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, or tetrahydronaphthalene-2,6. - diyl, any -CH ₂ - in these rings - may be replaced by -O-, arbitrary -CH = may be replaced by -N =,
And in all the rings, any hydrogen may be replaced by halogen; Zs are independently a single bond or alkylene having 1 to 20 carbons, and in this alkylene, any —CH ₂ — is -O-, -CO-, -C
OO-, -OCO-, -CH = CH-, -CF = CF
_{-, - CF 2 O -,} - OCF 2 - or -C≡C-, arbitrary hydrogen may be replaced by halogen; m and n an integer independently 0 Yes, the sum of these is 0-10. 2. The cyclone according to claim 1, wherein the polymerizable group is a group represented by formula (2), a group represented by formula (3), or a group represented by formula (4). Propane compound. In these formulas, R ³ , R ⁴ and R ⁵ are independently hydrogen or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — is —O—, —CO.
May be replaced by O-, -OCO- or -CH = CH- and any hydrogen may be replaced by halogen; k is an integer from 0 to 20, h and j are independently 0 or a is ;-( CH _{2) k} 1 - in any -
CH ₂ — may be replaced by —O—. 3. The cyclopropane compound according to claim 1, wherein the compound represented by the formula (1) is optically active. 4. The method according to claim ² , wherein only ^one of R ¹ and R ² is a group represented by formula (2), a group represented by formula (3) or a group represented by formula (4). The cyclopropane compound described. 5. R ¹ and R ² are independently a group represented by formula (2), a group represented by formula (3) or a group represented by formula (4). The cyclopropane compound described in 1. 6. Only ^one of R ¹ and R ² is a group represented by formula (2), a group represented by formula (3) or a group represented by formula (4), and R ³ and R ⁴ and R ⁵ are independently hydrogen,
The cyclopropane compound according to claim 2, which is alkyl having 1 to 10 carbons, alkoxycarbonyl having 2 to 10 carbons, or alkoxycarbonylalkyl having 3 to 10 carbons. 7. R ¹ and R ² are independently a group represented by formula (2), a group represented by formula (3) or a group represented by formula (4), and R ³ , R ⁴ and R ⁵ are independently hydrogen,
The cyclopropane compound according to claim 2, which is alkyl having 1 to 10 carbons, alkoxycarbonyl having 2 to 10 carbons, or alkoxycarbonylalkyl having 3 to 10 carbons. 8. The cyclopropane compound according to claim 1, which is represented by any one of formulas (G-1) to (G-11). R ¹ , B ¹ , R ² , A and Z in these formulas are
It is defined similarly to these symbols in equation (1). 9. Any one of formulas (G-1) to (G-6):
The cyclopropane compound according to claim 8, which is represented by: 10. A composition containing at least one cyclopropane compound according to any one of claims 1-9. 11. A composition containing at least one cyclopropane compound according to any one of claims 1 to 3 and a polymerizable compound which is not the cyclopropane compound according to claim 1. 12. A composition containing at least one compound selected from the group consisting of the cyclopropane compounds according to claim 4 and 5, and a polymerizable compound other than the cyclopropane compound according to claim 1. object. 13. A composition containing at least one compound selected from the group consisting of the cyclopropane compounds according to each of claims 6 and 7, and a polymerizable compound other than the cyclopropane compound according to claim 1. object. 14. A composition containing at least one cyclopropane compound according to claim 8 and a polymerizable compound other than the cyclopropane compound according to claim 1. 15. A composition containing at least one of the cyclopropane compounds according to claim 9 and a polymerizable compound which is not the cyclopropane compound according to claim 1. 16. A composition containing at least one of the cyclopropane compounds according to claim 1 and a non-polymerizable liquid crystal compound. 17. A composition containing at least one compound selected from the group consisting of the cyclopropane compounds according to each of claims 4 and 5 and a non-polymerizable liquid crystalline compound. 18. A composition containing at least one compound selected from the group consisting of cyclopropane compounds according to each of claims 6 and 7, and a non-polymerizable liquid crystal compound. 19. A composition containing at least one of the cyclopropane compounds according to claim 8 and a non-polymerizable liquid crystal compound. 20. A composition containing at least one of the cyclopropane compounds according to claim 9 and a non-polymerizable liquid crystal compound. 21. A polymer obtained from the cyclopropane compound according to any one of claims 1 to 9. 22. A polymer obtained by hydrogenating the polymer according to claim 21. 23. A polymer obtained from the composition according to any one of claims 10 to 15. 24. A polymer obtained by hydrogenating the polymer according to claim 23. 25. The polymer according to claim 21, wherein the polymer is optically active.
25. The polymer according to any one of 24. 26. An optical anisotropic body containing the polymer according to any one of claims 21 to 25. 27. A retardation film containing the polymer according to any one of claims 21 to 25. 28. A liquid crystal alignment film containing the polymer according to claim 21. 29. An antireflection film containing the polymer according to any one of claims 21 to 25. 30. A viewing angle compensation film containing the polymer according to any one of claims 21 to 25. 31. A polarizing element containing the polymer according to any one of claims 21 to 25. (32) The optical anisotropic body according to (26), the retardation film according to (27), the liquid crystal alignment film according to (28), the antireflection film according to (29), and (30). A liquid crystal display device comprising at least one of the viewing angle compensation film according to claim 21 and the polarizing device according to claim 31. 33. A liquid crystal display device containing the composition according to claim 10 or any one of claims 16 to 20. 34. The liquid crystal display element according to claim 33, further containing at least one optically active compound.