JP2006335655A - Polymerizable compound and polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymerizable compound which can suitably be used as a constituting member of a material for forming light-controlling layers capable of being driven at low voltages even in low temperature regions. <P>SOLUTION: This polymerizable compound represented by general formula (1). A light-scattering type liquid crystal device using the compound as a constituting member can be driven at a low voltage even at a low temperature. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel polymerizable compound, and more particularly to a polymerizable compound that can be suitably used as a light control layer forming material of a light scattering liquid crystal device that can be driven at a low voltage in a wide temperature range and is excellent in electro-optical characteristics.

  With the development of the information society, the demand for information and communication materials is increasing. In particular, light-scattering liquid crystal devices do not require polarizing plates and have little viewing angle dependency, so advertising boards, decorative display boards, watches, computers, projections, digital paper, portable information terminals, optical shutters, It is highly expected as a liquid crystal display element or an optical element used for the above.

A liquid crystal device having a light control layer comprising a polymer matrix and a liquid crystal composition, which is obtained by irradiating or heating a light control layer forming material comprising a radical polymerizable composition and a liquid crystal composition as a light scattering liquid crystal device. It has been known.
The device does not depend on the type of liquid crystal compound to be used, and the change in the drive voltage is small in a wide temperature range (for example, the temperature range of about −20 ° C. to 70 ° C.), and the absolute value of the drive voltage is It is required to be 20V or less. Particularly when the liquid crystal driving method is TFT driving, it is indispensable to reduce the voltage to 10 V or less.
Development of a polymerizable compound that satisfies these characteristics is underway, and some side chain type radically polymerizable compounds are disclosed (see cited documents 1 to 3). A side chain type radically polymerizable compound means a compound schematically represented by the following general formula (E) as an example.

（式中、Mcは主鎖を表し、Sc¹は側鎖1を表し、Sc²は側鎖2を表すが、Sc¹＞Sc²であり、Mc及びScは主に炭素原子により構成される。）当該構造は側鎖型ラジカル重合性化合物を模式的に示したものであり、全ての構造を網羅したものでは無い。しかしながら、当該基本骨格の範囲においても種々の化合物を包含することから主鎖、側鎖等の置換基を個別に検討することにより化合物の提案が行われてきた。しかも、その検討は主として、前述の式中の主鎖及び側鎖1について検討され側鎖2については多くの検討はなされていなかった。
例えば、特許文献１においては側鎖型ラジカル重合性化合物の主鎖構造（Mc）を改良することにより、駆動電圧の低減が図られており、主鎖にさらなる置換基を有する化合物も開示されている。しかし、当該化合物を構成部材とする液晶デバイスは、０から５０℃の範囲において約７Ｖの駆動電圧を達成しているが、０℃以下の極低温域では駆動電圧が上昇する傾向にあった。又、当該引用文献記載の化合物においては式（E）における側鎖2については検討が行われておらず、次に記載するような芳香環を主鎖とし側鎖2にメチル基を有する化合物が記載されるのみであり、当該化合物を構成部材とするデバイスもまた０℃以下の極低温域では駆動電圧が上昇する傾向にあった。

(In the formula, Mc represents a main chain, Sc ¹ represents a side chain 1, Sc ² represents a side chain 2, Sc ¹ > Sc ² , and Mc and Sc are mainly composed of carbon atoms. .) The structure schematically shows a side chain type radical polymerizable compound and does not cover all structures. However, since various compounds are included within the scope of the basic skeleton, compounds have been proposed by individually examining substituents such as main chains and side chains. Moreover, the investigation was mainly conducted on the main chain and side chain 1 in the above formula, and many studies on the side chain 2 were not made.
For example, in Patent Document 1, the driving voltage is reduced by improving the main chain structure (Mc) of the side chain type radically polymerizable compound, and a compound having a further substituent in the main chain is also disclosed. Yes. However, a liquid crystal device comprising the compound as a constituent member achieves a driving voltage of about 7 V in the range of 0 to 50 ° C., but the driving voltage tends to increase in an extremely low temperature range of 0 ° C. or lower. In addition, in the compound described in the cited document, side chain 2 in formula (E) has not been studied, and a compound having an aromatic ring as a main chain and having a methyl group in side chain 2 as described below. As described above, the device having the compound as a constituent member also had a tendency that the driving voltage increased in an extremely low temperature range of 0 ° C. or lower.

又、主鎖にカルボニル基を有する置換基をさらに設けた化合物についても開示されている（特許文献２参照）。しかしながら、当該化合物を構成部材とするデバイスにおいては低駆動電圧化には有利であるが、分子中の側鎖密度が高くなり過ぎてしまい、０℃以下の極低温域では印加した状態を保ってしまう現象がみられる問題があった。さらに、当該引用文献においても、その検討の範囲は大部分が主鎖上の置換基を対象としており、二種の側鎖相互間の関係については開示されていない。

Further, a compound further provided with a substituent having a carbonyl group in the main chain is also disclosed (see Patent Document 2). However, in a device having the compound as a constituent member, it is advantageous for lowering the driving voltage, but the side chain density in the molecule becomes too high, and the applied state is maintained in an extremely low temperature range of 0 ° C. or lower. There was a problem with the phenomenon. Furthermore, even in the cited document, the scope of the study is mostly directed to substituents on the main chain, and the relationship between the two types of side chains is not disclosed.

  On the other hand, there is a disclosure of a polyfunctional acrylate-based radical polymerizable compound having both a linear alkyl group having 4 to 25 carbon atoms and a branched alkyl group having 4 to 26 carbon atoms as a side chain 1 in one molecule. (See Patent Document 3). The compound described in the cited document can incorporate both a linear alkyl group and a branched alkyl group in the polymer matrix in a certain range of ratios, can achieve a driving voltage of 5 V, and the monomer remains. Since it is difficult, it has a feature that can prevent deterioration due to light, heat and the like. However, since the ratio of linear alkyl groups and branched alkyl groups that can be incorporated into one molecule is limited, the ratio of linear alkyl groups and branched alkyl groups that can be incorporated into the polymer matrix is limited, and there is a limit to the adjustment of temperature change of driving voltage. there were. In addition, the production cost is high because there are many synthesis steps of a polyfunctional (meth) acrylate having both a linear alkyl group having 4 to 25 carbon atoms and a branched alkyl group having 4 to 26 carbon atoms as side chains. There were drawbacks.

JP-A-11-29527 JP 2000-72717 A (page 16) JP 2002-293828 A

  A problem to be solved by the present invention is a light control layer of a light-scattering liquid crystal device having a light control layer comprising a polymer matrix and a liquid crystal composition that can be driven at a low voltage even in a wide temperature range of −20 ° C. to 70 ° C. An object of the present invention is to provide a novel polymerizable compound having an alkyl side chain in a material forming a polymer matrix, which can be suitably used as a forming material.

As a result of studying various polymerizable compounds, the inventors of the present application have found that the above-mentioned problems can be solved by using a polymerizable compound having a specific structure, and have been involved in the present invention.
The present invention provides a general formula (1)

（式中、Ｘ^１は−Ｏ−ＣＨ_２−、−Ｏ−ＣＨ_２−ＣＨ_２−ＣＯ−Ｏ−ＣＨ_２−、−Ｏ−ＣＨ_２−ＣＨ_２ＯＣＯ−、又は−Ｏ−ＣＨ_２−ＣＨ（ＣＨ_３）ＯＣＯ−を表し、
Ｒ^２は炭素数４から３０のアルキル基を表すが、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良く、
Ｒ^３は水素又はメチル基を表し、
Ｒ^４は炭素原子数１から５のアルキル基を表し、
Ｘ^２及びＸ^３はそれぞれ独立して、−ＣＨ_２Ｏ−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２ＣＯ−Ｏ−、−ＣＯＯ−又は単結合を表し、
Ｒ^１は、炭素数１から３０のアルキレン基を表すが、基中に存在する少なくとも一つのメチレン基は一般式（２）

^(Wherein, X ₁ is _{-O-CH 2 -, - O} -CH 2 -CH 2 -CO-O-CH 2 -, - O-CH 2 -CH 2 OCO-, or _-O-CH 2 -CH _(CH 3) OCO- represent,
R ² represents an alkyl group having 4 to 30 carbon atoms, and one or two or more carbon atoms present in the group may be replaced by oxygen atoms so that the oxygen atoms are not directly bonded to each other. Preferably, a single bond between one or more carbons present in the group may be replaced by a double bond or a triple bond, and a hydrogen atom present in the group may be replaced by a halogen. well,
R ³ represents hydrogen or a methyl group,
R ⁴ represents an alkyl group having 1 to 5 carbon atoms,
X ² and X ³ each independently represent —CH ₂ O—, —CH ₂ OCO—, —CH ₂ CO—O—, —COO— or a single bond,
R ¹ represents an alkylene group having 1 to 30 carbon atoms, and at least one methylene group present in the group is represented by the general formula (2)

（式中、Ｒ^１１及びＲ^１２はそれぞれ独立して、水素又は炭素数１から８のアルキル基を表すが、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良いが、Ｒ^１１及びＲ^１２の少なくともどちらか一方はアルキル基を表し、ｍは１から１０の整数を表す。）で表されるからからで表される置換基により置き換えられており、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良い。）で表される重合性化合物を提供し、併せて当該化合物を含有する重合性組成物及び当該組成物を構成部材とする光散乱型液晶デバイスを提供する。

(In the formula, R ¹¹ and R ¹² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and one or two or more carbon atoms present in the group are mutually bonded to oxygen atoms. It may be replaced by an oxygen atom as not directly bonded, and a single bond between one or more carbons present in the group may be replaced by a double bond or a triple bond. The hydrogen atom present therein may be substituted by halogen, but at least one of R ¹¹ and R ¹² represents an alkyl group, and m represents an integer of 1 to 10. Wherein one or two or more carbon atoms present in the group may be replaced by oxygen atoms so that the oxygen atoms are not directly bonded to each other. Exist in A single bond between one or more carbons present may be replaced by a double bond or a triple bond, and a hydrogen atom present in the group may be replaced by a halogen. ) And a light-scattering liquid crystal device having the composition as a constituent member.

  By using the polymerizable compound of the present invention, a light scattering liquid crystal device having a light control layer composed of a polymer matrix and a liquid crystal composition, which can be driven at a low voltage even in a wide temperature range of −20 ° C. to 70 ° C. is obtained. be able to.

In the general formula (1), X ¹ is preferably —O—CH ₂ — or —O—CH ₂ —CH ₂ —CO—O—CH ₂ —, more preferably —O—CH ₂ —.
In the general formula (1), R ² is preferably an alkyl group having 6 to 20 carbon atoms, and when the alkyl group is a linear alkyl group, a linear alkyl group having 7 to 14 carbon atoms is more preferable. When is a branched chain, a branched alkyl group having 9 to 18 carbon atoms is more preferable.
When R ² is a linear alkyl group having 6 to 20 carbon atoms, the constructed liquid crystal device is advantageous in terms of low voltage driving. In addition, when R ² is a branched alkyl group such as a 2-n-heptyl-nonyl group, it is advantageous in that the change of the driving voltage with temperature is small. In addition, specifically, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-octadecyl group, 2-n-heptylnonyl group, iso A myristyl group, 2-ethylhexyl group, butoxyethyl group, hexyloxyethyl group, n-butoxyethoxymethyl group, cyclohexyl group, polyethylene glycol monoether group, 4-nonylphenylene group, 4-octylcyclohexyl group and the like can be mentioned.

In the general formula (1), R ³ represents hydrogen or a methyl group, and hydrogen is more preferable because of high reactivity.
In the general formula (1), R ⁴ is preferably an ethyl group, a propyl group or a butyl group, particularly preferably an ethyl group or a propyl group. If the number of carbon atoms in R ⁴ is greater than 5, there is a risk of inhibiting the polymerizability of the acrylic group. By introducing an alkyl group having 1 to 5 carbon atoms into the R ⁴ site, the mobility of the group represented by —X ² —R ² in the general formula (1) is maintained even at an extremely low temperature of 0 ° C. or lower. This is a very important group. Furthermore, by having R ⁴ , a low driving voltage can be achieved even if R ² is a branched alkyl group. Accordingly, it is possible to obtain a light-scattering liquid crystal device with a lower driving voltage and less increase in driving voltage in a low temperature range.
In the general formula (1), X ² and X ³ are each independently preferably —CH ₂ O— or —CH ₂ OCO—.

In general formula (1), R ¹ is preferably an alkylene group having 10 to 25 carbon atoms, and more preferably an alkylene group having 12 to 22 carbon atoms. Furthermore, in the general formula (2) present in at least one of R ¹ , R ¹¹ and R ¹² are each independently preferably hydrogen or an alkyl group having 1 to 5 carbon atoms, and hydrogen or an alkyl group having 1 to 3 carbon atoms. Group is more preferred, but R ¹¹ and R ¹² do not represent hydrogen at the same time, so that R ¹¹ and R ¹² are each independently an alkyl group having 1 to 3 carbon atoms, or R ¹¹ is hydrogen and R ¹² Is an alkyl group having 1 to 3 carbon atoms, or R ¹² is hydrogen and R ¹¹ is an alkyl group having 1 to 3 carbon atoms. m is preferably 1 to 5, and more preferably 1 to 3. That is, the number of branched side chains present in R ^{1 as the} main chain is preferably 1 to 6, and more preferably 1 to 4.
In the present invention, it is important to have both the main chain structure having the side chain 1, the side chain 2, and the branched alkyl group represented by the general formula (E). Further, in such a substituent group is represented by formula (1), side chain 1 is equivalent to ^-X 2 -R ^2, side chain 2 corresponds to ^{R 4,} the main chain -X ³ -R ¹ It corresponds to the general formula (2) constituting -X ³ -and R ¹ . The cured product of the main chain monomer having long and short side groups and branched alkyl groups greatly improves molecular mobility compared to conventional compounds and compounds without branched chains. Therefore, it has a low Tg, and the liquid crystal molecules hardly approach the polymer surface due to the excluded volume effect, so that it is suitable for a light control layer forming material of a light scattering type liquid crystal device.
Specifically, the main chain is a 7,12-dimethyloctadecylene group, a 7-ethylhexadecylene group, a 2,2′-dimethyl-propylene group, a polyoxypropylene group having 2 to 6 repeats, a polyoxy Examples include butylene group and the following groups.

（これらの置換基の左右両末端はメチル基ではなく、他の炭素原子と結合していることを表す。）

(The left and right ends of these substituents are not methyl groups, but are bonded to other carbon atoms.)

R ² to R ⁴ and X ¹ to X ³ in the polymerizable compound represented by the present invention are present in two in one molecule, but need not be the same group or bond, and are appropriately selected depending on the purpose. Is done. For example, one of the groups represented by R ² may be a decyl group and the other may be an undecyl group.

Examples of the polymerizable compound represented by the general formula (1) include Tetrahedoron Letters, Vol. 23, No. 6, pp 681-684, and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 34, pp217-225 and the like. Specifically, a method of reacting a compound having a plurality of oxetane groups with a fatty acid chloride or a fatty acid capable of reacting with the oxetane group and further reacting with a polymerizable compound having active hydrogen such as acrylic acid, or oxetane It can be obtained by a method of reacting a compound having one group with a polyvalent fatty acid chloride or fatty acid capable of reacting with an oxetane group and further reacting with a polymerizable compound having active hydrogen such as acrylic acid. it can. As the polymerizable compound having active hydrogen, in addition to acrylic acid, for example, methacrylic acid, acrylic acid dimer, methacrylic acid dimer, hydroxyethyl acrylate, hydroxypropyl acrylate, and the like can be used. In the case of a reaction between oxetane and a fatty acid, acrylated chloride, methacrylated chloride, methyl acrylate, ethyl acrylate, or the like can be used.
Specifically, for example, when the polymerizable compound represented by the general formula (1) is the following compound,

By reacting p-toluenesulfonic acid diester of neopentyl glycol with 3-ethyl-3-hydroxymethyloxetane in the presence of sodium hydroxide, the following 3,3 ′-(2,2dimethylpropane-diylbis (oxy) Methylene)) bis- (3-ethyloxetane) can be obtained.

更にこの２官能のジオキセタン化合物とｎ−ウンデカノイルクロリドとをヨウ化ナトリウム、アセトニトリルの存在下、０℃で反応させ炭素数１０のメチレン鎖を有するヨード化合物を得る。次に、生成したヨード化合物とアクリル酸を１，８−ジアザビシクロ[５．４．０]−ウンデセン−７（以下ＤＢＵと略す）の存在下でジメチルスルホキシドを溶媒に用い、９０℃で１２時間反応させることにより目的物を得ることができる。
また、一般式（１）で表される重合性化合物が、下記化合物の場合は

Further, this bifunctional dioxetane compound and n-undecanoyl chloride are reacted at 0 ° C. in the presence of sodium iodide and acetonitrile to obtain an iodo compound having a methylene chain having 10 carbon atoms. Next, the produced iodo compound and acrylic acid were reacted at 90 ° C. for 12 hours using dimethyl sulfoxide as a solvent in the presence of 1,8-diazabicyclo [5.4.0] -undecene-7 (hereinafter abbreviated as DBU). By doing so, the target product can be obtained.
When the polymerizable compound represented by the general formula (1) is the following compound:

Tripropylene glycol dioxetanyl ethyl ether shown below can be obtained by reacting p-toluenesulfonic acid diester of tripropylene glycol with 3-ethyl-3-hydroxymethyloxetane in the presence of sodium hydroxide.

更にこの２官能のジオキセタン化合物とノルマルデカノイルクロリドとをヨウ化ナトリウム、アセトニトリルの存在下、０℃で反応させ炭素数９のメチレン鎖を有するヨード化合物を得る。次に、生成したヨード化合物とアクリル酸をＤＢＵの存在下でジメチルスルホキシドを溶媒に用い、９０℃、１２時間反応させることにより目的物を得ることができる。

Further, this bifunctional dioxetane compound and normal decanoyl chloride are reacted at 0 ° C. in the presence of sodium iodide and acetonitrile to obtain an iodo compound having a methylene chain having 9 carbon atoms. Next, the target product can be obtained by reacting the produced iodo compound and acrylic acid in the presence of DBU using dimethyl sulfoxide as a solvent at 90 ° C. for 12 hours.

  In addition to the above method, 1. 1. a method of introducing a polymerizable group after reacting a reaction product of an alkyl halogen compound and an alcohol having an oxetane group with mono (di) carboxylic acid chloride; 2. a method of introducing a polymerizable group after reacting a mono (di) carboxylic acid chloride with a reaction product of a mono (di) carboxylic acid and an alcohol having an oxetane group; 3. a method for introducing a polymerizable group into a compound obtained by reacting a mono (di) carboxylic acid chloride with a reaction product of an alcohol and a p-toluenesulfonic acid ester of an alcohol having an oxetane group; Examples thereof include a method of introducing a polymerizable group into a compound obtained by reacting a reaction product of an alcohol and a halogen compound having oxetane with mono (di) carboxylic acid chloride.

Further, as a method for synthesizing oxetane alcohol, it can be synthesized by a known method such as JP-A-11-012611 and JP-A-9-71545. Specifically, it can be obtained by a method of reacting trimethylolalkane and dimethyl carbonate.
For example, when oxetane alcohol is the following compound:

  Hexanal and paraformaldehyde are reacted in t-butyl methyl ether in the presence of sodium hydroxide to synthesize 2-butyl-2-hydroxymethylpropane-1,3-diol. Further, 2-butyl-2-hydroxymethylpropane-1,3-diol and dimethyl carbonate were reacted in the presence of potassium carbonate to remove the by-product methanol and carbonated, and then heated to 200 ° C. Can be synthesized by decarboxylation.

The polymerizable composition of the present invention is not particularly limited except that it contains the polymerizable compound represented by the general formula (1), and can contain a known and commonly used polymerizable compound or a polymerization initiator.
Examples of the polymerizable compound include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, bisphenol A di (meth) acrylate, urethane acrylate, polytetraethylene glycol dimaleimide and the like. The blending ratio of these polymerizable compounds is preferably 5 to 60%, and most preferably 10 to 50%, based on the total amount of the polymerizable compounds of the general formula (1).

  As the polymerization initiator, a radical polymerization initiator or an ionic polymerization catalyst can be used. As radical polymerization initiators, radical photopolymerization initiators such as benzoin isopropyl ether, benzyldimethyl ketal and 2-isopropylthioxanthone, and radical thermal polymerization initiators such as benzoyl peroxide and 2,2′-azobisisobutyronitrile Is mentioned. Examples of the ion polymerization catalyst include cationic polymerization catalysts such as Lewis acids such as boron trifluoride and aluminum chloride, protonic acids such as phosphoric acid, and anionic polymerization catalysts such as alkyl lithium and Grignard reagents. The addition rate of these polymerization initiators is preferably 0.01 to 10%, more preferably 1 to 5%, based on the polymerizable composition.

  In addition, antioxidants, ultraviolet absorbers, non-reactive oligomers and inorganic fillers, organic fillers, polymerization inhibitors, antifoaming agents, leveling agents, plasticizers, silane coupling agents, etc. It may be added.

The composition of the polymerizable compound represented by the general formula (1) and the liquid crystal composition is particularly useful as a light control layer forming material for a light scattering liquid crystal device.
The light-scattering liquid crystal device has, for example, a transparent electrode layer and at least one of the transparent liquid crystal devices is transparent. Between the two substrates that are spaced apart by using a spacer or the like with the transparent electrode layer facing each other, It can be obtained by sandwiching a composition of a polymerizable compound and a liquid crystal composition and irradiating with light or heating.

The liquid crystal composition is a composition that exhibits a phase that is generally recognized as a liquid crystal phase in this technical field. Among them, a liquid crystal phase that exhibits a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, a chiral nematic liquid crystal, or a chiral smectic liquid crystal. Is preferred. Specifically, it is a composition composed of the following compound group, and the characteristics of the liquid crystal material, that is, the phase transition temperature, melting point, viscosity, birefringence, dielectric anisotropy of isotropic liquid and liquid crystal In consideration of the positive / negative of the property (Δε), or for the purpose of adjusting the solubility with the polymerizable composition or the like, it can be appropriately selected, blended and used.
Liquid crystal materials include benzoic acid ester, cyclohexanecarboxylic acid ester, biphenyl, terphenyl, phenylcyclohexane, pyrimidine, pyridine, dioxane, cyclohexylcyclohexane ester, tolan, alkenyl, and fluorobenzene. , Cyano, naphthalene, etc., general formula (5)

（式中、Ａ、Ｂ及びＣは、それぞれ独立に、下記の環のいずれかを表し、

(In the formula, A, B and C each independently represent any of the following rings:

n represents an integer of 0 to 2, n ′ represents an integer of 1 to 4, and Y _a and Y _b each independently represent a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —OCF 2 —, —CF 2 O—, —CO—O—, —OCO—, —C≡C—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O— or —CH ₂ ═CHCH ₂ CH ₂ , Y _c represents a single bond, —CO—O—, or —OCO—, and R _a and R _b each independently represent a hydrogen atom or a halogen atom. , A cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, a fluoroalkyl group, or a fluoroalkoxy group. ) Can be used alone or in a composition in which a plurality of liquid crystal compounds are blended.

  The mixing ratio of the liquid crystal composition and the polymerizable composition can be adjusted according to desired electro-optical characteristics, and is preferably in the range of 50:50 to 97: 3, and in the range of 60:40 to 85:15. Is more preferable.

The polymerizable compound of the present invention can be adapted according to the use of the liquid crystal device and the kind of the liquid crystal composition to be used by appropriately changing the R ¹ and R ² structures which are side chains. For example, in the case of using a liquid crystal composition having a small dielectric anisotropy such as a fluorine-based liquid crystal in a display element such as a reflective liquid crystal display or digital paper, R ² is a polymer having a linear side chain group. More preferably, the compound is selected. For example, a compound represented by the general formula (1), wherein R ⁴ is an ethyl group, R ² is a linear C10 normal decyl group, and R ¹ is a 7,12-dimethyloctadecylene group. In the light scattering liquid crystal device used as the light control layer forming material, the molecular motion of the polymer matrix is hardly suppressed even at an extremely low temperature of −20 ° C. due to the presence of the ethyl group of R ⁴ and the dimethyl group of R ¹ . For this reason, it was possible to suppress an increase in drive voltage even in an extremely low temperature range of −20 ° C.

On the other hand, when a liquid crystal composition having a large dielectric anisotropy such as a cyano liquid crystal or a thioisocyanate liquid crystal is used as the liquid crystal composition or when it is desired to operate in a low temperature range of −20 ° C. or lower, R ² It is preferable to select a polymerizable compound in which is a branched side chain group.

  Examples of the present invention will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to these examples. In the following examples, “%” represents “% by mass” unless otherwise specified.

In this embodiment, the saturation voltage of the liquid crystal device and the temperature dependence of the saturation voltage are defined as follows.
T0: Light transmittance (%) when no voltage is applied.
T100: Light transmittance (%) when the light transmittance change due to the increase in applied voltage reaches saturation and the light transmittance does not change.
T90: Light transmittance (%) defined by T0 + 0.9 × (T100−T0).
Saturation voltage: Vr90 (V)
Applied voltage (V) at the transmittance of T90 when the applied voltage to the polymer dispersion type liquid crystal display element is increased from no application.
Temperature dependence of saturation voltage: ΔV (V / μm)
The difference between Vr90 at −20 ° C. and Vr90 at 70 ° C. represents the saturation voltage, which depends on the cell thickness. By dividing by the measured cell thickness, the value converted into the amount of change in Vr90 per 1 μm of cell thickness is Calculated by formula.
ΔV = (Vr90 (−20 ° C.) − Vr90 (70 ° C.)) / Cell thickness

(Production of Intermediate 1) Production of Oxetane Derivative (7) In a reaction vessel equipped with a stirrer and a thermometer, 7,12-dimethyloctadecanedicarboxylic acid (trade name: IPS-22, manufactured by Okamura Oil Co., Ltd.) 44. 5 g (0.12 mol), Doutite WSC (manufactured by Dojindo) 46 g (0.24 mol), N, N-dimethylaminopyridine 2.9 g (0.024 mol), and dichloromethane 500 ml are added. The flask was cooled to 5 ° C. or less with an ice water bath under a nitrogen atmosphere, and 28 g (0.24 mol) of 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd .: OXT-101) was slowly added dropwise. The reaction container was returned to room temperature after completion | finish of dripping, and also stirred for 5 hours, and reaction was complete | finished. After adding 500 ml of 10% hydrochloric acid to the reaction solution, it is washed with pure water and saturated saline in this order, the organic layer is dried over anhydrous sodium sulfate, and the organic solvent is distilled off under reduced pressure, and is represented by the formula (7). 50 g of oxetane derivative was obtained.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 4.45-4.36 (dd, 8H), 3.56 (s, 4H), 2.32 (t, 4H), 1.62 (m, 4H), 1.58 (m, 2H), 1.38-1.26 (m, 24H), 0.92-0.80 (m, 9H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.4, 165.7, 73.4, 71.5, 64.0, 63.7, 43.4, 40.6, 34.1, 31 .8, 29.3, 29.2, 29.1, 26.0, 24.9, 23.0, 22.6, 14.1, 7.3

(Production of Intermediate 2) Production of Compound (6) In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a cooling tube and a thermometer, 20.8 g (0.2 mol) of neopentyl glycol, 44.5 g of triethylamine ( 0.44 mol), 4.6 g of tetramethylethylenediamine (0.04 mol) and 500 ml of toluene were added and stirred while cooling with an ice-water bath so that the temperature became 5 ° C. or lower. 80 g (0.42 mol) of p-toluenesulfonium chloride was added in 5 portions over 1 hour. After completion of the addition, the reaction vessel was stirred at room temperature for 3 hours, and then the reaction was terminated. After filtration of the resulting hydrochloride, the reaction solution was washed with a 1/10 N hydrochloric acid solution, pure water and saturated brine in that order, the organic layer was dried over anhydrous sodium sulfate, and the organic solvent was distilled off under reduced pressure. 78 g of neopentyl glycol ditosylate represented by the formula (6) was obtained.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 7.79 (d, 4H), 7.73 (d, 4H), 3.81 (s, 4H), 2.48 (s, 6H), 0 .98 (s, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 146.8, 132.5, 130.2, 129.9, 129.6, 129.0, 128.2, 73.7, 37.9, 35 .4, 21.8, 21.6, 21.5, 21.0

(Production of Intermediate 3) Production of Oxetane Derivative (8) To a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 54 g (0.17 mol) of paraformaldehyde and 100 ml of t-butyl methyl ether were added. After dissolving at 0 ° C., 45 g (0.45 mol) of n-hexanal was simultaneously added dropwise over 1 hour, and 53.6 g of 50% sodium hydroxide solution was added dropwise over 1.5 hours. The reaction vessel was controlled so that the temperature rose due to exotherm but did not exceed 55 ° C. When the addition of 50% sodium hydroxide is completed, the reaction vessel is heated to 55 ° C., and 24 g of 50% sodium hydroxide is added dropwise over 30 minutes. After completion of the dropwise addition, the reaction is terminated by stirring at 55 ° C. for 2 hours. Add 300 ml of ethyl acetate to the reaction vessel and remove the aqueous layer. The organic layer was dried over anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure, and then recrystallization from isopropyl ether gave 48 g of 2-butyl-2-hydroxymethylpropane-1,3-diol.

Subsequently, 48 g (0.30 mol) of 2-butyl-2-hydroxymethylpropane-1,3-diol and 27 g of dimethyl carbonate were added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dropping funnel and a distillation tower. 0.3 mol) and 2.25 g of potassium carbonate are added and the reaction vessel is heated to 85 ° C. The mixture was stirred for 2 hours while removing methanol accompanying carbonation. Further, 10.8 g (0.12 mol) of dimethyl carbonate was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the reaction vessel was gradually heated to 100 ° C. and reacted for 3 hours. Thereafter, excess dimethyl carbonate and the like in the reaction vessel were distilled off using a decompressor.
Next, the reaction vessel was heated to 200 ° C. and heated for 4 hours to proceed the decarboxylation reaction. After completion of the reaction, the reaction product was distilled under reduced pressure to obtain 34 g of the desired product 3-butyl-3-hydroxymethyloxetane.
Furthermore, it was synthesized from 33 g (0.08 mol) of neopentylglycol ditosylate represented by the formula (6) synthesized in the production 2 of the intermediate, 2.6 g of tetrabutylammonium bromide, 150 ml of dimethyl sulfoxide, and the above reaction. After adding 34 g (0.24 mol) of 3-butyl-3-hydroxymethyloxetane and dissolving at 50 ° C., 12.8 g (0.32 mol) of granular sodium hydroxide was added in 5 portions for 1 hour. did. After completion of the addition, the reaction vessel was heated to 80 ° C. and stirred for 3 hours to complete the reaction. 1 L of ethyl acetate was added to the reaction solution, and then washed with 5% sodium carbonate, pure water, and saturated saline in this order. The organic layer was dried over anhydrous sodium sulfate, and the organic solvent was distilled off under reduced pressure to obtain the formula (8) 16.8 g of an oxetane derivative represented by the formula:

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 4.45-4.40 (dd, 8H), 3.56 (s, 4H), 3.40 (t, 4H), 1.40-1. 12 (m, 12H), 0.95 (s, 6H), 0.92 (t, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 73.7, 71.5, 37.9, 33.9, 29.5, 26.8, 26.3, 25.9, 23.1, 21 .0, 20.5, 14.0

(Production of intermediate 4) Production of oxetane derivative (9) In a reaction vessel equipped with a stirrer and a thermometer, 7,12-dimethyloctadecanedicarboxylic acid (trade name: IPS-22, manufactured by Okamura Oil Co., Ltd.) 44. 5 g (0.12 mol), Doutite WSC (manufactured by Dojindo) 46 g (0.24 mol), N, N-dimethylaminopyridine 2.9 g (0.024 mol), and dichloromethane 500 ml are added. The flask was cooled to 5 ° C. or lower with an ice-water bath under a nitrogen atmosphere, and 24.6 g (0.24 mol) of 3-methyl-3-hydroxymethyloxetane was slowly added dropwise. The reaction container was returned to room temperature after completion | finish of dripping, and also stirred for 5 hours, and reaction was complete | finished. After adding 500 ml of 10% hydrochloric acid to the reaction solution, it was washed with pure water and saturated brine in that order, the organic layer was dried over anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure, and the following formula (9) 48 g of the represented oxetane derivative was obtained.

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 4.45-4.36 (dd, 8H), 3.56 (s, 4H), 2.32 (t, 4H), 1.62 (m, 4H) ), 1.58 (m, 2H), 1.38-1.26 (m, 24H), 0.92-0.80 (m, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.4, 165.7, 73.4, 71.5, 64.0, 63.7, 43.4, 40.6, 34.1, 31 .8, 29.3, 29.2, 29.1, 26.0, 24.9, 23.0, 22.6, 14.1, 7.3

Example 1 Production of Polymerizable Compound “M-1” In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a cooling tube, and a thermometer, 36.3 g (0. 064 mol), 22.9 g (0.152 mol) of sodium iodide, and 300 ml of acetonitrile were stirred while cooling with an ice-water bath so that the temperature was 5 ° C. or lower. Decanoyl chloride 25.6 (0.134 mol) was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. A small amount of water was added to the reaction vessel, ethyl acetate was added, and iodine was decomposed with 10% sodium bisulfite. Further, the organic layer was washed in the order of pure water and saturated saline. After drying the organic layer with anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure to synthesize 65 g of a diiodide.

Next, in a reaction vessel equipped with a stirrer and a thermometer, 62 g (0.055 mol) of the diiodine synthesized by the above method, 15.7 g (0.218 mol) of acrylic acid, 80 mg of p-methoxyphenol, and 300 g of dimethyl sulfoxide was added, and 33.2 g (0.218 mol) of 1,8-diazabicyclo [5,4,0] 7-undecene (hereinafter abbreviated as DBU) was slowly added dropwise over 30 minutes while stirring at room temperature. . After completion of the dropwise addition, the reaction vessel was heated to 90 ° C. and stirred for 12 hours to complete the reaction. Ethyl acetate was added to the reaction vessel, and the organic layer was washed in the order of 1/10 N hydrochloric acid solution, 5% sodium hydroxide solution, pure water and saturated brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent of the organic layer was distilled off under reduced pressure. Then, the concentrated solution was purified by silica gel chromatography, and polymerizable compound “M-1” having two nonyl groups (X ₂ :- About 35 g of CH ₂ OCO—, X ₃ : —CH ₂ OCO—, R ₄ = ethyl group) was obtained.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H) 04 (s, 8H), 2.32 (t, 8H), 1.62 (m, 8H), 1.58 (m, 4H), 1.38-1.25 (m, 48H), 0.91 -80 (m, 18H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 165.7, 131.1, 127.9, 64.0, 63.7, 40.6, 34.2, 31.8, 29 .7-29.0, 26.8, 24.9, 23.0, 22.6, 14.0, 10.7, 7.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Example 2) Production of polymerizable compound "M-2" In a reaction vessel equipped with a stirrer and a thermometer, 89 g (0.36 mol) of 1-bromododecane, 2.6 g of tetrabutylammonium bromide, 150 ml of dimethyl sulfoxide , And 28 g (0.24 mol) of 3-ethyl-3-hydroxymethyloxetane were dissolved at 50 ° C., and 12.8 g (0.32 mol) of granular sodium hydroxide was divided into 5 portions. Added for hours. After completion of the addition, the reaction vessel was heated to 80 ° C. and stirred for 3 hours to complete the reaction. After adding 1 L of ethyl acetate to the reaction solution, it was washed with 5% sodium carbonate, pure water and saturated brine in that order, the organic layer was dried over anhydrous sodium sulfate, and the organic solvent was distilled off under reduced pressure to give 3-ethyl- 40 g of 3- (dodecyloxymethyl) oxetane was obtained.
In a reaction vessel similar to that in Example 1, 18.2 g (0.064 mol) of the above intermediate 3-ethyl-3- (dodecyloxymethyl) oxetane, 22.9 g (0.152 mol) of sodium iodide, and 300 ml of acetonitrile was added and stirred while cooling with an ice-water bath so as to be 5 ° C. or lower. 10.9 g (0.032 mol) of 7-ethylhexadecanedicarboxylic acid dichloride was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. After completion of the reaction, the same operation as in Example 1 was performed to synthesize 33 g of diiodine.

Next, in the same reaction vessel as in Example 1, 33 g (0.029 mol) of the diiodine synthesized by the above method, 8.3 g (0.116 mol) of acrylic acid, 40 mg of p-methoxyphenol, and dimethyl sulfoxide 300 g was added, and 17.7 g (0.116 mol) of DBU was slowly added dropwise over 30 minutes while stirring at room temperature. After completion of the dropwise addition, the reaction vessel was heated to 90 ° C. and stirred for 12 hours to complete the reaction. After completion of the reaction, the same operation as in Example 1 was performed, the concentrated solution was purified by silica gel chromatography, and a polymerizable compound “M-2” having two dodecyl groups (X ₂ : —CH ₂ O—, X ₃ : —CH ₂ OCO—, R ₄ = ethyl group) was obtained.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H) 05 (s, 4H), 3.34 (t, 4H), 3.29 (s, 4H), 2.32 (t, 4H), 1.62 (m, 4H), 1.6-1.47 (M, 8H), 1.25 (m, 64H), 0.92-0.8 (m, 15H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.6, 70.4, 64.7, 64.4, 41.5, 34 3, 32.7, 31.9, 29.6-29.2, 26.9, 26.1, 25.0, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Example 3) Production of polymerizable compound "M-3" 16 g (0.045 mol) of an oxetane derivative represented by formula (8) synthesized in Production 3 of intermediate in a reaction vessel similar to that in Example 1. Then, 20.2 g (0.135 mol) of sodium iodide and 300 ml of acetonitrile were added and stirred while cooling with an ice-water bath so that the temperature became 5 ° C. or lower. 20.2 g (0.1 mol) of n-myristic acid chloride was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. After completion of the reaction, the same operation as in Example 1 was performed to synthesize 44 g of diiodine.

Next, 44 g (0.043 mol) of the diiodine synthesized by the above method, 12.4 g (0.172 mol) of acrylic acid, 60 mg of p-methoxyphenol, and dimethyl sulfoxide were prepared in the same reaction vessel as in Example 1. 300 g was added, and 26.2 g (0.172 mol) of DBU was slowly added dropwise over 30 minutes while stirring at room temperature. After completion of the dropwise addition, the reaction vessel was heated to 90 ° C. and stirred for 12 hours to complete the reaction. After completion of the reaction, the same operation as in Example 1 was performed, and the concentrated solution was purified by silica gel chromatography, and a polymerizable compound “M-3” having a tridecyl group (X ₂ : —CH ₂ OCO—, X ₃ : — About 18.6 g of CH ₂ O—, R ₄ = butyl group) was obtained.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.10 (s, 4H) 99 (s, 4H), 3.34 (s, 4H), 3.29 (s, 4H), 2.29 (t, 4H), 1.74 (s, 4H), 1.6-1.25 (M, 52H), 0.90-0.83 (m, 18H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.7, 165.9, 130.6, 128.3, 71.5, 70.4, 65.4, 64.7, 50.3, 41 5, 34.3, 31.9, 29.6-29.1, 25.9, 24.9, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

Example 4 Production of Polymerizable Compound “M-4” In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a cooling tube, and a thermometer, the compound represented by the formula (7) synthesized in the production of the intermediate 1 described above The oxetane derivative 36.3 g (0.064 mol), sodium iodide 22.9 g (0.152 mol), and 300 ml of acetonitrile were added and stirred while cooling with an ice-water bath to 5 ° C. or less. 2-Ethylhexanoyl chloride 23.6 (0.134 mol) was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. A small amount of water was added to the reaction vessel, ethyl acetate was added, and iodine was decomposed with 10% sodium bisulfite. Further, the organic layer was washed in the order of pure water and saturated saline. After drying the organic layer with anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure to synthesize 60 g of a diiodide.

Next, 60.6 g (0.055 mol) of the diiodine synthesized by the above method, 15.7 g (0.218 mol) of acrylic acid, and 80 mg of p-methoxyphenol in a reaction vessel equipped with a stirrer and a thermometer. In addition, 300 g of dimethyl sulfoxide was added, and 33.2 g (0.218 mol) of 1,8-diazabicyclo [5,4,0] 7-undecene (hereinafter abbreviated as DBU) was slowly added over 30 minutes while stirring at room temperature. It was dripped. After completion of the dropwise addition, the reaction vessel was heated to 90 ° C. and stirred for 12 hours to complete the reaction. Ethyl acetate was added to the reaction vessel, and the organic layer was washed in the order of 1/10 N hydrochloric acid solution, 5% sodium hydroxide solution, pure water and saturated brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent of the organic layer was distilled off under reduced pressure. The concentrated solution was purified by silica gel chromatography, and polymerizable compound “M-4” (X ₂ ) having two 2-ethylhexyl groups. : -CH ₂ OCO-, X ₃ : -CH ₂ OCO-, R ₄ = ethyl group).

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H) 04 (s, 8H), 2.32 (t, 8H), 1.62 (m, 6H), 1.58 (m, 4H), 1.38-1.25 (m, 44H), 0.91 -80 (m, 24H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 165.7, 131.1, 127.9, 64.0, 63.7, 40.6, 34.2, 31.8, 29 .7-29.0, 26.8, 24.9, 23.0, 22.6, 14.0, 10.7, 7.6, 7.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Example 5) Manufacture of polymeric compound "M-5" It represents with Formula (9) synthesize | combined by manufacture 4 of the intermediate body in the reaction container provided with the stirring apparatus, the nitrogen introducing tube, the cooling tube, and the thermometer. 34.5 g (0.064 mol) of oxetane derivative, 22.9 g (0.152 mol) of sodium iodide, and 300 ml of acetonitrile were added and stirred while cooling with an ice-water bath so that the temperature was 5 ° C. or lower. Decanoyl chloride 25.6 (0.134 mol) was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. A small amount of water was added to the reaction vessel, ethyl acetate was added, and iodine was decomposed with 10% sodium bisulfite. Further, the organic layer was washed in the order of pure water and saturated saline. After drying the organic layer with anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure to synthesize 61 g of a diiodide.

Next, 60 g (0.055 mol) of the diiodide synthesized by the above method, 15.7 g (0.218 mol) of acrylic acid, 80 mg of p-methoxyphenol, and dimethyl were added to a reaction vessel equipped with a stirrer and a thermometer. 300 g of sulfoxide was added, and 33.2 g (0.218 mol) of DBU was slowly added dropwise over 30 minutes while stirring at room temperature. After completion of the dropwise addition, the reaction vessel was heated to 90 ° C. and stirred for 12 hours to complete the reaction. Ethyl acetate was added to the reaction vessel, and the organic layer was washed in the order of 1/10 N hydrochloric acid solution, 5% sodium hydroxide solution, pure water and saturated brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent of the organic layer was distilled off under reduced pressure. Then, the concentrated solution was purified by silica gel chromatography, and polymerizable compound “M-5” having two nonyl groups (X ₂ :- About 31 g of CH ₂ OCO—, X ₃ : —CH ₂ OCO—, R ₄ = methyl group) was obtained.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H) 04 (s, 8H), 2.32 (t, 8H), 1.62 (m, 8H), 1.58 (m, 2H), 1.38-1.25 (m, 48H), 0.91 -80 (m, 18H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 165.7, 131.1, 127.9, 64.0, 63.7, 40.6, 34.2, 31.8, 29 .7-29.0, 26.8, 24.9, 23.0, 22.6, 14.0, 10.7, 7.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
(Example 6) Preparation of polymerizable composition (MLC-1) 70% of liquid crystal composition A (dielectric anisotropy: 7.7) composed of a fluorine-based liquid crystal compound having the following structure was synthesized in Example 1. The compound “M-1” 29.4% and a photopolymerization initiator “Irgacure 651” 0.6% manufactured by Ciba Specialty Chemicals Co., Ltd. -1) was obtained.

Example 7 Production 1 of Light Scattering Type Liquid Crystal Device
This polymerizable composition (MLC-1) was sandwiched between two ITO electrode glass substrates coated with 6.0 μm glass fiber spacers, and the temperature of the entire substrate was controlled so as to maintain a uniform solution state. A light scattering type liquid crystal device having a thickness of about 6 μm was produced by irradiating with / cm ² ultraviolet rays for 60 seconds. The saturation voltage of the fabricated device and the temperature dependence of the saturation voltage were evaluated, and the results are shown in Table 1.
Example 8 Preparation of Polymerizable Composition (MLC-2) Example except that 29.4% of compound “M-5” synthesized in Example 5 was used instead of “M-1” in Example 6. In the same manner as in Example 6, a polymerizable composition (MLC-2) was prepared.
Example 9 Production 2 of Light Scattering Type Liquid Crystal Device
Using the polymerizable composition (MLC-2) prepared in Example 8, a light scattering liquid crystal device was produced in the same manner as in Example 7. The saturation voltage of the fabricated device and the temperature dependence of the saturation voltage were evaluated, and the results are shown in Table 1.
Comparative Example 1 Production 3 of Light Scattering Type Liquid Crystal Device
A polymerizable composition (MLC-3) comprising 29.4% of a polymerizable compound having the following structure, 70% of liquid crystal composition A and 0.6% of a photopolymerization initiator “Irgacure 651” was prepared. Using this polymerizable composition (MLC-3) as a light control layer forming material, a light scattering liquid crystal device was produced in the same manner as in Example 7. The saturation voltage of the obtained device and the temperature dependence of the saturation voltage were evaluated, and the results are shown in Table 1.

  As shown in Table 1, the liquid crystal device of the present invention showed an excellent value of ΔV of 0.2 or less, and could be driven at a low voltage in a wide temperature range from −20 ° C. to 70 ° C. On the other hand, the liquid crystal device of the comparative example had a high saturation voltage and a large temperature dependency.

The polymerizable compound and composition of the present invention display an electric field display screen such as a building window or a show window used outdoors, a curtain for lighting control, letters and figures, and display it electrically with high-speed response. It is particularly useful as a light control layer forming material for a light scattering type liquid crystal device useful as an advertising board or a decorative display board. It is also useful as a material for display elements such as watches and computer terminals, digital paper, information display on IC cards, portable information terminals such as electronic books and PDAs, display devices such as projections, and optical elements such as optical shutters. .

Claims (5)

A polymerizable compound represented by the general formula (1).

^(Wherein, X ₁ is _{-O-CH 2 -, - O} -CH 2 -CH 2 -CO-O-CH 2 -, - O-CH 2 -CH 2 OCO-, or _-O-CH 2 -CH _(CH 3) OCO- represent,
R ² represents an alkyl group having 4 to 30 carbon atoms, and one or two or more carbon atoms present in the group may be replaced by oxygen atoms so that the oxygen atoms are not directly bonded to each other. Preferably, a single bond between one or more carbons present in the group may be replaced by a double bond or a triple bond, and a hydrogen atom present in the group may be replaced by a halogen. well,
R ³ represents hydrogen or a methyl group,
R ⁴ represents an alkyl group having 1 to 5 carbon atoms,
X ² and X ³ each independently represent —CH ₂ O—, —CH ₂ OCO—, —CH ₂ CO—O—, —COO— or a single bond,
R ¹ represents an alkylene group having 1 to 30 carbon atoms, and at least one methylene group present in the group is represented by the general formula (2)

(In the formula, R ¹¹ and R ¹² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and one or two or more carbon atoms present in the group are mutually bonded to oxygen atoms. It may be replaced by an oxygen atom as not directly bonded, and a single bond between one or more carbons present in the group may be replaced by a double bond or a triple bond. The hydrogen atom present therein may be substituted by halogen, but at least one of R ¹¹ and R ¹² represents an alkyl group, and m represents an integer of 1 to 10.) One or more carbon atoms present in the group may be replaced by oxygen atoms as if the oxygen atoms are not directly bonded to each other, and one carbon atom present in the group Or 2 The above single bond between carbons may be replaced by a double bond or a triple bond, and a hydrogen atom present in the group may be replaced by a halogen. ) In the general formula (2), R ¹¹ represents an alkyl group having 1 to 2 carbon atoms, R ² represents an alkyl group having 4 to 30 carbon atoms, and one or more carbon atoms present in the group are The oxygen atom may be replaced by an oxygen atom as not directly bonded to each other, and a single bond between one or more carbons present in the group is replaced by a double bond or a triple bond. The polymerizable compound according to claim 1, wherein a hydrogen atom present in the group may be substituted by a halogen. The polymerizable compound according to claim 1, wherein m represents 1 or 2. A polymerizable composition comprising the polymerizable compound according to claim 1. A light scattering type liquid crystal device comprising the polymerizable composition according to claim 4 as a constituent member.