JP7528462B2 - Liquid crystal composition for polymer network type liquid crystal element, polymer network type liquid crystal display element using said liquid crystal composition, and method for producing same - Google Patents

Description

The present invention relates to a liquid crystalline composition for polymer network type liquid crystal elements, and liquid crystal elements using the same, as well as articles using the same, including architectural light control elements such as windows, skylights, roofs, walls, partitions, dividers, and doors, transportation light control elements such as doors, windows, doors, helmets, and sunroofs, decorative light control elements such as sunglasses, spectacles, sun visors, watches, mirrors, and reflectors, display components such as flexible liquid crystal display elements, reflective liquid crystal display elements, transparent liquid crystal display elements, and variable diffusion films.

As displays become more powerful, it is expected that there will be new displays, such as mobile terminals like smartphones and tablet devices with powerful graphics, transparent displays that are expected to be used in TVs and window displays, high-contrast liquid crystal displays, and light-adjusting elements with light shutter functions that can adjust the degree of transmission and scattering. The development of light-adjusting materials to realize these displays is an important issue. In addition, with the recent development of communication technology, it has become possible to control various types of equipment, both industrial and domestic, using mobile terminals in smart windows that use liquid crystal, such as private glass and variable projector screens, and light-adjusting materials are needed to realize these displays.

Among materials for light control elements, polymer-dispersed liquid crystal elements (polymer network type liquid crystal elements) using polymer-dispersed liquid crystal as a material for a transmission-scattering type light control element are liquid crystal element types in which the liquid crystal and the polymer are phase-separated from each other within the element, forming a polymer network by the polymer (see Patent Documents 1 and 2).

Polymer network type liquid crystal elements do not require optical films such as polarizing plates because their display method utilizes the contrast ratio between the transparent state and the opaque state. Therefore, they have the advantage of being able to achieve brighter displays than TN, STN, IPS or VA mode liquid crystal display elements that use polarizing plates, and because the element structure is simple, they are used in optical shutter applications such as light control glass and segment display applications such as clocks. In addition, in order to achieve high-definition displays, applications such as projectors and reflective displays are also being considered in combination with active drive display elements.

In recent years, development of liquid crystal display devices with unconventional designs, such as transmissive displays and flexible displays, has been progressing toward practical use. In particular, reverse mode type polymer-dispersed liquid crystal elements, which are transmissive when no voltage is applied and non-transmissive when voltage is applied, are said to be suitable for applications that contribute to low power consumption.

In particular, if a material with negative dielectric anisotropy is used as the liquid crystal and the liquid crystal material is configured to be oriented perpendicular to the substrate when no voltage is applied, alignment treatment of the substrate such as rubbing is unnecessary, and higher transparency is obtained compared to the transparent state of a normal mode type element (non-transmissive state when no voltage is applied, transmissive state when voltage is applied) that uses a liquid crystal material with positive dielectric anisotropy, and higher scattering is obtained compared to the non-transmissive state of a reverse mode type element that uses a liquid crystal material with positive dielectric anisotropy.

However, with only conventional technology using liquid crystal materials with negative dielectric anisotropy, there was a problem that, for example, when a flexible substrate was used, adhesion to the substrate was insufficient, leading to peeling from the substrate. When using a flexible substrate, a roll-to-roll process is generally used in which the liquid crystal material is applied to the substrate, one side of the liquid crystal material is covered with the substrate, and then a polymer network is formed using ultraviolet light or the like. However, when the resulting roll of display element is wound up, shear is applied, and the element is cut for use, so there was a need for adhesion that could withstand practical use without using a sealant or the like for the outer frame of the element. Similar problems also existed with polymer wall type liquid crystal elements, which are listed as transmissive displays that use flexible substrates.

JP 5-119302 A Patent Publication 2008-058374

As described in the above-mentioned prior art, when productivity is taken into consideration, it is necessary to obtain good adhesion to the substrate and to have electro-optical properties sufficient for practical use as a liquid crystal element. Therefore, the object of the present invention is to provide a liquid crystal composition for a polymer network type liquid crystal element that has electro-optical properties that are practical for use as a polymer network type liquid crystal element and can improve adhesion to the substrate, a polymer network type liquid crystal display element using the liquid crystal composition, a method for producing the same, and an article using a polymer network type liquid crystal element.

As a result of extensive research into the above-mentioned problems, the present invention has come to a solution by using a polymerizable compound having a mesogenic skeleton, a liquid crystal compound having negative dielectric properties, and a polymerizable compound having a polar group. It has also been found that the use of a polymerizable compound having a specific polar group makes it possible to control the alignment.

That is, the present invention provides a liquid crystal composition for a polymer network type liquid crystal element, which contains a polymerizable compound having a mesogenic skeleton as a first component, a liquid crystal compound having a negative dielectric constant as a second component, and a polymerizable compound having a polar group as a third component.

When the liquid crystalline composition for a polymer network type liquid crystal element of the present invention is used in a liquid crystal element, it has good electro-optical properties that are suitable for practical use, and also provides good adhesion as a polymer network type liquid crystal element.

FIG. 1 is a schematic diagram showing an example of the configuration of a liquid crystal element of the present invention in a state where no voltage is applied; FIG. 2 is a schematic diagram showing a state in which a voltage is applied in FIG. 1; A view of FIG. 2 seen from a direction perpendicular to the transparent substrate.

The liquid crystal composition for a polymer network type liquid crystal element of the present invention and the implementation of a polymer network type liquid crystal element using the same will be described.

It should be noted that the present embodiment is described as a specific example to allow a better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
<Liquid Crystal Composition>
As described above, the liquid crystal composition for a polymer network type liquid crystal element of the present invention contains the first to third components as essential components, and contains a polymerizable compound having a mesogenic skeleton as the first component, a liquid crystal compound having a negative dielectric constant as the second component, a polymerizable compound having a polar group as the third component, and other components as necessary. Each component will be specifically described below.
(First component: polymerizable compound having a mesogenic skeleton)
In the liquid crystal composition for a polymer network type liquid crystal element of the present invention, a polymerizable compound having a mesogenic skeleton is used as a first component. The polymerizable compound is a compound effective for controlling the alignment of the liquid crystal composition when no voltage is applied, and may be any polymerizable compound having a mesogenic skeleton, and the compound alone does not need to exhibit liquid crystallinity.

For example, Handbook of Liquid Crystals (edited by D. Demus, J.W. Goodby, G.W. Gray, H.W. Spiess, and V. Vill, published by Wiley-VCH, 1998), Quarterly Chemistry Review No. Examples of such a compound include rod-shaped polymerizable liquid crystal compounds having a rigid portion called a mesogen in which a plurality of structures such as 1,4-phenylene groups and 1,4-cyclohexene groups are linked together, and two or more polymerizable functional groups such as vinyl groups, acrylic groups, and (meth)acrylic groups, as described in JP-A-22, Chemistry of Liquid Crystals (edited by the Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, JP-A-11-116538, and JP-A-11-148079, and rod-shaped polymerizable liquid crystal compounds having two or more polymerizable groups having maleimide groups, as described in JP-A-2004-2373 and JP-A-2004-99446. Among these, rod-shaped liquid crystal compounds having two or more polymerizable groups are preferred because they make it easier to control the alignment of the liquid crystal composition when no voltage is applied to the polymer network type liquid crystal element.

The content of the polymerizable compound having a mesogenic skeleton as the first component is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 13% by mass or more, relative to the total amount of 100% by mass of the liquid crystal composition for polymer network type liquid crystal elements of the present invention, from the viewpoint of maintaining the network structure. Also, from the viewpoint of reducing the voltage, it is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

As the polymerizable compound having a mesogenic skeleton of the present invention, it is preferable to contain one or more compounds represented by the following general formula (I).

(In the formula, P ¹ and P ² each independently represent a polymerizable group.
S ¹ and S ² each independently represent a spacer group or a single bond;
When X ¹ and X ² are represented as the bond to S ¹ or S ² as the leftmost bond, they each independently represent -O-, -S-, -OCH ₂ -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH 2 -, -CF _{2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 - , -CH} =CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-,
represents —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —COO—CH ₂ —, —OCO—CH ₂ —, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond (with the proviso that —O—O— is not included in the groups represented by P ¹ -S ¹ -X ¹ — and P ² -S ² -X ² -);
Z ¹ is -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH 2 -, -CH 2 S- _{, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 - , -CH =} CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-R ^Z1 -, -OCO-R ^Z1 -, -R ^Z1 -COO-, -R ^Z1 -OCO- , -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ represents -OCO-, -CH=CH-, -CH ₂ CH ₂ -, -N=N-, -CH=N-N=CH-, -CF=CF-, -C≡C- or a single bond (wherein -R ^Z1 - represents an alkylene group having 2 to 6 carbon atoms); when there are a plurality of Z ^1's , they may be the same or different;
A ¹ and A ² each independently represent a divalent group selected from an aromatic ring, an alicyclic ring, a heterocyclic ring, and a fused ring, and when a plurality of A ¹ 's are present, they may be the same or different;
Each n independently represents an integer from 1 to 9.
In the general formula (I), the polymerizable groups represented by P ¹ and P ² are represented by the following formulae (P-1) to (P-20):

is preferred, and among these polymerizable groups, from the viewpoint of enhancing the polymerizability and storage stability, formula (P-1), formula (P-2), formula (P-7), formula (P-12), or formula (P-13) is preferred, and formula (P-1), formula (P-2), or formula (P-7) is more preferred.

In the general formula (I), S ¹ and S ² each independently represent a spacer group or a single bond, and the spacer group represents an alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms, CN groups, alkyl groups having 1 to 8 carbon atoms, or alkyl groups having 1 to 8 carbon atoms having the above-mentioned polymerizable group, and one CH ₂ group or two or more non-adjacent CH ₂ groups present in this group are each independently -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -CH(OH)-, CH(COOH), -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. Among these spacer groups, from the viewpoint of exhibiting liquid crystal properties, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and an alkylene group having 4 to 14 carbon atoms in which the alkylene group is partially replaced with -O- are preferred.

In the general formula (I), the groups represented by X ¹ and X ² are preferably each independently a group selected from a single bond, -O-, -S-, -CO-, -COO- and -OCO-.

However, in the general formula (I), the groups represented by P ¹ -S ¹ -X ¹ - and P ² -S ² -X ² - do not contain an -O-O- bond.

In the general formula (I), when there are a plurality of Z ^{1 's} , they may be the same or different, and are -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -O-CO-O-, -CF ₂ O-, -OCF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-(CH ₂ CH ₂ ) _m -, _-OCO- (CH ₂ CH 2 ) _m -, -(CH 2 CH ₂ ) _m -COO-, -(CH ₂ CH ₂ ) _m -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, _{-CH 2} -COO-, -CH ₂ -OCO-, -CH=CH-, -CH A group selected from _-2CH2- , _-C≡C- , or a single bond is preferable, but in order to reduce the driving voltage, m is preferably 1 to 3, and in order to exhibit liquid crystallinity, at least one of ^Z1 is preferably a group selected from _-OCH2- , _{-CH2O- , -COO- ,} -OCO-, -O _- CO-O-, -CF2O-, -OCF2-, -COO-CH2CH2-, -OCO _{- CH2CH2-} , _{-CH2CH2 -} COO- _, -CH2CH2 _- OCO-, or a single bond.

In the general formula (I), A ¹ and A ² each independently represent a divalent group selected from an aromatic ring, an alicyclic ring, a heterocyclic ring, and a condensed ring, and specifically, a group selected from the following (a) to (c) is preferable. When a plurality of A ¹ 's are present, they may be the same or different.
(a) a trans-1,4-cyclohexylene group (one methylene group or two or more non-adjacent methylene groups in this group may be replaced by -O- or -S-).
(b) a phenylene group (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by a nitrogen atom).
(c) a cyclohexenylene group, a bicyclo(2.2.2)octylene group, a piperidine group, a naphthalene group, a decahydronaphthalene group, and a tetrahydronaphthalene group (one or more hydrogen atoms present in the above groups (a), (b), and (c) may each be independently substituted with a fluorine atom, a chlorine atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated alkoxy group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms).
In the above general formula (I), n represents an integer of 1 to 9, preferably 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.

The content of the polymerizable compound represented by general formula (I) is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount (100% by mass) of the first component used in the liquid crystal composition for polymer network type liquid crystal elements of the present invention, from the viewpoint of maintaining the network structure. Also, from the viewpoint of reducing the voltage, it is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 60% by mass or less.

In the first component, examples of polymerizable compounds having a mesogenic skeleton other than general formula (I) include compounds represented by the following general formulas (2) and (4) to (8). A more specific example of a compound of general formula (I) is a compound represented by general formula (3).

In the above formulas (2) to (8), P ¹¹ to P ⁷⁴ represent polymerizable groups selected from the above formulas (P-1) to (P-20). Among these polymerizable groups, from the viewpoint of enhancing polymerizability and storage stability, formulas (P-1), (P-2), (P-7), (P-12) and (P-13) are preferred, and formulas (P-1), (P-7) and (P-12) are more preferred.

X ¹¹ to X ⁷² are each independently -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S- CO-, -O-CO-O-, -CO-NH- _, -NH-CO-, -SCH 2 -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S- , -SCF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO- CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -N═N-, -CH═N-N═CH-, -CF═CF-, -C≡C- or represents a single bond, but when there are a plurality of X ¹¹ to X ⁷² , they may be the same or different (however, each P—(S—X)— bond may not be —O—O—). (not including), and particularly a group selected from a single bond, -O-, -S-, -CO-, -COO-, and -OCO- are preferred.

S ¹¹ to S ⁷² each independently represent a spacer group or a single bond. The spacer group is preferably an alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms, a CN group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms having the above-mentioned polymerizable group, and one CH ₂ group or two or more non-adjacent CH ₂ groups present in this group may each be independently replaced by -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS-, or -C≡C- in a form in which oxygen atoms are not directly bonded to each other). When a plurality of S ¹¹ to S ⁷² are present, they may be the same or different from each other. Of these spacer groups, from the viewpoint of exhibiting liquid crystallinity, preferred are linear alkylene groups having 2 to 8 carbon atoms, alkylene groups having 2 to 6 carbon atoms substituted with a fluorine atom, and alkylene groups having 4 to 14 carbon atoms in which the alkylene group is partially replaced with -O-. In addition, in the above general formula (2), ^S11 is preferably a linear alkylene group having 2 to 8 carbon atoms from the viewpoint of further enhancing adhesion.

M ¹¹ , M ²¹ , M ³¹ , M ⁵¹ and M ⁷¹ each independently represent a mesogen group represented by the following general formula (9-a):

(In general formula (9-a), A ⁹¹ , A ⁹² , and A ⁹³ each independently represent a divalent group having at least one ring structure, and the divalent group is a 1,2-cyclopropylene group, a 1,3-cyclobutylene group, a 2,5-cyclopentylene group, an octahydro-4,7-methano-1H-indene-1,5-diyl group, an octahydro-4,7-methano-1H-indene-1,6-diyl group, an octahydro-4,7-methano-1H-indene-2,5-diyl group, a tricyclo[3.3.1.1 ^3,7 ]-1,3-diyl group, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, naphthylene-1,4-diyl group, naphthylene-1,5-diyl group, naphthylene-1,6-diyl group, naphthylene-2,5-diyl group, represents a group selected from a phenylene-2,6-diyl group, a phenanthrene-2,7-diyl group, a 9,10-dihydrophenanthrene-2,7-diyl group, a benzothiazole group, a 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, a benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, a benzo[1,2-b:4,5-b']diselenophene-2,6-diyl group, a [1]benzothieno[3,2-b]thiophene-2,7-diyl group, a [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or a fluorene-2,7-diyl group, and these groups are unsubstituted or have one or more L ¹ , but when A ⁹¹ and/or A ⁹² appear multiple times, they may be the same or different;
Z ⁹¹ and Z ⁹² are each independently -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH 2 -, -CH 2 S- _, -CF _{2 O-} , -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH 2 CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO- _{CH 2} -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -N═N-, -CH═N-, -N═CH-, -CH═N-N═CH-, -CF═CF-, -C≡C- or a single bond, but when a plurality of Z ⁹¹ and/or Z ⁹² appear, they may be the same or different;
j91 and j92 each independently represent an integer of 0 to 4, provided that j91 + j92 represents an integer of 1 to 4;
L ¹ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH ₂ - or two or more non-adjacent -CH ₂ - groups each independently represent -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, -N=N-, -CR ¹ =N-N=CR ¹ R 1 represents a straight-chain or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -, or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by a fluorine atom (R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may be straight-chain or branched, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, and one -CH ₂ - or two or more non-adjacent -CH ₂ - in the alkyl group may each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-).

Furthermore, M ⁴¹ is a trivalent organic group having a ring structure exemplified as the above-mentioned A ⁹¹ , A ⁹² and A ⁹³ , and M ⁶¹ is a tetravalent organic group having a ring structure exemplified as the above-mentioned A ⁹¹ , A ⁹² and A ⁹³ .

In the general formulae (2) to (8), R ¹¹ and R ³¹ each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, one -CH ₂ - in the alkyl group or two or more non-adjacent -CH ₂ - may each independently be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-,
m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent an integer of 0 to 5.

In the general formulas (2) to (8), S ¹¹ to S ⁷² each independently represent a spacer group or a single bond, and the spacer group represented by S ¹¹ to S ⁷² represents an alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms, CN groups, alkyl groups having 1 to 8 carbon atoms, or alkyl groups having 1 to 8 carbon atoms and a polymerizable functional group, and one CH ₂ group or two or more non-adjacent CH ₂ groups present in this group are each independently -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. Of these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, or an alkylene group having 5 to 14 carbon atoms in which an alkylene group is partially replaced with -O- is preferred. Furthermore, when a plurality of S ¹¹ to S ⁷² are present, they may be the same or different from each other.

In the general formulas (2) to (8), m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent an integer from 0 to 5, and m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent preferably 0 or 1, and more preferably 1.

Specifically, the polymerizable compound represented by the general formula (2) is preferably a polymerizable compound represented by the following formulas (2-1) to (2-31).

In the above formulas (2-1) to (2-31), n and m each independently represent an integer number of 1 to 10, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they may all be unsubstituted or substituted with one or more halogen atoms.

In the liquid crystal composition for polymer network type liquid crystal element of the present invention, it is preferable to use one or more compounds represented by general formula (I) as the first component together with one or more polymerizable compounds represented by general formula (2) in view of the adhesion of the resulting polymer network type liquid crystal element. The content of the polymerizable compound represented by general formula (2) is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the first component used in the liquid crystal composition for polymer network type liquid crystal element of the present invention (100% by mass), and from the viewpoint of maintaining the strength of the polymer network, it is preferably 80% by mass or less, and particularly preferably 70% by mass or less.

As the polymerizable compound represented by the general formula (3), the polymerizable compounds represented by the following formulas (3-1) to (3-66) are preferred.

In the above formulas (3-1) to (3-66), n and m each independently represent an integer number from 1 to 10, p1 and p2 each independently represent 0 or 1, q1 and 12 each independently represent an integer number from 1 to 10, and R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they may all be unsubstituted or may be substituted with one or more halogen atoms.

As the compound of general formula (3), the above formulas (3-1) to (3-8), (3-36), (3-38), (3-39), (3-41), (3-54), (3-58), (3-60), (3-62), and (3-63) are preferred.

The total content of the polymerizable compounds represented by general formula (3) is preferably 5% by mass or more, more preferably 20% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of the first component used in the liquid crystal composition for a polymer network type liquid crystal element of the present invention (100% by mass), from the viewpoint of maintaining the network structure. Also, from the viewpoint of reducing the voltage, it is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 60% by mass or less.

Specific examples of the compound represented by the above general formula (4) include compounds represented by the following formulas (4-1) to (4-9).

The polymerizable compound represented by the general formula (4) is preferable because it not only contributes to the formation of a polymer network, but also functions as a self-supporting alignment agent that eliminates the need for a polyimide alignment film. When the polymerizable compound is used, the content of the polymerizable compound is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and particularly preferably 2.0% by mass or more, relative to the total amount of the first component used in the liquid crystal composition for polymer network type liquid crystal element of the present invention (100% by mass), when a vertical alignment film is not used and the polymerizable compound is used as a monomer exhibiting vertical alignment. In addition, from the viewpoint of maintaining good vertical alignment, it is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 8% by mass or less.

Specific examples of the compound represented by the above general formula (5) include compounds represented by the following formulas (5-1) to (5-23).

In the above formulas (5-1) to (5-23), n and m each independently represent an integer number from 1 to 10, and R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they may all be unsubstituted or may be substituted with one or more halogen atoms.

When a polymerizable compound represented by general formula (5) is used, the content of the polymerizable compound is preferably 0% by mass or more, more preferably 1% by mass or more, and particularly preferably 5% by mass or more, relative to the total amount (100% by mass) of the first component used in the liquid crystal composition for polymer network type liquid crystal element of the present invention, from the viewpoint of strengthening the network structure. Also, from the viewpoint of reducing the voltage, the content is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

Specific examples of the compound represented by the above general formula (6) include compounds represented by the following formulas (6-1) to (6-11).

In the above formulas (6-1) to (6-11), n each independently represents an integer number from 1 to 10, and R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they may all be unsubstituted or may be substituted with one or more halogen atoms.

When a polymerizable compound represented by general formula (6) is used, the content of the polymerizable compound is preferably 0% by mass or more, more preferably 1% by mass or more, and particularly preferably 5% by mass or more, relative to the total amount of the first component used in the liquid crystal composition for polymer network type liquid crystal element of the present invention (100% by mass), from the viewpoint of strengthening the network structure. Also, from the viewpoint of reducing the voltage, the content is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

Specific examples of the compound represented by the above general formula (7) include compounds represented by the following formulas (7-1) to (7-14).

In the above formulas (7-1) to (7-14), n, m, l, and k each independently represent an integer number from 1 to 10, and R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they may all be unsubstituted or may be substituted with one or more halogen atoms.

When a polymerizable compound represented by general formula (7) is used, the content of the polymerizable compound is preferably 0% by mass or more, more preferably 1% by mass or more, and particularly preferably 5% by mass or more, relative to the total amount (100% by mass) of the first component used in the liquid crystal composition for polymer network type liquid crystal element of the present invention, from the viewpoint of strengthening the network structure. Also, from the viewpoint of reducing the voltage, the content is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

Specific examples of the compound represented by the above general formula (8) include compounds represented by the following formulas (8-1) to (8-10).

In the above formulas (8-1) to (8-10), each R independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they may all be unsubstituted or may be substituted with one or more halogen atoms.

When a polymerizable compound represented by general formula (8) is used, the content of the polymerizable compound is preferably 0% by mass or more, more preferably 1% by mass or more, and particularly preferably 5% by mass or more, relative to the total amount (100% by mass) of the first component used in the liquid crystal composition for polymer network type liquid crystal element of the present invention, from the viewpoint of strengthening the network structure. Also, from the viewpoint of reducing the voltage, the content is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

In the present invention, as described above, among the first components described above in detail, the polymerizable compounds represented by the general formulae (2-1) to (2-5), (2-11), (2-15) to (2-19), and (2-31), the polymerizable compounds represented by the general formulae (3-1) to (3-7), the polymerizable compounds represented by the general formulae (3-36), the polymerizable compounds represented by the general formulae (3-41) to (3-43), the polymerizable compounds represented by the general formulae (3-50) to (3-51), the compounds represented by the general formulae (3-54) to (3-60), the polymerizable compounds represented by the general formulae (3-62) to (3-66), and the polymerizable compounds represented by the general formulae (4-2) to (4-3) are particularly preferred. From the viewpoint of the effect of reducing the driving voltage, it is preferable to use the polymerizable compounds represented by the general formulae (5-13) to (5-14) and (5-18), the polymerizable compounds represented by the general formulae (6-10) to (6-11), the polymerizable compounds represented by the general formulae (7-8) and (7-12), and the polymerizable compounds represented by the general formulae (8-8) and (8-10). In particular, it is preferable to use the polymerizable compounds represented by the general formulae (2-1), (2-2), (2-3), (2-5), (2-11), (2-15), (2-17) and (2-19), and the polymerizable compounds represented by the general formulae (3-2), (3-6), (3-41), (3-54), (3-62) and (3-63).
From the viewpoint of adhesion, it is preferable to use, as the first component, a polymerizable compound represented by general formula (I), more specifically, a polymerizable compound represented by general formula (3), together with a polymerizable compound represented by general formula (2) which has smaller cure shrinkage among general formulas (2) and (4) to (8).
(Second Component: Liquid Crystal Compound Having Negative Dielectric Anisotropy)
The liquid crystal composition for a polymer network type liquid crystal element of the present invention contains a non-polymerizable liquid crystal compound. More specifically, it contains a compound having negative dielectric anisotropy as a second component. More specifically, the liquid crystal composition for a polymer network type liquid crystal element of the present invention preferably contains one or more compounds represented by the following general formula (IIa) as a compound having negative dielectric anisotropy.

(In the formula, R ⁴¹ and R ⁴⁴ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which one methylene group or two or more non-adjacent methylene groups may be substituted with -O- or -S-, and one or more hydrogen atoms in these groups may be substituted with a fluorine atom or a chlorine atom,
M ⁴¹ , M ⁴² and M ⁴³ are each independently
(a) a 1,4-cyclohexylene group (in which one -CH ₂ - or two or more non-adjacent -CH ₂ - groups may be replaced by -O-), and (b) a 1,4-phenylene group (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=).
(c) a naphthalene-2,6-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or a decahydronaphthalene-2,6-diyl group (one -CH= or two or more non-adjacent -CH= groups in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N=).
(d) a group selected from the group consisting of 1,4-cyclohexenylene groups, wherein the groups (a), (b), (c) and (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom;
L ⁴¹ , L ⁴² and L ⁴³ each independently represent a single bond, -COO-, -OCO-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O- or -C≡C-; when a plurality of M ⁴² , M ⁴³ L ⁴¹ and/or L ⁴³ are present, they may be the same or different;
^X41 and ^{X42 each} represent a fluorine atom, a chlorine atom, or a cyano group;
u and v each independently represent 0, 1, or 2, provided that u+v is 2 or less.
The compound having negative dielectric anisotropy as the second component may contain a liquid crystal compound other than the compound represented by general formula (IIa). For example, it can be composed of one or more compounds represented by general formula (IIa) and at least one or more compounds selected from the following general formulas (IIb) and (IIc) in any combination. The compounds represented by general formulas (IIa), (IIb) and (IIc) are dielectrically negative compounds (the sign of the dielectric anisotropy is negative and the absolute value is greater than 2).

(In the formula, R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which one methylene group or two or more non-adjacent methylene groups may be substituted with -O- or -S-, and one or more hydrogen atoms in these groups may be substituted with a fluorine atom or a chlorine atom,
M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ and M ⁴⁹ are each independently
(a) a 1,4-cyclohexylene group (in which one -CH ₂ - or two or more non-adjacent -CH ₂ - groups may be replaced by -O-), and (b) a 1,4-phenylene group (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=).
(c) a naphthalene-2,6-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or a decahydronaphthalene-2,6-diyl group (one -CH= or two or more non-adjacent -CH= groups in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N=).
(d) a group selected from the group consisting of 1,4-cyclohexenylene groups, wherein the groups (a), (b), (c) and (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom;
L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ and L ⁴⁹ each independently represent a single bond, -COO-, -OCO-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O- or -C≡C-; when a plurality of M ⁴⁵ , M ⁴⁶ , M ⁴⁸ , M ⁴⁹ , L ⁴⁴ , L ⁴⁶ , L ⁴⁷ and/or L ⁴⁹ are present, they may be the same or different;
X ⁴³ to X ⁴⁸ each represent a hydrogen atom, a fluorine atom, a chlorine atom, or a cyano group; G represents a methylene group or —O—;
w, x, y and z each independently represent 0, 1 or 2, provided that w+x and y+z are 2 or less.
The preferred lower limit of the content of the liquid crystal compound represented by formula (IIa) relative to the total amount of the non-polymerizable liquid crystal compound contained in the liquid crystal composition for a polymer network type liquid crystal element according to the present invention is 30% by mass, and the preferred upper limit is 95% by mass. The more preferred lower limit of the content is 45% by mass, and the more preferred upper limit is 80% by mass.

In the compounds represented by the above general formula (IIa), general formula (IIb) and general formula (IIc), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, a linear alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms (including those in which one methylene group or two or more non-adjacent methylene groups present in these groups are substituted with -O- or -S-, and those in which one or more hydrogen atoms present in these groups are substituted with fluorine atoms or chlorine atoms). A linear alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms is more preferable, and a linear alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is particularly preferable. M ⁴¹ , M ⁴² , M ⁴³ , M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ and M ⁴⁹ each independently represent a trans-1,4-cyclohexylene group (including those in which one methylene group or two or more non-adjacent methylene groups in this group are replaced by -O- or -S-), a 1,4-phenylene group (including those in which one -CH= or two or more non-adjacent -CH= are replaced by -N=), a 1,4-cyclohexenylene group, a 1,4-bicyclo[2.2.2]octylene group, a piperidine-2,5-diyl group, a naphthalene-2,6-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6 -diyl group and groups represented by decahydronaphthalene-2,6-diyl group (including those in which the hydrogen atoms contained in each group are substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a chlorine atom), are preferred, a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 3-fluoro-1,4-phenylene group, or a 2,3-difluoro-1,4-phenylene group is more preferred, a trans-1,4-cyclohexylene group or a 1,4-phenylene group is even more preferred, and a trans-1,4-cyclohexylene group is particularly preferred. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ and L ⁴⁹ each independently represent preferably a single bond, —CH ₂ CH ₂ —, —(CH ₂ ) ₄ —, —OCO—, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or —C≡C—, more preferably a single bond, —CH ₂ CH ² —, —OCH ₂ — or —CH ₂ O—. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ and X ⁴⁷ each independently represent a hydrogen atom or a fluorine atom, G represents a methylene group or -O-, and u, v, w, x, y and z each independently represent 0, 1 or 2, provided that u+v, w+x and y+z are 2 or less.

Of the structures formed by combining the above options, -CH=CH-CH=CH-, -C≡C-C≡C-, and -CH=CH-C≡C- are undesirable from the standpoint of chemical stability. Similarly, structures in which the hydrogen atoms in these structures are replaced with fluorine atoms are also undesirable. Similarly, structures in which oxygen atoms are bonded to each other, structures in which sulfur atoms are bonded to each other, and structures in which a sulfur atom is bonded to an oxygen atom are also undesirable. Similarly, structures in which nitrogen atoms are bonded to each other, structures in which a nitrogen atom is bonded to an oxygen atom, and structures in which a nitrogen atom is bonded to a sulfur atom are also undesirable.

In particular, the compound represented by general formula (IIa) preferably has a structure represented by the following general formula (IIa-1):

(In the formula, R ⁴⁷ and R ⁴⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms; L ⁵⁰ , L ⁵¹ , and L ⁵² each independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, or -C≡C-; M ⁵⁰ , M ⁵¹ , and M ⁵² each independently represent a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or a 2,5-tetrahydropyranyl group, and the 1,4-phenylene group or the trans-1,4-cyclohexylene group each independently may be substituted with a cyano group, a fluorine atom, or a chlorine atom;
Each of ^u1 and ^v1 independently represents 0 or 1.
More specifically, the following general formulae (IIa-2a) to (IIa-3p)

(wherein R ⁴⁷ and R ⁴⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms), is preferred, and it is more preferred that R ⁴⁷ and R ⁴⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, or an alkoxyl group having 1 to 8 carbon atoms.

In particular, the compound represented by general formula (IIb) preferably has a structure represented by the following general formula (IIb-1):

(In the formula, R ⁴⁹ and R ⁵⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms; L ⁵² , L ⁵³ , and L ⁵⁴ each independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, or -C≡C-; M ⁵¹ , M ⁵² , and M ⁵³ each represent a 1,4-phenylene group or a trans-1,4-cyclohexylene group; w1 and x1 each independently represent 0, 1, or 2, with the exception that w1+x1 is 2 or less.)
More specifically, the following general formulae (IIb-2a) to (IIb-3f)

(wherein R ⁴⁹ and R ⁵⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms) is preferred.

In the compound represented by general formula (IIc), it is preferable that the compound has the structure represented by the following general formula (IIc-1a) and general formula (IIc-1b).

(In the formula, R ⁵¹ and R ⁵² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms; L ⁵⁶ , L ⁵⁷ , and L ⁵⁸ each independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, or -C≡C-; M ⁵⁴ , M ⁵⁵ , and M ⁵⁶ each represent a 1,4-phenylene group or a trans-1,4-cyclohexylene group; y1 and z1 each independently represent 0, 1, or 2, with the exception that y1+z1 is 2 or less.)
More specifically, the following general formulae (IIc-2a) to (IIc-2g)

(In the formula, R ⁵¹ and R ⁵² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms.)
The third component contains at least one compound selected from the group consisting of compounds represented by general formula (IIIa), general formula (IIIb), and general formula (IIIc), preferably contains 2 to 10 kinds, particularly preferably contains 2 to 8 kinds. The lower limit of the content of the second component in the polymer network type liquid crystal composition of the present invention is preferably 5 mass%, more preferably 10 mass%, and more preferably 20 mass%, and the upper limit is preferably 80 mass%, preferably 70 mass%, preferably 60 mass%, and preferably 50 mass%.

In the liquid crystal composition of the present invention, Δn is preferably in the range of 0.08 to 0.30.
(Other Liquid Crystal Compounds)
The liquid crystal composition for polymer network type liquid crystal element of the present invention contains a non-polymerizable liquid crystal compound. More specifically, it is preferable that the non-polymerizable liquid crystal compound contains one or more liquid crystal compounds other than liquid crystal compounds having negative dielectric anisotropy. There is no particular limitation on such liquid crystal compounds, but it is preferable that the liquid crystal composition contains, for example, one or more liquid crystal compounds represented by general formula (L).

The liquid crystal compound represented by general formula (L) is a nearly dielectrically neutral compound (dielectric anisotropy Δε value of -2 to 2).

The compound represented by general formula (L) is shown below.

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which one methylene group or two or more non-adjacent methylene groups may be substituted with -O- or -S-, and one or more hydrogen atoms in these groups may be substituted with a fluorine atom or a chlorine atom,
M ²¹ , M ²² and M ²³ each independently represent (a) a trans-1,4-cyclohexylene group (in which one methylene group or two or more non-adjacent methylene groups may be replaced by —O— or —S—);
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= groups in this group may be replaced by a nitrogen atom), a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, and (c) a group selected from the group consisting of a 1,4-cyclohexenylene group, a 1,4-bicyclo[2.2.2]octylene group, a piperidine-2,5-diyl group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, wherein the above groups (a), (b), and (c) may each independently be substituted by a cyano group, a fluorine atom, or a chlorine atom,
o represents 0, 1 or 2;
L ²¹ and L ²² each independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CH=N-N=CH- or -C≡C-; when a plurality of L ²² are present, they may be the same or different; when a plurality of M ²³ are present, they may be the same or different.
In the compound represented by general formula (L), R ²¹ and R ²² are each independently preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (including those in which one methylene group or two or more non-adjacent methylene groups in these groups are replaced with -O- or -S-, and those in which one or more hydrogen atoms in these groups are replaced with fluorine atoms or chlorine atoms), more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 3 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

When importance is placed on reliability, it is preferable that ^R and ^R are both alkyl groups. When importance is placed on reducing the volatility of the compound, it is preferable that they are alkoxy groups. When importance is placed on reducing the viscosity, it is preferable that at least one of them is an alkenyl group.

The number of halogen atoms present in the molecule is preferably 0, 1, 2 or 3, with 0 or 1 being preferred, and 1 being preferred when compatibility with other liquid crystal molecules is important.

When the ring structure to which R ²¹ and R ²² are bonded is a phenyl group (aromatic), they are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 4 to 5 carbon atoms, and when the ring structure to which they are bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, they are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, it is preferable that the total number of carbon atoms and oxygen atoms, if present, is 5 or less, and it is preferable that they are linear.

The alkenyl group is preferably selected from groups represented by any of formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

M ²¹ , M ²² and M ²³ each independently represent a trans-1,4-cyclohexylene group (one CH ₂ group or two non-adjacent CH 2 groups in this group). [0043] A preferred example of _{the alkyl} group is a 1,4-phenylene group (including those in which one or more CH groups are replaced by oxygen atoms), a 1,4-phenylene group (including those in which one or more CH groups present in this group are replaced by nitrogen atoms), a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, a 1,4-cyclohexenylene group, a 1,4-bicyclo[2.2.2]octylene group, a piperidine-1,4-diyl group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferred are a trans-1,4-cyclohexylene group, a 1,4-phenylene group, or a 1,4-bicyclo[2.2.2]octylene group, and particularly preferred are a trans-1,4-cyclohexylene group or a 1,4-phenylene group. M ²¹ , M ²² and M ²³ are preferably aromatic when it is required to increase Δn, and are preferably aliphatic in order to improve the response speed, and each independently preferably represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, a 1,4-cyclohexenylene group, a 1,4-bicyclo[2.2.2]octylene group, a piperidine-1,4-diyl group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

More preferably, it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

o is preferably 0, 1 or 2, more preferably 0 or 1.

L ²¹ and L ²² each independently represent preferably a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CH=N-N=CH- or -C≡C-, more preferably a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ - or -CH ₂ O-, and even more preferably a single bond or -CH ₂ CH ₂ -.

Of the structures formed by combining the above options, -CH=CH-CH=CH-, -C≡C-C≡C-, and -CH=CH-C≡C- are undesirable from the standpoint of chemical stability. Similarly, structures in which the hydrogen atoms in these structures are replaced with fluorine atoms are also undesirable. Similarly, structures in which oxygen atoms are bonded to each other, structures in which sulfur atoms are bonded to each other, and structures in which a sulfur atom is bonded to an oxygen atom are also undesirable. Similarly, structures in which nitrogen atoms are bonded to each other, structures in which a nitrogen atom is bonded to an oxygen atom, and structures in which a nitrogen atom is bonded to a sulfur atom are also undesirable.

In the liquid crystal composition for a polymer network type liquid crystal element according to the present invention, the content of the liquid crystal compound represented by general formula (L) must be appropriately adjusted according to the required performance, such as solubility at low temperatures, transition temperature, electrical reliability, birefringence, process compatibility, drop marks, image sticking, and dielectric anisotropy.

The preferred lower limit of the content of the compound represented by formula (L) relative to the total amount of non-polymerizable liquid crystal compounds contained in the liquid crystal composition for polymer network type liquid crystal elements according to the present invention is 1 mass %, and the preferred upper limit is 85 mass %. More preferred lower limit of the content is 3 mass %, and the more preferred upper limit is 65 mass %.

When the viscosity of the composition is kept low and a composition with a fast response speed is required, it is preferable that the above lower limit value is high and the above upper limit value is high. Furthermore, when the _TNI of the composition according to the present invention is kept high and a composition with good temperature stability is required, it is preferable that the above lower limit value is high and the above upper limit value is high. Furthermore, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is low and the above upper limit value is low.

In more detail, the specific structure of general formula (L) is preferably a compound represented by the group consisting of the following general formulas (L-a) to (L-q).

(In the formula, R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 3 to 10 carbon atoms.)
R ²³ and R ²⁴ each independently preferably represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

Among the compounds represented by general formulas (L-a) to (L-q), compounds represented by general formulas (L-a), (L-b), (L-c), (L-e), (L-h), (L-i), (L-m), (L-o) or (L-q) are preferred, and compounds represented by general formulas (L-a), (L-c), (L-e), (L-h) or (L-i) are more preferred.

In the present invention, it is preferable to contain at least one type of compound represented by general formula (L), it is preferable to contain 1 to 10 types, and it is particularly preferable to contain 2 to 8 types.

The preferred lower limit of the total content of the compounds represented by general formula (IIa), general formula (IIb), general formula (IIc) and general formula (L) relative to the total amount of non-polymerizable liquid crystal compounds contained in the liquid crystal composition for polymer network type liquid crystal elements according to the present invention is 50% by mass, and the preferred upper limit is 95% by mass. A more preferred lower limit of the content is 70% by mass, and the more preferred upper limit is 90% by mass.

The preferred lower limit of the total content of the compounds represented by general formula (IIa) and general formula (L) relative to the total amount of non-polymerizable liquid crystal compounds contained in the liquid crystal composition for polymer network type liquid crystal elements according to the present invention is 50% by mass, and the preferred upper limit is 95% by mass. More preferably, the lower limit of the content is 70% by mass, and the upper limit is 90% by mass.

It is preferable that the liquid crystal composition for a polymer network type liquid crystal element according to the present invention does not contain a compound having a structure in which oxygen atoms are bonded together, such as a peroxy acid (-CO-OO-) structure, in the molecule.

When the reliability and long-term stability of the composition are important, the content of the compound having a carbonyl group is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and most preferably substantially none, relative to the total mass of the composition.

When stability against UV irradiation is important, the content of compounds substituted with chlorine atoms is preferably 15% by mass or less, more preferably 10% by mass or less, more preferably 8% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably substantially absent, relative to the total mass of the composition.

It is preferable to increase the content of compounds whose intramolecular ring structures are all six-membered rings, and the content of compounds whose intramolecular ring structures are all six-membered rings is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the total mass of the composition. It is most preferable that the composition is substantially composed of only compounds whose intramolecular ring structures are all six-membered rings.

In order to suppress deterioration of the composition due to oxidation, it is preferable to reduce the content of compounds having a cyclohexenylene group as a ring structure, and the content of compounds having a cyclohexenylene group is preferably 10% by mass or less, more preferably 8% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably substantially absent, relative to the total mass of the composition.

When emphasis is placed on improving the viscosity and the _TNI , it is preferable to reduce the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule, in which a hydrogen atom may be substituted with a halogen, and the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, more preferably 8% or less, more preferably 5% or less, more preferably 3% or less, and even more preferably substantially none, based on the total mass of the composition.

In this application, "substantially free" means "not contained" except for those that are unintentionally contained.

When the liquid crystal compound contained in the liquid crystal composition for a polymer network type liquid crystal element according to the present invention has an alkenyl group as a side chain, when the alkenyl group is bonded to cyclohexane, the alkenyl group preferably has 2 to 5 carbon atoms, and when the alkenyl group is bonded to benzene, the alkenyl group preferably has 4 to 5 carbon atoms, and it is preferable that the unsaturated bond of the alkenyl group is not directly bonded to benzene.
(Third Component: Polymerizable Compound Having a Polar Group)
In order to obtain good adhesion, the composition for a polymer network type liquid crystal element of the present invention can use a polymerizable compound having a polar group without a mesogenic skeleton as a third component. It is considered that the polymerizable compound having a polar group exerts an anchor function at the interface in contact with the polymer network liquid crystal layer, and exerts a strong interaction with the polymer network liquid crystal layer, thereby imparting adhesion. On the other hand, it is considered that the polymerizable group of the polymerizable compound reacts with other polymerizable compounds in the liquid crystal composition for a polymer network type liquid crystal element to be organically bonded to the liquid crystal layer, thereby exerting adhesion.

The polymerizable compound may have at least one polar group, and the number of polymerizable functional groups may be appropriately selected.

Examples of polar groups include hydroxyl groups, carboxyl groups, carbamoyl groups, amino groups, isocyanate groups, phosphate groups, cyano groups, isocyano groups, nitro groups, and hydroxysilyl groups.

Examples of the polymerizable functional group include polymerizable functional groups such as vinyl groups, acrylic groups, and (meth)acrylic groups, and the polymerizable groups represented by the following formulas (P-1) to (P-20) are preferred.

Specifically, to obtain good adhesion and good alignment when no voltage is applied, a polymerizable compound represented by the general formula (III) is used.

(In the formula, ^PP1 represents a polymerizable group,
SS ¹ represents an alkylene group having 1 to 22 carbon atoms (the alkylene group may be substituted with one or more halogen atoms, a CN group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and a polymerizable functional group, and one CH ₂ group or two or more non-adjacent CH ₂ groups present in this group may each be independently replaced by -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -CH(OH)-, CH(COOH), -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- in a form in which oxygen atoms are not directly bonded to each other), or a single bond;
XX ¹ represents -OH, -COOH, CONR ¹ R ² , -SH, -NR ¹ R ² , -NCO, -CN, -NO ₂ , -Si(OH) _3-α (CH ₃ ) _α , -P(═O)(OH) ₂ , or -P(═O)(OH)- (R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and α represents an integer of 1 or 2);
nn1 represents 1 when XX ¹ represents -OH, -COOH, CONR ¹ R ² , -SH, -NR ¹ R ² , -NCO, -CN, -NO ₂ , -Si(OH) _3-α (CH ₃ ) _α , -P(═O)(OH) ₂ , and represents 2 when XX ¹ represents -P(═O)(OH)-.
In the general formula (III), the polymerizable group represented by ^PP1 is represented by the following formulae (P-1) to (P-20):

A polymerizable group selected from the following is preferred, and among these polymerizable groups, from the viewpoint of enhancing polymerizability and storage stability, formula (P-1), formula (P-2), formula (P-7), formula (P-12), or formula (P-13) is preferred, and formula (P-1), formula (P-7), or formula (P-12) is more preferred.

The alkylene group having 1 to 22 carbon atoms represented by ^SS1 may be substituted with one or more halogen atoms, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group, and one _CH2 group or two or more non-adjacent _CH2 groups present in this group may each be independently replaced with -O-, -S-, -N( _CH3 )-, -CO-, -CH(OH)-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- in a form in which oxygen atoms are not directly bonded to each other. An alkylene group having 6 to 22 carbon atoms is preferred, and an alkylene group having 6 to 18 carbon atoms, an ethyleneoxy group having 4 to 12 carbon atoms, an alkylene group having 6 to 18 carbon atoms substituted with at least one polymerizable group identical to the polymerizable group, and an ethyleneoxy group having 4 to 12 carbon atoms substituted with at least one polymerizable group identical to the polymerizable group are particularly preferred.

From the viewpoint of improving adhesion, ^XX1 is preferably -OH, -COOH, -SH, ^-NR1R2 , -NCO, -Si(OH) _3-α ( _CH3 ) _α or _-P (=O)(OH) ² , and more preferably -P(=O)(OH) ₂ .

The general formula (III) is preferably a compound represented by the following general formulas (IIIa) to (IIIe):

(In the formula, XX1 and nn1 have the same meanings as XX1 and nn1 in general formula (III), n1 represents an integer of 1 to 10, n2 represents an integer of 1 to 6, and n3 and n4 each independently represent an integer of 1 to 4.)
Examples of the polymerizable compound represented by formula (III) include the polymerizable compounds represented by formulas (III-1) to (III-15).

(In the formula, n1 represents an integer of 1 to 10, n2 represents an integer of 1 to 6, and R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
Furthermore, when the integers n1 and n2 are large, for example, when n1 is 5 or more and n2 is 3, the liquid crystal material may be vertically aligned, which is preferable.

The content of the polymerizable compound represented by general formula (III) is, from the viewpoint of enhancing adhesion, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more, relative to the total amount (100% by mass) of the liquid crystal composition for a polymer network type liquid crystal element of the present invention; on the other hand, from the viewpoint of preventing deterioration of electro-optical properties due to an increase in the content ratio of polar groups, it is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.
(Fourth Component: Polymerization Initiator)
The liquid crystal composition for a polymer network type liquid crystal element of the present invention may contain a polymerization initiator. The polymerization initiator used in the present invention is used to polymerize the liquid crystal composition of the present invention. There is no particular limitation on the photopolymerization initiator used when polymerization is performed by light irradiation, but any known and commonly used initiator may be used to the extent that it does not inhibit the alignment state of the polymerizable compound having a mesogenic skeleton, which is the first component.

For example, 1-hydroxycyclohexyl phenyl ketone "Omnirad 184", 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one "Omnirad 1173", 2-methyl-1-[(methylthio)phenyl]-2-morpholinopropane-1 "Omnirad 907", 2,2-dimethoxy-1,2-diphenylethane-1-one "Omnirad BDK", 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-phenyl)butanone "Omnirad 369"; 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-phenyl)butan-1-one "Omnirad 379"; 2,2-Dimethoxy-1,2-diphenylethan-1-one; Bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide "Omnirad TPO"; 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide "Omnirad 819" (IGM Resins Co., Ltd.), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone "Irgacure OXE01"), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) "Irgacure OXE02", "Irgacure OXE04" (BASF Corporation), "ADEKA ARCLES NCI-831" Examples of such compounds include "ADEKA ARCLES NCI-930", "ADEKA ARCLES N-1919" (manufactured by ADEKA Corporation), a mixture of 2,4-diethylthioxanthone ("KAYACURE DETX" manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate ("KAYACURE EPA" manufactured by Nippon Kayaku Co., Ltd.), a mixture of isopropylthioxanthone ("CANTACURE-ITX" manufactured by Ward Prekinsop Co., Ltd.) and ethyl p-dimethylaminobenzoate, "ESACURE ONE", "ESACURE KIP150", "ESACURE KIP160", "ESACURE 1001M", "ESACURE A198", "ESACURE KIP IT", "ESACURE KTO46", "ESACURE TZT" (manufactured by Lamberti Corporation), "SPEEDCURE BMS", "SPEEDCURE PBZ", and "BENZOPHENONE" (manufactured by LAMBSON). Furthermore, a photoacid generator can be used as the photocation initiator. Examples of the photoacid generator include diazodisulfone compounds, triphenylsulfonium compounds, phenylsulfone compounds, sulfonylpyridine compounds, triazine compounds, and diphenyliodonium compounds.

The content of the photopolymerization initiator is preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 7% by mass, relative to 100% by mass of the total amount of the liquid crystal composition for a polymer network type liquid crystal element of the present invention. These may be used alone or in combination of two or more types.

As the thermal polymerization initiator used in the thermal polymerization, a known and commonly used one can be used, for example, methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxybenzoate, methyl ethyl ketone peroxide, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, isobutyl peroxide, di(3-methyl-3-methoxybutyl)peroxide, Examples of the usable compounds include organic peroxides such as dimethyl peroxycarbonate and 1,1-bis(t-butylperoxy)cyclohexane, azonitrile compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile), azoamide compounds such as 2,2'-azobis(2-methyl-N-phenylpropion-amidine)dihydrochloride, azoamide compounds such as 2,2'azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, and alkyl azo compounds such as 2,2'azobis(2,4,4-trimethylpentane). The content of the thermal polymerization initiator is preferably 0.1 to 10 mass%, particularly preferably 1 to 6 mass%, based on the total amount of the liquid crystal composition for the polymer network type liquid crystal element of the present invention (100 mass%). These can be used alone or in combination of two or more kinds.
(Fifth component)
The liquid crystal composition for a polymer network-type liquid crystal element of the present invention can contain a polymerizable compound having no mesogenic skeleton, a polymerization inhibitor, an antioxidant, a light stabilizer, a chain transfer agent, a dye, a pigment, particles having a particle size of less than 1 μm, a chiral compound, or an alignment material within a range that does not impair practical electro-optical properties and adhesion when made into a polymer network-type liquid crystal element.
(Polymerizable compound having no mesogenic skeleton)
The polymerizable compound having no mesogenic skeleton (excluding the polymerizable compound of the third component) used in the present invention can be used to control the electro-optical properties of the liquid crystal composition of the present invention or to supplement the efficacy of the polymerizable compound having polarity which is the third component. As such a compound, a publicly known and commonly used compound can be used.

For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyl adamantyl (meth)acrylate, butyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, methoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-phenoxydiethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-phenoxydiethylene glycol (meth)acrylate, Nylphenol ethoxy (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 1H,1H,3H-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,7H-dodecafluorobutyl (meth)acrylate, Oroheptyl (meth)acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl (meth)acrylate, 1H,1H-pentadecafluorooctyl (meth)acrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, etc., or the following structure:

Monofunctional (meth)acrylates having the following structure are preferred.

In addition, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyldiol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trichlorodecane dimethanol diacrylate, adamantane di(meth)acrylate, bisphenol A di(meth)acrylate, ) acrylate, hydrogenated bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, glycerin di(meth)acrylate, 1,6-hexanediol diglycidyl ether acrylic acid adduct, 1,4-butanediol diglycidyl ether acrylic acid adduct, etc., or the following structure

A bifunctional (meth)acrylate represented by the formula:

Also preferred are 4- and 2,6-tolylene diisocyanate (TDI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate, and various urethane acrylates obtained by reacting carbodiimide-modified MDI, diisocyanates, etc.

Also preferred are epoxy compounds such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, and bisphenol A diglycidyl ether.

Among these, monofunctional (meth)acrylates and bifunctional (meth)acrylates having the above structures, and various urethane acrylates are particularly preferred.
The content of the polymerizable compound having no mesogenic skeleton is preferably 0 to 50 mass%, particularly preferably 2 to 30 mass%, based on 100 mass% of the total amount of the liquid crystal composition for a polymer network type liquid crystal element of the present invention. These may be used alone or in combination of two or more kinds.
(Polymerization inhibitor)
The polymerization inhibitor used in the present invention can be used to control the electro-optical properties by controlling the polymerization reaction of the liquid crystal composition for a polymer network-containing liquid crystal element of the present invention, or to assist the efficacy of the polar polymerizable compound, which is the third component. As such a compound, any known and commonly used compound can be used.

For example, p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis(4-methyl-6-t-butylphenol), 2.2'-methylenebis(4-ethyl-6-t-butylphenol), 4.4'-thiobis(3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, and other phenolic compounds, hydroquinone, and methylhydroquinone. , tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone, and other quinone-based compounds are preferred, with p-methoxyphenol, 4-methoxy-1-naphthol, tert-butylhydroquinone, and 2-hydroxy-1,4-naphthoquinone being particularly preferred.

The content of the polymerization inhibitor is preferably 0 to 2.0% by mass, and more preferably 0 to 0.5% by mass, relative to 100% by mass of the total amount of the liquid crystal composition for a polymer network type liquid crystal device of the present invention.
(Antioxidant)
The antioxidant used in the present invention can be used to impart practical durability to the polymer network-containing liquid crystal element of the present invention. Examples of such compounds that can be used include hydroquinone derivatives, nitrosamine-based polymerization inhibitors, and hindered phenol-based antioxidants.

Specifically, tert-butyl hydroquinone, Wako Pure Chemical Industries' "Q-1300" and "Q-1301", pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate "IRGANOX1010", thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate "IRGANOX1035", octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate "IRGANOX1076", "IRGANOX1135", "IRGANOX1330", 4,6-bis( Octylthiomethyl)-o-cresol "IRGANOX1520L", "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565" (all manufactured by BASF Corporation), Adeka STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 manufactured by ADEKA Corporation, Sumilizer BHT, Sumilizer BBM-S, and Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd., and compounds having a structure represented by the following general formula, etc. are preferred.

In general formulae (H-1) to (H-4), R ^H1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, and one -CH ₂ - or two or more non-adjacent -CH ₂ - present in the group may each be independently replaced with -O- or -S-, and one or more hydrogen atoms present in the group may each be independently replaced with a fluorine atom or a chlorine atom. More specifically, it is preferably an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms, and more preferably an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

In general formula (H-4), M ^H4 represents an alkylene group having 1 to 15 carbon atoms (one or more -CH ₂ - in the alkylene group may be replaced by -O-, -CO-, -COO-, -OCO- so that the oxygen atom is not directly adjacent), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -C≡C-, a single bond, a 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom), or a trans-1,4-cyclohexylene group; however, an alkylene group having 1 to 14 carbon atoms is preferable, and in consideration of volatility, a larger number of carbon atoms is preferable, but in consideration of viscosity, it is preferable that the number of carbon atoms is not too large; therefore, an alkylene group having 2 to 12 carbon atoms is more preferable, an alkylene group having 3 to 10 carbon atoms is even more preferable, an alkylene group having 4 to 10 carbon atoms is even more preferable, an alkylene group having 5 to 10 carbon atoms is even more preferable, and an alkylene group having 6 to 10 carbon atoms is even more preferable.

Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the compounds represented by the general formulae (H-2) to (H-4) are particularly preferred.
The content of the antioxidant is preferably 0 to 2.0% by mass, and more preferably 0 to 0.5% by mass, relative to 100% by mass of the total amount of the liquid crystal composition for a polymer network type liquid crystal device of the present invention.
(Light stabilizer)
The light stabilizer used in the present invention can be used to impart practical durability to the polymer network type liquid crystal element of the present invention. Examples of such compounds include "TINUVIN 111FDL", "TINUVIN 123", "TINUVIN 144", "TINUVIN 152", "TINUVIN 292", "TINUVIN 622", "TINUVIN 770", "TINUVIN 765", "TINUVIN 780", "TINUVIN 905", "TINUVIN 5100", "TINUVIN 5050", "TINUVIN 5060", "TINUVIN 5151", "CHIMASSORB 119FL", "CHIMASSORB 944FL", "CHIMASSORB 51 ... 944LD (all manufactured by BASF Corporation), "ADK STAB LA-52", "ADK STAB LA-57", "ADK STAB LA-62", "ADK STAB LA-67", "ADK STAB LA-63P", "ADK STAB LA-68LD", "ADK STAB LA-77", "ADK STAB LA-82", and "ADK STAB LA-87" (all manufactured by ADEKA Corporation).
The amount of the ultraviolet absorber added is preferably 0.01 to 2.0% by mass, and more preferably 0.05 to 1.0% by mass, based on the total amount of the liquid crystal composition for a polymer network type liquid crystal device of the present invention.
(Chain Transfer Agent)
The chain transfer agent used in the present invention can be used to further improve the adhesion between the liquid crystal composition for a polymer network type liquid crystal element and a substrate. Examples of the chain transfer agent include mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, n-dodecyl mercaptan, t-tetradecyl mercaptan, and t-dodecyl mercaptan, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropion ... Thiol compounds such as methylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpinene, γ-terpinene, dipentene, etc.
Specifically, the compounds represented by the following general formulas (9-1) to (9-12), α-methylstyrene dimer, and α-terpinene are preferred.

In the formula, R ⁹⁵ represents an alkyl group having 2 to 18 carbon atoms, which may be linear or branched, and one or more methylene groups in the alkyl group may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or -CH=CH-, provided that the oxygen atom and the sulfur atom are not directly bonded to each other; and R ⁹⁶ represents an alkylene group having 2 to 18 carbon atoms, and one or more methylene groups in the alkylene group may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or -CH=CH-, provided that the oxygen atom and the sulfur atom are not directly bonded to each other.

The content of the chain transfer agent is preferably 0.5 to 10% by mass, and more preferably 1.0 to 5.0% by mass, relative to 100% by mass of the total amount of the liquid crystal composition for a polymer network type liquid crystal device of the present invention.
(Pigments)
The dye used in the present invention can be used to impart color to the polymer network-containing liquid crystal element of the present invention or to control the color. There are no particular limitations on such dyes, and any known and commonly used dyes can be used as long as they are soluble in liquid crystals or dispersible in the polymer network. Examples of the dyes include dichroic dyes and fluorescent dyes. Examples of such dyes include polyazo dyes, anthraquinone dyes, quinacridone dyes, dioxazine dyes, quinophthalone dyes, cyanine dyes, phthalocyanine dyes, perylene dyes, perinone dyes, and squarylium dyes, but from the viewpoint of addition, the dye is preferably a dye exhibiting liquid crystallinity. For example, polyazo dyes disclosed in JP-A-51-2885, JP-A-61-21163, JP-A-62-555, JP-A-63-301850, JP-A-7-48520, JP-A-7-179858, JP-A-10-279945, JP-A-11-172252, JP-A-2000-239664, JP-A-2012-82400, etc., and JP-A-59-20355 Examples of the dye include anthraquinone dyes shown in JP-A-59-172549, JP-A-61-148291, JP-A-1-161086, JP-A-8-67822, etc., quinophthalone dyes shown in JP-A-59-51947 and JP-A-61-148292, etc., and dioxazine dyes shown in JP-A-2000-44825 and JP-A-2001-49135, etc. The content of the dye is preferably 0 to 10% by mass, and more preferably 0 to 5% by mass, relative to 100% by mass of the total amount of the liquid crystal compounds used in the liquid crystal composition of the liquid crystal composition for polymer network type liquid crystal element of the present invention.
(Pigment)
The pigment used in the present invention can be used to impart color to the polymer network-containing liquid crystal element of the present invention or to control the color. There are no particular limitations on such dyes, and any known and commonly used dyes can be used as long as they disperse in the liquid crystal or network polymer. Examples of such pigments include azo pigments, diketopyrrolopyrrole pigments, quinacridone pigments, dioxazine pigments, perylene pigments, phthalocyanine pigments, carbon black pigments, etc., but from the viewpoint of effectively imparting coloring properties, the dye is preferably a pigment that has good dispersibility in the network polymer. (Particles with a particle diameter of less than 1 μm)
The particles having a particle diameter of less than 1 μm used in the present invention can be used to impart various functions to the polymer network-containing liquid crystal element of the present invention. There are no particular limitations on the type of particles, and they can be used within a range that does not impair the electro-optical properties or adhesion of the liquid crystal element.
(Chiral Compounds)
The chiral compound used in the present invention can be used to impart various functions to the polymer network-containing liquid crystal element of the present invention. There are no particular limitations on the chiral compound, and it can be used within a range that does not impair the electro-optical properties or adhesion of the liquid crystal element. Specific examples of such compounds include cholesterol pelargonate and cholesterol stearate having a cholesteryl group as a chiral group, BDH's "CB-15" and "C-15" having a 2-methylbutyl group as a chiral group, Merck's "S-1082", Chisso's "CM-19", "CM-20", and "CM", Merck's "S-811" having a 1-methylheptyl group as a chiral group, Chisso's "CM-21" and "CM-22", BASF's "LC756" having an isosorbide skeleton as a chiral group, and polymerizable chiral compounds disclosed in JP-T-2009-515818, JP-A-2010-90108, JP-A-2013-87109, and the like.

In the case where a chiral compound is contained, it is preferable to add the chiral compound in an amount such that the value (d/P) obtained by dividing the thickness (d) of the obtained polymer by the helical pitch (P) in the polymer is in the range of 0.1 to 100, and more preferably in the range of 0.1 to 20, depending on the application of the polymer of the polymerizable liquid crystal composition of the present invention.
(Alignment Material)
The liquid crystal composition for a polymer network type liquid crystal element of the present invention may contain an alignment material to control the alignment of the liquid crystal element. The alignment material used in the present invention may be any known or commonly used material within the range of dissolution in the liquid crystal composition. Examples of such alignment materials include polymerizable compounds having a polar group at one end of a mesogenic skeleton and a long-chain alkyl group at the other end, polymerizable liquid crystal compounds having a polar group at the lateral position of a mesogenic skeleton, and polymerizable compounds having multiple mesogenic skeletons and having a polar group on the side chain of a long-chain alkyl group that bonds one mesogenic skeleton to the other mesogenic skeleton.

In the liquid crystal composition for a polymer network type liquid crystal element of the present invention, the lower limit of the ratio of the total amount of the polymerizable compounds contained in the liquid crystal composition is preferably 3% by mass or more, preferably 8% by mass or more, and preferably 13% by mass or more of the total amount of the liquid crystal composition for a polymer network type liquid crystal element of the present invention. In addition, in the liquid crystal composition for a polymer network type liquid crystal element of the present invention, the upper limit of the ratio of the total amount of the polymerizable compounds contained in the liquid crystal composition is preferably 80% by mass or less, preferably 60% by mass or less, and preferably 50% by mass or less. The total amount of the polymerizable compounds contained in the liquid crystal composition means the total amount of all the polymerizable compounds contained in the liquid crystal composition, and is represented, for example, by the total amount of the polymerizable compound having a mesogenic skeleton as the first component, the polymerizable compound having a polar group as the third component, and the polymerizable compound not having a mesogenic skeleton as the fifth component, which is optionally contained.
<Polymer network type liquid crystal element>
A polymer network type liquid crystal element using the liquid crystal composition for a polymer network type liquid crystal element of the present invention comprises at least a layer in which liquid crystal and a network polymer are phase-separated (phase-separated liquid crystal layer), an electrode, and a substrate, or comprises a phase-separated liquid crystal layer, a vertical alignment film phase, an electrode, and a substrate supporting the phase-separated liquid crystal layer, the vertical alignment film phase, and the electrode.

The liquid crystal element of the present invention is not particularly limited in its specific embodiment as long as it has the above elements, but for example, it may have a configuration in which a phase-separated liquid crystal layer is sandwiched between a hollow element composed of two substrates, at least one of which has an electrode, and a vertical alignment film.

The liquid crystal element of the present invention maintains the homeotropic alignment of the liquid crystal in the phase-separated liquid crystal layer in the absence of a power source. Therefore, it can be used as an element that can be driven in the so-called reverse mode. In other words, the liquid crystal element is transparent when no voltage is applied, and can be in a scattering state when a voltage is applied.

In the liquid crystal element of the present invention, the alignment of the liquid crystal molecules is controlled not only by the vertical alignment film but also by a dense polymer network made of an aligning polymer. Therefore, the liquid crystal element of the present invention is less likely to be disturbed by external stress and has high stress resistance. The liquid crystal element of the present invention is less likely to cause display defects even in an environment where bending stress is applied, so it can be made bendable. Therefore, the liquid crystal element of the present invention may have a curved element surface.

Below, an example of a preferred embodiment of the liquid crystal element of the present invention will be described with reference to the drawings, but the present invention is not limited to these.

The polymer network type liquid crystal element of the present invention may be configured so that the orientation of the liquid crystal molecules can be controlled by applying a voltage, but is preferably configured as a vertical electric field type liquid crystal element. A vertical electric field type liquid crystal element is a liquid crystal element in which electrodes are arranged so that an electric field is generated perpendicular to the homeotropic alignment film. In a vertical electric field type liquid crystal element, electrodes are usually provided on both of the two transparent substrates that sandwich the phase-separated liquid crystal layer.

Figure 1 is a diagram showing a schematic configuration of a vertical electric field type liquid crystal element when no voltage is applied. Below, the vertical electric field type liquid crystal element according to the present invention will be explained with reference to Figure 1.

The polymer network vertical electric field type liquid crystal element according to the present invention is configured as shown in FIG. 1, which has a first substrate 11 and a second substrate 12 each having a transparent electrode (layer) 2 made of a transparent conductive material, a phase-separated liquid crystal layer sandwiched between the first substrate 11 and the second substrate 12, and the orientation of the liquid crystal molecules in the phase-separated liquid crystal layer when no voltage is applied is approximately perpendicular to the homeotropic alignment film 3. The phase-separated liquid crystal layer is composed of liquid crystal molecules 4 contained in a liquid crystal composition and an alignment polymer 5. For convenience, the alignment polymer 5 is represented by a large number of fixed polymerizable compounds in FIG. 1, but in reality, each polymerizable compound forms a polymer network in which the polymerizable compounds are intricately connected to each other. Furthermore, a pair of homeotropic alignment films 3 are formed on the surface of the transparent electrode (layer) 2 so as to be in direct contact with the phase-separated liquid crystal layer.

In other words, the polymer network vertical electric field type liquid crystal element of the present invention is configured by sequentially stacking a first substrate 11, an electrode 2, a homeotropic alignment film 3, a composite layer formed by phase separation of liquid crystal molecules 4 and an alignment polymer 5, the homeotropic alignment film 3, the electrode 2, and a second substrate 12.

Figure 2 is a schematic diagram showing an example of the configuration of a vertical electric field type element when a voltage is applied.

When a voltage is applied to the electrodes, the vertical electric field type liquid crystal element transitions from the state shown in FIG. 1 to the state shown in FIG. 2. At this time, the liquid crystal molecules 4 are oriented parallel to the homeotropic alignment film due to the generation of a vertical electric field. In the vertical electric field type liquid crystal element shown in FIG. 2, the liquid crystal molecules 4 and the alignment polymer 5 in the phase-separated liquid crystal layer are aligned in different directions, so light scattering occurs at the interface between the respective components, and the vertical electric field type liquid crystal element becomes in a non-light-transmitting state.

In this way, the vertical electric field type liquid crystal element of the present invention can change the light transmission state depending on whether or not a voltage is applied, and can be used as a liquid crystal light control element incorporated in a device that requires a light control function, or as a liquid crystal display element used in a display for displaying images. In particular, the vertical electric field type liquid crystal element of the present invention can be driven in reverse mode, and is therefore particularly suitable for applications that require power saving and transmission during a power outage or when there is no power source. (Base material: substrate 11 and substrate 12)
The substrate used in the polymer network type liquid crystal element of the present invention is a substrate that is commonly used in liquid crystal display elements, organic light-emitting display elements, other display elements, optical components, light control elements, colorants, markings, printed matter, and optical films, and is not particularly limited as long as it is a material that has heat resistance capable of withstanding the heating in the manufacturing process of the liquid crystal element and the temperature range in which it is used, or has transparency sufficient for practical use in applications where transparency is important.

Such substrates include glass substrates, metal substrates, ceramic substrates, plastic substrates, and organic materials such as paper. In particular, when the substrate is an organic material, examples of the substrate include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyethersulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, and polystyrenes. Among these, plastic substrates such as polyesters, polystyrenes, polyolefins, cellulose derivatives, polyarylates, polycarbonates, and polyimides are preferred.

When there are two substrates, such as substrates 11 and 12 in FIG. 1, it is sufficient that one of the substrates has transparency that allows it to be practical as a liquid crystal element, and the other substrate may or may not have transparency.

In the example shown in FIG. 1, the substrate has a flat plate shape, but it may have other shapes, such as a curved surface. In addition, the substrate may have an electrode layer, an anti-reflection function, or a reflection function, as necessary.

In order to improve the adhesion in the polymer network type liquid crystal element of the present invention, the surface of the substrate may be subjected to a surface treatment. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment. In addition, in order to adjust the light transmittance or reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, or the like may be provided on the substrate surface by a method such as deposition, or in order to add optical value, the substrate may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a microlens sheet, a color filter, or the like.
(Electrode: transparent electrode layer 2)
The electrodes used in the polymer network type liquid crystal element of the present invention are provided so as to generate an electric field capable of controlling the alignment of liquid crystal molecules in the phase-separated liquid crystal layer in the liquid crystal element. The electric field strength is controlled by the degree of voltage application to the electrodes.

The shape of the electrodes is not particularly limited, and the conductive portion may be striped or mesh-shaped, or may be a random mesh-like pattern.

Such electrode materials are preferably made of metal materials, specifically Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni, or alloys containing at least one of these, with Al or alloys containing Al being preferred.

In order to increase the transparency of the liquid crystal element, it is preferable that the electrodes are formed of a transparent electrode layer 2 as shown in Fig. 1. Such a transparent electrode layer can be formed of a known transparent conductive material such as ITO (indium tin oxide), IZO (indium zinc oxide), or IZTO (indium zinc tin oxide). In addition, when one of the substrates is formed of a material having no transparency, the electrode provided on the substrate having no transparency does not need to be transparent either, and can be appropriately selected from known metal materials.
(Vertical alignment film layer: Alignment layer 3)
The substrate may be subjected to an alignment treatment or provided with an alignment film so that the liquid crystal molecules in the polymer network type liquid crystal element of the present invention are aligned horizontally or vertically. Examples of the alignment treatment include stretching, rubbing, polarized ultraviolet and visible light irradiation, ion beam treatment, and oblique deposition of SiO ₂ on the substrate. When a vertical alignment film is used as shown in FIG. 1, a known and commonly used alignment film is used. Examples of such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, coumarin compound, chalcone compound, cinnamate compound, fulgide compound, anthraquinone compound, azo compound, arylethene compound, and other compounds, or polymers or copolymers of the above compounds. When a rubbing treatment is performed to give a tilt angle to the liquid crystal molecules, the compound to be aligned by rubbing is preferably one in which crystallization of the material is promoted by a heating step during or after the alignment treatment. Of the compounds to be aligned by other than rubbing, it is preferable to use a photoalignment material.

In general, when a liquid crystal composition is brought into contact with a substrate having an alignment function, the liquid crystal molecules are aligned in the direction of the alignment treatment of the substrate near the substrate. Whether the liquid crystal molecules are aligned parallel to the substrate, tilted, or perpendicular is greatly influenced by the alignment treatment method for the substrate.
(Example of a method for manufacturing a liquid crystal element)
From the viewpoint of productivity, the polymer network type liquid crystal element of the present invention is preferably produced from a polymerizable liquid crystal element in which a liquid crystal composition for a polymer network type liquid crystal element is sandwiched between, for example, a hollow element having a shape with a space between substrates, i.e., a so-called empty cell. In the polymerizable liquid crystal element, the liquid crystal compound in the composite liquid crystal composition and the polymerizable compound having a mesogenic group are in a homeotropic alignment state due to the alignment regulating force of the vertical alignment film. Alternatively, they are in a homogeneous alignment state due to the regulating force of the horizontal alignment film. In this alignment state, the polymerizable compound in the composite liquid crystal composition is ultraviolet-cured by the above-mentioned method to form a phase-separated liquid crystal layer from the composite liquid crystal composition, thereby obtaining a polymer network type liquid crystal element.

The method of sandwiching the liquid crystal composition for polymer network type liquid crystal elements between hollow elements may be a conventional method, and may include vacuum injection, ODF, roll-to-roll, and roll-to-sheet methods. In the liquid crystal element manufacturing process using the ODF method, a sealant such as an epoxy-based photothermal curable sealant is applied to either the backplane or frontplane of the hollow element in a closed-loop bank shape using a dispenser, and a predetermined amount of the liquid crystal composition is dropped into the sealant under degassing, and then the frontplane and backplane are joined to manufacture the liquid crystal element. The liquid crystal composition for polymer network type liquid crystal elements used in the present invention has high phase stability and is not easily volatilized, and therefore can be suitably used in the ODF process.

In addition, in the manufacturing process of the liquid crystal composition by the roll-to-roll method, the liquid crystal composition for polymer network type liquid crystal elements can be applied onto a first electrode, or a glass substrate having an alignment film and a first electrode, or a plastic substrate, and then laminated so that the liquid crystal composition is in contact with a second electrode, or a glass substrate having an alignment film and a second electrode, or a plastic substrate, and the electrode side or the alignment film side of the substrate is in contact with the liquid crystal composition, and the thickness is made uniform, thereby manufacturing the liquid crystal element. The method of applying the liquid crystal composition for polymer network type liquid crystal elements used in the present invention can be a known and commonly used method such as an applicator method, a bar coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, an inkjet method, a die coating method, or a cap coating method.

The liquid crystal composition for polymer network type liquid crystal elements of the present invention may be mixed with particles for determining the thickness of the liquid crystal element, and the composition may be sandwiched between a hollow element. As such particles, well-known and commonly used glass particles or polymer particles used in general liquid crystal display elements and liquid crystal displays may be used.

In this case, a method is preferred in which the liquid crystalline composition for a polymer network type liquid crystal element and a composition containing particles determining the thickness of the liquid crystal element are applied onto a plastic substrate containing a first electrode, a plastic substrate containing a second electrode is attached to the substrate so that the first electrode and the second electrode face each other, and ultraviolet light is irradiated while pressure is being applied to the first plastic substrate and the second plastic substrate. Alternatively, a method is preferred in which the liquid crystalline composition for a liquid crystal element and a composition containing particles determining the thickness of the liquid crystal element are applied onto a first plastic substrate containing a first electrode, the first plastic substrate and the applied liquid crystalline composition are placed in a vacuum state, and a second plastic substrate containing a second electrode is attached to the substrate so that the first electrode and the second electrode face each other, and ultraviolet light is irradiated in the vacuum state.
(Polymerization method)
The method for polymerizing the liquid crystal composition for a polymer network type liquid crystal element of the present invention includes a method of irradiating with active energy rays, a thermal polymerization method, etc. The method is appropriately selected depending on the application of the resulting polymer network type liquid crystal element.

When irradiating with light such as ultraviolet light, the temperature during irradiation is preferably a temperature at which the liquid crystal composition of the present invention can maintain a liquid crystal phase. When heating, the temperature is preferably a temperature at which the liquid crystal composition of the present invention can maintain a liquid crystal phase until the polymerizable compound component in the liquid crystal composition is sufficiently polymerized to form a phase separation structure with the liquid crystal composition component, and after the phase separation structure is formed, the temperature does not have to be a temperature at which the liquid crystal phase can be maintained.

The polymer network type liquid crystal element of the present invention can be used as it is or can be attached to another substrate for use. In addition, an adhesive or adhesive layer, a pressure sensitive adhesive or adhesive layer, a protective film, a polarizing film, or the like may be laminated thereon.
(Other electric field types)
The polymer network type liquid crystal element of the present invention may employ a horizontal electric field type or other electric field types in addition to the vertical electric field type. A fringe electric field employed in the FFS driving mode may also be employed. In this case, a horizontal alignment layer may be provided instead of the vertical alignment layer. The horizontal alignment layer may be made of a known material.

The polymer network type liquid crystal element of the present invention is preferably used, for example, in building materials, light control glass, smart windows for vehicles, or light control units in OLED displays. The liquid crystal display element of the present invention can be used for the same applications as conventional polymer dispersion type liquid crystal display elements, and is particularly preferably used in transmissive displays, flexible displays, and the like. More specifically, it can be used in products such as architectural light control elements such as windows, skylights, roofs, walls, partitions, dividers, and doors; transportation light control elements such as doors, windows, doors, helmets, and sunroofs; decorative light control elements such as sunglasses, glasses, sun visors, watches, mirrors, and reflectors; flexible liquid crystal display elements, reflective liquid crystal display elements, transparent liquid crystal display elements, and display members such as variable diffusion films.

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 addition, "parts" in the compositions of the following examples and comparative examples means "parts by weight."

The structures of the liquid crystal compounds (A-1) to (A-14) and (N-1) to (N-20) used in each of the Examples and Reference Examples are as follows. The liquid crystal compositions (LC-1) to (LC-7) used in each of the Examples and Reference Examples are shown in Table 1.

KEMISORB71: manufactured by Chemipro Chemical Co., Ltd. Irgacure 1076: manufactured by BASF Japan Ltd. The structures of the polymerizable compounds having a mesogenic skeleton (1-A) to (1-H) and (2-A) to (2-C) used in the respective Examples and Reference Examples are as follows:

The structures of the polymerizable compounds having a polar group and the polymerizable compounds not having a mesogenic skeleton used in each of the Examples and Reference Examples are as follows:

The polymerizable compositions, which are combinations of the polymerizable compound having a mesogenic skeleton, the polymerizable compound having a polar group, the polymerizable compound not having a mesogenic skeleton, and the polymerization initiator used in each Example and Reference Example, are shown in Tables 2 and 3.

(5-A): 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one (5-B): 2,2-dimethoxy-2-phenylacetophenone (Example 1)
A liquid crystal composition for a polymer network type liquid crystal element (polymerizable liquid crystal composition 1) was prepared by mixing 85 parts by weight of the liquid crystal composition "LC-1" and 15 parts by weight of the polymerizable composition "M-1". The obtained polymerizable liquid crystal composition 1 showed a nematic phase at room temperature.

A polyimide solution for vertical alignment film was applied to a PET film with a thickness of 188 μm and a size of 10 cm x 10 cm, with an ITO transparent electrode, to a thickness of approximately 0.1 μm, dried, and baked. An ethanol dispersion of 5 μm spherical spacer particles was applied to the vertical alignment film side of the resulting electrode substrate, and after drying, the polymerizable liquid crystal composition 1 was dropped using a dispenser and laminated on top of the polymerizable liquid crystal composition 1 so that it was in contact with the vertical alignment film side of the electrode substrate. At that time, the substrates were laminated with a shift of 5 mm so that the electro-optical properties could be evaluated.

Next, pressure was applied to the laminated substrate to make the overall thickness almost constant, and then the laminated substrate was irradiated with ultraviolet light while being kept at 25±1° C. to produce a polymer network-containing liquid crystal element. At this time, a metal halide lamp was used as the ultraviolet light source, and ultraviolet light was irradiated at an illuminance of 15 mW/cm ² for 200 seconds (total 3.0 J/cm ² ). The illuminance was measured using a unimeter UIT-101 with a UVD-365PD receiver manufactured by Ushio Inc.

The resulting liquid crystal element was transparent when no voltage was applied, and no scattering was observed, confirming that the liquid crystal was vertically aligned.

The electro-optical properties were measured by measuring the haze (Hz) of the liquid crystal element when a measuring light was incident on the obtained liquid crystal element in the normal direction using a haze meter (NDH-7000 manufactured by Nippon Denshoku Industries Co., Ltd.). The haze value was calculated from the total light transmittance (TT) and parallel light transmittance (PT) using the following formula.

Hz=[{TT-PT}/TT]×100 (%)
The haze of the liquid crystal element obtained before the application of a voltage was 1.5%. When the haze was measured while a voltage of AC 60 V (60 Hz, square wave) was applied to the liquid crystal element, the haze was 86.5%. Met.
Haze OFF: The ratio of diffuse light transmittance to total light transmittance when no voltage is applied
Haze ON: Proportion of diffuse light transmittance in total light transmittance when voltage is applied. The adhesion of the obtained liquid crystal element was measured by the following method.
(Cylindrical mandrel method)
The obtained liquid crystal element was cut with a cutter to a width of 1.5 cm, and after fixing it to a cylindrical mandrel bending tester, it was bent 180° for 2 seconds and the appearance was observed. The minor diameter was 25 mm. The mandrel diameters used in the mandrel bending tester were six types, namely, 10, 12, 16, 20, 25, and 32 mm.
(High temperature and humidity resistance)
The obtained liquid crystal element was placed in a thermohygrostat at 85° C. and a relative humidity of 85%, and was taken out after 24 hours, 96 hours, and 504 hours. The end faces of the liquid crystal element were visually observed, and the liquid crystal element was also manually inspected. The liquid crystal element was bent and the state of peeling from the substrate was observed. No peeling was observed even after 504 hours. The evaluation criteria were as follows.

◎: No peeling from the substrate after storage at high temperature and high humidity of 85°C/85% for 504 hours. ○: No peeling from the substrate after storage at high temperature and high humidity of 85°C/85% for 96 hours.
Peeling from the substrate occurred after 500 hours of high temperature and humidity. ×: No peeling from the substrate occurred after 24 hours of high temperature storage at 85° C./85%.
Peeling from the substrate occurred after 100 hours of high temperature and humidity (Examples 2 to 21, Reference Example 1)
In Examples 2 to 21 and Reference Example 1, polymer network-containing liquid crystal elements were prepared in the same manner as in Example 1, except that the liquid crystal composition (LC-1) and the polymerizable composition (M-1) were used.

The results obtained are shown in Table 4.

It was found that all of the polymer network-containing liquid crystal elements of Examples 2 to 21 exhibited good electro-optical characteristics and good adhesion.
(Example 22)
85 parts by weight of the liquid crystal composition "LC-2" and 15 parts by weight of the polymerizable composition "M-18" were mixed. Next, 0.5 parts by weight of 5 μm spherical spacer particles were added and stirred with a stirrer to prepare a liquid crystal composition for a polymer network type liquid crystal element (polymerizable liquid crystal composition 22).

A PET film with a 125 μm thick, 10 cm x 10 cm ITO transparent electrode was surface-treated using a UV ozone treatment device (UV253 manufactured by Filgen), and the polymerizable liquid crystal composition 22 was then dropped onto the ITO side of the resulting electrode substrate using a dispenser, and the substrate was laminated on top of the polymerizable liquid crystal composition 22 so that it was in contact with the ITO side of the electrode substrate. At that time, the substrates were laminated with a 5 mm offset from each other so that the electro-optical properties could be evaluated.

Next, pressure was applied to the laminated substrate to make the overall thickness approximately constant, and then the laminated substrate was irradiated with ultraviolet light while maintaining the pressure and keeping the temperature at 25±1° C. to produce a polymer network-containing liquid crystal element. At this time, a metal halide lamp was used as the ultraviolet light source, and ultraviolet light was irradiated at an illuminance of 15 mW/cm ² for 200 seconds (total 3.0 J/cm ² ).

The resulting liquid crystal element was transparent when no voltage was applied, and no scattering was observed, confirming that the liquid crystal was vertically aligned.

The haze of the obtained liquid crystal element before voltage application was 2.1%. When the haze was measured with a voltage of AC 60V (60Hz, square wave) applied to the liquid crystal element, the haze was 89.2%.

The resulting liquid crystal element was cut with a cutter to a width of 1.5 cm, and then fixed to a cylindrical mandrel bending tester, and bent 180° over 2 seconds, and the appearance was observed. The smallest diameter at which peeling did not occur was 16 mm.

The liquid crystal element thus obtained was placed in a thermohygrostat at 85° C. and a relative humidity of 85%, and was taken out after 24 hours, 96 hours, and 504 hours, and the end faces of the liquid crystal element were visually observed, and the liquid crystal element was also bent by hand to observe the state of peeling from the substrate. No peeling was observed even after 504 hours.
(Examples 23 to 25)
In Examples 23 to 25, a polymer network-containing liquid crystal element was prepared in the same manner as in Example 1, except that the liquid crystal composition (LC-2) and the polymerizable composition (M-18) were used.

The results are shown in Table 5.

It was found that all of the polymer network-containing liquid crystal devices of Examples 23 to 25 exhibited good electro-optical characteristics and good adhesion.
(Example 26)
A liquid crystal composition for a polymer network type liquid crystal element (polymerizable liquid crystal composition 26) was prepared by mixing 85 parts by weight of the liquid crystal composition "LC-2" and 15 parts by weight of the polymerizable composition "M-4". The obtained polymerizable liquid crystal composition 26 showed a nematic phase at room temperature.

A polyvinyl alcohol (PVA) aqueous solution was applied to a PET film with a thickness of 125 μm and a size of 10 cm x 10 cm, with an ITO transparent electrode, to a thickness of approximately 0.05 μm, and then dried to obtain an electrode substrate. An ethanol dispersion of 5 μm spherical spacer particles was applied to the PVA side of the electrode substrate, and after drying, the polymerizable liquid crystal composition 26 was dropped onto the PVA side of the electrode substrate using a dispenser, and the electrode substrate was laminated on top of the polymerizable liquid crystal composition 26 so that it was in contact with the ITO side of the electrode substrate. At this time, the substrates were laminated with a 5 mm offset from each other so that the electro-optical properties could be evaluated.

Next, pressure was applied to the laminated substrate to make the overall thickness approximately constant, and then the laminated substrate was placed in a movable vacuum chamber with a transparent upper surface, and the chamber was evacuated until the pressure therein reached 1 kPa, after which the laminated substrate was irradiated with ultraviolet light while being kept at 25±1° C., thereby producing a polymer network-containing liquid crystal element. At this time, a metal halide lamp was used as the ultraviolet light source, and ultraviolet light was irradiated at an illuminance of 15 mW/cm ² for 200 seconds (total 3.0 J/cm ² ).

The resulting liquid crystal element was transparent when no voltage was applied, and no scattering was observed, confirming that the liquid crystal was vertically aligned.

The haze of the obtained liquid crystal element before voltage application was 2.0%. When the haze was measured with a voltage of AC 60V (60Hz, square wave) applied to the liquid crystal element, the haze was 86.3%.

The resulting liquid crystal element was cut with a cutter to a width of 1.5 cm, and then fixed to a cylindrical mandrel bending tester, and bent 180° over 2 seconds, and the appearance was observed. The smallest diameter at which peeling did not occur was 12 mm.

The liquid crystal element thus obtained was placed in a thermohygrostat at 85° C. and a relative humidity of 85%, and was taken out after 24 hours, 96 hours, and 504 hours, and the end faces of the liquid crystal element were visually observed, and the liquid crystal element was also bent by hand to observe the state of peeling from the substrate. No peeling was observed even after 504 hours.
(Examples 27 to 31)
In Examples 27 to 31, polymer network-containing liquid crystal elements were prepared in the same manner as in Example 1, except that the liquid crystal composition (LC-2) and the polymerizable composition (M-4) were used.

The results are shown in Table 6.

It was found that all of the polymer network-containing liquid crystal elements of Examples 27 to 31 exhibited good electro-optical characteristics and good adhesion.
(Example 32)
A polymer network-containing liquid crystal element was prepared in the same manner as in Example 2, except that the PET film with an ITO transparent electrode measuring 10 cm × 10 cm and a thickness of 188 μm used in Example 2 was replaced with a polyimide film with an ITO transparent electrode measuring 10 cm × 10 cm and a thickness of 50 μm.
(Example 33)
A polymer network-containing liquid crystal element was prepared in the same manner as in Example 29, except that the PET film with an ITO transparent electrode measuring 10 cm × 10 cm and thickness 125 μm used in Example 26 was replaced with a polycarbonate film with an ITO transparent electrode measuring 10 cm × 10 cm and thickness 100 μm.

The results of Examples 32 and 33 are shown in Table 7.

The polymer network-containing liquid crystal elements of Examples 32 and 33 were found to exhibit good electro-optical properties and good adhesion.

(Examples 34 to 38)
A polymer network-containing liquid crystal element was prepared in the same manner as in Example 1, except that the liquid crystal composition was changed to (LC-2) and the polymerizable composition was changed to (M-26 to M-30) shown in Table 8. The obtained characteristics are shown in Table 9.

The polymer network-containing liquid crystal elements of Examples 34 to 38 all exhibited good electro-optical properties and low haze when in the OFF state, and furthermore, were found to exhibit good adhesion since they contained a polymerizable compound having a mesogenic skeleton represented by general formula (2) in the present invention and having a spacer group.

From the above results, the liquid crystalline composition for polymer network type liquid crystal elements of the present invention and the polymer network-containing liquid crystal element using the same can obtain good electro-optical properties and good adhesion between the substrate and the polymer network type liquid crystal element.

11...first transparent substrate 12...second transparent substrate 2...electrode 3...vertical alignment film 4...liquid crystal molecules 5...aligned polymer

Claims (8)

A polymer network type liquid crystal composition for a polymer network type liquid crystal device, comprising first to third components as essential components, the composition containing 5 to 60% by mass of a polymerizable compound having a mesogenic skeleton as the first component, a liquid crystal compound having a negative dielectric constant as the second component, and a polymerizable compound having no mesogenic skeleton and a polar group as the third component,
The first component polymerizable compound having a mesogenic skeleton contains one or more compounds represented by general formula (I) in an amount of 3.6 to 8.8% by mass,

(In the formula, P ¹ and P ² each independently represent the following formula (P-1) to formula (P-3):

represents a group selected from
S ¹ and S ² each independently represent an alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms, a CN group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms having the above-mentioned polymerizable group, and one CH ₂ group or two or more non-adjacent CH ₂ groups present in this group may each be independently replaced by -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -CH(OH)-, CH(COOH), -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- in a form in which oxygen atoms are not directly bonded to each other) or a single bond;
When X ¹ and X ² are represented as the bond to S ¹ or S ² as the leftmost bond, they each independently represent -O-, -S-, -OCH ₂ -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH 2 -, -CF _{2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 - , -CH} =CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-,
represents —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —COO—CH ₂ —, —OCO—CH ₂ —, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond (with the proviso that —O—O— is not included in the groups represented by P ¹ -S ¹ -X ¹ — and P ² -S ² -X ² -);
Z ¹ is -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH 2 -, -CH 2 S- _{, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 - , -CH =} CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-R ^Z1 -, -OCO-R ^Z1 -, -R ^Z1 -COO-, -R ^Z1 -OCO- , -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ represents -OCO-, -CH=CH-, -CH ₂ CH ₂ -, -N=N-, -CH=N-N=CH-, -CF=CF-, -C≡C- or a single bond (wherein -R ^Z1 - represents an alkylene group having 2 to 6 carbon atoms); when there are a plurality of Z ^1's , they may be the same or different;
A ¹ and A ² each independently represent a divalent group selected from an aromatic ring, an alicyclic ring, a heterocyclic ring, and a fused ring, and when a plurality of A ¹ 's are present, they may be the same or different;
Each n independently represents an integer from 1 to 9.
The second component liquid crystalline compound having a negative dielectric constant contains one or more compounds represented by general formula (IIa):

(In the formula, R ⁴¹ and R ⁴⁴ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which one methylene group or two or more non-adjacent methylene groups may be substituted with -O- or -S-, and one or more hydrogen atoms in these groups may be substituted with a fluorine atom or a chlorine atom,
M ⁴¹ , M ⁴² and M ⁴³ are each independently
(a) a 1,4-cyclohexylene group (in which one -CH ₂ - or two or more non-adjacent -CH ₂ - groups may be replaced by -O-), and (b) a 1,4-phenylene group (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=).
(c) a naphthalene-2,6-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or a decahydronaphthalene-2,6-diyl group (one -CH= or two or more non-adjacent -CH= groups in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N=).
(d) a group selected from the group consisting of 1,4-cyclohexenylene groups, wherein the groups (a), (b), (c) and (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom;
L ⁴¹ , L ⁴² and L ⁴³ each independently represent a single bond, -COO-, -OCO-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O- or -C≡C-; when a plurality of M ⁴² , M ⁴³ L ⁴¹ and/or L ⁴³ are present, they may be the same or different;
^X41 and ^X42 each represent a fluorine atom, a chlorine atom, or a cyano group;
u and v each independently represent 0, 1, or 2, provided that u+v is 2 or less.
As the third component, a polymerizable compound having no mesogenic skeleton and having a polar group,

(In the formula, ^PP1 represents a group selected from formulae (P-1) to (P-3),
SS ¹ represents an alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms, a CN group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and a polymerizable functional group, and one CH ₂ group or two or more non-adjacent CH ₂ groups present in this group may each be independently replaced by -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -CH(OH)-, CH(COOH), -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- in a form in which oxygen atoms are not directly bonded to each other), or a single bond;
XX ¹ represents -OH, -COOH, CONR ¹ R ² , -SH, -NR ¹ R ² , -NCO, -CN, -NO ₂ , -Si(OH) _3-α (CH ₃ ) _α , -P(═O)(OH) ₂ , or -P(═O)(OH)- (R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and α represents an integer of 1 or 2);
nn1 represents 1 when XX ¹ represents -OH, -COOH, CONR ¹ R ² , -SH, -NR ¹ R ² , -NCO, -CN, -NO ₂ , -Si(OH) _3-α (CH ₃ ) _α , -P(═O)(OH) ₂ , and represents 2 when XX ¹ represents -P(═O)(OH)-.
Contains 0.01 to 10 mass% of one or more compounds represented by the formula:
A liquid crystal composition for a polymer network type liquid crystal device. The liquid crystalline composition for a polymer network type liquid crystal device according to claim 1, comprising, in addition to the first component according to claim 1, one or more compounds selected from the group of compounds represented by general formulas (2) and (4) to (8) as a polymerizable compound having a mesogenic skeleton as the first component:

(In the above formulas (2) , (4) to (8), P ¹¹ to P ⁷⁴ are represented by the following formulas (P-1) to (P-20):

represents a group selected from
X ^{11 to} , -OCF 2 -, -CF _{2 S-, -SCF 2 -} , -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH 2 -, -OCO-CH _{2 CH 2 -, -CH 2 CH 2 -CO O-, -CH 2 CH 2 -OCO- , -COO - CH 2 - ,} -OCO-CH ₂ represents -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -N═N-, -CH═N-N═CH-, -CF═CF-, -C≡C- or a single bond, but when there are a plurality of X ¹¹ to X ⁷² they may be the same or different (however, each P-(S-X)- bond does not include -O-O-);
S ¹¹ to S ⁷² each independently represent an alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms, a CN group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms having the above-mentioned polymerizable group, and one CH ₂ group or two or more non-adjacent CH ₂ groups present in this group may each be independently replaced by -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -CH(OH)-, CH(COOH), -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- in a form in which oxygen atoms are not directly bonded to each other) or a single bond;
M ¹¹ , M ³¹ , M ⁵¹ and M ⁷¹ each independently represent a mesogen group represented by the following formula (9-a):

(In general formula (9-a), A ⁹¹ , A ⁹² , and A ⁹³ each independently represent a divalent group having at least one ring structure, and the divalent group is a 1,2-cyclopropylene group, a 1,3-cyclobutylene group, a 2,5-cyclopentylene group, an octahydro-4,7-methano-1H-indene-1,5-diyl group, an octahydro-4,7-methano-1H-indene-1,6-diyl group, an octahydro-4,7-methano-1H-indene-2,5-diyl group, a tricyclo[3.3.1.1 ^3,7 ]-1,3-diyl group, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, naphthylene-1,4-diyl group, naphthylene-1,5-diyl group, naphthylene-1,6-diyl group, naphthylene-2,5-diyl group, represents a group selected from a phenylene-2,6-diyl group, a phenanthrene-2,7-diyl group, a 9,10-dihydrophenanthrene-2,7-diyl group, a benzothiazole group, a 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, a benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, a benzo[1,2-b:4,5-b']diselenophene-2,6-diyl group, a [1]benzothieno[3,2-b]thiophene-2,7-diyl group, a [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or a fluorene-2,7-diyl group, and these groups are unsubstituted or have one or more L ¹ , but when A ⁹¹ and/or A ⁹² appear multiple times, they may be the same or different;
Z ⁹¹ and Z ⁹² are each independently -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH 2 -, -CH 2 S- _, -CF _{2 O-} , -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH 2 CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO- _{CH 2} -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -N═N-, -CH═N-, -N═CH-, -CH═N-N═CH-, -CF═CF-, -C≡C- or a single bond, but when a plurality of Z ⁹¹ and/or Z ⁹² appear, they may be the same or different;
j91 and j92 each independently represent an integer of 0 to 4, provided that j91 + j92 represents an integer of 1 to 4;
L ¹ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH ₂ - or two or more non-adjacent -CH ₂ - groups each independently represent -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, -N=N-, -CR ¹ =N-N=CR ¹ R 1 represents a straight-chain or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -, or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by a fluorine atom (R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be straight-chain or branched, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, and one -CH ₂ - or two or more non-adjacent -CH ₂ - in the alkyl group may each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, or -C≡C-).
represents
M ⁴¹ is a trivalent organic group having a ring structure exemplified as A ⁹¹ , A ⁹² or A ⁹³ above;
M ⁶¹ is a tetravalent organic group having a ring structure exemplified as A ⁹¹ , A ⁹² or A ⁹³ above;
R ¹¹ and R ³¹ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, one -CH ₂ - in the alkyl group or two or more non-adjacent -CH ₂ - groups may each independently be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-;
m1 , m3 to m7, n4 to n7, l4 , l6 and k6 each independently represent an integer of 0 to 5. The liquid crystal composition for a polymer network type liquid crystal element according to claim 1 or 2, which contains a polymerization initiator as a fourth component. The liquid crystal composition for a polymer network type liquid crystal element according to any one of claims 1 to 3, further comprising, as a fifth component, one or more selected from the group consisting of a polymerizable compound having no mesogenic skeleton, a polymerization inhibitor, an antioxidant, a light stabilizer, particles having a particle size of less than 1 μm, a dye, and a pigment. A polymer network type liquid crystal element using the liquid crystal composition according to any one of claims 1 to 4. An article using the polymer network type liquid crystal element according to claim 5. A method for producing a polymer network type liquid crystal element, comprising: applying the liquid crystalline composition for a polymer network type liquid crystal element according to any one of claims 1 to 4 onto a plastic substrate containing a first electrode; bonding the plastic substrate containing a second electrode so that the first electrode and the second electrode face each other; and irradiating the first plastic substrate and the second plastic substrate with ultraviolet light while applying pressure to each other. A method for producing a polymer network type liquid crystal element, comprising: applying the liquid crystal composition for a polymer network type liquid crystal element according to any one of claims 1 to 4 onto a first plastic substrate containing a first electrode; subjecting the first plastic substrate and the applied liquid crystal composition to a vacuum; and bonding a second plastic substrate containing a second electrode to the substrate so that the first electrode and the second electrode face each other; and irradiating the substrate with ultraviolet light in the vacuum state.

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