JP2021066873A - Polymerizable liquid crystal composition, polymer dispersion type liquid crystal material, and liquid crystal element and dimming element using the polymer dispersion type liquid crystal material - Google Patents

Abstract

To provide a liquid crystal composition that has electro-optic characteristics with practicality as a polymer dispersion type liquid crystal element, can improve adhesiveness to a substrate, and prevents bleeding of a liquid crystal component when processed, a polymer dispersion type liquid crystal display element using the liquid crystal composition and a method for manufacturing the display element, and an article using the polymer dispersion type liquid crystal element.SOLUTION: A polymerizable liquid crystal composition is provided, which comprises: one or more types of a polyfunctional (meth)acrylate monomer compound or a polyfunctional (meth)acrylate oligomer compound having an average molecular weight of 1000 or more as a first component; one or more types of a polymerizable compound expressed by general formula (ii) as a second component; one or more types of a polymerizable compound expressed by general formula (iii) as a third component; and one or more types of a non-polymerizable liquid crystal compound as a fourth component. The total content of the non-polymerizable liquid crystal compounds is 30 mass% or more and 70 mass% or less in the total content of the non-polymerizable liquid crystal compounds and the polymerizable compounds in the liquid crystal composition.SELECTED DRAWING: None

Description

The present invention relates to a polymerizable liquid crystal composition, a polymer-dispersed liquid crystal material obtained by polymerizing the polymerizable liquid crystal composition, a liquid crystal element using the polymer-dispersed liquid crystal material, and a dimming element using the liquid crystal element. Regarding. The liquid crystal element includes an article including an optical shutter used for dimming a digital camera, a smartphone, etc., a light scattering plate of a light source for a display, a light guide plate, a reflecting plate of a reflective display or a transparent display, a dimming element, and the like. Dimming elements are used for dimming elements used in buildings such as houses and buildings such as glass windows, doors, partitions, and private glass, and for transportation media such as automobiles, airplanes, ships, and trains such as glass windows, mirrors, and roofs. Includes articles such as dimming elements used, decorative dimming elements such as sunglasses, eyeglasses, sun visors, watches, mirrors, reflectors, etc.

Unlike general liquid crystal elements, polymer-dispersed liquid crystal elements in which the liquid crystal material is dispersed in the polymer matrix and polymer-dispersed liquid crystal elements in which the liquid crystal material is interposed in the polymer network are transparent / The degree of scattering can be adjusted. From the above characteristics, it is expected to be applied to high value-added displays such as reflective displays, transparent displays, local dimming light diffusing elements, and variable reflective elements. On the other hand, in recent years, it has been applied to smart glass and smart windows such as window glass for building materials and transportation, interior, exterior, private glass, variable projector screen, digital signage, etc. that utilize the dimming function of transmission / scattering. With the development of communication technology, it has become possible to control various equipments for both industrial and household use using mobile terminals, and therefore, a dimming material for realizing them is desired.
In particular, when deployed on the smart glass or smart window, the entire surface of the polymer-dispersed liquid crystal element or the polymer-dispersed liquid crystal element is dimmed, so that a transparent base material, a transparent electrode layer, or the liquid crystal element is generally used. A voltage is applied to the entire surface with a simple structure such as a layer, a transparent electrode layer, and a transparent base material layer. Therefore, it is necessary to save power, and a low drive voltage is desired in addition to adjusting the degree of transmission / scattering. Further, from the viewpoint of productivity, it is important that the roll-to-roll method can be directly formed on a flexible base material such as a PET film or a PC film.
On the other hand, from the viewpoint of use and processability, it is one of the characteristics that the base material and the liquid crystal element must have adhesiveness (adhesiveness). Therefore, it is preferable that the polymer-dispersed liquid crystal element or the polymer-dispersed liquid crystal element has a large amount of polymer components. However, when the liquid crystal material component in the liquid crystal element is reduced, problems such as a deterioration in the degree of scattering and an increase in the driving voltage occur.
For example, in Patent Document 1, a specific liquid crystal compound is used to suppress an increase in the drive voltage, and although a certain effect is observed in the decrease in the drive voltage, there is a problem that the adhesion is insufficient. there were. Further, Patent Document 2 uses a specific liquid crystal compound in order to improve the light resistance, and although a certain effect is observed in the light resistance, there is a problem that the light scattering property is insufficient. .. Further, in Patent Document 3, a specific polymerizable compound is used to improve the adhesion, and although a certain effect is observed in the adhesion, the liquid crystal component is present when the obtained liquid crystal element is processed. There was a problem of seeping out.

Japanese Unexamined Patent Publication No. 6-208107 Japanese Unexamined Patent Publication No. 2007-91850 Japanese Unexamined Patent Publication No. 2011-105902

When productivity is taken into consideration as described in the prior art, the transparent base material, or the transparent electrode layer and the liquid crystal element layer are used in various steps when producing using the flexible base material as described above. Good adhesion that does not come off is required. In addition, adhesion is also required in consideration of use and workability. Further, since the polymer-dispersed liquid crystal element and the polymer network liquid crystal element are cut into an appropriate shape and size according to the corresponding application, the liquid crystal component exudes at the time of cutting, that is, the liquid crystal composition is released from the element. Must not leak. Furthermore, as a basic performance, it is necessary to have electro-optical characteristics that can withstand practical use as a liquid crystal element.

Therefore, the subject of the present invention is that the adhesion to the substrate can be improved while having electro-optical characteristics having practicality as a polymer-dispersed liquid crystal element, and the liquid crystal component does not exude during processing. It is an object of the present invention to provide a liquid crystal composition, a polymer-dispersed liquid crystal display element using the liquid crystal composition, a method for producing the same, and an article using the polymer-dispersed liquid crystal element.

As a result of diligent studies on the above problems, the present invention can withstand practical use as a first component, a polymer compound having at least two or more polymerizable functional groups for enhancing adhesion, and as a second component. At least one polymerizable functional group for obtaining excellent electro-optical properties, and a polymerizable compound having a fatty chain, as a third component, at least for enhancing adhesion and for compatibility of each component. A polymerizable compound having one or more polymerizable functional groups and a cyclic skeleton, and a non-polymerizable liquid crystal composition as a fourth component are used, and the total of the non-polymerizable liquid crystal compounds in the entire polymerizable liquid crystal composition. The solution was reached by adjusting the content.

That is, the present invention comprises one or two polymerizable compounds selected from a polyfunctional (meth) acrylate monomer compound having an average molecular weight of 1000 or more or a polyfunctional (meth) acrylate oligomer compound as the first component. With the above,
As the second component, the following general formula (ii)

(In the formula, ^Pii1 represents a polymerizable functional group and represents
X ⁱⁱ¹ , X ^{ii 2} , X ^{ii 3} and X ^{ii 4} each independently represent a single bond or an alkylene group having 1 to 22 carbon atoms, and one or more -CH ₂ − in the alkylene group is -O-, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C- or -P (= O) (-OH) so that oxygen atoms are not directly adjacent to each other. It may be substituted with −, and one or more hydrogen atoms present in the alkylene group may be independently substituted with a fluorine atom or −OH.
R ⁱⁱ² , R ⁱⁱ³ and R ⁱⁱ⁴ each independently represent a hydrogen atom, a polymerizable functional group, or an alkyl group having 1 to 22 carbon atoms, and one or more of the alkyl groups are not adjacent to each other-CH. ₂ --is independently -O-, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C- or -P (= O) so that oxygen atoms are not directly adjacent to each other. It may be substituted with −OH) −, and one or more hydrogen atoms in the alkyl group are independently fluorine atoms, −OH, alkyl groups having 1 to 8 carbon atoms or carbon atoms. It may be substituted with 1 to 8 alkyl halide groups. )
One or more polymerizable compounds represented by
As the third component, the following general formula (iii)

(In the formula, ^Piii1 represents a polymerizable functional group and represents
Z ^III1 is a single bond or an alkylene group having 1 to 3 carbon atoms, -CH 2 not one or more adjacent in the alkylene group _- each so that oxygen atoms are not directly adjacent independently It may be substituted with −O−, −CO−, −COO− or −OCO−.
A ⁱⁱⁱ¹ is a general formula (iii-1) to (iii-16).

(Wherein one or more -CH ₂ - are each independently, -O -, - S -, - COO -, - OCO - NH -, - NCH 3 - or -CO- with substituted However, when a total of two or more oxygen atoms and / or sulfur atoms are present in the general formulas (iii-1) to (iii-12), these are -O-O- and -O-S-. or it is not to each other between coupling as -S-S-, and also, one or more _-CH 2 -CH ₂ - may be substituted with -CH = CH- group, the general formula The hydrogen atoms in (iii-1) to (iii-12) may be substituted with an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent-CH _{2 in the alkyl group may be substituted.} -Can be independently substituted with -O-, -CO-, -COO- or -OCO- so that oxygen atoms are not directly adjacent to each other. In addition, the black dot in the ^equation is a bond to Ziii1. Represents.)
One or more non-liquid crystal polymerizable compounds represented by
The fourth component contains one or more non-polymerizable liquid crystal compounds, and the total content of the non-polymerizable liquid crystal compounds is the non-polymerizable liquid crystal compound and the polymerizable compound in the liquid crystal composition. Provided is a polymerizable liquid crystal composition having a total content of 30% by mass or more and 70% by mass or less.

The polymerizable composition of the present invention has good electro-optical characteristics that can withstand practical use when used in a polymer-dispersed liquid crystal element, and has good adhesion and processing as a polymer-dispersed liquid crystal element. You can get sex.

When used in a polymer-dispersed liquid crystal element, the polymerizable composition of the present invention can have a low driving voltage while having good electro-optical characteristics to withstand practical use, and is a polymer-dispersed liquid crystal element. Good adhesion can be obtained as a liquid crystal element.

The polymerizable liquid crystal composition of the present invention and the implementation of the polymer-dispersed liquid crystal element using the same will be described.

It should be noted that the present embodiment is described as a specific example in order to better understand the gist of the invention, and is not limited to the present invention unless otherwise specified.
<Polymerizable liquid crystal composition>
As described above, the polymerizable liquid crystal composition of the present invention is polymerizable selected from a polyfunctional (meth) acrylate monomer compound having an average molecular weight of 1000 or more or a polyfunctional (meth) acrylate oligomer compound as a first component. A compound, a compound represented by the general formula (ii) as the second component, a compound represented by the general formula (iii) as the third component, a non-polymerizable liquid crystal compound as the fourth component, and, if necessary, a non-polymerizable liquid crystal compound. Contains other ingredients. Hereinafter, each component will be specifically described.
(The first component is a polyfunctional (meth) acrylate monomer compound having an average molecular weight of 1000 or more, or a polyfunctional (meth) acrylate oligomer compound).
The first component, the polyfunctional (meth) acrylate compound, or the polyfunctional (meth) acrylate oligomer, is a compound necessary for introducing a crosslinked structure into the network structure of the polymer and for obtaining good adhesion. is there. Among the polyfunctional (meth) acrylate compound or the polyfunctional (meth) acrylate oligomer, a bifunctional acrylate and a bifunctional acrylate oligomer are preferable. Further, in order to emphasize the adhesion to the substrate, a urethane-based or polyester-based acrylate oligomer is preferable, and a urethane acrylate oligomer is even more preferable. The urethane acrylate oligomer includes polyester type and polyether type, but the polyether type is preferable. As the molecular weight, the average molecular weight is 1000 or more, preferably 2000 to 60000, more preferably 5000 to 50000, and even more preferably 1000 to 40,000. This is because if the molecular weight is too small, the degree of curing shrinkage increases due to the increase in the crosslink density caused by the increase in the (meth) acrylic group contained in one molecule, and the adhesion deteriorates. On the contrary, the molecular weight is too small. This is because if the value is large, the distance between the crosslinks becomes long, the gap becomes large, and the liquid crystal can be easily taken in, so that the scatterability of the polymer-dispersed liquid crystal decreases. That is, if the polymer is left in an environment at a high temperature, the polymer absorbs the liquid crystal and the characteristics are significantly changed. Further, when the molecular weight is large, the degree of decrease in the transition point Tnm of the polymer-dispersed liquid crystal due to the addition of the polymerizable compound becomes small, and in order to keep the Tnm below room temperature, a material having a low Tni of the liquid crystal composition itself must be used. As a result, there is a problem that the operating temperature range is narrowed.

The polyfunctional urethane (meth) acrylate oligomer is obtained by reacting a hydroxyl group-containing acrylate with a polyol or polyisocyanate. Examples of the polyol include a polyether polyol, a polyester polyol, a polycarbonate polyol, a polybutadiene polyol, and the like, and examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
Polyisocyanates include 2,4- and 2,6-tolylene diisocyanate (TDI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate ( MDI), methylenebis (4-cyclohexylisocyanate), xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, transcyclohexane 1,4-diisocyanate, 1,6,11-undecantry isocyanate, 1,8-diisocyanate-4 -Isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, isophorone diisocyanate, and carbodiimide modified MDI, polymethylenepolyphenylisocyanate, polypeptide poly Examples include isocyanates.
Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polypropylene glycol mono (meth) acrylate. ) Acrylate, 1,4-cyclohexanedimethanol monoacrylate, mono (meth) acrylate modified with ε-caprolactone and the like.

Specifically, aliphatic urethane (meth) acrylates, aromatic urethane (meth) acrylates, and polyurethane diacrylate oligomers are preferable, and as the polyols to be used, polyether polyols, polyester polyols, and polycarbonate polyols are preferable, and polyether polyols and polyesters are preferable. Polyols are particularly preferable, and as the polyisocyanate to be used, a polyisocyanate having a cyclic structure is preferable, and a polyisocyanate having an alicyclic structure is particularly preferable. More specifically, orthotoluidine diisocyanate (TODI), methylenebis (4-cyclohexylisocyanate), xylylene diisocyanate, hydrogenated xylylene diisocyanate, transcyclohexane 1,4-diisocyanate, 1,6,11-undecantryisocyanate, bicyclo Heptane triisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, isophorone diisocyanate, and carbodiimide modified MDI are preferable, methylenebis (4-cyclohexylisocyanate), xylylene diisocyanate, hydrogenated xylylene diisocyanate, transcyclohexane 1,4-diisocyanate, 1,6. , 11-Undecantryisocyanate, bicycloheptanetriisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, isophorone diisocyanate are particularly preferable.
As the hydroxyl group-containing (meth) acrylate used, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4- Cyclohexanedimethanol monoacrylate and mono (meth) acrylate modified with ε-caprolactone are preferable, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-. Hydroxybutyl (meth) acrylates are particularly preferred.
Further, the compound of the following general formula (i-1) is also preferable.

(In the formula, X ⁱ¹ independently represents a hydrogen atom or a methyl group, ^Bi 1 represents an alkyl group having 1 to 4 carbon atoms, and one or more −CH ₂ − in the alkyl group represents. It may be substituted with an oxygen atom, -CO-, -COO-, -OCO-, b represents 1 to 20, and B ² is the following (i-2) or (i-3).

^{B 3} represents the following (i-4)

(In the formula, X ⁱ² represents a hydrogen atom or a methyl group, and t represents 20 to 300)
Represents. )
Further, aliphatic urethane acrylates and polyurethane diacrylate oligomers are particularly preferable.

The content of the polymerizable compound selected from the polyfunctional (meth) acrylate monomer compound having an average molecular weight of 1000 or more or the polyfunctional (meth) acrylate oligomer compound, which is the first component, is the polymerizable liquid crystal composition of the present invention. From the viewpoint of enhancing adhesion, it is preferably 5% by mass or more, more preferably 15% by mass or more, and 25% by mass or more, based on 100% by mass of the total amount of the polymerizable compounds contained in the product. Is particularly preferred. Further, from the viewpoint of lowering the voltage, it is preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
(2nd component compound represented by the general formula (ii))
The compound represented by the general formula (ii) of the second component is a compound particularly necessary for reducing the driving voltage in order to realize excellent electro-optical characteristics.

In the compound represented by the general formula (ii),

In the formula, ^Pii1 represents a polymerizable functional group, and preferably any of the following formulas (P-a) to (P-j) is preferable.

(In the above formulas (P-a) to (P-j), R ^{a1 to} R ^a7 are independently hydrogen atoms, fluorine atoms, or alkyl groups having 1 to 3 carbon atoms or alkyl halides. the expressed ^{independently} n a1 ^{~n a2} each represents an integer of 1 to ^{3, n a3} represents ^1, and n a4 ^{~n a5} is each independently represents an integer of 1 to 3. above formula In (P-a) to (P-j), * indicates a bond with a carbon atom or another atom.)
From the viewpoint of enhancing the polymerizable property and the storage stability, among the polymerizable groups represented by the above formulas (P-a) to (P-j), the formulas (P-a), the formula (P-c) and the formula (P-j) are used. -E) is preferable.

As the ^{polymerizable group represented by Pi1} and ^Pi2 , any of the following formulas (P-1) to (P-20) is more preferable independently of each other. Further, in the following formulas (P-1) to (P-20), * indicates a bond with a carbon atom or another atom.

Among the polymerizable groups represented by the above formulas (P-1) to (P-20), the formulas (P-1), the formula (P-2), and the formula (P) are used from the viewpoint of enhancing the polymerizable property and the storage stability. -7), formula (P-12), or formula (P-13) is preferable, and formula (P-1), formula (P-2), formula (P-7) is more preferable, and formula (P-) is particularly preferable. 1) and the formula (P-2) are preferable.
In the compound represented by general formula (ii), there may represent a wherein ^{X ii1, X ii2, X ii3} and ^{X ii4} each independently represent a single bond or an alkylene group having 1 to 22 carbon atoms, in the alkylene radical One or more of −CH ₂ − are independently −O−, −CO−, −COO−, −OCO−, −CH = CH−, −C so that oxygen atoms are not directly adjacent to each other. It may be substituted with ≡C− or −P (= O) (−OH) −, and one or more hydrogen atoms present in the alkylene group are independently fluorine atoms or −OH. Although it may be substituted with, it is preferably a single bond or an alkylene group having 1 to 18 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 12 carbon atoms.

R ⁱⁱ¹ , R ^{ii 2} and R ^{ii 3} independently represent hydrogen atoms, polymerizable functional groups, or alkyl groups having 1 to 22 carbon atoms, but hydrogen atoms, polymerizable functional groups, or 3 to 16 carbon atoms, respectively. It is preferable to represent an alkyl group of, more preferably a hydrogen atom, a polymerizable functional group, or an alkyl group having 5 to 14 carbon atoms, and a hydrogen atom, a polymerizable functional group, or 6 to 12 carbon atoms. It is particularly preferable to represent an alkyl group from the viewpoint that crystallinity can be suppressed.
When R ⁱⁱ¹ , R ^{ii 2} and R ^{ii 3} represent an alkyl group, one or more non-adjacent −CH ₂₋ in the alkyl group are independently −O− so that oxygen atoms are not directly adjacent to each other. , -CO-, -COO-, -OCO-, -CH = CH-, -C≡C- or -P (= O) (-OH)-may be substituted with 1 in the alkyl group. One or two or more hydrogen atoms may be independently substituted with a fluorine atom, −OH, an alkyl group having 1 to 8 carbon atoms or an alkyl halide group having 1 to 8 carbon atoms.

When R ⁱⁱ¹ , R ^{ii 2} and R ^{ii 3} represent a polymerizable group, the preferred polymerizable group is the same as the polymerizable group represented ^{by P ii 1.}

Formula (ii) it is, if it has only one polymerizable group, ^i.e., if R ^{ii1, R ii2} and ^{R ii3} do not represent a polymerizable group, represent the following general formula (ii-a) Is preferable.

(In the formula, ^Pia1 represents a polymerizable group and represents
^Ria2 represents a linear or branched alkyl group having 1 to 80 carbon atoms, and one or more -CH ₂ − in the alkyl group are independent so that oxygen atoms are not directly adjacent to each other. It may be substituted with −O−, −CO−, −COO−, −OCO−, −CH = CH−, −C≡C− or −P (= O) (−OH) −. One or more hydrogen atoms present in the alkyl group may be independently substituted with a fluorine atom or −OH. )
In the compound represented by the general formula (ii-a), wherein P ^IIA1 each represents a polymerizable functional group are the same as preferably polymerizable group formula (ii) P ⁱⁱ¹ in represents.

In the compound represented by the general formula (ii-a), ^Ria2 in the formula more preferably represents a linear or branched alkyl group having 3 to 20 carbon atoms, and a linear or branched alkyl group having 6 to 18 carbon atoms. It is particularly preferable to represent a branched alkyl group from the viewpoint of suppressing crystallinity, further preferably to represent a branched alkyl group, and even more preferably to represent a branched alkyl group having 9 to 24 carbon atoms.

When ^Ria2 represents a linear alkyl group, examples of the compound represented by the general formula (ii-a) include ethyl (meth) acrylate, 2-hydroxyethyl acrylate, propyl (meth) acrylate, and butyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Mono (meth) acrylate having a linear alkyl chain such as tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, docosyl (meth) acrylate, or linear chain represented by the following structure. Mono (meth) acrylates having an alkyl chain are preferred.

Further, as the compound represented by the general formula (ii-a) ^{, an acrylate in which Ria1} in the general formula (ii-a) has a linear ether chain structure is preferable. As the acrylate having the ether chain structure, a compound represented by the following structure is preferable.

(In the above general formulas (ii-a1) to (ii-a3), q represents an integer of 1 to 12)
Among the above general formulas (ii-a), a mono having a linear alkyl chain (from the viewpoint that the effect of reducing the driving voltage is remarkable while maintaining good transparency when no voltage is applied). It is preferable to use meta) acrylate.

When ^Ria2 represents a branched alkyl group, the compound represented by the general formula (iii-a) is preferably a mono (meth) acrylate having a branched alkyl chain represented by the following structure.

Further, as the compound represented by the general formula (ii-a) ^{, an acrylate in which Ria1} in the general formula (ii-a) has a linear ether chain structure is preferable. As the acrylate having the ether chain structure, a compound represented by the following structure is preferable.

(Q in the formula represents an integer from 1 to 10)
Among these, it is particularly preferable to use a mono (meth) acrylate having a branched alkyl chain from the viewpoint that the effect of reducing the driving voltage becomes remarkable while maintaining good transparency when no voltage is applied.

Formula (ii) is, if having a plurality of polymerizable groups, ^i.e., R ^ii1, if any one or more of ^{R ii2} and ^{R ii3} represent a polymerizable group, the following general formula (ii-b) It is preferable to represent it.

^{(Wherein, P ii1, X ii1, X} ii2, X ii3, X ii4, R ii3 and ^{R ii4} the ^P in the general formula ^{(ii) ii1, X ii1,} X ii2, X ii3, X ii4, R ii3 and It has the same meaning as ^Rii4,
Pii2 represents a polymerizable functional group. )
In the compound represented by the general formula (ii-b), but wherein ^{P ii1} and ^{P ii2} each independently represent a polymerizable functional group, the polymerizable group preferably ^{where P ii1} in the general formula (ii) represents Is the same as.

In the compound represented by the general formula (ii-b), wherein ^{X ii1, X ii2, X ii3} , X ii4, preferred ^{groups R ii3} and ^{R ii4} represented the general formula (ii) in the ^{P ii1,} X It is the same as the preferred group represented by ⁱⁱ¹ , X ⁱⁱ² , X ⁱⁱ³ , X ⁱⁱ⁴ and R ^ii3.

When the compound represented by the general formula (ii-b) has two polymerizable groups, that is, when ^Rii3 and ^Rii4 represent a group other than the polymerizable group, it is represented by the following general formula (ii-b1). It is preferable to use the polymerizable compound to be used.

(In the formula, Y ¹ and Y ² represent a hydrogen atom or a methyl group.
X ¹ represents a linear or branched alkylene having 2 to 80 carbon atoms, and any carbon atom of the alkylene may have -O-, -CO-, -COO-, so that oxygen atoms are not directly adjacent to each other. It may be substituted with −OCO−, −CH = CH−, −C≡C−, OH or −P (= O) (−OH) −. )
Here, in the general formula (ii-b1), X ¹ is a linear or branched alkylene in the range of 2 to 70 carbon atoms, but the carbon atom number is preferably in the range of 6 to 70. Above all, the range is preferably in the range of 8 to 60, and particularly preferably in the range of 9 to 50 from the viewpoint of lowering the drive voltage.

^{Further, as for X 1} in the general formula (ii-b1), one having an alkylidene group in an alkylene having 2 to 80 carbon atoms is preferable from the viewpoint of lowering the driving voltage. Here, the alkylidene group is preferably an ethylidene group or a 2,2-propyridene group.

More specifically, it is preferable that the X ¹ has a structural portion represented by the following structural formula (ii-1) or structural formula (ii-2) as a partial structure or as a repeating unit.

(In structural formula (i-1), Y ³ and Y ⁴ represent a methyl group or a hydrogen atom, respectively, but at least one is a methyl group, and Y ⁵ is a single bond, a methylene group, or a 1,3-propylene group. The broken line represents the bond.)

(In the structural formula (ii-2), Y ³ and Y ⁴ represent a methyl group or a hydrogen atom, respectively, but at least one is a methyl group, and Y ⁵ is a single bond, a methylene group, or a 1,3-propylene group. The broken line represents the bond.)
Examples of the polymerizable compound represented by the above general formula (ii-b1) include those having the following structure.

(In the formula, n and m are values where n + m is 1 to 10, n ² is 1 to 18, n ³ and m ² are ^{values where n 3} + m ² is 1 to 18, n ⁴ is 1 to 23, and n ⁵ is 1. ~ 23, n ⁶ represent 4 to 30, n ⁷ represents 2 to 10, n ⁸ and n ⁹ represent 2 to 10, respectively)
In the compound represented by the general formula (ii), for a composition that emphasizes adhesion, the general formula (VI-1)

It is preferable to add a compound having a group represented by. Specifically, it is preferable to add the following compounds.

(In the formula, X ⁶ , X ⁷ , and X ⁸ independently represent a hydrogen atom or a methyl group, and q, r, and s represent 1 to 4).
The content of the polymerizable compound represented by the general formula (ii), which is the second component, is 100% by mass of the total amount of the polymerizable compounds contained in the polymerizable liquid crystal composition of the present invention, and the electro-optical characteristics are improved. From the viewpoint, it is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and 50% by mass or less from the viewpoint of maintaining the strength of the polymer network. It is particularly preferable that it is 40% by mass or less, 30% by mass or less, and 25% by mass or less.
(Third component compound represented by the general formula (iii))
The compound represented by the general formula (iii) of the third component is a material having excellent flexibility, and when this compound is used, cloudiness can be maintained even in a bent state. In addition, the adhesion can be enhanced and the compatibility of each component in the polymerizable composition can be enhanced. The compound represented by the general formula (iii) is a non-liquid crystal compound.

In the compound represented by the general formula (iii), wherein P ^III1 each represents a polymerizable functional group are the same as preferably polymerizable group formula (ii) P ⁱⁱ¹ in represents.

In the compound represented by the general formula (iii), wherein Z ^III1 represents a single bond or an alkylene group having 1 to 9 carbon atoms, one in the alkylene group or two or more -CH 2 _- is The oxygen atoms may be independently substituted with -O-, -CO-, -COO- or -OCO- so that the oxygen atoms are not directly adjacent to each other, and one or more hydrogens present in the alkylene group. The atoms may be independently substituted with fluorine atoms, but are preferably single bonds or alkylene groups having 1 to 6 carbon atoms, and are single bonds or alkylene groups having 1 to 3 carbon atoms. Is more preferable.

In the compound represented by the general formula (iii), the ^Aiii1 in the formula preferably has a heterocyclic structure having a nitrogen atom, an oxygen atom, and a sulfur atom in the ^Aiii1 from the viewpoint of further improving the adhesion. More specifically, the following general formulas (iii-a1) to (iii-a11) are preferable.

(In the formula, one or more −CH ₂ − may be independently substituted with −CO−, and the hydrogen atom in the general formulas (iii−a1) to (iii−a11) is a carbon atom. may be substituted by 1-8C alkyl groups, -CH 2 not one or more adjacent in the alkyl group _- each so that oxygen atoms are not directly adjacent independently -O-, It may be substituted with −CO−, −COO− or −OCO−, and the black dots in the equation represent the bond to ^Ziii1.)
In particular, when the cyclic structure has a nitrogen atom, the adhesion can be further improved due to the presence of the nitrogen atom in the cyclic structure.

More specifically, the following compounds are preferable as the compound represented by the general formula (iii).

(X ¹ represents a hydrogen atom or a methyl group.)
The content of the compound represented by the general formula (iii), which is the third component, is from the viewpoint of improving the adhesion with respect to the total amount of the polymerizable compounds contained in the polymerizable liquid crystal composition of the present invention, which is 100% by mass. Further, from the viewpoint of enhancing the compatibility of each component in the polymerizable composition, it is preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. .. Further, from the viewpoint of lowering the voltage, it is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less.
(Other polymerizable compounds)
As the other polymerizable compound, a polymerizable compound having a mesogenic skeleton is preferable, and compounds represented by the following general formulas (2) to (8) are preferable compounds. The compounds represented by the general formulas (2) to (8) preferably exhibit liquid crystallinity.

The formula (2) to (8) ^in, P 11 ^{to P 74} represents a polymerizable group, preferably a preferred polymerizable group as a group represented by ^{P ii1} of Formula (ii) Formula (P-a) ~ Represents a polymerizable group selected from the formula (P-j), and among these polymerizable groups, the formulas (P-a) and (P-c) are used from the viewpoint of enhancing the polymerizable property and the storage stability. And formula (P-e) are more preferred.
X ^{11 to} X ⁷² are 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 Represents −, −CH = CH−, −N = N−, −CH = N−N = CH−, −CF = CF−, −C≡C− or a single bond, but there are multiple ^{X 11 to} X ^72. They may be the same or different from each other (although each P- (SX) -bond does not include -O-O-), especially single-bonds, -O-,-. Groups selected from S-, -CO-, -COO-, and -OCO- are preferred.

M ¹¹ , M ²¹ , M ³¹ , M ⁵¹ , and M ⁷¹ are independent mesogen groups represented by the following general formula (9-a).

(In the general formula (9-a), A ⁹¹ , A ⁹² , and A ⁹³ are divalent groups each independently having at least one ring structure, and the divalent group is 1,2-cyclopropylene. Group, 1,3-cyclobutylene group, 2,5-cyclopentylene group, octahydro-4,7-methano-1H-indene-1,5-diyl group, octahydro-4,7-methano-1H-inden- 1,6-diyl group, octahydro-4,7-methano-1H-inden-2,5-diyl group, 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-2,6-diyl group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, benzothiazole group, 1, 2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, benzo [1,2-b: 4,5-b'] dithiophene-2,6-diyl group, benzo [1 , 2-b: 4,5-b'] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselofeno [3 2-b] selenophene-2,7-diyl group, or represents a group selected from 2,7-diyl group, these groups may be substituted by unsubstituted or one or more L ¹ , A ⁹¹ and / or A ⁹² may appear the same or different from each other.
Z ⁹¹ and Z ⁹² are 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-,- It represents C≡C− or a single bond, but ^{when multiple Z 91} and / or Z ⁹² appear, they may be the same or different.
j91 and j92 each independently represent 0 to 4, while j91 + j92 represent an integer of 1 to 4.
L ¹ is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino. A group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -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 ^{Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by 1} − or −C≡C−, but any hydrogen atom in the alkyl group is substituted with a fluorine atom. (Note that R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and is included in the alkyl group. any hydrogen atom may be substituted by a fluorine atom, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C May be replaced by −). ).

Further, M ⁴¹ is a trivalent organic group having a ring structure exemplified as ^{A 91} , A ⁹² and A ^{93 , and M 61} has a ring structure exemplified as ^{A 91} , A ⁹² and A ^{93 4} It is an organic group of valence.

In the general formulas (2) to (8), R ¹¹ and R ³¹ are hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, or alkyl groups having 1 to 20 carbon atoms, respectively. However, the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one of the alkyl groups may be substituted. -CH ₂ − or two or more non-adjacent −CH ₂ − are independently −O−, −S−, −CO−, −COO−, −OCO−, −CO−S−, −S It may be replaced by -CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-.
m1 to m7, n2 to n7, l4 to l6, and k6 independently represent integers from 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 groups represented by the above S ^{11 to} S ⁷² have the number of carbon atoms. Represents an alkylene group of 1 to 18 (the alkylene group is composed of 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 a polymerizable functional group. It may be substituted, and one CH ₂ group existing in this group or two or more CH ₂ groups not adjacent to each other are independent of each other, and oxygen atoms are not directly bonded to each other. O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -CH (OH)-, CH (COOH), -COO-, -OCO-, -OCOO-, -SCO- , -COS- or -C≡C-. Among these spacer groups, a linear alkylene group having 2 to 8 carbon atoms and a carbon substituted with a fluorine atom from the viewpoint of orientation. An alkylene group having a number of 2 to 6 and an alkylene group having 5 to 14 carbon atoms in which a part of the alkylene group is replaced with —O— are preferable. Further, ^{when a plurality of S 11 to} S ⁷² are present, they are the same. It may or may not be different.

In the general formulas (2) to (8), m1 to m7, n2 to n7, l4 to l6, and k6 independently represent integers from 0 to 5, and m1 to m7, n2 to n7, and l4 to each. l6 and k6 are preferably 0 or 1 independently of each other.
In the polymerizable liquid crystal composition of the present invention, the lower limit of the ratio of the total amount of the polymerizable compounds such as the first component, the second component and the third component contained in the polymerizable liquid crystal composition is not in the liquid crystal composition. The total content of the polymerizable liquid crystal compound (fourth component) and the polymerizable compound is preferably 30% by mass or more, preferably 35% by mass or more, and preferably 40% by mass or more. Further, in the polymerizable liquid crystal composition of the present invention, the upper limit of the ratio of the total amount of the polymerizable compounds contained in the polymerizable liquid crystal composition is preferably 70% by mass or less, preferably 65% by mass or less. Is preferable, and it is preferably 60% by mass or less. The total amount of the polymerizable compound contained in the polymerizable liquid crystal composition means the total amount of all the polymerizable compounds contained in the polymerizable liquid crystal composition, and is, for example, the average of the first component. A polyfunctional (meth) acrylate monomer compound having a molecular weight of 1000 or more, a polyfunctional (meth) acrylate oligomer compound, a second component, a polymerizable compound represented by the general formula (ii), and a third component. It is represented by the total amount of the polymerizable compound represented by a certain general formula (iii), the polymerizable compound having a mesogenic skeleton which is another polymerizable compound, and the polymerizable compound arbitrarily contained.
(Fourth component non-polymerizable liquid crystal compound)
The non-polymerizable liquid crystal compound of the fourth component is represented by the following general formula (I), for example.

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, and one or two non-adjacent CH ₂ groups in the alkyl group are replaced with oxygen atoms, -COO- and -OCO-. Or, one or more methylene groups may be replaced by −CH = CH− or −CH≡CH−, preferably an alkyl group having 1 to 5 carbon atoms (in the alkyl group). One or more methylene groups of may be replaced by −CH = CH−).
R ² represents a fluorine atom, a chlorine atom, a cyano group, a CF ₃ group, an OCF ₃ group, an OCHF ₂ group, an NCS group, or an alkyl group having 1 to 10 carbon atoms, and is a non-adjacent 1 in the alkyl group. one or two CH ₂ groups represents an oxygen atom, -COO -, - OCO- may be replaced by, or one or more of the methylene groups is -CH = CH-, or -CH≡CH- been replaced by Alternatively, a fluorine atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms (one or two non-adjacent CH ₂ groups in the alkyl group may be replaced with an oxygen atom. ) And
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH _{2- CH 2-,} -CH = CH-, -CF ₂ O-, -OCF _2- , or represents -C≡C-, ^{if Z 2} is plurally present, it may be different even in the same, preferably a single _{bond, -COO -, - CF 2 O-} , or -C≡C - and (if Z ² is plurally present, may be different even in the same),
A ¹ , A ² , and A ³ are independent of each other.
(A) A divalent group having an alicyclic structure having 3 to 8 carbon atoms (one methylene group existing in this group or two or more methylene groups not adjacent to each other is -O- or -S-. And one of the two adjacent methylene groups present in this group may be replaced with -CH = CH-),
(B) A divalent group having an aromatic ring structure having 5 to 14 carbon atoms (one -CH = existing in this group or two or more -CH = not adjacent to each other is a nitrogen atom. May be replaced with)
Represents a group selected from the group consisting of, and the above groups (a) and (b) are independently cyano groups, fluorine atoms, chlorine atoms, alkyl groups having 1 to 4 carbon atoms, or carbon atoms. may be substituted with 1-4 alkoxy group, if a ³ is plurally present, may be different even in the same,
m is 0, 1 or 2. )
The non-polymerizable liquid crystal compound used as the polymerizable liquid crystal composition of the present invention may be a compound showing a liquid crystal phase by itself or a compound showing a liquid crystal phase when two or more kinds are combined. Usually, it is used as two or more kinds of liquid crystal compositions.

The total content of the compound represented by the general formula (I) with respect to the total amount of the polymerizable liquid crystal composition according to the present invention is the total of the non-polymerizable liquid crystal compound and the polymerizable compound in the polymerizable liquid crystal composition. Of the content of 100% by mass, the lower limit of the preferable content is 30% by mass, and the upper limit is 70% by mass. The lower limit of the more preferable content is 35% by mass, and the upper limit is 55% by mass. An even more preferable lower limit of the content is 40% by mass, and the upper limit is 60% by mass.

When two or more types of liquid crystal molecules are mixed and used, various combinations are possible, but at least one type contains the following general formula (L), and the dielectric anisotropy of the liquid crystal composition is positive. In the case of, the following general formula (2-A) or (2-B) is further included, and when the dielectric anisotropy of the liquid crystal composition is negative, the following general formulas (IIa), (IIb) or The compound represented by (IIc) may be contained.

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

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

(In the formula, R ²¹ and R ²² independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one methylene group or an adjacent methylene group present in these groups. Two or more methylene groups that are not used may be substituted with -O- or -S-, and one or two or more hydrogen atoms present in these groups are substituted with fluorine or chlorine atoms. May be
M ²¹ , M ²² and M ²³ are independent of each other (a) a divalent group having an alicyclic structure with 3 to 8 carbon atoms (one methylene group existing in this group or two not adjacent to each other). More than one methylene group may be replaced with -O- or -S-, and one of the two adjacent methylene groups present in this group is replaced with -CH = CH-. May be),
(B) A divalent group having an aromatic ring structure having 5 to 14 carbon atoms (one -CH = existing in this group or two or more -CH = not adjacent to each other is a nitrogen atom. May be replaced with)
Represents a group selected from the group consisting of, and the above groups (a) and (b) are independently cyano groups, fluorine atoms, chlorine atoms, alkyl groups having 1 to 4 carbon atoms, or groups. It may be substituted with an alkoxy group having 1 to 4 carbon atoms.
o represents 0, 1 or 2,
L ²¹ and ^{L 22} are independently of one another, are 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 -, - COO -, - OCO-, or -C≡C- ^{represent, if L 22} there are multiple, they be different it may be the same is good, if the M ²³ there are a plurality, they may be different may be the same. )
In the compound represented by the general formula (L), R ²¹ and R ²² are independent of each other as an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (1 existing in these groups). One methylene group or two or more non-adjacent methylene groups are substituted with -O- or -S-, and one or more hydrogen atoms present in these groups are fluorine atoms or It also includes those substituted with chlorine atoms), 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 3 to 6 carbon atoms. The alkenyloxy group is more preferable, and an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is particularly preferable.

When reliability is important, ^{both RL1} and ^RL2 are preferably alkyl groups, and when reducing the volatility of the compound is important, they are preferably alkoxy groups, and reduction of viscosity is important. 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, preferably 0 or 1, and preferably 1 when compatibility with other liquid crystal molecules is important.

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

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

M ²¹ , M ²² and M ²³ are independent of each other as a trans-1,4-cyclohexylene group (one CH ₂ group existing in this group or two non-adjacent CH ₂ groups become oxygen atoms. (Including those substituted), 1,4-phenylene group (including one in which one or more CH groups present in this group are substituted with a nitrogen atom), 3-fluoro-1, 4-phenylene group, 3,5-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group , Naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is preferable, and trans-1,4-cyclohexylene group. , 1,4-phenylene group or 1,4-bicyclo [2.2.2] octylene group is more preferable, and trans-1,4-cyclohexylene group or 1,4-phenylene group is particularly preferable. M ²¹ , M ²² and M ²³ are preferably aromatic when it is required to increase Δn, and preferably aliphatic in order to improve the response rate, and each of them is independently trans-trans. 1,4-Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group , 1,4-Cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 It preferably represents a −diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferably the following structure.

It is more preferable to represent 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} are independently of one another, are 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 -, - CH 2 O- or -C≡C- is more preferably a single bond, _-CH 2 CH ₂ - or -C≡C- is more preferred.

Among the structures formed by the combination of the above options, -CH = CH-CH = CH-, -C≡C-C≡C- and -CH = CH-C≡C- are preferable from the viewpoint of chemical stability. Absent. Further, it is also not preferable that the hydrogen atom in these structures is replaced with the fluorine atom. Similarly, it is also not preferable to have a structure in which oxygen is bonded to each other, a structure in which sulfur atoms are bonded to each other, and a structure in which sulfur atoms and oxygen atoms are bonded to each other. Further, a structure in which nitrogen atoms are bonded to each other, a structure in which a nitrogen atom and an oxygen atom are bonded, and a structure in which a nitrogen atom and a sulfur atom are bonded are also not preferable.

In the liquid crystal composition according to the present invention, the content of the liquid crystal compound represented by the general formula (L) is solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, and dropping marks. It is necessary to make appropriate adjustments according to the required performance such as seizure and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L) with respect to the total amount of the liquid crystal composition composed of a plurality of non-polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition according to the present invention is 5% by mass. The upper limit is 90% by mass. The lower limit of the more preferable content is 20% by mass, and the upper limit is 80% by mass. An even more preferable lower limit of the content is 25% by mass, and the upper limit is 70% by mass. An even more preferable lower limit of the content is 30% by mass, and the upper limit is 60% by mass.

When a composition having a low viscosity and a high response rate is required, it is preferable that the above lower limit value is high and the upper limit value is high. _{Further, when a composition having a high TNI} of the composition according to the present invention and having good temperature stability is required, it is preferable that the above lower limit value is high and the upper limit value is high. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is low and the upper limit value is low.

More specifically, the general formula (L) is preferably a compound represented by a group consisting of the following general formulas (La) to (Lq) as a specific structure.

(In the formula, R ²³ and R ²⁴ are independently alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or alkenyloxy groups having 3 to 10 carbon atoms, respectively. Represents.)
R ²³ and R ²⁴ are each independently preferably 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 an alkyl group or carbon having 1 to 5 carbon atoms. Alkoxy groups of numbers 1 to 10 are more preferred.

Among the compounds represented by the general formulas (La) to the general formula (Lq), the general formula (La), the general formula (Lb), the general formula (Lc), and the general formula (L). -E), general formula (L-h), general formula (Li), general formula (Lm), general formula (Lo) or compound represented by general formula (Lq) is preferable. , The compound represented by the general formula (La), the general formula (L-c), the general formula (Le), the general formula (Lh) or the general formula (Li) is more preferable.

In the present invention, the fourth component contains at least one compound represented by the general formula (L), preferably 1 to 10 kinds, and particularly preferably 2 to 8 kinds.

When the dielectric anisotropy of the liquid crystal composition contained in the polymerizable liquid crystal composition of the present invention is positive, it is further selected from the group represented by the general formula (2-A) and the general formula (2-B). Contains one or more compounds.

(In the formula, R ^2A1 and R ^2B1 are mutually independent alkyl groups having 1 to 7 carbon atoms, alkoxy groups having 1 to 7 carbon atoms, or alkenyl groups having 2 to 7 carbon atoms. One or more hydrogen atoms on R ^2A1 and R ^2B1 may be substituted with fluorine or chlorine atoms independently of each other.
C ^2A1 and C ^2B1 are independent of each other
(A) A divalent group having an alicyclic structure having 3 to 8 carbon atoms (one methylene group existing in this group or two or more methylene groups not adjacent to each other is -O- or -S-. And one of the two adjacent methylene groups present in this group may be replaced with -CH = CH-),
(B) A divalent group having an aromatic ring structure having 5 to 14 carbon atoms (one -CH = existing in this group or two or more -CH = not adjacent to each other is a nitrogen atom. May be replaced with)
The group (a) and the group (b) are independently selected from the group consisting of a cyano group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with an alkoxy group having 1 to 4 carbon atoms.
L ^2A1 and ^{L 2B1,} independently of one another, a single _{bond, -C 2 H 4 -, -} CH = CH -, - C≡C -, - COO -, - OCO -, - CH 2 O -, - Represents OCH _2- , -CF ₂ O- or -OCF _2-
X ^2A1 and X ^2B1 are independent of each other and have an alkyl group having 1 to 7 carbon atoms or at least one in which a fluorine atom, a chlorine atom, a cyano group, an NCS group, or at least one hydrogen atom is replaced with a halogen atom. Represents an alkoxy group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms in which hydrogen atoms are substituted with halogen atoms, and at least one or more hydrogen atoms on ^{X 2A1} and X ^{2B1 are independent of each other. Y 2A1} , Y ^2A2 , Y ^2B1 and Y ^2B2 may be substituted with a fluorine atom or a chlorine atom, and independently represent a hydrogen atom or a fluorine atom.
b ^2A1 and b ^2B1 represent 1, 2, 3 or 4 independently of each other. )

In the general formula (2-A) and the general formula (2-B), R ^2A1 and R ^2B1 are independent of each other and have an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms. An alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and 2 to 5 carbon atoms. An alkenyl group or an alkoxyoxy group having 2 to 5 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms is more preferable, and an alkyl group or carbon having 2 to 5 carbon atoms is more preferable. An alkenyl group having 2 to 3 atoms is more preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

^{R 2A1} and R ^2B1 are preferably alkyl groups when reliability is important, and alkenyl groups when reduction in viscosity is important.

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

The alkenyl group is preferably selected from the groups represented by any of the formulas (R1) to (R5).

The black dots in each equation represent the bond.

C ^2A1 and C ^2B1 are preferably aromatic when it is required to increase Δn independently of each other, and are preferably aliphatic in order to improve the response rate, as described below. It is more preferable to represent the structure.

L ^2A1 and L ^2B1 are independent of each other, preferably single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O- or -OCF _2- , and single-bonded. , -CH ₂ O- or -CF ₂ O- is preferable, single bond, -COO-, or -CF _{2 O- is preferable, and L 2} sandwiched between the rings C is preferably a single bond.

X ^2A1 and X ^2B1 are independent of each other and _{are preferably a fluorine atom, a chlorine atom, -CF 3} or -OCF ₃ or a cyano group, preferably a fluorine atom or a cyano group, and are preferably a cyano group. It is preferable to have.

It is preferable that Y ^2A1 , Y ^2A2 , Y ^2B1 and Y ^2B2 are all fluorine atoms, or one of the same molecules is a fluorine atom and the other is a hydrogen atom.

b ^2A1 and b ^2B1 are preferably 1, 2 or 3 independently of each other, and preferably 2 or 3 when the upper limit temperature of the liquid crystal phase of the liquid crystal composition is important. When the viscosity and dielectric anisotropy of the product are emphasized, it is preferably 1 or 2.

In the composition of the present invention, the content of the compound represented by the general formula (2-A) and / or the general formula (2-B) includes solubility at low temperature, transition temperature, electrical reliability, and birefringence. It is necessary to make appropriate adjustments according to the required performance such as refractive index and dielectric anisotropy.

Preferable compounds represented by the general formulas (2-A) and (2-B) with respect to the total amount of the liquid crystal composition composed of a plurality of non-polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition of the present invention. The lower limit of the content is 1% by mass, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, and 60%. It is mass%, 65 mass%, 70 mass%, 75 mass%, and 80 mass%. The upper limit of the preferable content is, for example, 95% by mass, 85% by mass, 80% by mass, and 75% by mass, based on the total amount of the composition of the present invention. , 65% by mass, 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

When a composition having a low viscosity and a high response rate is required, it is preferable to lower the lower limit value and lower the upper limit value. _{Further, when the TNI} of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the above lower limit value and raise the upper limit value.

As the compound represented by the general formula (2-A), the compounds represented by the general formulas (2-A-1) to (2-A-42) are preferable.

(R ^2A1 represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and Y ^2A1 and Y ^2A2 are independently hydrogen atoms or Represents a fluorine atom.)
As the compound represented by the general formula (2-B), the compounds represented by the general formulas (2-B-1) to (2-B-5) are preferable.

(R ^2B1 represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms.)
The compounds represented by the general formulas (2-A) and (2-B) may be selected from only one of the groups and used, or may be selected from each group and used in combination. ..

When the reliability of the liquid crystal composition used in the polymerizable liquid crystal composition of the present invention is emphasized, the general formulas (2-A-1) to (2-A-11) and (2-A-16) to (2) It is preferable to use a compound selected from the group represented by −A-20) and the general formulas (2-B-1) to (2-B-4), among which the general formula (2-A-1), It is more preferable to select from the group represented by (2-A-2), (2-A-4), (2-A-17) and (2-A-20). When emphasizing low viscosity, general formulas (2-A-12) to (2-A-15), (2-A-21) to (2-A-28) and (2-B-5) to It is preferable to use a compound selected from the group represented by (2-B-6), among which (2-A-12), (2-A-13), (2-A-22), (2). It is more preferable to select from the group represented by −A-23) and (2-A-26). When emphasizing the improvement of transmittance while emphasizing low viscosity, (2-A-14), (2-A-15), (2-A-25), (2-A-27) and ( It is preferable to use a compound selected from the group represented by 2-A-28). If scatterability is important, it is preferable to use a compound selected from the group represented by (2-A-29) to (2-A-42), and if both reliability and scatterability are to be achieved, it is preferable to use a compound. It is preferable to use a compound selected from the group represented by (2-A-29) to (2-A-36)).

The compounds represented by the general formula (2-A) and the general formula (2-B) can be appropriately selected according to the characteristics required for the liquid crystal display element, and a plurality of types can be used in combination as necessary. It is preferable to use 1 to 12 types, more preferably 2 to 10 types, and particularly preferably 3 to 8 types.
The lower limit of the content of the group consisting of the compounds represented by the general formula (2-A) and the general formula (2-B) is composed of a plurality of non-polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition of the present invention. It is preferably 10% by mass, more preferably 30% by mass, preferably 50% by mass, and the upper limit is preferably 95% by mass, preferably 80% by mass, based on the total mass of the liquid crystal composition. It is preferably 75% by mass, more preferably 70% by mass.

When the dielectric anisotropy of the liquid crystal composition composed of a plurality of non-polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition of the present invention is negative, a compound selected from the group represented by the general formula (IIa) is further selected. It is preferable to contain one kind or two or more kinds.

(In the formula, R ⁴¹ and R ⁴⁴ independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one methylene group existing in these groups or adjacent to each other. Two or more methylene groups that are not present may be substituted with -O- or -S-, and one or more hydrogen atoms present in these groups are substituted with fluorine or chlorine atoms. May be
M ⁴¹ , M ⁴² and M ⁴³ are independent of each other,
(A) A divalent group having an alicyclic structure having 3 to 8 carbon atoms (one methylene group existing in this group or two or more methylene groups not adjacent to each other is -O- or -S-. And one of the two adjacent methylene groups present in this group may be replaced with -CH = CH-),
(B) A divalent group having an aromatic ring structure having 5 to 14 carbon atoms (one -CH = existing in this group or two or more -CH = not adjacent to each other is a nitrogen atom. May be replaced with)
The group (a) and the group (b) are independently selected from the group consisting of a cyano group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with an alkoxy group having 1 to 4 carbon atoms.
L ^{41, L 42} and ^{L 43} are independently of one another, are a single _{bond, -COO -, - OCO -,} - CH 2 CH 2 -, - (CH 2) 4 -, - OCH 2 -, - CH 2 O-, Represents −OCF _2- , −CF ₂ O− or −C≡C−, ^{and if there are multiple M 42} , M ⁴³ L ⁴¹ and / or L ⁴³ , they may be the same or different.
X ⁴¹ and X ⁴² represent a fluorine atom or a cyano group.
u and v independently represent 0, 1 or 2, but u + v is 2 or less. )
It may contain a second component having a negative dielectric anisotropy other than the compound represented by the general formula (IIa). For example, at least one or two or more compounds selected from the following general formulas (IIb) and (IIc) are arbitrarily combined with one or more compounds represented by the general formula (IIa). Can be configured. The compounds represented by the general formula (IIa), the general formula (IIb) and the general formula (IIc) are dielectrically negative compounds (the sign of dielectric anisotropy is negative and the absolute value is greater than 2). Applicable.

(In the formula, R ⁴² , R ⁴³ , R ^45, and R ⁴⁶ independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and 1 is present in these groups. The methylene group or two or more non-adjacent methylene groups may be substituted with -O- or -S-, and one or more hydrogen atoms present in these groups are fluorine atoms. It may be replaced with an atom or a chlorine atom,
M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ and M ⁴⁹ are independent of each other,
(A) A divalent group having an alicyclic structure having 3 to 8 carbon atoms (one methylene group existing in this group or two or more methylene groups not adjacent to each other is -O- or -S-. And one of the two adjacent methylene groups present in this group may be replaced with -CH = CH-),
(B) A divalent group having an aromatic ring structure having 5 to 14 carbon atoms (one -CH = existing in this group or two or more -CH = not adjacent to each other is a nitrogen atom. May be replaced with)
The group (a) and the group (b) are independently selected from the group consisting of a cyano group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with an alkoxy group having 1 to 4 carbon atoms.
^{L 44, L 45, L 46} , L 47, L 48 and ^{L 49} are independently of one another, are a single _{bond, -COO -, - OCO -,} - CH 2 CH 2 -, - (CH 2) 4 -, - OCH _{2 -, - CH 2 O -} , - OCF 2 -, - CF 2 O- or represents ^{-C≡C-, M 45, M 46,} M 48, M 49, L 44, L 46, L 47 and / Or, ^{if there are multiple L 49s} , they may be the same or different.
X ⁴³ and X ⁴⁶ represent a hydrogen atom or a fluorine atom, X ⁴⁴ , X ⁴⁵ , X ⁴⁷ and X ⁴⁸ represent a fluorine atom, G represents a methylene group or −O−.
w, x, y and z independently represent 0, 1 or 2, but w + x and y + z are 2 or less. )
The lower limit of the preferable content of the liquid crystal compound represented by the formula (IIa) with respect to the total amount of the liquid crystal composition composed of a plurality of non-polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition according to the present invention is 30% by mass. The upper limit is 95% by mass. The lower limit of the more preferable content is 45%, and the upper limit is 80% by mass.

When a composition having a low viscosity and a high response speed according to the present invention is required, it is preferable that the above lower limit value is low and the upper limit value is low. Moreover, maintaining high T _NI of the polymer dispersion type liquid crystal device for a liquid crystal composition according to the present invention, it is preferred if good composition temperature stability is required a low upper limit lower the lower limit of the above. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is high and the upper limit value is high.

In the compounds represented by the above general formulas (IIa), general formula (IIb) and general formula (IIc), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ have independent carbon atoms. Alkyl groups from 1 to 10 or alkenyl groups having 2 to 10 carbon atoms, linear alkyl groups having 1 to 15 carbon atoms or alkenyl groups having 2 to 15 carbon atoms (one methylene group present in these groups). Alternatively, two or more methylene groups that are not adjacent to each other are substituted with -O- or -S-, and one or two or more hydrogen atoms present in these groups are replaced with fluorine or chlorine atoms. Substituted ones are also included), more preferably 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, and 1 carbon atom number. A linear alkyl group of ~ 8 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 are independent of each other and have a trans-1,4-cyclohexylene group (1 present in this group). One methylene group or two or more non-adjacent methylene groups are replaced with -O- or -S-), 1,4-phenylene group (one present in this group). -CH = or two or more non-adjacent -CH = are replaced with -N =), 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] With octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group The groups to be represented (including those in which the hydrogen atom contained in each group is substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, respectively) are preferable, and trans-1,4- Cyclohexylene group, 1,4-phenylene group, 3-fluoro-1,4-phenylene group or 2,3-difluoro-1,4-phenylene group is more preferable, and trans-1,4-cyclohexylene group or A 1,4-phenylene group is more preferable, and a trans-1,4-cyclohexylene group is particularly preferable. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ and L ⁴⁹ are single bonds independently of each other, -CH ₂ CH ₂ -,-(CH ₂ ) ₄ -,- OCO-, -COO-, -OCH _2- , -CH ₂ O-, -OCF _2- , -CF ₂ O- or -C≡C- are preferable, and single bond, -CH ₂ CH ^2- , -OCH ₂ -Or -CH ₂ O- is more preferable. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ and X ⁴⁷ are preferably hydrogen atoms, fluorine atoms or cyano groups independently of each other, G is preferably methylene group or −O−, u, v. , W, x, y and z independently represent 0, 1 or 2, but u + v, w + x and y + z are preferably 2 or less.

In the compound represented by the general formula (IIa), it is preferable to specifically represent the structure represented by the following general formula (IIa-1).

(In the formula, R ⁴⁷ and R ⁴⁸ 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, and 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 - represents ^C≡C-, represent M ^{50, M 51} and ^{M 52} each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, 2,5-tetrahydropyranyl group, the 1 , 4-Phenylene group or trans-1,4-cyclohexylene group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, respectively.
u ¹ and v ¹ independently represent 0 or 1, respectively. )
In the polymerizable liquid crystal composition of the present invention, the total content of the non-polymerizable liquid crystal compound as the fourth component is the total content of the non-polymerizable liquid crystal compound and the polymerizable compound in the polymerizable liquid crystal composition. It is 30% by mass or more and 70% by mass or less. From the viewpoint of improving the light scattering property when the polymer-dispersed device is used, 35% by mass or more is preferable, 40% by mass or more is preferable, and 45% by mass or more is preferable. Further, from the viewpoint of improving the adhesion, 70% by mass or less is preferable, 65% by mass or less is preferable, and 60% by mass or less is preferable.

The polymerizable liquid crystal composition of the present invention can contain a polymerization initiator. The polymerization initiator used in the present invention is used for polymerizing the liquid crystal composition of the present invention. The photopolymerization initiator used when the polymerization is carried out by light irradiation is not particularly limited, but has the above-mentioned one polymerizable group, a polymerizable compound satisfying the formula (I), and a mesogenic skeleton. Known and commonly used compounds can be used to the extent that the orientation state of the polymerizable compound is not impaired.

For example, 1-hydroxycyclohexylphenyl ketone "Omnirad 184", 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one "Omnirad 1173", 2-methyl-1-[(methylthio) phenyl]- 2-Moliphorinopropan-1 "Omnirad 907", 2,2-dimethoxy-1,2-diphenylethane-1-one "Omnirad BDK", 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -butanone "omnirad 369"), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholino-phenyl) butane-1-one "omnirad 379", 2,2-dimethoxy-1 , 2-Diphenylethane-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)], etanone "Irgacure OXE01"), 1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) "Irgacure OXE02", "Irgacure OXE04" (manufactured by BASF Co., Ltd.), "Adeca Arcurus NCI-831", "Adeca Arcurus NCI-930", "Adeka Arkuru's N-1919" (manufactured by ADEKA), 2,4-diethylthioxanthone ("Kayacure DETX" manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate (Japan) Mixture with "Kayacure EPA" manufactured by Kayakusha), mixture of isopropylthioxanthone ("CantaCure-ITX" manufactured by Ward Prekinsop) and ethyl p-dimethylaminobenzoate, "Esacure ONE", "Esacure KIP150", "Esacure KIP150" Esacure KIP160, Esacure 1001M, Esacure A198, Esacure KIP IT, Esacure KTO46, Esacure TZT (manufactured by Lamberti Co., Ltd.), Speedcure BMS, Speedcure PBZ, Benzoyl. "(Manufactured by LAMBSON) and the like. Further, as the photocation initiator, a photoacid generator can be used. 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, particularly preferably 0.2 to 6% by mass, based on 100% by mass of the total amount of the polymerizable compounds used in the polymerizable composition of the present invention. .. These can be used alone or in combination of two or more.

As the thermal polymerization initiator used in the thermal polymerization, known and commonly used agents can be used, for example, methylacetate acetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl). Peroxydicarbonate, t-butylperoxybenzoate, methylethylketone peroxide, 1,1-bis (t-hexylpaoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydro Organic peroxides such as peroxide, dicumyl peroxide, isobutyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2, 2'-Azobisisobutyronitrile, azonitrile compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methyl-N-phenylpropion-amidin) dihydro Azoamidin compounds such as chloride, azoamide compounds such as 2,2'azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2' azobis (2, An alkylazo compound such as 4,4-trimethylpentane) can be used. The content of the thermal polymerization initiator is preferably 0.1 to 10% by mass with respect to 100% by mass of the total amount of the polymerizable compounds used in the polymerizable composition of the liquid crystal composition for a polymer-dispersed liquid crystal element of the present invention. 1 to 6% by mass is particularly preferable. These can be used alone or in combination of two or more.

The polymerizable liquid crystal composition of the present invention has a polymerization inhibitor, an antioxidant, a light stabilizer, and a chain within a range that does not impair practical electro-optical properties and adhesion when made into a polymer-dispersed liquid crystal element. Transfer agents, dyes, pigments, particles with a particle size of less than 1 μm, chiral compounds, or alignment materials can be added.
(Polymerization inhibitor)
The polymerization inhibitor used in the present invention is used for controlling the electro-optical characteristics by controlling the polymerization reaction of the polymerizable liquid crystal composition of the present invention, or for the efficacy of a polymerizable compound having a polarity as a third component. Can be used to assist. As such a compound, a 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, 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 compounds are preferred, p-methoxyphenol, 4-methoxy- 1-naphthol, tert-butylhydroquinone and 2-hydroxy-1,4-naphthoquinone are particularly preferred.

The content of the polymerization inhibitor is preferably 0 to 2.0% by mass, preferably 0 to 2.0% by mass, based on 100% by mass of the total amount of the polymerizable compounds used in the polymerizable composition of the polymerizable liquid crystal composition of the present invention. More preferably, it is 0.5% by mass.
(Antioxidant)
The antioxidant used in the present invention can be used to impart practical durability to the polymer-dispersed liquid crystal device of the present invention. As such a compound, a hydroquinone derivative, a nitrosamine-based polymerization inhibitor, a hindered phenol-based antioxidant and the like can be used.

Specifically, tert-butylhydroquinone, Wako Pure Chemical Industries, Ltd. "Q-1300", "Q-1301", pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate "IRGANOX1010", thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate "IRGANOX1035", octadecyl-3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionates "IRGANOX 1076", "IRGANO X1135", "IRGANO X1330", 4,6-bis (octylthiomethyl) -o-cresol "IRGANO X1520L", "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114" IRGANOX3790 ”,“ IRGANOX5057 ”,“ IRGANOX565 ”(above, manufactured by BASF Co., Ltd.), Adecastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, Sumitomo manufactured by ADEKA Co., Ltd. Sumilyzer BHT, Sumilyzer BBM-S, and Sumilyzer GA-80 manufactured by Kagaku Co., Ltd., compounds having a structure represented by the following general formula, and the like are preferable.

In the general formulas (H-1) to (H-3), ^RH1 is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. It represents an alkenyloxy group having 2 to 10 carbon atoms, one -CH ₂ present in the radical - or non-adjacent two or more -CH ₂ - are each independently -O- or -S- In addition, one or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom, respectively. More specifically, it may be an alkyl group having 2 to 7 carbon atoms, an alkoxyl 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. It is more preferable that it is an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

Among them, 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 formulas (H-2) to (H-3) are particularly preferable.
The content of the antioxidant is preferably 0 to 2.0% by mass, preferably 0 to 0.5% by mass, based on 100% by mass of the total amount of the polymerizable compounds used in the polymerizable liquid crystal composition of the present invention. Is more preferable.
(Light stabilizer)
The light stabilizer used in the present invention can be used to impart practical durability to the polymer-dispersed liquid crystal device 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 765". 780 ”,“ TINUVIN 905 ”,“ TINUVIN 5100 ”,“ TINUVIN 5050 ”,“ TINUVIN 5060 ”,“ TINUVIN 5151 ”,“ CHIMASORB 119FL ”,“ CHIMASORB 944FL ” , "ADEKA STAB LA-52", "ADEKA STAB LA-57", "ADEKA STAB LA-62", "ADEKA STAB LA-67", "ADEKA STAB LA-63P", "ADEKA STAB LA-68LD", "ADEKA STAB LA-77", Examples thereof include "ADEKA STAB LA-82" and "ADEKA STAB LA-87" (all manufactured by ADEKA CORPORATION).
The amount of the ultraviolet absorber added is preferably 0.0 to 2.0% by mass with respect to the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. More preferably, it is 0.0 to 1.0% by mass.
(Chain transfer agent)
The chain transfer agent used in the present invention can be used to further improve the adhesion between the polymerizable liquid crystal composition and the substrate. Examples of the chain transfer agent are mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecylmel, n-dodecyl mercaptan, t-tetradecyl mercaptan, and t-dodecyl mercaptan. , Hexadithiol, Decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethyl propanthiol Glycolate, Trimethylol Propanetristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol tetraxthioglycolate, Pentaerythritol tetraxthiopropionate, Tristrimercaptopropionate (2-hydroxyethyl) Thiol compounds such as isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine ,, Examples thereof include pentaphenylethane, α-methylstyrene dimer, achlorine, allyl alcohol, turpinolene, α-terpinene, γ-terbinen, dipentene, and the like.
Specifically, compounds represented by the following general formulas (9-1) to (9-8), α-methylstyrene dimer, and α-terpinene are preferable.

In the formula, R ⁹⁵ represents an alkyl group having 2 to 18 carbon atoms, the alkyl group may be a straight chain or a branched chain, and one or more methylene groups in the alkyl group are oxygen atoms. , And sulfur atoms may be substituted with oxygen atoms, sulfur atoms, -CO-, -OCO-, -COO-, or -CH = CH-, assuming that they do not bond directly to each other, where R ⁹⁶ is a carbon atom. Representing the number 2 to 18 alkylene groups, one or more methylene groups in the alkylene group assume that the oxygen atom and the sulfur atom do not directly bond with each other, and the oxygen atom, the sulfur atom, -CO-, and -OCO- , -COO-, or -CH = CH- may be substituted.

The content of the chain transfer agent is preferably 0.0 to 10% by mass with respect to 100% by mass of the total amount of the polymerizable compounds used in the polymerizable composition of the polymerizable liquid crystal composition of the present invention. More preferably, it is 0 to 5.0% by mass.
(Dye)
The dye used in the present invention can be used to impart color to or control the color of the polymer-dispersed liquid crystal element of the present invention. The dye is not particularly limited, and known and commonly used dyes can be used as long as they are soluble in liquid crystal or dispersed in the polymer network. Examples of the dye include a dichroic dye and a fluorescent dye. Examples of such pigments include polyazo pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, quinophthalone pigments, cyanine pigments, phthalocyanine pigments, perylene pigments, perinone pigments, squarylium pigments, and the like. The dye is preferably a dye exhibiting liquidity. For example, JP-A-51-2885, JP-A-61-21163, JP-A-62-555, JP-A-63-301850, JP-A-7-48520, JP-A-7- Polyazo dyes shown in JP-A-179858, JP-A-10-279945, JP-A-11-172252, JP-A-2000-239664, JP-A-2012-82400, etc., JP-A-59-20355 Anthraquinone dyes shown in JP-A, JP-A-59-172549, JP-A-61-148291, JP-A-1-161806, JP-A-8-67822, etc., JP-A-59- Examples thereof include quinophthalone dyes shown in JP-A-51946, JP-A-61-148292, and dioxazine dyes shown in JP-A-2000-44825, JP-A-2001-49135, and the like. The content of the dye is preferably 0 to 8% by mass, preferably 0 to 4% by mass, based on 100% by mass of the total amount of the liquid crystal compounds used in the liquid crystal composition for the polymer-dispersed liquid crystal element of the present invention. More preferably.
(Pigment)
The pigment used in the present invention can be used to impart color to or control the color of the polymerizable liquid crystal device of the present invention. The dye is not particularly limited, and a liquid crystal or a known and commonly used dye can be used as long as it is dispersed in the network polymer. Examples of such pigments include azo pigments, diketopyrrolopyrrole pigments, quinacridone pigments, dioxazine pigments, perylene pigments, phthalocyanine pigments, carbon black pigments, etc. The pigment is preferably a pigment having good dispersibility in a network polymer. The content of the pigment is preferably 0 to 8% by mass, more preferably 0 to 4% by mass, based on 100% by mass of the total amount of the liquid crystal compounds used in the polymerizable liquid crystal composition of the present invention. ..
(Particles with a particle size of less than 1 μm)
The particles having a particle size of less than 1 μm used in the present invention can be used to impart various functions to the polymer-dispersed liquid crystal device of the present invention. Such particles are not particularly limited, but can be used as long as the electro-optical characteristics and adhesion of the liquid crystal element are not impaired. Such particles include inorganic fillers such as alumina, titanium white, titanium black, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide and glass fiber, metal powders such as silver powder and copper powder, and nitrided materials. Heat of aluminum, boron nitride, silicon nitride, gallium nitride, silicon carbide, magnesia (aluminum oxide), silica, crystalline silica (silicon oxide), molten silica (silicon oxide), graphite, carbon fiber containing carbon nanofibers, etc. Examples thereof include conductive fillers, silver nanoparticles, QD illuminant particles, perovskite type illuminant particles and the like.
The pigment is preferably a pigment having good dispersibility in a network polymer. The content of the pigment is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, based on 100% by mass of the total amount of the liquid crystal compounds used in the polymerizable liquid crystal composition of the present invention. ..
(Chiral compound)
The chiral compound used in the present invention can be used to impart various functions to the polymer-dispersed liquid crystal device of the present invention. Such a chiral compound is not particularly limited, but can be used as long as the electro-optical characteristics and adhesion of the liquid crystal element are not impaired. Specifically, for example, cholesterol pelargonate having a cholesteryl group as a chiral group, cholesterol stearate, and "CB-15", "C-15", Merck manufactured by BDH having a 2-methylbutyl group as a chiral group. "S-1082" manufactured by Chisso, "CM-19", "CM-20", "CM" manufactured by Chisso, "S-811" manufactured by Merck having a 1-methylheptyl group as a chiral group, Chisso. "CM-21" and "CM-22" manufactured by the same company, "LC756" of BASF company having an isosorbide skeleton as a chiral group, JP-A-2009-515818A, JP-A-2010-90108, JP-A-2013-87109 Examples thereof include polymerizable chiral compounds shown in Japanese Patent Publication No.

When a chiral compound is contained, it depends on the use of the polymer of the polymerizable liquid crystal composition of the present invention, but the value (d) obtained by dividing the thickness (d) of the obtained polymer by the spiral pitch (P) in the polymer. It is preferable to add an amount in which / P) is in the range of 0.1 to 100, and an amount in the range of 0.1 to 20 is more preferable.
The content of the chiral compound is preferably as small as possible to obtain a desired spiral pitch in order to bring out the characteristics of the liquid crystal composition. The content of the chiral compound is preferably 0 to 8% by mass, more preferably 0 to 4% by mass, based on 100% by mass of the total amount of the liquid crystal compounds used in the polymerizable liquid crystal composition of the present invention. preferable.
(Orientation material)
The polymerizable liquid crystal composition of the present invention can contain an alignment material in order to control the orientation of the liquid crystal element. As the orientation material used in the present invention, a known and commonly used material is used as long as it dissolves in the liquid crystal composition. Examples of such an orientation material include a polymerizable compound having a polar group at one end of the mesogen skeleton and a long-chain alkyl group at the other end, and a polymerizable liquid crystal compound having a polar group at the lateral position of the mesogen skeleton. Examples thereof include a polymerizable compound having a plurality of mesogen skeletons and having a polar group on the side chain of a long-chain alkyl group that binds one mesogen skeleton to the mesogen skeleton.
<Polymer dispersion type liquid crystal element>
The polymer-dispersed liquid crystal element using the polymerizable liquid crystal composition of the present invention includes at least a layer (phase-separated liquid crystal layer) in which the liquid crystal and the network polymer are phase-separated, an electrode, and a base material. Alternatively, it includes a phase-separated liquid crystal layer, an alignment film phase, an electrode, and a substrate that supports the phase-separated liquid crystal layer, the alignment film phase, and the electrode.

The phase-separated liquid crystal phase is obtained by polymerizing a polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition to form a polymer network derived from the first component, the second component, and the third component. Be done.

The specific embodiment of the liquid crystal element of the present invention is not particularly limited as long as it includes the above elements, but for example, two base materials having electrodes on at least one of them and a vertically oriented film. The phase-separated liquid crystal layer may be sandwiched in the hollow element composed of.

For example, when no voltage is applied, the liquid crystal element of the present invention can be brought into a light scattering state by a network structure made of a polymer and liquid crystal molecules existing in the voids thereof. On the other hand, when a voltage is applied, the liquid crystal molecules can be made transparent by distributing light perpendicularly to the substrate. As described above, since the vertical electric field type liquid crystal element of the present invention can change the light transmission state depending on the presence or absence of voltage application, it can be used in a liquid crystal dimming element used by incorporating it in a device requiring a dimming function or a display for displaying an image. It can be used as a liquid crystal display element to be used.

The 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 it is preferably configured as a vertical electric field type liquid crystal element. The 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 alignment film. In a vertical electric field type liquid crystal element, electrodes are usually provided on both of two transparent substrates sandwiching a phase-separated liquid crystal layer.

The configuration of the vertical electric field type liquid crystal element according to the present invention includes a first substrate and a second substrate provided with transparent electrodes (layers) made of a transparent conductive material, and the first substrate and the second substrate, respectively. It has a phase-separated liquid crystal layer sandwiched between the two. The phase-separated liquid crystal layer is composed of a polymer-dispersed liquid crystal material composed of liquid crystal molecules and polymer components contained in the liquid crystal composition.
(substrate)
The substrate used for the liquid crystal element of the present invention is a substrate usually used for a liquid crystal display element, an organic light emitting display element, other display elements, optical components, a dimming element, a colorant, marking, a printed matter or an optical film, and is described above. There is no particular limitation as long as it is a material having transparency that can withstand practical use in applications where heat resistance that can withstand heating in the manufacturing process of a liquid crystal element and the temperature range in which it is used, or transparency is important.
Examples of such a substrate include a glass base material, a metal base material, a ceramic base material, a plastic base material, and an organic material such as paper. In particular, when the base material is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfone, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons and polystyrenes. Above all, it is preferable to use a plastic base material such as polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate, and polyimide.

When having two substrates, one substrate may or may not have transparency that is practical as a liquid crystal element, and the other substrate may or may not have transparency.

As the shape of the substrate, the shape of a flat plate is shown, but other shapes such as those having a curved surface may be used. Further, the substrate may have an electrode layer, an antireflection function, and a reflection function, if necessary.

In order to improve the adhesion of the liquid crystal element of the present invention, the surface treatment of these substrates may be performed. 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 and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the base material by a method such as thin film deposition, or in order to add optical value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusing film, a microlens sheet, a color filter, or the like.
(Electrode: transparent electrode layer)
The electrodes used in the liquid crystal element of the present invention are provided in the liquid crystal element so as to generate an electric field capable of controlling the orientation of the liquid crystal molecules in the phase-separated liquid crystal layer. The electric field strength is controlled by the degree of voltage application to the electrodes.

The shape of the electrode is not particularly limited, and the conductive portion may have a striped shape, a mesh shape, or a random mesh shape.

Such an electrode material is preferably composed of a metal material, and specifically, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or at least one of these is used. Examples thereof include alloys containing Al, and alloys containing Al or Al are preferable.

In order to increase the transparency of the liquid crystal element, it is preferable that the electrode is composed of the transparent electrode layer 2 as shown in FIG. Such a transparent electrode layer can be made of a known transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and IZTO (Indium Zinc Tin Oxide). When one of the substrates is made of a non-transparent material, the electrodes provided on the non-transparent substrate do not need to have transparency, and are appropriately selected from known metal materials. can do.
(Vertical alignment film layer)
The substrate may be oriented so that the liquid crystal molecules in the polymer-dispersed liquid crystal element of the present invention are horizontally or vertically aligned, or may be provided with an alignment film. .. Examples of the orientation treatment include stretching treatment, rubbing treatment, polarized ultraviolet-visible light irradiation treatment, ion beam treatment, oblique vapor deposition treatment _{of SiO 2 on a substrate, and the like.} Examples of such an alignment film include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, and coumarin. Examples thereof include compounds such as compounds, chalcone compounds, cinnamate compounds, flugide compounds, anthraquinone compounds, azo compounds and arylethane compounds, and polymers and copolymers of the above compounds. When a rubbing treatment is performed to impart a tilt angle to the liquid crystal molecules, the compound to be oriented by rubbing is a compound in which crystallization of the material is promoted by an alignment treatment or a heating step after the orientation treatment. preferable. Among the compounds to be subjected to an orientation treatment other than rubbing, it is preferable to use a photoalignment material.

Generally, when the liquid crystal composition is brought into contact with a substrate having an alignment function, the liquid crystal molecules are oriented in the vicinity of the substrate along the direction in which the substrate is oriented. Whether the liquid crystal molecules are oriented horizontally, inclined or perpendicular to the substrate is greatly influenced by the orientation treatment method for the substrate.
(Example of manufacturing method of liquid crystal element)
From the viewpoint of productivity, the liquid crystal element of the present invention is, for example, a hollow element having a shape such that a space is provided between the substrates, that is, a polymerizable liquid crystal element in which a polymerizable liquid crystal composition is sandwiched in a so-called empty cell. It is preferable to produce it.

The method of narrowing the liquid crystal composition for a polymer-dispersed liquid crystal element in the hollow element may be a conventional method, and a vacuum injection method, an ODF method, a roll-to-roll method, a roll-to-sheet method, or the like can be used. In the liquid crystal element manufacturing process of the ODF method, a sealant having an epoxy-based photothermal combination curability is drawn on either the backplane or the frontplane of the hollow element in a closed-loop bank shape using a dispenser. The liquid crystal element can be manufactured by dropping a predetermined amount of the liquid crystal composition into the liquid crystal composition and then joining the front plane and the back plane. The liquid crystal composition for a polymer-dispersed liquid crystal element used in the present invention has high phase stability and is hard to volatilize, so that it can be suitably used in the ODF step.

Further, in the process of manufacturing the liquid crystal composition by the roll-to-roll method, the polymer-dispersed liquid crystal element is placed on a first electrode, a glass base material having an alignment film and a first electrode, or a plastic base material. The liquid crystal composition is applied, and the liquid crystal composition comes into contact with the second electrode, the glass base material having the alignment film and the second electrode, or the electrode side of the plastic base material, or the alignment film side. The liquid crystal element can also be manufactured by laminating and making the thickness uniform. Examples of the method for applying the liquid crystal composition for a polymer-dispersed liquid crystal element used in the present invention include an applicator method, a bar coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, an inkjet method, and a die coating method. A known and commonly used method such as a cap coating method can be used.

The polymerizable liquid crystal composition of the present invention may be sandwiched between hollow elements as a composition in which particles for determining the thickness of the liquid crystal element are mixed. As such particles, known and commonly used glass particles and polymer particles used in general liquid crystal display elements and liquid crystal displays are used.

In that case, the polymerizable liquid crystal composition and the composition containing the particles that determine the thickness of the liquid crystal element are applied onto a plastic base material containing the first electrode, and then the plastic containing the second electrode. A method of irradiating ultraviolet rays immediately after the base materials are bonded so that the first electrode and the second electrode face each other, and pressure is applied to the first plastic base material and the second plastic base material. A method of irradiating ultraviolet rays in a sprinkled state, or a composition containing the liquid crystal composition for a liquid crystal element and particles for determining the thickness of the liquid crystal element on a first plastic base material containing a first electrode. The first plastic base material and the applied liquid crystal composition are put into a vacuum state, and the second plastic base material containing the second electrode is placed on the first electrode and the second electrode. A method of irradiating ultraviolet rays in a vacuum state in which the electrodes of the above are bonded so as to face each other is preferable.
(Polymerization method)
Examples of the method for polymerizing the polymerizable liquid crystal composition of the present invention include a method of irradiating an active energy ray and a thermal polymerization method. It is appropriately selected according to the application of the obtained polymer-dispersed liquid crystal element.

When irradiating light such as ultraviolet rays, the temperature at the time of irradiation is preferably a temperature at which the liquid crystal composition of the present invention can hold the liquid crystal phase. In the case of heating, the temperature at which the liquid crystal composition of the present invention can hold the liquid crystal phase is high until the polymerizable compound component in the liquid crystal composition sufficiently polymerizes to form a phase-separated structure with the liquid crystal composition component. Preferably, after the phase-separated structure is formed, the temperature may not be high enough to hold the liquid crystal phase.

The crystal element of the present invention can be used as it is or can be used by being bonded to another base material. Further, an adhesive or an adhesive layer, an adhesive or an adhesive layer, a protective film, a polarizing film or the like may be laminated.
(Other electric field types)
In addition to the vertical electric field type, a horizontal electric field type or another electric field type may be adopted for the liquid crystal element of the present invention. The fringe electric field adopted in the FFS drive mode may be adopted. In this case, a horizontally oriented layer may be provided instead of the vertically oriented layer. The horizontally oriented layer can be made of a known material.

The liquid crystal element of the present invention is preferably used for, for example, a building material, a dimming glass, a dimming unit in a smart window for an automobile, an OLED display, or the like. The liquid crystal display element of the present invention can be used for the same purposes as the conventional polymer-dispersed liquid crystal display element, and can be particularly preferably used for a transmissive display, a flexible display, and the like. More specifically, architectural dimming elements such as windows, skylights, roofs, walls, partitions, partitions, doors, transport dimming elements such as doors, windows, doors, helmets, sun roofs, sunglasses, glasses, sun visors. It can be used for articles such as decorative dimming elements such as clocks, 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 with reference to Examples below, 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".
(Synthesis Example 1)
Put 44.4 parts (0.2 mol) of IPDI (isophorone diisocyanate) in a flask with a stirring blade, and be careful of heat generation of 810 parts (0.1 mol) of polypropylene glycol (average molecular weight Mw: 8100) while stirring. The temperature was raised to 70 ° C. The reaction was carried out at this temperature for 7 hours to obtain a urethane polymer having an isocyanate group at the terminal. Next, 23.2 parts (0.2 mol) of 2-hydroxyethyl acrylate (molecular weight 116) was charged, and the reaction was carried out at this temperature for another 7 hours. After confirming that the absorption of NCO had disappeared from the infrared absorption spectrum, the mixture was taken out to obtain urethane acrylate UA-1 (average molecular weight Mw: 29800).
(Example 1)
As the first component, 14.0 parts by weight of UA-1 produced in Synthesis Example 1, 10.0 parts by weight of isostearyl acrylate S-1800A (manufactured by Shin-Nakamura Chemical Co., Ltd.) as the second component, and as the third component. 16.0 parts by weight of acryloylmorpholin ACMO (registered trademark) (KJ Chemicals Co., Ltd.) and 10.0 parts by weight of (5-ethyl-1,3-dioxane-5-yl) methyl acrylate as the third component are mixed. , Stirred at 50 ° C. and dissolved to obtain a polymerizable composition 1.

To the obtained polymerizable composition 1, 50 parts by weight of the liquid crystal composition 1 (Tni: 90.8 ° C., Δε: 12.7, Δn0.202) having positive refractive index anisotropy was added, and the mixture was stirred at 50 ° C. Then, 0.25 parts by weight of Omnirad 651 (manufactured by IGM Resins Co., Ltd.) was further added as a polymerization initiator to obtain a composition 1 for a liquid crystal polymer composite.
The liquid crystal composition 1 contains 10 parts by weight of 4'-ethylbiphenyl-4-carbonitrile, 13 parts by weight of 4'-butylbiphenyl-4-carbonitrile, and 4'-pentylbiphenyl-4-carbonitrile. 35 parts by weight, 2'-fluoro-4 "-propyl- [1,1';4',1"-] 10 parts by weight of terphenyl-4-carbonitrile, 2,6-difluoro-4- (trans-) 4-propylcyclohexyl) 2 parts by weight of benzonitrile, 4 parts by weight of trans, trans-4'-(3,4-difluorophenyl) -4-propylbicyclohexyl, trans, trans-4'-propylbicyclohexyl-4 -Carboxylic acid = 4- (trans-4-propylcyclohexyl) phenyl by 4 parts by weight, trans, trans-4'-propylbicyclohexyl-4-carboxylic acid = 4- (trans-4-butylcyclohexyl) phenyl by 4 parts by weight , Trans, trans-4- (4-methylphenyl) -4'-propylbicyclohexyl, 4 parts by weight, trans, trans-4'-propyl-4- (4-propylphenyl) bicyclohexyl, 4 parts by weight, It was obtained by heating and mixing 5 parts by weight of 4'-ethyl-4- (trans-4-propylcyclohexyl) biphenyl and 5 parts by weight of 4'-ethyl-4- (trans-4-pentylcyclohexyl) biphenyl.
The obtained composition 1 for a liquid crystal polymer composite is injected into a glass cell having a thickness of 15 μm (composition is a glass base material / transparent electrode layer / air layer / transparent electrode layer / glass base material) at room temperature, and then the composition is injected. A liquid crystal polymer composite was obtained by irradiating with ultraviolet rays at room temperature. The conditions of ultraviolet rays at this time were that the light source was a high-pressure mercury lamp, the intensity was 20 mW / cm ² , and the time was 60 seconds.
(Haze evaluation)
Electrode wiring was attached to the obtained liquid crystal polymer composite element, and the voltage-transmission characteristic was evaluated using a haze meter (NDH-7000 manufactured by Nippon Denshoku Industries Co., Ltd.). The haze when no voltage was applied was 94.1%, and the haze when AC20V was applied was 1.5%.
(Adhesion evaluation)
The adhesion was evaluated by the following method. First, glass beads having a particle size of 15 μm were sprayed on the transparent electrode surface of a PET film with a protective film and a transparent electrode, and the composition was dropped onto the transparent electrode surface and applied with an applicator. After that, the transparent electrode surface of the PET film on the coated surface and the coated surface are bonded so as to be in contact with each other, and the film laminate in which pressure is uniformly applied to the entire surfaces of the upper and lower PET films is irradiated with ultraviolet rays at room temperature to form a liquid crystal. A polymer composite was obtained. The obtained liquid crystal polymer complex element was cut out with a cutter so as to have a width of 1 cm. At this time, there was no exudation of the liquid crystal. A 180 ° peeling test was performed using the cut out liquid crystal polymer complex element. For the adhesion evaluation, a tensile tester Tencilon RTG-1210 manufactured by A & D Co., Ltd. was used, and one side sandwiched between PET films with ITO was 180 ° in a sample width of 25 mm, a tensile speed of 300 mm / min, and an atmosphere of 23 ° C. The average strength when peeled in the direction was calculated. The intensity was 1.1 N / cm.
(Example 2)
As the first component, 14.0 parts by weight of UA-1 used in Example 1, 10.0 parts by weight of S-1800A as the second component, and light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.) as the second component. ) Is 0.05 parts by weight, ACMO (registered trademark) is 17.5 parts by weight as the third component, and (5-ethyl1,3-dioxane-5-yl) methyl acrylate is 8.5 parts by weight as the third component. The mixture was mixed and dissolved with stirring at 50 ° C. to obtain a polymerizable composition 2.

50 parts by weight of the liquid crystal composition 1 used in Example 1 was added to the obtained polymerizable composition 2 and dissolved while stirring at 50 ° C., and further, Kinopower (registered trademark) QS-20 (Kawasaki Kasei) was added as an additive. (Manufactured by Kogyo Co., Ltd.) 0.1 parts by weight and 0.25 parts by weight of Omnirad 651 as a polymerization initiator were added to obtain a composition 2 for a liquid crystal polymer composite.
Using the obtained composition for liquid crystal polymer complex 2, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 3)
In Example 2, the same as in Example 2 except that polypropylene glycol-based urethane acrylate oligomer Shikou UV-3700B (manufactured by Mitsubishi Chemical Corporation, Mw: 36700) was used as the first component instead of UA-1. , A composition 3 for a liquid crystal polymer complex was obtained.
Using the obtained composition for liquid crystal polymer complex 3, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 4)
In Example 2, the liquid crystal polymer composite was obtained in the same manner as in Example 2 except that polypropylene glycol-based urethane acrylate oligomer CN9023 (manufactured by SARTOMER, Mw: 13500) was used as the first component instead of UA-1. Composition 4 was obtained.
Using the obtained composition for liquid crystal polymer complex 4, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 5)
In Example 2, the same as in Example 2 except that polyester urethane acrylate oligomer art resin UN-7700 (manufactured by Negami Kogyo Co., Ltd., Mw: 17700) was used as the first component instead of UA-1. A liquid crystal polymer composite composition 5 was obtained.
Using the obtained composition 5 for a liquid crystal polymer complex, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 6)
As the first component, 14.0 parts by weight of UA-1 used in Example 1, 5.0 parts by weight of S-1800A as the second component, and 2-ethylhexyl acrylate (manufactured by Tokyo Kasei Co., Ltd.) as the second component. 5.0 parts by weight, 0.05 parts by weight of light ester P-2M as the second component, 16.0 parts by weight of ACMO (registered trademark) as the third component, and (5-ethyl 1,3) as the third component. 10.0 parts by weight of −dioxane-5-yl) methyl acrylate was mixed and dissolved with stirring at 50 ° C. to obtain a polymerizable composition 6.

50 parts by weight of the liquid crystal composition 1 used in Example 1 was added to the obtained polymerizable composition 6 and dissolved while stirring at 50 ° C., and 0.25 parts by weight of Omnirad 651 as a polymerization initiator was further added to the liquid crystal. The composition 6 for a polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex 6, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 7)
In Example 6, the composition for the liquid crystal polymer complex was the same as in Example 6 except that lauryl acrylate light acrylate LA (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of 2-ethylhexyl acrylate as the second component. I got the thing 7.
Using the obtained composition 7 for a liquid crystal polymer complex, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 8)
In Example 6, 5.0 parts by weight of S-1800A as the second component and 7.0 parts by weight of S-1800A (manufactured by Shin-Nakamura Chemical Co., Ltd.) instead of 5.0 parts by weight of 2-ethylhexyl acrylate as the second component. , Hydropylate Neopentyl glycol Acrylic Acid Adduct Light Acrylate HPP-A (manufactured by Kyoeisha Chemical Co., Ltd.) 3.0 parts by weight was used, and the composition 8 for the liquid crystal polymer composite was prepared in the same manner as in Example 6. Obtained.
Using the obtained composition 8 for a liquid crystal polymer complex, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 9)
In Example 8, a composition 9 for a liquid crystal polymer complex was obtained in the same manner as in Example 8 except that trimethylolpropane triacrylate TMPTA (manufactured by Daicel Ornex Co., Ltd.) was used instead of light acrylate HPP-A. It was.
Using the obtained composition 9 for a liquid crystal polymer complex, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 10)
As the first component, 14.0 parts by weight of UA-1 used in Example 1, 10.0 parts by weight of S-1800A as the second component, and 0.05 parts by weight of light ester P-2M as the second component. OXE-10 (Osaka Organic Chemical Industry Co., Ltd.), which is 17.5 parts by weight of ACMO (registered trademark) (KJ Chemicals Co., Ltd.) as the third component and (3-ethyloxetane-3-yl) methyl acrylate as the third component. 8.5 parts by weight (manufactured by the company) was mixed and dissolved with stirring at 50 ° C. to obtain a polymerizable composition 10.

50 parts by weight of the liquid crystal composition 1 used in Example 1 was added to the obtained polymerizable composition 10 and dissolved while stirring at 50 ° C., and 0.25 parts by weight of Omnirad 651 as a polymerization initiator was further added to the liquid crystal. The composition 10 for a polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex 10, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 11)
In Example 10, except that (2-methyl-2-ethyl-1,3-dioxolane-4-yl) methyl acrylate MODEL-10 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of OXE-10. The composition 11 for the liquid crystal polymer composite was obtained in the same manner as in Example 10.
Using the obtained composition for liquid crystal polymer complex 11, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 12)
As the first component, 18.0 parts by weight of UA-1, 10.0 parts by weight of S-1800A as the second component, 0.05 parts by weight of light ester P-2M as the second component, and ACMO as the third component. 14.0 parts by weight of (Registered Trademark) (KJ Chemicals Co., Ltd.) and 8.0 parts by weight of (5-ethyl-1,3-dioxane-5-yl) methyl acrylate as the third component were mixed and at 50 ° C. The mixture was dissolved with stirring to obtain a polymerizable composition 12.
50 parts by weight of the liquid crystal composition 2 (Tni: 67.0 ° C., Δε: 17.2, Δn: 0.219) was added to the obtained polymerizable composition 12 and dissolved with stirring at 50 ° C., and further. 0.25 parts by weight of Omnirad 651 was added as a polymerization initiator to obtain a composition 12 for a liquid crystal polymer composite.
The liquid crystal composition 2 contains 10 parts by weight of 4'-ethylbiphenyl-4-carbonitrile and 15 parts by weight of 4'-butylbiphenyl-4-carbonitrile and 4'-pentylbiphenyl-4-carbonitrile. 35 parts by weight of 2'-fluoro-4 "-propyl- [1,1';4',1"-] terphenyl-4-carbonitrile 23 parts by weight, 4- (trans-4-propylcyclohexyl) benzo Acid = 2 parts by weight of 4-cyano-3-fluorophenyl, 10 parts by weight of 2,6-difluoro-4- (trans-4-propylcyclohexyl) benzonitrile, trans, trans-4'-propylbicyclohexyl-4 − Carous acid = 2 parts by weight of 4- (trans-4-propylcyclohexyl) phenyl, trans, trans-4'-propylbicyclohexyl-4-carboxylic acid = 2 parts by weight of 4- (trans-4-butylcyclohexyl) phenyl Was obtained by heating and mixing.
Using the obtained composition for liquid crystal polymer complex 12, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 13)
As the first component, 12.0 parts by weight of UA-1, 10.0 parts by weight of S-1800A as the second component, 0.05 parts by weight of light ester P-2M as the second component, and ACMO as the third component. 20.0 parts by weight of (registered trademark) and 8.0 parts by weight of OXE-10 as a third component were mixed and dissolved with stirring at 50 ° C. to obtain a polymerizable composition 13.
50 parts by weight of the liquid crystal composition 1 is added to the obtained polymerizable composition 12, and the liquid crystal composition 1 is dissolved while stirring at 50 ° C., and further, 0.5 part by weight of Omnirad 651 as a polymerization initiator is added to the composition for the liquid crystal polymer composite. I got the thing 13.
Using the obtained composition for liquid crystal polymer complex 13, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 14)
As the first component, 17.5 parts by weight of UA-1 used in Example 1, 1.5 parts by weight of S-1800A as the second component, and 8.0 parts by weight of ACMO (registered trademark) as the third component. Methyl acrylate (5-ethyl 1,3-dioxane-5-yl) as the third component was mixed with 8.0 parts by weight and dissolved with stirring at 50 ° C. to obtain a polymerizable composition 14.

65 parts by weight of the liquid crystal composition 2 used in Example 12 was added to the obtained polymerizable composition 14, and the liquid crystal composition 2 was dissolved while stirring at 50 ° C., and further, 0.5 part by weight of Omnirad 651 as a polymerization initiator was added to the liquid crystal. The composition 14 for a polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex 14, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 15)
As the first component, 20.0 parts by weight of UA-1 used in Example 1, 11.0 parts by weight of S-1800A as the second component, and 0.1 parts by weight of light ester P-2M as the second component. , 23.0 parts by weight of ACMO® as the third component and 11.0 parts by weight of (5-ethyl1,3-dioxane-5-yl) methyl acrylate as the third component were mixed at 50 ° C. It was dissolved with stirring to obtain a polymerizable composition 15.

35 parts by weight of the liquid crystal composition 3 (Tni: 114.6 ° C., Δε: 13.2, Δn: 0.205) was added to the obtained polymerizable composition 15 and dissolved with stirring at 50 ° C., and further. 0.4 parts by weight of Omnirad 651 was added as a polymerization initiator to obtain a composition 15 for a liquid crystal polymer composite.

The liquid crystal composition 3 contains 10 parts by weight of 4'-ethylbiphenyl-4-carbonitrile, 30 parts by weight of 4'-pentylbiphenyl-4-carbonitrile, and 2'-fluoro-4 "-propyl-[. 1,1';4', 1 "-] Terphenyl-4-carbonitrile in 16 parts by weight, 2,6-difluoro-4- (trans-4-propylcyclohexyl) benzonitrile in 5 parts by weight, trans, trans 2 parts by weight of -4'-(3,4-difluorophenyl) -4-propylbicyclohexyl, 4'-(trans, trans-4'-ethylbicyclohexyl-4-yl) -3,4-difluorobiphenyl 2 parts by weight, 3,4-difluoro-4'-(trans, trans-4'-propylbicyclohexyl-4-yl) biphenyl by 3 parts by weight, 4'-(trans, trans-4'-butylbicyclohexyl- 4-yl) -3,4-difluorobiphenyl by 2 parts by weight, trans, trans-4'-propylbicyclohexyl-4-carboxylic acid = 4- (trans-4-propylcyclohexyl) phenyl by 3 parts by weight, trans, trans-4'-propylbicyclohexyl-4-carboxylic acid = 3 parts by weight of 4- (trans-4-butylcyclohexyl) phenyl, trans, trans-4- (4-methylphenyl) -4'-propylbicyclohexyl 4 parts by weight, trans, trans-4'-propyl-4- (4-propylphenyl) bicyclohexyl by 4 parts by weight, 4'-ethyl-4- (trans-4-propylcyclohexyl) by 5 parts by weight, 4 parts by weight, 4 parts by weight Obtained by heating and mixing 5 parts by weight of'-ethyl-4- (trans-4-pentylcyclohexyl) biphenyl and 6 parts by weight of trans, trans-4- (4-methylphenyl) -4'-vinylbicyclohexyl. It was.
Using the obtained composition for liquid crystal polymer complex 15, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Example 16)
As the first component, 12.0 parts by weight of UA-1 used in Example 1 was added, and as the first component, an epoxy acrylate in which acrylic acid was added to the solid component of EPICLON 1650-75MPX (manufactured by DIC Co., Ltd.), which is an epoxy resin. 2.0 parts by weight of (Mw: 2600), 10.0 parts by weight of S-1800A as the second component, 17.5 parts by weight of ACMO (registered trademark) as the third component, and (5-ethyl) as the third component. 8.5 parts by weight of 1,3-dioxane-5-yl) methyl acrylate was mixed and dissolved with stirring at 50 ° C. to obtain a polymerizable composition 16.

50 parts by weight of the liquid crystal composition 1 used in Example 1 was added to the obtained polymerizable composition 16 and dissolved while stirring at 50 ° C., and 0.5 part by weight of Omnirad 651 as a polymerization initiator was further added to the liquid crystal. A composition 16 for a polymer composite was obtained.
Using the obtained composition 16 for a liquid crystal polymer complex, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Comparative Example 1)
As the first component, 25.0 parts by weight of UA-1 used in Example 1 and 25.0 parts by weight of S-1800A as the second component were mixed and dissolved at 50 ° C. with stirring to form a polymerizable composition. I got the thing C1.
50.0 parts by weight of the liquid crystal composition 2 used in Example 12 was added to the obtained polymerizable composition C1 and dissolved with stirring at 50 ° C., and 0.5 part by weight of Omnirad 651 was further added as a polymerization initiator. The composition C1 for a liquid crystal polymer composite was obtained. The obtained composition C1 was phase-separated at room temperature, and a liquid crystal polymer composite could not be prepared.
(Comparative Example 2)
As the first component, 15.0 parts by weight of UA-1 used in Example 1, 0.1 parts by weight of light ester P-2M as the second component, and isobonyl acrylate IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.). ) Was mixed by 35 parts by weight and dissolved with stirring at 50 ° C. to obtain a polymerizable composition C2.

50.0 parts by weight of the liquid crystal composition 2 used in Example 12 was added to the obtained polymerizable composition C2 and dissolved with stirring at 50 ° C., and 0.5 part by weight of Omnirad 651 was further added as a polymerization initiator. The composition C2 for a liquid crystal polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex C2, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Comparative Example 3)
As the first component, 15.0 parts by weight of UA-1 used in Example 1, 28.0 parts by weight of ACMO (registered trademark) as the third component, and (5-ethyl 1,3-dioxane) as the third component. -5-Il) Methyl acrylate 7.0 parts by weight was mixed and dissolved with stirring at 50 ° C. to obtain a polymerizable composition C3.

50.0 parts by weight of the liquid crystal composition 1 used in Example 1 was added to the obtained polymerizable composition C3, dissolved with stirring at 50 ° C., and 0.5 parts by weight of Omnirad 651 was further added as a polymerization initiator. The composition C3 for a liquid crystal polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex C3, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Comparative Example 4)
As the first component, 13.5 parts by weight of UA-1 used in Example 1, 28.0 parts by weight of ACMO (registered trademark) as the third component, and 35 parts by weight of IBXA are mixed and stirred at 50 ° C. While dissolving, a polymerizable composition C4 was obtained.

50.0 parts by weight of the liquid crystal composition 1 used in Example 1 was added to the obtained polymerizable composition C4, dissolved with stirring at 50 ° C., and 0.5 parts by weight of Omnirad 651 was further added as a polymerization initiator. The composition C4 for a liquid crystal polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex C4, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Comparative Example 5)
20.0 parts by weight of S-1800A as the second component, 10.0 parts by weight of light acrylate HPP-A as the second component, and 20.0 parts by weight of ACMO (registered trademark) as the third component were mixed at 50 ° C. The mixture was dissolved with stirring to obtain a polymerizable composition C5.

50.0 parts by weight of the liquid crystal composition 1 used in Example 1 was added to the obtained polymerizable composition C5 and dissolved with stirring at 50 ° C., and 0.25 parts by weight of Omnirad 651 was further added as a polymerization initiator. The composition C5 for a liquid crystal polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex C5, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Comparative Example 6)
As the first component, 6.0 parts by weight of UA-1 used in Example 1, 4.0 parts by weight of S-1800A as the second component, and 10.0 parts by weight of ACMO (registered trademark) as the third component. The mixture was mixed and dissolved with stirring at 50 ° C. to obtain a polymerizable composition C6.

80.0 parts by weight of the liquid crystal composition 2 used in Example 12 was added to the obtained polymerizable composition C6 and dissolved with stirring at 50 ° C., and 0.25 parts by weight of Omnirad 651 was further added as a polymerization initiator. The composition C6 for a liquid crystal polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex C6, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.
(Comparative Example 7)
As the first component, 24.0 parts by weight of UA-1 used in Example 1, 16.0 parts by weight of S-1800A as the second component, and 40.0 parts by weight of ACMO (registered trademark) as the third component. The mixture was mixed and dissolved with stirring at 50 ° C. to obtain a polymerizable composition C7.

20.0 parts by weight of the liquid crystal composition 2 used in Example 12 was added to the obtained polymerizable composition C7, dissolved with stirring at 50 ° C., and 0.25 parts by weight of Omnirad 651 was further added as a polymerization initiator. The composition C7 for a liquid crystal polymer composite was obtained.
Using the obtained composition for liquid crystal polymer complex C7, a liquid crystal polymer complex was obtained in the same manner as in Example 1, and haze evaluation and adhesion evaluation were performed.

The results are shown in Tables 1 to 5 below.

Claims (11)

As the first component, one or more polymerizable compounds selected from a polyfunctional (meth) acrylate monomer compound having an average molecular weight of 1000 or more or a polyfunctional (meth) acrylate oligomer compound,
As the second component, the following general formula (ii)

(In the formula, ^Pii1 represents a polymerizable functional group and represents
X ⁱⁱ¹ , X ^{ii 2} , X ^{ii 3} and X ^{ii 4} each independently represent a single bond or an alkylene group having 1 to 22 carbon atoms, and one or more -CH ₂ − in the alkylene group is -O-, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C- or -P (= O) (-OH) so that oxygen atoms are not directly adjacent to each other. It may be substituted with −, and one or more hydrogen atoms present in the alkylene group may be independently substituted with a fluorine atom or −OH.
R ⁱⁱ² , R ⁱⁱ³ and R ⁱⁱ⁴ each independently represent a hydrogen atom, a polymerizable functional group, or an alkyl group having 1 to 22 carbon atoms, and one or more of the alkyl groups are not adjacent to each other-CH. ₂ --is independently -O-, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C- or -P (= O) so that oxygen atoms are not directly adjacent to each other. It may be substituted with −OH) −, and one or more hydrogen atoms in the alkyl group are independently fluorine atoms, −OH, alkyl groups having 1 to 8 carbon atoms or carbon atoms. It may be substituted with 1 to 8 alkyl halide groups. )
One or more polymerizable compounds represented by
As the third component, the following general formula (iii)

(In the formula, ^Piii1 represents a polymerizable functional group and represents
Z ^III1 is a single bond or an alkylene group having 1 to 3 carbon atoms, -CH 2 not one or more adjacent in the alkylene group _- each so that oxygen atoms are not directly adjacent independently It may be substituted with −O−, −CO−, −COO− or −OCO−.
A ⁱⁱⁱ¹ is a general formula (iii-1) to (iii-16).

(Wherein one or more -CH ₂ - are each independently, -O -, - S -, - COO -, - OCO -, - NH -, - NCH 3 -, or -CO- substituted by However, when a total of two or more oxygen atoms and / or sulfur atoms are present in the general formulas (iii-1) to (iii-12), these are -O-O- and -O-. it is not to each other between coupling as S- or -S-S-, and also, one or more _-CH 2 -CH ₂ - may be substituted with -CH = CH- group, and The hydrogen atoms in the general formulas (iii-1) to (iii-12) may be substituted with an alkyl group having 1 to 8 carbon atoms, and one or more of the alkyl groups are not adjacent to each other. CH ₂ − may be independently substituted with −O−, −CO−, −COO− or −OCO− so that oxygen atoms are not directly adjacent to each other, and the black dots in the equation are for ^Ziii1 . Represents a bond.)
One or more non-liquid crystal polymerizable compounds represented by
The fourth component contains one or more non-polymerizable liquid crystal compounds, and the total content of the non-polymerizable liquid crystal compounds is the non-polymerizable liquid crystal compound and the polymerizable compound in the liquid crystal composition. A polymerizable liquid crystal composition having a total content of 30% by mass or more and 70% by mass or less. Claim 1 in which the polymerizable compound selected from the polyfunctional (meth) acrylate monomer compound as the first component or the polyfunctional (meth) acrylate oligomer compound is a urethane-based or polyester-based (meth) acrylate oligomer. The polymerizable liquid crystal composition according to. The general formula (ii), which is the second component, is the following general formula (ii-a).

(In the formula, ^Pia1 represents a polymerizable group and represents
^Ria2 represents a linear or branched alkyl group having 1 to 22 carbon atoms, and one or more -CH ₂ − in the alkyl group are independent so that oxygen atoms are not directly adjacent to each other. It may be substituted with −O−, −CO−, −COO−, −OCO− or −P (= O) (−OH) −, and one or more hydrogens present in the alkyl group. The atoms may be independently substituted with a fluorine atom or −OH. )
Or general formula (ii-b)

^{(Wherein, P ii1, X ii1, X} ii2, X ii3, X ii4, R ii3 and ^{R ii4} the ^P in the general formula ^{(ii) ii1, X ii1,} X ii2, X ii3, X ii4, R ii3 and It has the same meaning as ^Rii4,
Pii2 represents a polymerizable functional group. )
The polymerizable liquid crystal composition according to claim 1 or 2. ^Aiii1 in the general formula (iii), which is the third component, is the general formulas (iii-a1) to (iii-a11).

(In the formula, one or more −CH ₂ − may be independently substituted with −CO−, and the hydrogen atom in the general formulas (iii−a1) to (iii−a11) is a carbon atom. may be substituted by 1-8C alkyl groups, -CH 2 not one or more adjacent in the alkyl group _- each so that oxygen atoms are not directly adjacent independently -O-, It may be substituted with −CO−, −COO− or −OCO−, and the black dots in the equation represent the bond to ^Ziii1.)
The polymerizable liquid crystal composition according to any one of claims 1 to 3. The non-polymerizable liquid crystal compound as the fourth component is the general formula (I).

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, and one or two non-adjacent CH ₂ groups in the alkyl group are replaced with oxygen atoms, -COO- and -OCO-. One or more methylene groups may be replaced by −CH = CH− or −CH≡CH−.
R ² represents a fluorine atom, a chlorine atom, a cyano group, ₃ CF groups, ₃ OCF groups, ₂ OCHF groups, an NCS group, or an alkyl group having 1 to 10 carbon atoms, and is a non-adjacent 1 in the alkyl group. one or two CH ₂ groups represents an oxygen atom, -COO -, - OCO- may be replaced by, or one or more of the methylene groups is -CH = CH-, or -CH≡CH- been replaced by May be
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH _{2- CH 2-,} -CH = CH-, -CF ₂ O-, -OCF _2- , or represents -C≡C-, if Z ² is plurally present, it may be different even in the same,
A ¹ , A ² , and A ³ are independent of each other.
(A) A divalent group having an alicyclic structure having 3 to 8 carbon atoms (one methylene group existing in this group or two or more methylene groups not adjacent to each other is -O- or -S-. And one of the two adjacent methylene groups present in this group may be replaced with -CH = CH-),
(B) A divalent group having an aromatic ring structure having 5 to 14 carbon atoms (one -CH = existing in this group or two or more -CH = not adjacent to each other is a nitrogen atom. May be replaced with)
Represents a group selected from the group consisting of, and the above groups (a) and (b) are independently cyano groups, fluorine atoms, chlorine atoms, alkyl groups having 1 to 4 carbon atoms, or carbon atoms. may be substituted with 1-4 alkoxy group, if a ³ is plurally present, may be different even in the same,
m is 0, 1 or 2. )
The polymerizable liquid crystal composition according to any one of claims 1 to 4. The polymerizable liquid crystal composition according to any one of claims 1 to 5, further comprising a polymerization initiator. Further, according to any one of claims 1 to 6, which contains any one or more selected from a polymerization inhibitor, an antioxidant, a light stabilizer, particles having a particle size of less than 1 μm, a dye, and a pigment. The polymerizable liquid crystal composition according to the above. The polymerizable liquid crystal composition according to any one of claims 1 to 7, which is a liquid crystal composition for a polymer dispersion type. A polymer-dispersed liquid crystal material having a polymer network derived from the first component, the second component, and the third component according to any one of claims 1 to 8. A liquid crystal device using the polymer-dispersed liquid crystal material according to claim 9. A pair of transparent electrode substrates,
A composite layer arranged between the transparent electrode substrates and containing a polymer network derived from the first component, the second component and the third component according to any one of claims 1 to 7 and a liquid crystal compound of the fourth component. And, a dimming element.