JP2006045416A - Light scattering-type liquid crystal device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light scattering-type liquid crystal device which has a substantially reduced optical hysteresis, especially has a small HS50 in a halftone zone. <P>SOLUTION: The light scattering type liquid crystal device having a dimming layer obtained by polymerizing a dimming layer-forming material containing a side chain radically polymerizable composition and a liquid crystal composition, is characterized in that the above side chain radically polymerizable composition satisfies simultaneously the following formulae: Δα=αmax-αmin≥5, α=N<SB>R1R2</SB>-ä(N<SB>R1</SB>-1)+(N<SB>R2</SB>-1)}/2, -3.16≤Σ(αi×βi)≤2, wherein, Δα is a difference between the maximal α and minimal α among a plurality of αs which are conducted from the radically polymerizable compounds; N<SB>R1R2</SB>is a distance between the adjacent side chains each other formed at the time of polymerizing the radically polymerizable compound; N<SB>R1</SB>and N<SB>R2</SB>are each a side chain length; and Σ(αi×βi) is a theoretical value of the sum of expected values for all αi's, in which a probability of occurrence βi is multiplied by such αi for a plurality of αi as is obtained when the reactivities among the radically polymerizable compounds are assumed to be the same. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a light scattering liquid crystal device, and more particularly to a polymer dispersed liquid crystal display device in which liquid crystal is dispersed in a polymer compound. This polymer-dispersed liquid crystal display device includes a polymer-dispersed liquid crystal in a narrow sense in which liquid crystal droplets are dispersed in a continuous phase of the polymer matrix, and a liquid crystal continuously in the network of the polymer matrix formed in a three-dimensional network. Both of the polymer network type liquid crystal dispersed in are included.

With the development of the information society, the demand for information and communication materials is increasing. In particular, light-scattering liquid crystal devices do not require polarizing plates and have little viewing angle dependency, so advertising boards, decorative display boards, watches, computers, projections, digital paper, portable information terminals, optical shutters, It is highly expected as a liquid crystal display element or an optical element.
As the light scattering type liquid crystal device, the light control layer forming material comprising the polymerizable composition and the liquid crystal composition is irradiated with light or heated to polymerize in a state where the polymerizable composition and the liquid crystal composition are phase-separated. A polymer dispersed liquid crystal display device having a light control layer comprising a polymer matrix and a liquid crystal composition obtained by curing the composition is known.

The conventional polymer dispersion type liquid crystal display device has a problem that the optical hysteresis is large.
Optical hysteresis is a phenomenon in which the transmittance does not follow the same trajectory in the voltage increasing process and voltage decreasing process at the same applied voltage in the relationship between the applied voltage and the light transmittance (applied voltage-light transmittance curve). is there. A device having a large optical hysteresis causes a problem such as that gradation display cannot be performed correctly or display burn-in occurs. In particular, an optical hysteresis HS50 (unit: mV) defined as a difference between a voltage that gives a transmittance with a transmittance change of 50% when the applied voltage is increased and a voltage that gives a transmittance with a transmittance change of 50% when the applied voltage is lowered (unit: mV). Since this has a strong influence on halftone gradation display performance, this reduction has been a major issue. Here, when the transmittance (%) at the transmittance change of 50% is expressed as T50 (%), T50 (%) is expressed by the formula (a).

(T100 represents the transmittance (%) when a voltage is applied until the transmittance does not change any more with respect to the light scattering type liquid crystal device, and T0 represents the transmittance (%) when no voltage is applied.)
Furthermore, HS50 (mV) is expressed by the mathematical formula (b).

(In the above formulas (a) and (b), Vr50 (mV) represents an applied voltage at which T50 (%) is obtained when the applied voltage to the light scattering liquid crystal device is increased from no application, and Vd50 (mV ) Represents an applied voltage at which T50 (%) is obtained when the applied voltage to the light scattering liquid crystal device is lowered from V100 (mV), where V100 (mV) represents the applied voltage at T100 (%).

  In general, the optical hysteresis of a light-scattering liquid crystal device is such that the cell gap of the light-scattering liquid crystal device is the same if the polymerizable composition used and the liquid crystal composition and the network size or liquid crystal droplet diameter of the polymer network to be formed are the same. Is proportional to the size of For this reason, the simplest means for reducing optical hysteresis is to reduce the cell gap of the light-scattering liquid crystal device. However, when the cell gap of the light scattering type liquid crystal device is reduced, the scattering intensity is lowered and good optical characteristics cannot be obtained.

As a measure for reducing the optical hysteresis, a method has been proposed in which the average liquid crystal droplet diameter in the light control layer is 15 μm or more (see, for example, Patent Document 1). However, this method cannot be carried out when the cell gap of the light scattering type liquid crystal device is 15 μm or less. In addition, this method cannot be applied to polymer network type liquid crystal having no clear liquid crystal droplets. Further, when the liquid crystal droplet diameter is increased in this way, the interface between the polymer matrix and the liquid crystal droplets is reduced, so that it is impossible to avoid a decrease in scattering intensity and a decrease in response speed.
In addition, proposals have been made to adjust the steepness of the electro-optical characteristics by changing the liquid crystal droplet diameter in the polymer matrix between the substrate interface and the inside of the polymer matrix, thereby reducing both the optical hysteresis and the driving voltage. (For example, patent document 2). This method accepts the existence of optical hysteresis in each liquid crystal droplet. By applying liquid crystal droplets with different applied voltage-transmittance change behavior and making the steepness within the optimum range, This is intended to reduce hysteresis. However, since this method cannot reduce the optical hysteresis in units of liquid crystal droplets, the reduction effect is not sufficient.

In addition, a proposal has been made that the alignment state of liquid crystal molecules to be used is bipolar alignment. In such a proposal, a molecule having a polar group at a lateral position with respect to the molecular long axis is used as a component of the liquid crystal composition (for example, Patent Document 3), or the polymerizable composition and the liquid crystal composition are phase-separated. In this case, the polymerizable composition is UV-cured, that is, the intensity of UV irradiation when forming the light control layer is controlled, and the liquid crystal droplets located in the region excluding the vicinity of the interface between the substrate and the polymer dispersed liquid crystal are almost the same. As the shape and size, a measure is taken such that the alignment form of the liquid crystal molecules in the liquid crystal droplet when no voltage is applied is a bipolar type (for example, Patent Document 4).
However, as in Patent Document 3, when a liquid crystal molecule having a polar group at a lateral position with respect to the molecular long axis direction is contained in the liquid crystal composition, there is a problem that the driving voltage increases. In order to solve this problem, if the cell gap of the device is reduced or the liquid crystal droplet diameter is increased, the scattering intensity is lowered. In Patent Document 4, the ultraviolet irradiation intensity is very strong, and there is a problem that liquid crystal molecules are deteriorated by the ultraviolet rays.
Furthermore, these proposals aim to obtain a bipolar alignment state in which liquid crystal molecules are horizontally aligned in the liquid crystal droplets, but even if the bipolar alignment state is obtained, there are many cases where the optical hysteresis is still not resolved. It was difficult to say that it has become possible to effectively reduce this.

JP-A-11-344663 JP 2000-137213 A Japanese Patent Laid-Open No. 10-195445 JP-A-10-232387

  An object of the present invention is to provide a light-scattering liquid crystal device in which the optical hysteresis per unit cell gap is essentially reduced, that is, a light scattering type liquid crystal device having a low HS50 in a halftone region important for gradation display. is there. (Hereinafter, the optical hysteresis per unit cell gap is simply abbreviated as optical hysteresis. HS50 (mV) per unit cell gap (μm) is abbreviated as HS50 / d (mV / μm).)

In order to solve the above-mentioned problems, the present inventors have intensively studied the cause of the occurrence of optical hysteresis.
In a polymer dispersion type liquid crystal display device in which liquid crystal is dispersed in a polymer compound, light scattering in each state of no voltage application state- (voltage application process) -application state- (voltage drop process) -no application state Display by strength. Explaining these states and processes:
1) No-voltage application state In the no-voltage application state, liquid crystal molecules are averagely oriented in all directions by interaction with the main chain or side chain of the polymer that is oriented in any direction on the average. , So-called random orientation. For this reason, it will be in a light-scattering state.
2) Voltage application process When a voltage is applied in the state where no voltage is applied, the liquid crystal molecules attempt to align in the direction of the electric field by shaking off the interaction with the main chain or side chain of the polymer.
At this time, if the liquid crystal-polymer interaction is strong, the voltage-light transmittance curve shifts to the high voltage side.
3) Voltage drop process When the electric field strength is weakened or no application is applied to the liquid crystal molecules arranged in the electric field direction by an electric field, the liquid crystal molecules attempt to return to an energy stabilized state due to the interaction between the liquid crystal and the polymer.
At this time, if the liquid crystal-polymer interaction is strong, the return to the stabilized state is promoted, and the voltage-light transmittance curve is shifted to the high voltage side.
On the other hand, when this interaction is weak, the return to the stabilized state is delayed, and the voltage-light transmittance curve is shifted to the low voltage side.

Thus, it can be seen that the voltage-transmittance curve shifts depending on the magnitude of the interaction between the liquid crystal molecules and the polymer.
For this reason, the optical hysteresis when using a polymer-dispersed liquid crystal display device as an electro-optic element is controlled by the interaction between the liquid crystal molecules and the polymer. It was found that this can be reduced by matching the curves. Based on this idea, we examined the voltage-light transmittance curve and optical hysteresis of voltage application process and voltage drop process for many combinations of liquid crystal molecules and polymers (especially side chain polymers),
1) The average value of the interaction between the liquid crystal molecules and the polymer,
2) It has been found that the hysteresis can be reduced by controlling the degree of non-uniformity of the interaction between the liquid crystal molecules and the polymer.
Based on these findings, the inventors have made an invention based on the following guidelines 1) to 3) to complete the present invention.
1) A main chain region and a side chain region in which strong interaction with liquid crystal occurs are mixed.
2) It is preferable that the interaction has a strong interaction in a limited and small region of the whole. (It does not become a big restraint at the start, but acts as a trigger at the fall)
3) However, the interaction between the liquid crystal and the polymer as a whole is not so great.
(It is preferable that multiple interactions cancel each other.)
That is, at the polymer interface in contact with the liquid crystal phase, a portion having a strong anchoring force on the liquid crystal molecules and a portion having a strong anchoring force on the side chain are mixed, and the portion having the strong anchoring described above Is a radically polymerizable composition used as a side chain polymer so that the anchoring force of the main chain or side chain is balanced as an average of the entire polymer interface. The said subject was solved by making a thing into the specific combination of a radically polymerizable compound.

That is, the present invention relates to a light-scattering liquid crystal device having a light control layer obtained by polymerizing a light control layer-forming material containing a radical polymerizable composition and a liquid crystal composition. There is provided a light scattering liquid crystal device which is a composition containing at least one radical polymerizable compound represented by the formula (1) and satisfies the formulas (1) and (3) at the same time.

（１）

(1)

(In the formula, R represents an alkyl group having 3 to 40 carbon atoms, provided that the carbon atom in the alkyl group is
a) Oxygen atoms are not directly bonded to each other and are replaced by —O—, —CO—O—, —OCO—, —NHCO—O—, —OCONH—, or an arylene group having 6 to 12 carbon atoms. You may,
b) You may have a C1-C15 alkyl group as a substituent.

A ₁ represents —O—, —CO—O—, —OCO—, —NHCO—O—, —OCONH—, or an alkylene group (provided that the oxygen atom is directly bonded to the carbon atom in the alkylene group). -O-, -CO-O-, -OCO-, -NHCO-O-, -OCONH-, an alicyclic group having 6 to 12 carbon atoms, or an arylene group having 6 to 12 carbon atoms And the number of bonds N _a1 included when following a bond between two carbon atoms to which A ₁ is bonded is 3 to 40, and A ₂ is- O-, -CO-O-, -OCO-, -NHCO-O-, -OCONH-, or an alkylene group (provided that oxygen atoms are not directly bonded to each other in carbon atoms in the alkylene group) -O-, -CO-O-, -OCO-, -NHCO-O -, -OCONH-, an alicyclic group having 6 to 12 carbon atoms, or an arylene group having 6 to 12 carbon atoms).
A ₃ represents —O—, —CO—O—, —OCO—, —NHCO—O—, —OCONH—, an alkylene group, an alkyltriyl group, or an alkyltetrayl group (provided that the alkylene group, the alkyl The carbon atom in the triyl group or the alkyltetrayl group is defined as —O—, —CO—O—, —OCO—, —NHCO—O—, —OCONH—, in which oxygen atoms are not directly bonded to each other. , Which may be substituted with an alicyclic group having 6 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms),
-A ₂ -A ₃ -A ₂ - bond number _{N a2} contained in represents a linking group which is 3 to 40.

Represents.
B ₁ represents a hydrogen atom or a methyl group, B ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of R, A ₁ , A ₂ , A ₃ , B ₁ and B ₂ are the same May be different. m represents an integer of 2 to 4. )

（１）

(1)

（２）

(2)

（３）

(3)

(In Formula (1), Δα represents a difference between a maximum value α (αmax) and a minimum value α (αmin) of a plurality of α derived from the radical polymerizable compound contained in the radical polymerizable composition, α represents a value derived from Formula (2) In Formula (2), N _R1R2 represents two adjacent Rs in R ₁ and R in the radical polymerizable compound represented by Formula (1). when a _2, and, the general radical-polymerizable compound represented by (1) is formed by the polymerization reaction, when two adjacent R and R ₁ and R _2, R ₁ and Represents the number of bonds between the carbon atoms to which R ₂ is bonded N _R1 and N _R2 are from the carbon atom to which R ₁ and R ₂ are bonded to the terminal carbon atom of R ₁ and R ₂ Represents the number of bonds included when following a bond. And, if R ₁ and R ₂ has a substituent, the more distal most atomic number bond number in the join until carbon atoms and N _R1 and N _R2. The atomic tip are hydrogen atoms In some cases, this is not counted.Σ (αi × βi) is a radical represented by the general formula (1) with respect to a plurality of αi derived from the radically polymerizable compound contained in the radically polymerizable composition. The so-called expected value obtained by multiplying the appearance probability βi of αi obtained on the assumption that all the reactivity between the radically polymerizable compounds contained in the radically polymerizable composition containing the polymerizable compound is the same, Represents the theoretical value summed with respect to αi in the above formula, provided that the above definition is satisfied even if B2 and R are replaced, R is the one with the larger number of bonds.)

According to the present invention, it is possible to provide a light-scattering liquid crystal device having an essentially small optical hysteresis, hardly causing image sticking, and high gradation display performance.
Specifically, HS50 / d can be set to 20 (mV / μm) or less. Furthermore, by setting HS50 / d to 10 (mV / μm), it is possible to perform display with high gradation.

(General formula (1))
In the general formula (1), R represents the following general formula (2)

（２）

(2)

It is preferable that it is group represented by these.
In general formula (2), V represents a single bond or an alkylene group having 1 to 5 carbon atoms. Among these, a single bond or a methylene group having 1 carbon atom is preferable.
X ₁ represents a single bond, —O—, —CO—O—, —OCO—, —NHCO—O—, or —OCONH—. Among these, -O-, -CO-O-, or -OCO- is preferable.

W represents an alkyl group having 3 to 30 carbon atoms. In addition, the alkyl group may have an alkyl group having 1 to 15 carbon atoms and the same or less number of carbon atoms constituting W as a substituent.
One or two or more methylene groups present in the substituents of W and W are optionally independently of one another, as those in which oxygen atoms are not directly bonded to each other, -O- or 6 to 6 carbon atoms It may be replaced by 12 arylene groups.
Specifically, W is a normal hexyl group, a 2-ethylhexyl group, a normal octyl group, a normal undecyl group, a normal tridecyl group, a normal tetradecyl group, a normal octadecyl group, a 2-n-heptylnonyl group, and an isomyostil group. 2-ethylhexyl group, butoxyethyl group, hexyloxyethyl group, normal butoxyethoxymethyl group, cyclohexyl group, polyethylene glycol monoether group, 4-nonylphenylene group, 4-octylcyclohexyl group and the like. Among them, an alkyl group having 6 to 20 carbon atoms is preferable. Further, when the alkyl group is a linear alkyl group, a linear alkyl group having 7 to 14 carbon atoms is more preferable. When the alkyl chain is branched, carbon is used. A branched alkyl group of several 9 to 18 is more preferable.
When W is, for example, a linear alkyl group having 6 to 20 carbon atoms such as a normal undecyl group or a normal tridecyl group, a liquid crystal device that can be driven at a lower voltage can be obtained. Also. When W is, for example, a branched alkyl group such as a 2-normal heptyl-nonyl group, it is possible to obtain a liquid crystal device with little change in drive voltage temperature.

Polymerization rate of the above general formula (1), A bond number contained _{when 1} followed the bond between two carbon atoms bonded N _a1 a radical polymerizable compound represented too large by the general formula (1) As a result, a sufficient network cannot be formed and light scattering becomes weak. Therefore _{N a1} is more preferably 3 to 20, 3 to 7 being most preferred.
_{Specifically, -O-CH 2 -, -} O-CH 2 -CH 2 -CO-O-CH 2 -, - O-CH 2 -CH 2 O-, or _-O-CH 2 -CH (CH ₃ ) O- is preferred.
A ₂ is specifically preferably —CH ₂ —O—, —CH ₂ —OCO—, —CH ₂ —CO—O— or —CH ₂ —.

In the general formula (1), when m is 2, A ₃ is an alkylene group having 2 to 30 carbon atoms (provided that one or two or more alkylene groups present in the group and not directly bonded to A ₂ are present). In some cases, the methylene groups may be replaced with —O—, an arylene group, or a cycloalkylene group having 3 to 10 carbon atoms, independently of one another so that oxygen atoms are not directly bonded to each other. , An arylene group having 6 to 18 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or —Y—R ₄ —Y— (wherein Y represents an arylene group or a cycloalkylene group having 3 to 10 carbon atoms, R ₄ represents a single bond or an alkylene group having 1 to 15 carbon atoms (provided that one or two or more methylene groups present in the alkylene group may be independently of each other, and oxygen atoms may be directly Shall not be combined Represents a represents a good) be replaced by -O-.). When m is 3, an alkyltriyl group having 2 to 30 carbon atoms (provided that one or two or more methylene groups present in the group and not directly bonded to A ₂ may be mutually independent depending on the case. And an oxygen atom that is not directly bonded to each other may be replaced by —O—, an arylene group, or a cycloalkylene group having 3 to 10 carbon atoms. When m is 4, an alkyltetrayl group having 2 to 30 carbon atoms (provided that one or two or more methylene groups present in the group and not directly bonded to A ₂ may be mutually independent depending on the case. In addition, it is preferable that the oxygen atoms are not directly bonded to each other, and may be replaced by —O—, an arylene group, or a cycloalkylene group having 3 to 10 carbon atoms. A ₃ preferably does not have a side chain having 3 or more atoms.

Specific examples of A ₃ when m is 2 include butylene, hexylene, octamethylene, 7,12-dimethyloctadecylene, 7-ethylhexadecylene, 2,2′-dimethyl. A propylene group, a polyoxyethylene group having a repeating number of 2 to 10, a polyoxypropylene group, a polyoxybutylene group, a polyoxytetramethylene group, a cyclohexylene group, a biphenylenediyl group,

(In the above group, p and q each independently represents an integer of 1 to 4, and r represents an integer of 1 to 3).
Moreover, as a specific example when m is 3 in A ₃ ,

(In the above group, s and t each independently represents an integer of 1 to 2).
Also, the A _3, as a specific example of when m is 4,

(In the above group, u represents an integer of 1 to 2).
In the general formula (1), m is more preferably 2. Further, as a preferable example of R in that case, a combination of V is a methylene group, X ₁ is —O—, —CO—O—, or —OCO—, and W is an alkylene group having 2 to 30 carbon atoms is most preferable. .

Further, _-A 2 -A 3 -A 2 _- for spatial interference between side chains and the adjacent minimum binding number N _a2 contained is too small, very large, extremely reduced motility of the side chain To do. As a result, there is a problem that the crystallinity of the polymer is increased and the driving voltage of the light scattering type liquid crystal device at a low temperature is increased. On the other hand, if the amount of _Na2 is too large, the polymerization rate of the radical polymerizable compound represented by the general formula (1) is lowered, so that a sufficient network is not formed and light scattering is weakened. The value of the order _{N a2} is more preferably 4 to 35, more preferably 6 to 30, most preferably 8 to 25.

In the general formula (1), B ₁ represents a hydrogen atom or a methyl group. Among these, a hydrogen atom is particularly preferable because of its high reactivity and ease of synthesis.
B ₂ is the same group as the general formula (1), specifically, an alkyl group having 1 to 5 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a normal butyl group, or a normal pentyl group. To express. When B ₂ is an alkyl group, the number of carbon atoms is equal to or less than the number of carbon atoms of R.
By introducing an alkyl group having 1 to 5 carbon atoms into the B ₂ site, the mobility of the group represented by —VX ₁ —W in the general formula (2) is maintained even at an extremely low temperature of 0 ° C. or lower. be able to. Further, by using B ₂ as an alkyl group having 1 to 5 carbon atoms, a low driving voltage can be achieved even when W is a branched alkyl group. Accordingly, it is possible to obtain a light-scattering liquid crystal device with a lower driving voltage and less increase in driving voltage in a low temperature range. The number of carbon atoms of B ₂ is larger than 5 since it may inhibit the polymerization of acrylic groups.

In general formula (1), a plurality of R, A ₁ , A ₂ , A ₃ , B ₁ , and B ₂ may be the same or different.

In addition, the radical polymerizable compound of the general formula (1) is disclosed in Tetrahedoron Letters, Vol. 30, pp 4985, Tetrahedron Letters, Vol. 23, No. 6, pp 681-684, and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 34, pp217-225 and the like.
For example, in the general formula (1), the radically polymerizable compound in which B ₁ is hydrogen is obtained by reacting a compound having a plurality of epoxy groups with a radically polymerizable compound having active hydrogen capable of reacting with the epoxy group. It can be obtained by synthesizing a radically polymerizable compound having it and then reacting with a saturated fatty acid.
For example, when the radical polymerizable compound represented by the general formula (1) is the following compound:

  1,6-hexanediol diglycidyl ether and acrylic acid are reacted at 80 to 120 ° C. in the presence of triphenylphosphine or N, N-dimethylbenzylamine to synthesize a radical polymerizable compound having a hydroxyl group. Next, a radically polymerizable compound having a hydroxyl group and lauric acid can be obtained by an esterification reaction using a dehydrating agent such as dicyclohexylcarbodiimide.

Furthermore, it can be obtained by reacting a compound having a plurality of epoxy groups with a saturated fatty acid to synthesize a compound having a hydroxyl group, and then reacting with a radical polymerizable compound having a group capable of reacting with a hydroxyl group.
For example, when the radically polymerizable compound represented by the general formula (1) is a compound represented by the following formula (1-1),

（１−１）

(1-1)

  1,6-hexanediol diglycidyl ether and butyric acid are reacted at 80 to 120 ° C. in the presence of triphenylphosphine or N, N-dimethylbenzylamine to synthesize a radically polymerizable compound having a hydroxyl group, Can be obtained by reacting acryloyl chloride in the presence of triethylamine.

In addition, when the radical polymerizable compound is, for example, B _{1 in the} general formula (1) is an alkyl group and V in the general formula (2) is a methylene group having 1 carbon atom, a compound having a plurality of oxetane groups A fatty acid chloride or a fatty acid capable of reacting with an oxetane group, and further reacting with a polymerizable compound having active hydrogen such as acrylic acid, a compound having one oxetane group, and an oxetane group It can be obtained by a method of reacting a polyvalent fatty acid chloride or a fatty acid capable of reacting with a polymerizable compound having active hydrogen such as acrylic acid.
Further, when V in the general formula (2) is a butylene group having 4 carbon atoms, it can be obtained by using a compound having a plurality of furan groups instead of the oxetane group. Furthermore, when V in the general formula (2) is a pentylene group having 5 carbon atoms, it can be obtained by using a compound having a plurality of pyran groups instead of an oxetane group.

  For example, when the radical polymerizable compound represented by the general formula (1) is a compound represented by the following formula (1-2),

（１−２）

(1-2)

  By reacting 1,6-hexanediol sulfonate with 3-ethyl-3-hydroxymethyloxetane in the presence of sodium hydroxide, 3,3 ′-(1,6-hexanediylbis (oxymethylene)) Bis- (3-ethyloxetane) can be obtained. Further, this bifunctional dioxetane compound and capric acid chloride are reacted at 0 ° C. in the presence of sodium iodide and acetonitrile to obtain an iodo compound having a C9 methylene chain. Next, the resulting iodo compound and acrylic acid are reacted in the presence of 1,8-diazabicyclo [5.4.0] -undecene-7 using dimethyl sulfoxide as a solvent at 90 ° C. for 12 hours. Can be obtained.

  Moreover, when the radically polymerizable compound represented by the general formula (1) is a compound represented by the following formula (1-3),

（１−３）

(1-3)

  3-Ethyl-3-dodecyloxyoxetane can be obtained by reacting sulfonic acid ester of lauryl alcohol with 3-ethyl-3hydroxymethyloxetane in the presence of sodium hydroxide. Further, this oxetane compound and sebacic acid chloride are reacted at 0 ° C. in the presence of sodium iodide and acetonitrile to obtain an iodo compound having a C11 methylene chain. Next, the resulting iodo compound and acrylic acid are reacted in the presence of 1,8-diazabicyclo [5.4.0] -undecene-7 using dimethyl sulfoxide as a solvent at 90 ° C. for 12 hours. Can be obtained.

  The compound having an oxetane group includes a reaction between a halogen compound and oxetane alcohol, a reaction between carboxylic acid and oxetane alcohol, a reaction between alcohol and a sulfonate ester of oxetane alcohol, a reaction between alcohol and a halogen compound having oxetane, dimethylol. It can be obtained by a reaction between a compound and dimethyl carbonate, or the like. In addition to 1,6-hexanediol, 1,4-butanediol, neopentyl glycol, polypropylene glycol, dimer acid diol, cyclohexanedimethanol, trimethylolpropane, ethylene oxide modified bisphenol, decanol, dodecanol, undecanol, Etc. Examples of the carboxylic acid include sebacic acid, adipic acid, itaconic acid, long-chain dibasic acid, dimer acid, caprylic acid, lauric acid, stearic acid, myristic acid, isomyristic acid, palmitic acid, and undecanoic acid. Examples of the halogen compound include 1,6-dibromohexane, 1,4-dibromobutane, 1-chlorohexane, 1-chlorodecane and the like.

  Fatty acid chlorides and fatty acids that can react with oxetane groups include caprylic chloride, caprylic chloride, lauric chloride, stearic chloride, myristic acid chloride, isomyristic acid chloride, palmitic acid chloride, undecanoic acid chloride, and capryl. Acid, lauric acid, stearic acid, myristic acid, isomyristic acid, palmitic acid, undecanoic acid, sebacic acid, adipic acid, dimer acid, itaconic acid, sebacic acid, adipic acid, itaconic acid and the like can be used.

  As the radically polymerizable compound having active hydrogen, in addition to acrylic acid, for example, methacrylic acid, acrylic acid dimer, methacrylic acid dimer, hydroxyethyl acrylate, hydroxypropyl acrylate, and the like can be used. In the case of a reaction between oxetane and a fatty acid, acrylated chloride, methacrylated chloride, methyl acrylate, ethyl acrylate, or the like can be used.

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

  Trimethylolbutane is synthesized by reacting hexanal and paraformaldehyde in methyl tertiary butyl ether in the presence of sodium hydroxide. Furthermore, it can be synthesized by reacting trimethylolbutane and dimethyl carbonate in the presence of potassium carbonate, removing methanol as a by-product and performing carbonation, followed by heating to 200 ° C. and decarboxylation.

  Moreover, when the radically polymerizable compound represented by the general formula (1) is a compound represented by the following formula (1-4), for example,

（１−４）

(1-4)

Dibutyl-1,3-propanediol and acrylic acid chloride are reacted in the presence of triethylamine, and this product and sebacic acid are further reacted with 1-ethyl-3- (3'-dimethylaminopropyl) carbodiimide hydrochloride and dimethylamino. It can be obtained by reacting in methylene chloride for 8 hours at room temperature in the presence of pyridine.

  Specific examples of the radical polymerizable compound represented by the general formula (1) used in the present invention include compounds as described in JP-A-6-32761 and JP-A-11-029527. .

  The radically polymerizable composition used in the present invention uses at least one radically polymerizable compound represented by the above general formula (1) and simultaneously satisfies the mathematical formulas (1) and (3). Select monomer.

（１）

(1)

（２）

(2)

（３）

(3)

In Formula (2), α represents an index indicating the degree of anchoring force of the main chain or side chain at the polymer interface.
As shown in FIG. 5, N _R1R2 is a radical-polymerizable compound represented by the general formula (1), when two adjacent Rs are R ₁ and R ₂ , and the general formula (1) in the radical polymerizable compound represented is formed by the polymerization reaction, when two adjacent R and R ₁ and R _2, is between the carbon atoms to which R ₁ and R ₂ are attached Represents the number of bonds. N _R1 and N _R2 represent the number of bonds included when following the bond from the carbon atom to which R ₁ and R ₂ are bonded to the terminal carbon atom of R ₁ and R ₂ . (However, when R ₁ and R ₂ have a substituent, the number of bonds included in the bond up to the terminal carbon atom having the largest number of atoms is N _R1 and N _R2 . If not, don't count this.)

These numbers are determined as follows.
N _R1 , N _R2 : Count the number of bonds that form the side chain skeleton from the base of the side chain to the tip. However, this is not counted when the atom at the tip is a hydrogen atom. In the present invention, when this value is less than 3, it is not regarded as a side chain.
N _R1R2 : Counts the number of bonds that form the main chain skeleton sandwiched between the two side chains of R ₁ and R ₂ .
For example, in the case of FIG. 5, N _R1 = 10, N _R2 = 7, N _R1R2 = 8, and α = 8 − {(10−1) + (7-1)} / 2 = 0.5.

For example, assuming that the polymer matrix is formed of only one kind of the radical polymerizable compound represented by the general formula (1), N _R1R2 has the number of bonds of -A ₂ -A ₃ -A _2- , and , —A ₁ —CO—CB ₁ (CH ₂ Z) —CH ₂ —CB ₁ Z—CO—A ₁ —, wherein Z is a linking group with a neighboring main chain or a double bond Represents the polymerization initiator after the reaction).
Specifically, when the radical polymerizable compound represented by the general formula (1) is a compound represented by the following formula (1-5), and a polymer matrix is formed only by the radical polymerizable compound, of _{N R1R2, -A 2 -A 3 -A} 2 - is _{25, -A 1 -CO-CB 1} (CH 2 Z) -CH 2 -CB 1 Z-CO-a 1 - is a 10 is there.

（１−５）

(1-5)

Moreover, the radically polymerizable compound represented by the general formula (1) is a compound represented by the formula (1-5) and a compound represented by the following formula (1-6). when the polymer matrix of radical-polymerizable compound is _formed, the _{N R1R2, -A 2 -A 3 -A} 2 - is a 25 and 8,
_{-A 1 -CO-CB 1 (CH} 2 Z) -CH 2 -CB 1 Z-CO-A 1 is 10.

（１−６）

(1-6)

As is clear from the definition, the value of α increases when the two side chains of adjacent R ₁ and R ₂ become smaller than the number of bonds between the side chains, and conversely the adjacent R ₁ and R ₂ two When the side chain of the book becomes larger than the number of bonds between the side chains, the value of α decreases. As is clear from the definition, α indicates the relationship between the side chain length and the side chain length in an arbitrary minute portion in the polymer matrix or polymer network.
The anchoring force at the polymer interface has a strong correlation with the relationship between the side chain length of the polymer chain forming the polymer interface and the length between the side chains. That is, the anchoring force of the main chain increases as the length between the side chains becomes longer than the side chain length, and the anchoring force of the main chain decreases when the length between the side chains becomes shorter than the side chain length. Further, when the length between the side chains becomes shorter than the side chain length, the portion has the anchoring force of the side chain, and the anchoring force of the side chain increases as the tendency becomes more prominent. This is due to the fact that the mobility between the side chains, that is, the main chain is low, and the mobility of the side chain is generally significantly higher than this. The liquid crystal molecules are easily aligned horizontally with respect to the main chain having low mobility. Accordingly, when the polymer main chain is exposed when the polymer interface is viewed from the liquid crystal bulk, the liquid crystal molecules are horizontally aligned at that portion. However, if a side chain with high mobility exists, the liquid crystal molecules cannot approach the main chain and cannot be aligned horizontally with respect to the main chain within the range of the excluded volume effect. Since the range covered by the excluded volume effect of the side chain is proportional to the side chain length, the longer the inter-chain length compared to the side chain length, that is, the greater the value of α is, the larger the portion is relative to the liquid crystal molecules. The horizontal anchoring force of the main chain is strong. On the other hand, when the side chain length is longer than the length between adjacent side chains, the excluded volume effect extends over the entire side chain and completely deprives the horizontal anchoring force of the main chain between the side chains. Further, when the side chain length becomes longer than the inter-chain length, adjacent side chains gradually interfere with each other and the steric hindrance impairs the mobility of both side chains. As the degree of steric hindrance increases, the side chain changes to a state of low mobility standing perpendicular to the polymer interface. The liquid crystal molecules are aligned in parallel with the side chain in this state, and the horizontal anchoring with respect to the side chain becomes strong. This orientation is substantially perpendicular to the polymer backbone. That is, as the value of α is negative and larger, the horizontal anchoring between the liquid crystal molecules and the side chains becomes stronger, in other words, the vertical anchoring force with respect to the main chain becomes stronger.

In addition, in the definition of α, the value of the side chain length of R ₁ and R ₂ is −1 because the bond at the base of the side chain is oriented in the vertical direction with respect to the main chain. Since this does not contribute to obscuring the main chain from the liquid crystal molecules due to the effect, this amount is subtracted.

On the other hand, the numerical formula (1) is a maximum value α (αmax) and a minimum value α of a plurality of α derived from a radical polymerizable composition containing at least one radical polymerizable compound represented by the general formula (1). This represents the difference in (αmin).
The larger Δα is, the higher the effect of reducing optical hysteresis is. As αα is larger, α is positive or large or negative and large. Therefore, a portion with a strong horizontal anchoring force on the main chain (when α is positive and large) or a portion with a strong horizontal anchoring force on the side chain (α This is because the reaction of the liquid crystal molecules returning from the vertical alignment state to the horizontal alignment state in the voltage drop process can be sharpened.

In the light scattering type liquid crystal device of the present invention, α of the portion having the horizontal anchoring force with respect to the main chain is a positive value, and the portion having the horizontal anchoring force with respect to the side chain (the vertical anchor with respect to the main chain) Α of the portion having a ring force indicates a negative value. It is important to reduce the optical hysteresis in the ratio of the portion having the horizontal anchoring force and the portion having the vertical anchoring force with respect to the main chain in the entire polymer matrix or polymer network. If the balance between the two is poor, the voltage-light transmittance curve, which is the cause of the optical hysteresis, shifts in different directions in the voltage application process and the voltage drop process, and the optical hysteresis increases. The index is Equation (3).
In Formula (3), Σ (αi × βi) is a plurality of radically polymerizable compounds derived from a radically polymerizable compound contained in a radically polymerizable composition containing at least one radically polymerizable compound represented by the general formula (1). The so-called expected value obtained by multiplying αi by the appearance probability βi of αi obtained on the assumption that the reactivity between radically polymerizable compounds contained in the radical polymerizable composition is all the same is obtained for all of the polymers. Represents the theoretical value of the sum of αi.
The appearance probability βi is derived by the following equation (9).

（９）

(9)

  In the formula, xi represents the total value of the numbers between the side chains having the value of αi among all the side chains existing in the polymer matrix or the entire polymer network. Y represents the number of all side chains in the entire polymer matrix or polymer network. If there are multiple inter-chain patterns with the same α value despite having different structures, these β i values may be calculated individually, or the inter-chain patterns with the same α value may be grouped together. Then, βi may be obtained.

  Hereinafter, a method for calculating Δα and Σ (αi × βi) will be described with specific examples. For example, a radical polymerizable compound represented by the following formula (1-7) and a radical polymerizable compound represented by the following formula (1-8) are mixed and used as the radical polymerizable compound, and the mixing ratio is represented by the formula Consider a case in which a radical polymerizable composition in which the radical polymerizable compound represented by (1-7) is 20 mol% and the radical polymerizable compound represented by formula (1-8) is 80 mol% is used. As described below, the main chain skeleton of the radically polymerizable compound represented by the formula (1-7) is divided at the carbon portion to which the side chain R is bonded, and is divided into three parts A part to C part. Similarly, the main chain skeleton of the compound of the radical polymerizable compound represented by the formula (1-8) as shown below is divided at the carbon portion to which the side chain R is bonded, and is divided into three parts, D part to F part. .

（１−７）

(1-7)

（１−８）

(1-8)

By mixing and polymerizing the radically polymerizable compound represented by the formula (1-7) and the radically polymerizable compound represented by the formula (1-8), in the polymer, An inter-chain pattern can be generated.
A) Between side chains generated by combining A and A parts a) Between side chains generated by combining A and C parts c) Between side chains generated by combining A and D parts A) between the side chains formed by combining the A part and the F part, e) between the side chains generated by combining the C part and the C part, and c) between the side chains generated by combining the C part and the D part. Between the side chains formed by combining the F part with the F part) and between the side chains formed by combining the D part and the D part. Side chain between parts formed by binding) B part ii) E part

The A part and the C part of the radical polymerizable compound represented by the formula (1-7) have the same structure, and the D part and the F part of the radical polymerizable compound represented by the formula (1-8) have the same structure. Therefore, the above a) to ii) can be summarized as the following 1) to 5).
1) Between the A or C part and the side chain formed by combining the A or C part, that is, a), i), o)
2) Between the side chains formed by combining the A or C moiety and the D or F moiety, ie, c), d), f), g)
3) D or F part and the side chain formed by combining D or F part.
4) Part B, ie)
5) Part E, ie)
When α is calculated for the inter-chain patterns 1) to 5) above, Table 1 is obtained.

At this time, the maximum value of α is 8 in the inter-chain pattern 4). The minimum value of α is −3 between the side chain patterns 3) and 5). Therefore, Δα = 8 − (− 3) = 11.

The appearance probability βi of each inter-chain pattern is obtained as follows.
The molar fraction of the radically polymerizable compound represented by the formula (1-7) in the entire radically polymerizable compound is 0.2. Similarly, the molar fraction of the radically polymerizable compound represented by the formula (1-8) is 0.8. The number of A to C moieties contained in one radical polymerizable compound represented by formula (1-7) is one by one. The number of D to F moieties contained in one radical polymerizable compound represented by formula (1-8) is one by one. Therefore, when the number of moles of the whole radical polymerizable compound is γ, the number of moles of the A to F portions present therein is as shown in Table 2.

The polymerization rate of the radically polymerizable compound represented by the formula (1-7) and the radically polymerizable compound represented by the formula (1-8) is the same, and the side chains between 1) to 3) produced by polymerization Assuming that the number of is sufficiently larger than the number of terminals of the polymer, the number of moles of the inter-chain patterns of the above 1) to 5) existing after polymerization is calculated from Table 2 as follows.
1) 0.4γ × 0.4γ / (0.4γ + 1.6γ) = 0.08γ
3) 1.6γ × 1.6γ / (0.4γ + 1.6γ) = 1.28γ
2) Using the results of 1) and 3) above, calculate as follows.
(0.4γ + 1.6γ) − (0.08γ + 1.28γ) = 0.64γ
4) 0.2γ
5) 0.8γ
The calculation results are summarized in Table 3 below.

As described above, βi is obtained from the following formula (9).

（９）

(9)

(In the above formula (9), xi is the total value of the numbers between the side chains in which the value of α is αi, and y is the total value of the numbers between all the side chains included in the entire polymer matrix or polymer network. )

In the inter-chain patterns 3) and 5), α is the same, but here βi is obtained separately. (When βi is calculated, when there are a plurality of inter-chain patterns having the same α value and different structures, βi may be calculated individually or the α values are the same. The inter-chain patterns may be calculated together.) Then, the xi of the inter-chain patterns 1) to 5) are as shown in the calculation results in Table 3, respectively. Since y is the sum of these values, y = 0.08γ + 0.64γ + 1.28γ + 0.2γ + 0.8γ = 3γ
It becomes. By substituting the calculation results of xi and y shown in Table 3 into Equation (9), βi of the inter-chain patterns 1) to 5) is calculated as shown in Table 4.

  Αi in the inter-chain patterns 1) to 5) are as shown in Table 1. From this and the βi calculation result of Table 4, (αi × βi) of each inter-chain pattern is calculated as shown in Table 5.

Σ (αi × βi) is calculated by summing all (αi × βi) of the inter-chain patterns 1) to 5) in Table 5. In this case:
Σ (αi × βi) = 0.081 + 0−1.281 + 0.536−0.801
= -1.465

If a light scattering type liquid crystal device is manufactured such that Σ (αi × βi) obtained in this way satisfies the formula (3), that is, −3.16 or more and 2.00 or less, the optical hysteresis is reduced. Can be small. In other words, the mathematical formulas (2) and (3) can be used as an index of a method for reducing optical hysteresis, and the radical polymerizable composition is adjusted to satisfy the mathematical formulas (2) and (3) at the same time. This method is useful as a method for obtaining a light-scattering liquid crystal device with small optical hysteresis.
Specifically, if Δα is 5 or more and (α × β) total is −3.16 or more and 2.00 or less, HS50 / d is 20 (mV / μm) or less. be able to.
Furthermore, when Δα is 12 or more under the above conditions, HS50 / d can be 10 (mV / μm) or less.
In particular, Σ (αi × βi) is preferably in the range of −1.79 or more and 2.00 or less, and the optical hysteresis can be further reduced.

  In the present invention, the larger the value of Δα, the better the effect of reducing optical hysteresis. However, when the side chain length is 20 or more as the number of bonds forming the skeleton (excluding the hydrogen atom at the tip), the driving voltage of the light scattering liquid crystal device tends to increase in a low temperature environment. Therefore, from the viewpoint of this low temperature driving voltage, the side chain length is preferably 19 or less, and most preferably 17 or less. Accordingly, there is a preferable lower limit for the value of α that can be actually selected. In addition, increasing the length between side chains also increases the length between cross-linking points. If the length between cross-linking points is too long, the polymerization rate is extremely lowered, and in the worst case, phase separation is not achieved, so that it cannot be made too long. From such a viewpoint, the length between side chains is preferably 35 or less. For this reason, there is a preferred upper limit for the value of α that can be selected in practice.

In the present invention, it was estimated why the optical hysteresis could be reduced by satisfying the mathematical expressions (1) to (3).
Satisfying the above mathematical formulas (1) to (3) is to prevent the average anchoring as a whole from being large although there is a portion where anchoring to the main chain or anchoring to the side chain is large. That is, making the anchoring force distribution non-uniform in the polymer interface. One reason for this configuration is that when the anchoring force distribution is uniform across the entire polymer interface, the shift of the voltage-light transmittance curve and the voltage during the voltage application process, which is the above-mentioned optical hysteresis generation factor, This is because the shift of the voltage-light transmittance curve in the descending process cannot be optimized. In other words, in order to optimally control the shift of the voltage-light transmittance curve during the voltage application process and the voltage drop process, which are the causes of optical hysteresis, the horizontal anchoring force on the polymer main chain or side chain is constant during the voltage application process. The conflicting condition that the horizontal anchoring force is stronger than a certain level must be satisfied in the voltage drop process.

  In the light scattering type liquid crystal device according to the present invention, a limited main chain or side chain portion in the polymer interface has a strong horizontal anchoring force. In this limited portion, the horizontal alignment of the liquid crystal molecules in the vicinity of the polymer interface is maintained even after most of the liquid crystal molecules rise perpendicularly to the main chain or side chain by applying a voltage. Therefore, when the voltage drops, this horizontally aligned liquid crystal molecule acts as a trigger to return most of the other liquid crystal molecules to the polymer interface horizontally, thereby preventing the applied voltage-light transmittance curve from shifting to the low voltage side. The occurrence of optical hysteresis is suppressed. Since the portion with this strong horizontal anchoring force is not high in the entire polymer interface, the horizontal anchoring force in this portion is a binding force that prevents most other liquid crystal molecules from rising at the time of rising voltage. There is little work. In addition, since the polymer interface includes a portion having an anchoring force with respect to the main chain and the side chain (perpendicular to the main chain), liquid crystal molecules in contact with the portion having the horizontal anchoring force are applied when a voltage is applied. The force to block the rise of most other liquid crystal molecules is further reduced. Thus, in the light scattering type liquid crystal device according to the present invention, it is considered that the shift of the voltage-light transmittance curve in the voltage application process and the voltage drop process of the optical hysteresis can be optimally controlled.

In the present invention, the radical polymerizable composition used for the light control layer forming material contains at least one radical polymerizable compound represented by the general formula (1), and the mathematical formulas (1) to (3) The radical polymerizable compound constituting the composition is selected so as to satisfy the above). Therefore, within this range, there is no problem in copolymerizing some known and commonly used radical polymerizable compounds.
Examples of the radical polymerizable compound include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, bisphenol A di (meth) acrylate, urethane acrylate, polytetraethylene glycol dimaleimide, 1,11-diacryloyloxy-2,10 -Didodecanoyloxy-6,6-dimethyl-4,8-dioxaundecane, 1,14-diacryloyloxy-2,10-didodecanoyloxy-4,11-dioxatetradecane, 1,14-di Acryloyloki -2,10-ditetradecanoyloxy-4,11-dioxatetradecane, 1,14-diacryloyloxy-2,10-dihexanoyloxy-4,11-dioxatetradecane, 2,13-diacryloyl Oxy-1,14- [di (2-n-heptylundecanoyloxy)]-4,11-dioxatetradecane, 2,13-diacryloyloxyethyl-1,14-diethyl-1,14-undeca Noyloxy-4,11-dioxatetradecane, 2,13-diacryloyloxyethyl-1,14-dimethyl-1,14-dodecanoyloxy-4,11-dioxatetradecane, 13,22-diacryloyloxyethyl -13,22-diethyl-15-oxycarbonyl-20-carbonyloxy-11,24-dioxatetra Riakontan, and the like. The blending ratio of these radical polymerizable compounds is preferably 30% or less, and most preferably 20% or less, based on the total amount of the radical polymerizable compounds of the general formula (1).

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

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

  The liquid crystal composition used in the present invention is a compound or composition showing a phase normally recognized as a liquid crystal phase in this technical field as a liquid crystal compound. Among them, nematic liquid crystal, cholesteric liquid crystal, chiral nematic liquid crystal is used as the liquid crystal phase. What is expressed is preferred. Examples of such a liquid crystal phase include, for example, benzoic acid ester, cyclohexanecarboxylic acid ester, biphenyl, terphenyl, phenylcyclohexane, pyrimidine, pyridine, dioxane, cyclohexanecyclohexane ester, Examples thereof include a composition comprising a liquid crystal compound such as a tolan series, an alkenyl series, a fluoro series, a cyano series, or a naphthalene series, and a composition containing the liquid crystal compound.

Among these, by using the liquid crystal compounds of the general formulas (Ia) and (Ib) shown below, a polymer dispersed liquid crystal device that can be driven by an active element can be obtained.
General formula (Ia) and general formula (Ib)

(In the formula, each of R ¹¹ and R ¹² independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more present in the alkyl group or alkenyl group or Two or more CH ₂ groups may be substituted with oxygen atoms on the assumption that oxygen atoms are not directly bonded to each other, and A ¹¹ and A ¹² are each independently a 1,4-phenylene group or 1, Represents a 4-cyclohexylene group, the 1,4-phenylene group being unsubstituted or having one or more fluorine, chlorine, methyl, trifluoromethyl or trifluoromethoxy groups as substituents may have, each independently X ¹¹ and X ^17, a fluorine atom, a chlorine atom, an isocyanate group, a trifluoromethyl group, a trifluoromethoxy group or a difluoromethoxy meth Represents a sheet group independently each X ²² is a X ¹⁶ and X ¹⁸ from X ^12, a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group or a trifluoromethoxy group, Z ¹¹ and Z ¹³ are each Independently represents a single bond or —CH ₂ —CH ₂ —, Z ¹² and Z ¹⁴ each independently represents a single bond, —CH ₂ —CH ₂ — or —CF ₂ O—, and n ¹¹ and n ¹² represents 0 or 1)
Furthermore, general formula (Ic) can also be used together.

(In the formula, R ²¹ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more CH ₂ groups present in the alkyl group or alkenyl group are The oxygen atoms may not be directly bonded to each other and may be substituted with an oxygen atom, A ²¹ represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and the 1,4-phenylene group is It may be unsubstituted or may have one or more fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoromethoxy group as a substituent, and Z ²¹ may be a single bond or —CH ₂ —. CH ₂ - represents, X ⁵¹ is one or more CH ₂ groups present in the alkenyl group (the alkyl group or alkenyl group of alkyl or 2 to 10 carbon atoms having 1 to 20 carbon atoms The oxygen The atoms may be substituted with oxygen atoms so that the atoms are not directly bonded to each other.), Fluorine atom, chlorine atom, isocyanate group, trifluoromethyl group, trifluoromethoxy group, difluoromethoxy group or general formula (I- d)

(In the formula, A ²² represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and the 1,4-phenylene group is unsubstituted or has one or more fluorine atoms as a substituent. , A chlorine atom, a methyl group or a trifluoromethyl group or a trifluoromethoxy group, and X ⁶⁰ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (the alkyl group or One or two or more CH ₂ groups present in the alkenyl group may be substituted with oxygen atoms as those in which oxygen atoms are not directly bonded to each other)), fluorine atom, chlorine atom, isocyanate group, Represents a trifluoromethyl group, a trifluoromethoxy group, or a difluoromethoxy group.)
X ⁵² to X ⁵⁷ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group, a trifluoromethoxy group, a methyl group, a methoxy group or an ethyl group,
n ¹⁰ represents 0 or 1. It is desirable to contain at least one compound selected from the group of compounds represented by

The light-scattering liquid crystal device of the present invention has, for example, two substrates having a transparent electrode layer, at least one of which is transparent, and using a spacer or the like with the transparent electrode layer facing each other. It is obtained by sandwiching a mixture of a radically polymerizable compound and a liquid crystal composition between them and performing phase separation.
The mixing ratio of the liquid crystal composition and the radical polymerizable composition can be adjusted according to desired electro-optical characteristics, and is preferably in the range of 59:41 to 89:11, and is in the range of 63:36 to 75:25. A range is more preferred.
As the radical polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used, but a photopolymerization initiator is preferable. Specifically, the following compounds are preferable.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- ( 2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- Acetophenone series such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone;
Benzoins such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Benzyl and methylphenylglyoxyesters;
Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4' -Benzophenone series such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone;
Thioxanthone systems such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone;
Aminobenzophenone series such as Michler's ketone and 4,4′-diethylaminobenzophenone;
10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like are preferable.
Of these, benzyldimethyl ketal is most preferred.

  A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate. Further, it is more preferable to use a transparent substrate with low wavelength dispersion because the light scattering ability of the device of the present invention is increased and the reflectance and contrast are improved. Examples of the low wavelength dispersion transparent substrate include borosilicate glass, a plastic transparent film such as polyethylene terephthalate or polycarbonate, and a transparent substrate coated with a dielectric multilayer film using a 1 / 4λ optical interference condition.

  In addition, a polymer film, an alignment film, and a color filter can be disposed on the substrate as necessary. As the alignment film, for example, a polyimide alignment film, a photo alignment film, or the like can be used. As a method for forming the alignment film, for example, in the case of a polyimide alignment film, the polyimide resin composition is applied on the transparent substrate, thermally cured at a temperature of 180 ° C. or higher, and further rubbed with a cotton cloth or a rayon cloth. be able to. In addition, a polymer film such as a polyimide film that has not been rubbed can also be used. Further, the substrate on one side may be an opaque material such as silicon.

  The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust the space | interval of this board | substrate so that the thickness of the light control layer obtained may be 1-100 micrometers, especially 2-50 micrometers. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

  The light control layer forming material is enclosed in the obtained liquid crystal cell, and the liquid crystal composition in the light control layer forming material is irradiated with light or heated and cooled in a state where the liquid crystal composition is maintained in an isotropic liquid state. A light scattering type liquid crystal device can be produced. The production method is not particularly limited, and energy rays such as ultraviolet rays, visible rays, and high frequencies can be used. Among them, the method utilizing the polymerization of the radical polymerizable compound using ultraviolet rays instantaneously proceeds the polymerization of the radical polymerizable compound while keeping the light control layer forming material in an isotropic liquid state. It is more preferable because the average gap interval in the inside can be made uniform and a three-dimensional network-like polymer matrix can be obtained. That is, when the polymer matrix has a three-dimensional network shape, the electro-optical characteristics of the obtained liquid crystal device are further improved.

  Moreover, a light absorption layer, a diffuse reflector, etc. can also be arrange | positioned at the back surface side of the liquid crystal device of this invention, and a reflective light-scattering type liquid crystal device with a high reflectance and contrast is obtained. Color display is possible by arranging light absorbing layers having different light absorption wavelengths such as cyan, magenta, and yellow so as to coincide with the positions of the pixel electrodes divided for each color. Functions such as specular reflection, diffuse reflection, retroreflection, and hologram reflection can also be added.

  EXAMPLES Hereinafter, although a synthesis example and an Example are given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.

(Synthesis example)
(Intermediate 1)
In a reaction vessel equipped with a stirrer and a thermometer, 30 g (0.12 mol) of 1-bromododecane, 1.9 g of tetrabutylammonium bromide, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toa Gosei Co., Ltd .: OXT-) 101) 28 g (0.24 mol) and 200 ml of dimethyl sulfoxide were added, and 26.5 g of 50% aqueous potassium hydroxide solution was slowly added dropwise. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours at room temperature. After adding 1 L of ethyl acetate to the reaction solution, it was washed with 5% sodium carbonate, pure water, and saturated saline in this order, the organic layer was dried over anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure, and purified by a silica gel column. And 24 g of intermediate 1 represented by formula (1) was obtained.

（１）

(1)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 4.45-4.40 (dd, 4H), 3.56 (s, 2H), 3.45 (t, 2H), 1.75 (m, 2H) ), 1.59 (m, 2H), 1.26 (m, 18H), 0.88 (t, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 78.6, 73.4, 71.6, 44.3, 43.4, 31.9, 29.5, 29.4, 29.3, 26 .7, 26.1, 22.7, 14.0, 8.2

(Intermediate 2)
In a reaction vessel equipped with a stirrer and a thermometer, 40 g (0.17 mol) of 1-bromoundecane, 2.7 g of tetrabutylammonium bromide, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toa Gosei Co., Ltd .: OXT-) 101) 30 g (0.25 mol) and 200 ml of dimethyl sulfoxide were added, and 23.5 g of a 50% aqueous potassium hydroxide solution was slowly added dropwise. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours at room temperature. After adding 1 L of ethyl acetate to the reaction solution, it was washed with 5% sodium carbonate, pure water, and saturated saline in this order, the organic layer was dried over anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure, and purified by a silica gel column. And 30 g of intermediate 2 represented by formula (2) was obtained.

（２）

(2)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 4.45-4.40 (dd, 4H), 3.56 (s, 2H), 3.45 (t, 2H), 1.75 (m, 2H) ), 1.59 (m, 2H), 1.26 (m, 16H), 0.88 (t, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 78.6, 73.4, 71.6, 44.3, 43.4, 31.9, 29.5, 29.4, 29.3, 26 .7, 26.1, 22.7, 14.0, 8.2

(Intermediate 3)
In a reaction vessel equipped with a stirrer and a thermometer, 1-bromohexane 20 g (0.12 mol), tetrabutylammonium bromide 1.9 g, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd .: OXT-) 101) 28 g (0.24 mol) and 200 ml of dimethyl sulfoxide were added, and 26.5 g of 50% aqueous potassium hydroxide solution was slowly added dropwise. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours at room temperature. After adding 1 L of ethyl acetate to the reaction solution, it was washed with 5% sodium carbonate, pure water, and saturated saline in this order, the organic layer was dried over anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure, and purified by a silica gel column. And 14 g of intermediate 3 represented by formula (3) was obtained.

（３）

(3)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 4.45-4.40 (dd, 4H), 3.56 (s, 2H), 3.45 (t, 2H), 1.75 (m, 2H) ), 1.59 (m, 2H), 1.26 (m, 6H), 0.88 (t, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 78.6, 73.4, 71.6, 44.3, 43.4, 31.9, 29.5, 29.3, 26.1, 22 .7, 14.0, 8.2

(Intermediate 4)
In a reaction vessel equipped with a stirrer, a nitrogen introducing tube, a cooling tube, and a thermometer, 23.6 g (0.2 mol) of 1,6-hexanediol, 44.5 g (0.44 mol) of triethylamine, tetramethylethylenediamine ( (0.04 mol) 4.6 g and 500 ml of toluene were added, and the mixture was stirred while cooling with an ice-water bath so that the temperature became 5 ° C. or lower. 80 g (0.42 mol) of p-toluenesulfonium chloride was added in 5 portions over 1 hour. After completion of the addition, the reaction vessel was stirred at room temperature for 3 hours, and then the reaction was terminated. After filtration of the resulting hydrochloride, the reaction solution was washed with a 1/10 N hydrochloric acid solution, pure water and saturated brine in that order, the organic layer was dried over anhydrous sodium sulfate, and the organic solvent was distilled off under reduced pressure. 83.6 g of a white solid of 1,6-hexanediol ditosylate was obtained.
Next, in a reaction vessel equipped with a stirrer and a thermometer, 50 g (0.12 mol) of 1,6-hexanediol ditosylate, 4 g of tetrabutylammonium bromide, 3-ethyl-3-hydroxymethyloxetane (Toa Gosei) Company: OXT-101) 41 g (0.35 mol) and dimethyl sulfoxide 150 ml were added and dissolved at 50 ° C., then 18.7 g (0.47 mol) of granular sodium hydroxide was divided into 5 portions. Over 1 hour. After completion of the addition, the reaction vessel was heated to 80 ° C. and stirred for 3 hours to complete the reaction. 1 L of ethyl acetate was added to the reaction solution, and then washed with 5% sodium carbonate, pure water, and saturated saline in this order. The organic layer was dried over anhydrous sodium sulfate, and the organic solvent was distilled off under reduced pressure to obtain the formula (4) 30 g of intermediate 4 represented by

（４）

(4)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 4.45-4.40 (dd, 8H), 3.56 (s, 4H), 3.45 (t, 4H), 1.70 (m, 4H) ), 1.60 (m, 4H), 1.38 (m, 4H), 0.88 (t, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 73.4, 71.5, 44.3, 43.4, 32.7, 29.5, 26.8, 26.2, 26.0, 25 .5,8.2

(Synthesis Example 1)
A reaction vessel equipped with a stirrer, a nitrogen introduction tube, a cooling tube and a thermometer was charged with 5 g of long-chain dibasic acid IPS-22 (Okamura Oil Co., Ltd.), 20 ml of tetrahydrofuran and 2 drops of dimethylformamide, and stirred at room temperature. did. Next, 1.8 g (0.014 mol) of oxalyl chloride was slowly added dropwise. After completion of dropping, hydrogen chloride generated while stirring at room temperature for 4 hours is removed. Thereafter, the reaction vessel was decompressed to remove tetrahydrofuran and hydrogen chloride to obtain 7.8 g of a long-chain dibasic acid chloride (IPS-22Cl).
Furthermore, 6 g (0.021 mol) of the intermediate 1 described above, 3.5 g (0.023 mol) of sodium iodide, and acetonitrile were added to a reaction vessel equipped with a stirrer, a nitrogen introducing tube, a cooling tube, and a thermometer. 50 ml was added and stirred while cooling with an ice water bath so that the temperature was 5 ° C. or lower. Next, 4.5 g of IPS-22Cl synthesized above was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. After adding a small amount of water to the reaction vessel, 100 ml of a hexane / ethyl acetate = 1/1 solution was added, and iodine was decomposed with 200 ml of a 10% aqueous sodium hydrogen sulfite solution. Further, the organic layer was washed in the order of pure water and saturated saline. After drying the organic layer with anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure to synthesize 10 g of intermediate M-1.

  Next, in a reaction vessel equipped with a stirrer and a thermometer, 4 g (0.003 mol) of intermediate M-1 synthesized by the above method, 1 g (0.013 mol) of acrylic acid, 6 mg of p-methoxyphenol, and Dimethylsulfoxide (40 ml) was added, and 2.1 g (0.013 mol) of 1,8-diazabicyclo [5,4,0] 7-undecene (hereinafter abbreviated as DBU) was slowly added dropwise with stirring at room temperature. After completion of the dropwise addition, the reaction vessel was heated to 90 ° C. and stirred for 12 hours to complete the reaction. To the reaction vessel, 100 ml of hexane / ethyl acetate = 1/1 was added, and the organic layer was washed in the order of 1/10 N hydrochloric acid solution, 5% sodium hydroxide solution, pure water, and saturated brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent of the organic layer was distilled off under reduced pressure. Then, the concentrated solution was purified by silica gel chromatography to obtain 3 g of radical polymerizable compound “M1”.

（Ｍ１）

(M1)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.43 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.21 (s, 4H) 4.07 (S, 4H), 3.37 (t, 4H), 3.32 (s, 4H), 2.32 (t, 4H), 1.75-1.38 (m, 8H), 1.25 ( m, 66H), 0.87 (t, 18H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.6, 70.4, 64.7, 64.4, 41.5, 34 3, 32.731.9, 29.6-29.2, 26.9, 26.1, 25.0, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Synthesis Example 2)
In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a cooling tube and a thermometer, 6.7 g (0.024 mol) of the intermediate 1 described above, 3.9 g (0.026 mol) of sodium iodide, and acetonitrile Was stirred while cooling with an ice-water bath so that the temperature became 5 ° C. or less. Subsequently, 2 g (0.012 mol) of dimethylmalonic acid chloride was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. After adding a small amount of water to the reaction vessel, 100 ml of a hexane / ethyl acetate = 1/1 solution was added, and iodine was decomposed with 200 ml of a 10% aqueous sodium hydrogen sulfite solution. Further, the organic layer was washed in the order of pure water and saturated saline. After drying the organic layer with anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure to synthesize 7 g of intermediate M-2.

  Next, 7 g (0.008 mol) of the intermediate M-2 synthesized by the above method, 2.2 g (0.030 mol) of acrylic acid, and 14 mg of p-methoxyphenol in a reaction vessel equipped with a stirrer and a thermometer. Then, 100 g of dimethyl sulfoxide was added, and 4.6 g (0.030 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of the dropwise addition, the reaction vessel was heated to 90 ° C. and stirred for 12 hours to complete the reaction. To the reaction vessel, 100 ml of hexane / ethyl acetate = 1/1 was added, and the organic layer was washed in the order of 1/10 N hydrochloric acid solution, 5% sodium hydroxide solution, pure water, and saturated brine. The organic layer was dried over anhydrous sodium sulfate, the solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified by silica gel chromatography to obtain 5 g of radical polymerizable compound “M2”.

（Ｍ２）

(M2)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.08 (s, 8H), 3. 35 (t, 4H), 3.27 (s, 4H), 1.63-1.38 (m, 14H), 1.25 (m, 36H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 172.2, 165.8, 130.7, 128.2, 71.6, 70.4, 65.4, 64.7, 64.6, 50 2, 41.7, 31.9, 29.5-29.3, 26.1, 233.1, 22.7, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Synthesis Example 3)
In a reaction vessel similar to Synthesis Example 2, 6.5 g (0.032 mol) of the intermediate 3 described above, 5.3 g (0.036 mol) of sodium iodide, and 50 ml of acetonitrile are placed at 5 ° C. or lower. The mixture was stirred while cooling with an ice-water bath. Next, 4 g (0.017 mol) of sebacic acid chloride was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. After adding a small amount of water to the reaction vessel, 100 ml of a hexane / ethyl acetate = 1/1 solution was added, and iodine was decomposed with 200 ml of a 10% aqueous sodium hydrogen sulfite solution. Further, the organic layer was washed in the order of pure water and saturated saline. After drying the organic layer with anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure to synthesize 10 g of Intermediate M-3.

  Subsequently, 3.5 g (0.048 mol) of acrylic acid, p-, except that 10 g (0.012 mol) of the intermediate M-3 was used instead of the intermediate M-2 of Synthesis Example 2. 14 mg of methoxyphenol and 100 ml of dimethyl sulfoxide were added, and 7.4 g (0.048 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of the dropwise addition, the reaction vessel was heated to 90 ° C. and stirred for 12 hours to complete the reaction. To the reaction vessel, 100 ml of hexane / ethyl acetate = 1/1 was added, and the organic layer was washed in the order of 1/10 N hydrochloric acid solution, 5% sodium hydroxide solution, pure water, and saturated brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent of the organic layer was distilled off under reduced pressure. Then, the concentrated solution was purified by silica gel chromatography to obtain 6 g of radical polymerizable compound “M3”.

（Ｍ３）

(M3)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.10 (s, 4H) 3.99 (S, 4H), 3.35 (t, 4H), 3.29 (s, 4H), 2.29 (t, 4H), 1.6-1.46 (m, 12H), 1.25 ( s, 20H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.7, 128.4, 71.7, 70.4, 64.7, 64.4, 41.5, 34 3, 31.6, 29.5-29.1, 25.8, 24.9, 23.1, 22.6, 14.0, 7.5
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Synthesis Example 4)
In a reaction vessel similar to Synthesis Example 2, 12 g (0.042 mol) of the intermediate 1 described above, 6.9 g (0.046 mol) of sodium iodide, and 70 ml of acetonitrile are placed so that the temperature is 5 ° C. or less. The mixture was stirred while cooling with an ice-water bath. Subsequently, 3.7 g (0.022 mol) of glutaric acid chloride was slowly added dropwise. After completion of dropping, the same operation as in Synthesis Example 2 was performed to synthesize 17 g of intermediate M-4.

  Subsequently, 5.0 g (0.070 mol) of acrylic acid, p− was similarly obtained except that 16 g (0.017 mol) of the intermediate M-4 was used instead of the intermediate M-2 of Synthesis Example 2. 30 mg of methoxyphenol and 200 ml of dimethyl sulfoxide were added, and 10.5 g (0.070 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of the dropwise addition, the same operation as in Synthesis Example 2 was performed, and 7.4 g of a radical polymerizable compound “M4” was obtained by silica gel chromatography purification.

（Ｍ４）

(M4)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.10 (s, 4H) 4.00 (S, 4H), 3.34 (t, 4H), 3.28 (s, 4H), 2.37 (t, 4H), 1.92 (m, 2H), 1.63 (m, 8H) , 1.25 (s, 36H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 172.6, 165.9, 130.7, 128.3, 71.7, 70.4, 64.7, 64.4, 41.5, 33 2, 31.9, 29.6-29.3, 26.1, 23.0, 22.6, 14.0, 7.5
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Synthesis Example 5)
In a reaction vessel similar to that of Synthesis Example 2, 10 g (0.035 mol) of the intermediate 1 described above, 5.8 g (0.039 mol) of sodium iodide, and 70 ml of acetonitrile are placed so that the temperature is 5 ° C. or less. The mixture was stirred while cooling with an ice-water bath. Subsequently, 2.9 g (0.018 mol) of succinic chloride was slowly added dropwise. After completion of dropping, the same operation as in Synthesis Example 2 was performed to synthesize 14 g of intermediate M-5.

  Subsequently, 4.4 g (0.061 mol) of acrylic acid, p-, except that 14 g (0.015 mol) of the intermediate M-5 was used instead of the intermediate M-2 of Synthesis Example 2. 25 mg of methoxyphenol and 200 ml of dimethyl sulfoxide were added, and 9.3 g (0.061 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of the dropwise addition, the same operation as in Synthesis Example 2 was performed, and 5.0 g of radical polymerizable compound “M5” was obtained by silica gel chromatography purification.

（Ｍ５）

(M5)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.10 (s, 4H) 4.02 (S, 4H), 3.34 (t, 4H), 3.29 (s, 4H), 2.37 (s, 4H), 1.64-1.38 (m, 8H), 1.25 ( m, 36H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 171.9, 165.9, 130.7, 128.3, 71.7, 70.4, 64.9, 64.6, 41.5, 31 .9, 29.6-29.0, 26.1, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Synthesis Example 6)
In a reaction vessel similar to Synthesis Example 2, 10 g (0.050 mol) of the intermediate 3 described above, 8.2 g (0.055 mol) of sodium iodide, and 70 ml of acetonitrile were placed so that the temperature was 5 ° C. or less. The mixture was stirred while cooling with an ice-water bath. Subsequently, 5.5 g (0.026 mol) of suberic acid chloride was slowly added dropwise. After completion of the dropwise addition, the same operation as in Synthesis Example 2 was performed to synthesize 17 g of intermediate M-6.

  Subsequently, 6.2 g (0.085 mol) of acrylic acid, p-, except that 17 g (0.021 mol) of the intermediate M-6 was used instead of the intermediate M-2 of Synthesis Example 2. 36 mg of methoxyphenol and 250 ml of dimethyl sulfoxide were added, and 13.0 g (0.085 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of the dropping, the same operation as in Synthesis Example 2 was performed, and 6.5 g of radical polymerizable compound “M6” was obtained by silica gel chromatography purification.

（Ｍ６）

(M6)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.14 (s, 4H) 4.07 (S, 4H), 3.35 (t, 4H), 3.29 (s, 4H), 2.29 (t, 4H), 1.63-1.43 (m, 12H), 1.25 ( m, 16H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.4, 165.9, 130.7, 128.3, 71.6, 70.4, 64.7, 64.4, 41.5, 34 3, 31.9, 29.6-29.1, 25.7, 24.7, 23.1, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Synthesis Example 7)
In a reaction vessel equipped with a stirrer, a nitrogen introducing tube, a cooling tube and a thermometer, 1,6-hexanediol diglycidyl ether “Epolite 1600” (manufactured by Kyoeisha) 60 g (0.26 mol), acrylic acid 41 g (0.57) Mol), 200 mg of p-methoxyphenol, and 0.5 g of N, N-dimethylbenzylamine as a catalyst were added and stirred at 80 ° C. Next, the reaction solution was heated to 100 ° C. and stirred for 5 hours, and then the reaction was completed. Subsequently, 500 ml of toluene was added, and the mixture was washed with 300 ml of 5% sodium hydroxide solution and saturated brine in this order. The organic layer was dried over anhydrous sodium sulfate, and the organic solvent was distilled off under reduced pressure to obtain a light brown transparent liquid intermediate M-7. 80 g of was obtained.

  Next, in a reaction vessel equipped with a stirrer, a nitrogen introducing tube, a cooling tube and a thermometer, 300 ml of methylene chloride, 26.7 g (0.23 mol) of n-hexanoic acid, 20 mg of p-methoxyphenol, 43 g of “Dotite WSC” (0.23 mol) and 2.7 g of 4-dimethylaminopyridine as a catalyst were added, and a 50 ml solution of methylene chloride in which 40 g of the intermediate M-7 was dissolved was slowly added dropwise over 1 hour while maintaining the temperature at 5 ° C. After completion of the dropwise addition, the reaction was terminated after stirring at room temperature for 10 hours. The organic layer was washed with 1 / 10N hydrochloric acid solution and saturated saline in this order, and dried over anhydrous sodium sulfate. After the solvent of the organic layer was distilled off under reduced pressure, the concentrated solution was purified by silica gel chromatography to obtain 45.2 g of a radical polymerizable compound “M7”.

Ｍ７

M7

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.45 (d, 2H), 6.17 (q, 2H), 5.87 (d, 2H), 5.28 (m, 2H), 4. 41 (m, 2H), 4.37 (m, 2H), 3.6 (m, 4H), 3.4 (m, 4H), 2.32 (t, 4H), 1.73-1.55 (M, 8H), 1.21 (s, 12H), 0.88 (t, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.0, 165.6, 131.1, 128.0, 71.5, 70.5, 69.9, 68.9, 63.0, 62 6,34.4,34.0,31.8,29.6-29.0,24.9,22.6,14.0,
Infrared absorption spectrum (IR) (KBr) cm ⁻¹ : 2930, 2861, 1744,
1652-1622, 1176, 807

(Synthesis Example 8)
In a reaction vessel equipped with a stirrer, a nitrogen introducing tube, a cooling tube and a thermometer, 100 g (0.46 mol) of neopentyl glycol diglycidyl ether “EX-211” (manufactured by Nagase Chemitex), 90 g of acrylic acid (1 0.2 mol), 200 mg of p-methoxyphenol, and 1 g of N, N-dimethylbenzylamine as a catalyst were added and stirred at 80 ° C. Next, the temperature of the reaction solution was raised to 100 ° C., and the reaction was completed after stirring for 5 hours while maintaining the temperature.
Next, 300 ml of toluene was added and washed with 300 ml of 5% sodium hydroxide solution and saturated brine in that order, the organic layer was dried over anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure, and 170 g of intermediate M-8 was obtained. Got.

Next, in a reaction vessel equipped with a stirrer, a nitrogen introducing tube, a cooling tube, and a thermometer, 300 ml of methylene chloride, 55 g (0.27 mol) of lauric acid, 20 mg of p-methoxyphenol, 1-ethyl produced by Dojin Chemical Co., Ltd. -3- (3-dimethylaminopropyl) carbodiimide hydrochloride “Dotite WSC” 53 g (0.27 mol) and 4-dimethylaminopyridine 3.3 g were added as a catalyst while maintaining the temperature at 5 ° C. 8 A 50 ml solution of methylene chloride in which 50 g was dissolved was slowly added dropwise over 1 hour. After completion of the dropwise addition, the reaction was terminated after stirring at room temperature for 10 hours. The organic layer was washed with 1 / 10N hydrochloric acid solution and saturated saline in this order, and dried over anhydrous sodium sulfate. After the solvent of the organic layer was distilled off under reduced pressure, the concentrated solution was purified by silica gel chromatography to obtain 60 g of a radical polymerizable compound “M8”.

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.45 (d, 2H), 6.17 (q, 2H), 5.87 (d, 2H), 5.28 (m, 2H), 4. 41 (m, 2H), 4.37 (m, 2H), 3.6 (m, 4H), 3.2 (m, 4H), 2.34 (t, 4H), 1.6 (m, 4H) ), 1.25 (s, 16H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.0, 165.6, 131.1, 128.0, 69.9, 69.5, 63.1, 36.4, 34.3, 31 .8, 29.5-29.0, 24.9, 22.6, 21.8, 14.0,
Infrared absorption spectrum (IR) (KBr) cm ⁻¹ : 2930, 2861, 1744,
1652-1622, 1176, 807

(Synthesis Example 9)
In a reaction vessel equipped with a stirrer, a nitrogen introducing tube, a cooling tube and a thermometer, 300 ml of methylene chloride, 28 g (0.14 mol) of lauric acid, 20 mg of p-methoxyphenol, 27 g (0.14 mol) of “Dotite WSC” and a catalyst As a solution, 1.7 g of 4-dimethylaminopyridine was added, and a 50 ml solution of methylene chloride in which 43.8 g of long-chain dibasic acid epoxy acrylate “IPS-22GA” manufactured by Okamura Oil Co., Ltd. was dissolved was added. Drip slowly over time. After completion of the dropwise addition, the reaction was terminated after stirring at room temperature for 10 hours. The organic layer was washed with 1 / 10N hydrochloric acid solution and saturated saline in this order, and dried over anhydrous sodium sulfate. After the solvent of the organic layer was distilled off under reduced pressure, the concentrated solution was purified by silica gel chromatography to obtain 33 g of a radical polymerizable compound “M9”.

Ｍ９

M9

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.45 (d, 2H), 6.17 (q, 2H), 5.67 (d, 2H), 5.30 (m, 2H), 4. 33 (m, 2H), 4.25 (m, 2H), 4.21 (m, 4H), 2.34 (m, 4H), 2.32 (t, 4H), 1.70-1.55 (M, 8H), 1.53 (m, 2H), 1.25 (s, 56H), 0.88 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 173.2, 165.9, 131.5, 128.0, 71.6, 69.9, 68.9, 68.8, 63 0.0, 62.6, 42.4, 34.9, 34.0, 31.8, 29.6-29.0, 24.9, 22.6, 14.0,
Infrared absorption spectrum (IR) (KBr) cm ⁻¹ : 2930, 2861, 1744,
1652-1622, 1176, 807

(Synthesis Example 10)
In a reaction vessel similar to Synthesis Example 2, 5.7 g (0.020 mol) of intermediate 1 described above, 3.3 g (0.022 mol) of sodium iodide, and 50 ml of acetonitrile are placed at 5 ° C. or lower. The mixture was stirred while cooling with an ice-water bath. Next, 2.5 g (0.010 mol) of sebacic acid chloride was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. After adding a small amount of water to the reaction vessel, 100 ml of a hexane / ethyl acetate = 1/1 solution was added, and iodine was decomposed with 200 ml of a 10% aqueous sodium hydrogen sulfite solution. Further, the organic layer was washed in the order of pure water and saturated saline. The organic layer was dried over anhydrous sodium sulfate, and then the organic solvent was distilled off under reduced pressure to synthesize 6.5 g of intermediate M-10.

  Subsequently, 1.4 g (0.020 mol) of acrylic acid was similarly obtained except that 6.5 g (0.012 mol) of the intermediate M-10 was used instead of the intermediate M-2 of Synthesis Example 2. 14 mg of p-methoxyphenol and 100 ml of dimethyl sulfoxide were added, and 3.0 g (0.020 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of dropping, the same operation as in Synthesis Example 2 was performed, and 3.5 g of radical polymerizable compound “M10” was obtained by silica gel chromatography purification.

（Ｍ１０）

(M10)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.14 (s, 4H) 4.03 (S, 4H), 3.36 (t, 4H), 3.29 (s, 4H), 2.29 (t, 4H), 1.61-1.38 (m, 12H), 1.25 ( m, 44H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 165.9, 130.6, 128.3, 71.5, 70.4, 64.7, 64.4, 41.4, 34 3, 31.9, 29.6-29.0, 26.1, 24.9, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Synthesis Example 11)
In a reaction vessel similar to Synthesis Example 2, 15 g (0.055 mol) of the intermediate 2 described above, 9.1 g (0.061 mol) of sodium iodide, and 150 ml of acetonitrile were placed so that the temperature was 5 ° C. or less. The mixture was stirred while cooling with an ice-water bath. Next, 5.3 g (0.029 mol) of adipic acid chloride was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. A small amount of water was added to the reaction vessel, 200 ml of a hexane / ethyl acetate = 1/1 solution was added, and iodine was decomposed with 300 ml of a 10% aqueous sodium bisulfite solution. Further, the organic layer was washed in the order of pure water and saturated saline. The organic layer was dried over anhydrous sodium sulfate, and then the organic solvent was distilled off under reduced pressure to synthesize 23.3 g of intermediate M-11.

  Subsequently, 7.4 g (0.102 mol) of acrylic acid was similarly obtained except that 23.3 g (0.026 mol) of the intermediate M-11 was used instead of the intermediate M-2 of Synthesis Example 2. 110 mg of p-methoxyphenol and 300 ml of dimethylsulfoxide were added, and 3.0 g (0.020 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of dropping, the same operation as in Synthesis Example 2 was performed, and 11.2 g of radical polymerizable compound “M11” was obtained by silica gel chromatography purification.

（Ｍ１１）

(M11)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.14 (s, 4H) 4.03 (S, 4H), 3.36 (t, 4H), 3.29 (s, 4H), 2.29 (t, 4H), 1.61-1.38 (m, 12H), 1.25 ( m, 36H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 165.9, 130.6, 128.3, 71.5, 70.4, 64.7, 64.4, 41.4, 34 3, 31.9, 29.6-29.0, 26.1, 24.9, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.

(Synthesis Example 12)
In a reaction vessel similar to Synthesis Example 2, 14.3 g (0.045 mol) of the intermediate 4 described above, 16.4 g (0.110 mol) of sodium iodide, and 150 ml of acetonitrile are placed at 5 ° C. or lower. The mixture was stirred while cooling with an ice-water bath. Next, 18.2 g (0.095 mol) of n-decanoyl chloride was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. A small amount of water was added to the reaction vessel, 300 ml of a hexane / ethyl acetate = 1/1 solution was added, and iodine was decomposed with 400 ml of a 10% aqueous sodium bisulfite solution. Further, the organic layer was washed in the order of pure water and saturated saline. After drying the organic layer with anhydrous sodium sulfate, the organic solvent was distilled off under reduced pressure to synthesize 28.2 g of intermediate M-12.

  Subsequently, 9.3 g (0.128 mol) of acrylic acid was similarly obtained except that 28.2 g (0.032 mol) of the intermediate M-12 was used instead of the intermediate M-2 of Synthesis Example 2. 60 mg of p-methoxyphenol and 300 ml of dimethyl sulfoxide were added, and 19.5 g (0.128 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of the dropwise addition, the same operation as in Synthesis Example 2 was performed, and 16.7 g of a radical polymerizable compound “M12” was obtained by silica gel chromatography purification.

（Ｍ１２）

(M12)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.10 (s, 4H) 3.99 (S, 4H), 3.34 (t, 4H), 3.29 (s, 4H), 2.29 (t, 4H), 1.62 (s, 4H), 1.6-1.4 ( m, 8H), 1.25 (m, 28H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.5, 70.4, 64.7, 64.3, 41.4, 34 3, 31.8, 29.5-29.1, 25.9, 24.9, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

(Synthesis Example 13)
9.4 g (0.029 mol) of the intermediate 4 described above, 10.3 g (0.069 mol) of sodium iodide, and 150 ml of acetonitrile are placed in a reaction vessel similar to that of Synthesis Example 2, and the temperature is 5 ° C. or lower. The mixture was stirred while cooling with an ice-water bath. Next, 14.7 g (0.060 mol) of n-myristolyl chloride was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and further stirred at room temperature for 3 hours to complete the reaction. After adding a small amount of water to the reaction vessel, 400 ml of a hexane / ethyl acetate = 1/1 solution was added, and iodine was decomposed with 500 ml of a 10% aqueous sodium bisulfite solution. Further, the organic layer was washed in the order of pure water and saturated saline. The organic layer was dried over anhydrous sodium sulfate, and then the organic solvent was distilled off under reduced pressure to synthesize 22.8 g of intermediate M-13.

  Subsequently, 6.8 g (0.095 mol) of acrylic acid was similarly obtained except that 22.8 g (0.032 mol) of the intermediate M-13 was used instead of the intermediate M-2 of Synthesis Example 2. 60 mg of p-methoxyphenol and 200 ml of dimethyl sulfoxide were added, and 14.4 g (0.094 mol) of DBU was slowly added dropwise with stirring at room temperature. After completion of the dropwise addition, the same operation as in Synthesis Example 2 was performed, and 9.6 g of a radical polymerizable compound “M13” was obtained by silica gel chromatography purification.

（Ｍ１３）

(M13)

(Physical property value)
1H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.10 (s, 4H) 3.99 (S, 4H), 3.34 (t, 4H), 3.29 (s, 4H), 2.29 (t, 4H), 1.62 (s, 4H), 1.6-1.4 ( m, 8H), 1.25 (m, 46H), 0.87 (t, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.7, 165.9, 130.6, 128.3, 71.5, 70.4, 64.7, 64.4, 41.5, 34 3, 31.9, 29.6-29.1, 25.9, 24.9, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

The light scattering type liquid crystal devices in the examples were produced by the following method.
A light control layer forming material comprising a liquid crystal composition, a radical polymerizable compound and a photopolymerization initiator was injected into a glass cell with ITO having a cell gap of 5 μm by a vacuum injection method. At this time, the temperature in the vacuum injection apparatus was controlled so that the light control layer forming material was always in a uniform state. The degree of vacuum was set to 2 Pascals. After the injection, the glass cell was taken out, the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond), and then the temperature was controlled to 1 to 2 ° C. higher than the isotropic-nematic transition point of the light control layer forming material. A light-scattering liquid crystal device was obtained by irradiating with a high-pressure mercury lamp adjusted to an irradiation intensity of 10 mW / cm ² through UV-35 (manufactured by Toshiba Glass Co., Ltd.) for 60 seconds.

Abbreviations and meanings of characteristics of the light-scattering liquid crystal devices shown in the examples are as follows.
In an indoor environment at 25 ° C., the voltage applied to the light-scattering liquid crystal device is gradually increased until no light transmittance changes under the conditions of 0.2 V / step and 5 seconds / step from no application. When the light transmittance does not change, the applied voltage is lowered to no application under the condition of 0.2 V step and 5 seconds / step. The following characteristic values are defined from the relationship between the applied voltage and the light transmittance when this operation is performed.
T0: Light transmittance (%) when no voltage is applied.
T100: Light transmittance (%) when the light transmittance change due to the increase in applied voltage reaches saturation and the light transmittance does not change.
T50: light transmittance (%) between T0 and T100 defined by T0 + 0.5 × (T100−T0).
V100: Applied voltage (V) at T100.
Vr50: Applied voltage (V) at the transmittance of T50 when the applied voltage to the light scattering type liquid crystal device is increased from no application.
Vd50: Applied voltage (V) at the transmittance of T50 when the applied voltage to the light scattering type liquid crystal device is lowered from V100.
HS50: Optical hysteresis (mV) defined by Vr50-Vd50. This definition is illustrated in FIG.
HS50 / d: a value (mV / μm) obtained by dividing HS50 of the light scattering type liquid crystal device by the cell gap d of the light scattering type device.

Example 1
The liquid crystal composition (A) is 70%, the mixture of the radical polymerizable compounds (M1) and (M2) is 29.4%, and the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) is 0.6%. A composition for a light scattering liquid crystal device was prepared, and a light scattering liquid crystal device was obtained by the above-described method. The liquid crystal temperature range of the liquid crystal composition (A) is -37 ° C to 82 ° C.

液晶組成物（Ａ）

Liquid crystal composition (A)

By polymerizing a mixture of the radically polymerizable compounds (M1) and (M2), the following five types of inter-chain patterns can be generated.
1) "Between M1 and M1" generated by M1 bonding
2) “Between M1 and M2” generated by the combination of M1 and M2
3) “Between M2 and M2” generated by M2 bonding
4) “In M1” which is between side chains R1 and R2 existing in M1 from before polymerization
5) “In M2” between side chains R1 and R2 existing in M2 from before polymerization
Table 6 shows the values of α calculated between the side chains of 1) to 5).

From Table 6, the value of Δα obtained from the mixture of the radical polymerizable compounds (M1) and (M2) is 12 − (− 5) = 17.

  Next, βi which is the abundance ratio between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radical polymerizable compounds (M1) and (M2) were randomly polymerized. In this example, the mixing ratio (mol / mol) of the radical polymerizable compounds (M1) and (M2) was changed as shown in Table 7. In Table 7, a monomer represents a radical polymerizable compound. Table 7 shows the abundance ratio βi of the side chain 1) to 5) contained in the light-scattering liquid crystal device obtained from the mixing ratios of the radically polymerizable compounds (M1) and (M2) in molar fractions. .

  Between αi in Table 6 and βi in Table 7, between the side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M1) and (M2) The values of (αi × βi) and Σ (αi × βi) can be obtained. Table 8 shows the calculated value and the HS50 / d evaluation result of the light scattering type liquid crystal device.

(Example 2)
70% of the liquid crystal composition (A), 29.4% of the mixture of the radical polymerizable compounds (M3) and (M4), and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals). A composition for a light scattering liquid crystal device was prepared, and a light scattering liquid crystal device was obtained by the above-described method.

By polymerizing a mixture of the radically polymerizable compounds (M3) and (M4), the following five types of inter-chain patterns can be generated.
1) “Between M3 and M3” generated by M3 bonding
2) “Between M3 and M4” generated by the combination of M3 and M4
3) “Between M4 and M4” generated by M4 joining
4) “In M3” which is between side chains R1 and R2 existing in M3 from before polymerization
5) “In M4” between the side chains R1 and R2 existing in M4 from before polymerization
Table 9 shows the values of α calculated between the side chains of 1) to 5).

From Table 9, the value of Δα obtained from the mixture of the radical polymerizable compounds (M3) and (M4) is 8 − (− 3) = 11.

  Next, the abundance ratio βi between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radical polymerizable compounds (M3) and (M4) were polymerized randomly. In this example, the mixing ratio (mol / mol) of the radical polymerizable compounds (M3) and (M4) was changed as shown in Table 10. In Table 10, a monomer represents a radical polymerizable compound. Table 10 shows the abundance ratio βi of side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M3) and (M4) in terms of mole fraction. .

  Between αi in Table 9 and βi in Table 10, between the side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M3) and (M4) The values of (αi × βi) and Σ (αi × βi) can be obtained. Table 11 shows the calculated value and the HS50 / d evaluation result of the light scattering liquid crystal device.

(Example 3)
Liquid crystal composition (A) 70%, radical polymerizable compound (M3) 5.9%, radical polymerizable compound (M5) 23.5%, photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) A composition for a light scattering liquid crystal device comprising 0.6% was prepared, and a light scattering liquid crystal device was obtained by the method described above.

By polymerizing a mixture of the radically polymerizable compounds (M3) and (M5), the following five types of inter-chain patterns can be generated.
1) “Between M3 and M3” generated by M3 bonding
2) “Between M3 and M5” generated by the combination of M3 and M5
3) “Between M5 and M5” generated by M5 bonding
4) “In M3” which is between side chains R1 and R2 existing in M3 from before polymerization
5) “In M5” which is between side chains R1 and R2 existing in M5 from before polymerization
Table 12 shows values of α calculated between the side chains of 1) to 5).

  From Table 12, the value of Δα obtained from the mixture of the radical polymerizable compounds (M3) and (M5) is 8-(− 4) = 12.

  Next, the abundance ratio βi between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radical polymerizable compounds (M3) and (M5) were polymerized randomly. In this example, the mixing ratio (mol / mol) of the radical polymerizable compound (M3) and (M5) is 0.22: 0.78. In Table 13, a monomer represents a radical polymerizable compound. Table 13 shows the abundance ratio βi of side chains 1) to 5) contained in the light-scattering liquid crystal device of this example in terms of mole fraction.

  From [alpha] in Table 12 and [beta] in Table 13, the values of ([alpha] i * [beta] i) and [Sigma] ([alpha] i * [beta] i) between the side chains 1) to 5) included in the light scattering liquid crystal device of this example. Can be requested. Table 14 shows the calculated value and the HS50 / d evaluation result of the light scattering liquid crystal device.

Example 4
Liquid crystal composition (A) 70%, radical polymerizable compound (M6) 5.9%, radical polymerizable compound (M5) 23.5%, photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) A composition for a light scattering liquid crystal device comprising 0.6% was prepared, and a light scattering liquid crystal device was obtained by the method described above. The liquid crystal temperature range of the liquid crystal composition (A) is -37 ° C to 82 ° C.

By polymerizing a mixture of the radically polymerizable compounds (M6) and (M5), the following five types of inter-chain patterns can be generated.
1) “Between M6 and M6” generated by M6 bonding
2) “Between M6 and M5” generated by the combination of M6 and M5
3) “Between M5 and M5” generated by M5 bonding
4) “In M6” which is between side chains R1 and R2 existing in M6 from before polymerization
5) “In M5” which is between side chains R1 and R2 existing in M5 from before polymerization
Table 15 shows values of α calculated between the side chains of 1) to 5).

  From Table 15, the value of Δα obtained from the mixture of the radical polymerizable compounds (M6) and (M5) is 6-(− 4) = 10.

  Next, the abundance ratio βi between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radical polymerizable compounds (M6) and (M5) were randomly polymerized. In this example, the mixing ratio (mol / mol) of the radical polymerizable compound (M6) and (M5) is 0.23: 0.77. In Table 16, a monomer represents a radical polymerizable compound. Table 16 shows the abundance ratio βi between side chains 1) to 5) contained in the light-scattering liquid crystal device of this example as a mole fraction.

  From αi in Table 15 and βi in Table 16, the values of (αi × βi) and Σ (αi × βi) between the side chains 1) to 5) included in the light-scattering liquid crystal device of this example. Can be requested. Table 17 shows the calculated value and the HS50 / d evaluation result of the light scattering type liquid crystal device.

(Example 5)
The liquid crystal composition (B) is 70%, the mixture of the radical polymerizable compounds (M7) and (M8) is 29.4%, and the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) is 0.6%. A composition for a light scattering liquid crystal device was prepared, and a light scattering liquid crystal device was obtained by the above-described method. The liquid crystal temperature range of the liquid crystal composition (B) is −41 ° C. to 80 ° C.

液晶組成物（Ｂ）

Liquid crystal composition (B)

By polymerizing a mixture of the radically polymerizable compounds (M7) and (M8), the following five types of inter-chain patterns can be generated.
1) “Between M7 and M7” generated by M7 bonding
2) "Between M7 and M8" generated by the combination of M7 and M8
3) “Between M8 and M8” that occurs when M8 bonds
4) “In M7” which is between side chains R1 and R2 existing in M7 before polymerization
5) “In M8” which is between side chains R1 and R2 existing in M8 before polymerization
Table 18 shows the values of α calculated between the side chains of 1) to 5).

  From Table 18, the value of Δα obtained from the mixture of the radical polymerizable compounds (M7) and (M8) is 5-(− 4) = 9.

  Next, the abundance ratio βi between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radically polymerizable compounds (M7) and (M8) were polymerized randomly. In this example, the mixing ratio (mol / mol) of the radical polymerizable compounds (M7) and (M8) was changed as shown in Table 19. In Table 19, a monomer represents a radically polymerizable compound. Table 19 shows the abundance ratio βi of the inter-chain 1) to 5) contained in the light-scattering type liquid crystal device obtained from the respective mixing ratios of the radically polymerizable compounds (M7) and (M8) as a mole fraction. .

  Between αi in Table 18 and βi in Table 19, between the side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M7) and (M8) The values of (αi × βi) and Σ (αi × βi) can be obtained. Table 20 shows the calculated value and the HS50 / d evaluation result of the light scattering liquid crystal device.

(Example 6)
70% of the liquid crystal composition (B), 29.4% of the mixture of the radical polymerizable compounds (M9) and (M8), and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals). A composition for a light scattering liquid crystal device was prepared, and a light scattering liquid crystal device was obtained by the above-described method. The liquid crystal temperature range of the liquid crystal composition (B) is −41 ° C. to 80 ° C.

By polymerizing a mixture of the radically polymerizable compounds (M9) and (M8), the following five types of inter-chain patterns can be generated.
1) “Between M9 and M9” generated by M9 bonding
2) "Between M9 and M8" generated by the combination of M9 and M8
3) “Between M8 and M8” that occurs when M8 bonds
4) “In M9” which is between side chains R1 and R2 existing in M9 from before polymerization
5) “In M8” which is between side chains R1 and R2 existing in M8 before polymerization
Table 21 shows values of α calculated between the side chains of 1) to 5).

  From Table 21, the value of Δα obtained from the mixture of the radical polymerizable compounds (M9) and (M8) is 13 − (− 4) = 17.

  Next, the abundance ratio βi between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radical polymerizable compounds (M9) and (M8) were polymerized randomly. In this example, the mixing ratio (mol / mol) of the radical polymerizable compounds (M9) and (M8) was changed as shown in Table 22. In Table 22, the monomer represents a radical polymerizable compound. Table 22 shows the abundance ratios βi of the inter-chain 1) to 5) contained in the light-scattering liquid crystal device obtained from the mixing ratios of the radically polymerizable compounds (M9) and (M8) in terms of mole fraction. .

  Between αi in Table 21 and βi in Table 22, between the side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M9) and (M8) The values of (αi × βi) and Σ (αi × βi) can be obtained. Table 23 shows this calculated value and the HS50 / d evaluation result of the light scattering type liquid crystal device.

(Example 7)
Liquid crystal composition (B) is 70%, radical polymerizable compound (M10) is 11.8%, radical polymerizable compound (M11) is 17.6%, photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) A composition for a light scattering liquid crystal device comprising 0.6% was prepared, and a light scattering liquid crystal device was obtained by the method described above. The liquid crystal temperature range of the liquid crystal composition (B) is −41 ° C. to 80 ° C.

By polymerizing a mixture of the radically polymerizable compounds (M10) and (M11), the following five types of inter-chain patterns can be generated.
1) “Between M10 and M10” generated by M10 bonding
2) “Between M10 and M11” generated by combining M10 and M11
3) "Between M11 and M11" generated by M11 bonding
4) “In M10” between the side chains R1 and R2 existing in M10 from before polymerization
5) “In M11” which is between side chains R1 and R2 existing in M11 before polymerization
Table 24 shows the values of α calculated between the side chains of 1) to 5).

  From Table 24, the value of Δα obtained from the mixture of the radical polymerizable compounds (M10) and (M11) is 2-(− 3) = 5.

  Next, the abundance ratio βi between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radical polymerizable compounds (M10) and (M11) were polymerized randomly. In this example, the mixing ratio (mol / mol) of the radical polymerizable compound (M10) and (M11) is 0.38: 0.62. In Table 25, the monomer represents a radical polymerizable compound. Table 25 shows the abundance ratio βi between side chains 1) to 5) included in the light-scattering liquid crystal device of this example in terms of mole fraction.

  From αi in Table 24 and βi in Table 25, between the side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M10) and (M11) The values of (αi × βi) and Σ (αi × βi) can be obtained. Table 26 shows the calculated value and the HS50 / d evaluation result of the light scattering liquid crystal device.

(Example 8)
The liquid crystal composition (C) is 70%, the mixture of the radical polymerizable compounds (M7) and (M8) is 29.4%, and the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) is 0.6%. A composition for a light scattering liquid crystal device was prepared, and a light scattering liquid crystal device was obtained by the above-described method.

液晶組成物（Ｃ）

Liquid crystal composition (C)

By polymerizing a mixture of the radically polymerizable compounds (M7) and (M8), the following five types of inter-chain patterns can be generated.
1) “Between M7 and M7” generated by M7 bonding
2) "Between M7 and M8" generated by the combination of M7 and M8
3) “Between M8 and M8” that occurs when M8 bonds
4) “In M7” which is between side chains R1 and R2 existing in M7 before polymerization
5) “In M8” which is between side chains R1 and R2 existing in M8 before polymerization
Table 27 shows the values of α calculated between the side chains of 1) to 5).

From Table 27, the value of Δα obtained from the mixture of the radical polymerizable compounds (M7) and (M8) is 5-(− 4) = 9.

  Next, the abundance ratio βi between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radically polymerizable compounds (M7) and (M8) were polymerized randomly. In this example, the mixing ratio (mol / mol) of the radical polymerizable compounds (M7) and (M8) was changed as shown in Table 28. In Table 28, the monomer represents a radical polymerizable compound. Table 28 shows the abundance ratio βi of the interchain side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M7) and (M8) in terms of mole fraction. .

  From αi in Table 27 and βi in Table 28, between the side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M7) and (M8) The values of (αi × βi) and Σ (αi × βi) can be obtained. Table 29 shows the calculated value and the HS50 / d evaluation result of the light-scattering liquid crystal device.

Example 9
The liquid crystal composition (C) is 70%, the mixture of the radical polymerizable compounds (M12) and (M13) is 29.4%, and the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) is 0.6%. A composition for a light scattering liquid crystal device was prepared, and a light scattering liquid crystal device was obtained by the above-described method.

By polymerizing a mixture of the radical polymerizable compounds (M12) and (M13), the following five types of inter-chain patterns can be generated.
1) "Between M12 and M12" generated by M12 bonding
2) “Between M12 and M13” generated by combining M12 and M13
3) “Between M13 and M13” generated by M13 bonding
4) “In M12” which is between side chains R1 and R2 existing in M12 before polymerization
5) “In M13” which is between side chains R1 and R2 existing in M13 from before polymerization
Table 30 shows values of α calculated between the side chains of 1) to 5).

  From Table 30, the value of Δα obtained from the mixture of the radical polymerizable compounds (M12) and (M13) is 0 − (− 5) = 5.

  Next, the abundance ratio βi between the side chains 1) to 5) contained in the light scattering type liquid crystal device is estimated. This abundance ratio βi was calculated stochastically assuming that all of the radical polymerizable compounds (M12) and (M13) were polymerized randomly. In this example, the mixing ratio (mol / mol) of the radical polymerizable compounds (M12) and (M13) was changed as shown in Table 31. In Table 31, a monomer represents a radical polymerizable compound. Table 31 shows the abundance ratio βi between side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the mixing ratios of the radically polymerizable compounds (M12) and (M13) in terms of mole fraction. .

  From αi in Table 30 and βi in Table 31, the distance between side chains 1) to 5) contained in the light-scattering liquid crystal device obtained from the respective mixing ratios of the radical polymerizable compounds (M12) and (M13) The values of (αi × βi) and Σ (αi × βi) can be obtained. Table 32 shows the calculated value and the HS50 / d evaluation result of the light scattering liquid crystal device.

(Comparative Example 1)
For light-scattering liquid crystal devices comprising 70% of the liquid crystal composition (A), 29.4% of the radical polymerizable compound (M2) and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) The composition was prepared and the light-scattering type liquid crystal device was obtained by the above-mentioned method. The liquid crystal temperature range of the liquid crystal composition (A) is -37 ° C to 82 ° C.

By polymerizing the radical polymerizable compound (M2), the following two types of inter-chain patterns can be generated.
1) "Between M2 and M2" generated by M2 bonding
2) “In M2” between side chains R1 and R2 existing in M2 from before polymerization
Table 33 shows the values of α calculated between the side chains of 1) to 2).

  From Table 33, the value of Δα obtained from the radical polymerizable compound (M2) is (−3) − (− 5) = 2.

The abundance ratio between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is the following molar fraction βi assuming that all of the radical polymerizable compound (M2) is polymerized.
1) βi between side chains: βi between side chains 2) = 0.67: 0.33
From αi in Table 33 and βi described above, Σ (αi × βi) between the side chains 1) and 2) included in the light-scattering liquid crystal device of this comparative example is −3.67.
When HS50 / d of the light-scattering liquid crystal device of this comparative example was evaluated, it was 102.7 mV / μm.

(Comparative Example 2)
For light-scattering liquid crystal devices comprising 70% of the liquid crystal composition (A), 29.4% of the radical polymerizable compound (M3), and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) The composition was prepared and the light-scattering type liquid crystal device was obtained by the above-mentioned method. The liquid crystal temperature range of the liquid crystal composition (A) is -37 ° C to 82 ° C.

By polymerizing the radical polymerizable compound (M3), the following two types of inter-chain patterns can be generated.
1) “Between M3 and M3” generated by M3 bonding
2) “In M3” which is between side chains R1 and R2 existing in M3 before polymerization
Table 34 shows the values of α calculated between the side chains of 1) to 2).

From Table 34, the value of Δα obtained from the radical polymerizable compound (M3) is 8-3 = 5.

The abundance ratio between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is the following molar fraction βi assuming that all of the radical polymerizable compound (M3) is polymerized.
1) βi between side chains: βi between side chains 2) = 0.67: 0.33
From αi in Table 34 and βi described above, Σ (αi × βi) between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is 4.67.
When HS50 / d of the light-scattering type liquid crystal device of this comparative example was evaluated, it was 49.4 mV / μm.

(Comparative Example 3)
For light-scattering liquid crystal devices comprising 70% of the liquid crystal composition (A), 29.4% of the radical polymerizable compound (M4) and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) The composition was prepared and the light-scattering type liquid crystal device was obtained by the above-mentioned method. The liquid crystal temperature range of the liquid crystal composition (A) is -37 ° C to 82 ° C.

By polymerizing the radical polymerizable compound (M4), the following two types of inter-chain patterns can be generated.
1) "Between M4 and M4" generated by M4 bonding
2) “In M4” between side chains R1 and R2 present in M4 before polymerization
Table 35 shows the values of α calculated for the side chains of 1) to 2).

  From Table 35, the value of Δα obtained from the radical polymerizable compound (M4) is (−3) − (− 3) = 0.

The abundance ratio between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is the following molar fraction βi assuming that all of the radical polymerizable compound (M4) is polymerized.
1) βi between side chains: βi between side chains 2) = 0.67: 0.33
From αi in Table 35 and βi described above, Σ (αi × βi) between the side chains 1) and 2) included in the light-scattering liquid crystal device of this comparative example is −3.00.
When HS50 / d of the light-scattering type liquid crystal device of this comparative example was evaluated, it was 43.1 mV / μm.

(Comparative Example 4)
For light-scattering liquid crystal devices comprising 70% of the liquid crystal composition (A), 29.4% of the radical polymerizable compound (M5) and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) The composition was prepared and the light-scattering type liquid crystal device was obtained by the above-mentioned method. The liquid crystal temperature range of the liquid crystal composition (A) is -37 ° C to 82 ° C.

By polymerizing the radically polymerizable compound (M5), the following two types of inter-chain patterns can be generated.
1) "Between M5 and M5" generated by M5 bonding
2) “In M5” between side chains R1 and R2 present in M5 from before polymerization
Table 36 shows the values of α calculated between the side chains of 1) to 2).

  From Table 36, the value of Δα obtained from the radical polymerizable compound (M5) is (−3) − (− 4) = 1.

The abundance ratio between the side chains 1) and 2) contained in the light-scattering type liquid crystal device of this comparative example is the following molar fraction βi assuming that all of the radical polymerizable compound (M5) is polymerized.
1) βi between side chains: βi between side chains 2) = 0.67: 0.33
From αi in Table 36 and βi described above, Σ (αi × βi) between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is −3.33.
When HS50 / d of the light-scattering type liquid crystal device of this comparative example was evaluated, it was 76.0 mV / μm.

(Comparative Example 5)
For light-scattering liquid crystal devices comprising 70% of the liquid crystal composition (A), 29.4% of the radical polymerizable compound (M6), and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals). The composition was prepared and the light-scattering type liquid crystal device was obtained by the above-mentioned method. The liquid crystal temperature range of the liquid crystal composition (A) is -37 ° C to 82 ° C.

By polymerizing the radical polymerizable compound (M6), the following two types of inter-chain patterns can be generated.
1) “Between M6 and M6” generated by M6 bonding
2) “In M6” which is between side chains R1 and R2 existing in M6 before polymerization
Table 37 shows the values of α calculated between the side chains of 1) to 2).

  From Table 37, the value of Δα obtained from the radical polymerizable compound (M6) is 6-3 = 3.

The abundance ratio between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is the following molar fraction βi assuming that all of the radical polymerizable compound (M6) is polymerized.
1) βi between side chains: βi between side chains 2) = 0.67: 0.33
From αi in Table 37 and βi described above, Σ (αi × βi) between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is 4.00.
When HS50 / d of the light-scattering type liquid crystal device of this comparative example was evaluated, it was 75.0 mV / μm.

(Comparative Example 6)
For light scattering type liquid crystal device comprising 70% of liquid crystal composition (C), 29.4% of radical polymerizable compound (M7) and 0.6% of photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) The composition was prepared and the light-scattering type liquid crystal device was obtained by the above-mentioned method.

By polymerizing the radical polymerizable compound (M7), the following two types of inter-chain patterns can be generated.
1) “Between M7 and M7” generated by M7 bonding
2) “In M7” between side chains R1 and R2 present in M7 from before polymerization
Table 38 shows values of α calculated between the side chains of 1) to 2).

  From Table 38, the value of Δα obtained from the radical polymerizable compound (M7) is 5-4 = 1.

The abundance ratio between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is the following molar fraction βi assuming that all of the radical polymerizable compound (M7) is polymerized.
1) βi between side chains: βi between side chains 2) = 0.67: 0.33
From αi in Table 38 and βi described above, Σ (αi × βi) between the side chains 1) and 2) contained in the light scattering type liquid crystal device of this comparative example is 4.33.
When HS50 / d of the light-scattering type liquid crystal device of this comparative example was evaluated, it was 68.0 mV / μm.

(Comparative Example 7)
For light-scattering liquid crystal devices comprising 70% of the liquid crystal composition (C), 29.4% of the radical polymerizable compound (M8), and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) The composition was prepared and the light-scattering type liquid crystal device was obtained by the above-mentioned method.

By polymerizing the radical polymerizable compound (M8), the following two types of side chain patterns can be generated.
1) “Between M8 and M8” generated by M8 joining
2) “In M8” which is between side chains R1 and R2 existing in M8 before polymerization
Table 39 shows values of α calculated between the side chains of 1) to 2).

  From Table 39, the value of Δα obtained from the radical polymerizable compound (M8) is (−2) − (− 4) = 2.

The abundance ratio between the side chains 1) and 2) contained in the light scattering liquid crystal device of this comparative example is the following molar fraction βi assuming that all of the radical polymerizable compound (M8) is polymerized.
1) βi between side chains: βi between side chains 2) = 0.67: 0.33
From αi in Table 39 and βi described above, Σ (αi × βi) between the side chains 1) and 2) contained in the light scattering liquid crystal device of this comparative example is -2.67.
When HS50 / d of the light-scattering type liquid crystal device of this comparative example was evaluated, it was 177.7 mV / μm.

(Comparative Example 8)
For light-scattering liquid crystal devices comprising 70% of the liquid crystal composition (B), 29.4% of the radical polymerizable compound (M9), and 0.6% of the photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) The composition was prepared and the light-scattering type liquid crystal device was obtained by the above-mentioned method. The liquid crystal temperature range of the liquid crystal composition (B) is −41 ° C. to 80 ° C.

By polymerizing the radical polymerizable compound (M9), the following two types of inter-chain patterns can be generated.
1) “Between M9 and M9” generated by M9 bonding
2) “In M9” which is between side chains R1 and R2 existing in M9 from before polymerization
Table 40 shows the values of α calculated between the side chains of 1) to 2).

  From Table 40, the value of Δα obtained from the radical polymerizable compound (M9) is 13 − (− 2) = 15.

The abundance ratio between the side chains 1) and 2) contained in the light scattering liquid crystal device of this comparative example is the following molar fraction βi assuming that all of the radical polymerizable compound (M9) is polymerized.
1) βi between side chains: βi between side chains 2) = 0.67: 0.33
From αi in Table 40 and βi described above, Σ (αi × βi) between the side chains 1) and 2) included in the light-scattering liquid crystal device of this comparative example is 3.00.
When HS50 / d of the light-scattering type liquid crystal device of this comparative example was evaluated, it was 48.8 mV / μm.

  Table 41 shows the relationship between Δα, Σ (αi × βi), and HS50 / d at 25 ° C. for the examples and comparative examples described above.

As shown in Table 41, the light scattering type liquid crystal device of the example satisfying the two conditions of Δα of 5 or more and Σ (αi × βi) of −3.16 to 2.00 at the same time per unit cell gap. The optical hysteresis HS50 / d was 20 mV / μm or less. Among them, when Δα was 12 or more, HS50 / d could be further reduced when Σ (αi × βi) was changed from −1.79 to 2.00.
On the other hand, the light scattering liquid crystal device of the comparative example that does not satisfy the two conditions of Δα of 5 or more and Σ (αi × βi) of −3.16 to 2.00 is the light scattering liquid crystal device of the example. HS50 / d was higher. In the light scattering liquid crystal device of the comparative example, HS50 / d could not be made 20 mV / μm or less.

  Since the light scattering liquid crystal device of the present invention has little optical hysteresis in the halftone region, it is possible to perform gradation display with high reproducibility and gradation display with high gradation. Furthermore, since the light scattering type device of the present invention provides low optical hysteresis without reducing the gap of the display cells, it is possible to achieve both the scattering characteristics of the light scattering type liquid crystal device and the low optical hysteresis. For this reason, it can be used for a high display quality display in a light scattering mode. Specifically, it can be used for a display element of a portable information terminal such as a PDA or a light-scattering direct-view / reflective paper-like display. It is also useful as an optical element such as digital paper, IC card information display, electronic book, and optical shutter.

It is a figure explaining the anchoring of a polymer principal chain and a liquid crystal molecule. It is a figure explaining anchoring of a polymer side chain and a liquid crystal molecule. It is a figure explaining a mode that a voltage-light transmittance curve shifted to the high voltage side in the process of voltage application by anchoring of a polymer principal chain or a side chain, and liquid crystal molecules. It is the figure explaining a mode that the voltage-light transmittance curve in a voltage drop process shifted to the low voltage side by anchoring of a polymer principal chain or a side chain, and a liquid crystal molecule. It is the figure which gave the specific example and demonstrated the definition of (alpha) in this invention. It is the figure shown about the definition of optical hysteresis HS50 which is the main evaluation items of the light-scattering type liquid crystal device of the present invention.

Claims (3)

In a light scattering liquid crystal device having a light control layer obtained by polymerizing a light control layer forming material containing a radical polymerizable composition and a liquid crystal composition, the radical polymerizable composition is represented by the general formula (1). A light-scattering liquid crystal device characterized in that it is a composition containing at least one radical polymerizable compound that satisfies the formulas (1) and (3).

(1)
(In the formula, R represents an alkyl group having 3 to 40 carbon atoms, provided that the carbon atom in the alkyl group is
a) Oxygen atoms are not directly bonded to each other and are replaced by —O—, —CO—O—, —OCO—, —NHCO—O—, —OCONH—, or an arylene group having 6 to 12 carbon atoms. You may,
b) You may have a C1-C15 alkyl group as a substituent.
A ₁ represents —O—, —CO—O—, —OCO—, —NHCO—O—, —OCONH—, or an alkylene group (provided that the oxygen atom is directly bonded to the carbon atom in the alkylene group). -O-, -CO-O-, -OCO-, -NHCO-O-, -OCONH-, an alicyclic group having 6 to 12 carbon atoms, or an arylene group having 6 to 12 carbon atoms And the number of bonds N _a1 included when following a bond between two carbon atoms to which A ₁ is bonded is 3 to 40, and A ₂ is- O-, -CO-O-, -OCO-, -NHCO-O-, -OCONH-, or an alkylene group (provided that oxygen atoms are not directly bonded to each other in carbon atoms in the alkylene group) -O-, -CO-O-, -OCO-, -NHCO-O -, - OCONH-, alicyclic group having 6 to 12 carbon atoms, or represent may) be replaced by an arylene group having 6 to 12 carbon _{atoms, A} 3 is, -O -, - CO-O -, -OCO-, -NHCO-O-, -OCONH-, an alkylene group, an alkyltriyl group, or an alkyltetrayl group (however, in the alkylene group, the alkyltriyl group, or the alkyltetrayl group) The carbon atom is -O-, -CO-O-, -OCO-, -NHCO-O-, -OCONH-, an alicyclic group having 6 to 12 carbon atoms, as oxygen atoms are not directly bonded to each other, or an may) be replaced by an arylene group having 6 to 12 carbon _{atoms, -A 2} -A 3 -A 2 - bond number _{N a2} contained in represents a linking group which is 3 to 40.
B ₁ represents a hydrogen atom or a methyl group, B ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of R, A ₁ , A ₂ , A ₃ , B ₁ and B ₂ are the same May be different. m represents an integer of 2 to 4. )

(1)

(2)

(3)
(In Formula (1), Δα represents a difference between a maximum value α (αmax) and a minimum value α (αmin) of a plurality of α derived from the radical polymerizable compound contained in the radical polymerizable composition, α represents a value derived from Formula (2) In Formula (2), N _R1R2 represents two adjacent Rs in R ₁ and R in the radical polymerizable compound represented by Formula (1). when a _2, and, the general radical-polymerizable compound represented by (1) is formed by the polymerization reaction, when two adjacent R and R ₁ and R _2, R ₁ and Represents the number of bonds between the carbon atoms to which R ₂ is bonded N _R1 and N _R2 are from the carbon atom to which R ₁ and R ₂ are bonded to the terminal carbon atom of R ₁ and R ₂ Represents the number of bonds included when following a bond. And, if R ₁ and R ₂ has a substituent, the more distal most atomic number bond number in the join until carbon atoms and N _R1 and N _R2. The atomic tip are hydrogen atoms In some cases, this is not counted.Σ (αi × βi) is a radical represented by the general formula (1) with respect to a plurality of αi derived from the radically polymerizable compound contained in the radically polymerizable composition. The so-called expected value obtained by multiplying the appearance probability βi of αi obtained on the assumption that all the reactivity between the radically polymerizable compounds contained in the radically polymerizable composition containing the polymerizable compound is the same, Represents the theoretical value summed with respect to αi in the above formula, provided that the above definition is satisfied even if B2 and R are replaced, R is the one with the larger number of bonds.) In the general formula (1), A ₁ is —O—CH ₂ —, —O—CH ₂ —CH ₂ —CO—O—CH ₂ —, —O—CH ₂ —CH ₂ O—, or —O—. CH ₂ —CH (CH ₃ ) O—, A ₂ is —CH ₂ —O—, —CH ₂ —OCO—, —CH ₂ —CO—O— or —CH ₂ —, and A ₃ is When m is 2, an alkylene group having 2 to 40 carbon atoms (provided that one or two or more methylene groups present in the group and not directly bonded to A ₂ are each independently of each other. The oxygen atoms are not directly bonded to each other, and may be replaced by —O—, an arylene group, or a cycloalkylene group having 3 to 10 carbon atoms), an arylene group having 6 to 18 carbon atoms, or a carbon number 3 to 10 cycloalkylene groups, or —Y—A ₄ —Y— (where Y is an aryl) Represents a ren group or a cycloalkylene group having 3 to 10 carbon atoms, and A ₄ is a single bond or an alkylene group having 1 to 15 carbon atoms (provided that one or two or more methylene groups present in the alkylene group are And independently of each other, the oxygen atoms may be replaced by -O- as if the oxygen atoms are not directly bonded to each other).
When m is 3, an alkyltriyl group having 2 to 30 carbon atoms (provided that one or two or more methylene groups present in the group and not directly bonded to A ₂ may be mutually independent depending on the case. And oxygen atoms may not be directly bonded to each other, and may be replaced by -O-, an arylene group, or a cycloalkylene group having 3 to 10 carbon atoms), and when m is 4, An alkyltetrayl group having 2 to 30 carbon atoms (provided that one or two or more methylene groups which are present in the group and are not directly bonded to A ₂ are each independently independent of each other, and oxygen atoms are The light-scattering liquid crystal device according to claim 1, which may be substituted with —O—, an arylene group, or a cycloalkylene group having 3 to 10 carbon atoms. 3. The light scattering liquid crystal device according to claim 1, wherein Δα in the formula (1) satisfies the formula (4) and satisfies the formula (5).

(4)

(5)
(However, [Delta] [alpha], [alpha] max, [alpha] min, and [Sigma] ([alpha] i * [beta] i) are the same as defined in the mathematical expressions (1) to (3)).

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