WO2015152694A1 - Liquid crystal element - Google Patents

Abstract

The present application relates to a liquid crystal element and the use of the same. An embodiment of a liquid crystal element of the present application, for example, is an element which can implement a normally transparent mode, shows a high contrast ratio, and can be driven by low driving voltage. This liquid crystal element may be applied to a variety of optical modulating devices such as a smart window, a window protection film, a flexible display element, an active retarder for a 3D image display, or a viewing angle adjustment film.

Description

Liquid crystal elements

The present application relates to a liquid crystal device and the use of the liquid crystal device.

Liquid Crystal Display (LCD) orientates a liquid crystal compound in a certain direction and implements an image by switching the orientation through the application of a voltage. The manufacturing process of LCD is an expensive process requiring a complicated process, and requires a large production line and equipment.

The so-called PDLC (Polymer Dispersed Liquid Crystal), which is implemented by dispersing a liquid crystal in a polymer matrix, in the present specification, the term PDLC is a higher concept including a so-called Polymer Network Liquid Crystal (PNLC) or Polymer Stabilized Liquid Crystal (PSLC). Known. Since PDLC can be manufactured by coating a liquid crystal solution, it can be manufactured by a simpler process than a conventional LCD.

As described in Patent Document 1 (Korean Patent Publication No. 199-0013794) and the like, a liquid crystal compound is usually present in an unaligned state in a PDLC. Thus, PDLC is a cloudy opaque state when no voltage is applied, and this state is called a scattering mode. When a voltage is applied to the PDLC, the liquid crystal compounds are aligned accordingly, thereby making it possible to switch between the transmission mode and the scattering mode.

However, since the PDCL mode which initially shows the scattering state shows the scattering state before the voltage is applied, the PDCL mode requires a voltage to be always applied to the cell in order to maintain the transparent state.

The present application provides a liquid crystal device and the use of the liquid crystal device.

An exemplary liquid crystal element of the present application includes a first substrate having a mold layer formed thereon and a second substrate having a resin layer formed thereon. The mold layer may have a convex portion and a concave portion. In addition, the second substrate may be disposed such that the resin layer is in contact with the convex portion of the mold layer. In one example, the resin layer may have surface properties that can induce vertical alignment with respect to the liquid crystal compound. The liquid crystal element may also include a liquid crystal compound present in the recessed portion of the mold layer.

1 is a schematic view of an exemplary liquid crystal device of the present application. In the liquid crystal device 1 of FIG. 1, a first substrate 102 having a mold layer 101 having convex portions 1011 and a concave portion 1012 formed thereon, and a resin layer 103 formed thereon And the resin layer includes a second substrate 104 disposed in contact with the convex portion 1011 of the mold layer and a liquid crystal compound 105 present in the concave portion 1012 of the mold layer. . As shown in FIG. 1, the liquid crystal compound may be included in the liquid crystal element in a state in which the liquid crystal compound is separated by the partition formed on the recess of the mold layer and one surface of the resin layer.

In one example, the mold layer may comprise a crosslinkable or polymerizable compound. In the present specification, the polymerizable or crosslinkable compound may mean a compound having a polymerizable or crosslinkable functional group. The mold layer may include, for example, a crosslinkable or polymerizable compound in a crosslinked or polymerized state. In the present specification, the polymerizable or crosslinkable functional group may include, for example, an alkenyl group, an epoxy group, a cyano group, a carboxyl group, a (meth) acryloyl group, or a (meth) acryloyloxy group, but is not limited thereto. no. When the mold layer contains a crosslinkable or polymerizable material, excellent adhesion to the resin layer can be exhibited.

In one example, an acrylate compound may be used as the crosslinkable or polymerizable compound. In the present specification, the acrylate compound means a compound containing an acryloyl group or a methacryloyl group as a functional group, and the compound containing one functional group is a monofunctional acrylate compound, and the compound containing two or more is multifunctional It may be foiled with an acrylate compound. For convenience of differentiation, the compound containing two functional groups below is referred to as a bifunctional acrylate compound, and the trifunctional or higher functional group, that is, the acrylate compound including three or more functional groups, is simply referred to as a polyfunctional acrylate compound. Call it. The multifunctional acrylate compound may include, for example, 3 to 8, 3 to 7, 3 to 6, 3 to 5 or 3 to 4 functional groups.

For example, the compound represented by following formula (1) can be used as a monofunctional acrylate compound.

[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is an alkyl group having 1 to 20 carbon atoms.

In addition, as a bifunctional acrylate compound, the compound represented by following formula (2) can be used.

[Formula 2]

In formula (2), each R is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is an alkylene group or alkylidene group having 1 to 20 carbon atoms.

In addition, a compound represented by the following formula (3) may be used as the polyfunctional acrylate compound.

[Formula 3]

N is a number of 3 or more, m is a number of 0 to 5, each R is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a (m + n) valent radical, Y is hydrogen or an alkyl group to be.

Examples of the alkyl group which may be present in R or Y in Formulas 1 to 3 include a methyl group or an ethyl group.

In Formula 1, the alkyl group of X may be, for example, a straight or branched chain alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 4 to 12 carbon atoms, and 6 to 12 carbon atoms.

In the formula (2), the alkylene group or alkylidene group of X is, for example, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 2 to 8 carbon atoms or 4 to 8 alkylene groups or alkyl. It may be a leaden group. The alkylene group or alkylidene group may be, for example, linear, branched or cyclic.

Meanwhile, n in Formula 3 may be any one of 3 or more, 3 to 8, 3 to 7, 3 to 6, 3 to 5, or 3 to 4 in the range. In addition, m in Formula 2 may be any number in the range of 0 to 5, 0 to 4, 0 to 3, 0 to 2 or 0 to 1.

X in formula (3) is a (m + n) valent radical, for example, a hydrocarbon having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 6 carbon atoms, for example For example, (m + n) derived from straight or branched alkanes may be a radical.

Substituents defined in Chemical Formulas 1 to 3, for example, an alkyl group, an alkylene group, an alkylidene group or a (m + n) radical, etc., may be substituted by one or more substituents, if necessary. For example, an alkyl group, an alkoxy group, an epoxy group, an oxo group, an oxetanyl group, a thiol group, a cyano group, a carboxyl group, or an aryl group may be exemplified, but is not limited thereto.

In another example, the mold layer may include a curable compound. In the present specification, the curable compound may mean a compound having a curable functional group. The mold layer may include, for example, a curable compound in a cured state. The kind of curable compound is not particularly limited, and may be appropriately selected within a range that does not impair the object of the present application, and for example, a heat curable compound or a photocurable compound may be used. As one specific example, the mold layer may include a curable silicone compound in terms of effectively inducing vertical alignment with respect to the liquid crystal compound present in the concave portion. Specific details of the curable silicone compound may be equally applicable to the contents described in the following resin layer section.

Surface characteristics of the mold layer can be appropriately adjusted within a range that does not impair the purpose of the present application. In one example, the mold layer may exhibit the following surface properties in terms of effectively inducing the vertical alignment of the liquid crystal compound present in the recess. The surface properties of the mold layer may be changed depending on, for example, the shape of the concave and convex portions of the mold layer, and the surface properties of the mold layer described below may be a mold in a flat state before forming the concave and convex portions in the mold layer. Surface properties for the layer.

The mold layer may satisfy the conditions of the following general formula (1), for example.

[Formula 1]

0 = | Y - {1 × 10 -4 X 3 - 1.2 × 10 -3 X 2 + 3.1 × 10 ^-3 X-1.6 × 10 ^-3 } | = 0.05

In Formula 1, X represents the AFM Z scale surface roughness of the mold layer, and Y represents the surface polarity of the mold layer. The surface energy (γ ^surface ) of the mold layer can be calculated by considering the dispersion force between the nonpolar molecules and the interaction force between the polar molecules (γ ^surface = γ ^ispersion + γ ^polar ), and the polar term (γ ^polar) at the surface energy γ ^surface Can be defined as the polarity of the surface. By considering the mutual relationship between the roughness and the polarity of the surface as in Formula 1, the mold layer can induce better vertical alignment with respect to the liquid crystal compound in a state in which no external alignment force is applied to the liquid crystal device.

The surface energy of the mold layer is, for example, 5 mN / m to 100 mN / m, 8 mN / m to 80 mN / m, 10 mN / m to 50 mN / m or 12 mN / m to 30 mN / m Can be. In addition, the polarity of the mold layer may be in the range of 0 to 0.5 or 0 to 0.4, for example. In addition, the AFM Z scale surface roughness of the mold layer may be, for example, in the range of 0.1 nm to 50 nm, 0.2 nm to 30 nm, 0.3 nm to 10 nm or 0.4 nm to 8 nm. Within the surface energy, polarity, or surface roughness range, the mold layer may effectively induce the vertical alignment of the liquid crystal compound present in the recess. However, the surface properties of the mold layer are not limited to the above, and may be appropriately changed depending on the degree of vertical alignment of the desired liquid crystal.

In the present specification, "surface energy" is a value measured by a known surface energy measurement method, and may be, for example, a value measured by Owens-Wendt method through a static contact angle measurement. As a specific example, the surface energy (γ ^surface , mN / m) can be calculated as γ ^surface = γ ^dispersion + γ ^polar , it can be measured using a drop shape analyzer (Drop Shape Analyzer, KRUSS DSA100). Surface energy is about 50 nm thick and 4 cm ² coating area (width: 2 cm, length: 2 cm) of the coating liquid diluted to about 2 wt% solids concentration in fluorobenzene. After drying at room temperature for about 1 hour can be measured for the film thermally annealed at 160 ° C for about 1 hour. The average value of the five contact angle values obtained is obtained by dropping the deionized water having a known surface tension on the thermally matured film and determining the contact angle five times. The procedure of dropping the known diiodomethane and determining the contact angle is repeated five times, and the average value of the five contact angle values obtained is obtained. Subsequently, the surface energy can be obtained by substituting the numerical value (Strom value) of the surface tension of the solvent by Owens-Wendt-Rabel-Kaelble method using the average value of the contact angles with respect to the deionized water and diiomethane obtained. In addition, in this specification, "surface roughness" is a value measured by a well-known average surface roughness measuring method, For example, it may be a value measured using the Bruker Multimode AFM apparatus.

The method for adjusting the surface properties of the mold layer as described above is not particularly limited. For example, as a material of the mold layer, a material capable of exhibiting the surface properties is selected, an additive that can exhibit the surface properties is added to the mold layer, or the manufacturing process is controlled such that the mold layer exhibits the surface properties. You may. In one example, the curable silicone compound may be selected as the material of the mold layer, an additive capable of inducing vertical orientation to the mold layer, or a corona treatment may be performed on the mold layer. Corona treatment conditions and methods are not particularly limited and may be appropriately adjusted in consideration of the surface properties of the desired mold layer.

As one specific example, the mold layer may include a vertically oriented polymer as an additive capable of inducing vertical alignment. As the vertically oriented polymer, for example, a polymer of a polymerization unit containing at least 4 carbon atoms, at least 5, at least 6, at least 7, at least 8, at least 9, or at least 10 straight hydrocarbon groups can be used. As used herein, the term "hydrocarbon group" means an organic compound composed of carbon and hydrogen, and unless otherwise specified, may mean an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. In addition, in the present specification, the "linear hydrocarbon group" may mean a hydrocarbon group having a structure in which several atoms are extended in a row. The upper limit of the carbon number of the straight chain hydrocarbon group is not particularly limited, but for example, it may mean a straight chain hydrocarbon group having 24 or less, 22 or less, 20 or less, 18 or less or 16 or less carbon atoms. Or a vertically oriented polymer, for example, a polymer containing chlorine (Cl) fluorine (F) or silicon (Si), more specifically, a chlorine (Cl), fluorine (F) or silicon (Si) substituted hydrocarbon Polymers of polymerized units containing groups can be used. In the above hydrocarbon group, for example, an alkyl group having 1 carbon atom, an alkyl group having 2 or more carbon atoms, an alkenyl group or an alkynyl group, a cycloalkyl group having 3 or more carbon atoms, or an aryl group having 6 or more carbon atoms may be exemplified.

As one specific example, polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol, modified polyvinyl alcohol, poly (N-methylol acrylamide) as a vertically oriented polymer , Styrene / vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, polyethylene , Polypropylene or polycarbonate may be used, but is not limited thereto.

As one specific example, the mold layer may include a vertically oriented polymer including polymerized units derived from the compound of Formula 4 below.

[Formula 4]

In Formula 4, R ₁ to R ₉ are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an alkoxy group, and A represents a single bond, an alkylene group, or an alkylidene group. In the above, the case where R ₅ to R ₉ is a halogen element may be excluded, and an alkyl group, alkenyl group, alkynyl group or alkoxy group substituted with halogen may be excluded.

As used herein, the term "single bond" means a case where no separate atom is present in a portion represented by A. For example, in Formula 1, when A is a single bond, a structure in which benzene and oxygen are directly connected to both sides of A may be formed.

In addition, the vertically oriented polymer may include, but is not limited to, a polymerized unit derived from the compound represented by Formula 5 below.

[Formula 5]

In Formula 5, R ₁₀ may represent hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.

In addition, the vertically oriented polymer may include, but is not limited to, polymerized units derived from the compound represented by Chemical Formula 6.

[Formula 6]

In the formula 6, R ₁₁ to R ₁₆ each independently represent a hydrogen, an alkyl group an alkenyl group, an alkynyl group or an alkoxy group or provided that -OQP, R ₁₁ to R ₁₆ is at least one of the at least one of R ₁₁ to R ₁₆ or either -OQP One is a halogen substituted alkyl group, a halogen substituted alkenyl group, a halogen substituted alkynyl group or a halogen substituted alkoxy group. In the above, Q is an alkylene group or an alkylidene group, and P is an acryloyl group, methacryloyl group, acryloyloxy group or methacryloyloxy group.

When the mold layer contains a vertically oriented polymer, the content of the vertically oriented polymer in the mold layer may be appropriately selected within a range that does not impair the purpose of the present application. For example, the solids content of the vertically oriented polymer in the mold layer may be in the range of 0.5% to 4.5%, 1% to 4%, 1.5% to 3.5% or 2% to 3.2% by weight. have. In the present specification, the solid content means a solid content at the time when the polymer is manufactured in the form of a coating solution or the like and applied to a mold layer manufacturing process. When the content of the vertical alignment polymer is within the above range, the mold layer can effectively implement the above-described vertical alignment characteristics.

The mold layer may be a radical or cationic initiator that can induce crosslinking or polymerization of a solvent, the crosslinkable or polymerizable compound, a basic substance, other reactives that can form crosslinking or polymerization, if necessary in addition to the aforementioned compounds. It may be formed from a precursor further comprising an additive such as a compound or a surfactant.

The mold layer may contain a liquid crystal compound, for example, a reactive liquid crystal compound. Even in this case, the ratio of the liquid crystal compound is appropriately adjusted in small amounts. In one example, the absolute value of the birefringence of the mold layer may be 30 nm or less or 20 nm or less. That is, the mold layer may be an isotropic mold layer or a mold layer having birefringence within the above range. Therefore, even when the liquid crystal compound is included, it is preferable that the mold layer is included in a range capable of exhibiting the above-mentioned birefringence. The birefringence may mean, for example, a plane phase difference calculated by Equation 1 below, or a phase difference in a thickness direction calculated by Equation 2 below.

[Equation 1]

Rin = d × (nx-ny)

[Formula 2]

Rth = d × (nz-ny)

In Equations 1 and 2, Rin is a retardation in phase, Rth is a retardation in thickness direction, d is a thickness of the mold layer, nx is a refractive index in the slow axis direction on the surface of the mold layer, and ny is a fast axis direction on the surface of the mold layer. Is the refractive index of nz, and nz is the refractive index in the thickness direction of the mold layer.

The spacing, width and thickness of the concave portion of the mold layer may be appropriately adjusted in consideration of the region in which the liquid crystal compound is contained within a range not impairing the object of the present application. For example, the spacing of the recesses may be in the range of 100 to 400 μm or 100 to 300 μm, the width may be in the range of 10 to 40 μm or 10 to 30 μm, and the height may be 10 to 30 μm or 10 to 20 μm. It may be within the scope of, but is not limited thereto.

The liquid crystal compound may be present in the recess of the mold layer. As the liquid crystal compound, various kinds can be used without particular limitation as long as the orientation is switchable and the light modulation characteristics of the liquid crystal device can be adjusted. In the present specification, the switchable orientation may mean that the alignment direction of the liquid crystal compound may be changed by an external action such as application of a voltage. As the liquid crystal compound, for example, when the alignment is regularly aligned in a predetermined direction, the liquid crystal compound may act in a transmission mode or a mode showing an appropriate phase difference according to the alignment direction, and the alignment is not regularly aligned in the predetermined direction. If it is randomly disposed without using a compound that can induce light scattering through the action with the mold layer.

As a liquid crystal compound, a smectic liquid crystal compound, a nematic liquid crystal compound, a cholesteric liquid crystal compound, etc. can be used, for example. The liquid crystal compound is not bonded to the mold layer, and may have a form in which an orientation may be changed under an external action such as a voltage from the outside. For this purpose, for example, the liquid crystal compound may be a compound having no polymerizable group or crosslinkable group. If necessary, the liquid crystal compound may be present in the recess with a small amount of crosslinkable or polymerizable compound for proper adhesion with the resin layer. The type of crosslinkable or polymerizable compound may be the same as described in the section of the mold layer. In this case, the content ratio of the crosslinkable or polymerizable compound may be appropriately selected within a range that does not impair the purpose of the present application. The crosslinkable or polymerizable compound may be included in, for example, 10 parts by weight to 15 parts by weight with respect to 100 parts by weight of the liquid crystal compound, but is not limited thereto.

In one example, the liquid crystal compound present in the concave portion of the mold layer may be present in an oriented state in an external non-applied state. The alignment direction of the liquid crystal compound present in the aligned state may be changed by external action. In the present specification, "external action" means all kinds of actions performed to change the orientation or alignment of the liquid crystal compound, and a representative example is application of voltage. In addition, in this specification, an "initial orientation" may mean the orientation or alignment direction of the liquid crystal compound in the state without the external action or the optical axis formed in the liquid crystal compound. In the liquid crystal device, the alignment direction of the liquid crystal compound in the initial alignment state may be converted by an external action, and when the external action disappears, the liquid crystal compound may return to the initial alignment state.

In one example, the liquid crystal compound present in the concave portion of the mold layer may be present in the vertically aligned state from the initial state. In the present specification, the vertically oriented state is that the optical axis of the liquid crystal layer including the liquid crystal compound is about 90 degrees to about 65 degrees, about 90 degrees to about 75 degrees, about 90 degrees to about 80 degrees, about 90 with respect to the plane of the liquid crystal layer. It may mean a case having an inclination angle of about 90 degrees to about 85 degrees. As used herein, the term “optical axis” may mean an axis in the long axis direction of the liquid crystal compound when the liquid crystal compound has a rod shape, and may mean an axis in the normal direction of the plane when the liquid crystal compound has a discotic shape.

The initial vertical alignment state of the liquid crystal compound can be changed by external action, for example, application of an external voltage. Accordingly, the liquid crystal device maintains the transparent mode in the initial state, and can be switched to various modes other than the transparent mode by external action. In one example, the liquid crystal device may be implemented as a device capable of mutual switching between a transparent mode and a scattering mode. For example, in the liquid crystal device of the present application, since the liquid crystal compounds are vertically arranged in a state in which there is no external action (that is, an initial state or a normal state), a transmission mode is realized, and the liquid crystal compounds are scattered while being arranged in a disordered direction under the external action. It may be a device which is switched to the mode and which is switched back to the transmission mode when the external action is removed (such a device may be referred to as a device of the normal transmission mode for convenience).

The phase difference Rc of the liquid crystal element may be appropriately determined depending on the mode or structure to be implemented. For example, the area of the liquid crystal compound may have a planar phase difference of 30 nm or less in an initial state and a thickness direction phase difference of 500 nm or more. This range of phase difference is suitable, for example, for implementing a device in normal transmission mode. The retardation value may be a value measured for light having a wavelength of 550 nm.

The resin layer on the top of the second substrate may have surface properties that can induce vertical alignment of the liquid crystal, for example. In one example, the resin layer is 45 mN / m or less, 42.5 mN / m or less, 40 mN / m or less, 37.5 mN / m or less, 35 mN / m or less, 32.5 mN / m or less or 30 mN / m or less May have surface energy. When the surface energy of a resin layer shows the said range, the vertical orientation with respect to the liquid crystal compound which exists in the recessed part of a mold layer can be effectively induced. The lower limit of the surface energy of the resin layer is not particularly limited, but for example, more than 0 mN / m, 1 mN / m or more, 2 mN / m or more, 3 mN / m or more, 4 mN / m or more, or 5 mN / m It may be abnormal.

The resin layer may also exhibit an AFM Z scale surface roughness in the range of, for example, 2 nm or less, 1.9 nm or less, 1.8 nm or less, 1.7 nm or less, 1.6 nm or less, or 1.5 nm or less. When the surface roughness of the resin layer shows the above range, the vertical alignment with respect to the liquid crystal compound present in the concave portion of the mold layer can be effectively induced. The lower limit of the AFM Z scale surface roughness of the resin layer is not particularly limited, but may be, for example, greater than 0 nm, 0.1 nm or more, 0.2 nm or more, 0.3 nm or more, or 0.4 nm or more.

In addition, if necessary, the resin layer may also satisfy the conditions of the following Formula 1, but is not limited thereto.

 [Formula 1]

0 = | Y - {1 × 10 -4 X 3 - 1.2 × 10 -3 X 2 + 3.1 × 10 ^-3 X-1.6 × 10 ^-3 } | = 0.05

In the general formula (1), X represents the AFM Z scale surface roughness of the resin layer, Y represents the surface polarity of the resin layer. In this case, the surface polarity of the resin layer may be, for example, in the range of 0 to 0.5 or 0 to 0.4, but is not limited thereto. In addition, the method of measuring the surface energy, surface roughness, and surface polarity of a resin layer can apply the same content of the measuring method described in the item of a mold layer.

The method for adjusting the surface properties of the resin layer as described above is not particularly limited. For example, as a material of the resin layer, a material capable of exhibiting the surface properties is selected, an additive capable of exhibiting the surface properties is added to the resin layer, or the manufacturing process is controlled such that the resin layer exhibits the surface properties. You may. In one example, the curable silicone compound may be selected as the material of the resin layer, an additive capable of inducing vertical alignment may be added to the resin layer, or a corona treatment may be performed on the mold layer. Corona treatment conditions and methods are not particularly limited and may be appropriately adjusted in consideration of the surface properties of the desired resin layer. In addition, the content described in the item of the mold layer may be equally applied to the additive capable of inducing vertical alignment.

In one example, the resin layer may include a curable compound. The resin layer may contain, for example, a curable compound in a cured state. As the curable compound, for example, as one specific example, the resin layer may include a curable silicone compound in terms of effectively inducing vertical alignment of the liquid crystal. The resin layer may include the curable silicone compound alone or may further include the crosslinkable or polymerizable compound described in the section of the mold layer. As the resin layer, for example, a heat curable silicone compound or an ultraviolet curable silicone compound can be used. Hereinafter, a curable silicone compound is demonstrated concretely.

In one aspect of the present application, the curable silicone compound is an addition-curable silicone compound, which comprises (1) an organopolysiloxane containing two or more alkenyl groups in a molecule and (2) contains two or more silicon-bonded hydrogen atoms in a molecule Organopolysiloxanes. Such a silicone compound can form hardened | cured material by addition reaction, for example in presence of a catalyst mentioned later.

In the above (1) organopolysiloxane, as a main component constituting the silicone cured product, it contains at least two alkenyl groups in one molecule. In this case, specific examples of the alkenyl group include a vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, or heptenyl group, and the like, but a vinyl group is preferable, but is not limited thereto. In said (1) organopolysiloxane, the bonding position of the above-mentioned alkenyl group is not specifically limited. For example, the alkenyl group may be bonded to the terminal of the molecular chain and / or the side chain of the molecular chain. Further, in the above (1) organopolysiloxane, examples of the substituent which may be included in addition to the alkenyl described above include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group or heptyl group; Aryl groups such as phenyl group, tolyl group, xylyl group or naphthyl group; Aralkyl groups such as benzyl or phenentyl; Halogen-substituted alkyl groups such as chloromethyl group, 3-chloropropyl group or 3,3,3-trifluoropropyl group, and the like, and the like, and a methyl group or a phenyl group is preferable, but is not limited thereto.

The molecular structure of the organopolysiloxane as described above (1) is not particularly limited, and may have any shape such as, for example, linear, branched, cyclic, networked, or linear form partly branched. have. In the present invention, it is preferable to have a linear molecular structure among the above molecular structures, but is not limited thereto. On the other hand, in the present invention, it is preferable to use an organopolysiloxane containing an aromatic group such as an aryl group or an aralkyl group in the molecular structure as the (1) organopolysiloxane in view of the hardness and the refractive index of the cured product. However, it is not necessarily limited thereto.

More specific examples of the (1) organopolysiloxane which can be used in the present invention include molecular chain sock end trimethylsiloxane group blockade dimethylsiloxane-methylvinylsiloxane copolymer, molecular chain sock end trimethylsiloxane group blockade methylvinylpolysiloxane, molecular chain Socks end trimethylsiloxane group blockade dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer, molecular chain sock end dimethylvinylsiloxane group blockade dimethylpolysiloxane, molecular chain sock end dimethylvinylsiloxane group blockade methylvinylpolysiloxane, molecular chain sock end dimethylvinylsiloxane acid groups blocked dimethylsiloxane-methylvinylsiloxane copolymer, a molecular chain, both ends dimethylvinylsiloxy group blocked dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer, R _{¹ 2} SiO ^_1/2 siloxane units and R is represented by ^{1 ₂} R ₂ including a siloxane unit represented by the siloxane unit, and SiO _4/2 represented by SiO _1/2 Organopolysiloxane copolymer, R ^{1 ₂} R ₂ SiO represented by _1/2 siloxane units and SiO _4/2 organopolysiloxane ^{_{copolymer, R 1 R 2 SiO 2/}} 2 containing a siloxane unit represented by the represented by the include siloxane units and R ¹ SiO _3/2 siloxane units, or an organopolysiloxane copolymer and a mixture of two or more of the above containing a siloxane unit represented by R ² SiO _3/2 represented by, but not limited to . In the above, R ¹ is a hydrocarbon group other than an alkenyl group, and specifically, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group or heptyl group; Aryl groups such as phenyl group, tolyl group, xylyl group or naphthyl group; Aralkyl groups such as benzyl or phenentyl; Halogen substituted alkyl groups such as chloromethyl group, 3-chloropropyl group or 3,3,3-trifluoropropyl group. In addition, in the above, R ² is an alkenyl group, and specifically, may be a vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, or heptenyl group.

In one aspect of the invention, the (1) organopolysiloxane may have a viscosity at 25 ℃ 50 to 500,000 CP (centipoise), preferably 400 to 100,000 CP. When the said viscosity is less than 50 CP, there exists a possibility that the mechanical strength of the hardened | cured material of a silicone compound may fall, and when it exceeds 500,000 CP, there exists a possibility that handleability or workability may fall.

In the addition-curable silicone compound, (2) the organopolysiloxane may serve to crosslink the (1) organopolysiloxane. In the organopolysiloxane (2), the bonding position of the hydrogen atom is not particularly limited, and may be, for example, bonded to the terminal and / or side chain of the molecular chain. Further, in the (2) organopolysiloxane, the type of substituents that may be included in addition to the silicon-bonded hydrogen atom is not particularly limited, and examples thereof include alkyl groups, aryl groups, and the like mentioned in (1) organopolysiloxanes. Aralkyl groups or halogen-substituted alkyl groups, and the like. Among these, methyl or phenyl groups are preferred, but are not limited thereto.

On the other hand, the molecular structure of (2) organopolysiloxane is not specifically limited, For example, it may have any shape, such as a linear form, a branched form, a cyclic form, a network form, or the linear form part partially branched. In the present invention, it is preferable to have a linear molecular structure among the above molecular structures, but is not limited thereto.

More specific examples of the above (2) organopolysiloxane which can be used in the present invention include molecular chain sock end trimethylsiloxane group blocked methylhydrogenpolysiloxane, molecular chain sock end trimethylsiloxane group blocked dimethylsiloxane-methylhydrogen copolymer, molecule Chain Socks End Trimethylsiloxane Group Blockade Dimethylsiloxane-Methylhydrogensiloxane-Methylphenylsiloxane Copolymer, Molecular Chain Socks End Dimethylhydrogensiloxane Blockade Dimethylpolysiloxane, Molecular Chain Socks End Dimethylhydrogensiloxane Blockade Dimethylsiloxane-Methylphenylsiloxane Copolymer , the siloxane unit represented by a molecular chain, both ends dimethyl hydrogen siloxane group containment methylphenyl polysiloxane, R _{¹ 3} SiO _^1/2 siloxane units and R _{¹ 2} HSiO ^_1/2 siloxane units and SiO _4/2 represented by the represented by the containing organopolysiloxane copolymer, R ¹ ₂ HSiO siloxane stage represented by _1/2 Above and SiO _4/2 siloxane units represented by or HSiO _3/2 and siloxane units represented by R ¹ SiO _3/2 represented by the organopolysiloxane copolymer, R ¹ HSiO _2/2 containing the siloxane unit represented by the Organopolysiloxane copolymers comprising siloxane units and mixtures of two or more of the above, but are not limited thereto. In the above, R ¹ is a hydrocarbon group other than an alkenyl group, and specifically, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group or heptyl group; Aryl groups such as phenyl group, tolyl group, xylyl group or naphthyl group; Aralkyl groups such as benzyl or phenentyl; Halogen substituted alkyl groups such as chloromethyl group, 3-chloropropyl group or 3,3,3-trifluoropropyl group.

In one aspect of the present invention, (2) the organopolysiloxane may have a viscosity at 25 ° C. of 1 to 500,000 CP (centipoise), preferably 5 to 100,000 CP. When the said viscosity is less than 1 CP, there exists a possibility that the mechanical strength of the hardened | cured material of a silicone compound may fall, and when it exceeds 500,000 CP, there exists a possibility that handleability or workability may fall.

In one aspect of the present invention, the content of the (2) organopolysiloxane is not particularly limited as long as it is included to the extent that appropriate curing can be achieved. For example, the (2) organopolysiloxane may be included in an amount such that 0.5 to 10 silicon-bonded hydrogen atoms are included with respect to one alkenyl group included in the aforementioned (1) organopolysiloxane. If the number of silicon atom-bonded hydrogen atoms is less than 0.5, the curing of the curable silicone compound may be insufficient, and if more than 10, the heat resistance of the cured product may be lowered. On the other hand, in the present invention, from the viewpoint of hardness and refractive index of the cured product, (2) organopolysiloxane containing (2) organopolysiloxane containing an aromatic group such as an aryl group or an aralkyl group in the molecular structure is used. It is preferred, but not necessarily limited thereto.

In one aspect of the present invention, the addition-curable silicone compound may further include platinum or a platinum compound as a catalyst for curing. Specific examples of such a platinum or platinum compound include platinum fine powder, platinum black, platinum supported silica fine powder, platinum supported activated carbon, chloroplatinic acid, platinum tetrachloride, alcohol solution of chloroplatinic acid, complex of platinum and olefin, platinum and 1,1, Finely divided thermoplastic resin fine powders (polystyrene resins, nylon resins, polycarbonate resins) having a particle diameter of less than 10 µm complexes with alkenylsiloxanes such as 3,3-tetramethyl-1,3-divinyldisiloxane, and those platinum or platinum compounds , Silicone resins, etc.), but is not limited thereto.

The content of the catalyst described above in the addition-curable silicone compound of the present invention is not particularly limited, and may be included, for example, in an amount of 0.1 to 500 ppm, preferably 1 to 50 ppm, by weight of the total compound. When content of the said catalyst is less than 0.1 ppm, there exists a possibility that sclerosis | hardenability of a composition may fall, and when it exceeds 500 ppm, there exists a possibility that economy may fall.

In one aspect of the present invention, the addition-curable silicone compound is 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyne- from the viewpoint of improving its storage stability, handleability and workability. Alkyne alcohols such as 3-ol and phenylbutynol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,2,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane And a hardening inhibitor such as benzotriazole. The content of the hardening inhibitor may be appropriately selected from a range that does not impair the object of the invention, for example, it may be included in the range of 10 ppm to 50,000 ppm by weight.

In another aspect of the present invention, the silicone compound is a condensation-curable silicone compound, for example, (a) an alkoxy group-containing siloxane polymer; And (b) hydroxyl group-containing siloxane polymers.

The (a) siloxane polymer that can be used in the present invention may be, for example, a compound represented by the following formula (7).

[Formula 7]

R ¹ _a R ² _b SiO _c (OR ³ ) _d

In the above formula, R ¹ and R ¹ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ³ represents an alkyl group, and in the case where a plurality of R ¹ , R ² and R ³ are each present, May be the same or different, a and b each independently represent a number greater than 0 and less than 1, a + b represents a number greater than 0 and less than 2, c represents a number greater than 0 and less than 2, d represents a number greater than 0 and less than 4, and a + b + c × 2 + d is 4.

In the present invention, the siloxane polymer represented by Formula 7 may be 1,000 to 100,000, preferably 1,000 to 80,000, more preferably 1,500 to 70,000, as measured by gel permeation chromatography. . (a) Since the weight average molecular weight of a siloxane polymer exists in the said range, favorable hardened | cured material can be obtained without causing defects, such as a crack, at the time of formation of a silicone hardened | cured material.

In the definition of Chemical Formula 7, the monovalent hydrocarbon may be, for example, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group or a tolyl group, and the like, and as the alkyl group having 1 to 8 carbon atoms, a methyl group, an ethyl group, or a propyl group , Isopropyl group, butyl group, pentyl group, hexyl group, heptyl group or octyl group and the like. In addition, in the definition of Chemical Formula 7, the monovalent hydrocarbon group may be substituted with a known substituent such as a halogen, an amino group, a mercapto group, an isocyanate group, a glycidyl group, a glycidoxy group, or a ureido group.

In addition, in the definition of Chemical Formula 7, examples of the alkyl group of R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group. Among such alkyl groups, methyl group or ethyl group is preferred, but is not limited thereto.

In the present invention, it is preferable to use a branched or tertiary crosslinked siloxane polymer in the polymer of the general formula (7). In addition, in this (a) siloxane polymer, the hydroxyl group may remain in the range which does not impair the objective of this invention, and specifically in the range which does not inhibit a dealcoholization reaction.

Such (a) siloxane polymer can be manufactured by hydrolyzing and condensing a polyfunctional alkoxysilane, a polyfunctional chloro silane, etc., for example. The average person skilled in the art can easily select an appropriate polyfunctional alkoxysilane or chloro silane according to the desired (a) siloxane polymer, and can also easily control the conditions of the hydrolysis and condensation reaction using the same. In addition, at the time of manufacture of the said (a) siloxane polymer, you may use together the appropriate monofunctional alkoxysilane according to the objective.

Examples of the above (a) siloxane polymers include commercially available ores such as X40-9220 or X40-9225 from Shin-Etsu Silicone Co., Ltd., XR31-B1410, XR31-B0270 or XR31-B2733, etc. The organosiloxane polymer can be used. On the other hand, in the present invention, from the viewpoint of hardness and refractive index of the cured product, (a) organopolysiloxane containing an aromatic group such as an aryl group or an aralkyl group in the molecular structure is used as the (a) organopolysiloxane. It is preferred, but not necessarily limited thereto.

On the other hand, as the (b) hydroxyl group-containing siloxane polymer contained in the condensation-curable silicone compound, for example, a compound represented by the following formula (8) can be used.

[Formula 8]

In Formula 8, R ₄ and R ₅ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and in the case where a plurality of R ₅ and R ₆ are present, they are the same as or different from each other. N may represent an integer of 5 to 2,000.

In the definition of Chemical Formula 8, specific examples of the monovalent hydrocarbon group include the same hydrocarbon group as in the case of Chemical Formula 7 described above.

In the present invention, the siloxane polymer of Chemical Formula 8 may have a polystyrene reduced weight average molecular weight of 500 to 100,000, preferably 1,000 to 80,000, and more preferably 1,500 to 70,000, as measured by gel permeation chromatography. (b) Since the weight average molecular weight of a siloxane polymer exists in the said range, favorable hardened | cured material can be obtained without causing defects, such as a crack, at the time of formation of a silicone hardened | cured material.

Such (b) siloxane polymer can be manufactured by hydrolyzing and condensing a dialkoxysilane, a dichlorosilane, etc., for example. The average person skilled in the art can easily select an appropriate dialkoxy silane or dichloro silane according to the desired (b) siloxane polymer, and can also easily control the conditions of the hydrolysis and condensation reaction using the same. As the above-mentioned (b) siloxane polymer, commercially available bifunctional organosiloxane polymers, such as GE Toray Silicone Co., Ltd. XC96-723, YF-3800, YF-3804, etc. can be used. On the other hand, in the present invention, from the viewpoint of hardness and refractive index of the cured product, (1) organopolysiloxane containing (1) organopolysiloxane containing an aromatic group such as an aryl group or an aralkyl group in the molecular structure is used. It is preferred, but not necessarily limited thereto.

In one example, the convex portions of the resin layer and the mold layer may be contacted by adhesive force, or the convex portions of the resin layer and the mold layer may be in contact with each other in a crosslinked state. The convex part of a resin layer and a mold layer can exhibit adhesive force, for example by containing the curable compound mentioned above. Alternatively, the resin layer and the mold layer may be in contact with each other in a crosslinked state through, for example, crosslinking between the polymerizable, crosslinkable or curable functional groups remaining in the mold layer and the resin layer.

As one specific example, the resin layer present on the upper portion of the second substrate may exhibit excellent adhesion to the convex portion and the liquid crystal compound of the adjacent mold layer. In one example, the 90-degree peeling force between the recess of the resin layer and the mold layer may be, for example, 0.2 N / cm or more, 0.25 or more N / cm, or 0.3 N / cm or more, but is not limited thereto. The type of adhesion of such a resin layer is not particularly limited, and may be appropriately selected according to the intended use. For example, a type of a solid adhesive, a semisolid adhesive, an elastic adhesive, or a liquid adhesive may be appropriately applied. Solid adhesives, semisolid adhesives or elastic adhesives may be referred to as pressure sensitive adhesives (PSAs) and may be cured before bonding objects are bonded. The liquid adhesive may be referred to as so-called optical clear resin (OCR), and may be cured after the bonding object is bonded. According to an embodiment of the present application, as a PSA type adhesive having a vertical alignment force, a polydimethyl siloxane adhesive or a polymethylvinyl siloxane adhesive may be used, and an OCR having a vertical alignment force may be used. Alkoxy silicone adhesive may be used as the type of adhesive, but is not limited thereto.

The 1st board | substrate and the 2nd board | substrate which form a liquid crystal element are affixed by the suitable adhesive force required for liquid crystal cell formation. Conventionally, a liquid crystal device including a liquid crystal region that is phase separated by polymerization of a polymer should generally have a low polymer content in order to implement a transmission mode. In this case, an adhesive force required for formation of a liquid crystal cell does not occur and liquid crystal flows. There was a problem coming out. On the other hand, in the liquid crystal device of the present application, since the liquid crystal compound is separated by the recess formed in the mold layer and the partition wall formed by the resin layer, and the first substrate and the second substrate are attached by an appropriate adhesive force, the liquid crystal does not flow out and thus High contrast ratios.

As the first substrate or the second substrate, a known material can be used without particular limitation. For example, inorganic films, plastic films, etc., such as a glass film, a crystalline or amorphous silicon film, a quartz, or an Indium Tin Oxide (ITO) film, can be used. As a base material layer, the optically isotropic base material layer and the optically anisotropic base material layer like retardation layer can be used.

Examples of the plastic substrate layer include triacetyl cellulose (TAC); COP (cyclo olefin copolymer) such as norbornene derivatives; Poly (methyl methacrylate); PC (polycarbonate); PE (polyethylene); PP (polypropylene); PVA (polyvinyl alcohol); DAC (diacetyl cellulose); Pac (Polyacrylate); PES (poly ether sulfone); PEEK (polyetheretherketon PPS (polyphenylsulfone), PEI (polyetherimide); PEN (polyethylenemaphthatlate); PET (polyethyleneterephtalate); PI (polyimide); PSF (polysulfone); PAR (polyarylate) or amorphous fluorine resin The substrate layer may include a coating layer of a silicon compound such as gold, silver, silicon dioxide or silicon monoxide, or a coating layer such as an antireflection layer, if necessary.

The liquid crystal device may also further comprise an electrode layer. The electrode layer may be formed on the surface of the first substrate or the second substrate, for example, the surface of the side surface of the mold layer or the resin layer. For example, the electrode layer may be formed by depositing a conductive polymer, a conductive metal, a conductive nanowire, or a metal oxide such as indium tin oxide (ITO). The electrode layer can be formed to have transparency. In this field, various materials and forming methods capable of forming a transparent electrode layer are known, and all of these methods can be applied. If necessary, the electrode layer formed on the surface of the base material layer may be suitably patterned.

The liquid crystal device can usually implement a transmission mode. Such a liquid crystal element has a haze of 10% or less, 8% or less, 6% or less, or 5% or less in an initial state, for example. The haze may be a percentage of the transmittance of the diffused light to the transmittance of the total transmitted light passing through the measurement object. The haze can be evaluated using a haze meter (NDH-5000SP). Haze can be evaluated in the following manner using the haze meter. In other words, the light is transmitted through the measurement target and is incident into the integrating sphere. In this process, light is divided into diffused light (DT) and parallel light (PT) by a measurement object, and the light is reflected in an integrating sphere and collected by a light receiving element, and the haze can be measured through the light. Do. That is, the total transmitted light TT is the sum of the diffused light DT and the parallel light PT (DT + PT), and the haze is the percentage of diffused light with respect to the total transmitted light (Haze (%) = 100). X DT / TT). In addition, such a liquid crystal device may exhibit excellent transparency in a state in which no external action is applied. For example, the liquid crystal device may exhibit a light transmittance of at least 45%, at least 50%, at least 55%, or at least 60% in an initial state. The light transmittance may be light transmittance for any wavelength in the visible light region, for example, in the range of about 400 nm to 700 nm.

The liquid crystal element is also capable of driving through low energy consumption, for example through low driving voltage. In the case of a device in a normally transparent mode, the scattering mode may be realized by changing the alignment direction of the liquid crystal compound by applying a voltage. The liquid crystal device of the present application may lower the driving voltage required in this process. It works. In general, in the case of implementing a transmissive mode device, RM (reactive mesogen) and a liquid crystal are used together. In this case, an anchoring with the liquid crystal is increased due to a system in which the RM is cured, thereby increasing driving voltage. have. On the other hand, since the liquid crystal device of the present application injects a liquid crystal or a liquid crystal and a small amount of a crosslinkable compound into the concave portion of the mold layer without using the RM, the driving voltage is only affected since the device is influenced only by an externally applied electric field. It has the advantage of being significantly lower.

The liquid crystal element can also exhibit excellent contrast ratio. As used herein, the term contrast ratio may refer to a ratio (T / S) of the luminance T in the transmission mode and the luminance S in the scattering mode. The higher the contrast ratio, the better the device performance. Therefore, the upper limit of the contrast ratio is not particularly limited. In the liquid crystal device of the present application, as described above, the liquid crystal compound separated by the concave portion of the mold layer and the partition wall formed of the resin layer maintains a high vertical alignment state, so that light leakage phenomenon is reduced, thereby resulting in the high contrast ratio. Can be represented.

The present application also relates to a method of manufacturing the liquid crystal device. In the exemplary liquid crystal device manufacturing method, after the liquid crystal compound is included in the concave portion of the first substrate on which the mold layer having the convex portion and the concave portion is formed, the surface energy is 45 mN / m or less on the upper portion, And laminating a second substrate on which a resin layer having an AFM Z scale surface roughness of 2 nm or less is formed on the first substrate so that the resin layer is in contact with the convex portion of the mold layer. 2 is a process schematic diagram of a method of manufacturing an exemplary liquid crystal element. Details of the mold layer, the resin layer, and the liquid crystal compound in the manufacturing method may be the same as described in the items of the liquid crystal device.

The manufacturing method of the liquid crystal element includes forming a convex portion and a concave portion in the mold layer after forming the mold layer on the first substrate. The mold layer may be polymerized or crosslinked and / or cured, for example, by coating a mold layer composition including a polymerizable or crosslinkable compound, a curable compound, and / or a vertically oriented polymer on top of a first substrate. Can be formed. The polymerization or crosslinking may be performed by irradiating suitable energy, for example, light, which may induce polymerization or crosslinking. In addition, irradiation of energy for crosslinking or polymerization can be carried out together with a process of appropriately heating and drying the resin layer composition. Heat drying can be performed at 70 degreeC-250 degreeC, 80 degreeC-240 degreeC, or 90 degreeC-230 degreeC. Drying time may be carried out for 1 to 60 minutes. By controlling the drying temperature and drying time in the above range, the present application can effectively implement the surface characteristics of the desired mold layer.

The method for forming the resin layer composition on the first substrate is not particularly limited, and for example, known methods such as roll coating, printing, inkjet coating, slit nozzle method, bar coating, comma coating, spin coating or gravure coating, etc. It can be formed by coating through a coating scheme.

The convex portion and the concave portion in the mold layer may be formed by, for example, an imprinting method. In this case, the imprinting process may be performed after volatilizing the solvent by drying the coating layer of the composition under appropriate conditions when the composition forming the mold layer includes a solvent or the like. The imprinting process can be carried out by a known method, for example, using a stamp or roller having a pattern capable of transferring the desired convex and concave portions to the coating layer of the mold layer composition. . In this case, application of energy for crosslinking or polymerization of the mold layer may be performed before, after or simultaneously with the imprinting process. The conditions of application of energy for polymerization or crosslinking, for example, irradiation of light, are not particularly limited as long as the mold layer is suitably cured to form recesses and convex portions. If necessary, an appropriate heat application or exposure step may be performed before or after the irradiation step of light or at the same time to promote the polymerization.

The manufacturing method of a liquid crystal element also includes the step of including a liquid crystal compound in the concave portion of the mold layer. The liquid crystal compound may be included in the concave portion by coating the liquid crystal composition including the liquid crystal compound on the concave portion and the convex portion and the formed mold layer. The layer of the composition comprising the liquid crystal compound may be formed by coating in a conventional coating manner such as, for example, bar coating, comma coating, inkjet coating or spin coating.

The manufacturing method of the liquid crystal element may further include laminating the second substrate on the first substrate so that the resin layer contacts the convex portion of the mold layer after the resin layer is formed on the second substrate. For example, the resin layer may be formed by coating a resin layer composition including a polymerizable or crosslinkable compound, a curable compound, and / or a vertically oriented polymer on the second substrate. The method of coating the resin layer composition is not particularly limited, and for example, coating through a known coating method such as roll coating, printing, inkjet coating, slit nozzle method, bar coating, comma coating, spin coating or gravure coating, and the like. It can form by. In this case, when the resin layer composition contains a solvent or the like, the resin layer is prepared in a dried state in which the solvent is dried under appropriate conditions to volatilize the solvent or irradiated with appropriate energy capable of inducing crosslinking or polymerization. can do.

The method of manufacturing the liquid crystal device may also include irradiating suitable energy, for example, light, which may induce crosslinking, polymerization or curing after laminating the second substrate to the first substrate. In the above, crosslinking or polymerization may be meant to include crosslinking or polymerization between the crosslinkable or polymerizable compounds included in the mold layer and crosslinking or polymerization between the crosslinkable or polymerizable compounds included in the resin layer. For this reason, the resin layer and the mold layer may be in a state of being completely crosslinked or polymerized, respectively.

In addition, the crosslinking or polymerization may be meant to include crosslinking or polymerization between the crosslinkable or polymerizable compound present in the resin layer and the crosslinkable compound present in the convex portion or the liquid crystal region of the mold layer. In this case, since the convex portions of the resin layer and the mold layer can be kept in contact with each other by crosslinking, the first substrate and the second substrate can exhibit an appropriate adhesive force required to form the liquid crystal cell, and the concave portion of the mold layer And the resin layer can form a partition for separating the liquid crystal compound appropriately. Accordingly, the liquid crystal device of the present application can properly maintain the initial alignment state without flowing down the liquid crystal compound even in the transmissive mode, so that not only a roll-to-roll process after manufacturing but also a high contrast ratio can be exhibited even at a low driving voltage.

The present application also relates to the use of the liquid crystal device. The liquid crystal device has a merit that it is possible to implement a transmission mode, exhibit excellent contrast ratio, and to drive at a low voltage. Such a liquid crystal element can be applied to, for example, an optical modulation device and used. As the optical modulation device, a smart window, a window protective film, a flexible display element, an active retarder for viewing 3D images, a viewing angle adjusting film, or the like may be exemplified, but is not limited thereto. The manner of configuring the above optical modulation device is not particularly limited, and a conventional manner may be applied as long as the liquid crystal element is used.

The liquid crystal device of the present application is, for example, a device capable of implementing a transmissive mode, and exhibits a high contrast ratio and can be driven at a low driving voltage. The liquid crystal device may be applied to various light modulation devices such as a smart window, a window protective film, a flexible display device, an active retarder or a viewing angle control film for 3D image display.

1 is a schematic diagram of an exemplary liquid crystal element.

2 shows a method of manufacturing an exemplary liquid crystal element.

3 shows whether or not the vertical alignment with respect to the liquid crystal according to the surface characteristics of the base film of Reference Examples 1 to 6.

4 is an OM image that can determine whether the vertical alignment of Example 1 and Comparative Example 1.

5 shows the peel force evaluation results of Example 1 and Comparative Example 1. FIG.

6 shows the results of evaluating straight transmittance according to the viewing angles of Example 1 and Comparative Example 1. FIG.

7 shows the results of evaluating the overall transmittance according to the driving voltages of Example 1 and Comparative Example 1. FIG.

Hereinafter, the above-described contents will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present application is not limited by the contents given below.

Measurement Example 1. Surface Energy Measurement

Surface energy was measured using a drop shape analyzer (Drop Shape Analyzer, DSA100 manufactured by KRUSS). Repeat the procedure of dropping the deionized water whose surface tension is known to the sample to be measured and determining the contact angle five times to obtain the average value of the five contact angle values obtained. Repeat the procedure of dropping the diiodomethane and calculating the contact angle five times, and average the five obtained contact angle values. Subsequently, the surface energy was determined by substituting a numerical value (Strom value) on the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method using the average value of the contact angles with the deionized water and diiomethane obtained. The surface energy (γ ^surface ) of the sample can be calculated by considering the dispersion force between nonpolar molecules and the interaction force between polar molecules (γ ^surface = γ ^dispersion + γ ^polar ), and the polar term (γ ^olar) at the surface energy γ ^surface Can be defined as the polarity of the surface.

Measurement Example 2. Surface Roughness Measurement

Surface roughness can be measured by measuring the AFM Z scale surface roughness (arithmetic mean roughness, Ra) using a Bruker Multimode AFM instrument (Measurement conditions: Parameters-Mode: ScanAsyst in air, Samples / line: 512 x 512). , Scan rate: 0.7 Hz, AFM probe: Silicon tip on nitride lever w / Al coating (Bruker), Material: Silicon Nitride, Resonance Frequency: 50 ~ 90 kHz, Force Constant: 0.4 N / m, Thickness: 0.65um, Length : 115 ± 10um, Width: 25um, Tip height: 5um, Software-Nanoscope 8.15)

Reference Example 1

After placing two substrate films having an ITO (Indium Tin Oxide) layer deposited on a PC (polycarbonate) film so as to face the ITO layer inside, a liquid crystal composition (7306, manufactured by HCCH Co., Ltd.) was placed therebetween. To a thickness of 30 μm to prepare a liquid crystal cell.

Reference Example 2

After depositing an Indium Tin Oxide (ITO) layer on a PC (polycarbonate) film, two substrate films subjected to corona treatment were disposed so as to face the ITO layer inside, and thereafter, the liquid crystal composition 7306, HCCH Company) was injected to a thickness of about 3um to 30um to prepare a liquid crystal cell.

Reference Example 3

After depositing an Indium Tin Oxide (ITO) layer on a PET (Polyethylene terephthalate) film, the adhesive layer has two substrate films on which the Si-Ahesvie of Daipo Paper Co., Ltd. has been transferred to a thickness of about 7 μm to 50 μm on the ITO layer. The liquid crystal composition (7306 (manufactured by HCCH Co., Ltd.)) was injected to have a thickness of about 3 µm to 30 µm after being disposed so as to face each other.

Reference Example 4

After depositing an Indium Tin Oxide (ITO) layer on the PC (polycarbonate) film, two substrate films having a SiOx-based barrier layer formed on the ITO layer are disposed to face each other so that the barrier layer is positioned inward. A liquid crystal cell was prepared by injecting a liquid crystal composition (7306, manufactured by HCCH, Inc.) to a thickness of about 3 μm to 30 μm.

Reference Example 5

After placing two substrate films on which a hard coating layer was formed on a PC (polycarbonate) film so as to face the hard coating layer inside, a liquid crystal composition (7306, manufactured by HCCH Co., Ltd.) had a thickness of about 3 μm to 30 μm therebetween. It was injected so as to prepare a liquid crystal cell.

Reference Example 6

After depositing an Indium Tin Oxide (ITO) layer on a PET (Polyethylene terephthalate) film, the adhesive layer was placed inside the two base films on which Henkel 3193H Adhesvie was transferred to a thickness of about 1 μm to 5 μm on the ITO layer. After arrange | positioning so that it may oppose, the liquid crystal composition (7306, HCCH Co., Ltd. product) was inject | poured so that it might become about 3 micrometers-30 micrometers in thickness, and the liquid crystal cell was produced.

Evaluation Example 1. Evaluation of Vertical Orientation According to Surface Characteristics

Surface energy and surface roughness were measured by the method described above with respect to the base film prepared in Reference Examples 1 to 6 and shown in FIG. 3 and Table 1, and evaluated the vertical alignment with respect to the liquid crystal cells prepared in Reference Examples 1 to 6 The results are shown in Table 1. Specifically, the surface energy and the surface roughness can be measured by the methods of Measurement Examples 1 and 2, and when the liquid crystal cell is observed from the front (incident angle 0 °), the case where the straight transmittance is 55% or more is said to be vertical alignment. Evaluated. As shown in FIG. 3 and Table 1, when the surface energy of the base film is 45 mN / m or less, and the surface roughness is 2 nm or less, the liquid crystal cell having the upper and lower base films can effectively induce vertical alignment with respect to the liquid crystal. You can see that.

Table 1

	Surface energy (mN / m)	Surface roughness (Ra, nm)	Transmittance (%)	Vertical orientation
Reference Example 1 (PC-ITO)	23.1	0.4	66	O
Reference Example 2 (PC-ITO_C)	29.7	0.4	65	O
Reference Example 3 (Si-A)	8.5	1.3	69	O
Reference Example 4 (Barrier)	61.0	2.3	48	X
Reference Example 5 (H / C)	46.5	11.4	45	X
Reference Example 6 (3193HS)	47.9	0.3	52	X

Example 1

After coating an acrylic-based mold layer composition (trade name: KAD-03, manufactured by Minutatec Co., Ltd.) on an ITO layer of a PET film (100 mm x 100 mm) (hereinafter referred to as a first substrate) on which an ITO transparent electrode layer was deposited, Honeycombo type pattern was formed by imprinting method (width of convex part of pattern: 10um ~ 50um, height of convex part: 3um ~ 20um, width of concave part: 300um ~ 750um). Subsequently, a liquid crystal composition containing 2 g of a liquid crystal compound (7306, manufactured by HCCH) and 20 mg of an anisotropic dye (X12, manufactured by BASF) was coated on the imprinted mold layer. Next, Si-Ahesvie of Daipo Paper Corporation was transferred to a thickness of about 10 μm as a resin layer on a PET film (100 mm × 100 mm) (hereinafter referred to as a second substrate) on which an ITO transparent electrode layer was deposited. Subsequently, after the second substrate was laminated on the first substrate so that the resin layer was in contact with the recess of the mold layer, a liquid crystal device was manufactured by irradiating light under Fusion UV 70% 3 m / min under the conditions.

Comparative Example 1

A liquid crystal device of Comparative Example 1 was prepared in the same manner as in Example 1, except that Henkel Corporation's 3193H Adhesvie was about 3 μm thick instead of Daipo Paper's Si-Ahesvie as a resin layer on the second substrate. .

Evaluation Example 2 Example and Comparative Example Evaluation of the vertical alignment of the liquid crystal device

4 shows the images of the liquid crystal devices prepared in Example 1 and Comparative Example 2 observed with a microscope (OM). As shown in FIG. 4, in Comparative Example 1, since the liquid crystal and the dye are not in the vertical alignment state, domains are formed and the brightness is dark. On the other hand, in Example 1, since the liquid crystal and the dye are in a vertical alignment state, no domain is observed and the chromaticity and brightness are bright.

Evaluation Example 3. Evaluation of Adhesion

The adhesion of the liquid crystal devices prepared in Example 1 and Comparative Example 1 was evaluated by measuring the 90-degree peeling force of the resin layer and the mold layer by using a texture analyzer, and the results are shown in FIG. 5 and Table 1. As shown in FIG. 5, it can be seen that Example 1 exhibits excellent adhesive strength compared to Comparative Example 1. FIG.

Evaluation Example 4. Permeability Evaluation

For the liquid crystal devices manufactured in Example 1 and Comparative Example 1, the linear transmittance according to the viewing angle was evaluated in the absence of voltage, and the results are shown in FIG. 6, and the total transmittance according to the driving voltage at the front was evaluated and the result. Is shown in FIG. 7. The linear transmittance according to the viewing angle was measured using the LCMS-200 equipment, and the linear transmittance change according to the angle of the light incident on the liquid crystal device. The transmittance according to the application of voltage was connected to the ITO layer of the upper and lower ITO-PET films The total transmittance according to the applied voltage while driving was measured using a haze meter (NDH-5000SP). As shown in FIG. 7, it can be seen that the liquid crystal device of Example 1 exhibits a high transmittance in a voltage-free state and a low transmittance in a voltage-applied state, thereby implementing a normal transmission mode. As shown in FIG. 6, it can be seen that the liquid crystal device of Example 1 exhibits a high transmittance at the front and viewing angles, that is, an excellent vertical alignment state, in a voltage-free state, as compared with the liquid crystal device of Comparative Example 1.

Claims (16)

1. A first substrate having a mold layer having convex portions and concave portions formed thereon; A second substrate having a surface energy of 45 mN / m or less and an AFM Z scale surface roughness of 2 nm or less, and having the resin layer in contact with the convex portion of the mold layer; And a liquid crystal compound present in the concave portion of the mold layer.
2. The liquid crystal device of claim 1, wherein the mold layer or the resin layer satisfies the following general formula (1):

   [Formula 1]

   0 = | Y - {1 × 10 -4 X 3 - 1.2 × 10 -3 X 2 + 3.1 × 10 ^-3 X-1.6 × 10 ^-3 } | = 0.05

   In Formula 1, X represents the AFM Z scale surface roughness of the mold layer or the resin layer, and Y represents the surface polarity of the mold layer or the resin layer, provided that the surface roughness and surface polarity of the mold layer It is the value measured about the surface of the mold layer of the state in which the convex part and the recessed part are not formed).
3. The liquid crystal device according to claim 1, wherein the mold layer or the resin layer contains a polymerizable or crosslinkable compound or a curable compound.
4. The liquid crystal device according to claim 3, wherein the polymerizable or crosslinkable compound is an acrylate compound.
5. The liquid crystal device according to claim 3, wherein the curable compound is a curable silicone compound.
6. 4. The liquid crystal device according to claim 3, wherein the mold layer or the resin layer further comprises an additive capable of inducing vertical alignment.
7. 7. The liquid crystal device according to claim 6, wherein the additive comprises a vertically oriented polymer comprising chlorine (Cl), fluorine (F) or silicon (Si).
8. The liquid crystal element according to claim 1, wherein the convex portions of the resin layer and the mold layer are in contact with each other by adhesive force, or the convex portions of the resin layer and the mold layer are in contact with each other in a crosslinked state.
9. The liquid crystal device according to claim 1, wherein in the initial state, the liquid crystal compound is present in the concave portion in the vertically oriented state.
10. The liquid crystal element according to claim 1, wherein in the initial state, the liquid crystal element has a plane phase difference of 30 nm or less, and a thickness direction phase difference of 500 nm or more.
11. The liquid crystal device according to claim 1, wherein in an initial state, a transmittance for light having a wavelength of 400 nm to 700 nm is 45% or more, and haze is 10% or less.
12. 12. The liquid crystal device according to claim 11, wherein a light transmittance of less than 45% and a haze of more than 10% is switched to a scattering mode by applying external energy.
13. After incorporating a liquid crystal compound into the concave portion of the first substrate having the mold layer having the convex portion and the concave portion formed thereon, the surface energy is 45 mN / m or less at the top, and the AFM Z scale surface roughness is 2 nm or less. A method for manufacturing a liquid crystal element, comprising laminating a second substrate on which a resin layer is formed on the first substrate so that the resin layer is in contact with the convex portion of the mold layer.
14. The method for manufacturing a liquid crystal element according to claim 13, wherein the convex portion and the concave portion of the mold layer are formed by imprinting.
15. The manufacturing method of the liquid crystal element of Claim 13 which crosslinks the convex part of a resin layer and a mold layer after laminating | stacking a 2nd board | substrate to a 1st board | substrate.
16. An optical modulation device comprising the liquid crystal element of claim 1.

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