WO2014042389A1

WO2014042389A1 - Inducer for vertically aligning liquid crystals and liquid crystal display device manufactured using same

Info

Publication number: WO2014042389A1
Application number: PCT/KR2013/008055
Authority: WO
Inventors: 강신웅; 김선수; 김진욱; 이명훈; 이승희
Original assignee: 전북대학교산학협력단
Priority date: 2012-09-17
Filing date: 2013-09-06
Publication date: 2014-03-20

Abstract

The present invention provides an inducer for vertically aligning liquid crystals, comprising at least one affinitive liquid crystal-non-affinitive liquid crystal compound. Said compound contains an affinitive liquid crystal region including an affinitive liquid crystal group having high chemical affinity to a liquid crystal host, and a non-affinitive liquid crystal region including a non-affinitive liquid crystal group having low chemical affinity to the liquid crystal host. At least one of the affinitive liquid crystal-non-affinitive liquid crystal compounds includes at least one liquid crystal having an affinity group having at least eight carbon atoms in the affinitive liquid crystal region. The ratio of non-affinity of liquid crystal, (X'), of the inducer for vertically aligning liquid crystals, calculated by the following equation 1, is 0.5 to 6. The present invention also provides a liquid crystal display device manufactured using the inducer. [Equation 1] n, X, and Y in the equation are the same as that which is defined in the specification.

Description

Name of the Invention: Liquid crystal vertical alignment inducer and liquid crystal display device manufactured using the same

Field of technology

The present invention relates to a liquid crystal vertical alignment inducer and a liquid crystal display device manufactured using the same.

Background

In the manufacture of a conventional vertical alignment liquid crystal display device, a thin film obtained by applying a vertical alignment polymer such as polyimide in a solution state and then firing to solidify the liquid crystal on the substrate surface was used. 1 is a process diagram schematically illustrating a manufacturing process of a liquid crystal display device using a polyimide thin film for vertical alignment of a conventional liquid crystal. Referring to FIG. 1, the electrodes 2, 2 'are patterned and formed on the first and second substrates 1, Γ as transparent conductive films for applying an electric field (S1), and polymer orientation thereon. After applying the agent in the form of a thin film in a solution state and applying high temperature heat to bake to form a polymer alignment layer (3, 3 ') (S2), and the first and second substrate on which the polymer alignment layer is formed to face each other After assembling at regular intervals, a liquid crystal was injected to form a liquid crystal layer 4 to manufacture a liquid crystal display (S3). At this time, the liquid crystal molecules in the liquid crystal layer 4 are arranged perpendicularly to the substrate surface under the influence of the polymer alignment agent. As such, the conventional method of manufacturing a vertically aligned liquid crystal display device separates the process of forming alignment layers on both substrates before forming the liquid crystal layer between the first and second substrates to control the alignment of the liquid crystals. It must be done.

However, when manufacturing a liquid crystal display device for controlling the alignment of the liquid crystal in the same manner as described above, since the liquid crystal does not have a pretilt angle in a specific direction, the direction of the liquid crystal reflected when applying the electric field is random (random), Problems such as low visibility and low reaction speed have occurred.

In order to solve this problem, methods for inducing the pretilt angle of the liquid crystal or controlling the direction in which the liquid crystal responds to the electric field using techniques such as rubbing, surface protrusion, patterned electrode, and the like have been proposed. However, these methods necessarily require a pretreatment process of the alignment layer for the alignment control of the liquid crystal, and did not provide a complete technical solution due to process problems and side effects due to the added technology. [Advanced technical paper]

Korean Patent Publication No. 2007-0102372 (published Oct. 18, 2007)

Korea Patent Publication 1999-002569 (1999. 01. 15 publication)

Detailed description of the invention

Technical challenges

SUMMARY OF THE INVENTION An object of the present invention is to induce vertical alignment of liquid crystals without a substrate alignment process, and to stabilize the pretilt angle of the liquid crystal to improve the performance and reliability of the liquid crystal display device. It is to provide a composition for.

It is another object of the present invention to stabilize the liquid crystal array by using the liquid crystal vertical alignment guide agent, to induce the pretilt angle of the pixel unit, to minimize the defects appearing when driving the device and to increase the reaction speed improved optical, electric The present invention provides a liquid crystal display device capable of exhibiting optical characteristics, and a method of manufacturing the liquid crystal display device in a simplified process as compared to the prior art without the pre-alignment process of the substrate.

It is still another object of the present invention to induce vertical alignment of a liquid crystal having alignment stability by using a composition for forming a liquid crystal layer in which a liquid crystal vertical alignment inducing agent forms a fine granule by self-assembly and is uniformly dispersed in a liquid crystal host. To provide a way.

It is still another object of the present invention to form a microassembly by self-assembly of the liquid crystal vertical alignment inducing agent, and to vertically align the liquid crystal and stabilize the light by using the composition for forming a liquid crystal layer uniformly dispersed in the liquid crystal host. It is to provide a way to guide.

It is still another object of the present invention to provide a method for forming an insulating liquid crystal vertical alignment and light stabilization layer between an electrode and a liquid crystal layer in a simplified process compared to the prior art without precoating a substrate.

Challenge solution

According to one embodiment of the present invention, a lipophilic crystalline region including a chemically high affinity for the liquid crystal host and a non-lipophilic crystalline region including a non-lipophilic crystalline group having a low affinity for the liquid crystal host One or more lipophilic crystalline-non-lipophilic crystalline compounds, and at least one of the lipophilic crystalline-non-lipophilic crystalline compounds includes at least one lipophilic crystalline group having 8 or more carbon atoms in the lipophilic crystalline region, Provided are liquid crystal vertical alignment inducers having a non-liquid crystalline ratio (Χ ′) calculated from 1 to 0.5 to 6.

[Equation 1] normal.

In Equation 1,

n is a kind of lipophilic-non-liquid crystalline compound constituting the liquid crystal vertical alignment inducer Is an integer of 1 or more indicating the number of,

X is a non-lipophilic crystalline ratio of any one of the lipophilic-non-lipophilic crystalline compounds constituting the liquid crystal vertical alignment inducer, and is calculated according to Equation 1-1 below. ，

[Equation 1-1]

Molecular weight of non-true liquid crystalline group in the compound

X = X10

Molecules of Fedang Lake ¾

Y is a weight ratio of any one of the lipophilic-non-liquid crystalline compounds of the lipophilic-non-liquid crystalline compounds constituting the liquid crystal vertical alignment inducing agent, and is calculated according to the following formula 1-2.

[Equation 1-2]

Weight of the compound

Y =

The total lipophilic crystalline group of the compounds is a linear, branched or cyclic substituted or unsubstituted saturated or unsaturated hydrocarbon group having 8 to 30 carbon atoms; Substituted or unsubstituted C8-C30 heteroalkyl group, heterocycle group, and heteroaromatic group containing 1 or more hetero atoms selected from the group which consists of Ν, 0, Ρ, S, and Si in a molecule | numerator; And it may be selected from the group consisting of a combination group having 8 to 30 carbon atoms consisting of a combination of the hydrocarbon group and heteroatom containing groups.

Preferably, the lipophilic group may be an alkyl group having 8 to 30 carbon atoms, an alkenylalkyl group, an alkynylalkyl group, a cycloalkyl group, an aryl group, and an arylalkyl group substituted or unsubstituted with a halogen atom; Intramolecular carbonyl group (-c (= o)-), ester group (-C (= 0) 0-), ether group (-0-), ethylene oxide group (-CH ₂ CH ₂ 0_), azo group (-N = N-), -COS- and -S- heteroalkyl group, heterocycloalkyl group and heteroaryl group having 8 to 30 carbon atoms containing a hetero atom-containing functional group selected from the group consisting of; And it may be selected from the group consisting of a combination thereof. The non-lipophilic crystalline group is alcohol, polyhydric alcohol, amine, polyamine, carboxylic acid, polycarboxylic acid, silane compound, siloxane compound, polyethylene glycol, polypropylene oxide, fluorinated carbon compound, thiol, polyvalent thiol , Selected from the group consisting of sulfonic acid, sulfuric acid, phosphonic acid, and phosphoric acid Functional groups derived from the compound.

Preferably, the non-lipophilic group is 1-ol (l-ol), 1,2-diol (l, 2-diol), glycerol (glycerol), glucose (glucose), dextrose (sorbate) sorbitol, pentaerythr i tol, dipentaerythritol, tripentaerythr it ol, sorbitan, fluctose, Compounds selected from the group consisting of sucrose, gallic acid, glucopyranoside, ascorbic acid, mannide and maltos i de It may be a functional group derived from.

Preferably, the non-lipophilic group is 1-amine (l-amine), 1,2-diamine (1,2-diamine), 1, 3-diamine (1, 3-di amine), ethylene diamine ), Diethylene diamine, tris (2-aminoethyl) amine

(tr is (2-aminoethyl) araine), cyclohexane diamine, diethylene triamine, phenyldiamine, phenyltriamine, 1,3,5-triazine 4 , 6-diamine (1, 3, 5—triazine 4,6-diamine), 1,3,5-triazine 2, 4, 6-triamine (1, 3, 5—tri azine 2,4,6- triamine) or a cyclic ethylene amine which may be a functional group derived from a compound selected from the group consisting of cyclen;-(CH CHsNH-where 1 is an integer of 2 to 6).

Preferably the non-lipophilic group is tris (trimethylsiloxy) silane

(tris (trimethylsiloxy) may be a functional group derived from.

Preferably, the non-lipophilic crystalline group may be a functional group derived from a linear, branched or cyclic siloxane compound containing 1 to 10 siloxy groups of Formula 1 below:

[Formula 1]

Wherein Ra and Rb are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a siloxy group, and a combination thereof, and m is an integer of 1 to 10)

Preferably, the non-lipophilic crystalline group is an ethylene oxide group It may be a functional group derived from a linear polyoxyethylene having 4 to 40 carbon atoms of the formula (2a) containing 2 to 20 or a cyclic polyethylene ether (crown ether) having 4 to 10 carbon atoms of the formula (2b):

[Formula 2a]

-CHCH ₉ -o4n m

[Formula 2b]

(In the formulas 2a and 2b, m is an integer of 2 to 20, n is an integer of 2 to 5)

Preferably, the non-lipophilic crystalline group may be a functional group which is a perfluoroalkyl group or a perfluoroaryl group derived from a fluorocarbon compound having 4 to 20 carbon atoms containing 9 to 41 fluoro groups.

Preferably, the non-lipophilic crystalline group is 1-thiol (1-thiol) ᅳ 1,2-dithiol (1,2-dithiol), thioglycerol (thioglycerol), thiopentaerythrite

(thiopentathiopentaerythritol) and dithiothreyl may be a functional group derived from a compound selected from the group consisting of (di thiothrei tol). Preferably, the non-lipophilic group is 1-carboxylic acid (1-carboxylic acid), 1,2-dicarboxylic acid (1,2-dicarboxylyc acid), 1,3-dicarboxylic acid (1,3 di carboxy lyc acid, benzenecarboxylic ic acid, benzenedicarboxylic acid, 1,2,3-tricarboxylic acid, benzene Tricarboxylic acid (benzene tri carboxy 1 ic acid), malic acid (maleic acid), maleic acid (taric acid), tartar acid (citric acid), maleamic acid (tnaleamic acid), gluta Consisting of glutamic acid, agaric acid, aconit ic acid, tricarballyl ic acid, and amino acid (amino acid, -CH (匪₂ ) -C00H) It may be a functional group derived from a compound selected from the group.

Preferably, the lipophilic-non-lipophilic crystalline compound may be selected from the group consisting of the compounds of the following formulas 3a to 3i and combinations thereof:

[Formula 3a]

[Formula 3b]

[Formula 3c]

[Formula 3d]

[Formula 3e]

0¾) ^ ¾ eu (PEO) _bs

[Formula 3f]

[Formula 3g]

[Formula 3h]

[Formula 3i]

In Chemical Formulas 3a to 3i,

Ri to R ₉ each independently represent an alkyl group having 8 to 30 carbon atoms; C8-C30 alkenylalkyl group; An alkynylalkyl group having 8 to 30 carbon atoms; Arylalkyl group having 8 to 30 carbon atoms; A cycloalkyl group having 8 to 30 carbon atoms; Aryl groups having 8 to 30 carbon atoms; Intramolecular carbonyl group (_C (= 0)-), ester group (-C (= 0) 0-), ether group (-0-), ethylene oxide group (-CH ₂ CH ₂ 0-), azo group (_N = N-), -COS- and -S— carbon number containing a heteroatom-containing functional group selected from the group consisting of 8-30 heteroalkyl group, heterocycloalkyl group, or heteroaryl group; And combinations thereof,

X _{1 (} X ₂ , X ₅ , X _7> X ₈ and Χ9 are each independently, -0-, -S-, -COO- ₍ -C0NH-, -C ₆ H ₄ 0-, -C ₆ H ₄ C00-, -C ₆ H ₄ C0NH- and selected from the group consisting of a single bond,

¾ and are each independently selected from the group consisting of a single bond, -0- and -C ₆ H ₄ 0-,

X ₆ is a single bond, ᅳ 0 ((-, -CH ₂ CH _2- , -C ₆ H ₄ 0C CH _2- , -C ₆ H ₄ C00CH ₂ CH ₂ -and-(SiRaRb) -CH ₂ CH _2- Wherein Ra and Rb are each hydrogen or an alkyl group having 1 to 3 carbon atoms, and

PA, PAm, PS, PEO, FC, PT, CA, and SP are non-lipophilic crystalline groups which form covalent bonds with R ₉ , respectively, directly or through a linking group of the above to ¾, and PA is a carbon number containing 1 to 8 hydroxyl groups. A functional group derived from an alcohol or a polyhydric alcohol of 1 to 30,

PAm is a functional group derived from an amine or a polyvalent amine having 1 to 20 carbon atoms containing 1 to 6 amine groups,

PS is a functional group derived from a silane compound having 1 to 20 carbon atoms containing 2 to 10 silyl groups, or from a linear, branched or cyclic siloxane compound containing 1 to 10 siloxy groups. It is a small container that is induced,

PE0 is a functional group derived from linear polyoxyethylene having 4 to 40 carbon atoms of Formula 2a or cyclic polyethylene glycol having 4 to 10 carbon atoms of Formula 2b including 2 to 20 ethylene oxide groups,

[Formula 2a]

-CH.CHa-O-H

[Formula 2b]

(In Formulas 2a and 2b, m is an integer of 2 to 20, n is an integer of 2 to 5)

FC is a perfluoroalkyl group or a perfluoroaryl group derived from a fluorocarbon compound having 4 to 20 carbon atoms containing 9 to 41 fluoro groups,

PT is a thiol having 1 to 20 carbon atoms containing 1 to 8 thiol groups (-SH) and And that approach derived from tieul _\ functionalities,

CA is a functional group derived from a carboxylic acid having 1 to 10 carbon atoms and a polyvalent carboxylic acid containing 1 to 4 carboxylic acid groups (-C00H),

SP is a functional group derived from a sulfonic acid or a polysulfonic acid having 1 to 10 carbon atoms containing 1 to 3 sulfonic acid groups (-S (= 0) ₂ 0H), or a sulfonic acid group (-0S (= 0) ₂ 0H) from 1 to, or functional groups derived from a sulfur acid or a polyvalent sulfur acid having 1 to 10 carbon atoms containing three, phosphonic sulphonic acid group (- P (= 0) ( 0H) carbon atoms, including ₂₎ 1-3 to Phosphoric acid having 1 to 10 carbon atoms, which is a functional group derived from 1 to 10 phosphonic acid or polyhydric phosphonic acid, or including 1 to 3 phosphoric acid groups (-0-P (= 0) (0H) ₂ ) Or a functional group derived from a polyphosphoric acid, and

Al to a9 and bl to b9 are numbers representing the number of functional groups, and are each independently an integer of 1 to 3.

More preferably, the lipophilic-non-lipophilic crystalline compound may be selected from the group consisting of the following compounds:

Sorbitan monolaurate;

Sorbitan monopalmitate;

Sorbitan monostearate;

Sorbitan tristearate;

Sorbitan monooleate;

Sorbitan sesquioleate;

Sorbitan trioleate;

Polyoxyethylenesorbitan tr i stearate;

Polyoxyethylene sorbitan trioleate;

Polyoxyethylene sorbitan stearate;

Polyoxyethylenesorbitan oleate; Dinudecanoyl glycerol, dipalmitin; Dioctadecanoyl glycerol; Dinudecanoyl glycerol;

Dioleoyl glycerol;

Octyl gallate;

Lauryl gallate;

Ascorbic acid 6-palmitate;

Mannide monooleate;

1,2-dodecanediol (1,2-1) 0 (1 ^ 3116 (1101);

1, 2-nuxadecanediol (1, 2-Hexadecaned i o 1);

Hexadecane 1,2-diamine;

Octinic acid; Decanoic acid;

Dodecanoic acid;

Hexadecanoic acid (Hexadecanoic acid, Palmitic acid);

Octadecanoic acid (Stearic acid);

Dihexadecyl phosphate;

Nuxadecylsulfonic acid;

Dodecylbenzene sul fonic acid;

1-decane (1-Decanol);

1-dodecanol;

1-nuxadecanol;

1-octadecanol (1-Octadecanol);

Octylamine;

Decylamine;

Dodecy 1 amine;

Methacryloxy methylphenethyl tris (trimethylsiloxy) silane isomer

(methacryloxy methy lpenethy 1 tris (trimethylsi loxy) silane isomer); methyl-octadecyl bis (trimethylsiloxy) silane (methyl-octadecyl

bis (tr imethylsi loxy) si lane);

Polyoxyethylenesorbitane tr i stearate;

Dodecylphenyl sul fonic acid;

To ⁰ Gale iteu derivative of formula 3j (Gallate derivative);

Polyoxyethylen (2) stearyl ether;

Decyl gallate;

Palmitic acid.

The lipophilic-non-lipophilic crystalline compound may further include a photobanung group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region.

The photo-banung group may be selected from the group consisting of an acryl group, methacryl group, cinnamate group, coumarin group, chacon group, vinyl group, thiol group, en group, diene group, thiol group, and acetylene group.

Preferably, the lipophilic-non-lipophilic crystalline compound is a photo-banung lipophilic crystalline-non-lipophilic crystalline compound further comprising a photobanung group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region. Photoreactive Hydrophilic Crystal-Mirrored The liquid crystalline compound may be selected from the group consisting of the following compounds:

Pentaerythritol diacrylate monostearate (Pentaerythritol di aery 1 at e monost earat e);

Pentaerythritol monopentathritol monoacrylate monostearate;

Glucosyl methacrylate (methacryloctyloxyphenolglucose) or derivatives thereof;

[4- (methacryloyloxymethyl) phenyl] ethyl-tris (trimethylsiloxy) silane ([4- (methacryloy loxymethy 1) henyl] ethy l ^- tris (tr imethy 1 si lyloxy) si 1 ane); Methacryloxymethylphenethyltris (trimethylsiloxy) silane

(me thacry loxymeth lphene thy 1 tris (trimethylsi loxy) s i 1 ane).

The photo-banung lipophilic-non-liquid crystalline compound may be included in an amount of 3 to 100% by weight based on the total weight of the liquid crystal vertical alignment derivative.

The liquid crystal vertical alignment inducing agent may further include a photoreactive Cg-2 non-lipophilic crystalline compound selected from the group consisting of the following compounds: pentaerythritol triacrylate (pentaerythritol triacrylate); Tetraacrylate (pentaerythritol tetraacrylate); poly (ethylene glycol) methyl ether methacrylate (poly (ethylene glycol) methyl ether methacry 1 ate);

Poly (ethylene glycol) methyl ether acrylate;

Hydroxybutyl acrylate;

A glycerol derivative of the formula 4j;

Glycosyloxyethyl methacrylate; Tridecaf luorooctyl

methacrylate);

Poly (ethylene glycol) methyl ether methacry 1 ate.

The liquid crystal vertical alignment inducer may further include a second lipophilic-non-liquid crystalline compound selected from the group consisting of the following compounds:

Hexyl gallate;

n-dodecyl β-D-maltoside; Propyl gal late;

1, 2-nucleic acid diol (1, 2-Hexanedio 1);

Hexanoic acid;

1-nuxanol;

1-hexylamine;

1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane (1,3-bi s (3-methacryloxypropy 1) tetrakis (trimethylsi 1 oxy) di s i loxane);

3-methacryloxypropyl pentamethyl di si loxane;

(3-acryloxypropyl) tris (trimethylsiloxy) silane-acry loy loxypropy 1) tris (trimethylsioxy) si lane);

(3-methacrylamidopropyl) bis (trimethylsiloxy) methylsilane ((3-methacry 1 amidopropy 1) bis (tr imethylsioxy) methyl s i lane).

According to another embodiment of the present invention, a liquid crystal host; And

A lipophilic-non-lipophilic compound comprising a lipophilic crystalline region including a lipophilic crystalline group having a high chemical affinity for a liquid crystal host and a non-lipophilic crystalline region including a non-lipophilic crystalline group having a low affinity for a liquid crystal host. And at least one of the lipophilic-non-lipophilic crystalline compounds include at least one lipophilic crystalline group having 8 or more carbon atoms in the lipophilic crystalline region, and a non-lipophilic crystal calculated according to Equation 1 below. Provided is a composition for forming a liquid crystal layer containing a liquid crystal vertical alignment guide having a sex ratio (Χ ′) of 0.5 to 6.

[Equation 1]

Η I ¾ ') _, (χ ^* ) _I

n is an integer of 1 or more indicating the number of types of lipophilic-non-liquid crystalline compounds constituting the liquid crystal vertical alignment inducer,

[Equation 1-1] Molecular weight of non-true liquid crystalline group in the compound

x- ― ： ~ ― X10

^ Molecular weight γ of the corresponding compound is the weight ratio of any one of the lipophilic crystalline-non-liquid crystalline compounds constituting the liquid crystal vertical alignment inducing agent, and is calculated according to the following formula 1-2. do.

[Equation 1-2],

Weight of compound

Y = —— ：

Of the wool

In the composition for forming a liquid crystal layer, the liquid crystal vertical alignment inducing agent may be present dispersed in the liquid crystal host in the form of a microassembly stabilized by self-assembly,

In the composition for forming a liquid crystal layer, the lipophilic-non-lipophilic crystalline compound may further include a photobanic group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region.

In the liquid crystal layer forming composition, the liquid crystal vertical alignment inducing agent may be included in an amount of 0.01 to 5% by weight based on the total weight of the liquid crystal layer forming composition. According to another embodiment of the present invention, an electrode forming step of forming a first electrode and a second electrode for each of the first substrate and the second substrate; The first substrate and the second substrate including the first and second electrodes, respectively, are bonded to each other so that the electrodes face each other, and then a liquid crystal layer forming composition is injected into a space between the first substrate and the second substrate, Alternatively, a liquid crystal layer is formed by dropping the liquid crystal layer forming composition under vacuum with respect to any one of the first substrate and the second substrate including the first and second electrodes, respectively, and bonding the remaining substrates 전극 to face the electrodes. Manufacturing an assembly by

The liquid crystal layer forming composition is a liquid crystal host, and

A lipophilic-non-lipophilic compound comprising a lipophilic crystalline region including a lipophilic crystalline group having a high chemical affinity for a liquid crystal host and a non-lipophilic crystalline region including a non-lipophilic crystalline group having a low affinity for a liquid crystal host. At least one of the lipophilic-non-lipophilic crystalline compounds include at least one lipophilic crystalline group having 8 or more carbon atoms in the lipophilic crystalline region, and It provides a liquid crystal display device manufacturing method comprising a liquid crystal vertical alignment guide having a liquid crystalline ratio (? ') Of 0.5 to 6.

[Equation 1]

In Equation 1,

[Equation 1-1]

Hi! Molecular weight of sugar-infused liquid crystalline liquid group

χ ₌ ； ′ χίό

The molecular weight γ of the H¾-compound is the weight ratio of any one of the lipophilic-non-liquid crystalline compounds constituting the liquid crystal vertical alignment inducer, and is represented by the following formula 1-2. Is calculated accordingly.

[Equation 1-2]

Weight of the corresponding compound

Ϋ = ^:

In the above manufacturing method, the composition for forming a liquid crystal layer may be present in the liquid crystal host in the form of a microassembly stabilized by the self-assembly liquid crystal vertical alignment inducing agent.

In the above production method, the lipophilic-non-lipophilic crystalline compound may further include a photobanung group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region.

In the above manufacturing method, the liquid crystal vertical alignment guide may be included in an amount of 0.01 to 5 wt ¾> based on the total weight of the composition for forming the liquid crystal layer.

The manufacturing method may further include applying an electric field between the first substrate and the second substrate after the manufacture of the assembly, and irradiating light.

According to another embodiment of the invention, the first substrate and the second substrate which are located facing each other; First and second electrodes formed on opposite surfaces of the first substrate and the second substrate, respectively; And a liquid crystal layer positioned between the first substrate and the second substrate— interposed therebetween.

The liquid crystal layer includes a liquid crystal host and a non-liquid crystalline region including a lipophilic crystalline region having a chemically high affinity for a liquid crystal host and a non-lipophilic crystalline group having a low affinity for a liquid crystal host. At least one lipophilic crystalline-non-lipophilic crystalline compound, at least one of the lipophilic crystalline-non-lipophilic crystalline compounds includes at least one lipophilic crystalline group having at least 8 carbon atoms in the lipophilic crystalline region,

¾ ¾ ^ Κ binchin liquid crystal rate (Χ ') the liquid is ^0.5 to 6 Provided is a liquid crystal display comprising a positive alignment guide.

[Equation 1] y! Chin ^ Serial Ratio # (x '> -∑ (X ᅳ γ) η

η is an integer of 1 or more indicating the number of types of lipophilic-non-liquid crystalline compounds constituting the liquid crystal vertical alignment inducing agent,

X is a non-lipophilic crystalline ratio of any one of the lipophilic-non-liquid crystalline compounds constituting the liquid crystal vertical alignment inducer, and is calculated according to Equation 1-1 below. ，

[Equation 1-1]

Molecular weight of non-liquid-free liquid group

xk: -xio;

Molecular weight of the compound

[Equation 1-2]

Weight of the compound

Ϋ =

Unit weight of #

In the above liquid crystal display device, a lipophilic crystalline-non-lipophilic crystalline compound is a photoreactive lipophilic crystalline-non-lipophilic crystalline compound further comprising a photobanung group in at least one of the lyophilic crystalline region and the non-lipophilic crystalline region. The liquid crystal layer may further include a photopolymer of the photo-reflective lipophilic-non-lipophilic crystalline compound.

The liquid crystal display may further include a vertical alignment and a light stabilization layer of a liquid crystal including a liquid crystal vertical alignment inducing agent between the liquid crystal layer and the first or second electrode. Either or both of the electrodes may be patterned.

According to another embodiment of the present invention, the liquid crystal vertical alignment inducing agent forms a fine assembly by self-assembly to form a vertical alignment of the liquid crystal having an alignment stability by using the composition for forming a liquid crystal layer uniformly dispersed in the liquid crystal host. Provide a way to induce.

According to another embodiment of the present invention, the liquid crystal vertical alignment inducer of light reflection is formed by the self-assembly to form a microassembly that is uniform in the liquid crystal host. It provides a method for inducing vertical alignment and photo stabilization of the liquid crystal using a liquid crystal layer forming composition which is dispersed.

According to another embodiment of the present invention, a photoreactive liquid crystal vertical alignment inducer forms a microassembly by self-assembly and applies an electric field to the liquid crystal layer forming composition uniformly dispersed in the liquid crystal host. By irradiating, there is provided a method of forming an insulating liquid crystal vertical alignment and light stabilization layer between the liquid crystal layer and the electrode layer.

Other specific details of the embodiments of the present invention are included in the following detailed description.

Effects of the Invention

The liquid crystal vertical alignment induction agent according to the present invention can be uniformly dispersed in the liquid crystal host by forming a self-assembled microassembly in the liquid crystal host, and induces vertical alignment of the liquid crystal host without the pre-treated alignment layer when forming the liquid crystal layer Also, the pretilt angle of the liquid crystal can be stabilized. As a result, the manufacturing process of the liquid crystal display can be simplified and the performance and reliability of the liquid crystal display can be improved. Brief description of the drawings

1 is a process diagram schematically showing a manufacturing process of a conventional liquid crystal display device.

Figure 2a is a schematic diagram showing a composition for forming a liquid crystal layer according to an embodiment of the present invention, Figure 2b is a schematic diagram showing the structure of the microassembly dispersed in the composition, Figure 2c is a lipophilic crystal contained in the composition Schematic diagram showing the structure of non-liquid crystalline compounds.

3 is a flowchart schematically illustrating a manufacturing process of a liquid crystal display according to an exemplary embodiment of the present invention.

FIG. 4A is a photograph of the liquid crystal layer of the liquid crystal display device manufactured in Example 1 under a polarization microscope under an orthogonal polarizer. FIG. 4B is a conoscopic image of FIG. 4A.

FIG. 5A is a photograph of an arrangement of liquid crystal molecules before applying an electric field to a liquid crystal layer in the liquid crystal display according to Example 1, FIG. 5B is a photograph of an arrangement of liquid crystal molecules immediately after an electric field is applied, and FIG. 5C. Is a photograph observing the change in the arrangement of liquid crystal molecules with the passage of time after application of the electric field.

FIG. 6A is a photograph of a liquid crystal array after an electric field application and light irradiation to a liquid crystal layer and before applying voltage in an electroless state in the liquid crystal display according to Example 1, and FIG. 6B is a liquid crystal array immediately after voltage application. 6C shows the arrangement of liquid crystal molecules over time after voltage application. This picture shows changes in the

FIG. 7A is a photograph of an arrangement of liquid crystal molecules before applying an electric field to a liquid crystal layer in the liquid crystal display according to Example 2, FIG. 7B is a photograph of an arrangement of liquid crystal molecules immediately after an electric field is applied, and FIG. 7C. Is a photograph observing the change in the arrangement of liquid crystal molecules with the passage of time after application of the electric field.

FIG. 8A is a photograph of the liquid crystal array after the electric field application and the light irradiation to the liquid crystal layer and before the voltage application in the electroless state in the liquid crystal display device manufactured in Example 2, and FIG. 8B is a liquid crystal array immediately after voltage application. Figure 8c is a photograph observing the switching, Figure 8c is a photograph observing the change in the arrangement of liquid crystal molecules over time after voltage application.

9A is a photograph observing the arrangement of liquid crystal molecules before applying an electric field to the liquid crystal layer in the liquid crystal display according to Example 3, and FIG. 9B is a photograph observing the arrangement of liquid crystal molecules immediately after the electric field is applied.

FIG. 10A is a photograph of a liquid crystal array after applying an electric field to a liquid crystal layer and irradiating light to the liquid crystal layer and before applying voltage in an electroless state in FIG. This is an observation of the switching.

FIG. 11A is a photograph observing an arrangement of liquid crystal molecules before applying an electric field to a liquid crystal layer in the liquid crystal display according to Example 4, and FIG. Lib is a photograph observing an arrangement of liquid crystal molecules immediately after an electric field is applied.

12A is a photograph of a liquid crystal array after applying an electric field to the liquid crystal layer and irradiating light to the liquid crystal layer and before applying voltage in an electroless state in FIG. It is a photograph observing switching.

FIG. 13A is a photograph of an arrangement of liquid crystal molecules before applying an electric field to a liquid crystal layer in the liquid crystal display according to Example 5, and FIG. 13B is a photograph of an arrangement of liquid crystal molecules immediately after an electric field is applied.

FIG. 14A is a photograph of a liquid crystal array after applying an electric field to a liquid crystal layer and irradiating light to the liquid crystal layer and before applying voltage in an electroless state in FIG. This is an observation of the switching.

FIG. 15A is a photograph of an arrangement of liquid crystal molecules before application of an electric field to a liquid crystal layer in the liquid crystal display according to Example 6, and FIG. 15B is an electric field It is a photograph observing the arrangement of liquid crystal molecules immediately after.

FIG. 16A is a photograph of a liquid crystal array after applying an electric field to a liquid crystal layer and irradiating light to the liquid crystal layer and before applying voltage in an electroless state in the liquid crystal display according to Example 6, and FIG. 16B illustrates a liquid crystal array after applying voltage. This is an observation of the switching.

FIG. 17A is a photograph of an arrangement of liquid crystal molecules before applying an electric field to a liquid crystal layer in the liquid crystal display according to Example 7, and FIG. 17B is a photograph of an arrangement of liquid crystal molecules immediately after an electric field is applied.

FIG. 18A is a photograph of a liquid crystal array after applying an electric field to a liquid crystal layer and irradiating light in the liquid crystal display according to Example 7 and before applying voltage in an electroless state, and FIG. 18B is a liquid crystal array after applying voltage. This is a photograph of the switching alley.

FIG. 19A is a photograph of an arrangement of liquid crystal molecules before application of an electric field to a liquid crystal layer in the liquid crystal display according to Example 8, FIG. 19B is a photograph of an arrangement of liquid crystal molecules immediately after an electric field is applied, and FIG. 19C. Is a photograph observing the change in the arrangement of liquid crystal molecules over time after applying the electric field.

FIG. 20A is a photograph of a liquid crystal array after an electric field application and light irradiation to a liquid crystal layer and before applying voltage in an electroless state in the liquid crystal display according to Example 8, and FIG. 20B illustrates a liquid crystal array immediately after voltage application. FIG. 20C is a photograph of observing a change in arrangement of liquid crystal molecules with time after voltage is applied.

FIG. 21A is a photograph of an arrangement of liquid crystal molecules before applying an electric field to a liquid crystal layer in the liquid crystal display according to Example 9, FIG. 21B is a photograph of an arrangement of liquid crystal molecules immediately after an electric field is applied, and FIG. 21C. Is a photograph observing the change in the arrangement of liquid crystal molecules over time after applying the electric field.

22A is a photograph of the liquid crystal array after the electric field application and light irradiation to the liquid crystal layer and before the voltage application in the electroless state in the liquid crystal display according to Example 9, and FIG. 22B is a liquid crystal array immediately after voltage application. FIG. 22C is a photograph of observing a change in arrangement of liquid crystal molecules with time after applying voltage. FIG.

FIG. 23A is a photograph of an arrangement of liquid crystal molecules before application of an electric field to a liquid crystal layer in the liquid crystal display according to Example 10, FIG. 23B is a photograph of an arrangement of liquid crystal molecules immediately after an application of an electric field, and FIG. 23C. After applying the electric field It is a photograph observing the change of the arrangement of liquid crystal molecules over time. FIG. 24A is a photograph of a liquid crystal array after applying an electric field to a liquid crystal layer and irradiating light to the liquid crystal layer and before applying voltage in an electroless state in the liquid crystal display according to Example 10, and FIG. 24B illustrates a liquid crystal array immediately after voltage application. FIG. 24C is a photograph of observing a change in arrangement of liquid crystal molecules over time after voltage application.

FIG. 25A is a photograph of an arrangement of liquid crystal molecules before application of an electric field to a liquid crystal layer in the liquid crystal display according to Example 11, and FIG. 25B is a photograph of an arrangement of liquid crystal molecules immediately after an application of an electric field.

FIG. 26A is a photograph of a liquid crystal array after applying an electric field to a liquid crystal layer and irradiating light on the liquid crystal layer and before applying voltage in an electroless state in the liquid crystal display according to Example 11, and FIG. 26B is a liquid crystal array after applying voltage. This picture shows the switching of.

FIG. 27 is a photograph of an arrangement of liquid crystal molecules using a polarizing microscope before application of an electric field to a liquid crystal display device manufactured by using the composition for forming a liquid crystal layer including nucleus gallate in Test Example 1. FIG.

FIG. 28 is a photograph of an arrangement of liquid crystal molecules using a polarizing microscope before application of an electric field to a liquid crystal display device manufactured by using the composition for forming a liquid crystal layer including decyl gallate in Test Example 1. FIG.

FIG. 29 is a photograph of the arrangement of liquid crystal molecules using a polarizing microscope before applying an electric field to a liquid crystal display device manufactured by using the composition for forming a liquid crystal layer including octadecane in Test Example 1. FIG.

FIG. 30A is a photograph of an arrangement of liquid crystal molecules using a polarizing microscope before application of an electric field to a liquid crystal display device manufactured using the composition for forming a liquid crystal layer including 1-octadecanol in Test Example 1, FIG. 30B. Is a picture of a constipation observation.

FIG. 31 is a photograph of liquid crystal alignment observation observed using a polarizing microscope before application of an electric field to a liquid crystal display device manufactured by using the composition for forming a liquid crystal layer of Example 2-1 in Test Example 2.

FIG. 32 is a photograph of liquid crystal alignment observation observed using a polarizing microscope before application of an electric field to a liquid crystal display device manufactured by using the composition for forming a liquid crystal layer of Example 2-4 in Test Example 2.

33 shows the composition for forming a liquid crystal layer of Example 2-5 in Test Example 2 The liquid crystal orientation observation photograph was observed using the polarizing microscope before the full-applied application to the liquid crystal display device manufactured.

FIG. 34 is a photograph of liquid crystal alignment observation observed using a polarizing microscope before applying an electric field to a liquid crystal display device manufactured using the composition for forming a liquid crystal layer of Example 2-6 in Test Example 2.

35A is a photograph of an arrangement of liquid crystal molecules before application of an electric field to a liquid crystal display device manufactured by using the composition for forming a liquid crystal layer of Example 2-6 in Test Example 2, and FIG. 35B is a view of liquid crystal molecules immediately after application of an electric field. It is a photograph observing the arrangement, Figure 35c is a photograph observing the change in the arrangement of the liquid crystal molecules over time after applying the electric field.

36A is a photograph of a liquid crystal array state after applying an electric field and irradiating light to a liquid crystal display device manufactured by using the composition for forming a liquid crystal layer of Example 2-6 in Test Example 2 before applying voltage in an electroless state. 36B is a photograph observing the switching of the liquid crystal array immediately after the voltage is applied, and FIG. 36C is a photograph observing the change of the liquid crystal molecule arrangement with time after applying the voltage.

The best mold for the implementation of the invention

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented by way of example, the present invention is not limited by the ah, the present invention is defined only by the scope of the claims to be described later.

As used herein, the term "lipophilic crystalline region" is a compound group having a chemical composition composed of elements similar to the elements constituting the liquid crystal compound in the compound and chemically compatible with the liquid crystal material due to similar chemical properties to the liquid crystal host. Liquid crystal is chemically similar to hydrocarbon because liquid crystal is a hydrocarbon compound mainly composed of carbon and hydrogen atoms and has some hetero atoms as substituents. Thus, the lipophilic group which may be included in the lipophilic region may be a hydrocarbon composed of carbon and hydrogen atoms, and may include a hetero atom at a very small portion. Examples of the lipophilic group include saturated hydrocarbon groups, unsaturated hydrocarbon groups, Aromatics, rigid-core in liquid crystal compounds A functional group used as a linking group of the d-core portion, and a mesogen group indicating the characteristics of the liquid crystal may be included.

As used herein, the term 'non-liquid crystalline region' refers to a functional group having a property that does not mix well or dissolve with a liquid crystal host due to a difference in chemical composition with the liquid crystal host due to a difference in chemical composition with the liquid crystal host. It means a portion containing a chemical group having a chemical affinity with. Non-liquid crystalline regions with different chemical properties from hydrocarbons consist mainly of chemical groups containing heteroatoms such as oxygen, nitrogen, silicon, fluorine, sulfur and phosphorus atoms. Compounds capable of hydrogen bonding or having high dielectric constant or polarity such as hydroxy groups, thiol groups, amine groups, etc., and (2) silicon-based groups containing silane and siloxane groups having different chemical compositions from those of the liquid crystal host. Compound, (3) Fluorocarbon-based compound group having a different chemical composition from the liquid crystal host, (4) Ethylene oxide group (or oxyethylene group) and propylene oxide group (or oxypropylene) having different chemical composition and dielectric constant from the liquid crystal host group

(oxypropylene group)), and more detailed examples will be described later. In the above examples, the non-lipophilic crystalline groups corresponding to (1) and (4) have a higher polarity and dielectric constant than hydrocarbons and liquid crystals, so they are well mixed with compounds having high polarity and dielectric constant such as water, ethylene glycol and glycerol. have. That is, it is a functional group that has a characteristic of dissolving well in a solvent having a high dielectric constant but insoluble in a hydrocarbon compound such as liquid crystal.

Unless stated otherwise in the present specification, an "alkyl group" means a linear or branched alkyl group having 1 to 20 carbon atoms, and the alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group. Specific examples of the alkyl group include, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, and the like.

Unless stated otherwise in the present specification, 'alkenyl' is a divalent atomic group obtained by subtracting two hydrogen atoms from alkanes, and may be represented by the general formula _C _n H _2n- (n is an integer of 2 or more). The term "alkynyl" refers to a divalent atomic group obtained by subtracting two hydrogen atoms from an alkene, and may be represented by the general formula -C _n H _n- (n is an integer of 2 or more).

Unless stated otherwise in the present specification, '-ene group' means a functional group including a carbon carbon double bond in a functional group, and '-diene group' refers to a carbon carbon double bond in a functional group. Means two containing functional groups

Unless stated otherwise in the present specification, a 'thiol-ene group' is a case where a functional group including a thiol (-SH) group and a functional group having an ethylene (C = C) group are combined. Thiol-ene polymerization through photopolymerization polymerization). Alternatively, the functional group in which one of the thiols or the en groups is substituted forms a chemical bond with the lipophilic-non-lipophilic crystalline compound, and the same or different structure of the lipophilic-non-crystalline liquid crystalline compound containing the other liquid crystal trace. This also includes the case where it is dissolved in the compound and used.

Unless specifically stated herein, all compounds or substituents may be substituted or unsubstituted. Herein, 'substituted' means that a hydrogen atom is a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, an alkoxy group, an aldehyde group, an epoxy group, an ether group, an ester group, a carbonyl group, Acetal group, ketone group, alkyl group, perfluoroalkyl group, cycloalkyl group, heterocycloalkyl group, allyl group, benzyl group, aryl group, heteroaryl group, derivatives thereof, and combinations thereof It means.

As used herein, unless otherwise indicated, two or more substituents may be a single bond or -COO-, -COS-, -0—, -S-, -CF _2- , -CF ₂ CF ₂ -and It is bonded by a linking group selected from the group consisting of N = N-, or two or more substituents are condensed to each other.

In addition, in the present specification, when a part such as a layer, a film, an area, or a substrate is 'on' another part, this includes not only the case where the other part is 'directly above' but also another part therebetween. On the other hand, when a part is "just above" another part, there is no other part in the middle. Conversely, when a part such as a layer, film, region, or substrate is 'underneath' another part, this includes not only the other part 'underneath' but also another part in the middle. On the other hand, when one part is directly below another part, it means that there is no other part in the middle.

The present invention provides a liquid crystal vertical alignment which can be uniformly dispersed by forming a microassembly by self-assembly of molecules in a liquid crystal host by controlling the molecular weight ratio of the non-liquid crystalline group included in the compound, that is, the non-liquid crystalline ratio. It is characterized in that the induction agent is provided, wherein the liquid crystal vertical alignment induction agent induces the vertical alignment of the liquid crystal without using a separate alignment layer forming process by using a composition for forming a liquid crystal layer uniformly dispersed in the liquid crystal host. And further including a photoreactive group in at least one of the liquid-liquid crystalline region and the non-liquid crystalline region of the liquid crystal vertical alignment inducing agent. It is another feature to induce stabilization of the liquid crystal alignment by the reaction. Hereinafter, in the present specification, the spherical dispersed phase (sphere or drop) generated by self-assembly of the liquid crystal vertical alignment inducing agent in the liquid crystal host is referred to as a 'fine assembly' or 'fine aggregate'. That is, the liquid crystal vertical alignment inducing agent according to the embodiment of the present invention includes a non-liquid crystal having a low affinity for the liquid crystal host and a liquid crystalline region including a lipophilic group having a high chemical affinity for the liquid crystal host in one molecule. At least one lipophilic-non-lipophilic crystalline compound comprising a non-lipophilic crystalline region including a penile group, wherein at least one of the lipophilic-non-lipophilic crystalline compounds has a C8 or higher lipophilic crystal in the lipophilic crystalline region It contains one or more genital groups, and the liquid crystal vertical alignment inducer is 0.5 to 6 non-liquid crystalline ratio (? ') Calculated according to the following formula (1).

[Equation 1]

In Equation 1,

[Equation 1-1]

Molecular weight of the lipophilic crystalline group

X = 10

Molecular weight γ of the compound is the weight ratio of any one of lipophilic crystalline-non-liquid crystalline compounds constituting the liquid crystal vertical alignment inducing agent, and is calculated according to the following formula 1-2. do.

[Equation 1-2]

Weight of the unit

Y =

Total weight of compound wool The non-lipophilic crystalline ratio is to distinguish the characteristics of the liquid crystal vertical alignment inducer according to the molecular weight ratio of the non-liquid crystalline group to the molecular weight of the compound, when x '= o indicates 100% lipophilic crystalline, when X = 10 100% non-liquid crystalline. As the value of X 'is close to 0, the mixture becomes more mixed with the liquid crystal, and thus the microassembly cannot be formed. As a result, the microcapsule may not form a liquid crystal composition in which the microassembly is evenly dispersed due to macroscopic phase separation.

As such, the vertical alignment of the liquid crystal may be induced according to the molecular weight ratio of the non-liquid crystalline group included in the liquid crystal vertical alignment inducing agent, that is, the non-liquid crystalline ratio, and thus the liquid crystal vertical alignment inducing agent usable in the present invention is represented by Equation 1 The non-liquid crystalline ratio (X ′), which is calculated to be included in the range of 0.5 to 6, and at the same time comprises a lipophilic crystalline group having at least 8 carbon atoms as a lipophilic-non-liquid crystalline compound constituting the liquid crystal vertical alignment guide. At least one lipophilic-non-liquid crystalline compound (hereinafter simply referred to as 'first lipophilic-non-liquid crystalline compound') should be included.

If it is out of the above range to be less than 0.5, the affinity with the liquid crystal is too high to induce the vertical alignment of the liquid crystal, or the vertical alignment inducing effect is low. In addition, in the case of more than 6, the affinity with the liquid crystal host is insufficient when the composition for forming the liquid crystal layer is formed, so that it is difficult to form a uniform mixture with the liquid crystal. As a result, the vertical alignment of the liquid crystal cannot be induced or the vertical alignment is induced. The effect is low. More preferably, it is 0.7 to 5.5, and even more preferably 1.3 to 5 may exhibit a better vertical alignment induction effect for the liquid crystal host.

In addition, the liquid crystal vertical alignment inducing agent may be composed of the above-mentioned first lipophilic-non-liquid crystalline compound alone, or at least two kinds of the first lipophilic-non-liquid crystalline compounds satisfying the above-mentioned lipophilic group conditions. Ordinary lipophilic-non-lipophilic qualities that do not satisfy the carbon number conditions of the lipophilic crystalline groups together with the first lipophilic-non-lipophilic crystalline compounds that include or satisfy the conditions of the lipophilic groups described above. It may further comprise a compound (hereinafter simply referred to as 'second lipophilic-non-lipophilic crystalline compound'). If the first lipophilic-non-lipophilic crystalline is included alone, the non-lipophilic crystalline ratio of the first lipophilic-non-lipophilic crystalline compound itself should be included in the range of 0.5 to 6. When the liquid crystal vertical alignment inducer comprises a mixture of two or more compounds including the first lipophilic ᅳ non-liquid crystalline compound described above, the liquid crystal vertical alignment induction agent is suitably adjusted by adjusting the mixing ratio between the compounds. It should be included within the non-lipophilic ratio range.

Specifically, in the case where the liquid crystal vertical alignment inducing agent includes one kind of lipophilic-non-liquid crystalline compound alone, the non-liquid crystalline ratio of the liquid crystal vertical alignment inducing agent is the non-lipophilic crystalline ratio of the lipophilic-non-liquid crystalline compound. It is the same as, and can be calculated according to the following equation (2).

Equation 2 Non-Sorting.

Ϊ́ non-liquid ^"

For example, the molecular weight is 202.3 g / mole and the molecular weight of -CH (0H) CH ₂ 0H, which is a non-lipophilic group, is 61 g in the case of 1,2-dodecanediol of the following structural formula (1) / mole, so the non-lipophilic ratio (Χ ') is 3.02. In addition, in the case of uryl gal late of Structural Formula 2, the molecular weight of the gallic acid ester group having a molecular weight of 338.4 g / mole and a non-lipophilic group is 169 g / mole, thus the non-lipophilic qualitative ratio becomes 5.0. .

If the liquid crystal vertical alignment inducer is a mixture containing two or more lipophilic-non-liquid crystalline compounds, the ratio of non-liquid crystallinity (Χ ′) of the liquid crystal vertical alignment inducing agent is expressed as shown in Equation 1 above. The value obtained by multiplying the fractions by the ratio of the liquid crystals of each compound is obtained. For example, when mixing 70 weight ¾ »1,2-dodetandi and 30 weight% lauryl gelate, the specific lipophilic ratio (Χ ') of the mixture is (0.7 X 3.02) + (0.3 X 5.0 ) = 3.61 In addition to the non-liquid crystalline ratio of the liquid crystal vertical alignment inducer described above, the conditions in which the lipophilic-non-liquid crystalline compound constituting the liquid crystal vertical alignment inducer must contain a lipophilic crystalline group having 8 or more carbon atoms are simultaneously satisfied. If the non-liquid qualitative ratio is met, the carbon number condition of the lipophilic group cannot be met. In other words, when the carbon number of the lipophilic group is less than 8, the vertical alignment of the liquid crystal is not induced or the induction effect is insignificant.

The liquid crystal vertical alignment inducing effect of the liquid crystal vertical alignment inducing agent is due to self-assembly of the liquid crystal vertical alignment inducing agent. That is, the liquid crystal vertical alignment guide agent which satisfies the above conditions forms a spherical microassembly by self-assembly of the liquid crystal vertical alignment guide molecule when added to the liquid crystal host.

Figure 2a is a schematic diagram showing the composition for forming a liquid crystal layer comprising a liquid crystal vertical alignment guide agent according to an embodiment of the present invention, Figure 2b is a fine assembly of the liquid crystal vertical alignment guide agent dispersed in the composition for forming a liquid crystal layer Figure 2c is a schematic diagram showing the structure of the liquid crystal crystalline-non-lipophilic crystalline compound contained in the liquid crystal vertical alignment guide. 2A to 2C are only examples for describing the present invention, and the present invention is not limited thereto.

Referring to FIGS. 2A to 2C, when the liquid crystal vertical alignment guide agent (B) that satisfies the above conditions is added to the liquid crystal host (C), the lipophilic crystalline non-biological liquid crystal constituting the liquid crystal vertical alignment guide agent (B) In the compound, the strong affinity between the non-liquid crystalline groups and the non-affinity between the non-liquid crystalline group and the liquid crystal cause fine phase separation. As a result, the non-liquid crystalline groups agglomerate with each other, and the liquid-crystalline lipophilic groups with good affinity are located on the surface separated from each other to form spherical fine granules of several nanometers to several hundred nanometers in diameter as shown in FIG. As a result, it is uniformly dispersed in the liquid crystal host as shown in FIG. The formation of such microassembly depends on the ratio of the liquid crystalline / non-liquid crystalline of the liquid crystal vertical alignment inducing agent to be added. Therefore, among the compounds having lipophilic-non-lipophilic crystalline, the first lipophilic crystalline region includes a lipophilic crystalline group having 8 or more carbon atoms and has a non-lipophilic crystalline ratio of 0.5 to 6 as calculated according to Equation 1 above. Liquid crystal vertical alignment inducer comprising a liquid crystalline non-liquid crystalline compound, or two or more compounds of the first lipophilic crystalline non-liquid crystalline compound described above, or the first lipophilic crystalline-non-liquid crystal described above It is preferable to use a liquid crystal vertical alignment inducer in which the non-lipophilic crystalline ratio of the mixture satisfies the above conditions when the mixed compound and the second lipophilic non-lipophilic crystalline compound are used.

When the liquid crystal layer forming composition in which the microassembly of the liquid crystal vertical alignment inducer is uniformly dispersed is injected between two substrates to form a liquid crystal layer, the microassembly is adsorbed on the interface between the newly formed substrate surface and the liquid crystal layer. Form a thin film. As a result, the liquid crystal vertical alignment inducer modifies the substrate surface. The liquid crystal molecules present at the top are arranged in the direction perpendicular to the surface on the modified surface. In addition, the formed thin film can improve the reliability of the device by preventing the performance degradation of the device that can occur when the transparent conductive film and the liquid crystal layer is in direct contact with the insulating layer.

Induction of vertical alignment of the liquid crystal by surface adsorption of the microassembly is possible without limitation to the kind of the compound forming the solid surface. For example, vertical alignment can be induced on the surface of various organic polymer compounds such as polyimide, polystyrene, polyacrylate, polyvinyl alcohol, as well as various inorganic oxides and nitrides. However, a change in characteristics may appear depending on the magnitude of the interfacial tension at the interface between the liquid crystal and the liquid crystal.

The lipophilic-non-liquid crystalline compound usable in the present invention includes a lipophilic region including a lipophilic crystalline group having a high chemical affinity for a liquid crystal host and a non-lipophilic crystalline group having a low affinity for a liquid crystal host in one molecule. At least one lipophilic-non-lipophilic crystalline compound comprising a non-lipophilic crystalline region, wherein at least one of the lipophilic-non-lipophilic crystalline compounds has at least 8 lipophilic crystalline groups in the lipophilic crystalline region. Any compound containing at least one of (ie, a first lipophilic-non-lipophilic crystalline compound) can be used without particular limitation.

As shown in Fig. 2C, the lipophilic-non-lipophilic crystalline compound (b) usable in the present invention includes a lipophilic crystalline region (bl2) and a non-lipophilic crystalline region (bll). In FIG. 2C, the regions are each shown to include one lipophilic group and a non-lipophilic group, but each region may include at least one lipophilic group or a non-lipophilic group, preferably the parent group. The liquid crystal-non-lipophilic crystalline compound may include 1 to 3 lipophilic crystalline groups or non-lipophilic crystalline groups.

The lipophilic region refers to a part including a lipophilic group, which is similar in chemical composition to a liquid crystal compound and exhibits affinity for the liquid crystal host, that is, a chemical group that mixes well with the liquid crystal.

Liquid crystals are chemically similar to the characteristics of hydrocarbons because liquid crystals are mainly hydrocarbon compounds consisting of carbon and hydrogen atoms and have some hetero atoms as substituents. Accordingly, the lipophilic crystalline group which may be included in the lipophilic region may be a hydrocarbon composed of carbon atoms and hydrogen atoms and may include a hetero atom at a very small portion thereof. However, the lipophilic crystalline region has at least 8 carbon atoms, preferably at least one lipophilic crystalline group having 8 to 30 carbon atoms, preferably

It is preferable to contain 1-3.

Specifically, the lipophilic group is a linear, branched or cyclic substituted or unsubstituted saturated or unsaturated hydrocarbon group having 8 to 30 carbon atoms, or 1 selected from the group consisting of N, 0, P, S and Si in the molecule. Substituted or unsubstituted heteroalkyl group containing 8 or more hetero atoms, He It may be a cyclic cycle or a heteroaromatic group, or a combination group having 8 to 30 carbon atoms consisting of a combination of the hydrocarbon group and heteroatom-containing groups.

Specific examples of the hydrocarbon group include substituted or unsubstituted alkyl groups having 8 to 30 carbon atoms, alkenylalkyl groups, alkynylalkyl groups, cycloalkyl groups, aryl groups or arylalkyl groups, and the like. It may be substituted with a logen atom, preferably a fluorine atom. In addition, specific examples of the substituted or unsubstituted heteroalkyl group, heterocycle group or heteroaromatic group containing the hetero atom include an intramolecular carbonyl group (-C (= 0)-) and an ester group (-C (= 0) 0-), ether group (-0-), ethylene oxide group (_CH ₂ CH ₂ 0-), azo group (-N = N-), -COS- and -S- C8-C30 heteroalkyl group, heterocycloalkyl group, or heteroaryl group containing a container is mentioned.

The lipophilic group may have a structure similar to that of the compound constituting the liquid crystal host to increase affinity with the liquid crystal host, that is, a structure consisting of a rigid-core group and a flexible chain group. . In addition, the lipophilic group may be a liquid crystal group or mesogen group exhibiting the properties of the liquid crystal. Specifically, the liquid crystalline group is CH ₃ CH ₂ CH ₂ CH ₂ CH ₂ 0-C ₆ H ₄ -C00-

_{_{_{_{C 6 H 4 -0CH 2 CH 2}}}} CH 2 CH 2 CH by conventional functional group that is derived from a liquid crystalline compound such as _3, specifically, Υ, Υ-Υ ', -Υ -Υ'-Υ ", -Υ- Ζ-Υ ', -Υ-Ζ-Υ'-Ζ'-Υ ", -YWY',

And liquid crystal groups such as -YWWY 'or -YZWY'. In this case, γ, τ and r are each independently an aryl group having 6 to 18 carbon atoms (for example, a phenyl group, a naphthyl group, a biphenyl group, etc.), a cycloalkyl group having 6 to 18 carbon atoms (for example, a cyclonuclear group, etc.) ), Heterocycle group containing one or more heteroatoms selected from the group consisting of N, S, 0 P in the ring (for example, thiadiazole, oxadiazole, pyrazine, etc.), -coo- and combinations thereof It may be selected from the group consisting of, Y, Y 'and Y "is F, Br, CN, alkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms and 1 selected from the group thereof In addition, the mesogenic group may be specifically substituted with CH ₂ = CH (CH ₃ )-(C = 0) -0- (CH ₂ ) ₃ -ph-C00-ph- (CH ₂ ) it can be a function of the reactive mesogenic origin having a liquid crystal and photo-reactive at the same time, such as ₅ -CH _3.

On the other hand, in the lipophilic-non-liquid crystalline compound, the non-lipophilic crystalline region is different in chemical properties from the liquid crystal and has a low affinity for the liquid crystal host, so that the functional group does not mix well or dissolve with the liquid crystal host, that is, It means a portion containing a chemical group having a chemical incompatibility with the liquid crystal. Non-liquid crystalline regions, which differ in chemical properties from hydrocarbons, consist mainly of non-lipophilic crystals containing heteroatoms such as oxygen, nitrogen, silicon, fluorine, sulfur and phosphorus atoms. Specifically, the non-lipophilic crystalline group is alcohol, polyhydric alcohol, amine, polyvalent amine, carboxylic acid, polycarboxylic acid, silane compound, siloxane compound, polyethylene glycol, polypropylene oxide, fluorinated carbon compound, thiol And, a functional group derived from polyhydric thiol, sulfonic acid, sulfonic acid, phosphonic acid, or phosphoric acid, and the like, and the non-lipophilic qualitative region may include a single group or a combination group of two or more thereof. Can be.

More specifically, examples of the non-lipophilic crystalline group include, but are not limited to, functional groups derived from the following compounds:

Alcohol: 1- (l-ol), 1, 2-di (1, 2- di ol), glycerol

glycerol, glucose, dextrose,

sorbitol, pentaerythritol, and pentaerythroli

(dipentaerythr itol), tripentaerythr (tr ipentaerythr i tol), sorbitan, fluctose, sucrose, gallic acid, glucopyranoside ( Functional groups derived from alcohols containing 1 to 8 carbon atoms or polyhydric alcohols containing 1 to 8 hydroxyl groups such as glucopyranoside, ascorbic acid, mannide or maltoside, etc. Non-lipophilic crystalline groups capable of hydrogen bonding and having high polarity and dielectric constant;

Amine: l-amine, 1, 2-diamine, 1,3-diamine, ethylene diamine, diethylene Diamine

(diethylene diamine), tris (2-aminoethyl) amine, cyclohexane diamine, diethylene triamine, phenyldiamine, phenyltriamine phenyltriamine), 1,3,5-triazine 4, 6-diamine (1, 3 ᅳ 5—tri az ine 4, 6-diamine), 1,3,5 리아 triazine 2, 4, 6-triamine ( 1, 3, 5-tri az ine 2,4,6-triamine) or cyclic ethylene amine (cyclen; — (CH ₂ CH ₂ NH) 广, where 1 is an integer from 2 to 6), and the like. A functional group derived from a amine or a polyvalent amine having 1 to 20 carbon atoms containing 1 to 6 amine groups, which may be hydrogen-bonded and has a high polarity and dielectric constant;

Silane (si lane): Tris (trimethylsiloxy,！ silane; ^！; ^！ ^！;！ ^ ^) functional groups derived from a silane compound having 1 to 20 carbon atoms containing 2 to 10 silyl groups such as si lane);

Siloxane (si loxane): a functional group derived from a linear, branched, or cyclic siloxane compound containing 1 to 10 siloxy groups of the formula (1);

(R a and R b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a siloxy group, and a combination thereof, and m is an integer of 1 to 10.)

Polyoxyethylene: derived from linear polyoxyethylene having 4 to 40 carbon atoms of Formula 2a containing 2 to 20 ethylene oxide groups or cyclic polyethylene glycol having 4 to 10 carbon atoms of Formula 2b Functional group;

[Formula 2a]

-CH _₂ CH ₂ -0-H

[Formula 2b]

Fluorocarbon-based compound: Perfluoroalkyl group or perfluoroaryl group derived from the C4-C20 fluorocarbon compound containing 9-41 fluoro groups;

Thiols: 1-thiol, 1,2-dithiol, 1,2-dithiol, thioglycerol, thiopentaerythr i tol or dithiotray Functional groups derived from tee and dgathiyl having 1 to 20 carbon atoms containing 1 to 8 thiol groups (-SH), such as (dithiothreitol);

Carboxylic acid: 1-carboxylic acid, 1,2- Dicarboxylic acid (1,2-dicarboxylyc acid), 1,3-dicarboxylic acid (1,3-dicarboxylyc acid), benzenecarboxylic acid (benzenecarboxyl ic acid), benzenedicarboxylic acid, 1, 2, 3-tricarboxylic acid (1,2,3— tricarboxylic acid), benzenetr i car boxy 1 ic acid, malic acid, maleic acid, Tartar acid, citric acid, maleamic acid, glutamic acid, agaric acid. (agaric acid), aconi tic acid, tricarballylic acid, or amino acid

functional groups derived from carboxylic acids having 1 to 10 carbon atoms and polyvalent carboxylic acids containing 1 to 4 carboxylic acid groups (-C00H) such as (amino acid, -CH (NH ₂ ) -C00H);

Sulfonic acid: a work container derived from a sulfonic acid or a polysulfonic acid having 1 to 10 carbon atoms containing 1 to 3 sulfonic acid groups (-S (= 0) ₂ 0H);

Sulfuric acid (sulfuric acid): a functional group derived from a sulfuric acid or a polyvalent sulfuric acid having 1 to 10 carbon atoms containing 1 to 3 sulfuric acid groups (-0SO0) ₂ 0H);

Phosphonic acid: a functional group derived from phosphonic acid or polyhydric phosphonic acid having 1 to 10 carbon atoms containing 1 to 3 phosphonic acid groups (-P (= 0) (0H) ₂ ); And

P osphoric acid: derived from phosphoric acid or polyhydric acid having 1 to 10 carbon atoms containing 1 to 3 phosphoric acid groups (-0-P (= 0) (0H) ₂ ) Functional group.

The lipophilic crystalline group and the non-lipophilic crystalline group may be directly connected by a single bond, or -0-, ᅳ S-, -C00-, -C0NH-, -C ₆ H ₄ 0—, -C ₆ H ₄ C00— ，-C ₆ H ₄ C0NH-, -OCH2CH2-, -CH ₂ CH _2- , — C ₆ H ₄ 0CH ₂ CH _2- , -C ₆ H ₄ C00CH ₂ CH ₂ -or-(SiRaRb)- It may be connected via a linking group, such as CH ₂ CH _2- (wherein Ra and Rb are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). More specifically, the lipophilic-non-lipophilic crystalline compound may be selected from the group consisting of the compounds of Formulas 3a to 3i and combinations thereof:

[Formula 3a]

(PA) bi [Formula 3b]

[Formula 3c]

[Formula 3f]

[Formula 3g]

Formula

In Chemical Formulas 3a to 3i,

Ri to R ₉ each independently represent an alkyl group having 8 to 30 carbon atoms; C8-C30 alkenylalkyl group; An alkynylalkyl group having 8 to 30 carbon atoms; Arylalkyl group having 8 to 30 carbon atoms; A cycloalkyl group having 8 to 30 carbon atoms; Aryl groups having 8 to 30 carbon atoms; Intramolecular carbonyl group (-C (= 0)-), ester group (-C (= 0) 0-), ether group (-0-), ethylene oxide group (_CH ₂ CH ₂ 0-), azo group (-N = N-), -COS- and -S- heteroalkyl group having 8 to 30 carbon atoms, heterocycloalkyl group or heteroaryl group containing a hetero atom-containing functional group selected from the group consisting of; and combinations thereof do. Xi, X ₂ , X ₅ , X ₇ , X ₈ and X ₉ are each independently, -0-, -S-, -COO-, -C0NH-, -C ₆ H ₄ 0-, -C ₆ H ₄ C00-, -C ₆ H ₄ C0NH- and selected from the group consisting of a single bond,

X 3 and X 4 are each independently selected from the group consisting of a single bond, -0- and -C ₆ H ₄ 0-,

X ₆ is a single bond, -0CH ₂ CH _2- , -CH ₂ CH _2- , -C ₆ H ₄ 0C¾CH _2- , -C ₆ H ₄ C00CH ₂ CH ₂ -and-(SiRaRb) -CH ₂ CH _2- Wherein Ra and Rb are each hydrogen or an alkyl group having 1 to 3 carbon atoms, and

PA, PAm, PS, PEO, FC, PT, CA, and SP are non-lipophilic crystalline groups which form covalent bonds with R ₉ , respectively, directly or through a linking group of to ¾, respectively, wherein PA comprises 1 to 8 hydroxy groups. A functional group derived from an alcohol having 1 to 30 carbon atoms or a polyhydric alcohol, the same as exemplified above,

PAm is a functional group derived from an amine or a polyvalent amine having 1 to 20 carbon atoms containing 1 to 6 amine groups, the same as exemplified above,

PS is a functional group derived from a silane compound having 1 to 20 carbon atoms containing 2 to 10 silyl groups, or from a linear, branched or cyclic real specialty compound containing 1 to 10 siloxy groups. It is a small container that is guided, same as exemplified above,

PE0 is a functional group derived from a linear polyoxyethylene having 4 to 40 carbon atoms of Formula 2a or a cyclic polyethylene glycol having 4 to 10 carbon atoms of Formula 2b including 2 to 20 ethylene oxide groups. Same as

FC is a perfluoroalkyl group or a perfluoroaryl group derived from a fluorocarbon compound having 4 to 20 carbon atoms containing 9 to 41 fluoro groups;

PT is the same as exemplified above with a functional group derived from a thiol and a polyvalent thiol having 1 to 20 carbon atoms containing 1 to 8 thiol groups (-SH),

CA is a functional group derived from a carboxylic acid having 1 to 10 carbon atoms and a polyvalent carboxylic acid containing 1 to 4 carboxylic acid groups (-C00H), and is the same as exemplified above.

SP is a functional group derived from a sulfonic acid or a polysulfonic acid having 1 to 10 carbon atoms containing 1 to 3 sulfonic acid groups (-S (= 0) ₂ 0H) or a sulfonic acid group (-0S (= 0) ₂ 0H) from 1 to 1 to 10 carbon atoms containing three sulfur acid or multivalent, or functional groups derived from a sulfur acid, phosphonic sulphonic acid group (- PO0) (0H) 2 ) from 1 to carbon atoms, 1 to comprising three 10 Phosphoric acid or polyhydric acid having 1 to 10 carbon atoms, which is a functional group derived from phosphonic acid or polyvalent phosphonic acid of 1 to 3 containing 1 to 3 phosphoric acid groups (-0-P (= 0) (0H) ₂ ) Is a functional group derived from perric acid, and

_A i to a9 and bl to b9 are numbers representing the number of functional groups, and are each independently an integer of 1 to 3, preferably, The non-liquid crystalline ratio (χ ') of the lipophilic-non-liquid crystalline compound calculated according to

It is determined within the range of satisfying 0.5 to 6.

Specifically, examples of the lipophilic crystalline-non-lipophilic crystalline compound which can be induced by liquid crystal vertical alignment even alone may include, but are not limited to, the following compounds:

Sorbitan monolaurate ^{(Sorbi tan monolaurate, Span ® 20} );

Sorbitan monopalmitate (Span ^® 40); Sorbitan monostearate (Span® 60); Sorbitan tristearate (Span ^® 65); Sorbitan monooleate (Span ^® mono) Span ^® 80);

Sorbitan sesquioleate (Span ^® 83); sorbitan trioleate (Span ^® 85);

Polyoxyethylenesorbitan tristearate (Tween ^® 65);

Polyoxyethylenesorbitan trioleate (Tween ^® 85);

Polyoxyethylene sorbitan stearate ^{(Polyoxyethylenesorbitan stearate, Tween ® 61)} ;

Polyoxyethylenesorbitan oleate (Tween ™ 81);

Dihexadecanoyl glycerol, dipalmit in; Dioctadecanoyl glycerol;

Dioleoyl glycerol;

Octyl gallate;

Lauryl gal late;

Ascorbic acid 6—palmitate;

Manide monooleate;

1,2-dodecanedi (1,2-1) 0 (1 ^ 31 ^ 01);

1, 2-nuxadecanediol (1, 2-Hexadecaned iol);

Nuxadecane 1,2-diamine;

Octanoic acid;

Decanoic acid;

Dodecanoic ^acid. (Dodecanoic acid);

Hexadecanoic acid (Palmetic acid);

Octadecanoic acid (Stearic acid);

Dihexadecyl phosphate;

Nucleus "hexadecyl sulfonic acid;

Dodecylbenzene sulfonic acid;

1-decanol;

1-dodecanol; 1-nuxadecanol;

1-octadecanol;

Octylamine;

Decylamine;

Dodecylamine;

Methacryloxy methylphenethyl tris (trimethylsiloxy) silane isomer

(methacryloxy methylpenethyl trisCtrimethylsi loxy) si lane isomer); Methyloctadecyl bis (trimethylsiloxy) silane (methy 卜 octadecyl

bi s (tr imethyl si loxy) si lane);

Polyoxyethylenesorbitane tr istearate (Tween ^® 65);

Dodecylphenyl sulfonic acid;

Gal late derivative of Formula 3j;

[Formula 3j]

Polyoxyethylen (2) stearyl ether;

Decyl gal late; And

Palmitic acid.

The lipophilic crystalline-non-lipophilic crystalline compound according to the present invention stabilizes the pretilt angle along with the vertical alignment of the liquid crystal through a photopolymerization reaction after inducing the vertical alignment of the liquid crystal, and forms a solid insulating solid film, thereby improving the performance and reliability of the liquid crystal display device. In order to improve the efficiency, the photoreactant group may be further included in one or both of the lipophilic crystalline region and the non-lipophilic crystalline region.

The photobanung group is a functional group capable of causing a photoreaction by light irradiation, specifically, an acryl group, a methacryl group, a c innamate group, a coumarin group ( coumar in group), chakongi

(chalcone group), vinyl group, thiol group, en group (一 ene group), diene group, thiol—ene group, acetylene group Etc. can be mentioned.

Specifically, the photo-banung compounds may be selected from the group consisting of compounds of the formula 4a to 4i and their mixtures:

[Formula 4a]

Formula

[Formula 4d]

ᅳ (Ρ¾¾4 '' '

[Formula 4e]

[Formula 4f]

[Formula 4h]

In Chemical Formulas 4a to 4i,

Ri 'to R ₉ ', Χι 'to V, ΡΑ', PAm ', PS', PEO ', FC, PT', AC and SP 'are the above defined in the formula 1 to 9 to R ₉ , Xi to X ₉ , Same as PA, PAm, PS, PEO, FC, PT, AC and SP,

At least one of Ri 'and PA', at least one of R ₂ 'and PAm', at least one of R ₃ 'and PS', at least one of R ₄ 'and PS ₂ ', At least one of R ₅ 'and PEO', at least one of R ₆ 'and FC, at least one of R ₇ ' and PT ', at least one of R ₈ ' and AC ', and R ₉ ' and SP At least one of the light is selected from the group consisting of an acrylate group, methacrylate group, cinnamate group, coumarin group, chacon group, vinyl group, thiol group, en group, diene group, thiene group and acetylene group And a reactive group, and al 'to a9' and bl 'to b9' are numbers representing the number of functional groups, each independently an integer of 1 to 3, preferably a non-lipophilic liquid crystal calculated according to Equation 1 The sex ratio (? ') Is determined within a range that satisfies 0.5 to 6, preferably 0.7 to 5.5, and more preferably 1.3 to 5.

More specifically, examples of the lipophilic-non-lipophilic crystalline compound further comprising a photoreactive group capable of inducing liquid crystal vertical alignment even by use alone include, but are not limited to:

Pentaerythritol diacrylate monostearate;

Pentaerythritol monopentathritol monoacrylate monostearate;

Glucosyl methacrylate (methacryloctyloxyphenolglucose) or derivatives thereof;

[4- (methacryloyloxymethyl) phenyl] ethyl-tris (trimethylsiloxy) silane ([4- (methacryloy loxymethy 1) phenyl] ethyl-tris (trimethylsi lyloxy) si 1 ane)); methacryloxymethyl Phenethyltris (trimethylsiloxy) silane

(me thacry loxymethy lphene thy 11 ris (trimethylsi loxy) si lane).

Even when the liquid crystal vertical alignment inducing agent according to the present invention includes a lipophilic-non-lipophilic crystalline compound including the photoreactive group as described above, the non-lipophilic crystalline ratio (Χ ′) calculated according to Equation 1 is 0.5 to 6, preferably 0.7 to 5.5, more preferably 1.3 to 5. As described above, when the liquid crystal vertical alignment inducer includes a lipophilic-non-lipophilic crystalline compound further comprising a photoreactive group under the conditions satisfying the non-lipophilic crystalline ratio, the photopolymerization reaction is performed in a state where the liquid crystal molecules form a specific arrangement. By forming the photopolymer, the formed photopolymer can induce vertical alignment and orientation stabilization of the liquid crystal host in the liquid crystal layer at the same time by an action mechanism for storing the specific surface arrangement of the liquid crystal. In addition, the lipophilic-non-liquid crystalline compound including the photoreactive group described above has a ratio of the photo-banung compounds forming the photopolymer by photoirradiation so that the liquid crystal vertical alignment and the alignment stabilization layer have an appropriate surface density. It is preferably included to be 3 to 100% by weight relative to the total weight of the derivative.

The liquid crystal vertical alignment inducer according to the present invention may optionally contain a liquid crystalline-non-liquid crystalline having or without a photobanic group as described above under conditions of satisfying the non-liquid crystalline ratio range of the liquid crystal vertical alignment inducer. A common lipophilic-non-lipophilic compound, ie, a lipophilic crystalline region including a lipophilic crystalline group and a non-lipophilic crystalline region including a lipophilic crystalline group, are included together with the compound. It may also comprise a lipophilic-non-lipophilic crystalline compound of type 2 that does not contain a lipophilic group.

In the lipophilic-non-lipophilic crystalline compound of the system 2, the lipophilic group and the non-lipophilic group included in the lipophilic crystalline region and the non-lipophilic crystalline region are the same as described above, and the second lipophilic crystalline-virin The liquid crystal compound may further include an optical semi-animal group in at least one of the lipophilic crystalline region or the non-lipophilic crystalline region.

Specifically, examples of the second lipophilic-non-liquid crystalline compound that do not include the photoreactive group include, but are not limited to:

Hexyl gallate;

n-dodecyl β-D-maltoside;

Propyl gallate;

1,2-nucleic acid (1,2-Hexanediol);

Hexanoic acid;

1-Hexanol;

1—nuxylamine;

1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane (1,3-bi s (3-methacryloxypropy 1) tetrakis (trimethylsi 1 oxy) di si loxane); 3-methacryl Oxypropylpentamethyldisiloxane (3— methacryloxypropyl pent amethy 1 disi loxane);

(3-Iacryloxypropyl) tris (trimethylsiloxy) silane ((3-acryloyloxypropyl) tr is (tr imethylsi loxy) si lane); (3-methacrylamidopropyl) bis (trimethylsiloxy) methylsilane ((3-methacry 1 ami dopropy 1) bis (tr imethylsi 1 oxy) methy 1 si lane).

In addition, specific examples of the second lipophilic-non-lipophilic crystalline compound including the photo-banung group may include, but are not limited to:

Pentaerythritol tr iacrylate; pentaerythritol tetraacrylate; poly (ethylene glycol) methyl ether methacr late;

Poly (ethylene glycol) methyl ether acrylate;

Hydroxybutyl acrylate;

A glycerol derivative of the formula 4j;

[Formula 4j]

Glycosyloxyethyl methacrylate; Tridecafluorooctyl

methacrylate); and

Poly (ethylene glycol) methyl ether methacrylate.

These compounds alone are difficult to induce vertical alignment of the liquid crystal, but the conditions of the non-liquid crystalline ratio defined by Equation 1 together with a lipophilic-non-liquid crystalline compound with or without the photoreactive group in the present invention. In mixed use, the vertical alignment of the liquid crystal can be induced. When the liquid crystal vertical alignment inducing agent according to the present invention is added to the liquid crystal host, the lipophilic-non-liquid crystalline compound molecules constituting the inducing agent form a microassembly that is stabilized by self-assembly and is uniformly dispersed in the liquid crystal host. In addition, the orientation defect by the low dispersibility or aggregation of the conventional liquid crystal aligning agent can be significantly reduced. In addition, the microassembly dispersed in the liquid crystal host can induce vertical alignment of the liquid crystal host without the alignment treatment pre-treated when forming the liquid crystal layer, and the formed microassembly is an insulating liquid crystal on the electrode layer. The vertical alignment induction and stabilization layer is formed and then stabilized through solidification by light irradiation, thereby improving reliability of the liquid crystal display. In addition, when the liquid crystal vertical alignment inducing agent constituting the microassembly further includes an optical reflector, the liquid crystal pretilt in a specific arrangement state is formed by forming a photopolymer according to the photopolymerization reaction through light irradiation while applying an electric field.

It is possible to form and stabilize the pretilt, and as a result, it is possible to further improve the performance of the liquid crystal device. Therefore, the liquid crystal vertical alignment guide according to the present invention induces vertical alignment of the liquid crystal without a line alignment treatment process, stabilizes the inclination angle of the liquid crystal, and forms an insulating liquid crystal vertical alignment and alignment stabilizer layer on the electrode layer. This excellent liquid crystal element can be produced.

According to another embodiment of the present invention provides a composition for forming a liquid crystal layer comprising the liquid crystal vertical alignment guide.

In detail, the composition for forming a liquid crystal layer includes the liquid crystal vertical alignment induction agent together with the liquid crystal host.

The liquid crystal host may be used without particular limitation as long as it is generally used in a liquid crystal display device. Specifically, a nematic liquid crystal having negative dielectric anisotropy can be used.

The liquid crystal vertical alignment guide is the same as described above.

However, when the content of the liquid crystal vertical alignment guide agent contained in the liquid crystal layer forming composition is too low, the vertical alignment and surface stabilization effect on the liquid crystal host is insignificant, whereas when the content is too high, the high density of the orientation misalignment and excessive stabilization There is a danger of deterioration of the performance of the liquid crystal display device. Accordingly, the liquid crystal vertical alignment inducing agent may be included in an amount of 0.01 to 5% by weight, and more preferably 0.05 to 3% by weight, based on the total weight of the liquid crystal layer forming composition. good.

In the liquid crystal layer forming composition, the liquid crystal vertical alignment inducing agent is dispersed in the liquid crystal host in the form of a microassembly stabilized by self-assembly. In this case, the size of the microassembly formed may vary depending on the characteristics and types of the lipophilic crystalline-non-lipophilic crystalline compounds constituting the liquid crystal vertical alignment inducer. In general, the minimum diameter of the microassembly is the lipophilic crystalline-non-liquid crystal used. It can be limited by the length of the compound and cannot be less than twice the average length of the lipophilic-non-lipophilic compound.

Diameter of the microassembly of the dispersed phase in the composition for forming a liquid crystal layer according to the present invention Silver can be present in a wide range from several nanometers to several tens of microns. However, when the diameter of the microassembly is too small, it is difficult to form the microassembly itself. On the other hand, when the diameter of the microassembly is too large, a large number of defects may occur to deteriorate the liquid crystal alignment characteristics. Therefore, the diameter of the microassembly that can be used for the purpose of controlling the vertical alignment of the liquid crystal is preferably 2nm to 800nm, more preferably 3nm to 600nm, even more preferably 3nm to 400nm.

In addition, the composition for forming a liquid crystal layer may further include a monomer capable of photopolymerization in order to induce vertical alignment of the liquid crystal and to stabilize the alignment and the pretilt angle. In this case, the photo-reflective monomer is used to prepare a liquid crystal display using a substrate pre-treated with a vertical alignment polymer film and a liquid crystal layer forming composition containing a small amount of reactive liquid crystal (reactive mesogen), and to stabilize the alignment under the application of an electric field. It acts similar to the function of reactive liquid crystals. The photoreactive monomer is not involved in the formation of microassembly by self-assembly of the liquid crystal vertical alignment inducing agent, and only a compound capable of stabilizing the orientation of a specific state after the vertical alignment induction of the liquid crystal by the liquid crystal vertical alignment inducing agent is used. It is preferable. Specifically, 4,4'-biphenol diacrylate, 4,4'-biphenol dimethacrylate, 1,4-bis [4- (6-acryloyloxynucleooxy) benzoyloxy] -2-methylbenzene (l, 4-bisS- [4— (6-acryloyl oxyhexyloxy) benzoyl oxy] -2-methyl benzene), or 1,6 'dicarboxylic acid diacrylate (l, 6-hexanediol diacrylate) etc. can be used.

In addition, the composition for forming a liquid crystal layer may further include a conventional photo-initiaror for inducing photo reaction of the surface reaction together with the liquid crystal host.

According to still another embodiment of the present invention, there is provided a liquid crystal display device manufactured using the liquid crystal layer shape composition including the liquid crystal vertical alignment inducing agent and a method of manufacturing the same.

Specifically, the liquid crystal display according to the embodiment of the present invention, the first substrate and the second substrate which are located facing each other; First and second electrodes formed on opposite surfaces of the first and second substrates, respectively; And a liquid crystal layer interposed between the first substrate and the second substrate, wherein the liquid crystal layer includes the liquid crystal host and the liquid crystal vertical alignment guide.

The liquid crystal layer is then an optional light step for stabilizing the liquid crystal alignment As the microassembly present in the composition for forming a liquid crystal layer is solidified by forming a passivation layer on the electrode layer, the liquid crystal vertical alignment and light stabilization layer including the microassembly of the liquid crystal vertical alignment guide (see FIGS. 14 and 24 of FIG. 3). ) May be further included.

In addition, when the liquid crystal vertical alignment guide in the liquid crystal layer includes a lipophilic-non-liquid crystalline compound including a photobanung group or includes a photoreactive compound, the liquid crystal layer is subjected to an electric field applied after inducing vertical alignment of the liquid crystal. Through the photopolymerization reaction process, the compound having the photoreactive group may further include a photopolymerized photopolymerized polymer. In this case, the photopolymer may be a homopolymer formed by photopolymerization of one photoreactive compound, or may be a copolymer formed by photopolymerization of two or more photoreactive compounds. In the liquid crystal display, any one or both of the first and second electrodes may be patterned.

According to another embodiment of the present invention, an electrode forming step of forming the first and second electrodes for each of the first substrate and the second substrate; The first substrate and the second substrate including the first and second electrodes, respectively, are bonded to each other so that the electrodes face each other, and then the liquid crystal layer forming composition is injected into the space between the first and second substrates. Alternatively, the liquid crystal layer is formed by dropping the liquid crystal layer forming composition under vacuum with respect to either the first substrate or the second substrate including the first and second electrodes, respectively, to form a liquid crystal layer, and then the other substrates are separated from each other. It provides a method for manufacturing a liquid crystal display device comprising the step of bonding so as to face the assembly. In this case, the manufacturing method may further include selectively irradiating light after applying an electric field between the first substrate and the second substrate of the assembly after fabrication of the assembly.

3 is a process diagram schematically illustrating a manufacturing process of a liquid crystal display according to an exemplary embodiment of the present invention. 3 is only an example for describing the present invention and the present invention is not limited thereto.

Hereinafter, each step will be described in detail with reference to FIG. 3.

Step 1 is a step of forming the first and second electrodes 12 and 22 for the first substrate 11 and the second substrate 21, respectively (S11).

The first and second substrates 11 and 21 may be used without particular limitation as long as they are generally used in liquid crystal displays, and specifically, glass or plastic substrates may be used.

One surface of the first substrate 11 has a common electrode (or transparent field) as the first electrode 12. Poles) and pixel electrodes as second electrodes 22 are formed on one surface of the second substrate 21, respectively. In this case, the first substrate and the second substrate, and the common electrode and the pixel electrode are divided according to the position and the function thereof. The common electrode may be formed on the second substrate or the pixel electrode may be formed on the first substrate.

The first and second electrodes 12 and 22 may be manufactured according to a conventional electrode forming method, and the first and second electrode forming materials may be particularly limited as long as they are materials used for forming electrodes of a liquid crystal display device. Can be used without Specifically, the first and second electrodes 12 and 22 may include one selected from the group consisting of metal oxides, carbon-based electrically conductive materials, and mixtures thereof. Preferably, indium tin oxide (ITO), zinc oxide (Z0), indium zinc oxide (IZO), tin oxide (TO), indium oxide ( indium oxide, 10), aluminum oxide (A1 ₂ 0 ₃ , AO), silver oxide (AgO), titanium oxide (Ti0 ₂ ), fluorine-doped tin oxide

(fluorine-doped tin oxide, FTO), aluminum doped zinc oxide

(aluminum doped zinc oxide (AZO), zinc indium tin oxide (ZITO), nickel oxide (NiO), nickel zinc tin oxide (NZTO), nickel titanium oxide (nickel titanium oxide (NTO), nickel tin oxide (nickel tin oxide), graphene (graphene), graphene oxide (graphene oxide, GO) and may include a compound selected from the group consisting of their mixtures.

In addition, the first and second electrodes 12 and 22 may be formed over the entire surface of the substrates 11 and 21, or may be patterned into predetermined shapes such as islands, sprites, and fishbones through a separate patterning process. (Not shown). Accordingly, according to another embodiment of the present invention, a liquid crystal display device in which at least one of the first and second electrodes 12 and 22 is patterned is provided.

Further, at least one of the first and the second electrodes 12 and 22 with respect to at least one of the first and second substrates 11 and 21 before the electrode forming step or after the formation of the electrode. A step of forming an electrically insulating compound layer (not shown) may be further performed on the step, or the step of forming the electrically insulating compound charge may be performed both before and after the electrode formation step. The formation of such an electrically insulating compound layer is more preferable when the electrode in the liquid crystal display device is patterned.

The passivation layer on top or bottom of the electrode as a result of the process

electrically insulating compound layer acting as a passivation layer or insulating layer In addition, an electrically insulating compound layer may be formed on both the upper and lower portions of the electrode by performing a process of forming an electrically insulating compound layer before and after forming the electrode. Accordingly, according to another embodiment of the present invention, there is provided a liquid crystal display device having an electrically insulating compound layer formed above, below, or both of at least one of the first and second electrodes 12 and 22. do .

The electrically insulating compound layer may include an organic insulating material, a nonmetal oxide, or a non metal nitride. Specifically, the electrically insulating compound layer may be a single layer composed of silicon oxide (SiOx) or silicon nitride (SiNx), or a double layer or multilayer structure composed of a silicon oxide layer and a silicon nitride layer.

Further, an aqueous solution using a detergent selectively for each of the substrates 11 and 21 on which the electrodes 12 and 22 are formed; Organic solvents such as acetone and isopropyl alcohol; ozone; Alternatively, a process of removing impurities and water from the surface of the electrode by washing and drying using a plasma or the like may be performed.

In step 2, the first and second substrates 11 and 21 including the first and second electrodes 12 and 22 are joined to each other so that the electrodes face each other, and thereafter, between the first and second substrates. The liquid crystal layer-forming composition 13a is injected into a space of the liquid crystal layer or under vacuum with respect to any one of the first and second substrates 11 and 21 including the above U and second electrodes 12 and 22. After dropping the composition 13 for forming a liquid crystal layer, the remaining substrates are bonded to each other so that the electrodes face each other (S12).

The composition 13 for forming a liquid crystal layer is the same as described above.

As the liquid crystal host, any one used in a liquid crystal display device may be used without particular limitation. Specifically, a nematic liquid crystal having negative dielectric anisotropy can be used.

The composition for forming a liquid crystal layer including the liquid crystal vertical alignment inducer as described above may further include a conventional photo-initiaror for inducing photo reaction of the surface reaction together with the liquid crystal host.

The bonding process of the said 1st board | substrate and the 2nd board | substrates 11 and 21 and the injection | pouring or dripping process of the liquid crystal layer formation composition 13 can be carried out according to a conventional method.

When the composition 13 for forming a liquid crystal layer is injected according to the above process, as shown in FIG. 3, the liquid crystal is vertically oriented even without coating of a conventional alignment layer. It is faced (S12).

In this case, in order to effectively induce the vertical alignment of the liquid crystal, after the injection or dropping of the composition for forming a liquid crystal layer, the nematic of the mixture of the liquid crystal host and the liquid crystal vertical alignment inducing agent is heated to 10 to 20 ° C higher silver than the isotropic phase transition temperature After inducing the vertical alignment of the liquid crystal to be cooled at a rate of 0.1 to 10 ^° C. per minute may be further carried out.

In addition, after the manufacturing step of the assembly, optionally applying an electric field between the first substrate and the second substrate (11, 21) of the assembly may be further performed to manufacture a liquid crystal display by light irradiation (S13) .

The electric field applying process is preferably performed under a condition of applying a direct current or an alternating electric field such that the light transmittance of the liquid crystal display becomes 5% (T ₀₅ ) to 100% (Τ ₁₀₀ ) of the maximum transmittance under a cross polarizer.

Under the above conditions, a specific optical state is induced for the liquid crystal in the assembly by applying an electric field, and then light of a wavelength capable of chemically reacting a photoreactive group is irradiated with ultraviolet rays. Preferably, irradiating ultraviolet light in the wavelength range of 200 nm to 400 nm at three groups of ₁₀₀ mW / cm ² to 50yW / cm ² for 1 to 60 minutes may improve the photostabilization efficiency of the photoreactive group in the photoreactive compound. It is good because it can maximize and obtain the surface stabilization effect of liquid crystal orientation. In addition, the light irradiation step may be carried out in two or more steps by varying the electric field to be applied or the intensity of light to be irradiated.

The light irradiation process is preferably performed after applying an electric field and waiting for the defect to be minimized before the arrangement of the liquid crystals becomes stable.

As the microassembly of the liquid crystal vertical alignment guide agent present in the liquid crystal layer forming composition solidifies to form a passivation layer on the electrode, the liquid crystal layer is a passivation layer formed by the microassembly and the liquid crystal vertical alignment and light stabilization layers 13b and 13b. ') May be further included.

In addition, when the compound forming the liquid crystal vertical alignment inducing agent is a photo-reflective compound including a photo-neutral group, the photo-reflective group of the photo-reflective compound causes a photoreaction to form a photopolymer by the light irradiation process as described above. As a result, the arrangement and optical state of the liquid crystal can be further stabilized, and the surface pretilt angle induction of the liquid crystal and the surface stabilization in pixel units can be realized.

Specifically, when an electric field perpendicular to the substrate is applied to the liquid crystal display device without the light stabilization process through the first and second substrates 11 and 21, the liquid crystal molecules rotate in a direction perpendicular to the electric field, and thus transmittance is achieved. Will increase. LCD Since the molecules do not have a pretilt angle in a specific direction, the rotation direction of the liquid crystal occurs irregularly according to the portion of the liquid crystal cell. Therefore, the defect of the liquid crystal array is generated, which acts as a cause of deterioration of the characteristics of the device. However, when the inclination angle is induced in a specific direction with respect to the surface of the liquid crystal host through the light irradiation and the light reaction process as described above, and then the applied electric field is removed, as shown in step S13, the liquid crystal host has the liquid crystal pretilt direction of the surface. Is transferred to a vertical alignment state that stores. As such, the alignment of the liquid crystal is stabilized to have a pretilt angle, thereby eliminating defects, thereby improving the reaction properties of the liquid crystal and the brightness and contrast ratio of the device. Therefore, when manufacturing a liquid crystal display device using the surface stabilization technology of the liquid crystal array proposed in the present invention, that is, the liquid crystal array stabilization method through the chemical reaction of the photo-banung organic group of the photoreactive compound, the brightness and contrast of the liquid crystal display device The contrast ratio can be improved and the switching speed of the liquid crystal can be increased.

As described above, the manufacturing method according to the present invention has an optimized non-lipophilic crystalline ratio, and when mixed with a liquid crystal host, forms a fine assembly by self-assembly in the liquid crystal host, thereby using a liquid crystal vertical alignment inducer that can be uniformly dispersed. The vertical alignment of the liquid crystal can be induced without the application of the polymer alignment film and the high temperature baking process. In addition, the manufacturing method is different from the conventional liquid crystal display device manufacturing method of achieving alignment stabilization by mixing and reacting a reactive liquid crystal as a liquid crystal host in a liquid crystal cell treated with an alignment agent to achieve an alignment stabilization. By implementing the stabilization of the alignment of the liquid crystal through the photopolymerization by light irradiation under the electric field application it can significantly reduce the defects that can occur after the light stabilization. As a result, the productivity of the liquid crystal display device manufacturing and the reliability of the liquid crystal display device can be improved.

In addition, due to stabilization of the liquid crystal array, it is possible to prevent the occurrence of defects in the liquid crystal generated when driving the device and improve the reaction speed, thereby improving the performance and reliability of the device. In particular, it is possible to induce the surface liquid crystal pretilt angle in the pixel unit and to purify the director, thereby further improving the optical and electro-optical characteristics such as brightness, contrast ratio, and reaction speed of the liquid crystal device. In addition, since the process is performed at room temperature, the process temperature is significantly lower than the firing temperature of the conventional polymer alignment layer, and the process is simple. As a result, not only a high-quality liquid crystal display device using a glass substrate, but also a flexible substrate Flexer with It is useful for manufacturing a liquid crystal display device having a high temperature process such as a liquid crystal display device.

The liquid crystal display according to the present invention manufactured by such a manufacturing method is stabilized liquid crystal arrangement, it is possible to induce the pre-tilt angle of the pixel unit, minimize the defects appearing when driving the device and improve the reaction speed is improved optical, Electro-optic properties. As a result, it can be applied to electro-optical device products using liquid crystal, especially flat panel displays, such as TV, 3D-TV, monitor, tablet PC, and various mobile devices.

According to another embodiment of the present invention, the liquid crystal vertical alignment inducing agent forms a fine assembly by self-assembly to form a vertical alignment of the liquid crystal having an alignment stability by using the composition for forming a liquid crystal layer uniformly dispersed in the liquid crystal host. Provide a way to induce. At this time, the composition for forming a liquid crystal layer includes the liquid crystal vertical alignment induction agent together with the liquid crystal host, each of which is the same as described above.

According to another embodiment of the present invention, the vertical alignment of the liquid crystal using the composition for forming a liquid crystal layer in which the photoreactive liquid crystal vertical alignment inducing agent forms a fine assembly by self-assembly and is uniformly dispersed in the liquid crystal host. And a method of inducing photostabilization. In this case, the composition for forming a liquid crystal layer includes the liquid crystal vertical alignment inducer together with a liquid crystal host, wherein the liquid crystal vertical alignment inducing agent includes a photoreactive group in at least one region of the lipophilic crystalline region or the non-lipophilic crystalline region. A lipophilic-non-lipophilic crystalline compound comprising a lipophilic crystalline-non-lipophilic crystalline compound and including the photobanung group is the same as described above.

According to another embodiment of the present invention, there is provided a method of forming an insulating liquid crystal vertical alignment and a light stabilization layer between an electrode layer and a liquid crystal layer in a simplified process as compared to the prior art without a line coating treatment of the substrate.

The liquid crystal vertical alignment and light stabilization layer forming method includes a liquid crystal host and a liquid crystal layer forming composition in which a liquid crystal vertical alignment inducing agent of photoreactive liquid crystal is uniformly dispersed in the liquid crystal host by forming a microassembly by self-assembly. After injection into the can be applied by applying an electric field and light irradiation.

When the liquid crystal layer-forming composition is injected into the liquid crystal layer and subjected to light irradiation, the fine granules present in the liquid crystal layer-forming composition are solidified to form the liquid crystal vertical alignment and the light stabilization layer as a passivation layer on the electrode layer. In this case, the liquid crystal host and the photoreactive liquid crystal vertical alignment guide and the light irradiation process are the same as described above.

Embodiment for Invention

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. That However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Example 1

According to the manufacturing process of the liquid crystal display device shown in FIG. 3, using a substrate on which an unpatterned transparent electrode (ΠΌ) and a patterned pixel electrode (ΠΌ) in the form of fishbone are formed as the first and second substrates, respectively, A liquid crystal display device was manufactured.

3, the unpatterned transparent electrode IT0 and the patterned pixel electrodes IT0K12 and 12 'are formed on the first and second substrates 11 and 1Γ, respectively. After ultrasonic cleaning in distilled water, and then washed with acetone and isopropyl alcohol, respectively, and dried. After assembling the transparent electrode 12 and the pixel electrode 12 'on the first and second substrates to face each other without a separate alignment treatment, negative dielectric anisotropy with respect to the total weight of the liquid crystal layer forming composition It is a liquid host with 99.9 weight ¾ and a photoreactive lipophilic-non-liquid qualitative compound, with a pentaerythr i tol diacrylate monostearate of the following structural formula: The liquid crystal layer forming composition was injected to prepare a liquid crystal display device.

The photo-banung lipophilic-non-lipophilic crystalline compound is a compound in which two photoreactive groups (ie, acryl groups) and one lipophilic hydrocarbon chain are substituted with a non-liquid crystalline polyhydric alcohol pentaerythri, The pentaerythri containing one hydroxyl group forms a non-lipophilic crystalline region. In addition, the ratio of non-liquid crystalline ratio (Χ ′) of the light semi-male compound was calculated according to Equation 1 above, and it was (133/511) X 10 = 2.60.

In addition, the gap between the first substrate and the second substrate was maintained at 4.2 / gram when the assembly was formed, and the injection process of the liquid crystal layer forming composition was performed at 8 (rc), which is an isotropic temperature of the liquid crystal layer forming composition.

After injecting the composition for forming a liquid crystal layer, the assembly is cooled at a rate of 5 ^° C. per minute, and the alignment state of the liquid crystal is observed using a polarizing microscope and a conoscopy. It was. As a result, it was confirmed that the liquid crystal is arranged in a direction perpendicular to the substrate inside the liquid crystal cell without a separate alignment treatment process.

Subsequently, an alternating electric field was applied between the first and second substrates of the manufactured liquid crystal display device under a T ₈₀ (80% transmittance to maximum transmittance) condition to confirm that defects were minimized and the arrangement of the liquid crystals was stable. This applied liquid crystal display device was irradiated with ultraviolet rays of 365 nm wavelength at 30 mW / cm ² intensity for 10 minutes to form a liquid crystal layer. Photoreaction was induced to induce the surface pretilt angle of the liquid crystal and to surface stabilize the alignment of the liquid crystal.

The liquid crystal layer of the liquid crystal display device was observed with a polarizing microscope, and the results are shown in FIG. 4A. In addition, the arrangement of liquid crystal molecules was observed through conoscopy images, and the results are shown in FIG. 4B.

As shown in FIGS. 4A and 4B, the liquid crystal layer in the liquid crystal display showed a completely quenched state under a quadrature polarizer, and confirmed that the liquid crystal molecules were arranged perpendicularly to the surface of the substrate through a conoscopy image. In addition, the liquid crystal display device has an intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) of the liquid crystal display before the electric field is applied to the liquid crystal layer and the liquid crystal display device before performing the alignment stabilization process through light irradiation. The orientation state of the liquid crystal molecules after applying the electric field of was observed, and the results are shown in FIGS. 5A to 5C, respectively.

In general, a liquid crystal layer vertically aligned with respect to a substrate exhibits an extinction state as shown in FIG. 5A under a quadrature polarizer. When an electric field is applied thereto, liquid crystal molecules rotate in a direction perpendicular to the electric field to increase transmittance. However, since the liquid crystal molecules did not have a pretilt angle in a specific direction before the alignment stabilization through light irradiation, the rotation direction of the liquid crystal occurs randomly at the portion of the liquid crystal cell. In this case, as shown in FIG. 5B, a large number of defects in the liquid crystal array are generated, resulting in deterioration of characteristics of the liquid crystal display device. However, the defect shown in FIG. 5B is slowly removed and transitions to a uniform brightness state as shown in FIG. 5C.

In addition, it was observed whether a liquid crystal defect occurred during on-off (0n-0ff) switching of the liquid crystal display device after the stabilization treatment due to the electric field application and light irradiation. The results are shown in Figures 6a to 6c. In the initial dark state (dark, black) as shown in Figure 6a as above, if the electric field of the intensity corresponding to T ₈₀ (transmittance 80% of the transmittance of the maximum) is added to the liquid crystal reacts to change the arrangement state, accordingly It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, so that it immediately transitioned to the same bright state as in 6b and 6c without generating a liquid crystal defect. This is because the photoreaction of the lipophilic-non-liquid crystalline compound that induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. As a phenomenon that appears to be stabilized, it can be seen that through this improvement of the reaction speed of the liquid crystal and the brightness and contrast ratio of the device is improved.

In addition, when comparing FIG. 5B without stabilization with FIG. 6B with stabilization, the stabilization process of FIG. 6B eliminates defects and increases reaction speed, thereby improving electro-optical characteristics of the device by stabilization. It can be seen that.

Example 2

Glucosyl methacrylate derivative represented by the following structural formula as a liquid crystalline host having a negative dielectric anisotropy with respect to the total weight of the liquid crystal layer forming composition and a photophilic lipophilic-non-lipophilic compound (2) Was carried out in the same manner as in Example 1 except for forming a liquid crystal layer using a composition for forming a liquid crystal layer uniformly mixed at a ratio of 0.1% by weight to prepare a liquid crystal display device.

At this time, the photobanung lipophilic crystalline-non-lipophilic crystalline compound is a non-lipophilic polyhydric alcohol group in which one photobanung group (that is, methacryl group) is octyloxyphenol (octyloxyphenol) group at the end of the lipophilic group Substituted lipophilic-non-liquid crystalline compound, the photo-banung group is substituted at the end of the lipophilic crystalline region, the non-lipophilic ratio (Χ ') of the photo-banung compound is calculated according to Equation 1 As a result, (179/468) X 10 = 3.82.

Same as in Example 1 for the liquid crystal layer of the manufactured liquid crystal display device In one method, the alignment state of the liquid crystal molecules was observed after applying an electric field having an intensity corresponding to T ₈₀ (80% transmittance versus maximum transmittance) between the first substrate and the second substrate. The results before and after applying the electric field are shown in FIGS. 7A to 7C, respectively. As shown in FIG. 7A, in general, the liquid crystal layer vertically aligned with respect to the substrate exhibits an extinction state under a quadrature polarizer. When the electric field is applied thereto, the liquid crystal molecules rotate in a direction perpendicular to the electric field to increase transmittance. However, before the alignment stabilization through light irradiation, since the liquid crystal molecules did not have a pretilt angle in a specific direction, as shown in FIG. 7B, a plurality of defects of the liquid crystal array were generated. Is transferred. As a result, the response speed of the liquid crystal display device is slowed and the visibility is deteriorated.

In addition, after the stabilization treatment by applying the electric field and light irradiation in the same manner as in Example 1 for the prepared liquid crystal display device, it was observed whether the occurrence of liquid crystal defects during On-Off switching of the device. The results are shown in Figures 8a to 8c.

In the initial dark state (dark, black) as shown in Figure 8a as above, when the electric field of the intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied, the liquid crystal reacts to change the arrangement state, accordingly It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, so that it immediately transitioned to the bright state as in 8b and 8c without generating the liquid crystal defect. This is because the photoreaction of the lipophilic-non-liquid crystalline compound which induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. As a phenomenon that appears to be stabilized, it can be seen that through this improvement the reaction speed of the liquid crystal and the brightness and contrast ratio of the device is improved.

In addition, when comparing the stabilization process of FIG. 7B and the stabilization process of FIG. 8B, the stabilization process of FIG. 8B eliminates the occurrence of defects and increases the reaction speed, thereby improving the electro-optical characteristics of the device by the stabilization process. It can be seen.

Example 3

The liquid crystal display device was manufactured according to the manufacturing process of the liquid crystal display device shown in FIG. 3, using the unpatterned transparent electrode (Ό) and the pixel electrode (Ό) as the first and second substrates, respectively. Referring to FIG. 3, the unpatterned transparent electrode IT0 and the pixel electrodes IT0K12 and 12 'are formed on the first and second substrates 11 and 11', respectively, and then a cleaning agent is used. After ultrasonic cleaning in distilled water, the mixture was washed with acetone and isopropyl alcohol, respectively, and dried. After the transparent electrodes 12 and the pixel electrodes 12 ′ of the first and second substrates were assembled to face each other without an alignment process, a composition for forming a liquid crystal layer was injected. At this time, the thickness of the composition for forming a liquid crystal layer, that is, the cell gap was set to 10 mm 3.

The composition for forming a liquid crystal layer is tetraacrylate of a pentaerythride of the following structural formula as 99.9% by weight of a liquid crystal host having a negative dielectric anisotropy relative to the total weight of the composition and a photoreactive lipophilic-non-liquid crystalline compound.

(pentaerythritol tetraacrylate) (3) 0.03% by weight and a lipophilic-non-lipophilic compound were uniformly mixed with 0.07% by weight of nuxadecane-1,2-diamine (4) The mixture was used.

At this time, the non-lipophilic crystalline ratio (Χ ') in the mixture of the photoreactive lipophilic-non-lipophilic crystalline compound and the lipophilic-non-liquid crystalline compound was calculated according to Equation 2 above, and (O ^ xXi UxX ^^ where the non-liquid crystalline ratio of tetraacrylate was determined to be the non-lipophilic crystalline ratio () = (132/352) X 10 = 3.75, and the non-lipophilic crystalline ratio of the nucleus decane -1,2-diamine ( X ₂ ) = (59/256) X 10 = 2.30.

Before performing the alignment stabilization process through the light irradiation, the manufactured liquid crystal display device corresponds to T ₈₀ (80% transmittance relative to the maximum transmittance) between the first substrate and the second substrate in the same manner as in Example 1, After the electric field of intensity was applied, the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field are shown in FIGS. 9A and 9B, respectively.

As shown in FIG. 9A, when the composition for forming a liquid crystal layer was injected into a liquid crystal cell, the optical axis of the liquid crystal was perpendicular to the substrate without a conventional alignment layer treatment process, and thus an extinction state was exhibited under orthogonal polarizers. When the electric field is applied, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing the permeability. However, prior to light irradiation, as shown in FIG. 9B, a large number of defects of the liquid crystal array are generated, resulting in deterioration of characteristics of the liquid crystal display. This defect occurs because the liquid crystal molecules do not have a pretilt angle in a specific direction, which means that the alignment is not stabilized before the photopolymerization.

In addition, the liquid crystal display device manufactured according to Example 1 was subjected to the stabilization process according to the electric field application and the light irradiation in the same manner as in Example 1, and the occurrence of liquid crystal defects during the on-off switching of the device. Observed. The results are shown in FIGS. 10A and 10B.

In the initial dark state (dark, black) as shown in Figure 10a as above, if the electric field of the intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied, the liquid crystal reacts to change the arrangement state, accordingly It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, so that the optical axis was transferred to the same bright state as in FIG. 9b without generating a liquid crystal defect. This is because the photoreaction of the lipophilic and non-lipophilic crystalline compounds that induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. As a phenomenon that appears to be stabilized, it can be seen that through this improvement of the reaction rate of the liquid crystal and the brightness and contrast ratio of the device is improved.

In addition, when comparing FIG. 9B with no stabilization and FIG. 10B with stabilization, the stabilization process of FIG. 10B eliminates the occurrence of defects and speeds up the reaction rate, thereby stabilizing the electro-optical characteristics of the device. It can be seen that it can be improved.

Example 4

Poly (ethylene glycol) methyl ether methacrylate of the following structural formula as 99.9% by weight of liquid crystal host having a negative dielectric anisotropy and a photobanung lipophilic non-liquid crystalline compound with respect to the total amount of the composition for forming a liquid crystal layer.

(poly (ethylene glycol) methyl ether methacrylate) (5) 0.04 weight ¾, and a sorbitan-derived group as a non-lipophilic region, and a palmitate-derived group as a lipophilic region, respectively. Formation of a liquid crystal layer prepared by adding a homogeneous mixture of sorbitan monopalmitate (6) to a hydrophilic crystalline-visible liquid crystalline compound of 0.06% by weight of sorbitan monopalmitate (6) A liquid crystal display device was manufactured in the same manner as in Example 3 except that the liquid crystal layer was formed using the composition for sol.

At this time, the non-liquid crystalline ratio of the mixture of the photo-banung compound and the non-liquid crystalline non-liquid crystalline compound is (θ Λ ^χ χ ^ + δ ^χ χ ^ ^ θ ^. Sex ratio Ο ^ χι δ ^ ^ χιθδ.δδ, and the non-lipophilic crystalline ratio of sorbitan monopalmitate (Fig. ₂ ) = (164/403) Fig. 10 = 4.07.

Before the alignment stabilization process by light irradiation, the intensity corresponding to Τ ₈₀ (80% transmittance relative to the maximum transmittance) between the first substrate and the second substrate in the same manner as in Example 1 for the liquid crystal display device manufactured above After the electric field of was applied, the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field are shown in FIGS. 11A and lib, respectively.

As shown in FIG. 11A, when the composition for forming a liquid crystal layer was injected into a liquid crystal cell, the optical axis of the liquid crystal was perpendicular to the substrate without a conventional alignment layer treatment process, thereby exhibiting an quenched state under orthogonal polarizers. When the electric field is applied, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing the transmittance. However, prior to light irradiation, as shown in FIG. Lib, a large number of defects in the liquid crystal array are generated, resulting in deterioration of characteristics of the liquid crystal display device. This defect occurs because the liquid crystal molecules do not have a linear inclination angle in a specific direction, which means that the alignment is not stabilized before photopolymerization.

After performing the stabilization treatment according to the electric field application and light irradiation in the same manner as in Example 1 with respect to the manufactured liquid crystal display device, the occurrence of liquid crystal defects during the on-off switching of the device is observed. It was. The result 12A and 12B.

In the initial dark state (dark, Mack) as shown in Figure 12a as above, if the electric field of intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied, the liquid crystal reacts to change the arrangement state, accordingly It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, so that the optical axis was transferred to the same bright state as in FIG. 12b without generating a liquid crystal defect. This is because the photoreactor containing the lipophilic-non-liquid crystalline compound that induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. As a phenomenon that appears to be stabilized, it can be seen that through this improvement of the reaction speed of the liquid crystal and the brightness and contrast ratio of the device is improved.

In addition, when comparing the stabilization process lib and the stabilization process FIG. 12b, the stabilization process of FIG. 12b eliminates the occurrence of defects and the reaction rate is faster, so that the electro-optical characteristics of the device are stabilized. It can be seen that it can be improved.

Example 5

A liquid crystal host having a negative dielectric anisotropy with respect to the total weight of the composition for forming a liquid crystal layer> 99.9 weight ¾> and a photophilic lipophilic-non-lipophilic compound, in which the methacryloxymethyl group is substituted at the 3 or 4 position of the phenyl group A mixture of methacryloxy methylphenethyl tris (trimethylsiloxy) silane isomer of the structural formula (methacry 1 oxy methylphenethyl tris (trimethylsil oxy) si 1 ane, mixed isomer, manufactured by Gelst) (7) 0.07 wt% and light reaction Except for forming a liquid crystal layer using a liquid crystal layer-forming composition prepared by uniformly mixing 0.03 weight% of a liquid-crystalline non-liquid crystalline compound of Chemical Formula 8 (manufactured by Gel st) without a penis group. The liquid crystal display device was produced in the same manner as in Example 3.

(7)

(8) In this case, the compound (7) includes a silane (trisiloxy silane) group in which one photoreactive group (that is, methacryl group) is substituted in the lipophilic region and has three siloxy groups as the non-lipophilic region. Photophilic lyophilic crystalline-non-liquid crystalline compound, calculated by Equation 1, non-lipophilic ratio Od ^ l

(160/498) X 10 = 3.21. The compound (8) is also reflected as a lipophilic-non-liquid crystalline compound containing octadecyl hydrocarbon as the liquid crystalline region and trimethyl as the non-lipophilic crystalline region without photoreactive group. The liquid crystalline ratio was () = (116/474) X 10 = 2.45). Therefore, as a result of calculating the non-lipophilic crystalline ratio of the mixture of Compounds 7 and 8 according to Equation 2, X '= (0.7XX _! ) + (0.3XX ₂ ) = 2.98.

Subsequently, before the alignment stabilization process through light irradiation, the liquid crystal display device manufactured above corresponds to Τ ₈₀ (80% transmittance relative to maximum transmittance) between the first substrate and the second substrate in the same manner as in Example 1. After applying the electric field of the intensity, the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field are shown in FIGS. 13A and 13B, respectively.

As shown in FIG. 13A, when the composition for forming a liquid crystal layer was injected into a liquid crystal cell, the optical axis of the liquid crystal was perpendicular to the substrate without a conventional alignment layer treatment process, thereby exhibiting an quenched state under a cross polarizer. When the electric field is applied, the liquid crystal molecules are dilute in the direction perpendicular to the electric field and the transmittance increases. However, prior to light irradiation, as shown in FIG. 13B, a large number of defects in the liquid crystal array occur, resulting in deterioration of characteristics of the liquid crystal display. This defect occurs because the liquid crystal molecules do not have a linear inclination angle in a specific direction, which means that the alignment is not stabilized before the photopolymerization.

In addition, the liquid crystal display device prepared above was observed in the same manner as in Example 1 after the stabilization treatment due to the application of electric field and light irradiation, and the occurrence of liquid crystal defects when switching on / off (Οη-Off) of the device was observed. It was. The results are shown in FIGS. 14A and 14B. As shown in FIG. 14A, when an electric field of an intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied in the same way as above, the liquid crystal reacts to change the arrangement state. It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, thereby transitioning to the bright state as in FIG. 14b without generating the liquid crystal defect. This is because the photoreaction of the lipophilic-non-liquid crystalline compound that induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. As a phenomenon that appears to be stabilized, it can be seen that through this improvement of the reaction speed of the liquid crystal and the brightness and contrast ratio of the device is improved.

In addition, when comparing the stabilization process of FIG. 13B and the stabilization process of FIG. 14B, the stabilization process of FIG. 14B eliminates the occurrence of defects and increases the reaction speed. It can be seen that it can be improved.

Example 6

99.85% by weight of a liquid crystal host having negative dielectric anisotropy with respect to the total weight of the composition for forming a liquid crystal layer, polyoxyethylene sorbitan tristearate (Tween ^® 65, manufactured by Sigma Aldrich Co., Ltd.) (9), and a hydroxide of the following structural formula: Except for forming a liquid crystal layer using a liquid crystal layer forming composition prepared by uniformly mixing the citryl acrylate (10) at 0.07% and 0.08% by weight, respectively, in the same manner as in Example 3 above. It carried out and produced the liquid crystal display device.

(9)

At this time, the compound (9) is a lipophilic-non-lipophilic crystalline compound containing a sorbitan group in which three stearates are substituted in the lipophilic region, and a polyoxyethylene group is substituted as the non-lipophilic crystalline region, The non-lipophilic ratio 00, calculated according to 1, is 5.3. In addition, the compound (10) has a non-lipophilic ratio of 1.18, and therefore, the non-lipophilic ratio (Χ ′) of these mixtures according to Equation 2 is (0.07 / 1.15) Χ 5.3 + (0.08 / 1.15) xl. 18 = 3.1.

Before the alignment stabilization process through light irradiation, the intensity corresponding to T ₈₀ (80% transmittance versus maximum transmittance) between the first substrate and the second substrate in the same manner as in Example 1 for the liquid crystal display device manufactured above. After the electric field of was applied, the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field are shown in Figs. 15A and 15B, respectively.

As shown in FIG. 15A, when the liquid crystal layer-forming composition was injected into a liquid crystal cell, the optical axis of the liquid crystal was perpendicular to the substrate without a conventional alignment layer treatment process, and the light axis was exhibited under an orthogonal polarizer. When applied, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing the permeability. However, prior to light irradiation, as shown in FIG. 15B, a large number of defects in the liquid crystal array are generated, resulting in deterioration of characteristics of the liquid crystal display. This defect occurs because the liquid crystal molecules do not have a pretilt angle in a specific direction, which means that the alignment is not stabilized before the photopolymerization.

In addition, the liquid crystal display device was observed in the same manner as in Example 1 after the stabilization treatment due to electric field application and light irradiation, and the occurrence of liquid crystal defects during on / off switching of the device. The results are shown in FIGS. 16A and 16B.

In the initial dark state (dark, black) as shown in FIG. 16a, when the electric field of intensity corresponding to T ₈₀ (transmittance ratio 80¾>) is applied in the same manner as above, the liquid crystal reacts to change the arrangement state. It was observed that the optical axis of was formed at an angle of 45 degrees with the transmission axis of the polarizer on the substrate surface, so that the optical axis was transferred to the same bright state as in 16b without generating a liquid crystal defect. It contains the lipophilic-non-liquid crystalline compound that induced the vertical alignment of the liquid crystal. This is a phenomenon in which the alignment of liquid crystals is surface stabilized by causing the liquid crystal molecules to form a pretilt angle in a specific direction through the light irradiation process through the light irradiation process, thereby improving the reaction speed of the liquid crystal and the brightness and contrast of the device. It can be seen that the rain is improved.

In addition, when comparing FIG. 15B without stabilization and FIG. 16B with stabilization, stabilization of FIG. 16B eliminates the occurrence of defects and increases the reaction speed, thereby improving the electro-optical characteristics of the device by stabilization. It can be seen that it can be improved.

Example 7

99.8 wt% of the liquid crystal host having negative dielectric anisotropy with respect to the total weight of the composition for forming the liquid crystal layer and 0.1 wt% of the glycerol derivative of the structural formula (11) as a photophilic lipophilic-non-lipophilic compound Except for forming a liquid crystal layer using a composition for forming a liquid crystal layer prepared by uniformly mixing each of the sulfonic acid compound (12) of the structural formula (12) 0.1 weight ¾> as a sex-non-liquid crystalline compound, The liquid crystal display device was manufactured by the same method.

The compound (11) is a glycerol derivative in which an acryl group and a methacrylate group are each substituted one by one, and the compound (12) is a sulfonic acid as a non-lipophilic crystalline region as a dodecylbenzene group without a photoreactive group. It is a lipophilic-non-lipophilic crystalline compound containing (sulfonic acid). In addition, the non-lipophilic ratio of the photoreactive lipophilic-non-lipophilic crystalline compound and the lipophilic-non-lipophilic crystalline compound was calculated according to equation (2).

X '= (0.5XX ₁ ) + (0.5XX ₂ ) = 3.35, wherein the non-lipophilic ratio of the compound of Formula 11 was Χ _{1 =} 4.2 and the non-lipophilic ratio of the compound of Formula 12 was ¾ = 2.5. Before the alignment stabilization process through the above, between the first substrate and the second substrate in the same manner as in Example 1 for the liquid crystal display device After applying an electric field of intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance), the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field are shown in Figs. 17A and 17B, respectively.

As shown in FIG. 17A, when the composition for forming a liquid crystal layer was injected into a liquid crystal cell, the optical axis of the liquid crystal was perpendicular to the substrate without a conventional alignment layer treatment process, thereby exhibiting an quenched state under orthogonal polarizers. When the electric field is applied, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing the transmittance. However, prior to light irradiation, as shown in FIG. 17B, a large number of defects in the liquid crystal array occur, resulting in deterioration of characteristics of the liquid crystal display. This defect occurs because the liquid crystal molecules do not have a linear inclination angle in a specific direction, which means that the alignment is not stabilized before the photopolymerization.

In addition, the liquid crystal display device was observed in the same manner as in Example 1 after the stabilization treatment due to electric field application and light irradiation, and the occurrence of liquid crystal defects during on-off (0n-0ff) switching of the device. The results are shown in FIGS. 18A and 18B.

In the initial dark state (dark, black) as shown in Figure 18a as above, T ₈₀ (approximately transmittance of ₈₀ ¾ of the maximum transmittance of the intensity of the electric field corresponding to the intensity of the liquid crystals react to change the arrangement state, accordingly the optical axis of the liquid crystal By forming the angle of 45 degrees to the transmission axis of the polarizer on the surface of the substrate, it was observed that the transition to the bright state as shown in Figure 18b without the formation of liquid crystal defects, which was induced by the liquid-crystal crystalline—non-liquid crystalline compound that induced the vertical alignment of the liquid crystal This photoreflector causes the liquid crystal molecules to form a pretilt angle in a specific direction through the light irradiation process, resulting in surface stabilization of the liquid crystal, thereby improving the reaction velocity of the liquid crystal and It can be seen that the brightness and contrast ratio are improved.

Also, when comparing FIG. 17B without stabilization and FIG. 18B with stabilization, stabilization of FIG. 18B eliminates the occurrence of defects and speeds up reaction speed, thereby improving the electro-optical characteristics of the device by stabilization. It can be seen that it can be improved.

Example 8

99.92% by weight of liquid crystal host having negative dielectric anisotropy with respect to the total weight of the composition for forming a liquid crystal layer and a half-reflective lipophilic-non-lipophilic crystalline compound Except for forming a liquid crystal layer using a liquid crystal layer forming composition prepared by homogeneously mixing by adding a gallate derivative (13) of the following structural formula containing a male liquid crystal in a ratio of 0.08% by weight and The liquid crystal display device was manufactured by the same method.

The compound (13) includes a photoreactive lipophilic-non-lipophilic crystalline compound as a lipophilic crystalline region and a semi latent liquid crystal group and a gal late derived group as the lipophilic crystalline region. The non-lipophilic crystalline ratio (Χ ') of the compound (13) was calculated according to Formula (1), and it was (169/566) X 10 = 2.99.

Before the alignment stabilization process through light irradiation, the intensity corresponding to Τ ₈₀ (80% transmittance versus maximum transmittance) between the first substrate and the second substrate in the same manner as in Example 1 for the liquid crystal display device manufactured above. After the electric field of was applied, the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field are shown in Figs. 19A to 19C, respectively.

As shown in FIG. 19A, when the composition for forming a liquid crystal layer was injected into a liquid crystal cell, the optical axis of the liquid crystal was perpendicular to the substrate without a conventional alignment layer treatment process, thereby exhibiting an quenched state under orthogonal polarizers. When the electric field is applied, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing the transmittance. However, prior to light irradiation, as shown in FIG. 19B, a large number of defects in the liquid crystal array occur, resulting in deterioration of characteristics of the liquid crystal display. This defect occurs because the liquid crystal molecules do not have a linear inclination angle in a specific direction, which means that the alignment is not stabilized before the photopolymerization. The defect shown in FIG. 19B is removed as time goes by and transitions to a uniform brightness state as shown in FIG. 19C, thereby adversely affecting not only the visibility of the display device but also the reaction speed.

In addition, after the stabilization treatment according to the same electric field application and light irradiation as in Example 1 for the liquid crystal display device, it was observed whether the liquid crystal defect occurs during the on-off switching of the device. The results are shown in Figures 20a to 20c. In the initial dark state (dark, black) as shown in FIG. 20a, when the electric field of intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied as above, the liquid crystal reacts to change the arrangement state. It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, so that the optical axis was transferred to the bright state as shown in FIGS. 20b and 20c without generating a liquid crystal defect. This is because the photoreactor containing the lipophilic-non-liquid crystalline compound that induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. Surface stabilization is a phenomenon that can be seen that through this improves the reaction speed of the liquid crystal and the brightness and contrast ratio of the device.

In addition, when comparing FIG. 19B with no stabilization and FIG. 20B with stabilization, the stabilization process of FIG. 20B eliminates the occurrence of defects and increases the reaction speed, thereby improving the electro-optical characteristics of the device. It can be seen that it can be improved.

Example 9

Composition for forming a liquid crystal layer ^'' 99.8 wt% of a liquid crystal host having a negative dielectric anisotropy with respect to the total weight, and 0.1 wt% of a dihexadecyl phosphate (14) having the following structural formula as a lipophilic-non-liquid crystalline compound. And pentaerythride of the following structural formula as a photoreactive lipophilic-non-lipophilic compound by adding 0.1% by weight of triacrylate (pentaerythritol triaery 1 at e) in a proportion of 0.1% by weight. A liquid crystal display device was manufactured in the same manner as in Example 1, except that the liquid crystal layer was formed using the combined composition for forming a liquid crystal layer. \

At this time, the non-lipophilic ratio (Χ ') of the mixture of the lipophilic-non-lipophilic crystalline compound (14) and the photophilic lipophilic-non-lipophilic crystalline compound (15) is (Ο.δΧΧ ^ + ίΟ.δΧΧ ^-^ θ ^ where the non-lipophilic crystalline ratio of dinuxadecyl phosphate (14) = (80/547) Χ 10 = 1.46, and pentaerythritol triacrylate (15 Non-liquid crystalline ratio (X ₂ ) = (133/298) xl0 = 4.46).

Before the alignment stabilization process through light irradiation, the intensity corresponding to T ₈₀ (transmittance ratio 80¾>) between the first substrate and the second substrate in the same manner as in Example 1 for the liquid crystal display device manufactured above. After the electric field of was applied, the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field are shown in Figs. 21A to 21C, respectively.

As shown in FIG. 21A, a liquid crystal layer arranged perpendicularly to a substrate generally exhibits an extinction state under a quadrature polarizer. When an electric field is applied thereto, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing transmittance. However, before the alignment stabilization through light irradiation, since the liquid crystal molecules did not have a pretilt angle in a specific direction, as shown in FIG. 21B, a plurality of defects of the liquid crystal array were generated, thereby transitioning to the bright state of FIG. 21C. do. As a result, the reaction speed of the liquid crystal display device is slowed, leading to deterioration of visibility.

In addition, the liquid crystal display device was observed in the same manner as in Example 1 after the stabilization treatment due to the electric field application and light irradiation, the occurrence of liquid crystal defects during On-Off switching of the device. The results are shown in Figs. 22A to 22C.

In the initial dark state (dark, black) as shown in Figure 22a as above, when the electric field of the intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied, the liquid crystal reacts to change the arrangement state, accordingly It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, so that it immediately transitioned to the same bright state as in 22b and 22c without generating a liquid crystal defect. This is because the photoreaction of the lipophilic-non-liquid crystalline compound which induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. As a phenomenon that appears to be stabilized, it can be seen that through this improvement of the reaction speed of the liquid crystal and the brightness and contrast ratio of the device is improved.

In addition, when comparing FIG. 21B without stabilization and FIG. 22B with stabilization, stabilization of FIG. 21B eliminates the occurrence of defects and increases the reaction speed, thereby improving the electro-optical characteristics of the device by stabilization. When improving It can be seen that.

Example 10

99.5 weight ¾ of liquid crystal host having negative dielectric anisotropy with respect to the total weight of the composition for forming a liquid crystal layer and 0.4 wt ¾ of palmitic acid (16) having a structure of the following formula as a non-liquid crystalline compound. The liquid crystal display device was fabricated in the same manner as in Example 1 except that hydroxy butyl acrylate was added at a ratio of 0.1% by weight to form a liquid crystal layer using a uniformly mixed composition for forming a liquid crystal layer. Produced.

At this time, the non-lipophilic ratio (χ ') of the mixture of the lipophilic-non-lipophilic crystalline compound (16) and the photoreactive compound is (ο.δ ^χ χ + υ ^χ χ ^ ι.δ The liquid crystalline ratio (Χι) = (45/256) Χ 10 = 1.76 and the non-lipophilic crystalline ratio of the hydroxybutyl acrylate (Χ ₂ ) = (Γ 7/144) X 10 = 1.18).

Before performing the alignment stabilization process through light irradiation, between the first substrate and the second substrate in the same manner as in Example 1 with respect to the liquid crystal display device

After applying an electric field of an intensity corresponding to Τ ₈₀ (transmittance ratio 80¾ »), the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field

23a to 23c, respectively.

As shown in FIG. 23A, when the composition for forming a liquid crystal layer was injected into a liquid crystal cell, the optical axis of the liquid crystal was perpendicular to the substrate without a conventional alignment layer treatment process, thereby exhibiting an quenched state under orthogonal polarizers. When the electric field is applied, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing the transmittance. However, since the liquid crystal molecules did not have a pretilt angle in a specific direction before alignment stabilization through light irradiation, as shown in FIG. 23B, a plurality of defects of the liquid crystal array were generated, thereby transitioning to the bright state of FIG. 23C. do .

In addition, the liquid crystal display device was observed in the same manner as in Example 1 after the stabilization treatment due to the electric field application and light irradiation, the occurrence of liquid crystal defects during On-Off switching of the device. The results are shown in Figures 24a to 24c.

Same as above in the initial dark state (dark, black) as shown in Figure 24a When an electric field with an intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied, the liquid crystal reacts to change the arrangement state. Accordingly, the optical axis of the liquid crystal forms an angle of 45 degrees with the transmission axis of the polarizer on the substrate surface. It was observed that the transition to the bright state as in FIG. 24B and FIG. 24C without the generation of liquid crystal defects was observed. This is because the photoreaction of the lipophilic-non-liquid crystalline compound that induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. As a phenomenon that appears to be stabilized, it can be seen that through this improvement of the reaction speed of the liquid crystal and the brightness and contrast ratio of the device is improved.

Also, when comparing FIG. 23B without stabilization with FIG. 24B with stabilization, stabilization of FIG. 24B eliminates the occurrence of defects and speeds up the reaction speed, thereby stabilizing the electro-optical characteristics of the device by stabilization. It can be seen that it can be improved.

Example 11

99 weight ¾> of liquid crystal host having negative dielectric anisotropy with respect to the total weight of the composition for forming a liquid crystal layer and a lyophilic-non-lipophilic crystalline compound, 0.8 wt% of dodecyl amine (17) of the following structural formula and photoreactivity Pentaery three as a compound was carried out in the same manner as in Example 3, except that the liquid crystal layer was formed using a uniformly mixed composition for forming a liquid crystal layer by adding triacrylate in a ratio of 0.2% by weight. A liquid crystal display device was manufactured.

GH3 (CH2) ioCH ₂ NH2 ( ₁₇ ) At this time, the non-lipophilic ratio (χ ') of the mixture of the lipophilic-non-lipophilic crystalline compound (17) and the photoreactive compound is (ο.δ ^χ χ + ω ^ ^χ χ ^ -ι.δδ *: The ratio of the non-liquid crystallinity of dodecylamine to 0 (= (16/185)><10 = 0.86 and the ratio of non-liquid crystallinity of the pentaerythride to triacrylate () = (133/298 X 10 = 4.46).

Before the alignment stabilization process through light irradiation, the intensity corresponding to Τ ₈₀ (80% transmittance versus maximum transmittance) between the first substrate and the second substrate in the same manner as in Example 1 for the liquid crystal display device manufactured above. After the electric field of was applied, the alignment state of the liquid crystal molecules was observed. The results before and after applying the electric field are shown in Figs. 25A and 25B, respectively.

As shown in FIG. 25A, the liquid crystal layer forming composition is applied to a liquid crystal cell. Upon entering, the optical axis of the liquid crystal was perpendicular to the substrate without the usual alignment film treatment process, and exhibited an quenched state under the orthogonal polarizer. When the electric field is applied, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing the transmittance. However, prior to light irradiation, as shown in FIG. 25B, a large number of defects in the liquid crystal array occur, resulting in deterioration of characteristics of the liquid crystal display. This defect occurs because the liquid crystal molecules do not have a linear inclination angle in a specific direction, which means that the alignment is not stabilized before photopolymerization.

In addition, the liquid crystal display device was observed in the same manner as in Example 1 after the stabilization treatment due to the electric field application and light irradiation, the occurrence of liquid crystal defects during On-Off switching of the device. The results are shown in FIGS. 26A and 26B.

In the initial dark state (dark, black) as shown in Figure 26a as above, if the electric field of the intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied, the liquid crystal reacts to change the arrangement state, accordingly It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, so that the optical axis was transferred to the same bright state as in FIG. 26B without generating a liquid crystal defect. This is because the photoreaction of the lipophilic-non-liquid crystalline compound that induced the vertical alignment of the liquid crystal causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. As a phenomenon that appears to be stabilized, it can be seen that through this, the reaction speed of the liquid crystal is improved and the brightness and contrast ratio of the device are improved.

In addition, when comparing FIG. 25B without stabilization with FIG. 26B with stabilization, stabilization of FIG. 26B eliminates defects and speeds up the reaction speed, thereby stabilizing the electro-optical characteristics of the device. It can be seen that it can be improved.

Example 12

Polyoxyethylene (2) stearyl ether of the following structural formula as a liquid crystal alignment inducing agent having 99% by weight of a liquid crystal host having a negative dielectric anisotropy and a lipophilic-non-liquid crystalline region relative to the total weight of the composition for forming a liquid crystal layer

(polyoxyethylen (2) stearyl ether) (18) Polyethyleneglycol methyl ether acrylate of the following structural formula as 0.8 wt%

(Poly (ethylene glycol) methyl ether acrylate) (19) in 0.2% by weight A liquid crystal display device was fabricated in the same manner as in Example 3, except that the liquid crystal layer was formed by using a composition for forming a liquid crystal layer uniformly added thereto.

At this time, the non-lipophilic ratio (χ ') of the mixture of the lipophilic crystalline non-lipophilic crystalline compound (18) and the photoreactive compound (19) is (ο.β ^χ χ ^ + ω ^ ^χ χ ^ ^ θθ Non-lipophilic ratio of oxyethylene (2) stearyl ether (Χ ^ ΙΟδ / βδ ^ ΧΚ ^ Θδ and non-lipophilic ratio of polyethylene glycol methyl ether acrylate () = (160/246) X 10 = 3.25 Was.

Before the alignment stabilization process through light irradiation, the intensity corresponding to Τ ₁₀₀ (100% transmittance versus maximum transmittance) between the first substrate and the second substrate in the same manner as in Example 1 for the liquid crystal display device manufactured above. After the electric field of was applied, the alignment state of the liquid crystal molecules was observed.

When the liquid crystal layer-forming composition prepared above was injected into the liquid crystal cell, the optical axis of the liquid crystal was perpendicular to the substrate without the usual alignment layer treatment process, and exhibited an quenched state under orthogonal polarizers. When the electric field is applied, the liquid crystal molecules rotate in a direction perpendicular to the electric field, thereby increasing the transmittance. However, prior to light irradiation, as in the above embodiments, a large number of defects in the liquid crystal array are generated, resulting in deterioration of characteristics of the liquid crystal display device. These defects indicate that orientation stabilization did not occur prior to photopolymerization.

In addition, the liquid crystal display device was observed in the same manner as in Example 1 after the stabilization treatment due to the electric field applied and light irradiation, the occurrence of liquid crystal defects during the on-off switching of the device.

Applying an electric field with an intensity equal to T ₁₀₀ (transmittance to 100¾>) in the initial dark state (dark, Mack) as above, the liquid crystal reacts to change the arrangement state and thus the optical axis of the liquid crystal Of polarizer By forming an angle of 45 degrees with the hyperaxial, it was observed that the transition to the bright state as shown in Fig. 15b without the formation of liquid crystal defects. This is because the photoreaction of the lipophilic-non-liquid crystalline compound, which induced the vertical alignment of the liquid crystal, causes the liquid crystal molecules to form a pretilt angle in a specific direction on the inner surface of the cell through a light irradiation process. Surface stabilization, which can be seen to improve the response rate of the liquid crystal and the brightness and contrast ratio of the device.

Test Example 1

The photoreactive compound and the lipophilic-non-liquid crystalline compound used in the present invention induce vertical alignment of the liquid crystal without a separate alignment layer process, induce vertical alignment, and then undergo a specific polymerization through photopolymerization by light irradiation under electric field application. Stabilizes the state. As a result, in order to achieve the effect of the present invention, the vertical alignment of the liquid crystal must be preceded.

The factor influencing this primary vertical orientation is the ratio of non-lipophilic regions in the lipophilic-non-lipophilic molecules. In this test example, the vertical alignment induction effect of the liquid crystal was evaluated according to the non-liquid crystalline ratio (χ ') value.

A non-lipophilic crystalline ratio calculated according to Equation 1 as a lipophilic-non-lipophilic crystalline compound together with a liquid crystal host having negative dielectric anisotropy (nusil gallate of the following structural formula: (169/254) X10 = 6.65) Decyl gal late (21) of the following structural formula having a hexyl gal late) (20) or a liquid crystalline ratio (X ₂ ) of (169/310) X 10 = 5.45 was added to the total weight of the composition for liquid crystal layer formation. 0.5 parts by 3/4 "of each was added to prepare a composition for forming a liquid crystal layer.

The affinity with the liquid crystal is not sufficient to make a homogeneous mixture with the liquid crystal All.

Further, after injecting the prepared non-uniform liquid crystal layer-forming composition into the liquid crystal layer of the granules prepared in the same manner as described in Example 1, the alignment state of the liquid crystal was observed by a polarizing microscope. The result is shown in FIG.

As shown in FIG. 27, it was confirmed that the liquid crystal molecules were randomly horizontally aligned inside the cell, and it can be seen that the vertical alignment of the liquid crystals was not induced therefrom.

On the other hand, the ratio of lipophilic groups with the same non-liquid crystalline group was increased, so that the decyl gallate having an X ₂ value of 5.45 was uniformly mixed in the liquid crystal due to improved lipophilic crystallinity.

In addition, the liquid crystal alignment was observed after injecting the prepared composition for forming a liquid crystal layer into the liquid crystal layer of the assembly prepared by the same method as described in Example 1. The results are shown in FIG.

As shown in FIG. 28, it was confirmed that the liquid crystal molecules were uniformly aligned vertically. Conoscopy images (not shown) also clearly show the isozyres that appear when the liquid crystals are oriented perpendicular to the substrate.

From the above experimental results, even though the same non-lipophilic crystalline group, the nucleosil gallate contained a shorter lipophilic group than decyl gallate, and thus exhibited more non-lipophilic crystalline properties than decyl gallate. In addition, as the non-liquid crystalline ratio becomes too large to have a hydrocarbon length of less than 8 carbon atoms and the non-liquid crystalline ratio (Χ ′) exceeds 6, which is the X value, the mixing with the liquid crystal compound is poor, There was no vertical orientation of. Therefore, it can be seen that the non-liquid crystalline ratio (Χ ′) should have a value of 6 or less in order to form a uniform mixture with the liquid crystal and induce vertical alignment of the liquid crystal.

Apart from the above, in addition to the liquid crystal host having negative dielectric anisotropy, an octadecane (22) of the following structural formula or a parent having a non-liquid crystalline ratio 0 ^ calculated according to Equation 1 as a lipophilic compound 1-octadecanol (23) of the following structural formula having a liquid crystalline non-liquid crystalline compound having a non-liquid crystalline ratio (X ₂ ) of (17/270) X 10 = 0.63. The liquid crystal layer-forming composition was prepared by adding 1.0 wt ¾ of the total weight.

CH3 (CH2) i6CH ₂ OH (2 ₃ ) The octadecane is a compound consisting of a ₁₀₀ % lipophilic group, which is easily dissolved in a liquid crystal because of the non-lipophilic ratio Od 0. On the other hand, the 1-octadecane has a small affinity in the compound of the hydroxy group as the non-liquid crystalline group compared to the hydrocarbon chain as the lipophilic group and has a high affinity with the liquid crystal, thereby forming a uniform mixture with the liquid crystal.

After injecting the prepared composition for forming a liquid crystal layer into a liquid crystal layer of a granule prepared in the same manner as described in Example 1, the alignment state of the liquid crystal was observed with a polarizing microscope. The results are shown in FIG. 29.

As a result, since the composition for forming a liquid crystal layer containing octadecane does not affect the liquid crystal array, the liquid crystal layer is formed by adding 1-octadecane while showing a random horizontal arrangement as shown in FIG. 29. In the liquid crystal cell in which the composition was injected, it was confirmed that the alignment of the liquid crystals was uniformly arranged perpendicularly to the substrate.

30A and 30B are polarization microscopes and conoscopy photographs showing the alignment state of a liquid crystal cell in which the composition for forming a liquid crystal layer to which 1-octadecane was added in Test Example 2 was injected. As shown in FIGS. 30A and 30B, the uniform quenching state of the liquid crystal cell and the cross-shaped isozyres located at the center of the liquid crystal well show that the liquid crystal is vertically oriented so that the optical axis is formed perpendicular to the substrate.

As described above, when the lipophilic crystallinity of the additive is too large and the non-lipophilic crystalline characteristic is too small, the property to be dissolved in the liquid crystal is too strong to induce vertical alignment of the liquid crystal. Therefore, the non-liquid crystalline ratio (X) of the lipophilic-non-liquid crystalline compound which is a vertical alignment inducing agent has an appropriate range for inducing vertical alignment of the liquid crystal.

This phenomenon indicates that the balance between lipophilic crystalline and non-lipophilic crystalline in non-liquid crystalline compounds is an important factor in inducing the vertical alignment of liquid crystals. It means that there is. Therefore, it is preferable that the X value of the lipophilic-non-lipophilic crystalline compound which is effective for the result consistent with the object of the present invention is at least 0.5. If the X value is less than 0.5, the lipophilic-non-lipophilic compound The affinity for the liquid crystal is too great to induce vertical alignment of the liquid crystal.

Test Example 2

When a mixture of lipophilic-non-lipophilic compounds was used, the effects of the range of non-lipophilic crystalline ratios were evaluated.

Specifically, n-dodecyl β-D-maltoside of the following structural formula (n-dodecyl β-D-maltoside, non-lipophilic ratio (Χ = (342/510) x 10 = 6.69) (24) (Compound A ), 1-octadecanol (non-liquid crystalline ratio (X ₂ ) = (17/270) X 10 = 0.63) (Compound B), glycosyloxyethyl methacry 1 ate non-liquid crystal Sex ratio (X ₃ ) = (179/292) X 10 = 6.13) (25) (Compound C) or Palmitic acid (non-liquid crystalline ratio)

(X ₄ ) = (45/256) xi0 = 1.76) (26) Using (Compound D), a composition for forming a liquid crystal layer was mixed with a liquid crystal host having negative dielectric anisotropy at the mixing ratios shown in Table 1 below. Prepared.

TABLE 1

First, when compound A is mixed with 0.3% by weight of the total amount of the composition for forming a liquid crystal layer (Example No. 2-1), since the X value of compound A is too large, it does not mix uniformly with the liquid crystal and induces vertical alignment of the liquid crystal. I could not confirm.

On the other hand, Compound B was well mixed with the liquid crystal host, it was confirmed that induces the vertical alignment of the liquid crystal.

However, when a mixture of compounds A and B were mixed at a weight ratio of 40 to 60 was mixed at 0.3 weight ¾> and 0,5 wt%, respectively, based on the total weight of the composition for forming a liquid crystal layer (Examples 2-3 and 2 ᅳ). 4), It was confirmed that the compounds A and B are uniformly dispersed in the liquid crystal. In addition, when a composition for forming a liquid crystal layer in which Compounds A and B were uniformly mixed was injected into the liquid crystal layer of the granules prepared in the same manner as in Example 1, vertical alignment of the liquid crystal was induced.

31 and 32 show that when Compound A is mixed with 0.3% by weight in the composition for forming a liquid crystal layer (Example No. 2-1), a mixture of Compound A and B in a weight ratio of 40 to 60 is added to the composition for forming a liquid crystal layer. It is the polarization microscope photograph which shows the liquid-crystal orientation in case of mixing by 0.5 weight ¾ (Example No. 2-4).

In the case of FIG. 31, the random horizontal alignment is shown, whereas in FIG. 32, the vertical alignment is uniformly shown.

This indicates that the non-lipophilic crystalline ratio (Χ ′) of the mixture containing the lipophilic-non-liquid crystalline compoundol contained in the composition for forming a liquid crystal layer of Example No. 2-4

(0.4X6.69) + (0.6X0.63) = 3.05, which is a value within the range of the preferred non-liquid crystalline ratio (Χ ') value presented in the present invention. These results indicate that lipophilic crystalline-non-lipophilic compounds that are too large or too small, respectively, are opposite to each other. When the lipophilic crystalline-non-lipophilic crystalline compound is mixed, the lipophilic crystalline and the non-lipophilic crystalline are balanced to have a desirable X value range, thereby showing that the effect of the present invention can be obtained by appropriately adjusting the mixing ratio. It is.

In addition, when the compound C was included in an amount of 0.2% by weight based on the total weight of the liquid crystal layer-forming composition (Example No. 2-5), the non-lipophilic crystallinity of the compound C was so strong that it was not uniformly mixed with the liquid crystal and injected into the liquid crystal layer. It does not induce the vertical alignment of the liquid crystal It was confirmed that no. However, in the case where a mixture of compounds C and D was mixed at a weight ratio of 40 to 60 at 0.2% by weight based on the total amount of the composition for forming a liquid crystal layer (Example 2-6), compounds C and D were uniformly liquid crystal. We confirmed that it is distributed to hosts. In this case, the non-lipophilic ratio (Χ ') of the mixture of compounds C and D is

It is a value included in the range of the preferable X value proposed by this invention as (0 * 4 * 6.13) + (0.6 * 1.76) = 3.51. In addition, the liquid crystal layer forming composition in which the compounds C and D are uniformly mixed is injected into the liquid crystal layer of the assembly patterned in the form of fishbone by the electrode of the lower substrate as in Example 1, vertical alignment showing excellent characteristics. The obtained liquid crystal cell was obtained.

33 and 34 show that when Compound C is mixed with 0.2% by weight of the liquid crystal (Example No. 2-5) and the mixture of Compounds C and D in a weight ratio of 40 to 60 is mixed with 0.2% by weight ¾ of the liquid crystal. It is a polarizing microscope micrograph which shows the liquid-crystal orientation of (No. 2-6).

In the case of FIG. 33, the random horizontal alignment is shown, and in the case of FIG. 34, the vertical alignment is uniformly shown.

In addition, using the composition for forming a liquid crystal layer (Examples No. 2-6) in which Compounds C and D were mixed, an alignment stabilization was performed through irradiation of light under an electric field on a liquid crystal cell in which vertical alignment was induced.

Specifically, in the same manner as in Example 1, an alternating electric field of Τ ₈₀ (80% transmittance to 80% transmittance) is applied to the liquid crystal display device between the first and the second substrates, and defects are minimized. After confirming that the arrangement of was stabilized, ultraviolet rays of 365 nm wavelength were irradiated for 30 minutes at an intensity of 30 mW / cm ² for the assembly to which the electric field was applied.

The arrangement of the liquid crystals before and after the electric field application to the liquid crystal display device was observed, and the results are shown in FIGS. 35A to 35C.

As shown in FIG. 35A, the liquid crystal layer in the manufactured liquid crystal display device exhibited a completely quenched state under a quadrature polarizer. Also, as a result of observing the arrangement of liquid crystal molecules through a conoscopy image (not shown), It was confirmed that the substrate is oriented perpendicular to the surface. As a result of observing the switching state of the liquid crystal molecules after applying an electric field of intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance), as shown in FIGS. 35B and 35C, a plurality of defects in the liquid crystal array are generated. It was observed that the transition to the state of FIG. 34C through the 35b state caused the deterioration of characteristics of the liquid crystal display element. In addition, it was observed whether a liquid crystal defect occurred during on-off switching of the device after stabilization treatment due to electric field application and light irradiation. The results are shown in Figs. 36A to 36C.

In the initial dark state (dark, black) as shown in Figure 36a as above, when the electric field of the intensity corresponding to T ₈₀ (80% transmittance to maximum transmittance) is applied, the liquid crystal reacts to change the arrangement state, accordingly It was observed that the optical axis of was formed at an angle of 45 degrees to the transmission axis of the polarizer on the substrate surface, so that the optical axis was transferred to the bright state as shown in FIGS. 36b and 36c without generating a liquid crystal defect. This is a phenomenon in which the alignment of the liquid crystal is surface stabilized during the light stabilization process, thereby improving the reaction speed of the liquid crystal and improving the brightness and contrast ratio of the device.

Test Example 3

A liquid crystal device was manufactured in the same manner as in Example 3, except that the liquid crystal vertical alignment inducer was used as the compound type and content shown in Table 2, and the alignment state of the liquid crystal was evaluated. The X value and the vertical alignment of the used liquid crystal vertical alignment inducing compound are shown together in Table 2 below.

TABLE 2

S1: Sorbitan monolaurate (Span ^® 20) S2: Sorbitan monopalmitate (Span ^® 40)

S3 ： Sorbitan monostearate (Span ^® 60)

S4 sorbitan tristearate (Sorbitan tristearate, Span ^® 65)

S5: Sorbitan monooleate (Span ^® 80)

S6 sorbitan sesquioleate (Sorbitan sesquioleate, Span ^® 83)

S7 sorbitan trioleate (Sorbitan trioleate, Span ^® 85) As shown in Table 2, the non-liquid crystalline groups include the same sorbitan group as the polyhydric alcohol-derived working container, and the lipophilic crystalline groups containing the various kinds of hydrocarbon groups in various contents of the embodiments Nos. 3-1 to 3-7 The liquid crystal vertical alignment inducer had an X value in the range of 1.69 to 4.71 to induce good liquid crystal vertical alignment.

However, the liquid crystal vertical alignment guide used in the present test example did not include a photoreactive group, and thus no additional process for photostabilization was performed after the vertical alignment of the liquid crystal.

Test Example 4

A liquid crystal device was manufactured in the same manner as in Example 3 except that the liquid crystal vertical alignment guide was used as the compound type and content shown in Table 3 below, and the alignment state of the liquid crystal was evaluated. The X value and the vertical alignment of the used liquid crystal vertical alignment inducing compound are shown in Table 3 together.

TABLE 3

PS1: polyoxyethylene sorbitan tristearate (Tween® 65)

PS2: polyoxyethylene sorbitan trioleate (Tween® 85)

PS3: polyoxyethylene sorbitan stearate (Tween® 61)

PS4: polyoxyethylene sorbitan oleate (Tween® 81)

As shown in Table 3 above, run numbers 4-1 to 4-4 including the same sorbitan group substituted with polyoxyethylene as the non-lipophilic group and various kinds of hydrocarbon groups as the lipophilic group. The lipophilic-non-liquid crystalline compounds used in Eq., 4.9 to 6.0 had a corresponding X value to induce a good liquid crystal vertical alignment.

However, the liquid crystal layer-forming composition used in this test example did not include a photobanner, so no additional process for photostabilization was performed.

Test Example 5

To the liquid crystal vertical alignment guide to the compound type and content shown in Table 4 A liquid crystal device was fabricated in the same manner as in Example 3 except that the liquid crystal device was used, and the alignment state of the liquid crystal was evaluated. The X value and the vertical alignment of the used liquid crystal vertical alignment inducing compound are shown in Table 4 together.

TABLE 4

G1: dinuxadecanoyl glycerol (Dipalmitin)

G2: dioctadecanoyl glycerol

G3: dioleoyl glycerol

As shown in Table 4, in Examples Nos. 5-1 to 5-3 containing the same sorbitan group as a small container derived from polyhydric alcohol as a non-lipophilic crystalline group, and containing various kinds of hydrocarbon groups as various lipophilic groups. The lipophilic-non-lipophilic compounds used had X values in the range of 1.44 to 1.58, leading to good liquid crystal vertical alignment.

However, the composition for forming a liquid crystal layer used in the present test example did not include a photobanner, so no additional process for photostabilization was performed. Test Example 6

A liquid crystal device was manufactured in the same manner as in Example 3, except that the liquid crystal vertical alignment inducer was used as the compound type and amount shown in Table 5, and the alignment state of the liquid crystal was evaluated. The X value and the vertical alignment of the used liquid crystal vertical alignment inducing compound are shown in Table 5 together.

TABLE 5

PAcl: Propyl gal late

PAc2: octyl gallate

PAc3: lauryl gallate

PAc4: diacrylate monostearate to pentaerythrone

PAc5: Pentaerythrone monoacrylate monostearate

PAc6: ascorbic acid 6-palmitate

PAc7: mannide monooleate

As shown in Table 5, the liquid crystal vertical alignment guider of the embodiments 6-2 to 6-7 having an X value in the range of 2.6 to 5.99 showed a vertical alignment induction effect on the liquid crystal. However, the liquid crystal vertical alignment inducer of Example No. 6-1, in which the number of carbon atoms of the lipophilic crystalline hydrocarbon group is less than 8 and the X value exceeds 6.0, did not induce the vertical alignment of the liquid crystal.

Further, photo-stabilization was performed under the electric field application in the same manner as in Example 3 with respect to Examples Nos. 6-4 and 6_5 (Compounds PAc4 and PAc5) containing a photoreactive acrylate group in the compound.

As a result, in Example Nos. 6-4 and 6-5, the pretilt angle of the liquid crystal was induced by the alignment stabilization by light irradiation after the induction of vertical alignment, and the electro-optical characteristics of the liquid crystal small were improved.

Test Example 7

A liquid crystal device was manufactured in the same manner as in Example 3 except that the liquid crystal vertical alignment inducer was used as the compound type and amount shown in Table 6, and the alignment state of the liquid crystal was evaluated. The X value and the vertical alignment of the used liquid crystal vertical alignment inducing compound are shown in Table 6 together.

TABLE 6

DAcl: 1,2-Hexanediol

DAc2: 1,2-dodecanediol DAc3: 1,2-hexadecanediol

DAc4: nucleodecane 1,2-diamine

As shown in Table 6, the liquid crystal vertical alignment guide agent of Examples No. 7-2 to 7-4 in the X value range of 2.3 to 3.02 induced the vertical alignment of the liquid crystal. However, in the case of Example No. 7-1 using compound DAcl having less than 8 carbon atoms and having an X value of 5.17 of the lipophilic crystalline hydrocarbon group, the X value was in the range of 6.0 or less, The vertical orientation of was not induced.

Since the composition for forming a liquid crystal layer used in this test example does not include a photoreactive group, an additional process for photostabilization was not performed.

Test Example 8

A liquid crystal device was manufactured in the same manner as in Example 3 except that the liquid crystal vertical alignment inducer was used as the compound type and content shown in Table 7 below, and the alignment state of the liquid crystal was evaluated. The X value and the vertical alignment of the used liquid crystal vertical alignment inducing agent compound are shown together in Table 7 below.

TABLE 7

Cal: Hexanoic acid

Ca2 Octanoic Acid

Ca3 decanoic acid

Ca4 Dodecanoic Acid

Ca5 nucleodecanoic acid

Ca6 octadecanoic acid Pal: dinuxadecyl phosphate

Sal: nucleodecylsulfonic acid

Sa2: dodecylbenzenesulfonic acid

As shown in Table 7, the liquid crystal vertical alignment inducers of the reference numbers 8-2 to 8-9 having the X value in the range of 1.47 to 3.13 induced the liquid crystal vertical alignment. However, in the case of the implementation No. 8-1 using the compound Cal having less than 8 carbon atoms of the lipophilic crystalline hydrocarbon group and having an X value of 3.88, the X value was included in the range of 6.0 or less, No vertical orientation of was induced.

Test Example 9

A liquid crystal device was manufactured in the same manner as in Example 3 except that the liquid crystal vertical alignment inducer was used as the compound type and content shown in Table 8, and the alignment state of the liquid crystal was evaluated. The X value of the liquid crystal vertical alignment inducer compound used and whether or not the manual alignment is shown in Table 8 below.

TABLE 8

Ami: 1-Hexylamine

Am2: octylamine

Am3: decylamine

Am4: dodecylamine

As shown in Table 8, the liquid crystal vertical alignment inducers of the embodiments 9-2 to 9-5, and the implementation number 9-7 to 9-9 in which the X value is in the range of 0.63 to 2.07 are used. Induced. In the case of the embodiments Nos. 9-1 and 9 ᅳ 6 containing the compound having less than 8 carbon atoms of the lipophilic crystalline hydrocarbon group as the liquid crystal vertical alignment inducing agent, the X value is included in the range of 6.0 or less, Vertical alignment of the liquid crystal was not induced.

Since the composition for forming a liquid crystal layer used in the test examples does not include a photoreactive group, an additional process for photostabilization was not performed.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvement forms of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.

[Description of the code]

1, Γ, 11, 11 ': substrate

2, 2 ', 12, 12': electrode

3, 3 ': polymer alignment film

4, 23: liquid crystal layer

13: composition for liquid crystal layer formation

13a: first liquid crystal layer

13b, 13b ': liquid crystal vertical alignment and light stabilization layer

Industrial availability

The present invention relates to a liquid crystal vertical alignment guide and a liquid crystal display device manufactured using the same. The liquid crystal vertical alignment guide can be uniformly dispersed in the liquid crystal host by forming a self-assembled microassembly in the liquid crystal host. When forming the liquid crystal layer, it is possible to induce vertical alignment of the liquid crystal host without stabilizing the alignment layer, stabilize the pretilt angle of the liquid crystal, and as a result, simplify the manufacturing process of the liquid crystal display and improve the performance and reliability of the liquid crystal display. .

Claims

Claims [Claim 1] A lipophilic crystal comprising a lipophilic region including a lipophilic crystalline group having a high chemical affinity for a liquid crystal host and a non-lipophilic crystalline region including a non-lipophilic crystalline group having a low affinity for a liquid crystal host. At least one lipophilic crystalline compound, at least one of the lipophilic crystalline non-lipophilic crystalline compounds includes at least one lipophilic crystalline group having 8 or more carbon atoms in the lipophilic crystalline region, Liquid crystal vertical orientation inducers having a non-liquid crystalline ratio (Χ ') of 0.5 to 6, calculated according to:

[Equation 1] fcj |; i 聽: | ¾o

In Equation 1,

[Equation 1-1]

Molecular weight of the corresponding compound

x = ^ ■ — cio

^ Sugar compound and ^ ja ^ Y is the weight ratio of any one of lipophilic crystalline-non-lipophilic crystalline compounds constituting the liquid crystal vertical alignment inducing agent, Is calculated accordingly. '^'

[Equation 1-2]

Weight of fructose compound

Y =

Total weight of compounds

[Claim 2]

The method of claim 1 The lipophilic group may be a linear, branched or cyclic substituted or unsubstituted saturated or unsaturated hydrocarbon group having 8 to 30 carbon atoms; A substituted or unsubstituted heteroalkyl group having 8 to 30 carbon atoms, a heterocycle group and a heteroaromatic group containing at least one hetero atom selected from the group consisting of N, 0, P, S and Si in a molecule; And a liquid crystal vertical alignment inducing agent selected from the group consisting of a combination thereof.

[Claim 3]

The method of claim 1,

The lipophilic group may be substituted or unsubstituted with a halogen atom, having 8 to 30 carbon atoms, an alkyl group, an alkenylalkyl group, an alkynylalkyl group, a cycloalkyl group, an aryl group and an arylalkyl group; Intramolecular carbonyl group (_C (= 0) —), ester group (-C (= 0) 0-), ether group (-0-), ethylene oxide group (-CH ₂ CH ₂ 0-), azo group (-N = N-), -COS- and S-C8 heteroalkyl group, heterocycloalkyl group and heteroaryl group containing a hetero atom-containing functional group selected from the group consisting of; And a liquid crystal vertical alignment guide agent selected from the group consisting of a combination thereof.

[Claim 4]

According to claim 1,

The non-lipophilic crystalline group is alcohol, polyhydric alcohol, amine, polyamine, carboxylic acid, polycarboxylic acid, silane compound, siloxane compound, polyethylene glycol, polypropylene oxide, fluorinated carbon compound, thiol, polyvalent thiol , Liquid crystal vertical alignment inducing agent which is a functional group derived from a compound selected from the group consisting of sulfonic acid, sulfuric acid, phosphonic acid and phosphoric acid.

[Claim 5]

The method of claim 1,

The non-lipophilic group may be selected from 1-ol (l-ol), 1,2-diol (l, 2-diol), and glycerol.

glycerol, glucose, dextrose,

sorbitol, pent aerythr i to 1

(dipentaerythr itol), tripentaerythr (tr ipent aerythr i tol), sorbitan, fluctose, sucrose, gallic acid, glucopyranoside ( Liquid crystal vertical alignment inducing agent which is a functional group derived from a compound selected from the group consisting of glucopyranoside, ascorbic acid, mannide and maltoside.

[Claim 6] The method of claim 1,

The non-lipophilic groups include 1-amine, 1, 2-diamine, 1,3-diamine, 1,3-diamine, ethylene diamine, and di-amine. Diethylene diamine, tris (2-aminoethyl) amine (tris (2—

aminoethy 1) amine), cyclohexane diamine, diethylene triamine, phenyldiamine, phenyltriamine, 1,3,5 phenyltriazine 4, 6-diamine (1, 3, 5-tri az ine 4, 6-diamine), 1,3,5-triazine 2, 4, 6-triamine (1, 3, 5-tri az ine 2,4,6- triamine Liquid crystal vertical alignment inducing agent which is a functional group derived from a compound selected from the group consisting of

[Claim 7]

The method of claim 1,

The non-liquid crystalline group is tris (trimethylsiloxy) silane

Liquid crystal vertical alignment inducing agent which is a functional group derived from tris (trimethylsiloxy).

[Claim 8]

The method of claim 1,

The non-lipophilic crystalline group is a liquid crystal vertical alignment inducing agent which is a functional group derived from a linear, branched or cyclic siloxane compound containing 1 to 10 siloxy groups of Formula 1 below:

[Formula 1]

(In Formula 1, Ra and Rb are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a siloxy group, and combinations thereof, m is an integer of 1 to 10)

[Claim 9]

According to claim 1,

The non-lipophilic group includes a linear polyoxyethylene having 4 to 40 carbon atoms of Formula 2a or a cyclic polyethylene glycol having 4 to 10 carbon atoms of Formula 2b including 2 to 20 ethylene oxide groups. liquid crystal vertical alignment inducing agent which is a functional group derived from ether)

[Formula 2a]

Formula

(In Formulas 2a and 2b, m is an integer of 2 to 20, n is an integer of 2 to 5)

[Claim 10]

The method of claim 1,

The non-lipophilic crystalline group is a liquid crystal vertical alignment inducing agent which is a functional group which is a perfluoroalkyl group or a perfluoroaryl group derived from a fluorocarbon compound having 4 to 20 carbon atoms containing 9 to 41 fluoro groups.

[Claim 11]

The non-lipophilic crystalline group of claim 1, wherein 1-thiol, 1,2-dithiol, thioglycerol, or thiopentaerythritol are used.

(thiopentathiopentaerythritol) and dithiothracene (di thiothrei tol) is a vertical group of liquid crystals derived from a compound selected from the group consisting of

ΤΓ Apprenticeship.

[Claim 12]

The method of claim 1,

The non-lipophilic group is 1-carboxylic acid (1-carboxylic acid), 1,2-dicarboxylic acid (1,2-dicarboxylyc acid), 1,3-dicarboxylic acid (1,3-dicarboxylyc acid) benzene Carboxylic acid, benzenedicarboxylic acid

(benzenedicarboxyl ic acid), 1,2,3-tricarboxylic acid (1,2,3-tr icarboxyl ic acid), benzenetricarboxylic acid, malic acid, maleic acid acid), tartar acid, citric acid, maleamic acid, glutamic acid

liquid crystal vertical, which is a functional group derived from a compound selected from the group consisting of (glutamic acid), agaric acid, aconitic acid, tricarballylic acid, and amino acid Orientation inducing agent.

[Claim 13]

According to claim 1,

The lipophilic-non-lipophilic crystalline compound is a liquid crystal vertical alignment inducing agent is selected from the group consisting of compounds of the following formulas 3a to 3i and mixtures thereof:

[Formula 3a]

[Formula 3b]

[Formula 3d]

[Formula 3ί]

[Formula 3g]

(R7) d-@ — (T) b

[Formula 3h]

Formula

Formula 3a to

Ri to R ₉ each independently represent an alkyl group having 8 to 30 carbon atoms; C8-C30 alkenylalkyl group; An alkynylalkyl group having 8 to 30 carbon atoms; Arylalkyl group having 8 to 30 carbon atoms; A cycloalkyl group having 8 to 30 carbon atoms; Aryl groups having 8 to 30 carbon atoms; Intramolecular carbonyl group (-C (= 0)-), ester group (-C (= 0) 0—), ether group (-0—), ethylene oxide group (-CH ₂ CH ₂ 0-), azo group (- N = N-), a heteroalkyl group having 8 to 30 carbon atoms, a heteroacycloalkyl group or a heteroaryl group including a heteroatom-containing functional group selected from the group consisting of -COS- and -S-; And it is selected from the group consisting of a combination thereof,

Xi, ¾,, X ₇ , X ₈ and Xg are each independently, -0-, -S-, -C00-, -C0NH-, -C ₆ H ₄ 0-, -C ₆ H ₄ C00-,- C ₆ H ₄ C0NH- and selected from the group consisting of a single bond,

¾ and X ₄ are each independently selected from the group consisting of a single bond, -0- and -C ₆ H ₄ 0-,

X ₆ is a single bond, _0CH ₂ CH _2- , -CH ₂ CH ₂ —, -C ₆ H ₄ 0CH ₂ CH _2- , -C ₆ H ₄ C00CH ₂ CH ₂ -and-(SiRaRb) -CH ₂ CH ₂ (Wherein Ra and Rb are each hydrogen or an alkyl group having 1 to 3 carbon atoms),

PA, PAm, PS, PEO, FC, PT, CA and SP are non-lipophilic crystalline groups which form a covalent bond with each of directly or through a linking group of) d to ¾, respectively, wherein PA is 1 to 8 carbon atoms containing 1 to 8 hydroxyl groups. A functional group derived from an alcohol of 1 to 30 or a polyhydric alcohol,

PS is a functional group derived from a silane compound having 1 to 20 carbon atoms containing 2 to 10 silyl groups or derived from a linear, branched or cyclic siloxane compound containing 1 to 10 siloxy groups. It's a small container,

[Formula 2a]

-CH, CH ₂ -0¾

[Formula 2b]

(In Formulas 2a and 2b, m is an integer of 2 to 20, n is an integer of 2 to 5)

PT is a functional group derived from a tee and a polyvalent thiol having 1 to 20 carbon atoms containing 1 to 8 thiol groups,

CA is a functional group derived from carboxylic acid having 1 to 10 carbon atoms and polyvalent carboxylic acid containing 1 to 4 carboxylic acid groups,

SP is a functional group derived from a sulfonic acid or polyhydric sulfonic acid having 1 to 10 carbon atoms containing 1 to 3 sulfonic acid groups, or a sulfuric acid or polyvalent sulfur having 1 to 10 carbon atoms containing 1 to 3 sulfonic acid groups Is a functional group derived from lactic acid, or a functional group derived from phosphonic acid or polyhydric phosphonic acid having 1 to 10 carbon atoms containing 1 to 3 phosphonic acid groups or 1 to 3 carbon atoms containing 1 to 3 phosphoric acid groups It is a functional group derived from the phosphoric acid or polyhydric phosphoric acid of 10, and said al-a9 and bl-b9 are the numbers which show the number of the said functional groups, and are each independently an integer of 1-3.

[Claim 14]

The method of claim 1,

Liquid crystal vertical alignment inducing agent wherein the lipophilic-non-lipophilic crystalline compound is selected from the group consisting of the following compounds:

Sorbitan monolaurate;

Sorbitan monopalmitate;

Sorbitan monostearate;

Sorbitan tristearate;

Sorbitan monooleate;

Sorbitan sesquioleate;

Sorbitan trioleate;

Polyoxyethylene sorbitan tristearate;

Polyoxyethylene sorbitan trioleate;

Polyoxyethylene sorbitan stearate;

Polyoxyethylenesorbitan oleate; Dihexadecanoyl glycerol (dipalmitin); Dioctadecanoyl glycerol;

Dileoyl glycerol;

Octyl gallate;

Lauryl gallate;

Ascorbic acid 6-palmitate;

Manide monooleate;

1,2-dodecanediol (1,2-1) 0 (1 ^^ 6 (1101);

1,2-nucleatedcandi (1,2- ^ 8 (1 ^ 31 ^ 01);

Nuxadecane 1,2 diamine (Hexadecane 1, 2-di amine);

Octanoic acid;

Decanoic acid;

Dodecanoic acid;

Nuclear "decanoic acid (Hexadecanoic acid, Palmitic acid);

Octadecanoic acid (Stearic acid);

Dihexadecyl phosphate;

Hexadecyl sulfonic acid;

Dodecylbenzene sulfonic acid;

1-decanol;

1-dodecane (1-Dodecanol);

1-nucledecane (1-Hexadecanol);

1-octadecanol (1-Oc t adecano 1);

Octylamine;

Decylamine;

Dodecyl amine;

Methacryloxy methy lpenethyl tris (trimethylsi loxy) si lane isomer; methyl octadecyl bis (trimethylsiloxy) silane (methyl-octadecyl

bis (tr imethylsi loxy) si lane);

Polyoxyethylenesorbitane tr i stearate;

Dodecylphenyl sulfonic acid;

Gallate derivative of Formula 3j;

Polyoxyethylen (2) stearyl ether;

Decyl gal late; Palmitic acid.

[Claim 15]

The method of claim 1,

The liquid crystalline-non-lipophilic compound further comprises a photoreactive group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region.

[Claim 16]

The method of claim 15,

Liquid crystal vertical alignment inducing agent wherein the photo-banung group is selected from the group consisting of acryl group, methacryl group, cinnamate group, coumarin group chacon group, vinyl group, thiol group, en group, diene group, thiene group, and acetylene group.

[Claim 17]

The method of claim 15,

The lipophilic-non-lipophilic crystalline compound is a photo-banung lipophilic crystalline-non-lipophilic crystalline compound further comprising a photobanung group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region,

The photo-banung lipophilic crystalline-non-lipophilic crystalline compound is selected from the group consisting of the following liquid crystal vertical alignment inducer:

Pentaerythritol to pentaerythritol diacrylate monostearate;

Pentaerythritol monopentathritol monoacrylate monostearate;

Glucosyl methacrylate (methacryloctyloxyphenolglucose) or derivatives thereof;

[4- (methacryloyloxymethyl) phenyl] ethyl-tris (trimethylsiloxy) silane ([4- (methacryloyloxymethyl) phenyl] ethyl-tris (trimethylsiyloxy) si 1 ane)); methacryloxymethylphene Ethyltris (trimethylsiloxy) silane

(methacryloxymethylphenethyl tr i s (tr imethylsi loxy) si lane).

[Claim 18]

The method of claim 17,

The photoreactive lipophilic-non-liquid crystalline compound is a liquid crystal vertical alignment inducer is included in an amount of 3 to 100% by weight based on the total amount of the liquid crystal vertical alignment derivative.

[Claim 19]

The method of claim 1, Wherein the liquid crystal vertical alignment inducer further comprises a second photoliquid crystalline -non-liquid crystalline compound selected from the group consisting of the following compounds:

Pentaerythritol tr iacrylate; pentaerythritol tetraacrylate; poly (ethylene glycol) methyl ether methacry 1 at e;

Poly (ethylene glycol) methyl ether acrylate;

Hydroxybutyl acrylate;

A glycerol derivative of the formula 4j;

Glycosyloxyethyl methacrylate; Tridecafluorooctyl

methacrylate); and

Poly (ethylene glycol) methyl ether methacrylate.

[Claim 20]

According to claim 1,

Liquid crystal vertical alignment inducer wherein the liquid crystal vertical alignment inducer further comprises a second lipophilic-non-liquid crystalline compound selected from the group consisting of the following compounds:

Hexyl gal late;

n-dodecyl β-D-mal toside;

Propyl gal late;

1, 2-hexanedi (1, 2-Hexanedi o 1);

Hexanoic acid;

1-nuxanol;

1-Hexylamine;

1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane (1,3-bis (3-methacryloxypropyl) tetraki s (tr imethy lsi loxy) di s i loxane);

3-methacryloxypropylpentamethyldisiloxane (3-methacryloxypropyl

pentamethyl disi loxane); (3-acryloxypropyl) tris (trimethylsiloxy) silane ^ -acryloy loxypropy 1) tris (tr imethylsi loxy) si lane); and

(3-methacrylamidopropyl) bis (trimethylsiloxy) methylsilane ((3-methacryl ami dopropyl) bis (trimethylsi 1 oxy) methy 1 s i lane).

[Claim 21]

Liquid crystal host; And

A lipophilic-non-lipophilic compound comprising a lipophilic crystalline region including a lipophilic crystalline group having a high chemical affinity for a liquid crystal host and a non-lipophilic crystalline region including a non-lipophilic crystalline group having a low affinity for a liquid crystal host. At least one of the above-mentioned lipophilic crystalline non-lipophilic crystalline compounds includes at least one lipophilic crystalline group having 8 or more carbon atoms in the lipophilic crystalline region, and is calculated according to Equation 1 below. Composition for forming a liquid crystal layer comprising a liquid crystal vertical alignment guide having a sex ratio (χ ') of 0.5 to 6.

[Equation 1]

In Equation 1,

n is an integer equal to or greater than 1 indicating the number of lipophilic-non-liquid crystalline compounds total constituting the liquid crystal vertical alignment inducing agent,

[Equation 1-1]

Molecular weight of non-separable liquid crystalline group

X = —— ΧΪ0

^ Weight of the unit

[Equation 1-2]

Weight of the compound

Y =

O | 2E

-ϊ-Γ

i = d s s― I o o o

[Claim 22] The method of claim 21,

The liquid crystal layer forming composition wherein the liquid crystal vertical alignment inducing agent is dispersed in the liquid crystal host in the form of a fine assembly stabilized by self-assembly.

[Claim 23]

The method of claim 21,

The composition for forming a liquid crystal layer, wherein the lipophilic-non-lipophilic crystalline compound further includes an optical semi-animal group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region.

[Claim 24]

The method of claim 21, wherein.

The composition for forming a liquid crystal layer, wherein the liquid crystal vertical alignment inducing agent is contained in an amount of 0.01 to 5 weight ¾ with respect to the total weight of the composition for forming a liquid crystal layer.

[Claim 25]

An electrode forming step of forming first and second electrodes on the first substrate and the second substrate, respectively; And

The first substrate and the second substrate including the first and second electrodes, respectively, are bonded to each other by facing each other, and then the liquid crystal layer forming composition is injected into the space between the first substrate and the second substrate, or A liquid crystal layer is formed by dropping the liquid crystal layer forming composition under vacuum with respect to any one of the first substrate and the second substrate including the first and second electrodes, respectively, and then bonding the remaining substrates so that the electrodes face each other. Including manufacturing step,

The liquid crystal layer forming composition

Liquid crystal host, and

A lipophilic-non-lipophilic compound comprising a lipophilic crystalline region including a lipophilic crystalline group having a high chemical affinity for a liquid crystal host and a non-lipophilic crystalline region including a non-lipophilic crystalline group having a low affinity for a liquid crystal host. At least one of the lipophilic-non-lipophilic crystalline compounds include at least one lipophilic crystalline group having 8 or more carbon atoms in the lipophilic crystalline region, and A liquid crystal display device manufacturing method comprising a liquid crystal vertical alignment guide having a liquid crystal ratio (χ ') of 0.5 to 6.

[Equation 1]

Η | u | ¾ (X ') ί-V),

X is one of the lipophilic-non-liquid crystalline compounds constituting the liquid crystal vertical alignment inducing agent. Ha

Supernatant

Instrument,

The non-lipophilic crystalline ratio of any one of the lipophilic-non-lipophilic crystalline compounds is calculated according to Equation 1-1 below,

[Equation 1 ᅳ 1]

[Equation 1-2]

Weight of Failed Unit

Ϋ = ： ^■

1% of harmony

[Claim 26]

The method of claim 25,

The composition for forming a liquid crystal layer is a method of manufacturing a liquid crystal display device in which the liquid crystal vertical alignment inducing agent is dispersed in the liquid crystal host in the form of a fine assembly stabilized by self-assembly.

[Claim 27]

The method of claim 25,

And wherein the lipophilic-non-lipophilic crystalline compound further comprises a photoreactive group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region.

[Claim 28]

The method of claim 25,

The liquid crystal display of claim 1, wherein the liquid crystal vertical alignment inducing agent is contained in an amount of 0.01 to 5% by weight based on the total weight of the composition for forming a liquid crystal layer.

[Claim 29]

The method of claim 25,

The manufacturing method of the liquid crystal display device further comprising the step of applying an electric field between the first substrate and the second substrate after the assembly and light irradiation.

[Claim 30]

A first substrate and a second substrate positioned opposite to each other;

First and second electrodes formed on opposite surfaces of the first substrate and the second substrate, respectively; And

A liquid crystal layer interposed between the first substrate and the second substrate, the liquid crystal layer comprising: a liquid crystal host; and

Containing a lipophilic group that is chemically affinity for the host At least one lipophilic-non-lipophilic crystalline compound comprising a lipophilic crystalline region and a non-lipophilic crystalline region including a non-lipophilic crystalline group having a low affinity for a liquid crystal host, wherein the lipophilic-non-lipophilic crystalline At least one of the compounds includes at least one lipophilic crystalline group having 8 or more carbon atoms in the lipophilic crystalline region, and a liquid crystal vertical alignment inducing agent having a non-lipophilic crystalline ratio (Χ ') calculated according to Equation 1 below. Liquid crystal display comprising a.

[Equation 1]

In Equation 1,

[Equation 1-1]

Molecular weight of non-lipophilic crystalline group in the compound

X = ~ ―—— X 10

^ Volume of Sea Compound

[Equation 1—2]

Hi!

Y = ——

¾ of unity wool

[Claim 31]

The method of claim 30,

The lipophilic-non-lipophilic crystalline compound is a photoreactive lipophilic-non-lipophilic crystalline compound further comprising a photoreactive group in at least one of the lipophilic crystalline region and the non-lipophilic crystalline region,

Wherein the liquid crystal layer further comprises a photopolymer of the photo-banung lipophilic-non-liquid crystalline compound.

[Claim 32]

The method of claim 30, The liquid crystal display device further comprises a vertical alignment and light stabilization layer of the liquid crystal comprising a liquid crystal vertical alignment guide between the liquid crystal layer and the first or second electrode.

[Claim 33]

The method of claim 30,

A liquid crystal display device in which one or both of the first and second electrodes are patterned.

[Claim 34]

A method of inducing vertical alignment of liquid crystals having alignment stability by using a composition for forming a liquid crystal layer in which a liquid crystal vertical alignment inducing agent forms a microassembly by self-assembly and is uniformly dispersed in a liquid crystal host.

[Claim 35]

A method of inducing vertical alignment and photo stabilization of a liquid crystal using a composition for forming a liquid crystal layer in which a photoreactive liquid crystal vertical alignment inducing agent forms a microassembly by self-assembly and is uniformly dispersed in a liquid crystal host.

[Claim 36]

The self-assembly liquid crystal vertical alignment inducing agent forms a microassembly by self-assembly and applies an electric field to the composition for forming a liquid crystal layer uniformly dispersed in the liquid crystal host, and irradiates light between the liquid crystal layer and the electrode layer by applying light irradiation. Formation of Liquid Crystal Vertical Orientation and Light Stabilization Layers.