# US 10,119,075 B2 · Liquid crystal display device and method for manufacturing the same

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- Number: US 10,119,075 B2
- Document ID: US10119075B2
- Status: Granted
- Kind: B2
- Application number: 15/023,149
- Filed: 2014-09-18
- Published: 2016-08-11
- Granted: 2018-11-06
- Earliest claimed: 2013-09-20
- Assignees: DIC Corporation
- Applicants: DIC Corporation
- Inventors: Shinji Ogawa; Yoshinori Iwashita; Takeshi Kuriyama; Hyobok Cha
- Web page: https://patentgrep.com/patent/US10119075B2

## CPC

- C08F 222/1025: {of aromatic dialcohols}
- C09K 19/2014: {containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-}
- C09K 19/3003: {Compounds containing at least two rings in which the different rings are directly linked (covalent bond)}
- C09K 19/56: Aligning agents
- G02F 1/133707: {Structures for producing distorted electric fields, e.g. bumps, protrusions, recesses, slits in pixel electrodes}
- G02F 1/133753: {with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle}
- G02F 1/133788: {by light irradiation, e.g. linearly polarised light photo-polymerisation}
- G02F 1/1341: Filling or closing of cells
- G02F 1/134309: {characterised by their geometrical arrangement}
- C09K 2019/0448: {the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate}
- C09K 2019/122: {Ph-Ph}
- C09K 2019/123: {Ph-Ph-Ph}
- C09K 2019/3004: {Cy-Cy}
- C09K 2019/3009: {Cy-Ph}
- C09K 2019/301: {Cy-Cy-Ph}
- C09K 2019/3016: {Cy-Ph-Ph}
- C09K 2019/3027: {Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene}
- G02F 1/133514: {Colour filters}
- G02F 1/133723: {Polyimide, polyamide-imide}
- G02F 1/133742: {for homeotropic alignment}
- G02F 1/133761: {with different pretilt angles}
- G02F 1/13415: {Drop filling process}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS

## Abstract

A liquid crystal display device with few drop marks left during manufacture is provided without degrading the image-sticking characteristics of the liquid crystal display device or other characteristics fundamental to liquid crystal display devices, such as dielectric anisotropy, viscosity, upper nematic phase temperature limit, and rotational viscosity (γ1), and a method for manufacturing such a liquid crystal display device is also provided. A liquid crystal display device 10 according to the present invention includes a first substrate 11, a second substrate 12, a liquid crystal composition layer 13 disposed therebetween, and vertical alignment layers 16 and 17 containing a polymer of a monofunctional reactive-group-containing polymerizable compound and a polyfunctional reactive-group-containing polymerizable compound.

## Claims

### Claim 1

A liquid crystal display device comprising a first substrate having a common electrode, a second substrate having a pixel electrode, and a liquid crystal composition layer disposed between the first and second substrates, wherein a charge is applied across the common electrode and the pixel electrode substantially perpendicularly to the first and second substrates to control liquid crystal molecules in the liquid crystal composition layer,
at least one of the first and second substrates having a vertical alignment layer that controls the orientation of the liquid crystal molecules in the liquid crystal composition layer substantially perpendicularly to surfaces of the first and second substrates adjacent to the liquid crystal composition layer, the vertical alignment layer comprising a polymer of a monofunctional reactive-group-containing polymerizable compound and a polyfunctional reactive-group-containing polymerizable compound,
wherein the monofunctional reactive-group-containing polymerizable compound is a polymerizable compound represented by general formula (VI):
(wherein X3 is hydrogen or methyl; Sp3 is a single bond, an alkylene group of 1 to 8 carbon atoms, or —O—(CH2)t— (wherein t is an integer of 2 to 7, and the oxygen atom is linked to the aromatic ring); V is a linear or branched polyvalent alkylene group of 2 to 20 carbon atoms or a polyvalent cyclic substituent of 5 to 30 carbon atoms, wherein the alkylene group in the polyvalent alkylene group is optionally substituted with oxygen such that no oxygen atoms are adjacent to each other, is optionally substituted with an alkyl group of 5 to 20 carbon atoms (wherein the alkylene group in the group is optionally substituted with oxygen such that no oxygen atoms are adjacent to each other), and is optionally substituted with a cyclic substituent; and W is hydrogen, halogen, or an alkylene group of 1 to 8 carbon atoms); and
wherein the polyfunctional reactive-group-containing polymerizable compound is a polymerizable compound represented by general formula (V):
(wherein X1 and X2 are each independently hydrogen or methyl; Sp1 and Sp2 are each independently a single bond, an alkylene group of 1 to 8 carbon atoms, or —O—(CH2)s— (wherein s is an integer of 2 to 7, and the oxygen atom is linked to the aromatic ring); U is a linear or branched polyvalent alkylene group of 2 to 20 carbon atoms or a polyvalent cyclic substituent of 5 to 30 carbon atoms, wherein the alkylene group in the polyvalent alkylene group is optionally substituted with oxygen such that no oxygen atoms are adjacent to each other, is optionally substituted with an alkyl group of 5 to 20 carbon atoms (wherein the alkylene group in the group is optionally substituted with oxygen such that no oxygen atoms are adjacent to each other), and is optionally substituted with a cyclic substituent; and k is an integer of 1 to 5).

### Claim 2 (depends on 1)

The liquid crystal display device according to claim 1, wherein the liquid crystal display device has a plurality of pixels, each comprising two or more domains with different pretilt angles.

### Claim 3 (depends on 1)

The liquid crystal display device according to claim 1, wherein the vertical alignment layer further comprises a polyimide structure.

### Claim 4 (depends on 1)

The liquid crystal display device according to claim 1, wherein the vertical alignment layer is disposed on each of the surfaces of the first and second substrates adjacent to the liquid crystal composition layer, and the first substrate has a color filter layer.

### Claim 5 (depends on 1)

The liquid crystal display device according to claim 1, wherein the pixel electrode has a comb-like pattern of slits extending from the center of the pixel in four directions and has four domains in which the liquid crystal molecules in the liquid crystal composition layer are oriented in different directions.

### Claim 6 (depends on 1)

The liquid crystal display device according to claim 1, wherein the liquid crystal composition layer is formed by one-drop filling process.

### Claim 7 (depends on 1)

The liquid crystal display device according to claim 1, wherein the liquid crystal composition layer comprises a liquid crystal composition comprising a compound represented by general formula (I):
(wherein R1 are R2 are each independently an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an alkenyloxy group of 2 to 8 carbon atoms; A is 1,4-phenylene or trans-1,4-cyclohexylene; and 1 is 1 or 2, wherein if 1 is 2, each A may be the same or different) and a compound represented by general formula (II):
(wherein R3 is an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an alkenyloxy group of 2 to 8 carbon atoms; R4 is an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 4 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an alkenyloxy group of 3 to 8 carbon atoms; B and D are each independently 1,4-phenylene or trans-1,4-cyclohexylene; Z2 is a single bond, —OCH2—, —OCO—, —CH2O—, or —COO—; and m is 0, 1, or 2, wherein if m is 2, each B may be the same or different).

### Claim 8 (depends on 7)

The liquid crystal display device according to claim 7, wherein the compound represented by general formula (I) is present in the liquid crystal composition in an amount of 30% to 60% by mass, and the compound represented by general formula (II) is present in the liquid crystal composition in an amount of 30% to 65% by mass.

### Claim 9 (depends on 7)

uid crystal display device according to claim 7, wherein the liquid crystal composition further comprises 5% to 20% by mass of a compound represented by general formula (III):
(wherein R7 and R8 are each independently an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an alkenyloxy group of 2 to 8 carbon atoms; Y1 and Y2 and each independently hydrogen or fluorine; E, F, and G are each independently 1,4-phenylene or trans-1,4-cyclohexylene; Z3 is a single bond, —OCH2—, —OCO—, —CH2O—, or —COO—; and n is 0 or 1).

### Claim 10

A method for manufacturing a liquid crystal display device, comprising applying an alignment material comprising a monofunctional reactive-group-containing polymerizable compound, a polyfunctional reactive-group-containing polymerizable compound, and a vertical alignment material to at least one of a first substrate having a common electrode and a second substrate having a pixel electrode; heating the alignment material to form an alignment layer; providing a liquid crystal composition between the first and second substrates; and irradiating the liquid crystal composition with radiation to polymerize the polymerizable compounds in the alignment layer while applying a voltage across the common electrode and the pixel electrode, wherein
the monofunctional reactive-group-containing polymerizable compound is a polymerizable compound represented by general formula (VI):
(wherein X3 is hydrogen or methyl; Sp3 is a single bond, an alkylene group of 1 to 8 carbon atoms, or —O—(CH2)t— (wherein t is an integer of 2 to 7, and the oxygen atom is linked to the aromatic ring); V is a linear or branched polyvalent alkylene group of 2 to 20 carbon atoms or a polyvalent cyclic substituent of 5 to 30 carbon atoms, wherein the alkylene group in the polyvalent alkylene group is optionally substituted with oxygen such that no oxygen atoms are adjacent to each other, is optionally substituted with an alkyl group of 5 to 20 carbon atoms (wherein the alkylene group in the group is optionally substituted with oxygen such that no oxygen atoms are adjacent to each other), and is optionally substituted with a cyclic substituent; and W is hydrogen, halogen, or an alkylene group of 1 to 8 carbon atoms); and
the polyfunctional reactive-group-containing polymerizable compound is a polymerizable compound represented by general formula (V):
(wherein X1 and X2 are each independently hydrogen or methyl; Sp1 and Sp2 are each independently a single bond, an alkylene group of 1 to 8 carbon atoms, or —O—(CH2)s— (wherein s is an integer of 2 to 7, and the oxygen atom is linked to the aromatic ring); U is a linear or branched polyvalent alkylene group of 2 to 20 carbon atoms or a polyvalent cyclic substituent of 5 to 30 carbon atoms, wherein the alkylene group in the polyvalent alkylene group is optionally substituted with oxygen such that no oxygen atoms are adjacent to each other, is optionally substituted with an alkyl group of 5 to 20 carbon atoms (wherein the alkylene group in the group is optionally substituted with oxygen such that no oxygen atoms are adjacent to each other), and is optionally substituted with a cyclic substituent; and k is an integer of 1 to 5).

### Claim 11 (depends on 10)

The method for manufacturing a liquid crystal display device according to claim 10, wherein the radiation is ultraviolet radiation, and the liquid crystal composition is irradiated with the radiation at an intensity of 2 to 100 mW/cm−2 to a total dose of 10 to 300 J.

### Claim 12 (depends on 10)

The method for manufacturing a liquid crystal display device according to claim 10, wherein the compound represented by general formula (I) is present in the liquid crystal composition in an amount of 30% to 50% by mass, and the compound represented by general formula (II) is present in the liquid crystal composition in an amount of 30% to 50% by mass.