WO2014196589A1 - Method for producing substrate having liquid crystal alignment film for in-plane switching liquid crystal display elements - Google Patents
Method for producing substrate having liquid crystal alignment film for in-plane switching liquid crystal display elements Download PDFInfo
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- WO2014196589A1 WO2014196589A1 PCT/JP2014/064925 JP2014064925W WO2014196589A1 WO 2014196589 A1 WO2014196589 A1 WO 2014196589A1 JP 2014064925 W JP2014064925 W JP 2014064925W WO 2014196589 A1 WO2014196589 A1 WO 2014196589A1
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- 0 C*C(C)(C)c1ccc(C(C)(C)*(C)O*(C)C(*(C)*(C)(C)C)=O)cc1 Chemical compound C*C(C)(C)c1ccc(C(C)(C)*(C)O*(C)C(*(C)*(C)(C)C)=O)cc1 0.000 description 10
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
Definitions
- the present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element. More specifically, the present invention relates to a novel method for manufacturing a liquid crystal display device having excellent image sticking characteristics.
- the liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years.
- the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
- an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.
- the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates.
- the liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
- alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
- the rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction).
- This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements.
- an organic film used for the liquid crystal alignment film a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
- Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.
- a decomposition type photo-alignment method is known as a main photo-alignment method.
- the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see, for example, Patent Document 1).
- photocrosslinking type and photoisomerization type photo-alignment methods are also known.
- polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1).
- the liquid crystal alignment film alignment treatment method by the photo alignment method does not require rubbing, and there is no fear of generation of dust or static electricity.
- An alignment process can be performed even on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial production process.
- the photo-alignment method eliminates the rubbing process itself as compared with the rubbing method that has been used industrially as an alignment treatment method for liquid crystal display elements, and thus has a great advantage. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light.
- the photo-alignment method in order to achieve the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required or stable liquid crystal alignment may not be realized. .
- the present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate.
- the object of the present invention is a lateral electric field drive type liquid crystal element having high reliability that does not deteriorate characteristics such as voltage holding ratio even under severe conditions such as high temperature and high humidity. And providing a liquid crystal alignment film for the device.
- the (A) side chain polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure, In the cyclic amine structure, two carbon atoms adjacent to the nitrogen atom are each represented by the following formula (S) (wherein R 11 is a single bond or an optionally substituted hydrocarbon group; X is a single bond, an oxygen atom, a sulfur atom, —CO—, —CO—O— or —O—CO—, R 12 is an optionally substituted hydrocarbon group.
- R 11 and R 12 may be bonded to each other to form a ring structure.
- the phenol structure has a heavy structure in which at least one carbon atom in the ortho position relative to the hydroxyl group has a substituent represented by the following formula (S).
- S a substituent represented by the following formula (S).
- the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
- the first repeating unit is represented by the following formula (1-1) (in formula (1-1), R is a hydrogen atom or a methyl group, and R 11 is Each may be the same or different and have the same definition as above; X may each be the same or different and have the same definition as above; and R 12 is each the same.
- B 1 is a hydrogen atom, oxygen atom, halogen atom, hydroxyl group or monovalent organic group, and m is an integer of 0 to 4.
- the second repeating unit is represented by the following formula (1-2) (in the formula (1-2), R is a hydrogen atom or a methyl group, and R 11 may be the same or different. X may be the same or different, each having the same definition as above, and R 12 may each be the same or different and have the same definition as above. N is an integer of 0 to 3).
- the first repeating unit is represented by the following formula (1-1-1) (in the formula (1-1-1), R represents a hydrogen atom or methyl
- a 1 is a single bond or a divalent linking group
- R 13 may be the same or different, each is an alkyl group having 1 to 5 carbon atoms
- B 1 is a hydrogen atom
- the second repeating unit is represented by the following formula (1-2-1) (in the formula (1-2-1), R is a hydrogen atom or a methyl group
- a 1 is a single bond or a divalent linking group.
- R 13 is an alkyl group having 1 to 5 carbon atoms
- R 14 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6). Good.
- A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
- S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
- T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
- Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof
- the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a
- R 51 May be substituted with an alkyloxy group of R 51 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
- X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
- X may be the same or different;
- Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
- P or Q on the side to which —CH ⁇ CH— is bonded is an aromatic ring;
- the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
- l1 is 0 or 1;
- l2 is an integer from 0 to 2; when l1 and l2 are both 0,
- A represents a single bond when T is a single bond; when l1 is 1, B represents a single bond when T is a single bond;
- H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
- the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10): Good.
- the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13): Good.
- A, X, l, m, m1 and R 51 have the same definition as above.
- the component (A) preferably has a photosensitive side chain represented by the following formula (14) or (15).
- A, Y 1 , l, m1 and m2 have the same definition as above.
- the component (A) preferably has a photosensitive side chain represented by the following formula (16) or (17).
- A, X, l and m have the same definition as above.
- the component (A) preferably has a photosensitive side chain represented by the following formula (18) or (19).
- A, B, Y 1 , q1, q2, m1, and m2 have the same definition as above.
- R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
- the component (A) preferably has a photosensitive side chain represented by the following formula (20).
- A, Y 1 , X, l and m have the same definition as above.
- the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Good.
- A, B, q1 and q2 have the same definition as above;
- Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
- each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
- R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1
- ⁇ 16> a step of preparing the substrate (first substrate) of ⁇ 14>above;
- a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and two carbon atoms adjacent to a nitrogen atom are each represented by the following formula (S). At least one carbon atom ortho-positioned to the cyclic amine structure or hydroxyl group having two substituents is represented by the following formula (S) (wherein R 11 is a single bond or substituted): Is an optionally substituted hydrocarbon group, X is a single bond, oxygen atom, sulfur atom, —CO—, —CO—O— or —O—CO—, and R 12 is an optionally substituted carbon atom.
- substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
- the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
- the repeating unit is represented by the following formula (1-1) or (1-2) (in the formula (1-1) and the formula (1-2), R is a hydrogen atom or a methyl group
- a 1 is a single bond or a divalent linking group
- R 11 is a single bond or an optionally substituted hydrocarbon group
- X is a single bond, oxygen atom, sulfur, respectively.
- R 12 is an optionally substituted hydrocarbon group, provided that when X is not a single bond, R 11 And R 12 may be bonded to each other to form a ring structure, wherein B 1 is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group; Is an integer from 0 to 4. In formula (1-2), n is an integer from 0 to 3. Manufacturing method.
- the repeating unit is represented by the following formula (1-1-1) or (1-2-1) (in the formulas (1-1-1) and (1-2-1): , R is a hydrogen atom or a methyl group, A 1 is a single bond or a divalent linking group, R 13 is an alkyl group having 1 to 5 carbon atoms, and R 14 is a hydrogen atom or a carbon group. An alkyl group having a number of 1 to 5.
- B 1 is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group.
- the component (A) may have any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).
- A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
- S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
- T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
- Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof
- the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a
- R 51 May be substituted with an alkyloxy group of R 51 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
- X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
- Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and one is 0; q3 is 0 or 1; P and Q are each independently a single bond, a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof.
- I is a group selected from However, when X is —CH ⁇ CH—CO—O— or —O—CO—CH ⁇ CH—, P or Q on the side to which —CH ⁇ CH— is bonded is an aromatic ring; H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
- the component (A) preferably has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
- the component (A) preferably has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
- A, X, l, m and R 51 have the same definition as above.
- the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).
- A, Y 1 , X, 1, m1, and m2 have the same definition as above.
- the component (A) may have a photosensitive side chain represented by the following formula (16) or (17).
- A, X, l and m have the same definition as above.
- the component (A) may have a photosensitive side chain represented by the following formula (18) or (19).
- A, B, Y1, q1, q2, m1, and m2 have the same definition as above.
- R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
- the component (A) may have a photosensitive side chain represented by the following formula (20).
- A, Y 1 , X, l and m have the same definition as above.
- the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Good.
- A, B, q1 and q2 have the same definition as above;
- Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
- each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
- R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in the formulas (25) to (26), the sum of all m is 2 or more, and the formulas (27) to (28 ), The sum of all m
- ⁇ P13> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device manufactured by any of the above ⁇ P1> to ⁇ P12>.
- ⁇ P14> A lateral electric field drive type liquid crystal display device having the substrate of ⁇ P13> above.
- ⁇ P15> Step of preparing a substrate (first substrate) of ⁇ P13>above; [I ′] A polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent is applied onto a second substrate.
- ⁇ P16> A lateral electric field drive type liquid crystal display device manufactured according to the above ⁇ P15>.
- ⁇ P17> (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, wherein two carbon atoms adjacent to the nitrogen atom are each represented by the following formula (S) (wherein R 11 Is a single bond or an optionally substituted hydrocarbon group, X is a single bond, an oxygen atom, a sulfur atom, —CO—, —CO—O— or —O—CO—, and R 12 is A hydrocarbon group which may be substituted, provided that when X is not a single bond, R 11 and R 12 may be bonded to each other to form a ring structure.
- S A side chain polymer having the above repeating unit
- B an organic solvent.
- ⁇ P18> The composition according to ⁇ P17>, wherein the repeating unit is represented by the following formula (1-1) or (1-2).
- R is a hydrogen atom or a methyl group
- a 1 is a single bond or a divalent linking group
- R 11 is a single bond or a substituted group, respectively.
- X is a single bond, oxygen atom, sulfur atom, —CO—, —CO—O— or —O—CO—, respectively
- R 12 is each substituted It may be a hydrocarbon group. However, when X is not a single bond, R 11 and R 12 may be bonded to each other to form a ring structure.
- B 1 is a hydrogen atom, oxygen atom, halogen atom, hydroxyl group or monovalent organic group
- m is an integer of 0-4.
- n is an integer of 0 to 3.
- R is a hydrogen atom or a methyl group
- a 1 is a single bond or a divalent linking group
- R 13 is a carbon atom, respectively.
- R 14 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- B 1 represents a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group.
- a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics
- a horizontal electric field drive type liquid crystal display element having the substrate can do. Since the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even when continuously driven for a long time. Further, according to the present invention, in addition to the above-described effects, a lateral electric field drive type liquid crystal element having high reliability in which characteristics such as voltage holding ratio do not deteriorate even under severe conditions such as high temperature and high humidity, and the like A liquid crystal alignment film for the device can be provided.
- the polymer composition used in the production method of the present invention has a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter, also simply referred to as a side chain polymer), and the polymer composition
- the coating film obtained by using the product is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity.
- This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth a liquid crystal aligning film) to which the orientation control ability was provided through the process of heating the side chain type polymer film.
- the method for producing a substrate having the liquid crystal alignment film of the present invention is [I] (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) a polymer composition containing an organic solvent, particularly a liquid crystal alignment for a lateral electric field drive type liquid crystal display device A composition for producing a membrane,
- the (A) side chain polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure, In the cyclic amine structure, two carbon atoms adjacent to the nitrogen atom are each represented by the following formula (S) (wherein R 11 is a single bond or an optionally substituted hydrocarbon group; X is a single bond, an oxygen atom, a sulfur atom,
- R 11 and R 12 may be bonded to each other to form a ring structure.
- the phenol structure has a heavy structure in which at least one carbon atom in the ortho position relative to the hydroxyl group has a substituent represented by the following formula (S).
- a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.
- a lateral electric field drive type liquid crystal display element can be obtained.
- the second substrate instead of using a substrate having no lateral electric field driving conductive film instead of a substrate having a lateral electric field driving conductive film, the above steps [I] to [III] (for lateral electric field driving) Since a substrate having no conductive film is used, for the sake of convenience, in this application, the steps [I ′] to [III ′] may be abbreviated as steps), thereby providing a first liquid crystal alignment film having alignment controllability. Two substrates can be obtained.
- the manufacturing method of the horizontal electric field drive type liquid crystal display element is [IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween; Have Thereby, a horizontal electric field drive type liquid crystal display element can be obtained.
- step [I] a polymer composition containing a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and an organic solvent is applied onto a substrate having a conductive film for driving a lateral electric field. To form a coating film.
- ⁇ Board> Although it does not specifically limit about a board
- the substrate has a conductive film for driving a lateral electric field.
- the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
- examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
- a method for forming a conductive film on a substrate a conventionally known method can be used.
- a polymer composition is applied on a substrate having a conductive film for driving a lateral electric field, particularly on the conductive film.
- the polymer composition used in the production method of the present invention contains (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent.
- the component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range.
- the side chain polymer preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100 ° C. to 250 ° C.
- the (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
- the (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 250 ° C.
- the (A) side chain polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure.
- a first repeating unit having a cyclic amine structure two carbon atoms adjacent to the nitrogen atom each have two substituents represented by the above formula (S).
- the phenol structure has a substituent in which at least one of the carbon atoms ortho to the hydroxyl group is represented by the above formula (S).
- the number of the carbon atoms which form the ring structure is 2-7, More preferably, it is five.
- bonds in a benzene ring is arbitrary, Preferably it is a para-position with respect to the carbon atom couple
- the preferred structure of the repeating unit (a1) is a structure represented by the following formula (1-1) having a hindered amine structure when it has a cyclic amine structure.
- the preferred structure of the repeating unit (a1) is a structure represented by the following formula (1-1) having a hindered amine structure when it has a cyclic amine structure.
- it when it has a phenol structure, it has a hindered phenol structure and is a structure represented by the following formula (1-2).
- R is a hydrogen atom or a methyl group
- a 1 is a single bond or a divalent linking group
- B 1 is , Hydrogen atom, oxygen atom, halogen atom, hydroxyl group or monovalent organic group
- m is an integer of 0-4.
- n is an integer of 0 to 3.
- the definitions of R 11 , X and R 12 are the same as in the above formula (S).
- the hydrocarbon group of R 11 is specifically a divalent chain hydrocarbon group having 1 to 10 carbon atoms, Examples thereof include a divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Among these, a methylene group or an alkylene group having 2 to 5 carbon atoms is preferable. Specific examples of the alkylene group having 2 to 5 carbon atoms include an ethylene group, a propylene group, a butylene group, and a pentylene group, and these may be either linear or branched. Examples of the substituent that the hydrocarbon group may have include a halogen atom such as a fluorine atom or a chlorine atom, a hydroxyl group, and the like.
- R 12 is specifically an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or carbon.
- Examples of the aralkyl group include 7 to 13.
- the hydrogen atom of the benzene ring of the aryl group and the aralkyl group may be substituted with a formyl group or an alkoxy group having 1 to 4 carbon atoms.
- Examples of the alkyl group having 1 to 6 carbon atoms of R 12 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-butyl group, an i-butyl group, and a t-butyl group. Etc .;
- Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, 4-formylphenyl group, 3,4,5-trimethoxyphenyl group, and the like;
- Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group.
- Examples of the ring structure formed by combining R 11 and R 12 with each other include groups in which one hydrogen atom has been removed from furan, thiophene, 2H-pyran, 4H-pyran, and the like.
- —R 11 —XR 12 is preferably, for example, methyl group, ethyl group, n-propyl group, i-propyl.
- -R 11 -XR 12 is more preferably an alkyl group having 1 to 5 carbon atoms, and in the case of the above formula (1-1), a methyl group or an ethyl group is particularly preferable, and the above formula (1- In the case of 2), a methyl group or a t-butyl group is particularly preferable.
- n is preferably 0 or 1.
- the formula (1-1) and the formula (1-2) are preferably represented by the following formula (1-1-1). ) And the following formula (1-2-1).
- R 13 is an alkyl group having 1 to 5 carbon atoms
- R 14 is A hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the definitions of R, A 1 and B 1 are the same as in the above formula (1-1) and the above formula (1-2). )
- a 1 is preferably a divalent linking group.
- the divalent linking group represented by A 1 it may include those represented by the following formula (A1).
- a 11 is a single bond, a methylene group, an alkylene group having 2 to 5 carbon atoms, or a phenylene group
- a 12 is a single bond, —O—, —CO—, —CO—O—, or —O—CO—
- a 13 is a single bond or an optionally substituted methylene group or alkylene group having 2 to 5 carbon atoms
- a 14 is a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR′—, or —NR′—CO—O—, wherein R ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- * 1 represents a bond bonded to a carbon atom of a cyclic amine structure or a carbon atom of a phenol structure.
- examples of the alkylene group having 2 to 5 carbon atoms of A 11 and A 13 include those exemplified for R 11 above.
- examples of the substituent that the methylene group of A 13 or the alkylene group having 2 to 5 carbon atoms may have include those exemplified for the above R 11 .
- examples of the alkyl group of 1 to 6 carbon atoms for R ′ include those exemplified for R 12 above.
- Examples of the divalent linking group represented by the formula (A1) include, but are not limited to, groups represented by the formulas (A1-1) to (A1-17).
- * 1 represents a bond bonded to a carbon atom of a cyclic amine structure or a carbon atom of a phenol structure.
- the divalent linking group of A 1 is preferably a formula (A1-2) for suitably improving the durability of the obtained liquid crystal alignment film.
- Formula (A1-5), formula (A1-8), formula (A1-10), formula (A1-11), formula (A1-16) and formula (A1-17) More preferably, it is represented by any one of formula (A1-2), formula (A1-5) and formula (A1-10).
- examples of the halogen atom for B 1 include a fluorine atom and a chlorine atom.
- examples of the monovalent organic group for B 1 include those represented by the following formula (B1).
- B 11 is a single bond, —O—, —CO—, —CO—O—, —O—CO—, —O—CO—NR ′′ —, or —CO—NR ′′ —.
- R ′′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- B 12 is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a monovalent heterocyclic group having 3 to 10 carbon atoms, or 3 to 15 carbon atoms.
- the hydrogen atom which these groups have may be substituted.
- examples of the alkyl group having 1 to 6 carbon atoms represented by R ′′ include those exemplified for R 12 above.
- the alkyl group having 1 to 15 carbon atoms of B 12 may be linear or branched.
- the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, 4-ethylphenyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, and anthryl group
- Examples of the aralkyl group having 7 to 13 carbon atoms include benzyl group, phenethyl group, ⁇ -methylbenzyl group, naph
- each group of B 12 may have include a halogen atom such as a fluorine atom and a chlorine atom, a hydroxyl group, a nitro group, and a cyano group.
- Examples of the monovalent organic group (—B 11 —B 12 ) represented by the above formula (B1) include a methyl group, an n-butyl group, an n-pentyl group, a t-pentyl group, an n-octyl group, Benzyl group, 4-ethylphenyl group, 4-methylcyclohexyl group, methoxy group, octyloxy group, cyclohexyloxy group, acetyl group, acetyloxy group, tetradecanoyl group, ⁇ -methylbenzyloxy group, piperidinocarbonyl Group, morpholinocarbonyl group, 2-hydroxy-2-methylpropoxy group, —O—CONH—C 6 H 5 and the like.
- B 1 is preferably a hydrogen atom, an oxygen atom, a chlorine atom in order to suitably improve the durability of the obtained liquid crystal alignment film.
- Methyl group, n-butyl group, n-pentyl group, t-pentyl group, benzyl group, methoxy group, octyloxy group, acetyl group, acetyloxy group, cyclohexyloxy group more preferably hydrogen An atom, an oxygen atom, a methyl group, a benzyl group, or an octyloxy group.
- the repeating unit (a1) having a hindered amine structure is specifically represented by the following formulas (a1-1-1) to (a1-1-20) (wherein R is a hydrogen atom or a methyl group). Things can be mentioned.
- the monomer which gives the hindered amine structure repeating unit (a1) can be easily synthesized by combining organic chemistry methods.
- halogenated (meth) acryloyl and the following formula (C-1) (wherein , A 13 , A 14 , B 1 and R 13 are the same as those already described.) And can be obtained by reacting according to a known esterification reaction. .
- each of the above-mentioned monomers may be a commercially available one, for example, 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 1,2,2,6,6-methacrylic acid.
- Pentamethyl-4-piperidyl is commercially available from Hitachi Chemical Co., Ltd. as FA-712HM and FA-711MM, respectively.
- repeating unit (a1) having a hindered phenol structure include the following formulas (a1-2-1) to (a1-2-10) (wherein R is a hydrogen atom or a methyl group). Can be mentioned.
- the monomer that gives the hindered phenol structure repeating unit (a1) can be easily synthesized by combining organic chemistry methods.
- the repeating unit (a1) preferably has a hindered amine structure rather than a hindered phenol structure in order to improve the durability of the obtained liquid crystal alignment film.
- the polymer [A] may have the repeating unit (a1) alone or in combination of two or more.
- the ultraviolet ray irradiated from the backlight or the like is suitably absorbed by the polymer [A], and the ultraviolet ray
- the influence of is difficult to reach at least one polymer selected from the group consisting of a polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine and an imidized polymer thereof.
- the alignment performance of the liquid crystal can be maintained even for long-term use, and a liquid crystal display element having long-term durability can be obtained.
- the content ratio of the repeating unit (a1) in the polymer [A] (or the copolymerization ratio of the monomer giving the repeating unit (a1)) for enhancing the effect is the total weight of the polymer [A].
- the total weight of monomers used in the synthesis of the polymer [A] is preferably 1% by weight or more, more preferably 1% by weight or more and 50% by weight or less, and still more preferably Is 1 wt% or more and 30 wt% or less, and particularly preferably 1 wt% or more and 20 wt% or less.
- the side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement in response to light.
- the structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time.
- the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film.
- the polymer structure has, for example, a main chain and a side chain bonded to the main chain, and the side chain includes a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip.
- a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip.
- the main chain is preferably a structure having a main chain and a side chain comprising at least one of the following formulas (1) to (6).
- A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
- S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
- T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
- Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof
- the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a
- R 51 May be substituted with an alkyloxy group of R 51 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
- X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
- X may be the same or different;
- Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
- P or Q on the side to which —CH ⁇ CH— is bonded is an aromatic ring;
- the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
- l1 is 0 or 1;
- l2 is an integer from 0 to 2; when l1 and l2 are both 0,
- A represents a single bond when T is a single bond; when l1 is 1, B represents a single bond when T is a single bond;
- H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
- the side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
- the side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
- A, X, l, m, m1 and R 51 have the same definition as above.
- the side chain may be a photosensitive side chain represented by the following formula (14) or (15).
- A, Y 1 , l, m1 and m2 have the same definition as above.
- the side chain may be a photosensitive side chain represented by the following formula (16) or (17).
- A, X, l and m have the same definition as above.
- the side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
- A, B, Y 1 , q1, q2, m1, and m2 have the same definition as above.
- R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
- the side chain is preferably a photosensitive side chain represented by the following formula (20).
- A, Y 1 , X, l and m have the same definition as above.
- the (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
- A, B, q1 and q2 have the same definition as above;
- Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
- each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
- R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1
- the present application relates to compounds (1) to (11) represented by the following formulas (1) to (11) as photoreactive and / or liquid crystalline side chain monomers; and the following formulas (12) to (17):
- R represents a hydrogen atom or a methyl group
- S represents an alkylene group having 2 to 10 carbon atoms
- R 10 represents Br or CN
- S represents an alkylene group having 2 to 10 carbon atoms
- u represents Represents 0 or 1
- Py represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.
- V represents 1 or 2.
- the photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.
- the liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
- a mesogenic group having a side chain even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good.
- the mesogenic group possessed by the side chain the following structure is preferable.
- liquid crystalline side chain monomer examples include a main chain composed of at least one selected from the group consisting of hydrocarbon, (meth) acrylate, maleimide, norbornene and siloxane, and the above formula (21).
- a structure having a side chain composed of at least one of (31) to (31) is preferable.
- the side chain polymer can be obtained by the polymerization reaction of the above-described photoreactive side chain monomer that exhibits liquid crystallinity. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. it can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.
- Examples of other monomers include industrially available monomers capable of radical polymerization reaction. Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
- the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
- the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
- methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
- (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.
- Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
- Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
- Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- the production method of the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
- RAFT reversible addition-cleavage chain transfer
- the radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher.
- radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation).
- the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
- examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (
- the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
- the organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.
- organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer
- the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C.
- the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.
- the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
- the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
- the content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
- the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
- impurities in the polymer can be reduced.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the molecular weight of the (A) side chain polymer of the present invention is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film.
- the weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.
- the polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent.
- the resin component is a resin component containing a photosensitive side chain polymer capable of exhibiting the liquid crystallinity already described.
- the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
- the resin component described above may be a photosensitive side chain polymer that can all exhibit the above-described liquid crystallinity, but does not impair the liquid crystal developing ability and the photosensitive performance.
- Other polymers may be mixed within the range.
- the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
- examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.
- the organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone,
- the polymer composition used in the present invention may contain components other than the above components (A) and (B). Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
- the present invention is not limited to this.
- solvent poor solvent which improves the uniformity of film thickness and surface smoothness.
- solvents may be used alone or in combination.
- it is preferably 5% by mass to 80% by mass of the total solvent, more preferably so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. Is 20% by mass to 60% by mass.
- Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition
- the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
- phenoplasts and epoxy group-containing compounds for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed
- An agent may be contained in the polymer composition. Specific phenoplast additives are shown below, but are not limited to this structure.
- Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl- , 4'-diaminodip
- the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
- a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
- photosensitizers aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-b
- Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
- a dielectric, a conductive substance, or the like for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired.
- a crosslinkable compound may be added for the purpose of increasing the hardness and density of the liquid crystal alignment film.
- the method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
- the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like.
- Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
- the polymer composition After the polymer composition is applied on a substrate having a conductive film for driving a horizontal electric field, it is 50 to 200 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven.
- the solvent can be evaporated at 150 ° C. to obtain a coating film.
- the drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer. If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered.
- it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is. In addition, it is also possible to provide the process of cooling the board
- step [II] the coating film obtained in step [I] is irradiated with polarized ultraviolet rays.
- the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
- ultraviolet rays to be used ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used.
- the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used.
- ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
- the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
- the irradiation amount of polarized ultraviolet rays depends on the coating film used.
- the amount of irradiation is polarized ultraviolet light that realizes the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light.
- the amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.
- step [III] the ultraviolet-irradiated coating film polarized in step [II] is heated.
- An orientation control ability can be imparted to the coating film by heating.
- a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
- the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
- the heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature).
- the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk.
- the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C.
- the liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase).
- the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm for the same reason described in the step [I].
- the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board
- the step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving.
- the obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method.
- This is a step of manufacturing a lateral electric field drive type liquid crystal display element.
- a substrate having no lateral electric field driving conductive film was used in place of the substrate having the lateral electric field driving conductive film in the step [I].
- steps [I] to [III] It can be carried out in the same manner as in steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.
- the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
- the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
- Etc. can be illustrated.
- the diameter of the spacer at this time is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
- substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply
- the coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. .
- an embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is the first embodiment, a structure having a photofleece rearrangement group or a group causing isomerization as a photoreactive group
- An embodiment using the side chain type polymer will be referred to as a second embodiment.
- FIG. 1 schematically shows an anisotropic introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated to.
- FIG. 1 (a) is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light
- FIG. 1 (b) is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light
- FIG. 1 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the first aspect of the present invention.
- 1 is a schematic diagram when the ultraviolet ray irradiation amount in the step [II] is within a range of 1% to 15% of the ultraviolet ray irradiation amount that maximizes ⁇ A.
- FIG. 2 is a schematic illustration of anisotropy introduction treatment in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated to.
- FIG. 2A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light
- FIG. 2B is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light.
- FIG. 2 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is large, that is, the first aspect of the present invention.
- 1 is a schematic diagram when the ultraviolet ray irradiation amount in the step [II] is within a range of 15% to 70% of the ultraviolet ray irradiation amount that maximizes ⁇ A.
- FIG. 3 shows a side chain polymer having a structure having a photo-isomerizable group as a photoreactive group or a photo-Fleece rearrangement group represented by the above formula (18) in the second embodiment of the present invention. It is a figure of one example which illustrates typically the introduction process of anisotropy in the manufacturing method of the used liquid crystal aligning film.
- FIG. 3A is a diagram schematically showing the state of the side chain polymer film before polarized light irradiation
- FIG. 3B is a schematic diagram of the state of the side chain polymer film after polarized light irradiation.
- 3 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the first aspect of the present invention.
- 2 is a schematic diagram when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
- FIG. 4 shows the production of a liquid crystal alignment film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (19) as a photoreactive group in the second embodiment of the present invention. It is a figure of one example which illustrates typically the introduction processing of anisotropy in a method.
- FIG. 4A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light
- FIG. 4B is a schematic diagram of the state of the side chain polymer film after irradiation with polarized light.
- FIG. 4 (c) is a diagram schematically showing the state of the side-chain polymer film after heating.
- 2 is a schematic diagram when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
- the ultraviolet irradiation amount in the step [II] is in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ⁇ A.
- the coating film 1 is formed on the substrate.
- Fig.1 (a) in the coating film 1 formed on the board
- the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
- the coating film 3 is formed on the substrate. As shown in FIG. 2A, the coating film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the mesogenic components and the photosensitive groups of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.
- a side chain type having a structure having a photo-isomerizable group or a photo-Fleece rearrangement group represented by the above formula (18) in the treatment for introducing anisotropy into the coating film In the case of using a liquid crystal alignment film using a polymer, when the ultraviolet irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A, first, The coating film 5 is formed. As shown in FIG. 3A, the coating film 5 formed on the substrate has a structure in which the side chains 6 are randomly arranged. According to the random arrangement of the side chain 6 of the coating film 5, the mesogenic component and the photosensitive group of the side chain 6 are also randomly oriented, and the side chain type polymer film 5 is isotropic.
- liquid crystal alignment using a side chain type polymer having a structure having a light Fleece rearrangement group represented by the above formula (19) in the treatment for introducing anisotropy into the coating film In the case of using a film, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A, first, the coating film 7 is formed on the substrate. . As shown in FIG. 4A, the coating film 7 formed on the substrate has a structure in which the side chains 8 are arranged at random. According to the random arrangement of the side chains 8 of the coating film 7, the mesogenic components and the photosensitive groups of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.
- the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ⁇ A
- polarized ultraviolet rays are irradiated.
- the photosensitive group of the side chain 2a having the photosensitive group among the side chains 2 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like.
- Dimerization reaction or the like causes a photoreaction.
- the density of the side chain 2a that has undergone photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet light, and as a result, very small anisotropy is imparted to the coating film 1.
- the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A
- polarized ultraviolet rays are irradiated.
- the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like.
- the density of the side chain 4a that has undergone photoreaction increases in the polarization direction of the irradiated ultraviolet light, and as a result, a small anisotropy is imparted to the coating film 3.
- the density of the side chain 6a subjected to photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 5.
- the amount of ultraviolet irradiation in the step [II] is obtained using a coating film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (19). Is within the range of 1% to 70% of the amount of UV irradiation that maximizes ⁇ A, the isotropic coating film 7 is irradiated with polarized UV light. Then, as shown in FIG. 4 (b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like. Causes a photoreaction. As a result, the density of the side chain 8a that has undergone photoreaction increases in the polarization direction of the irradiated ultraviolet light, and as a result, small anisotropy is imparted to the coating film 7.
- the coating film 1 after the polarized light irradiation 1 Is heated to a liquid crystal state. Then, as shown in FIG.1 (c), in the coating film 1, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet ray is very small, this crosslinking reaction site functions as a plasticizer.
- the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is higher than the liquid crystallinity in the parallel direction, and the side chain 2 containing the mesogenic component is reoriented by self-organizing in the direction parallel to the polarization direction of the irradiated ultraviolet light.
- the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 1.
- the coating film after polarized light irradiation 3 is heated to a liquid crystal state.
- the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. Therefore, the side chain 4 containing the mesogenic component is reoriented by self-organizing in a direction parallel to the polarization direction of the irradiated ultraviolet light.
- the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 3.
- a coating film using a side-chain polymer having a structure having a photo-isomerizable group or a photo-Fleece rearrangement group represented by the above formula (18) is used.
- the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A
- the coating film 5 after polarized irradiation is heated to be in a liquid crystal state.
- generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of irradiation ultraviolet rays, and a perpendicular
- the liquid crystal alignment force of the light fleece rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, it is self-organized in the direction perpendicular to the polarization direction of the irradiated ultraviolet light.
- the side chain 6 containing the mesogenic component is reoriented.
- the very small anisotropy of the coating film 5 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 5.
- a coating film using a side chain type polymer having a structure having a photofleece rearrangement group represented by the above formula (19) is used.
- the ultraviolet irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A
- the coated film 7 after polarized irradiation is heated to a liquid crystal state.
- the amount of the generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. .
- the anchoring force of the optical fleece rearrangement 8 (a) is stronger than that of the side chain 8 before the rearrangement, when a certain amount or more of the optical fleece rearrangement occurs, it is self-assembled in a direction parallel to the polarization direction of the irradiated ultraviolet light.
- the side chain 8 containing the mesogenic component is reoriented.
- the small anisotropy of the coating film 7 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 7.
- the coating film used in the method of the present invention is a liquid crystal alignment film having anisotropy introduced with high efficiency and excellent alignment control ability by sequentially performing irradiation of polarized ultraviolet rays on the coating film and heat treatment. can do.
- the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.
- the optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction in the coating film.
- the photo-crosslinking reaction, photoisomerization reaction, or photo-fleece rearrangement reaction has few photosensitive groups in the side chain, the amount of photoreaction will not be sufficient. . In that case, sufficient self-organization does not proceed even after heating.
- the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating.
- the coating film used in the present invention is irradiated with polarized ultraviolet rays to the structure having the light Fleece rearrangement group, if the photosensitive group of the side chain that undergoes the light Fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Will drop too much.
- the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side-chain polymer is photodegraded, preventing the subsequent self-organization by heating. It may become.
- the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the side chain polymer film. It is preferably 0.1 to 40 mol%, more preferably 0.1 to 20 mol% of the photosensitive group possessed by.
- the coating film used in the method of the present invention by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.
- the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured.
- ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.
- the maximum value of ⁇ A ( ⁇ Amax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained.
- a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ⁇ Amax.
- the amount of irradiation of polarized ultraviolet rays onto the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that realizes ⁇ Amax. More preferably, it is within the range of 50%.
- the irradiation amount of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that realizes ⁇ Amax is 0. 0% of the entire photosensitive group of the side chain polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.
- a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 90 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
- the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.
- the lateral electric field drive type liquid crystal display element substrate manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.
- MA1 and M2 were synthesized as follows. That is, MA1 was synthesized by a synthesis method described in a patent document (WO2011-084546). MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717). MA3 used was commercially available. MA4BC (manufactured by Midori Chemical Co., Ltd.) that can be purchased commercially was used for MA4.
- MA5 is a novel compound that has not been published yet. MA5 was synthesized using MA2 and MA5-1, and details thereof will be described in “ ⁇ Synthesis of Compound MA5>” below. MA5-1 was synthesized by the synthesis method described in the literature (Liquid Crystals (2005), 32 (8), 1031-1044.).
- Example 1 Using the liquid crystal aligning agent A1 obtained in Synthesis Example 1, a liquid crystal cell was prepared according to the procedure shown below.
- the substrate used was a glass substrate having a size of 30 mm ⁇ 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
- the pixel electrode had a comb-like shape formed by arranging a plurality of dog-shaped electrode elements having a bent central portion.
- the width of each electrode element in the short direction was 10 ⁇ m, and the distance between the electrode elements was 20 ⁇ m. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji.
- Each pixel was divided vertically with a central bent portion as a boundary, and had a first region on the upper side of the bent portion and a second region on the lower side.
- the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
- the electrode elements of the pixel electrode were formed so as to form an angle of ⁇ 15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It was configured to be in the opposite direction.
- the liquid crystal aligning agent A1 obtained in Synthesis Example 1 was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the surface of the coating film was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 10 mJ / cm 2 and then heated on a hot plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.
- a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
- a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate.
- the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell.
- a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element was prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by vacuum injection and sealing the injection port. Obtained.
- IPS In-Planes Switching
- Example 2 the same method as in Example 1 was used, except that the liquid crystal aligning agent A2 was used to heat on a 200 ° C. hot plate, and that in Example 3 the liquid crystal aligning agent A3 was used to heat the plate at 180 ° C. A liquid crystal cell was prepared.
- VHR voltage holding ratio
- FIG. 1 Side chain polymer membrane 2, 2a Side chain Fig. 2 3 Side chain polymer membrane 4, 4a Side chain Fig. 3 5 Side chain polymer membrane 6, 6a Side chain Fig. 4 7 Side chain polymer membrane 8, 8a Side chain
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Abstract
Description
また、本発明の目的は、上記目的に加えて、高温、多湿等の過酷な条件下でも、電圧保持率等の特性が低下することのない、高い信頼性を備えた横電界駆動型液晶素子及び該素子のための液晶配向膜を提供することにある。 The present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. With the goal.
In addition to the above object, the object of the present invention is a lateral electric field drive type liquid crystal element having high reliability that does not deteriorate characteristics such as voltage holding ratio even under severe conditions such as high temperature and high humidity. And providing a liquid crystal alignment film for the device.
<1> (A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び
(B)有機溶媒
を含有する重合体組成物、特に横電界駆動型液晶表示素子用液晶配向膜製造用組成物であって、
該(A)側鎖型高分子は、環状アミン構造を有する第1の繰り返し単位、及びフェノール構造を有する第2の繰り返し単位からなる群から選ばれる少なくとも1種の繰り返し単位を有し、
前記環状アミン構造は、窒素原子に隣接する2つの炭素原子がそれぞれ下記式(S)(式中、R11は、単結合又は置換されていてもよい炭化水素基であり、
Xは、単結合、酸素原子、硫黄原子、-CO-、-CO-O-又は-O-CO-であり、
R12は、置換されていてもよい炭化水素基である。但し、Xが単結合ではない場合、R11及びR12が互いに結合して環構造を形成していてもよい。)で表される置換基2個を有し、前記フェノール構造は、水酸基に対してオルト位の炭素原子のうち少なくとも1つの炭素原子が下記式(S)で表される置換基を有する、重合体組成物、特に横電界駆動型液晶表示素子用液晶配向膜製造用組成物。 As a result of intensive studies to achieve the above problems, the present inventors have found the following invention.
<1> (A) a photosensitive side-chain polymer that exhibits liquid crystallinity within a predetermined temperature range, and (B) a polymer composition containing an organic solvent, particularly a liquid crystal alignment for a lateral electric field drive type liquid crystal display element A composition for producing a membrane,
The (A) side chain polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure,
In the cyclic amine structure, two carbon atoms adjacent to the nitrogen atom are each represented by the following formula (S) (wherein R 11 is a single bond or an optionally substituted hydrocarbon group;
X is a single bond, an oxygen atom, a sulfur atom, —CO—, —CO—O— or —O—CO—,
R 12 is an optionally substituted hydrocarbon group. However, when X is not a single bond, R 11 and R 12 may be bonded to each other to form a ring structure. ), Wherein the phenol structure has a heavy structure in which at least one carbon atom in the ortho position relative to the hydroxyl group has a substituent represented by the following formula (S). A combined composition, particularly a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element.
<3> 上記<1>又は<2>において、前記第1の繰り返し単位が、下記式(1-1)(式(1-1)中、Rは水素原子又はメチル基であり、R11は各々、同じであっても異なってもよく、上記と同じ定義を有し、Xは各々、同じであっても異なってもよく、上記と同じ定義を有し、R12は各々、同じであっても異なってもよく、上記と同じ定義を有し、B1は、水素原子、酸素原子、ハロゲン原子、水酸基又は1価の有機基であり、mは0~4の整数である)で表され、
前記第2の繰り返し単位が、下記式(1-2)(式(1-2)中、Rは水素原子又はメチル基であり、R11は各々、同じであっても異なってもよく、上記と同じ定義を有し、Xは各々、同じであっても異なってもよく、上記と同じ定義を有し、R12は各々、同じであっても異なってもよく、上記と同じ定義を有し、nは0~3の整数である)で表されるのがよい。 <2> In the above item <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
<3> In the above <1> or <2>, the first repeating unit is represented by the following formula (1-1) (in formula (1-1), R is a hydrogen atom or a methyl group, and R 11 is Each may be the same or different and have the same definition as above; X may each be the same or different and have the same definition as above; and R 12 is each the same. And B 1 is a hydrogen atom, oxygen atom, halogen atom, hydroxyl group or monovalent organic group, and m is an integer of 0 to 4. And
The second repeating unit is represented by the following formula (1-2) (in the formula (1-2), R is a hydrogen atom or a methyl group, and R 11 may be the same or different. X may be the same or different, each having the same definition as above, and R 12 may each be the same or different and have the same definition as above. N is an integer of 0 to 3).
前記第2の繰り返し単位が、下記式(1-2-1)(式(1-2-1)中、Rは水素原子又はメチル基であり、A1は単結合又は2価の連結基であり、R13は、炭素数1~5のアルキル基であり、R14は、水素原子又は炭素数1~5のアルキル基である)で表されるのがよい。 <4> In any one of the above items <1> to <3>, the first repeating unit is represented by the following formula (1-1-1) (in the formula (1-1-1), R represents a hydrogen atom or methyl A 1 is a single bond or a divalent linking group, R 13 may be the same or different, each is an alkyl group having 1 to 5 carbon atoms, B 1 is a hydrogen atom, An oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group),
The second repeating unit is represented by the following formula (1-2-1) (in the formula (1-2-1), R is a hydrogen atom or a methyl group, and A 1 is a single bond or a divalent linking group. R 13 is an alkyl group having 1 to 5 carbon atoms, and R 14 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Sは、炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Tは、単結合または炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
Y2は、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R51は、ヒドロキシ基、炭素数1~6のアルコキシ基を表すか、又はY1と同じ定義を表す;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表し、Xの数が2となるときは、X同士は同一でも異なっていてもよい;
Couは、クマリン-6-イル基またはクマリン-7-イル基を表し、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
q1とq2は、一方が1で他方が0である;
q3は0または1である;
P及びQは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である;ただし、Xが-CH=CH-CO-O-、-O-CO-CH=CH-である場合、-CH=CH-が結合する側のP又はQは芳香環であり、Pの数が2以上となるときは、P同士は同一でも異なっていてもよく、Qの数が2以上となるときは、Q同士は同一でも異なっていてもよい;
l1は0または1である;
l2は0~2の整数である;
l1とl2がともに0であるときは、Tが単結合であるときはAも単結合を表す;
l1が1であるときは、Tが単結合であるときはBも単結合を表す;
H及びIは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。 In the formula, A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R 51 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
式中、A、B、D、Y1、X、Y2、及びR51は、上記と同じ定義を有する;
lは1~12の整数を表す;
mは、0~2の整数を表し、m1、m2は1~3の整数を表す;
nは0~12の整数(ただしn=0のときBは単結合である)を表す。 <6> In any one of the above items <1> to <4>, the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10): Good.
In which A, B, D, Y 1 , X, Y 2 and R 51 have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).
式中、A、X、l、m、m1及びR51は、上記と同じ定義を有する。 <7> In any one of the above items <1> to <4>, the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13): Good.
In the formula, A, X, l, m, m1 and R 51 have the same definition as above.
式中、A、Y1、l、m1及びm2は上記と同じ定義を有する。 <8> In any one of the above items <1> to <4>, the component (A) preferably has a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y 1 , l, m1 and m2 have the same definition as above.
式中、A、X、l及びmは、上記と同じ定義を有する。 <9> In any one of the above items <1> to <4>, the component (A) preferably has a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.
式中、A、B、Y1、q1、q2、m1、及びm2は、上記と同じ定義を有する。
R1は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基を表す。 <10> In any one of the above items <1> to <4>, the component (A) preferably has a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y 1 , q1, q2, m1, and m2 have the same definition as above.
R 1 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
式中、A、Y1、X、l及びmは上記と同じ定義を有する。 <11> In any one of the above items <1> to <4>, the component (A) preferably has a photosensitive side chain represented by the following formula (20).
In the formula, A, Y 1 , X, l and m have the same definition as above.
式中、A、B、q1及びq2は上記と同じ定義を有する;
Y3は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R3は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、炭素数5~8の脂環式炭化水素、炭素数1~12のアルキル基、又は炭素数1~12のアルコキシ基を表す;
lは1~12の整数を表し、mは0から2の整数を表し、但し、式(23)~(24)において、全てのmの合計は2以上であり、式(25)~(26)において、全てのmの合計は1以上であり、m1、m2およびm3は、それぞれ独立に1~3の整数を表す;
R2は、水素原子、-NO2、-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、アルキル基、又はアルキルオキシ基を表す;
Z1、Z2は単結合、-CO-、-CH2O-、-CH=N-、-CF2-を表す。 <12> In any one of the above items <1> to <11>, the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Good.
In which A, B, q1 and q2 have the same definition as above;
Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 each represents a single bond, —CO—, —CH 2 O—, —CH═N—, —CF 2 —.
[II] [I]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された横電界駆動型液晶表示素子用液晶配向膜を得る、前記液晶配向膜を有する基板の製造方法。
<14> 上記<13>の方法により製造された横電界駆動型液晶表示素子用液晶配向膜を有する基板。
<15> 上記<14>の基板を有する横電界駆動型液晶表示素子。 <13> [I] A step of applying the composition according to any one of the above <1> to <12> onto a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
<14> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device manufactured by the method of <13>.
<15> A lateral electric field drive type liquid crystal display device having the substrate of <14> above.
[I’] 第2の基板上に
(A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び
(B)有機溶媒
を含有する重合体組成物を、塗布して塗膜を形成する工程;
[II’] [I’]で得られた塗膜に偏光した紫外線を照射する工程;
[III’] [II’]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された液晶配向膜を得る、前記液晶配向膜を有する第2の基板を得る工程;及び
[IV] 液晶を介して前記第1及び第2の基板の液晶配向膜が相対するように、前記第1及び第2の基板を対向配置して液晶表示素子を得る工程;
を有することにより、横電界駆動型液晶表示素子を得る、該液晶表示素子の製造方法。 <16> a step of preparing the substrate (first substrate) of <14>above;
[I ′] A polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent is applied onto a second substrate. Forming a coating film;
[II ′] A step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays;
[III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film having alignment control ability by providing a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.
<P1> [I] (A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子であって、窒素原子に隣接する2つの炭素原子がそれぞれ下記式(S)で表される置換基2個を有している環状アミン構造
又は
水酸基に対してオルト位の炭素原子のうち少なくとも1つの炭素原子が下記式(S)(式中、R11は、単結合又は置換されていてもよい炭化水素基であり、Xは、単結合、酸素原子、硫黄原子、-CO-、-CO-O-又は-O-CO-であり、R12は、置換されていてもよい炭化水素基である。但し、Xが単結合ではない場合、R11及びR12が互いに結合して環構造を形成していてもよい。)で表される置換基を有しているフェノール構造
から選ばれる一種以上の繰り返し単位を有する側鎖型高分子、及び
(B)有機溶媒
を含有する重合体組成物を、横電界駆動用の導電膜を有する基板上に塗布して塗膜を形成する工程;
[II] [I]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された横電界駆動型液晶表示素子用液晶配向膜を得る、前記液晶配向膜を有する基板の製造方法。 Moreover, the following invention was found as another aspect.
<P1> [I] (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and two carbon atoms adjacent to a nitrogen atom are each represented by the following formula (S). At least one carbon atom ortho-positioned to the cyclic amine structure or hydroxyl group having two substituents is represented by the following formula (S) (wherein R 11 is a single bond or substituted): Is an optionally substituted hydrocarbon group, X is a single bond, oxygen atom, sulfur atom, —CO—, —CO—O— or —O—CO—, and R 12 is an optionally substituted carbon atom. A hydrogen group, provided that when X is not a single bond, R 11 and R 12 may be bonded to each other to form a ring structure.) A side chain polymer having one or more selected repeating units, and (B) an organic solvent Applying a polymer composition containing a medium on a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
<P3> 上記<P1>において、前記繰り返し単位が、下記式(1-1)又は(1-2)(式(1-1)及び式(1-2)中、Rは水素原子又はメチル基であり、A1は単結合又は2価の連結基であり、R11は、それぞれ、単結合又は置換されていてもよい炭化水素基であり、Xは、それぞれ、単結合、酸素原子、硫黄原子、-CO-、-CO-O-又は-O-CO-であり、R12は、それぞれ、置換されていてもよい炭化水素基である。但し、Xが単結合ではない場合、R11及びR12が互いに結合して環構造を形成していてもよい。式(1-1)中、B1は、水素原子、酸素原子、ハロゲン原子、水酸基又は1価の有機基であり、mは0~4の整数である。式(1-2)中、nは0~3の整数である。)で表されることを特徴とする製造方法。 <P2> In the above <P1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
<P3> In the above <P1>, the repeating unit is represented by the following formula (1-1) or (1-2) (in the formula (1-1) and the formula (1-2), R is a hydrogen atom or a methyl group A 1 is a single bond or a divalent linking group, R 11 is a single bond or an optionally substituted hydrocarbon group, and X is a single bond, oxygen atom, sulfur, respectively. An atom, —CO—, —CO—O— or —O—CO—, wherein each of R 12 is an optionally substituted hydrocarbon group, provided that when X is not a single bond, R 11 And R 12 may be bonded to each other to form a ring structure, wherein B 1 is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group; Is an integer from 0 to 4. In formula (1-2), n is an integer from 0 to 3. Manufacturing method.
Sは、炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Tは、単結合または炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
Y2は、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R51は、ヒドロキシ基、炭素数1~6のアルコキシ基を表すか、又はY1と同じ定義を表す;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Couは、クマリン-6-イル基またはクマリン-7-イル基を表し、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
q1とq2は、一方が1で一方が0である;
q3は0または1である;
P及びQは、各々独立に、単結合、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である。ただし、Xが-CH=CH-CO-O-、-O-CO-CH=CH-である場合、-CH=CH-が結合する側のP又はQは芳香環である;
H及びIは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。 In the formula, A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R 51 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and one is 0;
q3 is 0 or 1;
P and Q are each independently a single bond, a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof. Is a group selected from However, when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
式中、A、B、D、Y1、X、Y2、及びR51は、上記と同じ定義を有する;
lは1~12の整数を表す;
mは、0~2の整数を表し、m1、m2は1~3の整数を表す;
nは0~12の整数(ただしn=0のときBは単結合である)を表す。 <P6> In the above <P1> or <P2>, the component (A) preferably has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y 1 , X, Y 2 and R 51 have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).
式中、A、X、l、m及びR51は、上記と同じ定義を有する。 <P7> In the above <P1> or <P2>, the component (A) preferably has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m and R 51 have the same definition as above.
式中、A、Y1、X、l、m1及びm2は上記と同じ定義を有する。 <P8> In the above <P1> or <P2>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y 1 , X, 1, m1, and m2 have the same definition as above.
式中、A、X、l及びmは、上記と同じ定義を有する。 <P9> In the above <P1> or <P2>, the component (A) may have a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.
式中、A、B、Y1、q1、q2、m1、及びm2は、上記と同じ定義を有する。
R1は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基を表す。 <P10> In the above <P1> or <P2>, the component (A) may have a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y1, q1, q2, m1, and m2 have the same definition as above.
R 1 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
式中、A、Y1、X、l及びmは上記と同じ定義を有する。 <P11> In the above <P1> or <P2>, the component (A) may have a photosensitive side chain represented by the following formula (20).
In the formula, A, Y 1 , X, l and m have the same definition as above.
式中、A、B、q1及びq2は上記と同じ定義を有する;
Y3は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R3は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、炭素数5~8の脂環式炭化水素、炭素数1~12のアルキル基、又は炭素数1~12のアルコキシ基を表す;
lは1~12の整数を表し、mは0から2の整数を表し、但し、式(25)~(26)において、全てのmの合計は2以上であり、式(27)~(28)において、全てのmの合計は1以上であり、m1、m2およびm3は、それぞれ独立に1~3の整数を表す;
R2は、水素原子、-NO2、-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、アルキル基、又はアルキルオキシ基を表す;
Z1、Z2は単結合、-CO-、-CH2O-、-CH=N-、-CF2-を表す。 <P12> In any one of the above items <P1> to <P11>, the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Good.
In which A, B, q1 and q2 have the same definition as above;
Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in the formulas (25) to (26), the sum of all m is 2 or more, and the formulas (27) to (28 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 each represents a single bond, —CO—, —CH 2 O—, —CH═N—, —CF 2 —.
<P14> 上記<P13>の基板を有する横電界駆動型液晶表示素子。 <P13> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device manufactured by any of the above <P1> to <P12>.
<P14> A lateral electric field drive type liquid crystal display device having the substrate of <P13> above.
[I’] 第2の基板上に
(A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び
(B)有機溶媒
を含有する重合体組成物を、塗布して塗膜を形成する工程;
[II’] [I’]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III’] [II’]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された液晶配向膜を得る、該液晶配向膜を有する第2の基板を得る工程;及び
[IV] 液晶を介して第1及び第2の基板の液晶配向膜が相対するように、第1及び第2の基板を対向配置して液晶表示素子を得る工程;
を有することにより、横電界駆動型液晶表示素子を得る、該液晶表示素子の製造方法。 <P15> Step of preparing a substrate (first substrate) of <P13>above;
[I ′] A polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent is applied onto a second substrate. Forming a coating film;
[II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays; and [III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control ability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment films of the first and second substrates via liquid crystal The liquid crystal display element is obtained by disposing the first and second substrates so as to face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.
<P17> (A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子であって、窒素原子に隣接する2つの炭素原子がそれぞれ下記式(S)(式中、R11は、単結合又は置換されていてもよい炭化水素基であり、Xは、単結合、酸素原子、硫黄原子、-CO-、-CO-O-又は-O-CO-であり、R12は、置換されていてもよい炭化水素基である。但し、Xが単結合ではない場合、R11及びR12が互いに結合して環構造を形成していてもよい。)で表される置換基2個を有している環状アミン構造
又は
水酸基に対してオルト位の炭素原子のうち少なくとも1つの炭素原子が下記式(S)で表される置換基を有しているフェノール構造
から選ばれる一種以上の繰り返し単位を有する側鎖型高分子、及び
(B)有機溶媒
を含有する、横電界駆動型液晶表示素子用液晶配向膜製造用組成物。 <P16> A lateral electric field drive type liquid crystal display device manufactured according to the above <P15>.
<P17> (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, wherein two carbon atoms adjacent to the nitrogen atom are each represented by the following formula (S) (wherein R 11 Is a single bond or an optionally substituted hydrocarbon group, X is a single bond, an oxygen atom, a sulfur atom, —CO—, —CO—O— or —O—CO—, and R 12 is A hydrocarbon group which may be substituted, provided that when X is not a single bond, R 11 and R 12 may be bonded to each other to form a ring structure. One selected from a cyclic amine structure having two or a phenol structure in which at least one of the carbon atoms ortho to the hydroxyl group has a substituent represented by the following formula (S) A side chain polymer having the above repeating unit, and (B) an organic solvent. A horizontal electric field drive type liquid crystal display device for a liquid crystal alignment film composition for producing.
<P19> 上記<P17>において、前記繰り返し単位が、下記式(1-1-1)又は(1-2-1)で表されることを特徴とする組成物。 In formulas (1-1) and (1-2), R is a hydrogen atom or a methyl group, A 1 is a single bond or a divalent linking group, and R 11 is a single bond or a substituted group, respectively. And X is a single bond, oxygen atom, sulfur atom, —CO—, —CO—O— or —O—CO—, respectively, and R 12 is each substituted It may be a hydrocarbon group. However, when X is not a single bond, R 11 and R 12 may be bonded to each other to form a ring structure. In formula (1-1), B 1 is a hydrogen atom, oxygen atom, halogen atom, hydroxyl group or monovalent organic group, and m is an integer of 0-4. In the formula (1-2), n is an integer of 0 to 3.
<P19> The composition according to <P17>, wherein the repeating unit is represented by the following formula (1-1-1) or (1-2-1).
本発明の方法によって製造された横電界駆動型液晶表示素子は、高効率に配向制御能が付与されているため長時間連続駆動しても表示特性が損なわれることがない。
また、本発明により、上記効果に加えて、高温、多湿等の過酷な条件下でも、電圧保持率等の特性が低下することのない、高い信頼性を備えた横電界駆動型液晶素子及び該素子のための液晶配向膜を提供することができる。 According to the present invention, there are provided a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. Can do.
Since the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even when continuously driven for a long time.
Further, according to the present invention, in addition to the above-described effects, a lateral electric field drive type liquid crystal element having high reliability in which characteristics such as voltage holding ratio do not deteriorate even under severe conditions such as high temperature and high humidity, and the like A liquid crystal alignment film for the device can be provided.
本発明の製造方法において用いられる重合体組成物は、液晶性を発現し得る感光性の側鎖型高分子(以下、単に側鎖型高分子とも呼ぶ)を有しており、前記重合体組成物を用いて得られる塗膜は、液晶性を発現し得る感光性の側鎖型高分子を有する膜である。この塗膜にはラビング処理を行うこと無く、偏光照射によって配向処理を行う。そして、偏光照射の後、その側鎖型高分子膜を加熱する工程を経て、配向制御能が付与された塗膜(以下、液晶配向膜とも称する)となる。このとき、偏光照射によって発現した僅かな異方性がドライビングフォースとなり、液晶性の側鎖型高分子自体が自己組織化により効率的に再配向する。その結果、液晶配向膜として高効率な配向処理が実現し、高い配向制御能が付与された液晶配向膜を得ることができる As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The polymer composition used in the production method of the present invention has a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter, also simply referred to as a side chain polymer), and the polymer composition The coating film obtained by using the product is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity. This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth a liquid crystal aligning film) to which the orientation control ability was provided through the process of heating the side chain type polymer film. At this time, the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-organization. As a result, a highly efficient alignment process can be realized as a liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.
<液晶配向膜を有する基板の製造方法>及び<液晶表示素子の製造方法>
本発明の液晶配向膜を有する基板の製造方法は、
[I] (A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び
(B)有機溶媒
を含有する重合体組成物、特に横電界駆動型液晶表示素子用液晶配向膜製造用組成物であって、
該(A)側鎖型高分子は、環状アミン構造を有する第1の繰り返し単位、及びフェノール構造を有する第2の繰り返し単位からなる群から選ばれる少なくとも1種の繰り返し単位を有し、
前記環状アミン構造は、窒素原子に隣接する2つの炭素原子がそれぞれ下記式(S)(式中、R11は、単結合又は置換されていてもよい炭化水素基であり、
Xは、単結合、酸素原子、硫黄原子、-CO-、-CO-O-又は-O-CO-であり、
R12は、置換されていてもよい炭化水素基である。但し、Xが単結合ではない場合、R11及びR12が互いに結合して環構造を形成していてもよい。)で表される置換基2個を有し、前記フェノール構造は、水酸基に対してオルト位の炭素原子のうち少なくとも1つの炭素原子が下記式(S)で表される置換基を有する、重合体組成物、特に横電界駆動型液晶表示素子用液晶配向膜製造用組成物を、横電界駆動用の導電膜を有する基板上に塗布して塗膜を形成する工程;
[II] [I]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有する。 Hereinafter, embodiments of the present invention will be described in detail.
<Manufacturing method of substrate having liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>
The method for producing a substrate having the liquid crystal alignment film of the present invention is
[I] (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) a polymer composition containing an organic solvent, particularly a liquid crystal alignment for a lateral electric field drive type liquid crystal display device A composition for producing a membrane,
The (A) side chain polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure,
In the cyclic amine structure, two carbon atoms adjacent to the nitrogen atom are each represented by the following formula (S) (wherein R 11 is a single bond or an optionally substituted hydrocarbon group;
X is a single bond, an oxygen atom, a sulfur atom, —CO—, —CO—O— or —O—CO—,
R 12 is an optionally substituted hydrocarbon group. However, when X is not a single bond, R 11 and R 12 may be bonded to each other to form a ring structure. ), Wherein the phenol structure has a heavy structure in which at least one carbon atom in the ortho position relative to the hydroxyl group has a substituent represented by the following formula (S). Applying a combined composition, particularly a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, onto a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
Have
第2の基板は、横電界駆動用の導電膜を有する基板に代わって、横電界駆動用の導電膜を有しない基板を用いる以外、上記工程[I]~[III](横電界駆動用の導電膜を有しない基板を用いるため、便宜上、本願において、工程[I’]~[III’]と略記する場合がある)を用いることにより、配向制御能が付与された液晶配向膜を有する第2の基板を得ることができる。 Further, by preparing a second substrate in addition to the obtained substrate (first substrate), a lateral electric field drive type liquid crystal display element can be obtained.
For the second substrate, instead of using a substrate having no lateral electric field driving conductive film instead of a substrate having a lateral electric field driving conductive film, the above steps [I] to [III] (for lateral electric field driving) Since a substrate having no conductive film is used, for the sake of convenience, in this application, the steps [I ′] to [III ′] may be abbreviated as steps), thereby providing a first liquid crystal alignment film having alignment controllability. Two substrates can be obtained.
[IV] 上記で得られた第1及び第2の基板を、液晶を介して第1及び第2の基板の液晶配向膜が相対するように、対向配置して液晶表示素子を得る工程;
を有する。これにより横電界駆動型液晶表示素子を得ることができる。 The manufacturing method of the horizontal electric field drive type liquid crystal display element is
[IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween;
Have Thereby, a horizontal electric field drive type liquid crystal display element can be obtained.
<工程[I]>
工程[I]では、横電界駆動用の導電膜を有する基板上に、所定の温度範囲で液晶性を発現する感光性の側鎖型高分子及び有機溶媒を含有する重合体組成物を塗布して塗膜を形成する。 The steps [I] to [III] and [IV] of the production method of the present invention will be described below.
<Process [I]>
In step [I], a polymer composition containing a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and an organic solvent is applied onto a substrate having a conductive film for driving a lateral electric field. To form a coating film.
基板については、特に限定はされないが、製造される液晶表示素子が透過型である場合、透明性の高い基板が用いられることが好ましい。その場合、特に限定はされず、ガラス基板、またはアクリル基板やポリカーボネート基板等のプラスチック基板等を用いることができる。
また、反射型の液晶表示素子への適用を考慮し、シリコンウェハなどの不透明な基板も使用できる。 <Board>
Although it does not specifically limit about a board | substrate, When the liquid crystal display element manufactured is a transmission type, it is preferable that a highly transparent board | substrate is used. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
In consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.
基板は、横電界駆動用の導電膜を有する。
該導電膜として、液晶表示素子が透過型である場合、ITO(Indium Tin Oxide:酸化インジウムスズ)、IZO(Indium Zinc Oxide:酸化インジウム亜鉛)などを挙げることができるが、これらに限定されない。
また、反射型の液晶表示素子の場合、導電膜として、アルミなどの光を反射する材料などを挙げることができるがこれらに限定されない。
基板に導電膜を形成する方法は、従来公知の手法を用いることができる。 <Conductive film for driving lateral electric field>
The substrate has a conductive film for driving a lateral electric field.
Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
In the case of a reflective liquid crystal display element, examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.
横電界駆動用の導電膜を有する基板上、特に導電膜上に、重合体組成物を塗布する。
本発明の製造方法に用いられる、該重合体組成物は、(A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子および(B)有機溶媒;を含有する。 <Polymer composition>
A polymer composition is applied on a substrate having a conductive film for driving a lateral electric field, particularly on the conductive film.
The polymer composition used in the production method of the present invention contains (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent.
(A)成分は、所定の温度範囲で液晶性を発現する感光性の側鎖型高分子である。
(A)側鎖型高分子は、250nm~400nmの波長範囲の光で反応し、かつ100℃~250℃の温度範囲で液晶性を示すのがよい。
(A)側鎖型高分子は、250nm~400nmの波長範囲の光に反応する感光性側鎖を有することが好ましい。
(A)側鎖型高分子は、100℃~250℃の温度範囲で液晶性を示すためメソゲン基を有することが好ましい。 << (A) Side chain polymer >>
The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range.
(A) The side chain polymer preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100 ° C. to 250 ° C.
The (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
The (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 250 ° C.
該(A)側鎖型高分子は、環状アミン構造を有する第1の繰り返し単位、及びフェノール構造を有する第2の繰り返し単位からなる群から選ばれる少なくとも1種の繰り返し単位を有する。
環状アミン構造は、窒素原子に隣接する2つの炭素原子がそれぞれ上記式(S)で表される置換基2個を有する。
フェノール構造は、水酸基に対してオルト位の炭素原子のうち少なくとも1つの炭素原子が上記式(S)で表される置換基を有する。 [Repeat unit]
The (A) side chain polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure.
In the cyclic amine structure, two carbon atoms adjacent to the nitrogen atom each have two substituents represented by the above formula (S).
The phenol structure has a substituent in which at least one of the carbon atoms ortho to the hydroxyl group is represented by the above formula (S).
また、上記フェノール構造としては、ベンゼン環において水酸基が結合する位置は任意であるが、好ましくは、当該ベンゼン環において主鎖側と結合する炭素原子に対してパラ位の位置である。 As said cyclic amine structure, it is preferable that the number of the carbon atoms which form the ring structure is 2-7, More preferably, it is five.
Moreover, as said phenol structure, although the position which a hydroxyl group couple | bonds in a benzene ring is arbitrary, Preferably it is a para-position with respect to the carbon atom couple | bonded with the principal chain side in the said benzene ring.
一方、フェノール構造を有するものである場合にはヒンダードフェノール構造を有するものであり、下記式(1-2)で表される構造である。 More specifically, the preferred structure of the repeating unit (a1) is a structure represented by the following formula (1-1) having a hindered amine structure when it has a cyclic amine structure.
On the other hand, when it has a phenol structure, it has a hindered phenol structure and is a structure represented by the following formula (1-2).
炭素数6~12のアリール基としては、例えばフェニル基、4-ホルミルフェニル基、3,4,5-トリメトキシフェニル基等を;
炭素数7~13のアラルキル基としては、ベンジル基等を
それぞれ挙げることができる。
R11及びR12が互いに結合して形成する環構造としては、例えばフラン、チオフェン、2H-ピラン、及び4H-ピラン等から1個の水素原子を除いた基を挙げることができる。 Examples of the alkyl group having 1 to 6 carbon atoms of R 12 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-butyl group, an i-butyl group, and a t-butyl group. Etc .;
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, 4-formylphenyl group, 3,4,5-trimethoxyphenyl group, and the like;
Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group.
Examples of the ring structure formed by combining R 11 and R 12 with each other include groups in which one hydrogen atom has been removed from furan, thiophene, 2H-pyran, 4H-pyran, and the like.
式(A1-1)~式(A1-17)中、*1は、環状アミン構造の炭素原子又はフェノール構造の炭素原子に結合する結合手を示す。 Examples of the divalent linking group represented by the formula (A1) include, but are not limited to, groups represented by the formulas (A1-1) to (A1-17).
In formulas (A1-1) to (A1-17), * 1 represents a bond bonded to a carbon atom of a cyclic amine structure or a carbon atom of a phenol structure.
上記式(1-1)及び上記式(1-1-1)中、B1の1価の有機基としては、下記式(B1)で表されるものを挙げることができる。 In the formula (1-1) and the formula (1-1-1), examples of the halogen atom for B 1 include a fluorine atom and a chlorine atom.
In the formula (1-1) and the formula (1-1-1), examples of the monovalent organic group for B 1 include those represented by the following formula (B1).
上記式(B1)中、R’’の炭素数1~6のアルキル基としては、上記R12で例示したものを挙げることができる。 In the formula, B 11 is a single bond, —O—, —CO—, —CO—O—, —O—CO—, —O—CO—NR ″ —, or —CO—NR ″ —. , R ″ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. B 12 is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a monovalent heterocyclic group having 3 to 10 carbon atoms, or 3 to 15 carbon atoms. The hydrogen atom which these groups have may be substituted.
In the above formula (B1), examples of the alkyl group having 1 to 6 carbon atoms represented by R ″ include those exemplified for R 12 above.
炭素数6~12のアリール基としては、例えば、フェニル基、トリル基、4-エチルフェニル基、ジメチルフェニル基、2,4,6-トリメチルフェニル基、ナフチル基、アントリル基等を;
炭素数7~13のアラルキル基としては、例えば、ベンジル基、フェネチル基、α-メチルベンジル基、ナフチルメチル基等を;
炭素数3~10の1価の複素環基としては、含窒素複素環化合物が挙げられ、例えば、ピペリジン、モルホリン、ピリジン、ピラジン等を;
炭素数3~15の脂環式炭化水素基としては、例えば、シクロペンチル基、シクロへキシル基、4-メチルシクロへキシル基等を
それぞれ挙げることができる。 In the above formula (B1), the alkyl group having 1 to 15 carbon atoms of B 12 may be linear or branched. For example, a methyl group, an ethyl group, a propyl group, a butyl group, A pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and the like;
Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, 4-ethylphenyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, and anthryl group;
Examples of the aralkyl group having 7 to 13 carbon atoms include benzyl group, phenethyl group, α-methylbenzyl group, naphthylmethyl group and the like;
Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms include nitrogen-containing heterocyclic compounds such as piperidine, morpholine, pyridine, pyrazine and the like;
Examples of the alicyclic hydrocarbon group having 3 to 15 carbon atoms include a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, and the like.
繰り返し単位(a1)としては、得られる液晶配向膜の耐久性の向上を好適に図る上では、ヒンダードフェノール構造を有するものよりも、ヒンダードアミン構造を有するものが好ましい。 The monomer that gives the hindered phenol structure repeating unit (a1) can be easily synthesized by combining organic chemistry methods.
The repeating unit (a1) preferably has a hindered amine structure rather than a hindered phenol structure in order to improve the durability of the obtained liquid crystal alignment film.
Sは、炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Tは、単結合または炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
Y2は、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R51は、ヒドロキシ基、炭素数1~6のアルコキシ基を表すか、又はY1と同じ定義を表す;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表し、Xの数が2となるときは、X同士は同一でも異なっていてもよい;
Couは、クマリン-6-イル基またはクマリン-7-イル基を表し、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
q1とq2は、一方が1で他方が0である;
q3は0または1である;
P及びQは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である;ただし、Xが-CH=CH-CO-O-、-O-CO-CH=CH-である場合、-CH=CH-が結合する側のP又はQは芳香環であり、Pの数が2以上となるときは、P同士は同一でも異なっていてもよく、Qの数が2以上となるときは、Q同士は同一でも異なっていてもよい;
l1は0または1である;
l2は0~2の整数である;
l1とl2がともに0であるときは、Tが単結合であるときはAも単結合を表す;
l1が1であるときは、Tが単結合であるときはBも単結合を表す;
H及びIは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。 In the formula, A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R 51 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
式中、A、B、D、Y1、X、Y2、及びR51は、上記と同じ定義を有する;
lは1~12の整数を表す;
mは、0~2の整数を表し、m1、m2は1~3の整数を表す;
nは0~12の整数(ただしn=0のときBは単結合である)を表す。 The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y 1 , X, Y 2 and R 51 have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).
式中、A、X、l、m、m1及びR51は、上記と同じ定義を有する。 The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m, m1 and R 51 have the same definition as above.
式中、A、Y1、l、m1及びm2は上記と同じ定義を有する。 The side chain may be a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y 1 , l, m1 and m2 have the same definition as above.
式中、A、X、l及びmは、上記と同じ定義を有する。 The side chain may be a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.
式中、A、B、Y1、q1、q2、m1、及びm2は、上記と同じ定義を有する。
R1は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基を表す。 The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y 1 , q1, q2, m1, and m2 have the same definition as above.
R 1 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
式中、A、Y1、X、l及びmは上記と同じ定義を有する。 The side chain is preferably a photosensitive side chain represented by the following formula (20).
In the formula, A, Y 1 , X, l and m have the same definition as above.
式中、A、B、q1及びq2は上記と同じ定義を有する;
Y3は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R3は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、炭素数5~8の脂環式炭化水素、炭素数1~12のアルキル基、又は炭素数1~12のアルコキシ基を表す;
lは1~12の整数を表し、mは0から2の整数を表し、但し、式(23)~(24)において、全てのmの合計は2以上であり、式(25)~(26)において、全てのmの合計は1以上であり、m1、m2およびm3は、それぞれ独立に1~3の整数を表す;
R2は、水素原子、-NO2、-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、アルキル基、又はアルキルオキシ基を表す;
Z1、Z2は単結合、-CO-、-CH2O-、-CH=N-、-CF2-を表す。 The (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
In which A, B, q1 and q2 have the same definition as above;
Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 each represents a single bond, —CO—, —CH 2 O—, —CH═N—, —CF 2 —.
式中、Rは水素原子またはメチル基を示す;Sは炭素数2~10のアルキレン基を表す;R10はBrまたはCNを示す;Sは炭素数2~10のアルキレン基を表す;uは0または1を表す;及びPyは2-ピリジル基、3-ピリジル基または4-ピリジル基を表す。また、vは1または2を表す。 The present application relates to compounds (1) to (11) represented by the following formulas (1) to (11) as photoreactive and / or liquid crystalline side chain monomers; and the following formulas (12) to (17): The compounds (12) to (17) represented by the formula:
In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; R 10 represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms; u represents
上記の液晶性を発現し得る感光性の側鎖型高分子は、上記の感光性側鎖を有する光反応性側鎖モノマーおよび液晶性側鎖モノマーを重合することによって得ることができる。 << Production Method of Photosensitive Side Chain Polymer >>
The photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.
液晶性側鎖モノマーとは、該モノマー由来の高分子が液晶性を発現し、該高分子が側鎖部位にメソゲン基を形成することができるモノマーのことである。
側鎖の有するメソゲン基として、ビフェニルやフェニルベンゾエートなどの単独でメソゲン構造となる基であっても、安息香酸などのように側鎖同士が水素結合することでメソゲン構造となる基であってもよい。側鎖の有するメソゲン基としては下記の構造が好ましい。 [Liquid crystal side chain monomer]
The liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good. As the mesogenic group possessed by the side chain, the following structure is preferable.
その他のモノマーの具体例としては、不飽和カルボン酸、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物及びビニル化合物等が挙げられる。 Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、2,2,2-トリフルオロエチルアクリレート、tert-ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、2-メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、2-エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、3-メトキシブチルアクリレート、2-メチル-2-アダマンチルアクリレート、2-プロピル-2-アダマンチルアクリレート、8-メチル-8-トリシクロデシルアクリレート、及び、8-エチル-8-トリシクロデシルアクリレート等が挙げられる。 Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.
スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。
マレイミド化合物としては、例えば、マレイミド、N-メチルマレイミド、N-フェニルマレイミド、及びN-シクロヘキシルマレイミド等が挙げられる。 Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
チルエステル、パーオキシ 2-エチルシクロヘキサン酸-tert-アミルエステル等)、過硫酸塩類(過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等)、アゾ系化合物(アゾビスイソブチロニトリル、および2,2′-ジ(2-ヒドロキシエチル)アゾビスイソブチロニトリル等)が挙げられる。このようなラジカル熱重合開始剤は、1種を単独で使用することもできるし、あるいは2種以上を組み合わせて使用することもできる。 The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation). Hydrogen, tert-butyl hydride peroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxy cyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohex Sanic acid-tert-amyl ester), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2′-di (2-hydroxyethyl) And azobisisobutyronitrile). Such radical thermal polymerization initiators can be used singly or in combination of two or more.
また、ラジカル重合において有機溶媒中の酸素は重合反応を阻害する原因となるので、有機溶媒は可能な程度に脱気されたものを用いることが好ましい。 These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate.
In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.
上述の反応により得られた、液晶性を発現し得る感光性の側鎖型高分子の反応溶液から、生成した高分子を回収する場合には、反応溶液を貧溶媒に投入して、それら重合体を沈殿させれば良い。沈殿に用いる貧溶媒としては、メタノール、アセトン、ヘキサン、ヘプタン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン、ジエチルエーテル、メチルエチルエーテル、水等を挙げることができる。貧溶媒に投入して沈殿させた重合体は、濾過して回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。また、沈殿回収した重合体を、有機溶媒に再溶解させ、再沈殿回収する操作を2回~10回繰り返すと、重合体中の不純物を少なくすることができる。この際の貧溶媒として、例えば、アルコール類、ケトン類、炭化水素等が挙げられ、これらの中から選ばれる3種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。 [Recovery of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side chain polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent, The coalescence can be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
本発明に用いられる重合体組成物は、液晶配向膜の形成に好適となるように塗布液として調製されることが好ましい。すなわち、本発明に用いられる重合体組成物は、樹脂被膜を形成するための樹脂成分が有機溶媒に溶解した溶液として調製されることが好ましい。ここで、その樹脂成分とは、既に説明した液晶性を発現し得る感光性の側鎖型高分子を含む樹脂成分である。その際、樹脂成分の含有量は、1質量%~20質量%が好ましく、より好ましくは3質量%~15質量%、特に好ましくは3質量%~10質量%である。 [Preparation of polymer composition]
The polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side chain polymer capable of exhibiting the liquid crystallinity already described. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
そのような他の重合体は、例えば、ポリ(メタ)アクリレートやポリアミック酸やポリイミド等からなり、液晶性を発現し得る感光性の側鎖型高分子ではない重合体等が挙げられる。 In the polymer composition of the present embodiment, the resin component described above may be a photosensitive side chain polymer that can all exhibit the above-described liquid crystallinity, but does not impair the liquid crystal developing ability and the photosensitive performance. Other polymers may be mixed within the range. In that case, the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
Examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.
本発明に用いられる重合体組成物に用いる有機溶媒は、樹脂成分を溶解させる有機溶媒であれば特に限定されない。その具体例を以下に挙げる。
N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-メチルカプロラクタム、2-ピロリドン、N-エチルピロリドン、N-ビニルピロリドン、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ-ブチロラクトン、3-メトキシ-N,N-ジメチルプロパンアミド、3-エトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、1,3-ジメチル-イミダゾリジノン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、ジグライム、4-ヒドロキシ-4-メチル-2-ペンタノン、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール-tert-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、3-メチル-3-メトキシブチルアセテート、トリプロピレングリコールメチルエーテル等が挙げられる。これらは単独で使用しても、混合して使用してもよい。 <Organic solvent>
The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. Is mentioned. These may be used alone or in combination.
例えば、イソプロピルアルコール、メトキシメチルペンタノール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチルカルビトールアセテート、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノn-ブチルエーテル、プロピレングリコール-tert-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、3-メチル-3-メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、3-メチル-3-メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、1-ヘキサノール、n-へキサン、n-ペンタン、n-オクタン、ジエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸n-ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチルエチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸、3-メトキシプロピオン酸、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、1-ブトキシ-2-プロパノール、1-フェノキシ-2-プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート、プロピレングリコール-1-モノエチルエーテル-2-アセテート、ジプロピレングリコール、2-(2-エトキシプロポキシ)プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸n-プロピルエステル、乳酸n-ブチルエステル、乳酸イソアミルエステル等の低表面張力を有する溶媒等が挙げられる。 The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono n-butyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, Ethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene , Propyl ether, dihexyl ether, 1-hexanol N-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3 -Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy -2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether Ter-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n- And solvents having a low surface tension such as butyl ester and isoamyl lactate.
より具体的には、例えば、エフトップ(登録商標)301、EF303、EF352(トーケムプロダクツ社製)、メガファック(登録商標)F171、F173、R-30(DIC社製)、フロラードFC430、FC431(住友スリーエム社製)、アサヒガード(登録商標)AG710(旭硝子社製)、サーフロン(登録商標)S-382、SC101、SC102、SC103、SC104、SC105、SC106(AGCセイミケミカル社製)等が挙げられる。これらの界面活性剤の使用割合は、重合体組成物に含有される樹脂成分の100質量部に対して、好ましくは0.01質量部~2質量部、より好ましくは0.01質量部~1質量部である。 Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.
例えば、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、2-アミノプロピルトリメトキシシラン、2-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリメトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリエトキシシラン、N-トリエトキシシリルプロピルトリエチレントリアミン、N-トリメトキシシリルプロピルトリエチレントリアミン、10-トリメトキシシリル-1,4,7-トリアザデカン、10-トリエトキシシリル-1,4,7-トリアザデカン、9-トリメトキシシリル-3,6-ジアザノニルアセテート、9-トリエトキシシリル-3,6-ジアザノニルアセテート、N-ベンジル-3-アミノプロピルトリメトキシシラン、N-ベンジル-3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリメトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリエトキシシラン等が挙げられる。 Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Examples thereof include propyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.
光増感剤としては、芳香族ニトロ化合物、クマリン(7-ジエチルアミノ-4-メチルクマリン、7-ヒドロキシ4-メチルクマリン)、ケトクマリン、カルボニルビスクマリン、芳香族2-ヒドロキシケトン、およびアミノ置換された、芳香族2-ヒドロキシケトン(2-ヒドロキシベンゾフェノン、モノ-もしくはジ-p-(ジメチルアミノ)-2-ヒドロキシベンゾフェノン)、アセトフェノン、アントラキノン、キサントン、チオキサントン、ベンズアントロン、チアゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトチアゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾチアゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾチアゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾチアゾリン、2-(β-ナフトイルメチレン)-3-メチル-β-ナフトチアゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトチアゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトチアゾリン)、オキサゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトオキサゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾオキサゾリン、2-(β-ナフトイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトオキサゾリン)、ベンゾチアゾール、ニトロアニリン(m-もしくはp-ニトロアニリン、2,4,6-トリニトロアニリン)またはニトロアセナフテン(5-ニトロアセナフテン)、(2-[(m-ヒドロキシ-p-メトキシ)スチリル]ベンゾチアゾール、ベンゾインアルキルエーテル、N-アルキル化フタロン、アセトフェノンケタール(2,2-ジメトキシフェニルエタノン)、ナフタレン、アントラセン(2-ナフタレンメタノール、2-ナフタレンカルボン酸、9-アントラセンメタノール、および9-アントラセンカルボン酸)、ベンゾピラン、アゾインドリジン、メロクマリン等がある。
好ましくは、芳香族2-ヒドロキシケトン(ベンゾフェノン)、クマリン、ケトクマリン、カルボニルビスクマリン、アセトフェノン、アントラキノン、キサントン、チオキサントン、およびアセトフェノンケタールである。 A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
塗布方法は、工業的には、スクリーン印刷、オフセット印刷、フレキソ印刷またはインクジェット法などで行う方法が一般的である。その他の塗布方法としては、ディップ法、ロールコータ法、スリットコータ法、スピンナ法(回転塗布法)またはスプレー法などがあり、目的に応じてこれらを用いてもよい。 The method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
In general, the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
塗膜の厚みは、厚すぎると液晶表示素子の消費電力の面で不利となり、薄すぎると液晶表示素子の信頼性が低下する場合があるので、好ましくは5nm~300nm、より好ましくは10nm~150nmである。
尚、[I]工程の後、続く[II]工程の前に塗膜の形成された基板を室温にまで冷却する工程を設けることも可能である。 After the polymer composition is applied on a substrate having a conductive film for driving a horizontal electric field, it is 50 to 200 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven. The solvent can be evaporated at 150 ° C. to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.
工程[II]では、工程[I]で得られた塗膜に偏光した紫外線を照射する。塗膜の膜面に偏光した紫外線を照射する場合、基板に対して一定の方向から偏光板を介して偏光された紫外線を照射する。使用する紫外線としては、波長100nm~400nmの範囲の紫外線を使用することができる。好ましくは、使用する塗膜の種類によりフィルター等を介して最適な波長を選択する。そして、例えば、選択的に光架橋反応を誘起できるように、波長290nm~400nmの範囲の紫外線を選択して使用することができる。紫外線としては、例えば、高圧水銀灯から放射される光を用いることができる。 <Process [II]>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. For example, ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.
工程[III]では、工程[II]で偏光した紫外線の照射された塗膜を加熱する。加熱により、塗膜に配向制御能を付与することができる。
加熱は、ホットプレート、熱循環型オーブンまたはIR(赤外線)型オーブンなどの加熱手段を用いることができる。加熱温度は、使用する塗膜の液晶性を発現させる温度を考慮して決めることができる。 <Step [III]>
In step [III], the ultraviolet-irradiated coating film polarized in step [II] is heated. An orientation control ability can be imparted to the coating film by heating.
For heating, a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
なお、液晶発現温度は、側鎖型高分子または塗膜表面が固体相から液晶相に相転移がおきるガラス転移温度(Tg)以上であって、液晶相からアイソトロピック相(等方相)に相転移を起こすアイソトロピック相転移温度(Tiso)以下の温度をいう。
加熱後に形成される塗膜の厚みは、工程[I]で記した同じ理由から、好ましくは5nm~300nm、より好ましくは50nm~150nmであるのがよい。 The heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk. The Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C. lower than the upper limit of the liquid crystal temperature range. It is preferable that it is the temperature of the range which makes an upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
The liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
The thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm for the same reason described in the step [I].
[IV]工程は、[III]で得られた、横電界駆動用の導電膜上に液晶配向膜を有する基板(第1の基板)と、同様に上記[I’]~[III’]で得られた、導電膜を有しない液晶配向膜付基板(第2の基板)とを、液晶を介して、双方の液晶配向膜が相対するように対向配置して、公知の方法で液晶セルを作製し、横電界駆動型液晶表示素子を作製する工程である。なお、工程[I’]~[III’]は、工程[I]において、横電界駆動用の導電膜を有する基板の代わりに、該横電界駆動用導電膜を有しない基板を用いた以外、工程[I]~[III]と同様に行うことができる。工程[I]~[III]と工程[I’]~[III’]との相違点は、上述した導電膜の有無だけであるため、工程[I’]~[III’]の説明を省略する。 <Process [IV]>
The step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving. The obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method. This is a step of manufacturing a lateral electric field drive type liquid crystal display element. In the steps [I ′] to [III ′], a substrate having no lateral electric field driving conductive film was used in place of the substrate having the lateral electric field driving conductive film in the step [I]. It can be carried out in the same manner as in steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.
本発明に用いる塗膜では、側鎖の光反応と液晶性に基づく自己組織化によって誘起される分子再配向の原理を利用して、塗膜への高効率な異方性の導入を実現する。本発明の製造方法では、側鎖型高分子に光反応性基として光架橋性基を有する構造の場合、側鎖型高分子を用いて基板上に塗膜を形成した後、偏光した紫外線を照射し、次いで、加熱を行った後、液晶表示素子を作成する。 The manufacturing method of the board | substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply | coating a polymer composition on a board | substrate and forming a coating film. Next, by heating, high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
The coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. . In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, after forming a coating film on the substrate using the side chain polymer, polarized ultraviolet rays are formed. After irradiation and then heating, a liquid crystal display element is formed.
以下、実施例を用いて本発明を説明するが、本発明は、該実施例に限定されるものではない。 As described above, the lateral electric field drive type liquid crystal display element substrate manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.
EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.
なお、MA1及びM2は、それぞれ、次のようにして合成した。即ち、MA1は特許文献(WO2011-084546)に記載の合成法にて合成した。MA2は特許文献(特開平9-118717)に記載の合成法にて合成した。
MA3は市販購入可能であるものを用いた。
MA4は市販購入可能であるM6BC(みどり化学株式会社製)を用いた。
MA5は文献等未公開の新規化合物である。MA5は、MA2及びMA5-1を用いて合成したが、その詳細は以下の「<化合物MA5の合成>」で説明する。なお、MA5-1は文献(Liquid Crystals (2005), 32(8), 1031-1044.)に記載の合成法にて合成した。 The methacrylic monomers MA1 to MA5 used in the examples are shown below.
MA1 and M2 were synthesized as follows. That is, MA1 was synthesized by a synthesis method described in a patent document (WO2011-084546). MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717).
MA3 used was commercially available.
MA4BC (manufactured by Midori Chemical Co., Ltd.) that can be purchased commercially was used for MA4.
MA5 is a novel compound that has not been published yet. MA5 was synthesized using MA2 and MA5-1, and details thereof will be described in “<Synthesis of Compound MA5>” below. MA5-1 was synthesized by the synthesis method described in the literature (Liquid Crystals (2005), 32 (8), 1031-1044.).
(有機溶媒)
THF:テトラヒドロフラン。
NMP:N-メチル-2-ピロリドン。
BC:ブチルセロソルブ。
(有機合成試薬)
EDC: 1-(3-ジメチルアミノプロピル)-3-エチルカルボジイミド塩酸塩。
DMAP: 4-ジメチルアミノピリジン。
(重合開始剤)
AIBN:2,2’-アゾビスイソブチロニトリル。 In addition, the abbreviations of the reagents used in this example are shown below.
(Organic solvent)
THF: tetrahydrofuran.
NMP: N-methyl-2-pyrrolidone.
BC: Butyl cellosolve.
(Organic synthesis reagent)
EDC: 1- (3-Dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
DMAP: 4-dimethylaminopyridine.
(Polymerization initiator)
AIBN: 2,2′-azobisisobutyronitrile.
500mL四つ口フラスコに、化合物MA2(20.00g、65.3mmol)、化合物MA5-1(14.09g、71.8mmol)、EDC(15.02g、78.4mmol)、DMAP(0.80g、6.53mmol)、THF(200g)を加え23℃で反応を行った。HPLCにて反応追跡を行い、反応終了を確認後、反応溶液を蒸留水(1.2L)に注ぎ、酢酸エチル(2L)を加え、分液操作にて水層を除去した。有機層を蒸留水(500mL)で3回洗浄した後、有機層を硫酸マグネシウムで乾燥した。その後、ろ過、エバポレーターにて溶媒留去することで、オイル状化合物として化合物MA5-2を得た。引き続き、得られた化合物MA5-2にピリジニウム p-トルエンスルホン酸(PPTSと表記)(1.59g、6.3mmol)、エタノール(100g)を加え、60℃で加熱撹拌を行った。HPLCにて反応追跡を行い、反応終了を確認後、反応溶液を氷浴で冷却し、析出した固体をろ過、エタノールで洗浄した。得られた固体を減圧乾燥することで、化合物MA5を19.2g(収率69%)得た。
1H-NMR(400MHz, CDCl3, δppm):8.22-8.18(2H, m), 8.17-8.14(2H, m), 7.36-7.32(2H, m), 7.00-6.96(2H, m), 6.12-6.11(1H, m), 5.57-5.55(1H, m), 4.20-4.16(2H, m), 4.06(2H, t), 1.96-1.95(3H, m), 1.90-1.46(8H, m). <Synthesis of Compound MA5>
In a 500 mL four-necked flask, compound MA2 (20.00 g, 65.3 mmol), compound MA5-1 (14.09 g, 71.8 mmol), EDC (15.02 g, 78.4 mmol), DMAP (0.80 g, 6.53 mmol) and THF (200 g) were added, and the reaction was performed at 23 ° C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was poured into distilled water (1.2 L), ethyl acetate (2 L) was added, and the aqueous layer was removed by a liquid separation operation. The organic layer was washed 3 times with distilled water (500 mL), and then the organic layer was dried over magnesium sulfate. Thereafter, filtration and evaporation of the solvent with an evaporator gave Compound MA5-2 as an oily compound. Subsequently, pyridinium p-toluenesulfonic acid (expressed as PPTS) (1.59 g, 6.3 mmol) and ethanol (100 g) were added to the resulting compound MA5-2, and the mixture was heated and stirred at 60 ° C. The reaction was monitored by HPLC, and after confirming the completion of the reaction, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and washed with ethanol. The obtained solid was dried under reduced pressure to obtain 19.2 g (yield 69%) of compound MA5.
1 H-NMR (400 MHz, CDCl3, δ ppm): 8.22-8.18 (2H, m), 8.17-8.14 (2H, m), 7.36-7.32 (2H, m), 7.00-6.96 (2H, m), 6.12- 6.11 (1H, m), 5.57-5.55 (1H, m), 4.20-4.16 (2H, m), 4.06 (2H, t), 1.96-1.95 (3H, m), 1.90-1.46 (8H, m).
MA1(1.99g、6.0mmol)、MA2(7.35g、24.0mmol)、MA3(0.33g、1.5mmol)をTHF(85.45g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.246g、1.5mmol)を加え再び脱気を行った。この後50℃で24時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をジエチルエーテル(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をジエチルエーテルで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末を得た。
得られた粉末6.0gにNMP54.0gを加え、室温で3時間攪拌した。この溶液に、BC(40.0g)を加え攪拌することにより液晶配向剤溶液A1を得た。 <Synthesis Example 1>
MA1 (1.99 g, 6.0 mmol), MA2 (7.35 g, 24.0 mmol), MA3 (0.33 g, 1.5 mmol) are dissolved in THF (85.45 g), and deaerated with a diaphragm pump. After that, AIBN (0.246 g, 1.5 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 50 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (2000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.
56.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. By adding BC (40.0 g) to this solution and stirring, a liquid crystal aligning agent solution A1 was obtained.
MA1(9.97g,30.0mmol)、MA3(0.41g,1.8mmol)、MA4(11.47g,30.0mmol)をTHF(126.7g)中に溶解し、ダイヤフラムポンプで脱気を行った後、AIBN(0.49g,3.0mmol)を加え再び脱気を行い窒素置換を行った。この後50℃で24時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をジエチルエーテル(4000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をジエチルエーテルで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末を得た。
得られた粉末6.0gにNMP54.0gを加え、40℃で3時間攪拌した。この溶液に、BC(40.0g)を加え攪拌することにより液晶配向剤溶液A2を得た。 <Synthesis Example 2>
MA1 (9.97 g, 30.0 mmol), MA3 (0.41 g, 1.8 mmol), MA4 (11.47 g, 30.0 mmol) are dissolved in THF (126.7 g), and deaerated with a diaphragm pump. Then, AIBN (0.49 g, 3.0 mmol) was added and deaeration was performed again to perform nitrogen substitution. Thereafter, the mixture was reacted at 50 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (4000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.
56.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at 40 ° C. for 3 hours. To this solution, BC (40.0 g) was added and stirred to obtain a liquid crystal aligning agent solution A2.
MA1(9.97g,30.0mmol)、MA3(0.41g,1.8mmol)、MA5(12.79g,30mmol)をTHF(134.1g)中に溶解し、ダイヤフラムポンプで脱気を行った後、AIBN(0.49g,3.0mmol)を加え再び脱気を行い窒素置換を行った。この後50℃で24時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をジエチルエーテル(4000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をジエチルエーテルで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末を得た。
得られた粉末6.0gにNMP54.0gを加え、室温で3時間攪拌した。この溶液に、BC(40.0g)を加え攪拌することにより液晶配向剤溶液A3を得た。 <Synthesis Example 3>
MA1 (9.97 g, 30.0 mmol), MA3 (0.41 g, 1.8 mmol), MA5 (12.79 g, 30 mmol) were dissolved in THF (134.1 g), and deaeration was performed with a diaphragm pump. Thereafter, AIBN (0.49 g, 3.0 mmol) was added, and deaeration was performed again to perform nitrogen substitution. Thereafter, the mixture was reacted at 50 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (4000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.
56.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. To this solution, BC (40.0 g) was added and stirred to obtain a liquid crystal aligning agent solution A3.
合成例1で得られた液晶配向剤A1を用いて下記に示すような手順で液晶セルの作製を行った。基板は、30mm×40mmの大きさで、厚さが0.7mmのガラス基板であり、ITO膜をパターニングして形成された櫛歯状の画素電極が配置されたものを用いた。 <Example 1>
Using the liquid crystal aligning agent A1 obtained in Synthesis Example 1, a liquid crystal cell was prepared according to the procedure shown below. The substrate used was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
各画素は、その中央の屈曲部分を境にして上下に分割され、屈曲部分の上側の第1領域と下側の第2領域を有した。各画素の第1領域と第2領域とを比較すると、それらを構成する画素電極の電極要素の形成方向が異なるものとなっていた。すなわち、後述する液晶配向膜の配向処理方向を基準とした場合、画素の第1領域では画素電極の電極要素が+15°の角度(時計回り)をなすように形成され、画素の第2領域では画素電極の電極要素が-15°の角度(時計回り)をなすように形成されていた。すなわち、各画素の第1領域と第2領域とでは、画素電極と対向電極との間の電圧印加によって誘起される液晶の、基板面内での回転動作(インプレーン・スイッチング)の方向が互いに逆方向となるように構成されていた。 The pixel electrode had a comb-like shape formed by arranging a plurality of dog-shaped electrode elements having a bent central portion. The width of each electrode element in the short direction was 10 μm, and the distance between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji.
Each pixel was divided vertically with a central bent portion as a boundary, and had a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode were formed so as to form an angle of −15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It was configured to be in the opposite direction.
合成例1で得られた液晶配向剤A1を、準備された上記電極付き基板にスピンコートした。次いで、70℃のホットプレートで90秒間乾燥し、膜厚100nmの液晶配向膜を形成した。次いで、塗膜面に偏光板を介して313nmの紫外線を10mJ/cm2照射した後に140℃のホットプレートで10分間加熱し、液晶配向膜付き基板を得た。また、対向基板として電極が形成されていない高さ4μmの柱状スペーサーを有するガラス基板にも、同様に塗膜を形成させ、配向処理を施した。一方の基板の液晶配向膜上にシール剤(協立化学製XN-1500T)を印刷した。次いで、もう一方の基板を、液晶配向膜面が向き合い配向方向が0°になるようにして張り合わせた後、シール剤を熱硬化させて空セルを作製した。この空セルに減圧注入法によって、液晶MLC-2041(メルク株式会社製)を注入し、注入口を封止して、IPS(In-Planes Switching)モード液晶表示素子の構成を備えた液晶セルを得た。 << Preparation of liquid crystal cell >>
The liquid crystal aligning agent A1 obtained in Synthesis Example 1 was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the surface of the coating film was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 10 mJ / cm 2 and then heated on a hot plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell. A liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element was prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by vacuum injection and sealing the injection port. Obtained.
実施例2では液晶配向剤A2を用いて200℃のホットプレートで加熱し、実施例3では液晶配向剤A3を用いて180℃のホットプレート加熱した以外は実施例1と同様の方法を用いて液晶セルを調製した。 <Example 2 and Example 3>
In Example 2, the same method as in Example 1 was used, except that the liquid crystal aligning agent A2 was used to heat on a 200 ° C. hot plate, and that in Example 3 the liquid crystal aligning agent A3 was used to heat the plate at 180 ° C. A liquid crystal cell was prepared.
[液晶配向性の評価]
上記の如くに製造した液晶表示素子につき、光学顕微鏡により観察したとき、光漏れが観察されないものを液晶配向性「良好」、光漏れが観察されたものを液晶配向性「不良」として評価した。 <Evaluation of liquid crystal cell>
[Evaluation of liquid crystal alignment]
When the liquid crystal display element manufactured as described above was observed with an optical microscope, the liquid crystal orientation was evaluated as “good” when no light leakage was observed, and the liquid crystal alignment was evaluated as “bad” when light leakage was observed.
上記で作製した液晶セルを用い、70℃温下で5Vの電圧を60μs間印加し、16.67ms後の電圧を測定し電圧保持率を測定した。この初期電圧保持率をVHR1(%)とした。その後、70℃の恒温環境下、周波数30Hzで16Vppの交流電圧を168時間印加した。その後、液晶セルの画素電極と対向電極との間をショートさせた後に、上記と同様の方法にて電圧保持率を測定した。この電圧保持率をVHR2(%)とした。
電圧保持率の減少量ΔVHR(%)を下記式から求め、表1に記載した。
ΔVHR(%)=VHR1-VHR2
なお、電圧保持率の測定には、東陽テクニカ社製の電圧保持率測定装置VHR-1を使用した。
実施例1の液晶配向性及びVHRの結果を表1に示す。 << Evaluation of voltage holding ratio (VHR) >>
Using the liquid crystal cell produced above, a voltage of 5 V was applied for 60 μs at a temperature of 70 ° C., the voltage after 16.67 ms was measured, and the voltage holding ratio was measured. This initial voltage holding ratio was VHR1 (%). Thereafter, an alternating voltage of 16 Vpp was applied for 168 hours at a frequency of 30 Hz in a constant temperature environment of 70 ° C. Then, after short-circuiting between the pixel electrode and counter electrode of a liquid crystal cell, the voltage holding rate was measured by the method similar to the above. This voltage holding ratio was set to VHR2 (%).
The decrease amount ΔVHR (%) of the voltage holding ratio was calculated from the following formula and listed in Table 1.
ΔVHR (%) = VHR1-VHR2
The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.
The liquid crystal orientation and VHR results of Example 1 are shown in Table 1.
MA1(1.99g、6.0mmol)、MA2(7.35g、24.0mmol)をTHF(85.45g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.246g、1.5mmol)を加え再び脱気を行った。この後50℃で24時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をジエチルエーテル(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をジエチルエーテルで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末を得た。
得られた粉末6.0gにNMP54.0gを加え、室温で3時間攪拌した。この溶液に、BC(40.0g)を加え攪拌することにより液晶配向剤溶液B1を得た。上記方法で得られたポリマー溶液を液晶配向剤B1として用いた以外、実施例1と同様に液晶セルを調製し、電圧保持率を測定および液晶配向性の評価をした。結果を表1に示す。 <Comparative Example 1>
MA1 (1.99 g, 6.0 mmol) and MA2 (7.35 g, 24.0 mmol) were dissolved in THF (85.45 g), deaerated with a diaphragm pump, and then AIBN (0.246 g, 1 mmol). .5 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 50 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (2000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.
56.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. To this solution, BC (40.0 g) was added and stirred to obtain a liquid crystal aligning agent solution B1. A liquid crystal cell was prepared in the same manner as in Example 1 except that the polymer solution obtained by the above method was used as the liquid crystal aligning agent B1, and the voltage holding ratio was measured and the liquid crystal alignment was evaluated. The results are shown in Table 1.
MA1(9.97g,30.0mmol)、MA4(11.47g,30mmol)をTHF(124.3g)中に溶解し、ダイヤフラムポンプで脱気を行った後、AIBN(0.49g,3.0mmol)を加え再び脱気を行い窒素置換を行った。この後50℃で24時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をジエチルエーテル(4000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をジエチルエーテルで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末を得た。
得られた粉末6.0gにNMP54.0gを加え、40℃で3時間攪拌した。この溶液に、BC(40.0g)を加え攪拌することにより液晶配向剤溶液B2を得た。上記方法で得られたポリマー溶液を液晶配向剤B2として用いた。実施例1のホットプレートでの加熱温度を200℃で実施した以外は同様の方法を用いて液晶セルを調製し、電圧保持率を測定および液晶配向性の評価をした。結果を表1に示す。 <Comparative example 2>
MA1 (9.97 g, 30.0 mmol) and MA4 (11.47 g, 30 mmol) were dissolved in THF (124.3 g), deaerated with a diaphragm pump, and then AIBN (0.49 g, 3.0 mmol). ) Was added and deaerated again to perform nitrogen substitution. Thereafter, the mixture was reacted at 50 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (4000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.
56.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at 40 ° C. for 3 hours. To this solution, BC (40.0 g) was added and stirred to obtain a liquid crystal aligning agent solution B2. The polymer solution obtained by the above method was used as the liquid crystal aligning agent B2. A liquid crystal cell was prepared using the same method except that the heating temperature on the hot plate of Example 1 was 200 ° C., the voltage holding ratio was measured, and the liquid crystal orientation was evaluated. The results are shown in Table 1.
MA1(9.97g,30.0mmol)、MA5(12.79g,30mmol)をTHF(131.8g)中に溶解し、ダイヤフラムポンプで脱気を行った後、AIBN(0.49g,3.0mmol)を加え再び脱気を行い窒素置換を行った。この後50℃で24時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をジエチルエーテル(4000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をジエチルエーテルで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末を得た。
得られた粉末6.0gにNMP54.0gを加え、室温で3時間攪拌した。この溶液に、BC(40.0g)を加え攪拌することにより液晶配向剤溶液B3を得た。上記方法で得られたポリマー溶液を液晶配向剤B3として用いた。実施例1のホットプレートでの加熱温度を180℃で実施した以外は同様の方法を用いて液晶セルを調製し、電圧保持率を測定および液晶配向性の評価をした。結果を表1に示す。 <Comparative Example 3>
MA1 (9.97 g, 30.0 mmol) and MA5 (12.79 g, 30 mmol) were dissolved in THF (131.8 g), deaerated with a diaphragm pump, and then AIBN (0.49 g, 3.0 mmol). ) Was added and deaerated again to perform nitrogen substitution. Thereafter, the mixture was reacted at 50 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (4000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.
56.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. To this solution, BC (40.0 g) was added and stirred to obtain a liquid crystal aligning agent solution B3. The polymer solution obtained by the above method was used as the liquid crystal aligning agent B3. A liquid crystal cell was prepared using the same method except that the heating temperature on the hot plate of Example 1 was 180 ° C., the voltage holding ratio was measured, and the liquid crystal alignment was evaluated. The results are shown in Table 1.
MA3(0.33g、10.0mmol)をTHF(30.9g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.08g、0.5mmol)を加え再び脱気を行った。この後50℃で24時間反応させメタクリレートのポリマー溶液T1を得た。液晶配向剤溶液B1 50gに対し、T1を0.8g加え液晶配向剤B4を得た。上記方法で得られたポリマー溶液を液晶配向剤B4として用いた以外、実施例1と同様に液晶セルを調製し、電圧保持率を測定した。結果を表1に示す。 <Comparative example 4>
MA3 (0.33 g, 10.0 mmol) was dissolved in THF (30.9 g), deaerated with a diaphragm pump, and then AIBN (0.08 g, 0.5 mmol) was added to deaerate again. . Thereafter, the mixture was reacted at 50 ° C. for 24 hours to obtain a polymer solution T1 of methacrylate. 0.8 g of T1 was added to 50 g of the liquid crystal aligning agent solution B1 to obtain a liquid crystal aligning agent B4. A liquid crystal cell was prepared in the same manner as in Example 1 except that the polymer solution obtained by the above method was used as the liquid crystal aligning agent B4, and the voltage holding ratio was measured. The results are shown in Table 1.
1 側鎖型高分子膜
2、2a 側鎖
図2
3 側鎖型高分子膜
4、4a 側鎖
図3
5 側鎖型高分子膜
6、6a 側鎖
図4
7 側鎖型高分子膜
8、8a 側鎖 FIG.
1 Side
3 Side
5 Side
7 Side
Claims (16)
- (A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び
(B)有機溶媒
を含有する重合体組成物であって、
該(A)側鎖型高分子は、環状アミン構造を有する第1の繰り返し単位、及びフェノール構造を有する第2の繰り返し単位からなる群から選ばれる少なくとも1種の繰り返し単位を有し、
前記環状アミン構造は、窒素原子に隣接する2つの炭素原子がそれぞれ下記式(S)(式中、R11は、単結合又は置換されていてもよい炭化水素基であり、
Xは、単結合、酸素原子、硫黄原子、-CO-、-CO-O-又は-O-CO-であり、
R12は、置換されていてもよい炭化水素基である。但し、Xが単結合ではない場合、R11及びR12が互いに結合して環構造を形成していてもよい。)で表される置換基2個を有し、前記フェノール構造は、水酸基に対してオルト位の炭素原子のうち少なくとも1つの炭素原子が下記式(S)で表される置換基を有する、重合体組成物。
The (A) side chain polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure,
In the cyclic amine structure, two carbon atoms adjacent to the nitrogen atom are each represented by the following formula (S) (wherein R 11 is a single bond or an optionally substituted hydrocarbon group;
X is a single bond, an oxygen atom, a sulfur atom, —CO—, —CO—O— or —O—CO—,
R 12 is an optionally substituted hydrocarbon group. However, when X is not a single bond, R 11 and R 12 may be bonded to each other to form a ring structure. ), Wherein the phenol structure has a heavy structure in which at least one carbon atom in the ortho position relative to the hydroxyl group has a substituent represented by the following formula (S). Combined composition.
- (A)成分が、光架橋、光異性化、または光フリース転移を起こす感光性側鎖を有する請求項1に記載の組成物。 The composition according to claim 1, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
- 前記第1の繰り返し単位が、下記式(1-1)(式(1-1)中、Rは水素原子又はメチル基であり、R11は各々、同じであっても異なってもよく、上記と同じ定義を有し、Xは各々、同じであっても異なってもよく、上記と同じ定義を有し、R12は各々、同じであっても異なってもよく、上記と同じ定義を有し、B1は、水素原子、酸素原子、ハロゲン原子、水酸基又は1価の有機基であり、mは0~4の整数である)で表され、
前記第2の繰り返し単位が、下記式(1-2)(式(1-2)中、Rは水素原子又はメチル基であり、R11は各々、同じであっても異なってもよく、上記と同じ定義を有し、Xは各々、同じであっても異なってもよく、上記と同じ定義を有し、R12は各々、同じであっても異なってもよく、上記と同じ定義を有し、nは0~3の整数である)で表される請求項1又は2に記載の組成物。
The second repeating unit is represented by the following formula (1-2) (in the formula (1-2), R is a hydrogen atom or a methyl group, and R 11 may be the same or different. X may be the same or different, each having the same definition as above, and R 12 may each be the same or different and have the same definition as above. And n is an integer of 0 to 3).
- 前記第1の繰り返し単位が、下記式(1-1-1)(式(1-1-1)中、Rは水素原子又はメチル基であり、A1は単結合又は2価の連結基であり、R13はそれぞれ同じであっても異なってもよく、炭素数1~5のアルキル基であり、B1は、水素原子、酸素原子、ハロゲン原子、水酸基又は1価の有機基である)で表され、
前記第2の繰り返し単位が、下記式(1-2-1)(式(1-2-1)中、Rは水素原子又はメチル基であり、A1は単結合又は2価の連結基であり、R13は、炭素数1~5のアルキル基であり、R14は、水素原子又は炭素数1~5のアルキル基である)で表される請求項1~3のいずれか1項に記載の組成物。
The second repeating unit is represented by the following formula (1-2-1) (in the formula (1-2-1), R is a hydrogen atom or a methyl group, and A 1 is a single bond or a divalent linking group. The R 13 is an alkyl group having 1 to 5 carbon atoms, and the R 14 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The composition as described.
- (A)成分が、下記式(1)~(6)
(式中、A、B、Dはそれぞれ独立に、単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Sは、炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Tは、単結合または炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
Y2は、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R51は、ヒドロキシ基、炭素数1~6のアルコキシ基を表すか、又はY1と同じ定義を表す;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表し、Xの数が2となるときは、X同士は同一でも異なっていてもよい;
Couは、クマリン-6-イル基またはクマリン-7-イル基を表し、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
q1とq2は、一方が1で他方が0である;
q3は0または1である;
P及びQは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である;ただし、Xが-CH=CH-CO-O-、-O-CO-CH=CH-である場合、-CH=CH-が結合する側のP又はQは芳香環であり、Pの数が2以上となるときは、P同士は同一でも異なっていてもよく、Qの数が2以上となるときは、Q同士は同一でも異なっていてもよい;
l1は0または1である;
l2は0~2の整数である;
l1とl2がともに0であるときは、Tが単結合であるときはAも単結合を表す;
l1が1であるときは、Tが単結合であるときはBも単結合を表す;
H及びIは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。)
からなる群から選ばれるいずれか1種の感光性側鎖を有する請求項1~4のいずれか1項に記載の組成物。
(Wherein A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R 51 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof. )
The composition according to any one of claims 1 to 4, which has any one photosensitive side chain selected from the group consisting of:
- (A)成分が、下記式(7)~(10)
(式中、A、B、Dはそれぞれ独立に、単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表し、Xの数が2となるときは、X同士は同一でも異なっていてもよい;
lは1~12の整数を表す;
mは、0~2の整数を表し、m1、m2は1~3の整数を表す;
nは0~12の整数(ただしn=0のときBは単結合である)を表す;
Y2は、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R51は、ヒドロキシ基、炭素数1~6のアルコキシ基を表すか、又はY1と同じ定義を表す)
からなる群から選ばれるいずれか1種の感光性側鎖を有する請求項1~4のいずれか1項に記載の組成物。
(Wherein A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (provided that when n = 0, B is a single bond);
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R 51 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 )
The composition according to any one of claims 1 to 4, which has any one photosensitive side chain selected from the group consisting of:
- (A)成分が、下記式(11)~(13)
(式中、Aは、それぞれ独立に、単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表し、Xの数が2となるときは、X同士は同一でも異なっていてもよい;
lは、1~12の整数を表し、mは0~2の整数を表し、m1は1~3の整数を表す;
R51は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良いか、又はヒドロキシ基もしくは炭素数1~6のアルコキシ基を表す)
からなる群から選ばれるいずれか1種の感光性側鎖を有する請求項1~4のいずれか1項に記載の組成物。
(Wherein A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—) Or represents —O—CO—CH═CH—;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m1 represents an integer of 1 to 3;
R 51 represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms (It may be substituted with an alkyloxy group or represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms)
The composition according to any one of claims 1 to 4, which has any one photosensitive side chain selected from the group consisting of:
- (A)成分が、下記式(14)又は(15)
(式中、Aはそれぞれ独立に、単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
lは1~12の整数を表し、m1、m2は1~3の整数を表す)
で表される感光性側鎖を有する請求項1~4のいずれか1項に記載の組成物。
(Wherein each A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or represents —O—CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3)
The composition according to any one of claims 1 to 4, which has a photosensitive side chain represented by the formula:
- (A)成分が、下記式(16)又は(17)
(式中、Aは単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表し、Xの数が2となるときは、X同士は同一でも異なっていてもよい;
lは、1~12の整数を表し、mは0~2の整数を表す)
で表される感光性側鎖を有する請求項1~4のいずれか1項に記載の組成物。
Wherein A is a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or —O—. Represents CO—CH═CH—;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
The composition according to any one of claims 1 to 4, which has a photosensitive side chain represented by the formula:
- (A)成分が、下記式(18)又は(19)
(式中、A、Bはそれぞれ独立に、単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
q1とq2は、一方が1で他方が0である;
lは1~12の整数を表し、m1、m2は1~3の整数を表す;
R1は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基を表す)
からなる群から選ばれるいずれか1種の感光性側鎖を有する請求項1~4のいずれか1項に記載の組成物。
(Wherein A and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O) Represents — or —O—CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3;
R 1 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group)
The composition according to any one of claims 1 to 4, which has any one photosensitive side chain selected from the group consisting of:
- (A)成分が、下記式(20)(式中、Aは、単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表し、Xの数が2となるときは、X同士は同一でも異なっていてもよい;
lは1~12の整数を表し、mは0~2の整数を表す)で表される感光性側鎖を有する請求項1~4のいずれか1項に記載の組成物。
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
The composition according to any one of claims 1 to 4, which has a photosensitive side chain represented by the following formula: l represents an integer of 1 to 12, and m represents an integer of 0 to 2.
- (A)成分が、下記式(21)~(31)(式中、A及びBは上記と同じ定義を有する;
Y3は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R3は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、炭素数5~8の脂環式炭化水素、炭素数1~12のアルキル基、又は炭素数1~12のアルコキシ基を表す;
q1とq2は、一方が1で他方が0である;
lは1~12の整数を表し、mは0から2の整数を表し、但し、式(23)~(24)において、全てのmの合計は2以上であり、式(25)~(26)において、全てのmの合計は1以上であり、m1、m2およびm3は、それぞれ独立に1~3の整数を表す;
R2は、水素原子、-NO2、-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、アルキル基、又はアルキルオキシ基を表す;
Z1、Z2は単結合、-CO-、-CH2O-、-CH=N-、-CF2-を表す)からなる群から選ばれるいずれか1種の液晶性側鎖を有する請求項1~11のいずれか1項に記載の組成物。
Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 each have a liquid crystalline side chain selected from the group consisting of a single bond, —CO—, —CH 2 O—, —CH═N—, —CF 2 —. Item 12. The composition according to any one of Items 1 to 11.
- [I] 請求項1~12のいずれか1項に記載の組成物を、横電界駆動用の導電膜を有する基板上に塗布して塗膜を形成する工程;
[II] [I]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された横電界駆動型液晶表示素子用液晶配向膜を得る、前記液晶配向膜を有する基板の製造方法。 [I] A step of applying the composition according to any one of claims 1 to 12 onto a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having. - 請求項13記載の方法により製造された横電界駆動型液晶表示素子用液晶配向膜を有する基板。 A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element produced by the method according to claim 13.
- 請求項14記載の基板を有する横電界駆動型液晶表示素子。 A lateral electric field drive type liquid crystal display device comprising the substrate according to claim 14.
- 請求項14記載の基板(第1の基板)を準備する工程;
[I’] 第2の基板上に
(A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び
(B)有機溶媒
を含有する重合体組成物を、塗布して塗膜を形成する工程;
[II’] [I’]で得られた塗膜に偏光した紫外線を照射する工程;
[III’] [II’]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された液晶配向膜を得る、前記液晶配向膜を有する第2の基板を得る工程;及び
[IV] 液晶を介して前記第1及び第2の基板の液晶配向膜が相対するように、前記第1及び第2の基板を対向配置して液晶表示素子を得る工程;
を有することにより、横電界駆動型液晶表示素子を得る、該液晶表示素子の製造方法。 Preparing a substrate (first substrate) according to claim 14;
[I ′] A polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent is applied onto a second substrate. Forming a coating film;
[II ′] A step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays;
[III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film having alignment control ability by providing a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.
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CN107109228A (en) * | 2015-01-19 | 2017-08-29 | 默克专利股份有限公司 | Polymerizable compound and its purposes in a liquid crystal display |
JPWO2017199986A1 (en) * | 2016-05-18 | 2019-03-14 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
WO2020203631A1 (en) * | 2019-03-29 | 2020-10-08 | 日産化学株式会社 | Polymer composition and single-layer retardation material |
WO2023095925A1 (en) * | 2021-11-29 | 2023-06-01 | 日産化学株式会社 | Polymer composition and single-layer retardation material |
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CN107109228A (en) * | 2015-01-19 | 2017-08-29 | 默克专利股份有限公司 | Polymerizable compound and its purposes in a liquid crystal display |
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JP2020125482A (en) * | 2015-01-19 | 2020-08-20 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | Polymerizable compound and use of the same in liquid crystal display |
CN107109228B (en) * | 2015-01-19 | 2021-03-19 | 默克专利股份有限公司 | Polymerizable compounds and their use in liquid crystal displays |
JPWO2017199986A1 (en) * | 2016-05-18 | 2019-03-14 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
JP6992746B2 (en) | 2016-05-18 | 2022-01-13 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
WO2020203631A1 (en) * | 2019-03-29 | 2020-10-08 | 日産化学株式会社 | Polymer composition and single-layer retardation material |
WO2023095925A1 (en) * | 2021-11-29 | 2023-06-01 | 日産化学株式会社 | Polymer composition and single-layer retardation material |
Also Published As
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JP6744717B2 (en) | 2020-08-19 |
KR102174142B1 (en) | 2020-11-04 |
JPWO2014196589A1 (en) | 2017-02-23 |
CN105452370A (en) | 2016-03-30 |
TW201510045A (en) | 2015-03-16 |
KR20160016913A (en) | 2016-02-15 |
TWI626269B (en) | 2018-06-11 |
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