Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element.
• the present invention also relates to a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured using the composition, a substrate having the film, and a manufacturing method thereof.
• this invention relates to the liquid crystal display element which has this liquid crystal aligning film or substrate, and its manufacturing method.
• the present invention provides a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device in which the light irradiation amount range is expanded and the manufacturing efficiency of the liquid crystal alignment film is increased in the photo alignment method used for the alignment treatment of the liquid crystal alignment film.
• the present invention relates to a composition, a liquid crystal alignment film manufactured using the composition or a substrate having a liquid crystal alignment film, a liquid crystal display element having them, a liquid crystal alignment film, a substrate having a liquid crystal alignment film, or a method for manufacturing a liquid crystal display element.
• 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.
• a photo-alignment method is known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability.
• the photo-alignment method eliminates the need for rubbing, does not cause the generation of dust and static electricity, and can perform the alignment treatment even on the substrate of the liquid crystal display element having the uneven surface. There is an advantage that you can.
• the photo-alignment method As the photo-alignment method, a decomposition-type photo-alignment method, a photo-crosslinking type, a photo-isomerization-type photo-alignment method, and the like are known.
• the decomposition type photo-alignment method is, for example, that a polyimide film is irradiated with polarized ultraviolet rays, and an anisotropic decomposition is generated by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. This is a method of aligning the liquid crystal by the method (for example, see Patent Document 1).
• the photo-crosslinking type or photoisomerization type photo-alignment method uses, for example, polyvinyl cinnamate, irradiates polarized ultraviolet rays, and performs a dimerization reaction (cross-linking reaction) at the double bond portion of two side chains parallel to the polarized light. This is a method of generating and aligning the liquid crystal in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1).
• Patent Document 3 discloses a liquid crystal alignment film obtained by using a photo-alignment method by photocrosslinking, photoisomerization or photo-fleece rearrangement.
• the photo-alignment method has a great advantage because it eliminates the rubbing process itself as compared with the rubbing method conventionally used industrially as an alignment treatment method for liquid crystal display elements. 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 alignment controllability of the main component used in the photo-alignment method is too sensitive to the amount of polarized light, the alignment may be incomplete in part or all of the liquid crystal alignment film, and stable liquid crystal alignment cannot be realized. Occurs.
• an object of the present invention is to produce a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, which can efficiently obtain a liquid crystal alignment film having a good quality by expanding the range of light irradiation amount in which the alignment control ability is stably generated. It is to provide a composition for use.
• the object of the present invention is a liquid crystal alignment film or a substrate having a liquid crystal alignment film produced using the composition, and a lateral electric field drive type liquid crystal display device having them. Is to provide.
• the objective of this invention is providing the manufacturing method of a liquid crystal aligning film, the board
• A a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range
• B A composition having a structure represented by the following formula (B)
• C a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, which comprises an organic solvent.
• C 1 , C 2 , C 3 , and C 4 each independently represent a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear chain having 1 to 10 carbon atoms. Or a branched alkoxy group, a hydroxyl group, a cyano group, a dialkylamino group (the alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a straight chain having 1 to 10 carbon atoms.
• P 1 and P 2 each independently represent * —CH ⁇ N— * or * —N ⁇ CH— * (* represents a bonding position with C 1 , C 2 , C 3 or C 4 ).
• L represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted with a substituent selected from the first group.
• —CH 2 — in L consists of —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH— and —CO—. It may be substituted with a group selected from the second group. However, groups selected from the second group are not adjacent to each other. n1 represents an integer of 0 to 5, and m4 represents an integer of 1 to 5.
• (B) the compound having the structure represented by the formula (B) is independently selected from the group consisting of the following formulas CL-1 to CL-23 at both ends.
• Terminal group in the formula, * indicates a position bonded to the structure represented by the formula (B), particularly a position bonded to C 1 or C 4 of the structure represented by the formula (B).
• R 11 is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms substituted with halogen.
• R 12 is substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, or a linear or branched chain having 1 to 12 carbon atoms or halogen.
• Z 11 , Z 12 and Z 13 are each independently R 13 , OR 13 or OCOR 13 (wherein R 13 is a linear or branched hydrocarbon group having 1 to 4 carbon atoms).
• Z 11 , Z 12 and Z 13 are all R 13 ;
• BL represents a blocking group for protecting any isocyanate group of the following formulas BL-1 to BL-6 (wherein ** represents a bonding position with the isocyanate group)); It is good to have.
• ⁇ 4> In the above item ⁇ 2> or ⁇ 3>, between (B) a compound having a structure represented by the above formula (B) during or C 4 and the terminal groups of the C 1 and the terminal group, It may have a spacer group.
• the spacer groups are each independently —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH—, —CO—, —N.
• a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a substituent selected from the first group (wherein —CH 2 — in the alkylene group is independently —O Substituted with a group selected from the second group consisting of —, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH— and —CO—. Provided that the groups selected from the second group are not adjacent to each other).
• the structure represented by the formula (B) may be any one of (B1) to (B14).
• R 14 represents a hydrogen atom or a substituent selected from the first group.
• the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece rearrangement.
• 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 May be substituted with an alkyloxy group of R 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, m2 and R 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 , X, 1, 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 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
• a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element according to any one of the above ⁇ 1> to ⁇ 14> is applied onto a substrate having a conductive film for driving a horizontal electric field.
• ⁇ 17> A lateral electric field drive type liquid crystal display device having the substrate of ⁇ 16> above.
• ⁇ 18> a step of preparing a substrate (first substrate) of ⁇ 16>above;
• [I ′] A step of applying a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element according to any one of the above ⁇ 1> to ⁇ 14> on a second substrate 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 liquid crystal display element is obtained by disposing the first and second substrates so as to face each other;
• a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element which can efficiently obtain a liquid crystal alignment film with good quality by expanding the range of light irradiation amount in which alignment control ability is stably generated.
• a liquid crystal alignment film or a substrate having a liquid crystal alignment film manufactured using the composition a liquid crystal display device having them, particularly a lateral electric field drive type A liquid crystal display element can be provided.
• a method for producing a liquid crystal alignment film, a substrate having a liquid crystal alignment film, or a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element is provided. it can.
• the composition of the present invention comprises (A) a photosensitive side-chain polymer that exhibits liquid crystallinity within a predetermined temperature range (WO 2014/054785 (the contents of which are incorporated herein in its entirety by reference)). (Hereinafter also referred to simply as a side chain polymer); and (C) an organic solvent; and a coating obtained by using this composition is subjected to a photo-alignment method by irradiation with polarized light, and is similar to WO 2014/054785. In addition, a liquid crystal alignment film can be obtained.
• composition of the present invention uses a compound having a structure represented by the above formula (B) as the component (B) in addition to the components (A) and (C).
• 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; (B) A compound having a structure represented by the above formula (B), and (C) a polymer composition containing an organic solvent, specifically, a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device.
• 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 photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range on a substrate having a conductive film for driving a lateral electric field
• step [B) in the above formula (B) A polymer composition containing a compound having the structure represented and an organic solvent is applied 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 specifically, a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element is applied onto a substrate having a conductive film for driving a horizontal electric field, particularly on the conductive film.
• the polymer composition used in the production method of the present invention includes (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) the above formula (B And a compound having a structure represented by (C); and (C) an organic solvent.
• the component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range.
• the (A) 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 300 ° 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 300 ° C.
• 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 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.
• More specific examples of the structure of the photosensitive side chain polymer that can exhibit liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl , A main chain composed of at least one selected from the group consisting of radical polymerizable groups such as maleimide and norbornene and siloxane, and a side chain consisting of at least one of the following formulas (1) to (6) It is preferable that
• 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 May be substituted with an alkyloxy group of R 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, m2 and R 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 , X, 1, 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, 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 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 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
• 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 photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
• the photoreactive group possessed by the side chain the following structures and derivatives thereof are preferred.
• photoreactive side chain monomer examples include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene, etc.
• a polymerizable side group composed of at least one selected from the group consisting of siloxane and a photosensitive side chain consisting of at least one of the above formulas (1) to (6), preferably, for example, the above formula (7 ) To (10), a photosensitive side chain comprising at least one of the above formulas (11) to (13), and a photosensitivity represented by the above formula (14) or (15).
• a photosensitive side chain a photosensitive side chain represented by the above formula (16) or (17), a photosensitive side chain represented by the above formula (18) or (19), and a photosensitivity represented by the above formula (20).
• Sex side chain It is preferable that it has a structure.
• the photoreactive and / or liquid crystalline side chain monomers may include, but are not limited to, compounds represented by the following formulas (A01) to (A20).
• 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 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. Even if the side chain has a mesogenic group such as biphenyl or phenylbenzoate alone, or a group that forms a mesogen structure by hydrogen bonding between side chains such as benzoic acid. Good. As the mesogenic group that the side chain has, the following structure is preferable.
• liquid crystalline side chain monomers include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups
• a structure having a polymerizable group composed of at least one selected from the group consisting of siloxanes and a side chain composed of at least one of the above formulas (21) 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
• a radical thermal polymerization initiator is a compound that generates radicals when heated 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 200,000.
• 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 polymer composition used in the present invention contains a compound having a structure represented by the following formula (B) as the component (B).
• C 1 , C 2 , C 3 , and C 4 each independently represent a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear chain having 1 to 10 carbon atoms. Or a branched alkoxy group, a hydroxyl group, a cyano group, a dialkylamino group (the alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a straight chain having 1 to 10 carbon atoms.
• P 1 and P 2 each independently represent * —CH ⁇ N— * or * —N ⁇ CH— * (* represents a bonding position with C 1 , C 2 , C 3 or C 4 ).
• L represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted with a substituent selected from the first group.
• —CH 2 — in L consists of —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH— and —CO—. It may be substituted with a group selected from the second group. Provided that the groups selected from the second group are not adjacent to each other; n1 represents an integer of 0 to 5, and m4 represents an integer of 1 to 5.
• the compound having the structure represented by the formula (B) preferably has, independently at each end thereof, a terminal group selected from the group consisting of the following formulas CL-1 to CL-23.
• * represents a position bonded to the structure represented by the above formula (B), particularly a position bonded to C 1 or C 4 of the structure represented by the above formula (B).
• R 11 is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms substituted with halogen.
• R 12 is substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, or a linear or branched chain having 1 to 12 carbon atoms or halogen.
• Z 11 , Z 12 and Z 13 are each independently R 13 , OR 13 or OCOR 13 (wherein R 13 is a linear or branched hydrocarbon group having 1 to 4 carbon atoms).
• Z 11 , Z 12 and Z 13 are all R 13 ;
• BL represents a blocking group for protecting any isocyanate group of the following formulas BL-1 to BL-6; (wherein, ** represents a bonding position with the isocyanate group).
• the compound having the structure represented by the formula (B) is independently represented at each end thereof by the formulas CL-1 to CL-3, CL-5, CL-10, CL-12 to CL- 14 and a terminal group selected from the group consisting of CL-17 to CL-21.
• the compound having the structure represented by the formula (B) preferably has a spacer group between C 1 and the terminal group or between C 4 and the terminal group.
• the spacer groups are each independently —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH—, —CO—, —N.
• the content of the component (B), that is, the compound having the structure represented by the above formula (B), is 1 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). Part, more preferably 1 to 15 parts by weight.
• the composition of the present invention that is, the liquid crystal aligning agent contains a compound having a structure represented by the above formula (B) to obtain a liquid crystal aligning film by irradiating polarized light
• the range of light irradiation amount (so-called “irradiation amount margin”) in which the orientation control ability is stably generated can be expanded.
• irradiation amount margin By expanding the so-called “irradiation amount margin”, it is possible to obtain a liquid crystal alignment film in which the quality does not change even when the polarized light irradiation time slightly deviates from the control value in the manufacturing process of the liquid crystal alignment film.
• the manufacturing efficiency of the liquid crystal alignment film can be increased.
• 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), (B) and (C).
• 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.
• 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.
• 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). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
• 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. .
• the lateral electric field drive type liquid crystal display element substrate produced by the composition of the present invention or the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate is excellent in reliability.
• the composition of the present invention or the method of the present invention can expand the range of light irradiation amount (so-called “irradiation amount margin”) in which the alignment control ability of the liquid crystal alignment film is stably generated, the liquid crystal alignment film In this manufacturing process, even when the polarized light irradiation time slightly deviates from the control value, a liquid crystal alignment film having the same quality can be obtained, and the manufacturing efficiency of the liquid crystal alignment film can be increased.
• the lateral electric field drive type liquid crystal display element substrate produced by the composition of the present invention or the method of the present invention or the horizontal electric field drive type liquid crystal display element having the substrate is suitable for a large-screen high-definition liquid crystal television or the like.
• Available to: EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.
• T-1 was synthesized by a synthesis method described in non-patent literature (Journal of Polymer Science: Part B: Polymer Physics, (2004) Vol. 42, 758-765).
• T-2 is a novel compound that has not been disclosed yet, and its synthesis method will be described in detail in Synthesis Example 1 below.
• a commercial product manufactured by ADEKA
• T-4 was synthesized by a synthesis method described in non-patent literature (Polymer 42 (2001) 2379-2385).
• T-5 to T-8 were synthesized by the synthesis method described in non-patent literature (Journal of Applied Polymer Science (2004) Vol. 92, 3721-3729).
• T-9 to T-10 are novel compounds that have not been disclosed in the literature, and their synthesis methods will be described in detail in Synthesis Examples 2 to 3 below.
• T-11 was synthesized by a synthesis method described in non-patent literature (Phosphorus, Sulfur and Silicon and the Related Elements (2006) 181 (6), 1323-1330.).
• T-12 was synthesized by a synthesis method described in non-patent literature (Journal of Molecular Structure, (2013) 1040, 149-154).
• T-13 was synthesized by a synthesis method described in non-patent literature (Journal of the Indian Chemical Society, (1984) 61 (1), 62-4).
• T-14 to T-15 are novel compounds that have not yet been disclosed in literatures, and their synthesis methods are described in detail in Synthesis Examples 4 to 5 below.
• T-16 was synthesized by a synthesis method described in non-patent literature (Journal of Polymer Science: Part B: Polymer Physics, (2004) Vol. 42, 758-765).
• T-17 was synthesized by a synthesis method described in non-patent literature (Medicinal Chemistry Research, (2014) 23 (5), 2476-2485).
• T-18 to T-22 are new compounds that have not been disclosed yet, and their synthesis methods will be described in detail in Synthesis Examples 6 to 10 below.
• T-23 was synthesized by a synthesis method described in non-patent literature (Polymer Composites, (2013) 34 (4), 468-476).
• the molecular weight of the acrylic polymer in the examples was as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex. It was measured.
• GPC room temperature gel permeation chromatography
• FT-NMR Fourier transform type superconducting nuclear magnetic resonance apparatus
• INOVA-400 manufactured by Varian 400 MHz.
• Solvent deuterated chloroform (CDCl 3 ) or deuterated N, N-dimethyl sulfoxide ([D 6 ] -DMSO).
• Standard substance Tetramethylsilane (TMS).
• DSC Differential scanning calorimeter
• DSC1 Differential scanning calorimeter
• methacrylate polymer powder This polymer had a number average molecular weight of 35,000 and a weight average molecular weight of 126,000.
• NMP 54.0 g was added to 6.0 g of the obtained powder, and dissolved by stirring at room temperature for 3 hours. By adding BC (40.0 g) to this solution and stirring, a methacrylate polymer solution PMA-1 was obtained.
• Example 2 to 23 and Comparative Examples 1 to 3 Liquid crystal aligning agents A-2 to A-23 of Examples 2 to 23 were obtained with the compositions shown in Table 1 using the same method as in Example 1. In Comparative Examples 1 to 3, liquid crystal aligning agents B-1 to B-3 were prepared in the same manner.
• an order parameter measurement substrate was prepared in the following procedure.
• a quartz substrate having a size of 40 mm ⁇ 40 mm and a thickness of 1.0 mm was used as the substrate.
• the liquid crystal alignment agent A-1 obtained in Example 1 was filtered through a 1.0 ⁇ m filter, spin-coated on a quartz substrate, dried on a hot plate at 70 ° C. for 90 seconds, and then a liquid crystal alignment with a film thickness of 100 nm. A film was formed.
• the coating film surface was irradiated with 5 to 60 mJ / cm 2 of 313 nm ultraviolet rays via a polarizing plate, and then heated on a hot plate at 140 ° C. to 170 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.
• liquid crystal aligning agents A-2 to A-23 and B-1 to B-3 obtained in Examples 2 to 23 and Comparative Examples 1 to 3 were also ordered using the same method as the liquid crystal aligning agent A-1.
• a parameter measurement substrate was prepared.
• a para represents the absorbance in the direction parallel to the irradiated polarized UV direction
• a per represents the absorbance in the direction perpendicular to the irradiated polarized UV direction.
• a large represents the absorbance having a larger value by comparing the absorbance in the parallel direction and the vertical direction
• a small represents the absorbance having a smaller value by comparing the absorbance in the parallel direction and the vertical direction.
• the absolute value of the calculated order parameter S is shown in Table 2 using the following criteria.
• the absolute value of S is 0.5 or more ⁇ ⁇ : The absolute value of S is 0.4 or more to less than 0.5 ⁇ : The absolute value of S is 0.3 or more to less than 0.4 ⁇ : The absolute value of S Is less than 0.3
• the liquid crystal aligning agents of Examples 1 to 23 to which the additive of the present invention was added had a better range of order parameters than the liquid crystal aligning agent of Comparative Example 1 to which nothing was added. It was confirmed that was expanded to the high temperature side and / or the high irradiation amount side.
• the liquid crystal aligning agents of Comparative Example 2 and Comparative Example 3 using the additive T-2 having liquid crystallinity and the additive T-3 having similar absorption like the additive of the present invention it is good. It was confirmed that the range of order parameters was not expanded.

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