WO2015012341A1 - 重合体、重合体組成物および横電界駆動型液晶表示素子用液晶配向膜 - Google Patents
重合体、重合体組成物および横電界駆動型液晶表示素子用液晶配向膜 Download PDFInfo
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- WO2015012341A1 WO2015012341A1 PCT/JP2014/069529 JP2014069529W WO2015012341A1 WO 2015012341 A1 WO2015012341 A1 WO 2015012341A1 JP 2014069529 W JP2014069529 W JP 2014069529W WO 2015012341 A1 WO2015012341 A1 WO 2015012341A1
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- XJXFTMJZMSFHNW-UHFFFAOYSA-N CCC1(COCCCCOC(c(cc2)ccc2[O]2C(C)(CCC(C)(C)OC(C(C)=C)=O)C(C)C2)=O)COC1 Chemical compound CCC1(COCCCCOC(c(cc2)ccc2[O]2C(C)(CCC(C)(C)OC(C(C)=C)=O)C(C)C2)=O)COC1 XJXFTMJZMSFHNW-UHFFFAOYSA-N 0.000 description 1
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- 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
- G02F1/1343—Electrodes
- G02F1/134309—Electrodes characterised by their geometrical arrangement
- G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- 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
- G02F1/133703—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by introducing organic surfactant additives into the liquid crystal material
Definitions
- the present invention relates to a novel polymer, a composition containing the polymer, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element using the same, and a method for producing a substrate having the alignment film. Furthermore, the present invention relates to a novel method for producing 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.
- an object of the present invention is to provide a lateral electric field drive type liquid crystal element having an improved voltage holding ratio and a liquid crystal alignment film for the element.
- a photosensitive side-chain polymer that exhibits liquid crystallinity within a predetermined temperature range which is represented by the following formula (0):
- a and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O
- 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
- 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;
- 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.
- R 50 represents a group selected from a hydrogen atom, a halogen atom, an alkyl group, a phenyl group having 1 to 3 carbon atoms, if R 50 is more mutually the same or different T is an integer of 1 to 7, J represents O, S, NH or NR 51 , and R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group)
- T is an integer of 1 to 7
- J represents O, S, NH or NR 51
- R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group
- the side chain polymer preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
- the side chain polymer 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 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 polymer preferably has any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
- the side chain polymer may have any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
- A, X, l, m, m1 and R have the same definition as above.
- the side chain polymer 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 side chain polymer 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 side chain polymer may have 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.
- the side chain polymer 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 side chain polymer has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31): Is good.
- a and B 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; 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,
- a polymer composition comprising (A) the side chain polymer according to any one of ⁇ 1> to ⁇ 10> above and (B) an organic solvent.
- the polymer composition further includes (C) one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is aliphatic carbonized. It is preferable to contain an amine compound bonded to a hydrogen group or a non-aromatic cyclic hydrocarbon group.
- the component (C) is represented by the following formula A- [1] (wherein Y 11 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group) And Y 12 is a nitrogen-containing aromatic heterocyclic ring).
- ⁇ 14> A step of applying a composition according to any one of the above ⁇ 11> to ⁇ 13> 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];
- 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.
- ⁇ 15> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device produced by the method of ⁇ 14>.
- ⁇ 16> A lateral electric field drive type liquid crystal display device having the substrate of ⁇ 15> above.
- ⁇ 17> a step of preparing a substrate (first substrate) of ⁇ 15>above;
- [I ′] A step of applying a polymer composition according to any one of the above ⁇ 11> to ⁇ 13> on the 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 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 effects, a lateral electric field drive type liquid crystal element having improved voltage holding ratio by adsorbing ionic impurities in the liquid crystal at the liquid crystal alignment film interface and a liquid crystal alignment film for the element are provided. 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 further having a side chain represented by the above formula (0), and B) The process of apply
- 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] is 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, and is represented by the above formula (0).
- a side chain polymer further having a side chain, an organic solvent, and optionally, one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is aliphatic carbonized
- a polymer composition containing an amine compound bonded to a hydrogen group or a non-aromatic cyclic hydrocarbon group 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 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 comprises: (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) an organic solvent; and, if desired, (C) a molecule having one primary amino group and a nitrogen-containing aromatic heterocyclic ring, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; Containing amine compounds.
- the component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and further has a side chain represented by the above formula (0).
- 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 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 side chain type polymer has a group represented by the above formula (0), thereby giving a highly reliable liquid crystal alignment film such as a voltage holding ratio (VHR).
- VHR voltage holding ratio
- 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 film capable of exhibiting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, A main chain composed of at least one selected from the group consisting of radically polymerizable groups such as vinyl, maleimide, norbornene and siloxane, a group represented by the above formula (0), and the following formula (1) ( The structure having a side chain comprising at least one kind of 6) is preferred.
- 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, m1 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 , 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.
- 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 and B 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; 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,
- 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 monomer having a side chain represented by the formula (0) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, and maleimide. It is preferably a structure having a polymerizable group composed of at least one selected from the group consisting of radical polymerizable groups such as norbornene and siloxane, and a side chain represented by the above formula (0).
- monomers having an epoxy group include compounds such as glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allyl glycidyl ether.
- the monomer having thiirane include those in which the epoxy structure of the monomer having the epoxy group is replaced with thiirane.
- the monomer having aziridine include those in which the epoxy structure of the monomer having the epoxy group is replaced with aziridine or 1-methylaziridine.
- Examples of the monomer having an oxetane group include (meth) acrylic acid ester having an oxetane group.
- monomers 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3- Ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (Acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl)
- the monomer having a thietane group for example, a monomer in which the oxetane group of the monomer having an oxetane group is replaced with a thietane group is preferable.
- the monomer having an azetan group for example, a monomer in which an oxetane group of a monomer having an oxetane group is replaced with an azetan group is preferable.
- a monomer having an epoxy group and a monomer having an oxetane group are preferable from the viewpoint of availability and the like, and a monomer having an epoxy group is more preferable.
- glycidyl (meth) acrylate is preferable from the viewpoint of availability.
- 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 present application relates to novel compounds (1) to (11) represented by the following formulas (1) to (11), and the following formulas (12) to (17) as photoreactive and / or liquid crystalline side chain monomers. (12) to (17) are provided.
- 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.
- 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 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.
- unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
- acrylic ester compound examples 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.
- vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
- styrene compound examples include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
- maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. *
- the content of the side chain represented by the formula (0) in the side chain polymer of the present invention is preferably from 0.1 mol% to 20 mol% from the viewpoint of improving reliability and affecting liquid crystal orientation. 0.5 mol% to 10 mol% is more preferable, and 1 mol% to 5 mol% is still more preferable.
- the content of the photoreactive side chain in the side chain polymer of the present invention is preferably 20 mol% to 99.9 mol%, more preferably 30 mol% to 95 mol%, from the viewpoint of liquid crystal alignment. More preferred is mol% to 90 mol%.
- the content of the liquid crystalline side chain in the side chain type polymer of the present invention is preferably 80 mol% or less, more preferably 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol% from the viewpoint of liquid crystal alignment. Is more preferable.
- the side chain polymer of the present invention may contain other side chains other than the side chain represented by the above formula (0), the photoreactive side chain, and the liquid crystalline side chain.
- the content is the remaining portion when the total content of the side chain, photoreactive side chain and liquid crystalline side chain represented by the above formula (0) is less than 100%.
- 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 during coating film formation, 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 has a specific amine compound, specifically, one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is a fatty acid. It is preferable to have an amine compound bonded to an aromatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. By including such an amine compound, it is possible to reduce elution of ionic impurities and promote the crosslinking reaction of the group represented by the above formula (0) or more durable when it is used as a liquid crystal alignment film. A liquid crystal alignment film having a high thickness can be obtained.
- the specific amine compound is not particularly limited as long as it exhibits the following effects i) and / or ii) when the polymer composition used in the present invention forms a liquid crystal alignment film. i) Adsorbs ionic impurities in the liquid crystal at the liquid crystal alignment film interface and / or ii) exhibits improved voltage holding ratio.
- the amount of the specific amine compound is not particularly limited as long as the above effect is obtained, but is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass in 100 parts by mass of the polymer composition used in the present invention. It is good that it is a mass part.
- aliphatic hydrocarbon group examples include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond.
- the aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- divalent non-aromatic cyclic hydrocarbon group examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane Ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, Examples include a decahydronaphthalene ring, a norbornene ring
- it is a ring having 3 to 20 carbon atoms, more preferably a ring having 3 to 15 carbon atoms, and even more preferably a non-aromatic cyclic hydrocarbon group having a ring having 3 to 10 carbon atoms. It is.
- the nitrogen-containing aromatic heterocyclic ring contained in the amine compound has the following formula [20a], formula [20b] and formula [20c] (wherein Z 2 is a linear or branched alkyl group having 1 to 5 carbon atoms) And an aromatic cyclic hydrocarbon containing at least 1, preferably 1 to 4 structures selected from the group consisting of:
- More preferred amine compounds are those represented by the following formula A- [1] (wherein Y 11 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y 12 is a nitrogen-containing group. It is preferable that the amine compound be an aromatic heterocyclic ring.
- Y 12 is not particularly limited as long as Y 12 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.
- Preferred Y 11 in formula A- [1] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. It is good to be.
- Examples of the non-aromatic cyclic hydrocarbon group include the above-described structures.
- Y 11 is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring. , Cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y 11 is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.
- —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y 11 is —O—, —NH—, —CO—O—.
- —O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, — C (CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O -It may be replaced by a divalent cyclic hydrocarbon group or a heterocyclic ring.
- a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.
- divalent cyclic hydrocarbon group examples include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring , Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring Ring, cyclon
- divalent heterocyclic ring examples include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring.
- Y 12 in the formula A- [1] is a nitrogen-containing aromatic heterocyclic ring, and as described above, at least one selected from the group consisting of the formula [20a], the formula [20b], and the formula [20c]
- An aromatic cyclic hydrocarbon containing the structure Specific examples thereof include the structure described above.
- pyrrole ring imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring
- a phenazine ring and a phthalazine ring are preferable.
- Y 11 is a formula [20a], a formula included in Y 12 It is preferably bonded to a substituent not adjacent to [20b] and formula [20c].
- the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y 12 in formula A- [1] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom, sulfur You may contain hetero atoms, such as an atom and a nitrogen atom.
- a preferred combination of Y 11 and Y 12 in the formula A- [1] is a group in which Y 11 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms.
- Y 12 is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, A benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring.
- the carbon atom of the nitrogen-containing aromatic heterocycle of Y 12 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
- Y 13 is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms
- Y 14 Is a single bond, or —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms
- the total of carbon atoms of Y 13 and Y 14 Is an amine compound represented by:
- Y 15 is a nitrogen-containing aromatic heterocyclic ring.
- Y 13 in the formula A- [2] is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclo Octane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cycloo
- a linear or branched alkylene group having 1 to 10 carbon atoms cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane And a ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring.
- Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.
- —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y 13 is —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —C ( CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O—, It may be replaced with a divalent cyclic hydrocarbon group or a heterocyclic ring.
- a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.
- the cyclic hydrocarbon group and the heterocyclic ring mentioned here have the same meaning as defined for Y 11 in the formula A- [1].
- Y 14 in the formula A- [2] is a single bond, —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms.
- the divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y 14 are given below.
- Y 15 in the formula A- [2] is a nitrogen-containing aromatic heterocyclic ring, and has the same definition as Y 12 in the formula A- [1]. Specific examples may include the same structure as Y 12 described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring, or a phthalazine ring is preferable.
- Y 14 is a formula [20a] or formula included in Y 15. It is preferably bonded to a carbon atom that is not adjacent to [20b] or formula [20c]. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y 15 in the formula A- [2] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom or a sulfur atom. And may contain a hetero atom such as a nitrogen atom.
- Y 13 is a linear or branched alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring , Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring, and Y 14 is a single bond, having 1 carbon atom To 10 linear or branched alkylene groups, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CO—, —, —CO—, —
- the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
- Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane A ring, a cycloheptane ring, a norbornene ring, or an adamantane ring
- Y 14 is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CH (OH) —, —NH—CH 2 —, —S— CH 2 —, —O—CH 2 —, —O—C 2 H 4
- the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
- Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or A cyclohexane ring
- Y 14 is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—.
- the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
- a particularly preferred combination of Y 13 , Y 14 and Y 15 in the formula A- [2] is that Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane ring, and Y 14 is , Single bond, —O—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CH (OH) —, benzene ring, naphthalene ring, fluorene ring, or anthracene Y 15 is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring.
- the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
- Specific examples of the specific amine compound of the component (B) of the present invention include compounds M1 to M156.
- More preferable compounds include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, M128 to M137, M139 to M143, and M149 to M156.
- M6 to M8 M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116 M118 to M121, M125, M134 to M136, M139, M140, M143, M150, and M152 to M156.
- 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), (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.
- 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 Company), 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
- 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 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 isotropic coating film 5 is irradiated with polarized ultraviolet rays.
- the photosensitive group of the side chain 6a having the photosensitive group among the side chains 6 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like.
- 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.
- GMA, HBAGE, G1, and additive T1 are shown below as monomers having methacrylic monomers MA1 and MA2 and epoxy side chains used in the examples.
- MA1 and M2 were synthesized as follows. That is, MA1 was synthesized by the synthesis method described in the patent document (WO2011-084546). MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717). G1 was synthesized by the synthesis method described in Synthesis Example 1 below. GMA (glycidyl methacrylate), HBAGE (hydroxybutyl acrylate glycidyl ether), and additive T1 (3-aminomethylpyridine) were commercially available.
- Carboxylic acid derivative (MA2) (18.4 g, 60 mmol) in THF (tetrahydrofuran) solution (184 g) was mixed with (COCl) 2 (oxalyl chloride) (11.4 g, 90 mmol) and DMF (dimethylformamide). The solution was added dropwise and reacted at room temperature for 2 hours. The solid obtained by concentrating this solution was dissolved in THF (350 g). This solution was added dropwise to a THF solution (88 g) of glycidol (8.89 g, 120 mmol) and triethylamine (13.4 g, 132 mmol) over 1 hour and allowed to react for 18 hours.
- THF tetrahydrofuran
- Glycidyl derivative (G1) 1 H-NMR (CDCl 3 , ⁇ ppm): 8.01 (d, 2H), 7.01 (d, 2H), 6.01 (s, 1H), 5.56 (s, 1H), 4.65 -4.61 (m, 1H), 4.18-4.12 (m, 3H), 4.02 (t, 2H), 3.36-3.32 (m, 1H), 2.91-2 .89 (m, 1H), 2.74-2.72 (m, 1H), 1.95-1.94 (m, 3H), 1.86-1.79 (m, 2H), 1.76 -1.69 (m, 2H), 1.57-1.44 (m, 4H).
- Carboxylic acid derivative (M2) (21.4 g, 70 mmol), dimethylaminopyridine (0.85 g, 7 mmol), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (14, 8 g, 77 mmol) in THF
- 3-ethyl-3-oxetanemethanol (8.58 g, 73.5 mmol) was added and reacted at room temperature for 18 hours.
- the precipitated insoluble matter was removed by filtration, ethyl acetate (500 g) was added, washed three times with water (200 g), and dried over magnesium sulfate.
- Magnesium sulfate was removed by filtration and then concentrated to obtain G2 as a colorless liquid (yield 27.3 g, yield 96%).
- Oxetane compound (G3) 1 H-NMR (CDCl 3 , ⁇ ppm): 7.98 (d, 2H), 6.90 (d, 2H), 6.10 (s, 1H), 5.55 (s, 1H), 4.45 (D, 2H), 4.39 (d, 2H), 4.31 (t, 2H), 4.16 (t, 2H), 4,01 (t, 2H), 4.01 (t, 2H) 3.54-3.50 (m, 4H), 1.87-1.66 (m, 10H) 1.56-1.44 (m, 4H), 0.89 (t, 3H).
- NMP 54.0 g was added to the methacrylate polymer powder P1 (6.0 g) obtained in Polymer Synthesis 1, and dissolved by stirring for 5 hours at room temperature.
- Polymer solution A1 was obtained by adding BC (40.0g) to this solution and stirring. This polymer solution was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.
- Examples 2 to 12 The compositions shown in Table 2 were adjusted using the same method as in Example 1 to obtain liquid crystal aligning agents A2 to A12 of Examples 2 to 12.
- Control polymer synthesis example 2> Using a method similar to Control 1 with the composition of MA1 (5.9 g, 18 mmol), MA2 (3.7 g, 12 mmol), THF (55.5 g), AIBN (0.15 g, 3 mmol), methacrylate polymer powder CP2 Got.
- Control 1 liquid crystal aligning agent B1 was obtained in the same manner as in Example 1 using CP1. Similarly, Control 2 liquid crystal aligning agent B2 was obtained using CP2.
- liquid crystal aligning agent A1 obtained in 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 configured by arranging a plurality of electrode elements having a dogleg shape with 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 up and down with the central bent portion as a boundary, and had a first region above the bent portion and a second region below.
- 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).
- 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 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 coating film surface was irradiated with 20 mJ / cm 2 of 313 nm ultraviolet rays via a polarizing plate and then heated on a hot plate at 150 ° 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 ⁇ 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. 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-Plane Switching) mode liquid crystal display element was prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by a reduced pressure injection method, sealing the injection port. Obtained.
- liquid crystal cells were similarly prepared.
- VHR voltage holding ratio
- VHR1 is improved by copolymerizing a monomer having an epoxy group as compared with Controls 1 and 2 which are not copolymerized. It can also be seen that the results of VHR2 are good by adding the additive T1 in Examples 5 to 8, 11 and 12.
- the liquid crystal cell for IPS mode prepared in Examples 1 to 8 is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the backlight is turned on with no voltage applied.
- the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the liquid crystal cell became the smallest.
- the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the pixel was darkest to the angle at which the first region was darkest was calculated as the initial orientation azimuth.
- an alternating voltage of 16 V PP was applied in a 60 ° C. oven at a frequency of 30 Hz for 168 hours.
- the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for 1 hour.
- the orientation azimuth was measured in the same manner, and the difference in orientation azimuth before and after AC driving was calculated as an angle ⁇ (deg.). The same measurement was performed in other examples.
- the angle ⁇ was 0.1 or less.
- the long-chain polymer film that exhibits liquid crystallinity is irradiated with ultraviolet rays and then heated in the liquid crystal expression temperature range, so that the liquid crystal alignment ability is imparted to the entire polymer by self-organization. Even after AC driving, the alignment azimuth was hardly observed.
- 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、向上した電圧保持率を有する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。
<1> 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、下記式(0)
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;
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;
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;
Gは、下記式(G-1)、(G-2)、(G-3)及び(G-4)
から選ばれる基である]
で表される側鎖をさらに有する側鎖型高分子。
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;
R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。
式中、A、B、D、Y1、X、Y2、及びR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。
式中、A、X、l、m、m1及びRは、上記と同じ定義を有する。
式中、A、Y1、l、m1及びm2は上記と同じ定義を有する。
式中、A、X、l及びmは、上記と同じ定義を有する。
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。
式中、A、Y1、X、l及びmは上記と同じ定義を有する。
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。
[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。
<16> 上記<15>の基板を有する横電界駆動型液晶表示素子。
[I’] 第2の基板上に、上記<11>~<13>のいずれかの重合体組成物を、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。
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、液晶配向膜界面において液晶中のイオン性不純物を吸着し、向上した電圧保持率を有する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。
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
<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であって、上記式(0)で表される側鎖をさらに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。
上記工程により、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ことができ、該液晶配向膜を有する基板を得ることができる。
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。
[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。
<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であって、上記式(0)で表される側鎖をさらに有する側鎖型高分子、有機溶媒及び、所望により、分子内に1級アミノ基を1個と窒素含有芳香族複素環とを有し、かつ前記1級アミノ基が脂肪族炭化水素基又は非芳香族環式炭化水素基に結合しているアミン化合物を含有する重合体組成物を塗布して塗膜を形成する。
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。
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。
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;(B)有機溶媒;及び、所望に応じて(C)分子内に1級アミノ基を1個と窒素含有芳香族複素環とを有し、かつ前記1級アミノ基が脂肪族炭化水素基又は非芳香族環式炭化水素基に結合しているアミン化合物を含有する。
(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って、上記式(0)で表される側鎖をさらに有する。
(A)側鎖型高分子は、250nm~400nmの波長範囲の光で反応し、かつ100℃~300℃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℃~300℃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。
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;
R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。
式中、A、B、D、Y1、X、Y2、及びR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。
式中、A、X、l、m、m1及びRは、上記と同じ定義を有する。
式中、A、Y1、l、m1及びm2は上記と同じ定義を有する。
式中、A、X、l及びmは、上記と同じ定義を有する。
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。
式中、A、Y1、X、l及びmは上記と同じ定義を有する。
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。
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。
前記式(0)で表される側鎖を有するモノマーのより具体的な例としては、炭化水素、(メタ)アクリレート、イタコネート、フマレート、マレエート、α-メチレン-γ-ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン等のラジカル重合性基およびシロキサンからなる群から選択される少なくとも1種から構成された重合性基と、上記式(0)で表される側鎖を有する構造であることが好ましい。
光反応性側鎖モノマーとは、高分子を形成した場合に、高分子の側鎖部位に感光性側鎖を有する高分子を形成することができるモノマーのことである。
側鎖の有する光反応性基としては下記の構造およびその誘導体が好ましい。
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。
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。
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。
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。
-2-モルホリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸イソアミル、4,4’-ジ(t-ブチルペルオキシカルボニル)ベンゾフェノン、3,4,4’-トリ(t-ブチルペルオキシカルボニル)ベンゾフェノン、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、2-(4’-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(3’,4’-ジメトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(2’,4’-ジメトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(2’-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4’-ペンチルオキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、4-[p-N,N-ジ(エトキシカルボニルメチル)]-2,6-ジ(トリクロロメチル)-s-トリアジン、1,3-ビス(トリクロロメチル)-5-(2’-クロロフェニル)-s-トリアジン、1,3-ビス(トリクロロメチル)-5-(4’-メトキシフェニル)-s-トリアジン、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンズチアゾール、2-メルカプトベンゾチアゾール、3,3’-カルボニルビス(7-ジエチルアミノクマリン)、2-(o-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラキス(4-エトキシカルボニルフェニル)-1,2’-ビイミダゾール、2,2’-ビス(2,4-ジクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’ビス(2,4-ジブロモフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’-ビス(2,4,6-トリクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、3-(2-メチル-2-ジメチルアミノプロピオニル)カルバゾール、3,6-ビス(2-メチル-2-モルホリノプロピオニル)-9-n-ドデシルカルバゾール、1-ヒドロキシシクロヘキシルフェニルケトン、ビス(5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム、3,3’,4,4’-テトラ(t-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(t-ヘキシルペルオキシカルボニル)ベンゾフェノン、3,3’-ジ(メトキシカルボニル)-4,4’-ジ(t-ブチルペルオキシカルボニル)ベンゾフェノン、3,4’-ジ(メトキシカルボニル)-4,3’-ジ(t-ブチルペルオキシカルボニル)ベンゾフェノン、4,4’-ジ(メトキシカルボニル)-3,3’-ジ(t-ブチルペルオキシカルボニル)ベンゾフェノン、2-(3-メチル-3H-ベンゾチアゾール-2-イリデン)-1-ナフタレン-2-イル-エタノン、又は2-(3-メチル-1,3-ベンゾチアゾール-2(3H)-イリデン)-1-(2-ベンゾイル)エタノン等を挙げることができる。これらの化合物は単独で使用してもよく、2つ以上を混合して使用することもできる。
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。
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。
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。
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。
本発明に用いられる重合体組成物は、特定のアミン化合物、具体的には分子内に1級アミノ基を1個と窒素含有芳香族複素環とを有し、かつ前記1級アミノ基が脂肪族炭化水素基又は非芳香族環式炭化水素基に結合しているアミン化合物を有することが好ましい。かかるアミン化合物を含有することにより、液晶配向膜としたときに、イオン性不純物の溶出を低減するとともに、前記の式(0)で表される基の架橋反応を促進するためか、より耐久性の高い液晶配向膜を得ることができる。
さらに、式A-[1]のY12である窒素含有芳香族複素環の炭素原子は、ハロゲン原子及び/又は有機基の置換基を有していてもよく、該有機基は酸素原子、硫黄原子、窒素原子等のヘテロ原子を含有してもよい。
さらに好ましいアミン化合物としては、下記の式A-[2](式中、Y13は炭素数1~10の2価の脂肪族炭化水素基又は非芳香族環式炭化水素基であり、Y14は、単結合、若しくは-O-、-NH-、-S-、-SO2-又は炭素数1~19の2価の有機基である。また、Y13とY14が有する炭素原子の合計は1~20である。Y15は窒素含有芳香族複素環である。)で表されるアミン化合物である。
さらに、式A-[2]のY15である窒素含有芳香族複素環の炭素原子はハロゲン原子及び/又は有機基の置換基を有していてもよく、該有機基は酸素原子、硫黄原子、窒素原子等のヘテロ原子を含有してもよい。
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。
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-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。
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。
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。
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。
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。
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。
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。
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。
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。
[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。
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。
G1は下記合成例1に記載の合成法にて合成した。
GMA(メタクリル酸グリシジル)、HBAGE(ヒドロキシブチルアクリレートグリシジルエーテル)、添加剤T1(3-アミノメチルピリジン)は、市販購入可能であるものを用いた。
特定グリシジル化合物(G1)の合成
1H-NMR(CDCl3,δppm):8.01(d,2H),7.01(d,2H),6.01(s,1H),5.56(s,1H),4.65-4.61(m,1H),4.18-4.12(m,3H),4.02(t,2H),3.36-3.32(m,1H),2.91-2.89(m,1H),2.74-2.72(m,1H),1.95-1.94(m,3H),1.86-1.79(m,2H),1.76-1.69(m,2H),1.57-1.44(m,4H).
特定オキセタン化合物(G2)の合成
1H-NMR(CDCl3,δppm):7.97(d,2H),6.91(d,2H),6.10(s,1H),5.55(s,1H),4.60(d,2H),4.48(d,2H),4.43(s,2H),4.16(t,2H),4,02(t,2H),1.94(s,3H),1.88-1.79(m,4H),1.76-1.69(m,2H),1.57-1.43(m,4H),0.97(t,3H).
特定オキセタン化合物(G3)の合成
上記合成例と同様にして、以下のオキセタン化合物(G3)を合成した。
1H-NMR(CDCl3,δppm):7.98(d,2H),6.90(d,2H),6.10(s,1H),5.55(s,1H),4.45(d,2H),4.39(d,2H),4.31(t,2H),4.16(t,2H),4,01(t,2H),4.01(t,2H),3.54-3.50(m,4H),1.87-1.66(m,10H)1.56-1.44(m,4H),0.89(t,3H).
(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。
(重合開始剤)
AIBN:2,2’-アゾビスイソブチロニトリル。
MA1(9.67g、29.1mmol)、GMA(0.13g、0.9mmol)をTHF(56.3g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.15g、3mmol)を加え再び脱気を行った。この後、60℃で12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(1000ml)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P1を得た。
表1に示す組成をポリマー合成例1と同様の方法を用いて合成した。
ポリマー合成1にて得られたメタクリレートポリマー粉末P1(6.0g)にNMP(54.0g)を加え、室温で5時間攪拌して溶解させた。この溶液に、BC(40.0g)を加え攪拌することにより、ポリマー溶液A1を得た。このポリマー溶液は、そのまま液晶配向膜を形成するための液晶配向剤とした。
表2に示す組成を実施例1と同様の方法を用いて調整し、実施例2~12の液晶配向剤A2~A12を得た。
MA1(9.97g、30mmol)、をTHF(57.5g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.15g、3mmol)を加え再び脱気を行った。この後、60℃で12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(1000ml)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CP1を得た。
MA1(5.9g、18mmol)、MA2(3.7g、12mmol)、THF(55.5g)、AIBN(0.15g、3mmol)の組成でコントロール1と同様の方法を用いて、メタクリレートポリマー粉末CP2を得た。
CP1を用いて実施例1と同様の方法でコントロール1の液晶配向剤B1を得た。同様に、CP2を用いてコントロール2の液晶配向剤B2を得た。
実施例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。
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、電圧がどのくらい保持できているかを電圧保持率(VHR1)として計算した。さらに測定したセルを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状態にし、そのまま室温に1時間放置した。その得られたセルをVHR1と同様の条件で測定し、電圧がどのくらい保持できているかを電圧保持率(VHR2)として計算した。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1~8で用意したIPSモード用液晶セルを、偏光軸が直交するように配置された2枚の偏光板の間に設置し、電圧無印加の状態でバックライトを点灯させておき、透過光の輝度が最も小さくなるように液晶セルの配置角度を調整した。そして、画素の第2領域が最も暗くなる角度から第1領域が最も暗くなる角度まで液晶セルを回転させたときの回転角度を初期配向方位角として算出した。
次いで、60℃のオーブン中で、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状態にし、そのまま室温に1時間放置した。放置の後、同様にして配向方位角を測定し、交流駆動前後の配向方位角の差を角度Δ(deg.)として算出した。
その他の実施例でも同様に測定した。
液晶性を発現する側鎖型高分子膜に紫外線を照射後、液晶発現温度範囲で加熱することで、自己組織化によって高分子全体で高効率に液晶配向能が付与されているためか、長期のAC駆動後も配向方位のズレはほとんど観測されなかった。
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
Claims (18)
- 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、下記式(0)
[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;
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;
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;
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;
Gは、下記式(G-1)、(G-2)、(G-3)及び(G-4)
(式中、破線は結合手を表し、R50は水素原子、ハロゲン原子、炭素数1~3のアルキル基、フェニル基から選ばれる基を表し、R50が複数ある場合は互いに同一でも異なっていてもよく、tは1~7の整数であり、JはO、S、NHまたはNR51を表し、R51は炭素数1~3のアルキル基およびフェニル基から選ばれる基を表す)
から選ばれる基である]
で表される側鎖をさらに有する側鎖型高分子。 - 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に記載の側鎖型高分子。
- 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;
R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;
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;
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;
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または2に記載の側鎖型高分子 - 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;
R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1~3のいずれか1項に記載の側鎖型高分子。
- 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;
R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1~3のいずれか1項に記載の側鎖型高分子。
- 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1~3のいずれか1項に記載の側鎖型高分子。
- 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1~3のいずれか1項に記載の側鎖型高分子。
- 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1~3のいずれか1項に記載の側鎖型高分子。
- 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1~9のいずれか1項に記載の側鎖型高分子。
- (A)請求項1~10のいずれかに記載の側鎖型高分子と、(B)有機溶媒とを含有する重合体組成物。
- 重合体組成物がさらに、(C)分子内に1級アミノ基を1個と窒素含有芳香族複素環とを有し、かつ前記1級アミノ基が脂肪族炭化水素基又は非芳香族環式炭化水素基に結合しているアミン化合物を含有する請求項11記載の組成物。
- [I] 請求項11~13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。 - 請求項14に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。
- 請求項15記載の基板を有する横電界駆動型液晶表示素子。
- 請求項15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、請求項11~13のいずれか1項に記載の重合体組成物を、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、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。 - 請求項17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。
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| WO2017018501A1 (ja) * | 2015-07-30 | 2017-02-02 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
| JP2017076045A (ja) * | 2015-10-14 | 2017-04-20 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
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| CN117186663A (zh) * | 2015-07-30 | 2023-12-08 | 日产化学工业株式会社 | 液晶取向剂、液晶取向膜和液晶表示元件 |
| KR102674352B1 (ko) * | 2015-07-30 | 2024-06-11 | 닛산 가가쿠 가부시키가이샤 | 액정 배향제, 액정 배향막 및 액정 표시 소자 |
| JP2017076045A (ja) * | 2015-10-14 | 2017-04-20 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
| JP2017082140A (ja) * | 2015-10-29 | 2017-05-18 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
| CN110546560A (zh) * | 2017-02-27 | 2019-12-06 | 日产化学株式会社 | 液晶取向剂、液晶取向膜及液晶表示元件 |
| WO2019117082A1 (ja) * | 2017-12-15 | 2019-06-20 | 富士フイルム株式会社 | 光配向性共重合体、光配向膜および光学積層体 |
| JPWO2019117082A1 (ja) * | 2017-12-15 | 2020-11-26 | 富士フイルム株式会社 | 光配向性共重合体、光配向膜および光学積層体 |
| JP2019214553A (ja) * | 2018-06-07 | 2019-12-19 | 住友化学株式会社 | 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法 |
| JP7389567B2 (ja) | 2018-06-07 | 2023-11-30 | 住友化学株式会社 | 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105593751B (zh) | 2019-07-30 |
| JP6523169B2 (ja) | 2019-05-29 |
| KR102290811B1 (ko) | 2021-08-17 |
| TWI637044B (zh) | 2018-10-01 |
| CN105593751A (zh) | 2016-05-18 |
| JPWO2015012341A1 (ja) | 2017-03-02 |
| KR20160035010A (ko) | 2016-03-30 |
| TW201522583A (zh) | 2015-06-16 |
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