WO2016076348A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- WO2016076348A1 WO2016076348A1 PCT/JP2015/081715 JP2015081715W WO2016076348A1 WO 2016076348 A1 WO2016076348 A1 WO 2016076348A1 JP 2015081715 W JP2015081715 W JP 2015081715W WO 2016076348 A1 WO2016076348 A1 WO 2016076348A1
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- liquid crystal
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- KAGIRXVDTGQWKF-UHFFFAOYSA-N CC(C(OCCCCCCOc(cc1)ccc1C(O)=O)=O)=C Chemical compound CC(C(OCCCCCCOc(cc1)ccc1C(O)=O)=O)=C KAGIRXVDTGQWKF-UHFFFAOYSA-N 0.000 description 1
- JHOMRDSMJKYMIV-FMIVXFBMSA-N CC(C(OCCCCCCOc1ccc(/C=C/C(O)=O)cc1)=O)=C Chemical compound CC(C(OCCCCCCOc1ccc(/C=C/C(O)=O)cc1)=O)=C JHOMRDSMJKYMIV-FMIVXFBMSA-N 0.000 description 1
- JXRXOFWDMPTNOG-UHFFFAOYSA-N CC(C(OCCOC(c1ccncc1)=O)=O)=C Chemical compound CC(C(OCCOC(c1ccncc1)=O)=O)=C JXRXOFWDMPTNOG-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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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
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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
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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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]
Definitions
- the present invention relates to a novel polymer composition (liquid crystal aligning agent), 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. More specifically, the present invention relates to a novel method for manufacturing a liquid crystal display device having excellent image sticking characteristics.
- the liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years.
- the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
- an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.
- the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates.
- the liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
- alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
- the rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction).
- This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements.
- an organic film used for the liquid crystal alignment film a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
- Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.
- a decomposition type photo-alignment method is known as a main photo-alignment method.
- a polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependency of 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).
- photo-crosslinking type and photoisomerization type photo-alignment methods are also known.
- the photo-crosslinking type photo-alignment method for example, polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (cross-linking reaction) at double bond portions of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction orthogonal 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 has a great advantage because the rubbing process itself is not necessary as compared with the rubbing method that has been industrially used as an alignment treatment method for liquid crystal display elements. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light. However, the photo-alignment method may require a large amount of polarized light irradiation to achieve the same degree of alignment control ability as the rubbing method, and stable liquid crystal alignment cannot be realized. There is.
- the present invention relates to a novel polymer composition that provides a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element that is highly efficient, has alignment control ability, and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display using the same.
- An object is to provide a liquid crystal alignment film for an element, a substrate having the alignment film, and a lateral electric field drive type liquid crystal display element having the substrate.
- Another object of the present invention is to provide a liquid crystal alignment film having an improved voltage holding ratio and a method for producing a substrate having the same even by low-temperature firing.
- ⁇ 1> (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more diamine compounds; And (C) A polymer composition containing an organic solvent, particularly a polymer composition for producing a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element.
- the component (B) is a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more diamine compounds, and is derived from a diamine. It is preferable that the polymer has a structure represented by the formula (Y2-1).
- Z 3 is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bond part between Z 3 and the benzene ring is a single bond. Bond, ether bond, ester bond, urea bond or amide bond).
- the polymer of the component (B) may be a polyurea obtained by polymerizing a diisocyanate component and a diamine component.
- the polymer of the component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component. Is good.
- the polymer of the component (B) may be a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.
- A a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range
- B A polyurea polyimide produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound and then imidizing
- C a polymer composition comprising an organic solvent object.
- the component (B) preferably has a structure represented by the formula (Y2-1) as a structure derived from diamine.
- Z 3 is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bond part between Z 3 and the benzene ring is a single bond. Bond, ether bond, ester bond, urea bond or amide bond).
- the diisocyanate component may be an aromatic diisocyanate and / or an aliphatic diisocyanate.
- the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
- the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6). Good.
- A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
- S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
- T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
- Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof
- the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a
- R May be substituted with an alkyloxy group of R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
- X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
- X may be the same or different;
- Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
- P or Q on the side to which —CH ⁇ CH— is bonded is an aromatic ring;
- the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
- l1 is 0 or 1;
- l2 is an integer from 0 to 2; when l1 and l2 are both 0,
- A represents a single bond when T is a single bond; when l1 is 1, B represents a single bond when T is a single bond;
- H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
- the component (A) may have 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,
- ⁇ 13> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device produced by the method of ⁇ 12>.
- ⁇ 14> A lateral electric field drive type liquid crystal display device having the substrate of ⁇ 13> above.
- ⁇ 15> a step of preparing a substrate (first substrate) of ⁇ 13>above;
- [I ′] A step of applying the polymer composition of any one of the above ⁇ 1> to ⁇ 11> 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, and a horizontal electric field drive type liquid crystal display element having the substrate.
- a lateral electric field drive type liquid crystal device having an excellent voltage holding ratio even by low-temperature baking, and for the device A liquid crystal alignment film can be provided.
- a lateral electric field driving type liquid crystal element having excellent voltage holding ratio even by low-temperature baking and liquid crystal alignment for the element A membrane can be provided. That is, according to the present invention, a higher voltage holding ratio than that of the polyacrylate-based alignment film alone can be obtained in low-temperature firing.
- 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 slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-organization.
- a highly efficient alignment process can be realized as the liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.
- the component (B) in addition to the side chain polymer as the component (A) and the organic solvent as the component (C), the component (B) is selected from a diisocyanate component and a tetracarboxylic acid derivative.
- a polymer produced using at least one kind and two or more kinds of diamine compounds is contained.
- a diisocyanate compound in addition to the side chain polymer as the component (A) and the organic solvent as the component (C), a diisocyanate compound, a tetracarboxylic acid derivative as the component (B), It contains polyurea polyimide produced by polymerization reaction with a diamine compound and then imidization.
- the present inventors exerted the interaction between the component (A) and the component (B), and jumped to the desired effect. (Note that these include the inventor's view on the mechanism of the present invention and do not bind the present invention).
- 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 is selected from (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) a diisocyanate component and a tetracarboxylic acid derivative. A polymer produced using at least one selected from the above and two or more diamine compounds; and (C) an organic solvent.
- the polymer composition of the present invention comprises (A) a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range; (B) a diisocyanate compound, and a tetracarboxylic acid.
- the component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range.
- the (A) side chain polymer preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100 ° C. to 300 ° C.
- the (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
- the (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 300 ° C.
- the side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement in response to light.
- the structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time.
- the structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film.
- the polymer structure has, for example, a main chain and a side chain bonded to the main chain, and the side chain includes a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip.
- a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip.
- More specific examples of the structure of the photosensitive side chain polymer that can exhibit liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl , A main chain composed of at least one selected from the group consisting of radical polymerizable groups such as maleimide and norbornene and siloxane, and a side chain consisting of at least one of the following formulas (1) to (6) It is preferable that
- A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
- S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
- T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
- Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
- Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof
- the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a
- R May be substituted with an alkyloxy group of R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
- X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
- X may be the same or different;
- Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
- P or Q on the side to which —CH ⁇ CH— is bonded is an aromatic ring;
- the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
- l1 is 0 or 1;
- l2 is an integer from 0 to 2; when l1 and l2 are both 0,
- A represents a single bond when T is a single bond; when l1 is 1, B represents a single bond when T is a single bond;
- H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
- the side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
- the side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
- A, X, l, m, 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, Y1, q1, q2, m1, and m2 have the same definition as above.
- R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
- the side chain is preferably a photosensitive side chain represented by the following formula (20).
- A, Y 1 , X, l and m have the same definition as above.
- the (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
- A, B, q1 and q2 have the same definition as above;
- Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
- each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
- R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1
- the photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.
- the photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
- the photoreactive group possessed by the side chain the following structures and derivatives thereof are preferred.
- photoreactive side chain monomer examples include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene, etc.
- a polymerizable side group composed of at least one selected from the group consisting of siloxane and a photosensitive side chain consisting of at least one of the above formulas (1) to (6), preferably, for example, the above formula (7 ) To (10), a photosensitive side chain comprising at least one of the above formulas (11) to (13), and a photosensitivity represented by the above formula (14) or (15).
- a photosensitive side chain a photosensitive side chain represented by the above formula (16) or (17), a photosensitive side chain represented by the above formula (18) or (19), and a photosensitivity represented by the above formula (20).
- Sex side chain It is preferable that it has a structure.
- the 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.
- the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
- the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
- methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
- (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.
- Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
- Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
- Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- the production method of the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
- RAFT reversible addition-cleavage chain transfer
- a radical thermal polymerization initiator is a compound that generates radicals when heated to a decomposition temperature or higher.
- radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation).
- the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
- examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (
- the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
- the organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.
- organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer
- the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C.
- the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.
- the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
- the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
- the content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
- the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
- impurities in the polymer can be reduced.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the molecular weight of the (A) side chain polymer of the present invention is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film.
- the weight average molecular weight is preferably 2,000 to 2,000,000, and more preferably 5,000 to 150,000.
- the weight average molecular weight is preferably 2,000 to 1,000,000, and more preferably 5,000 to 200,000.
- the polymer composition used in the present invention has, as the component (B), a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more diamine compounds.
- the polymer of the component (B) includes a polyurea produced using a diisocyanate component and a diamine component, a polyimide precursor produced using a diisocyanate component and a tetracarboxylic acid derivative, and a diisocyanate component and a tetracarboxylic acid derivative.
- a polyurea polyimide precursor produced using a diamine component that is, a copolymer of polyurea and a polyimide precursor.
- the polymer composition used in the present invention undergoes a polymerization reaction of a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound as component (B), and then imidizes. It has polyurea polyimide manufactured by this.
- Diisocyanate component ⁇ Diisocyanate component
- Examples of the diisocyanate component that is a raw material for the component (B) include aromatic diisocyanates and aliphatic diisocyanates.
- Preferred diisocyanate components are aromatic diisocyanates and aliphatic diisocyanates.
- the aromatic diisocyanate means one in which the R group of the diisocyanate structure (O ⁇ C ⁇ N—R ⁇ N ⁇ C ⁇ O) contains a structure containing an aromatic ring.
- the aliphatic diisocyanate means that the R group of the isocyanate structure is composed of a cyclic or acyclic aliphatic structure.
- aromatic diisocyanates include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (eg, tolylene 2,4-diisocyanate), 1,4-diisocyanate-2-methoxybenzene.
- 2,5-diisocyanate xylenes 2,2′-bis (phenyl diisocyanate) propane, 4,4′-diisocyanate diphenylmethane, 4,4′-diisocyanate diphenyl ether, 4,4′-diisocyanate Examples include diphenyl sulfone, 3,3′-diisocyanate diphenyl sulfone, and 2,2′-diisocyanate benzophenone.
- the aromatic diisocyanate is preferably tolylene 2,4-diisocyanate.
- aliphatic diisocyanate examples include isophorone diisocyanate, hexamethylene diisocyanate, and tetramethylethylene diisocyanate.
- isophorone diisocyanate preferably, isophorone diisocyanate is used.
- isophorone diisocyanate and 2,4-diisocyanate tolylene are preferable from the viewpoint of polymerization reactivity and voltage holding ratio, and isophorone diisocyanate is more preferable from the viewpoint of availability, polymerization reactivity, and voltage holding ratio. .
- tetracarboxylic acid derivative ⁇ tetracarboxylic acid derivative
- tetracarboxylic acid derivative that is a raw material for the component (B)
- tetracarboxylic dianhydrides examples include the following tetracarboxylic dianhydrides.
- Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane.
- Tetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,4,5-pentanetetracarboxylic Dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride
- nonane-3,4,7,8-tetracarboxylic acid-3,4 7,8-dianhydride, hexacyclo [6.6.0.1 2,7 . 0 3,6 . 1 9,14 . 0 10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 And naphthalene succinic dianhydride.
- Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid And dianhydrides and 2,3,6,7-naphthalenetetracarboxylic dianhydride.
- the above-mentioned tetracarboxylic dianhydrides can be used alone or in combination of two or more according to the properties of the liquid crystal alignment film to be formed, such as liquid crystal alignment properties, voltage holding properties, and accumulated charges.
- tetracarboxylic-acid dialkyl ester and tetracarboxylic-acid dialkyl diester dichloride as a tetracarboxylic-acid component which is a raw material of (B) component.
- the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamic acid ester that is a polyimide precursor.
- the tetracarboxylic acid dialkyl ester that can be used is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters. Specific examples are given below.
- aliphatic tetracarboxylic acid diester examples include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2 , 3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy- 1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy 1,2,3,4-tetrahydro-1-naphthalene
- aromatic tetracarboxylic acid dialkyl ester examples include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, and 2,2 ′, 3,3′-biphenyltetra.
- Carboxylic acid dialkyl ester 2,3,3 ′, 4′-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4′-benzophenone Tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2 , 3,6,7-Naphthalenetetracarboxylic Dialkyl ester, and the like.
- Examples of the tetracarboxylic acid diester dichloride include diester dichloride obtained by converting the carboxyl group of the tetracarboxylic acid dialkyl ester into a chlorocarbonyl group by a known method.
- tetracarboxylic dianhydrides tetracarboxylic acid diesters, tetracarboxylic acid diester dichlorides, etc. are each one or two depending on the properties such as liquid crystal alignment properties, voltage holding properties, accumulated charges, etc. when formed into a liquid crystal alignment film. More than one type can be used in combination.
- diamine component which is a raw material of (B) component
- the following alicyclic diamine, aromatic diamine, heterocyclic diamine, aliphatic diamine, and urea bond containing diamine are mentioned, for example.
- alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone diamine Etc.
- aromatic diamines examples include o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino- 2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 ′ -Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3
- aromatic-aliphatic diamines examples include diamines represented by the following formula [DAM].
- Ar represents a benzene ring or a naphthalene ring
- R 1 represents an alkylene group having 1 to 5 carbon atoms
- R 2 represents a hydrogen atom or a methyl group.
- aromatic-aliphatic diamine examples include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4 -Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) ) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4- Methylaminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopen) L) aniline, 3- (5-methylaminopenty
- heterocyclic diamines examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole and the like.
- aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1,12-diaminododecane, Examples thereof include 1,18-diaminooc
- urea bond-containing diamines examples include N, N′-bis (4-aminophenethyl) urea.
- a diamine having a vertical alignment side chain may be included as a diamine component to be polymerized with the diisocyanate component as long as the effects of the present invention are not impaired.
- the diamine component in the component (B) may contain the following diamine.
- n and n are each an integer from 1 to 11, m + n is an integer from 2 to 12, h is an integer from 1 to 3, and j is an integer from 0 to 3.
- examples of the diamine component in the component (B) include diaminosiloxanes represented by the following formula.
- n is an integer of 1 to 10.
- the diamine compound further has a nitrogen atom in the middle of two amino groups
- the nitrogen atom present in the middle of the two amino groups is bonded to carbonyl or has two or more benzene rings and a single atom. Bonding by bonding is preferable in that salt formation with the component (A) can be prevented.
- a diamine component that is a raw material of the component (B), for example, a diamine having a structure represented by the following formula (Y2-1) can be mentioned.
- Z 3 is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bonding part between Z 3 and the benzene ring is a single bond, ether A bond, an ester bond, a urea bond, or an amide bond.
- formula (Y2-1) include the following formulas (Y2-2) to (Y2-9).
- R 13 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. If the number of carbon atoms is too large, the liquid crystal orientation is lowered. A methyl group or an ethyl group is preferred.
- Y 2 is preferably formula (Y2-2), (Y2-3), or (Y2-5), and particularly preferably formula (Y2-2) or formula (Y2-5).
- the polymer represented by the formula (Y2-1) can be used when the polymer as the component (B) is produced.
- a diamine having a structure may be used.
- Such diamines include 4,4′-diaminodiphenylmethane, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-amino).
- Phenyl) butane 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4 -Aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, bis (4-aminophenoxy) methane, 1,2-bis (4-amino) Phenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pen 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-amin
- the proportion in the case where the structure represented by the above formula (Y2-1) is contained is preferably 15 to 90 mol%, and preferably 40 to 85 mol, based on all structural units derived from diamine. % Is more preferable.
- diamine components in the component (B) are used in combination of two or more according to characteristics such as liquid crystal alignment properties, voltage holding characteristics and accumulated charges when the liquid crystal alignment film is formed.
- the mixing ratio is not limited, but in order to achieve the effect of improving the voltage holding ratio by mixing two or more diamines, the content ratio of each diamine is 10 with respect to all structural units derived from diamine. It is preferably ⁇ 90 mol%, more preferably 15 to 85 mol%.
- at least two of the diamines are mixed so as to fall within the range of 10 to 90 mol% with respect to the total structural units derived from the diamine, and the total is 100 mol%. It is preferred to mix so that less than one part is occupied by another or more diamines.
- the type of diamine is not limited as long as it is 2 or more, but it is preferably 6 or less in consideration of economic factors.
- the molecular weight of the polymer of component (B) is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained liquid crystal alignment film, workability when forming the liquid crystal alignment film, and uniformity of the liquid crystal alignment film.
- the weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 200,000.
- a known synthesis method can be used. Generally, it is a method in which at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine component are reacted in an organic solvent.
- the reaction of at least one selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.
- the organic solvent used for the reaction of at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine component is not particularly limited as long as the produced polymer is soluble. Specific examples are given below.
- organic solvents examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, and tetramethyl.
- a method of adding at least one selected from the above as it is or dispersed or dissolved in an organic solvent and conversely, adding a diamine component to a solution in which at least one selected from a diisocyanate component and a tetracarboxylic acid derivative is dispersed or dissolved in an organic solvent
- a method of alternately adding at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine component may be used.
- a diisocyanate component and a tetracarboxylic acid derivative or a diamine component consists of a plurality of kinds of compounds
- they may be reacted in a premixed state, may be individually reacted sequentially, and further individually
- the reacted low molecular weight substance may be mixed and reacted to obtain a high molecular weight substance.
- the polymerization temperature at that time can be selected from -20 ° C. to 150 ° C., but is preferably in the range of ⁇ 5 ° 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 total concentration of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 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 ratio of the total number of moles of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative to the total number of moles of the diamine component is 0.8 to 1.2. It is preferable. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polymer produced.
- the reaction solution may be poured into a poor solvent and precipitated.
- the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
- the polymer precipitated in a poor solvent and collected by filtration can be 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.
- polyurea is a polymer having a repeating unit represented by the following formula [1], for example.
- a 1 is a divalent organic group
- a 2 is a divalent organic group
- C 1 and C 2 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, It can be the same or different.
- a 1 and A 2 may each be one kind and a polymer having the same repeating unit, or A 1 and A 2 may be plural kinds and a polymer having a repeating unit having a different structure. But you can.
- a 1 is a group derived from a diisocyanate component as a raw material.
- a 2 is a group derived from a diamine component as a raw material.
- a 1 is preferably a group derived from the preferred diisocyanate components listed above. Further, as A 2 are groups derived from the preferred diamine components listed above are preferred.
- the polyimide precursor is, for example, a polymer having a repeating unit represented by the following formula [2].
- a 3 is each independently a tetravalent organic group
- a 2 is each independently a divalent organic group.
- R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- C 1 to C 2 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, An alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms.
- R 11 Specific examples of the alkyl group in R 11 include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group. Etc. From the viewpoint of ease of imidization by heating, R 11 is preferably a hydrogen atom or a methyl group.
- the polyurea polyimide precursor is, for example, a polymer having a repeating unit represented by the above formula [1] and a repeating unit represented by the above formula [2].
- the molar ratio of the tetracarboxylic acid derivative and the diisocyanate in the polyurea polyimide precursor is preferably 99: 1 to 1:99.
- Polyurea polyimide is obtained by ring-closing the above-mentioned polyurea polyamic acid or polyurea polyamic acid ester.
- the ring closure rate (also referred to as imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
- Examples of the method for imidizing polyurea polyamic acid or polyurea polyamic acid ester include thermal imidization in which a solution of a polyimide precursor is heated as it is or catalytic imidization in which a catalyst is added to a solution of polyurea polyamic acid or polyurea polyamic acid ester. .
- the temperature when the polyurea polyamic acid or polyurea polyamic acid ester is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., while removing water generated by the imidization reaction from the system. It is preferable to do this.
- a basic catalyst and an acid anhydride are added to a solution of polyurea polyamic acid or polyurea polyamic acid ester, and -20 ° C to 250 ° C, preferably 0 ° C to It can carry out by stirring at 180 degreeC.
- the amount of the basic catalyst is 0.5 mol times to 30 mol times, preferably 2 mol times to 20 mol times of the amic acid groups, and the amount of the acid anhydride is 1 mol times to 50 mol times of the amic acid groups, The amount is preferably 3 mole times to 30 mole times.
- Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
- Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
- the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
- the reaction solution may be poured into a solvent and precipitated.
- the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
- the polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
- the polymer collected by precipitation is redissolved in a solvent and then re-precipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
- the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.
- the blending ratio (mass basis) of the component (A) and the component (B) described above is the total (the sum of the component (A) and the component (B). ) Is 1, the component (A) is 0.01 to 0.99, more preferably 0.1 to 0.9, and still more preferably 0.2 to 0.5.
- Organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone
- the polymer composition used in the present invention may contain components other than the above components (A), (B) and (C).
- examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
- solvents and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
- solvent poor solvent which improves the uniformity of film thickness and surface smoothness.
- solvents may be used alone or in combination.
- it is preferably 5% by mass to 80% by mass of the total solvent, more preferably so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. Is 20% by mass to 60% by mass.
- Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition
- the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
- phenoplasts and epoxy group-containing compounds for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed
- An agent may be contained in the polymer composition. Specific phenoplast additives are shown below, but are not limited to this structure.
- Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl- , 4'-diaminodip
- the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
- a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
- photosensitizers aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-b
- Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
- a dielectric, a conductive substance, or the like for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired.
- a crosslinkable compound may be added for the purpose of increasing the hardness and density of the liquid crystal alignment film.
- the 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 the above-described component (A), component (B) and the above-described solvent and compound that improve the film thickness uniformity and surface smoothness, and the adhesion between the liquid crystal alignment film and the substrate. It is preferable that the compound etc. which improve a property are prepared as a solution which melt
- the total content of the component (A) and the component (B) 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. is there.
- 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 method for producing a substrate having the liquid crystal alignment film of the present invention is [I] (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) a polymer produced using at least one selected from diisocyanate components and tetracarboxylic acid derivatives and two or more diamine compounds, and (C) a polymer composition comprising an organic solvent Applying an object on a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II]; Have Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal
- a method for producing a substrate having the liquid crystal alignment film of the present invention comprises: [I] (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) A polyurea polyimide produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound and then imidizing, and (C) a polymer composition comprising an organic solvent Applying an object on a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II]; Have Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.
- a lateral electric field drive type liquid crystal display element can be obtained.
- the second substrate instead of using a substrate having no lateral electric field driving conductive film instead of a substrate having a lateral electric field driving conductive film, the above steps [I] to [III] (for lateral electric field driving) Since a substrate having no conductive film is used, for the sake of convenience, in this application, the steps [I ′] to [III ′] may be abbreviated as steps), thereby providing a first liquid crystal alignment film having alignment controllability. Two substrates can be obtained.
- the manufacturing method of the horizontal electric field drive type liquid crystal display element is: [IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween; Have Thereby, a horizontal electric field drive type liquid crystal display element can be obtained.
- a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, a polymer of the component (B), and an organic solvent are formed on a substrate having a conductive film for driving a lateral electric field.
- the polymer composition contained 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.
- 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 a temperature range of a temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature).
- the liquid crystallinity expression temperature of the coating film surface may be lower than the liquid crystallinity expression temperature when a photosensitive side chain polymer capable of expressing liquid crystallinity is observed in bulk. is expected.
- the heating temperature is more preferably within the temperature range of the liquid crystallinity 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.
- the temperature is in a range where the temperature is the upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
- the liquid crystallinity temperature is equal to or higher 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). Refers to a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
- Tg glass transition temperature
- the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board
- the step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving.
- the obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method.
- This is a step of manufacturing a lateral electric field drive type liquid crystal display element.
- a substrate having no lateral electric field driving conductive film was used in place of the substrate having the lateral electric field driving conductive film in the step [I].
- steps [I] to [III] It can be carried out in the same manner as in steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.
- the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
- the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
- Etc. can be illustrated.
- the diameter of the spacer at this time is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
- substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply
- the coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. .
- the coating film used in the method of the present invention is a liquid crystal alignment film having anisotropy introduced with high efficiency and excellent alignment control ability by sequentially performing irradiation of polarized ultraviolet rays on the coating film and heat treatment. can do.
- the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.
- the optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction in the coating film.
- the photo-crosslinking reaction, photoisomerization reaction, or photo-fleece rearrangement reaction has few photosensitive groups in the side chain, the amount of photoreaction will not be sufficient. . In that case, sufficient self-organization does not proceed even after heating.
- the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating.
- the coating film used in the present invention is irradiated with polarized ultraviolet rays to the structure having the light Fleece rearrangement group, if the photosensitive group of the side chain that undergoes the light Fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Will drop too much.
- the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side-chain polymer is photodegraded, preventing the subsequent self-organization by heating. It may become.
- the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the side chain polymer film. It is preferably 0.1 to 40 mol%, more preferably 0.1 to 20 mol% of the photosensitive group possessed by.
- the coating film used in the method of the present invention by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.
- the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured.
- ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.
- the maximum value of ⁇ A ( ⁇ Amax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained.
- a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ⁇ Amax.
- the amount of irradiation of polarized ultraviolet rays onto the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that realizes ⁇ Amax. More preferably, it is within the range of 50%.
- the irradiation amount of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that realizes ⁇ Amax is 0. 0% of the entire photosensitive group of the side chain polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.
- a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 90 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
- the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.
- the lateral electric field drive type liquid crystal display element substrate manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.
- MA1 was synthesized by a synthesis method described in a patent document (WO2011-084546).
- MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717).
- HBAGE was purchased from Nippon Kasei Co., Ltd.
- A1 was synthesized by a synthesis method described in a patent document (WO2014-054785).
- ⁇ Diisocyanate component> ISO: isophorone diisocyanate DI-1: isophorone diisocyanate DI-2: diphenylmethane-4,4'-diisocyanate DI-3: 1,4-phenylene diisocyanate DI-4: tolylene 2,4-diisocyanate
- DDM 4,4′-diaminodiphenylmethane
- Me-4APhA N-methyl-2- (4-aminophenyl) ethylamine
- Me-DADPA 4,4′-diaminodiphenyl (N-methyl) amine
- DA-2MG 1,3 -Bis (4-aminophenoxy) ethane
- BAPU 1,3-bis [2- (4-aminophenyl) ethyl] urea
- p-PDA p-phenylenediamine
- DADPA 4,4'-diaminodiphenylamine
- TDA 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride
- BODA bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid Dianhydride
- NMP (2.35 g) is added to 0.1 g of the methacrylate polymer powder (MP1) obtained in the above methacrylate polymer synthesis example 1, and stirred for 30 minutes to obtain a methacrylate polymer solution.
- 2.8 g of polyamic acid solution (PAA-1) and gBL (5.25 g) were added thereto and stirred at room temperature for 1 hour.
- 5.5 g of BCS was added to this solution and stirred for 1 hour at room temperature to obtain a polymer solution (A1) having a solid content concentration of 3.5 wt%.
- This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.
- Examples 2 to 7, Comparative Examples 1 to 9 Polymer solutions of Examples 2 to 7 having the compositions shown in Table 5 were obtained in the same manner as in Example 1. Controls 1 to 9 were also adjusted in the same manner.
- Example 1 [Production of liquid crystal cell] Using the liquid crystal aligning agent (A1) obtained in Example 1, a liquid crystal cell was produced 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 has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width of each electrode element in the short direction was 10 ⁇ m, and the distance between the electrode elements was 20 ⁇ m.
- each 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 had a shape that bends and resembles a bold-faced koji.
- Each pixel was divided vertically with the central bent portion as a boundary, and had a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different.
- the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
- the electrode elements of the pixel electrode were formed so as to form an angle of ⁇ 15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It was configured to be in the opposite direction.
- the liquid crystal aligning agent (A1) obtained in 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 313 nm ultraviolet rays through a polarizing plate for 15 mJ / cm 2 and then heated on a hot plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ 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. Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, the injection port was sealed, and a liquid crystal cell having the configuration of an IPS (In-Plane Switching) mode liquid crystal display element was obtained. Obtained.
- IPS In-Plane Switching
- liquid crystal cells were prepared using the same method as A1. .
- VHR Voltage holding ratio
- VHR voltage holding ratio
- DA-2MG (2.15 g, 8.8 mmol) and DADPA (0.46 g, 2.2 mmol) are taken into a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 25.4 g of NMP is added and a nitrogen atmosphere is added. Under stirring, DI-1 (2.40 g, 10.8 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution ( 14) was obtained. The number average molecular weight of this polymer was 14,300, and the weight average molecular weight was 29,700.
- DA-2MG (2.15 g, 8.8 mmol) and DA8 (0.87 g, 2.2 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 27.6 g of NMP is added and a nitrogen atmosphere is added. Under stirring, DI-1 (2.40 g, 10.8 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution ( 15) was obtained. The number average molecular weight of this polymer was 6,500, and the weight average molecular weight was 11,900.
- DA-2MG (2.15 g, 8.8 mmol) and Me-4APhA (0.31 g, 2.2 mmol) are added to a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 27.6 g of NMP is added. While stirring under a nitrogen atmosphere, DI-1 (2.40 g, 10.8 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the polymer was stirred at 50 ° C. for 15 hours. A solution (16) was obtained. The number average molecular weight of this polymer was 9,700, and the weight average molecular weight was 19,500.
- DA-2MG (2.15 g, 8.8 mmol) and DDM (0.43 g, 2.2 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 27.6 g of NMP is added and a nitrogen atmosphere is added. Under stirring, DI-1 (2.40 g, 10.8 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution ( 17) was obtained. The number average molecular weight of this polymer was 13,700, and the weight average molecular weight was 32,400.
- DA-2MG (2.93 g, 12.0 mmol) and BAPU (0.89 g, 3.0 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 37.6 g of NMP is added, and a nitrogen atmosphere is added. Under stirring, DI-1 (3.27 g, 14.7 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution ( 18) was obtained. The number average molecular weight of this polymer was 11,300, and the weight average molecular weight was 25,400.
- DA-2MG (2.34 g, 9.6 mmol) and Me-DADPA (0.51 g, 2.4 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 28.1 g of NMP is added. While stirring under a nitrogen atmosphere, DI-1 (2.13 g, 9.6 mmol) was added, and the mixture was stirred at 25 ° C. for 3 hours. Thereafter, DI-2 (0.51 g, 2.0 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution (19). It was. The number average molecular weight of this polymer was 13,500, and the weight average molecular weight was 33,100.
- DA-2MG (2.34 g, 9.6 mmol) and Me-DADPA (0.51 g, 2.4 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 28.1 g of NMP is added. While stirring under a nitrogen atmosphere, DI-1 (2.13 g, 9.6 mmol) was added, and the mixture was stirred at 25 ° C. for 3 hours. Thereafter, DI-4 (0.32 g, 2.0 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution (21). It was. The number average molecular weight of this polymer was 11,800, and the weight average molecular weight was 25,300.
- Table 11 shows the composition of the polymer obtained as described above.
- Example 11 To 0.12 g of the methacrylic acid polymer (MP11) obtained in Synthesis Example 1 above, 6.4 g of the polyurea polymer solution, the polymer (11), 3.98 g of NMP, and 10.5 g of GBL were added, and 3 hours at room temperature. Stir. Further, 9.0 g of BCS was added to this solution and stirred at room temperature for 3 hours to obtain a polymer solution (A11) having a solid content concentration of 4.0 wt%. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.
- Example 12 to 22 control rules 11 to 12
- Polymer solutions of Examples 12 to 22 were obtained with the compositions shown in Table 12 using the same method as in Example 11. Controls 11 to 12 were also adjusted in the same manner.
- a liquid crystal cell was produced as follows.
- 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 has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent.
- 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.
- Each pixel has a shape that bends and resembles a bold, bold character.
- Each pixel was divided vertically with the central bent portion as a boundary, and had a first region on the upper side of the bent portion and a second region on the lower side.
- the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
- the electrode elements of the pixel electrode were formed so as to form an angle of ⁇ 15 ° (clockwise).
- 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 was filtered through a 1.0 ⁇ m filter, and then spin coated on the 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 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 140 ° C. for 20 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.
- VHR Voltage holding ratio
- a voltage of 5 V was applied to the obtained liquid crystal cell at a temperature of 70 ° C. for 60 ⁇ s, and a holding voltage of the liquid crystal cell was measured after 1667 ms.
- VHR1 was an initial value, and a value measured after applying a stress for one week with an LED backlight was VHR2.
- the voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.
- Examples 11 to 22 according to the present invention contained a component (B) and had a higher voltage holding ratio (VHR) than the control.
- NMP 50 g was added to the 15 wt% solution (PUPAA-1, 30 g) obtained in the above polyurea-amic acid synthesis example 1 to dilute to 6 wt%, and then acetic anhydride (6 .42 g) and pyridine (2.49 g) were added, and the mixture was stirred at room temperature for 30 minutes and then reacted at 50 ° C. for 3 hours.
- This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. to obtain polyurea-imide powder. The imidation ratio of this polyurea-imide was 96%.
- NMP was added and redissolved to obtain a polyurea-imide solution (PUPI 31) having a concentration of 15 wt%.
- NMP 50 g was added to the 15 wt% solution (PUPAA-22, 30 g) obtained in the above polyurea-amic acid synthesis example 2 and diluted to a concentration of 6 wt%, and then acetic anhydride (6 .42 g) and pyridine (2.49 g) were added, and the mixture was stirred at room temperature for 30 minutes and then reacted at 50 ° C. for 3 hours.
- This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 40 ° C. to obtain a polyurea-imide powder. The imidation ratio of this polyurea-imide was 73%.
- NMP was added and redissolved to obtain a polyurea-imide solution (PUPI32) having a concentration of 15 wt%.
- NMP (2.35 g) is added to 0.1 g of the methacrylate polymer powder (MP1) obtained in the above methacrylate polymer synthesis example 1, and stirred for 30 minutes to obtain a methacrylate polymer solution.
- MP1 methacrylate polymer powder
- GBL methacrylate polymer powder
- BCS 5.5 g was added to this solution, followed by stirring at room temperature for 1 hour to obtain a polymer solution (A31) having a solid content concentration of 3.5 wt%.
- This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.
- Example 32 to 34 Polymer solutions (A32 to A34) of Examples 32 to 34 were obtained by the same method as in Example 31 with the compositions shown in Table 21.
- Example 31 [Production of liquid crystal cell] Using the liquid crystal aligning agent (A31) obtained in Example 31, a liquid crystal cell was produced 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 has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width of each electrode element in the short direction was 10 ⁇ m, and the distance between the electrode elements was 20 ⁇ m.
- each 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 had a shape that bends and resembles a bold-faced koji.
- Each pixel was divided vertically with the central bent portion as a boundary, and had a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different.
- the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
- the electrode elements of the pixel electrode were formed so as to form an angle of ⁇ 15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It was configured to be in the opposite direction.
- the liquid crystal aligning agent (A31) obtained in Example 31 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 313 nm ultraviolet rays through a polarizing plate for 15 mJ / cm 2 and then heated on a hot plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ 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. Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, the injection port was sealed, and a liquid crystal cell having the configuration of an IPS (In-Plane Switching) mode liquid crystal display element was obtained. Obtained.
- IPS In-Plane Switching
- liquid crystal aligning agents (A32 to A34) obtained in Examples 32 to 34, liquid crystal cells were prepared using the same method as A31.
- VHR Voltage holding ratio
- a voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 70 ° C., the voltage after 1000 ms was measured, and how much the voltage could be held was calculated as a voltage holding ratio.
- the initial voltage holding ratio measured after manufacturing the liquid crystal cell was VHR1, and the voltage holding ratio measured after one week after performing the backlight aging test was VHR2.
- the voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.
- Examples 31 to 34 according to the present invention all have high initial voltage holding ratio (VHR1) and voltage holding ratio after backlight aging (VHR2). It can be seen that the voltage holding ratios of Examples 31, 32, and 34 are further improved compared to Example 33 using PUPAA 31 that is the same as PUPAA1.
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Abstract
Description
<1> (A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、
(B)ジイソシアネート成分及びテトラカルボン酸誘導体から選ばれる少なくとも一種と、ジアミン化合物の2種以上とを用いて製造された重合体、
及び
(C)有機溶媒
を含有することを特徴とする重合体組成物、特に横電界駆動型液晶表示素子用液晶配向膜製造用重合体組成物。 As a result of intensive studies to achieve the above problems, the present inventors have found the following invention.
<1> (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range;
(B) a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more diamine compounds;
And (C) A polymer composition containing an organic solvent, particularly a polymer composition for producing a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element.
<4> 上記<1>又は<2>において、(B)成分の重合体が、ジイソシアネート成分と、テトラカルボン酸誘導体と、ジアミン成分とを重合反応させることにより得られるポリウレアポリイミド前駆体であるのがよい。
<5> 上記<1>又は<2>において、(B)成分の重合体が、テトラカルボン酸誘導体と、ジアミン成分とを重合反応させることにより得られるポリイミド前駆体であるのがよい。 <3> In the above item <1> or <2>, the polymer of the component (B) may be a polyurea obtained by polymerizing a diisocyanate component and a diamine component.
<4> In the above item <1> or <2>, the polymer of the component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component. Is good.
<5> In the above item <1> or <2>, the polymer of the component (B) may be a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.
(B)ジイソシアネート化合物と、テトラカルボン酸誘導体と、ジアミン化合物とを重合反応させ、次いでイミド化することにより製造されるポリウレアポリイミド、及び
(C)有機溶媒
を含有することを特徴とする重合体組成物。 <6> (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range;
(B) A polyurea polyimide produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound and then imidizing, and (C) a polymer composition comprising an organic solvent object.
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。 In the formula, A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
式中、A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。 <11> In any one of the above items <1> to 10>, the component (A) may have any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31): .
In which 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. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 each represents a single bond, —CO—, —CH 2 O—, —CH═N—, —CF 2 —.
[II] [I]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された横電界駆動型液晶表示素子用液晶配向膜を得る、前記液晶配向膜を有する基板の製造方法。 <12> [I] A step of applying the composition according to any one of <1> to <11> above onto a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
<14> 上記<13>の基板を有する横電界駆動型液晶表示素子。 <13> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device produced by the method of <12>.
<14> A lateral electric field drive type liquid crystal display device having the substrate of <13> above.
[I’] 第2の基板上に上記<1>~<11>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。 <15> a step of preparing a substrate (first substrate) of <13>above;
[I ′] A step of applying the polymer composition of any one of the above <1> to <11> 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 ′];
Obtaining a liquid crystal alignment film imparted with alignment control ability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment films of the first and second substrates via liquid crystal The liquid crystal display element is obtained by disposing the first and second substrates so as to face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.
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。 According to the present invention, there are provided a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. Can do.
Since the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even when continuously driven for a long time.
本発明の製造方法において用いられる重合体組成物は、液晶性を発現し得る感光性の側鎖型高分子(以下、単に側鎖型高分子とも呼ぶ)を有しており、前記重合体組成物を用いて得られる塗膜は、液晶性を発現し得る感光性の側鎖型高分子を有する膜である。この塗膜にはラビング処理を行うこと無く、偏光照射によって配向処理を行う。そして、偏光照射の後、その側鎖型高分子膜を加熱する工程を経て、配向制御能が付与された塗膜(以下、液晶配向膜とも称する)となる。このとき、偏光照射によって発現した僅かな異方性がドライビングフォースとなり、液晶性の側鎖型高分子自体が自己組織化により効率的に再配向する。その結果、液晶配向膜として高効率な配向処理が実現し、高い配向制御能が付与された液晶配向膜を得ることができる。 As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The polymer composition used in the production method of the present invention has a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter, also simply referred to as a side chain polymer), and the polymer composition The coating film obtained by using the product is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity. This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth a liquid crystal aligning film) to which the orientation control ability was provided through the process of heating the side chain type polymer film. At this time, the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-organization. As a result, a highly efficient alignment process can be realized as the liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.
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)ジイソシアネート成分及びテトラカルボン酸誘導体から選ばれる少なくとも一種と、ジアミン化合物の2種以上とを用いて製造された重合体;及び(C)有機溶媒;を含有する。 <Polymer composition>
A polymer composition is applied on a substrate having a conductive film for driving a lateral electric field, particularly on the conductive film.
The polymer composition used in the production method of the present invention is selected from (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) a diisocyanate component and a tetracarboxylic acid derivative. A polymer produced using at least one selected from the above and two or more diamine compounds; and (C) an organic solvent.
(A)成分は、所定の温度範囲で液晶性を発現する感光性の側鎖型高分子である。
(A)側鎖型高分子は、250nm~400nmの波長範囲の光で反応し、かつ100℃~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。 << (A) Side chain polymer >>
The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range.
The (A) side chain polymer preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100 ° C. to 300 ° C.
The (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
The (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 300 ° C.
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;
Xは、単結合、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表し、Xの数が2となるときは、X同士は同一でも異なっていてもよい;
Couは、クマリン-6-イル基またはクマリン-7-イル基を表し、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
q1とq2は、一方が1で他方が0である;
q3は0または1である;
P及びQは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である;ただし、Xが-CH=CH-CO-O-、-O-CO-CH=CH-である場合、-CH=CH-が結合する側のP又はQは芳香環であり、Pの数が2以上となるときは、P同士は同一でも異なっていてもよく、Qの数が2以上となるときは、Q同士は同一でも異なっていてもよい;
l1は0または1である;
l2は0~2の整数である;
l1とl2がともに0であるときは、Tが単結合であるときはAも単結合を表す;
l1が1であるときは、Tが単結合であるときはBも単結合を表す;
H及びIは、各々独立に、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。
In the formula, A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
式中、A、B、D、Y1、X、Y2、及び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。 The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y 1 , X, Y 2 and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).
式中、A、X、l、m、m1及びRは、上記と同じ定義を有する。 The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m, m1 and R have the same definition as above.
式中、A、Y1、l、m1及びm2は上記と同じ定義を有する。 The side chain may be a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y 1 , l, m1 and m2 have the same definition as above.
式中、A、X、l及びmは、上記と同じ定義を有する。 The side chain may be a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.
式中、A、B、Y1、q1、q2、m1、及びm2は、上記と同じ定義を有する。
R1は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基を表す。 The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y1, q1, q2, m1, and m2 have the same definition as above.
R 1 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
式中、A、Y1、X、l及びmは上記と同じ定義を有する。 The side chain is preferably a photosensitive side chain represented by the following formula (20).
In the formula, A, Y 1 , X, l and m have the same definition as above.
式中、A、B、q1及びq2は上記と同じ定義を有する;
Y3は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R3は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、炭素数5~8の脂環式炭化水素、炭素数1~12のアルキル基、又は炭素数1~12のアルコキシ基を表す;
lは1~12の整数を表し、mは0から2の整数を表し、但し、式(23)~(24)において、全てのmの合計は2以上であり、式(25)~(26)において、全てのmの合計は1以上であり、m1、m2およびm3は、それぞれ独立に1~3の整数を表す;
R2は、水素原子、-NO2、-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、アルキル基、又はアルキルオキシ基を表す;
Z1、Z2は単結合、-CO-、-CH2O-、-CH=N-、-CF2-を表す。 The (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
In which A, B, q1 and q2 have the same definition as above;
Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 each represents a single bond, —CO—, —CH 2 O—, —CH═N—, —CF 2 —.
上記の液晶性を発現し得る感光性の側鎖型高分子は、上記の感光性側鎖を有する光反応性側鎖モノマーおよび液晶性側鎖モノマーを重合することによって得ることができる。 << Production Method of Photosensitive Side Chain Polymer >>
The photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.
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。 [Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
As the photoreactive group possessed by the side chain, the following structures and derivatives thereof are preferred.
液晶性側鎖モノマーとは、該モノマー由来の高分子が液晶性を発現し、該高分子が側鎖部位にメソゲン基を形成することができるモノマーのことである。
側鎖の有するメソゲン基として、ビフェニルやフェニルベンゾエートなどの単独でメソゲン構造となる基であっても、安息香酸などのように側鎖同士が水素結合することでメソゲン構造となる基であってもよい。側鎖の有するメソゲン基としては下記の構造が好ましい。 [Liquid crystal side chain monomer]
The liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good. As the mesogenic group possessed by the side chain, the following structure is preferable.
その他のモノマーの具体例としては、不飽和カルボン酸、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物及びビニル化合物等が挙げられる。 Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、2,2,2-トリフルオロエチルアクリレート、tert-ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、2-メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、2-エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、3-メトキシブチルアクリレート、2-メチル-2-アダマンチルアクリレート、2-プロピル-2-アダマンチルアクリレート、8-メチル-8-トリシクロデシルアクリレート、及び、8-エチル-8-トリシクロデシルアクリレート等が挙げられる。 Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.
スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。
マレイミド化合物としては、例えば、マレイミド、N-メチルマレイミド、N-フェニルマレイミド、及びN-シクロヘキシルマレイミド等が挙げられる。 Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
また、ラジカル重合において有機溶媒中の酸素は重合反応を阻害する原因となるので、有機溶媒は可能な程度に脱気されたものを用いることが好ましい。 These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate.
In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.
上述の反応により得られた、液晶性を発現し得る感光性の側鎖型高分子の反応溶液から、生成した高分子を回収する場合には、反応溶液を貧溶媒に投入して、それら重合体を沈殿させれば良い。沈殿に用いる貧溶媒としては、メタノール、アセトン、ヘキサン、ヘプタン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン、ジエチルエーテル、メチルエチルエーテル、水等を挙げることができる。貧溶媒に投入して沈殿させた重合体は、濾過して回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。また、沈殿回収した重合体を、有機溶媒に再溶解させ、再沈殿回収する操作を2回~10回繰り返すと、重合体中の不純物を少なくすることができる。この際の貧溶媒として、例えば、アルコール類、ケトン類、炭化水素等が挙げられ、これらの中から選ばれる3種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。 [Recovery of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side chain polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent, The coalescence can be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
本発明に用いられる重合体組成物は、(B)成分として、ジイソシアネート成分及びテトラカルボン酸誘導体から選ばれる少なくとも一種と、ジアミン化合物の2種以上とを用いて製造された重合体を有する。かかる(B)成分の重合体は、ジイソシアネート成分及びジアミン成分とを用いて製造されたポリウレア、ジイソシアネート成分及びテトラカルボン酸誘導体を用いて製造されたポリイミド前駆体、および、ジイソシアネート成分、テトラカルボン酸誘導体及びジアミン成分を用いて製造されたポリウレアポリイミド前駆体、すなわち、ポリウレアとポリイミド前駆体との共重合体が挙げられる。 << (B) component >>
The polymer composition used in the present invention has, as the component (B), a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more diamine compounds. The polymer of the component (B) includes a polyurea produced using a diisocyanate component and a diamine component, a polyimide precursor produced using a diisocyanate component and a tetracarboxylic acid derivative, and a diisocyanate component and a tetracarboxylic acid derivative. And a polyurea polyimide precursor produced using a diamine component, that is, a copolymer of polyurea and a polyimide precursor.
(B)成分の原料であるジイソシアネート成分として、例えば、芳香族ジイソシアネート、脂肪族ジイソシアネートなどが挙げられる。好ましいジイソシアネート成分は、芳香族ジイソシアネート、脂肪族ジイソシアネートである。 <<< Diisocyanate component >>>
Examples of the diisocyanate component that is a raw material for the component (B) include aromatic diisocyanates and aliphatic diisocyanates. Preferred diisocyanate components are aromatic diisocyanates and aliphatic diisocyanates.
ジイソシアネート成分のなかでも、イソホロンジイソシアネートと2,4-ジイソシアン酸トリレンが重合反応性、電圧保持率の観点から好ましく、さらに、イソホロンジイソシアネートが、入手性、重合反応性、電圧保持率の観点からより好ましい。 Specific examples of the aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, and tetramethylethylene diisocyanate. As the aliphatic diisocyanate, preferably, isophorone diisocyanate is used.
Of the diisocyanate components, isophorone diisocyanate and 2,4-diisocyanate tolylene are preferable from the viewpoint of polymerization reactivity and voltage holding ratio, and isophorone diisocyanate is more preferable from the viewpoint of availability, polymerization reactivity, and voltage holding ratio. .
(B)成分の原料であるテトラカルボン酸誘導体として、例えば以下のテトラカルボン酸二無水物が挙げられる。 << tetracarboxylic acid derivative >>
Examples of the tetracarboxylic acid derivative that is a raw material for the component (B) include the following tetracarboxylic dianhydrides.
その具体例を以下に挙げる。 Moreover, you may use tetracarboxylic-acid dialkyl ester and tetracarboxylic-acid dialkyl diester dichloride as a tetracarboxylic-acid component which is a raw material of (B) component. When the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamic acid ester that is a polyimide precursor. The tetracarboxylic acid dialkyl ester that can be used is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters.
Specific examples are given below.
(B)成分の原料であるジアミン成分としては、例えば、以下の脂環式ジアミン、芳香族ジアミン、複素環式ジアミン、脂肪族ジアミンやウレア結合含有ジアミンが挙げられる。 <<< diamine component >>>
As a diamine component which is a raw material of (B) component, the following alicyclic diamine, aromatic diamine, heterocyclic diamine, aliphatic diamine, and urea bond containing diamine are mentioned, for example.
(式中、Arはベンゼン環またはナフタレン環を表し、R1は炭素原子数が1~5のアルキレン基であり、R2は水素原子またはメチル基である。)
(In the formula, Ar represents a benzene ring or a naphthalene ring, R 1 represents an alkylene group having 1 to 5 carbon atoms, and R 2 represents a hydrogen atom or a methyl group.)
Z3はエーテル結合、エステル結合、アミド結合及びウレア結合から選ばれる結合で中断されていてもよい炭素数1~20のアルキレン基であり、Z3とベンゼン環との結合部分は単結合、エーテル結合、エステル結合、ウレア結合又はアミド結合である。 In formula (Y2-1),
Z 3 is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bonding part between Z 3 and the benzene ring is a single bond, ether A bond, an ester bond, a urea bond, or an amide bond.
その具体例を以下に挙げる。 The organic solvent used for the reaction of at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine component is not particularly limited as long as the produced polymer is soluble.
Specific examples are given below.
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。 << (C) Organic solvent >>
The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. Is mentioned. These may be used alone or in combination.
例えば、イソプロピルアルコール、メトキシメチルペンタノール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチルカルビトールアセテート、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール-tert-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、3-メチル-3-メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、3-メチル-3-メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、1-ヘキサノール、n-へキサン、n-ペンタン、n-オクタン、ジエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸n-ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチルエチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸、3-メトキシプロピオン酸、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、1-ブトキシ-2-プロパノール、1-フェノキシ-2-プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート、プロピレングリコール-1-モノエチルエーテル-2-アセテート、ジプロピレングリコール、2-(2-エトキシプロポキシ)プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸n-プロピルエステル、乳酸n-ブチルエステル、乳酸イソアミルエステル等の低表面張力を有する溶媒等が挙げられる。 The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl isoamyl ester, etc. Examples include solvents having surface tension.
より具体的には、例えば、エフトップ(登録商標)301、EF303、EF352(トーケムプロダクツ社製)、メガファック(登録商標)F171、F173、R-30(DIC社製)、フロラードFC430、FC431(住友スリーエム社製)、アサヒガード(登録商標)AG710(旭硝子社製)、サーフロン(登録商標)S-382、SC101、SC102、SC103、SC104、SC105、SC106(AGCセイミケミカル社製)等が挙げられる。これらの界面活性剤の使用割合は、重合体組成物に含有される樹脂成分の100質量部に対して、好ましくは0.01質量部~2質量部、より好ましくは0.01質量部~1質量部である。 Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.
例えば、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、2-アミノプロピルトリメトキシシラン、2-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリメトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリエトキシシラン、N-トリエトキシシリルプロピルトリエチレントリアミン、N-トリメトキシシリルプロピルトリエチレントリアミン、10-トリメトキシシリル-1,4,7-トリアザデカン、10-トリエトキシシリル-1,4,7-トリアザデカン、9-トリメトキシシリル-3,6-ジアザノニルアセテート、9-トリエトキシシリル-3,6-ジアザノニルアセテート、N-ベンジル-3-アミノプロピルトリメトキシシラン、N-ベンジル-3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリメトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリエトキシシラン等が挙げられる。 Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Examples thereof include propyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.
光増感剤としては、芳香族ニトロ化合物、クマリン(7-ジエチルアミノ-4-メチルクマリン、7-ヒドロキシ4-メチルクマリン)、ケトクマリン、カルボニルビスクマリン、芳香族2-ヒドロキシケトン、およびアミノ置換された、芳香族2-ヒドロキシケトン(2-ヒドロキシベンゾフェノン、モノ-もしくはジ-p-(ジメチルアミノ)-2-ヒドロキシベンゾフェノン)、アセトフェノン、アントラキノン、キサントン、チオキサントン、ベンズアントロン、チアゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトチアゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾチアゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾチアゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾチアゾリン、2-(β-ナフトイルメチレン)-3-メチル
-β-ナフトチアゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトチアゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトチアゾリン)、オキサゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトオキサゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾオキサゾリン、2-(β-ナフトイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトオキサゾリン)、ベンゾチアゾール、ニトロアニリン(m-もしくはp-ニトロアニリン、2,4,6-トリニトロアニリン)またはニトロアセナフテン(5-ニトロアセナフテン)、(2-[(m-ヒドロキシ-p-メトキシ)スチリル]ベンゾチアゾール、ベンゾインアルキルエーテル、N-アルキル化フタロン、アセトフェノンケタール(2,2-ジメトキシフェニルエタノン)、ナフタレン、アントラセン(2-ナフタレンメタノール、2-ナフタレンカルボン酸、9-アントラセンメタノール、および9-アントラセンカルボン酸)、ベンゾピラン、アゾインドリジン、メロクマリン等がある。
好ましくは、芳香族2-ヒドロキシケトン(ベンゾフェノン)、クマリン、ケトクマリン、カルボニルビスクマリン、アセトフェノン、アントラキノン、キサントン、チオキサントン、およびアセトフェノンケタールである。 A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
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、上述の(A)成分、(B)成分及び上述の膜厚均一性や表面平滑性を向上させる溶媒や化合物、液晶配向膜と基板との密着性を向上させる化合物等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、(A)成分と(B)の含有量の合計は、1質量%~20質量%が好ましく、より好ましくは3質量%~15質量%、特に好ましくは3質量%~10質量%である。 [Preparation of polymer composition]
The polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is the above-described component (A), component (B) and the above-described solvent and compound that improve the film thickness uniformity and surface smoothness, and the adhesion between the liquid crystal alignment film and the substrate. It is preferable that the compound etc. which improve a property are prepared as a solution which melt | dissolved in the organic solvent. Here, the total content of the component (A) and the component (B) 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. is there.
そのような他の重合体は、例えば、ポリ(メタ)アクリレートやポリアミック酸やポリイミド等からなり、液晶性を発現し得る感光性の側鎖型高分子ではない重合体等が挙げられる。 In the polymer composition of the present embodiment, in addition to the components (A) and (B), other polymers may be mixed as long as the liquid crystal expression ability and the photosensitive performance are not impaired. In that case, the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
Examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.
本発明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、
(B)ジイソシアネート成分及びテトラカルボン酸誘導体から選ばれる少なくとも一種と、ジアミン化合物の2種以上とを用いて製造された重合体、及び
(C)有機溶媒
を含有することを特徴と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。 <Manufacturing method of substrate having liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>
The method for producing a substrate having the liquid crystal alignment film of the present invention is
[I] (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range;
(B) a polymer produced using at least one selected from diisocyanate components and tetracarboxylic acid derivatives and two or more diamine compounds, and (C) a polymer composition comprising an organic solvent Applying an object on a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
Have
Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.
[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、
(B)ジイソシアネート化合物と、テトラカルボン酸誘導体と、ジアミン化合物とを重合反応させ、次いでイミド化することにより製造されるポリウレアポリイミド、及び
(C)有機溶媒
を含有することを特徴と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。 In the second aspect of the present invention, a method for producing a substrate having the liquid crystal alignment film of the present invention comprises:
[I] (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range;
(B) A polyurea polyimide produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound and then imidizing, and (C) a polymer composition comprising an organic solvent Applying an object on a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
Have
Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.
第2の基板は、横電界駆動用の導電膜を有する基板に代わって、横電界駆動用の導電膜を有しない基板を用いる以外、上記工程[I]~[III](横電界駆動用の導電膜を有しない基板を用いるため、便宜上、本願において、工程[I’]~[III’]と略記する場合がある)を用いることにより、配向制御能が付与された液晶配向膜を有する第2の基板を得ることができる。 Further, by preparing a second substrate in addition to the obtained substrate (first substrate), a lateral electric field drive type liquid crystal display element can be obtained.
For the second substrate, instead of using a substrate having no lateral electric field driving conductive film instead of a substrate having a lateral electric field driving conductive film, the above steps [I] to [III] (for lateral electric field driving) Since a substrate having no conductive film is used, for the sake of convenience, in this application, the steps [I ′] to [III ′] may be abbreviated as steps), thereby providing a first liquid crystal alignment film having alignment controllability. Two substrates can be obtained.
[IV] 上記で得られた第1及び第2の基板を、液晶を介して第1及び第2の基板の液晶配向膜が相対するように、対向配置して液晶表示素子を得る工程;
を有する。これにより横電界駆動型液晶表示素子を得ることができる。 The manufacturing method of the horizontal electric field drive type liquid crystal display element is:
[IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween;
Have Thereby, a horizontal electric field drive type liquid crystal display element can be obtained.
<工程[I]>
工程[I]では、横電界駆動用の導電膜を有する基板上に、所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、(B)成分の重合体、及び有機溶媒を含有する重合体組成物を塗布して塗膜を形成する。 The steps [I] to [III] and [IV] of the production method of the present invention will be described below.
<Process [I]>
In the step [I], a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, a polymer of the component (B), and an organic solvent are formed on a substrate having a conductive film for driving a lateral electric field. The polymer composition contained is applied to form a coating film.
基板については、特に限定はされないが、製造される液晶表示素子が透過型である場合、透明性の高い基板が用いられることが好ましい。その場合、特に限定はされず、ガラス基板、またはアクリル基板やポリカーボネート基板等のプラスチック基板等を用いることができる。
また、反射型の液晶表示素子への適用を考慮し、シリコンウェハなどの不透明な基板も使用できる。 <Board>
Although it does not specifically limit about a board | substrate, When the liquid crystal display element manufactured is a transmission type, it is preferable that a highly transparent board | substrate is used. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
In consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.
基板は、横電界駆動用の導電膜を有する。
該導電膜として、液晶表示素子が透過型である場合、ITO(Indium Tin Oxide:酸化インジウムスズ)、IZO(Indium Zinc Oxide:酸化インジウム亜鉛)などを挙げることができるが、これらに限定されない。
また、反射型の液晶表示素子の場合、導電膜として、アルミなどの光を反射する材料などを挙げることができるがこれらに限定されない。
基板に導電膜を形成する方法は、従来公知の手法を用いることができる。 <Conductive film for driving lateral electric field>
The substrate has a conductive film for driving a lateral electric field.
Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
In the case of a reflective liquid crystal display element, examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.
塗布方法は、工業的には、スクリーン印刷、オフセット印刷、フレキソ印刷またはインクジェット法などで行う方法が一般的である。その他の塗布方法としては、ディップ法、ロールコータ法、スリットコータ法、スピンナ法(回転塗布法)またはスプレー法などがあり、目的に応じてこれらを用いてもよい。 The method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
In general, the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
塗膜の厚みは、厚すぎると液晶表示素子の消費電力の面で不利となり、薄すぎると液晶表示素子の信頼性が低下する場合があるので、好ましくは5nm~300nm、より好ましくは10nm~150nmである。
尚、[I]工程の後、続く[II]工程の前に塗膜の形成された基板を室温にまで冷却する工程を設けることも可能である。 After the polymer composition is applied on a substrate having a conductive film for driving a horizontal electric field, it is 50 to 200 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven. The solvent can be evaporated at 150 ° C. to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.
工程[II]では、工程[I]で得られた塗膜に偏光した紫外線を照射する。塗膜の膜面に偏光した紫外線を照射する場合、基板に対して一定の方向から偏光板を介して偏光された紫外線を照射する。使用する紫外線としては、波長100nm~400nmの範囲の紫外線を使用することができる。好ましくは、使用する塗膜の種類によりフィルター等を介して最適な波長を選択する。そして、例えば、選択的に光架橋反応を誘起できるように、波長290nm~400nmの範囲の紫外線を選択して使用することができる。紫外線としては、例えば、高圧水銀灯から放射される光を用いることができる。 <Process [II]>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. For example, ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.
工程[III]では、工程[II]で偏光した紫外線の照射された塗膜を加熱する。加熱により、塗膜に配向制御能を付与することができる。
加熱は、ホットプレート、熱循環型オーブンまたはIR(赤外線)型オーブンなどの加熱手段を用いることができる。加熱温度は、使用する塗膜の液晶性を発現させる温度を考慮して決めることができる。 <Step [III]>
In step [III], the ultraviolet-irradiated coating film polarized in step [II] is heated. An orientation control ability can be imparted to the coating film by heating.
For heating, a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
なお、液晶性発現温度は、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。 The heating temperature is preferably within a temperature range of a temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature). In the case of a thin film surface such as a coating film, the liquid crystallinity expression temperature of the coating film surface may be lower than the liquid crystallinity expression temperature when a photosensitive side chain polymer capable of expressing liquid crystallinity is observed in bulk. is expected. For this reason, the heating temperature is more preferably within the temperature range of the liquid crystallinity 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 upper limit of the liquid crystal temperature range, with the temperature being 10 ° C. lower than the lower limit of the temperature range of the liquid crystalline expression temperature of the side chain polymer used. It is preferable that the temperature is in a range where the temperature is the upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
The liquid crystallinity temperature is equal to or higher 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). Refers to a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
[IV]工程は、[III]で得られた、横電界駆動用の導電膜上に液晶配向膜を有する基板(第1の基板)と、同様に上記[I’]~[III’]で得られた、導電膜を有しない液晶配向膜付基板(第2の基板)とを、液晶を介して、双方の液晶配向膜が相対するように対向配置して、公知の方法で液晶セルを作製し、横電界駆動型液晶表示素子を作製する工程である。なお、工程[I’]~[III’]は、工程[I]において、横電界駆動用の導電膜を有する基板の代わりに、該横電界駆動用導電膜を有しない基板を用いた以外、工程[I]~[III]と同様に行うことができる。工程[I]~[III]と工程[I’]~[III’]との相違点は、上述した導電膜の有無だけであるため、工程[I’]~[III’]の説明を省略する。 <Process [IV]>
The step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving. The obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method. This is a step of manufacturing a lateral electric field drive type liquid crystal display element. In the steps [I ′] to [III ′], a substrate having no lateral electric field driving conductive film was used in place of the substrate having the lateral electric field driving conductive film in the step [I]. It can be carried out in the same manner as in steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.
本発明に用いる塗膜では、側鎖の光反応と液晶性に基づく自己組織化によって誘起される分子再配向の原理を利用して、塗膜への高効率な異方性の導入を実現する。本発明の製造方法では、側鎖型高分子に光反応性基として光架橋性基を有する構造の場合、側鎖型高分子を用いて基板上に塗膜を形成した後、偏光した紫外線を照射し、次いで、加熱を行った後、液晶表示素子を作成する。 The manufacturing method of the board | substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply | coating a polymer composition on a board | substrate and forming a coating film. Next, by heating, high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
The coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. . In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, after forming a coating film on the substrate using the side chain polymer, polarized ultraviolet rays are formed. After irradiation and then heating, a liquid crystal display element is formed.
以下、実施例を用いて本発明を説明するが、本発明は、該実施例に限定されるものではない。 As described above, the lateral electric field drive type liquid crystal display element substrate manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.
EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.
<メタクリルモノマー> Abbreviations used in the examples are as follows.
<Methacrylic monomer>
MA2は、特許文献(特開平9-118717)に記載の合成法にて合成した。
HBAGEは、日本化成株式会社より購入した。
A1は、特許文献(WO2014-054785)に記載の合成法にて合成した。 MA1 was synthesized by a synthesis method described in a patent document (WO2011-084546).
MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717).
HBAGE was purchased from Nippon Kasei Co., Ltd.
A1 was synthesized by a synthesis method described in a patent document (WO2014-054785).
ISO:イソホロンジイソシアネート
DI―1:イソホロンジイソシアネート
DI-2:ジフェニルメタン-4,4’-ジイソシアネート
DI-3:1,4-フェニレンジイソシアネート
DI-4:トリレン2,4-ジイソシアネート <Diisocyanate component>
ISO: isophorone diisocyanate DI-1: isophorone diisocyanate DI-2: diphenylmethane-4,4'-diisocyanate DI-3: 1,4-phenylene diisocyanate DI-4: tolylene 2,4-diisocyanate
DDM:4,4’-ジアミノジフェニルメタン
Me-4APhA:N-メチル-2-(4-アミノフェニル)エチルアミン
Me-DADPA: 4,4’-ジアミノジフェニル(N-メチル)アミン
DA-2MG:1,3-ビス(4-アミノフェノキシ)エタン
BAPU:1,3-ビス[2-(4-アミノフェニル)エチル]ウレア
p-PDA:p-フェニレンジアミン
DADPA:4,4’-ジアミノジフェニルアミン <Diamine component>
DDM: 4,4′-diaminodiphenylmethane Me-4APhA: N-methyl-2- (4-aminophenyl) ethylamine Me-DADPA: 4,4′-diaminodiphenyl (N-methyl) amine DA-2MG: 1,3 -Bis (4-aminophenoxy) ethane BAPU: 1,3-bis [2- (4-aminophenyl) ethyl] urea p-PDA: p-phenylenediamine DADPA: 4,4'-diaminodiphenylamine
TDA: 3,4-ジカルボキシ-1,2,3,4-テトラヒドロ-1-ナフタレンコハク酸二無水物
BODA: ビシクロ[3.3.0]オクタン-2,4,6,8-テトラカルボン酸二無水物 <Tetracarboxylic dianhydride>
TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride BODA: bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid Dianhydride
THF: テトラヒドロフラン
NMP: N-メチル-2-ピロリドン
BCS: ブチルセロソルブ
GBL: γ-ブチロラクトン <Organic solvent>
THF: Tetrahydrofuran NMP: N-Methyl-2-pyrrolidone BCS: Butylcellosolve GBL: γ-Butyrolactone
AIBN: 2,2’-アゾビスイソブチロニトリル <Polymerization initiator>
AIBN: 2,2'-azobisisobutyronitrile
上記のような成分、原料、有機溶媒および重合開始剤等を使用して、下記のようにして重合組成物を調製し、評価した。 [Test I]
Using the above components, raw materials, organic solvent, polymerization initiator and the like, a polymerization composition was prepared and evaluated as follows.
MA1(5.3g)とMA2(19.6g)をTHF(101.3g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.39g)を加え再び脱気を行なった。この後60℃で8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メタノール(600ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、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MP1を得た。 <Methacrylate polymer synthesis example 1>
MA1 (5.3 g) and MA2 (19.6 g) were dissolved in THF (101.3 g), deaerated with a diaphragm pump, and then AIBN (0.39 g) was added to deaerate again. . Thereafter, the mixture was reacted at 60 ° C. for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder MP1.
表1に示す組成をメタクリレートポリマー合成例1と同様の方法を用いて合成した。 <Methacrylate polymer synthesis examples 2 and 3>
The compositions shown in Table 1 were synthesized using the same method as in the methacrylate polymer synthesis example 1.
ジアミン成分として、DDM(4.76g)とMe-DADPA(1.28g)をNMP75.9gに溶解し、そこへ、酸二無水物成分としてBODA(7.35g)を室温で添加し、60度で18時間反応させポリアミック酸(PAA-1)の濃度15wt%の溶液を得た。 <Polyamic acid synthesis example 1>
As a diamine component, DDM (4.76 g) and Me-DADPA (1.28 g) were dissolved in 75.9 g of NMP, and BODA (7.35 g) as an acid dianhydride component was added thereto at room temperature, and 60 ° C. For 18 hours to obtain a 15 wt% solution of polyamic acid (PAA-1).
表2に示す組成をポリアミック酸合成例1と同様の方法を用いて合成した。 <Polyamic acid synthesis examples 2 and 3>
The compositions shown in Table 2 were synthesized using the same method as in Polyamic Acid Synthesis Example 1.
ジアミン成分として、DDM(4.76g)とMe-DADPA(1.28g)をNMP71.2gに溶解し、そこへ、ジイソシアネートとしてISO(6.53g)を室温で添加し、60度で18時間反応させポリウレア(PU-1)の濃度15wt%の溶液を得た。 <Polyurea synthesis example 1>
As a diamine component, DDM (4.76 g) and Me-DADPA (1.28 g) were dissolved in NMP 71.2 g, and ISO (6.53 g) as a diisocyanate was added thereto at room temperature and reacted at 60 ° C. for 18 hours. To give a polyurea (PU-1) solution having a concentration of 15 wt%.
表3に示す組成をポリアミック酸合成例1と同様の方法を用いて合成した。 <Polyurea synthesis examples 2 to 4>
The compositions shown in Table 3 were synthesized using the same method as in Polyamic Acid Synthesis Example 1.
ジアミン成分として、DDM(5.35g)、Me-DADPA(0.32g)、Me-4APhA(0.22g)をNMP76.8gに溶解し、そこへ、ジイソシアネートとしてISO(6.53g)を室温で添加し1時間撹拌、その後酸二無水物としてTDA(4.32g)を室温で添加し、60度で18時間反応させポリウレア-アミック酸(PUPAA-1)の濃度15wt%の溶液を得た。 <Polyurea-amic acid synthesis example 1>
As a diamine component, DDM (5.35 g), Me-DADPA (0.32 g), Me-4APhA (0.22 g) were dissolved in N6.87 g, and ISO (6.53 g) as a diisocyanate was dissolved at room temperature. The mixture was added and stirred for 1 hour, and then TDA (4.32 g) was added as an acid dianhydride at room temperature and reacted at 60 ° C. for 18 hours to obtain a polyurea-amic acid (PUPAA-1) solution having a concentration of 15 wt%.
表4に示す組成をポリアミック酸合成例1と同様の方法を用いて合成した。 <Polyurea-amic acid synthesis examples 2 and 3>
The compositions shown in Table 4 were synthesized using the same method as in Polyamic Acid Synthesis Example 1.
上記メタクリレートポリマー合成例1にて得られたメタクリレートポリマー粉末(MP1)0.1gにNMP(2.35g)を加え、30分撹拌させメタクリレートポリマー溶液を得る。そこにポリアミック酸溶液(PAA-1)2.8g、GBL(5.25g)をg加え室温で1時間攪拌した。さらにこの溶液にBCS5.5gを加え、室温で1時間攪拌し、固形分濃度が3.5wt%、のポリマー溶液(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なる。 (Example 1)
NMP (2.35 g) is added to 0.1 g of the methacrylate polymer powder (MP1) obtained in the above methacrylate polymer synthesis example 1, and stirred for 30 minutes to obtain a methacrylate polymer solution. 2.8 g of polyamic acid solution (PAA-1) and gBL (5.25 g) were added thereto and stirred at room temperature for 1 hour. Further, 5.5 g of BCS was added to this solution and stirred for 1 hour at room temperature to obtain a polymer solution (A1) having a solid content concentration of 3.5 wt%. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.
表5に示す組成で、実施例1と同様の方法を用いて実施例2~7のポリマー溶液を得た。またコントロール1~9も同様の方法で調整した。 (Examples 2 to 7, Comparative Examples 1 to 9)
Polymer solutions of Examples 2 to 7 having the compositions shown in Table 5 were obtained in the same manner as in Example 1. Controls 1 to 9 were also adjusted in the same manner.
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。画素電極は、中央部分が屈曲したくの字形状の電極要素を複数配列して構成された櫛歯状の形状を有する。各電極要素の短手方向の幅は10μmであり、電極要素間の間隔は20μmであった。各画素を形成する画素電極が、中央部分の屈曲したくの字形状の電極要素を複数配列して構成されているため、各画素の形状は長方形状ではなく、電極要素と同様に中央部分で屈曲する、太字のくの字に似た形状を備えていた。そして、各画素は、その中央の屈曲部分を境にして上下に分割され、屈曲部分の上側の第1領域と下側の第2領域を有した。各画素の第1領域と第2領域とを比較すると、それらを構成する画素電極の電極要素の形成方向が異なるものとなっていた。すなわち、後述する液晶配向膜の配向処理方向を基準とした場合、画素の第1領域では画素電極の電極要素が+15°の角度(時計回り)をなすように形成され、画素の第2領域では画素電極の電極要素が-15°の角度(時計回り)をなすように形成されていた。すなわち、各画素の第1領域と第2領域とでは、画素電極と対向電極との間の電圧印加によって誘起される液晶の、基板面内での回転動作(インプレーン・スイッチング)の方向が互いに逆方向となるように構成されていた。 [Production of liquid crystal cell]
Using the liquid crystal aligning agent (A1) obtained in Example 1, a liquid crystal cell was produced 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 has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width of each electrode element in the short direction was 10 μm, and the distance between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It had a shape that bends and resembles a bold-faced koji. Each pixel was divided vertically with the central bent portion as a boundary, and had a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode were formed so as to form an angle of −15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It was configured to be in the opposite direction.
VHRの評価は、得られた液晶セルに、70℃の温度下で1Vの電圧を印加し、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。 (Voltage holding ratio (VHR) evaluation)
For the evaluation of VHR, a voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 70 ° C., the voltage after 16.67 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio.
The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.
上記のような成分、原料、有機溶媒および重合開始剤等を使用して、下記のようにして重合組成物を調製し、評価した。 [Test II]
Using the above components, raw materials, organic solvent, polymerization initiator and the like, a polymerization composition was prepared and evaluated as follows.
MA1(6.65g、20.0mmol)とMA2(24.51g、80.0mmol)をTHF(181.2g)中に溶解し、ダイアフラムポンプで脱気し窒素置換を行なった後、AIBNを(0.82g、5.0mmol)を加え再び脱気し窒素置換を行なった。この後50℃で24時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をジエチルエーテル(5000ml)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MP11を得た。 <Methacrylate polymer synthesis example 11>
MA1 (6.65 g, 20.0 mmol) and MA2 (24.51 g, 80.0 mmol) were dissolved in THF (181.2 g), deaerated with a diaphragm pump and purged with nitrogen. .82 g, 5.0 mmol) was added and the mixture was deaerated again and replaced with nitrogen. Thereafter, the mixture was reacted at 50 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (5000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder MP11.
MA1(5.3g)、MA2(19.6g)、HBAGE(0.34g)およびA1(0.18g)をTHF(102.6g)中に溶解し、ダイアフラムポンプで脱気し窒素置換を行なった後、AIBNを(0.39g)を加え再び脱気し窒素置換を行なった。この後60℃で24時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(600ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、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MP12を得た。 <Methacrylate polymer synthesis example 12>
MA1 (5.3 g), MA2 (19.6 g), HBAGE (0.34 g) and A1 (0.18 g) were dissolved in THF (102.6 g) and deaerated with a diaphragm pump to perform nitrogen substitution. Thereafter, AIBN (0.39 g) was added and deaerated again to perform nitrogen substitution. Thereafter, the mixture was reacted at 60 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (600 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder MP12.
<合成例11>
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA―2MG(1.47g、6.0mmol)、DA8(0.79g,2.0mmol)、DADPA(0.39g,2.0mmol)を取り、NMPを24.4g加え窒素雰囲気下において撹拌しながらDI―1(2.18g,9.8mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(11)を得た。また、この重合体の数平均分子量は7,100、重量平均分子量は13,400であった。 <Synthesis of polyurea polymer>
<Synthesis Example 11>
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, DA-2MG (1.47 g, 6.0 mmol), DA8 (0.79 g, 2.0 mmol), DADPA (0.39 g, 2.0 mmol) 24.4 g of NMP was added, DI-1 (2.18 g, 9.8 mmol) was added with stirring under a nitrogen atmosphere, and NMP was further added so that the solid concentration was 15% by mass. The mixture was stirred at 0 ° C. for 15 hours to obtain a polymer solution (11). The number average molecular weight of this polymer was 7,100, and the weight average molecular weight was 13,400.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA―2MG(1.47g、6.0mmol)、DA8(0.79g,2.0mmol)、Me-4APhA(0.33g,2.0mmol)を取り、NMPを24.2g加え窒素雰囲気下において撹拌しながらDI―1(2.18g,9.8mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(12)を得た。また、この重合体の数平均分子量は4,800、重量平均分子量は8,100であった。 <Synthesis Example 12>
To a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, DA-2MG (1.47 g, 6.0 mmol), DA8 (0.79 g, 2.0 mmol), Me-4APhA (0.33 g, 2.. 04.2), 24.2 g of NMP was added, DI-1 (2.18 g, 9.8 mmol) was added with stirring under a nitrogen atmosphere, and NMP was further added so that the solid content concentration was 15% by mass. The polymer solution (12) was obtained by stirring at 50 ° C. for 15 hours. The number average molecular weight of this polymer was 4,800, and the weight average molecular weight was 8,100.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA―2MG(1.47g、6.0mmol)、DADPA(0.39g,2.0mmol)、Me-4APhA(0.33g,2.0mmol)を取り、NMPを24.4g加え窒素雰囲気下において撹拌しながらDI―1(2.18g,9.8mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(13)を得た。また、この重合体の数平均分子量は10,300、重量平均分子量は22,000であった。 <Synthesis Example 13>
To a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, DA-2MG (1.47 g, 6.0 mmol), DADPA (0.39 g, 2.0 mmol), Me-4APhA (0.33 g, 2.. 04.4), 24.4 g of NMP was added, DI-1 (2.18 g, 9.8 mmol) was added with stirring under a nitrogen atmosphere, and NMP was further added so that the solid concentration was 15% by mass. The polymer solution (13) was obtained by stirring at 50 ° C. for 15 hours. The number average molecular weight of this polymer was 10,300, and the weight average molecular weight was 22,000.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA―2MG(2.15g、8.8mmol)、DADPA(0.46g,2.2mmol)を取り、NMPを25.4g加え窒素雰囲気下において撹拌しながらDI―1(2.40g,10.8mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(14)を得た。また、こ重合体の数平均分子量は14,300、重量平均分子量は29,700であった。 <Synthesis Example 14>
DA-2MG (2.15 g, 8.8 mmol) and DADPA (0.46 g, 2.2 mmol) are taken into a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 25.4 g of NMP is added and a nitrogen atmosphere is added. Under stirring, DI-1 (2.40 g, 10.8 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution ( 14) was obtained. The number average molecular weight of this polymer was 14,300, and the weight average molecular weight was 29,700.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA―2MG(2.15g、8.8mmol)、DA8(0.87g,2.2mmol)を取り、NMPを27.6g加え窒素雰囲気下において撹拌しながらDI―1(2.40g,10.8mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(15)を得た。また、この重合体の数平均分子量は6,500、重量平均分子量は11,900であった。 <Synthesis Example 15>
DA-2MG (2.15 g, 8.8 mmol) and DA8 (0.87 g, 2.2 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 27.6 g of NMP is added and a nitrogen atmosphere is added. Under stirring, DI-1 (2.40 g, 10.8 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution ( 15) was obtained. The number average molecular weight of this polymer was 6,500, and the weight average molecular weight was 11,900.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA-2MG(2.15g、8.8mmol)、Me-4APhA(0.31g,2.2mmol)を取り、NMPを27.6g加え窒素雰囲気下において撹拌しながらDI―1(2.40g,10.8mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(16)を得た。また、この重合体の数平均分子量は9,700、重量平均分子量は19,500であった。 <Synthesis Example 16>
DA-2MG (2.15 g, 8.8 mmol) and Me-4APhA (0.31 g, 2.2 mmol) are added to a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 27.6 g of NMP is added. While stirring under a nitrogen atmosphere, DI-1 (2.40 g, 10.8 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the polymer was stirred at 50 ° C. for 15 hours. A solution (16) was obtained. The number average molecular weight of this polymer was 9,700, and the weight average molecular weight was 19,500.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA―2MG(2.15g、8.8mmol)、DDM(0.43g,2.2mmol)を取り、NMPを27.6g加え窒素雰囲気下において撹拌しながらDI―1(2.40g,10.8mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(17)を得た。また、この重合体の数平均分子量は13,700、重量平均分子量は32,400であった。 <Synthesis Example 17>
DA-2MG (2.15 g, 8.8 mmol) and DDM (0.43 g, 2.2 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 27.6 g of NMP is added and a nitrogen atmosphere is added. Under stirring, DI-1 (2.40 g, 10.8 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution ( 17) was obtained. The number average molecular weight of this polymer was 13,700, and the weight average molecular weight was 32,400.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA-2MG(2.93g、12.0mmol)、BAPU(0.89g,3.0mmol)を取り、NMPを37.6g加え窒素雰囲気下において撹拌しながらDI―1(3.27g,14.7mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(18)を得た。また、この重合体の数平均分子量は11,300、重量平均分子量は25,400であった。 <Synthesis Example 18>
DA-2MG (2.93 g, 12.0 mmol) and BAPU (0.89 g, 3.0 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 37.6 g of NMP is added, and a nitrogen atmosphere is added. Under stirring, DI-1 (3.27 g, 14.7 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution ( 18) was obtained. The number average molecular weight of this polymer was 11,300, and the weight average molecular weight was 25,400.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA―2MG(2.34g、9.6mmol)、Me-DADPA(0.51g,2.4mmol)を取り、NMPを28.1g加え窒素雰囲気下において撹拌しながらDI―1(2.13g,9.6mmol)を添加し、25℃で3時間撹拌した。その後DI-2(0.51g,2.0mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(19)を得た。また、この重合体の数平均分子量は13,500、重量平均分子量は33,100であった。 <Synthesis Example 19>
DA-2MG (2.34 g, 9.6 mmol) and Me-DADPA (0.51 g, 2.4 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 28.1 g of NMP is added. While stirring under a nitrogen atmosphere, DI-1 (2.13 g, 9.6 mmol) was added, and the mixture was stirred at 25 ° C. for 3 hours. Thereafter, DI-2 (0.51 g, 2.0 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution (19). It was. The number average molecular weight of this polymer was 13,500, and the weight average molecular weight was 33,100.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DDM(1.90g、9.6mmol)、Me-DADPA(0.51g,2.4mmol)を取り、NMPを28.1g加え窒素雰囲気下において撹拌しながらDI―1(2.13g,9.6mmol)を添加し、25℃で3時間撹拌した。その後DI-3(0.32g,2.0mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(20)を得た。また、この重合体の数平均分子量は8,600、重量平均分子量は18,200であった。 <Synthesis Example 20>
DDM (1.90 g, 9.6 mmol) and Me-DADPA (0.51 g, 2.4 mmol) are taken into a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 28.1 g of NMP is added and a nitrogen atmosphere is added. Under stirring, DI-1 (2.13 g, 9.6 mmol) was added and stirred at 25 ° C. for 3 hours. Thereafter, DI-3 (0.32 g, 2.0 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution (20). It was. The number average molecular weight of this polymer was 8,600, and the weight average molecular weight was 18,200.
撹拌装置及び窒素導入管付きの100mLの四つ口フラスコに、DA―2MG(2.34g、9.6mmol)、Me-DADPA(0.51g,2.4mmol)を取り、NMPを28.1g加え窒素雰囲気下において撹拌しながらDI―1(2.13g,9.6mmol)を添加し、25℃で3時間撹拌した。その後DI-4(0.32g,2.0mmol)を添加し、さらに、固形分濃度が15質量%になるようにNMPを加え、50℃で15時間撹拌して重合体溶液(21)を得た。また、この重合体の数平均分子量は11,800、重量平均分子量は25,300であった。 <Synthesis Example 21>
DA-2MG (2.34 g, 9.6 mmol) and Me-DADPA (0.51 g, 2.4 mmol) are taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 28.1 g of NMP is added. While stirring under a nitrogen atmosphere, DI-1 (2.13 g, 9.6 mmol) was added, and the mixture was stirred at 25 ° C. for 3 hours. Thereafter, DI-4 (0.32 g, 2.0 mmol) was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at 50 ° C. for 15 hours to obtain a polymer solution (21). It was. The number average molecular weight of this polymer was 11,800, and the weight average molecular weight was 25,300.
上記合成例1にて得られたメタクリル酸ポリマー(MP11)0.12gに、ポリウレア重合体溶液、重合体(11)を6.4g、NMP3.98g、GBLを10.5gを加え室温で3時間攪拌した。さらにこの溶液にBCS9.0gを加え、室温で3時間攪拌し、固形分濃度が4.0wt%、のポリマー溶液(A11)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なる。 (Example 11)
To 0.12 g of the methacrylic acid polymer (MP11) obtained in Synthesis Example 1 above, 6.4 g of the polyurea polymer solution, the polymer (11), 3.98 g of NMP, and 10.5 g of GBL were added, and 3 hours at room temperature. Stir. Further, 9.0 g of BCS was added to this solution and stirred at room temperature for 3 hours to obtain a polymer solution (A11) having a solid content concentration of 4.0 wt%. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.
表12に示す組成で、実施例11と同様の方法を用いて実施例12~22のポリマー溶液を得た。またコントロール11~12も同様の方法で調整した。 (Examples 12 to 22, control rules 11 to 12)
Polymer solutions of Examples 12 to 22 were obtained with the compositions shown in Table 12 using the same method as in Example 11. Controls 11 to 12 were also adjusted in the same manner.
各液晶配向処理剤を用いて、以下のようにして液晶セルを作製した。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。画素電極は、中央部分が屈曲したくの字形状の電極要素を複数配列して構成された櫛歯状の形状を有する。各電極要素の短手方向の幅は10μmであり、電極要素間の間隔は20μmであった。各画素を形成する画素電極が、中央部分の屈曲したくの字形状の電極要素を複数配列して構成されているため、各画素の形状は長方形状ではなく、電極要素と同様に中央部分で屈曲する、太字のくの字に似た形状を備えている。そして、各画素は、その中央の屈曲部分を境にして上下に分割され、屈曲部分の上側の第1領域と下側の第2領域を有した。各画素の第1領域と第2領域とを比較すると、それらを構成する画素電極の電極要素の形成方向が異なるものとなっていた。すなわち、後述する液晶配向膜の配向処理方向を基準とした場合、画素の第1領域では画素電極の電極要素が+15°の角度(時計回り)をなすように形成され、画素の第2領域では画素電極の電極要素が-15°の角度(時計回り)をなすように形成されていた。すなわち、各画素の第1領域と第2領域とでは、画素電極と対向電極との間の電圧印加によって誘起される液晶の、基板面内での回転動作(インプレーン・スイッチング)の方向が互いに逆方向となるように構成されていた。 [Production of liquid crystal cell]
Using each liquid crystal aligning agent, a liquid crystal cell was produced as follows. 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 has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width of each electrode element in the short direction was 10 μm, and the distance between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold, bold character. Each pixel was divided vertically with the central bent portion as a boundary, and had a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode were formed so as to form an angle of −15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It was configured to be in the opposite direction.
上記の方法にて液晶セルを作製した。その後、偏光板をクロスニコル状態にした偏光顕微鏡を通して観察した。液晶セルを回転し黒表示状態にしたときに輝点や配向不良が無い状態を良好な状態を○、輝点や配向欠陥がある状態を×とした。液晶セルを液晶の等方相温度領域まで加熱し、同様に観察した結果について表12に示す。 (Orientation observation)
A liquid crystal cell was produced by the above method. Thereafter, the polarizing plate was observed through a polarizing microscope in a crossed Nicol state. When the liquid crystal cell is rotated to be in a black display state, a state where there is no bright spot or alignment defect is good, and a state where there is a bright spot or alignment defect is shown as x. Table 12 shows the results obtained by heating the liquid crystal cell to the isotropic phase temperature range of the liquid crystal and observing similarly.
VHRの評価は、得られた液晶セルに、70℃の温度下で5Vの電圧を60μs間印加し、1667ms後に該当液晶セルの保持電圧を測定した。VHR1を初期値とし、LEDバックライトにて1週間ストレスを与えた後に測定した値をVHR2とした。
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。 (Voltage holding ratio (VHR) evaluation)
For evaluation of VHR, a voltage of 5 V was applied to the obtained liquid crystal cell at a temperature of 70 ° C. for 60 μs, and a holding voltage of the liquid crystal cell was measured after 1667 ms. VHR1 was an initial value, and a value measured after applying a stress for one week with an LED backlight was VHR2.
The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.
上記のような成分、原料、有機溶媒および重合開始剤等を使用して、下記のようにして重合組成物を調製し、評価した。 [Test III]
Using the above components, raw materials, organic solvent, polymerization initiator and the like, a polymerization composition was prepared and evaluated as follows.
MA1(5.3g)、MA2(19.6g)、HBAGE(0.34g)およびA1(0.18g)をTHF(102.6g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.39g)を加え再び脱気を行なった。この後60℃で8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メタノール(600ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、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MP31を得た。 <Methacrylate polymer synthesis example 31>
MA1 (5.3 g), MA2 (19.6 g), HBAGE (0.34 g) and A1 (0.18 g) were dissolved in THF (102.6 g), deaerated with a diaphragm pump, and then AIBN. (0.39 g) was added and deaeration was performed again. Thereafter, the mixture was reacted at 60 ° C. for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (600 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder MP31.
ジアミン成分として、DDM(5.35g)、Me-DADPA(0.32g)、Me-4APhA(0.22g)をNMP76.8gに溶解し、そこへ、ジイソシアネートとしてISO(6.53g)を室温で添加し1時間撹拌、その後酸二無水物としてTDA(4.32g)を室温で添加し、60℃で18時間反応させポリウレア-アミック酸(PUPAA-31)の濃度15wt%の溶液を得た。 <Polyurea-amic acid synthesis example 31>
As a diamine component, DDM (5.35 g), Me-DADPA (0.32 g), Me-4APhA (0.22 g) were dissolved in N6.87 g, and ISO (6.53 g) as a diisocyanate was dissolved at room temperature. The mixture was added and stirred for 1 hour, and then TDA (4.32 g) was added as an acid dianhydride at room temperature and reacted at 60 ° C. for 18 hours to obtain a polyurea-amic acid (PUPAA-31) solution having a concentration of 15 wt%.
ジアミン成分として、DDM(5.35g)、Me-DADPA(0.32g)、Me-4APhA(0.22g)をNMP76.8gに溶解し、そこへ、ジイソシアネートとしてISO(6.53g)を室温で添加し1時間撹拌、その後酸二無水物としてBODA(1.93g)を室温で添加し、60℃で1時間反応させた。その後さらに酸二無水物TDA(2.14g)を添加し、18時間反応させ、ポリウレア-アミック酸(PUPAA-
32)の濃度15wt%の溶液を得た。 <Polyurea-amic acid synthesis example 32>
As a diamine component, DDM (5.35 g), Me-DADPA (0.32 g), Me-4APhA (0.22 g) were dissolved in N6.87 g, and ISO (6.53 g) as a diisocyanate was dissolved at room temperature. The mixture was added and stirred for 1 hour, and then BODA (1.93 g) was added as an acid dianhydride at room temperature and reacted at 60 ° C. for 1 hour. Thereafter, acid dianhydride TDA (2.14 g) was further added and reacted for 18 hours, and polyurea-amic acid (PUPAA-
32) having a concentration of 15 wt% was obtained.
上記ポリウレア-アミック酸合成例1にて得られた濃度15wt%の溶液(PUPAA-1、30g)に、NMP(50g)を加えて濃度6wt%に希釈した後、イミド化触媒として無水酢酸(6.42g)、ピリジン(2.49g)を加え、室温にて30分撹拌後、50℃にて3時間反応させた。この反応溶液をメタノール(300ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、40℃で減圧乾燥し、ポリウレア-イミド粉末を得た。このポリウレア-イミドのイミド化率は96%であった。その後、NMPを加えて再溶解させ、濃度15wt%のポリウレア-イミド溶液(PUPI31)を得た。 <Polyurea-imide synthesis example 31>
NMP (50 g) was added to the 15 wt% solution (PUPAA-1, 30 g) obtained in the above polyurea-amic acid synthesis example 1 to dilute to 6 wt%, and then acetic anhydride (6 .42 g) and pyridine (2.49 g) were added, and the mixture was stirred at room temperature for 30 minutes and then reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. to obtain polyurea-imide powder. The imidation ratio of this polyurea-imide was 96%. Thereafter, NMP was added and redissolved to obtain a polyurea-imide solution (PUPI 31) having a concentration of 15 wt%.
上記ポリウレア-アミック酸合成例2にて得られた濃度15wt%の溶液(PUPAA-22、30g)に、NMP(50g)を加えて濃度6wt%に希釈した後、イミド化触媒として無水酢酸(6.42g)、ピリジン(2.49g)を加え、室温にて30分撹拌後、50℃にて3時間反応させた。この反応溶液をメタノール(300ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、40℃で減圧乾燥しポリウレア-イミド粉末を得た。このポリウレア-イミドのイミド化率は73%であった。その後、NMPを加えて再溶解させ、濃度15wt%のポリウレア-イミド溶液(PUPI32)を得た。 <Polyurea-imide synthesis example 32>
NMP (50 g) was added to the 15 wt% solution (PUPAA-22, 30 g) obtained in the above polyurea-amic acid synthesis example 2 and diluted to a concentration of 6 wt%, and then acetic anhydride (6 .42 g) and pyridine (2.49 g) were added, and the mixture was stirred at room temperature for 30 minutes and then reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 40 ° C. to obtain a polyurea-imide powder. The imidation ratio of this polyurea-imide was 73%. Thereafter, NMP was added and redissolved to obtain a polyurea-imide solution (PUPI32) having a concentration of 15 wt%.
上記メタクリレートポリマー合成例1にて得られたメタクリレートポリマー粉末(MP1)0.1gにNMP(2.35g)を加え、30分撹拌させメタクリレートポリマー溶液を得る。そこにポリウレア-イミド溶液(PUPI-21)2.8g、GBL(5.25g)を加え室温で1時間攪拌した。さらにこの溶液にBCS(5.5g)を加え、室温で1時間攪拌し、固形分濃度が3.5wt%、のポリマー溶液(A31)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なる。 (Example 31)
NMP (2.35 g) is added to 0.1 g of the methacrylate polymer powder (MP1) obtained in the above methacrylate polymer synthesis example 1, and stirred for 30 minutes to obtain a methacrylate polymer solution. Thereto were added 2.8 g of a polyurea-imide solution (PUPI-21) and GBL (5.25 g), and the mixture was stirred at room temperature for 1 hour. Further, BCS (5.5 g) was added to this solution, followed by stirring at room temperature for 1 hour to obtain a polymer solution (A31) having a solid content concentration of 3.5 wt%. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.
表21に示す組成で、実施例31と同様の方法を用いて実施例32~34のポリマー溶液(A32~A34)を得た。 (Examples 32 to 34)
Polymer solutions (A32 to A34) of Examples 32 to 34 were obtained by the same method as in Example 31 with the compositions shown in Table 21.
実施例31で得られた液晶配向剤(A31)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。画素電極は、中央部分が屈曲したくの字形状の電極要素を複数配列して構成された櫛歯状の形状を有する。各電極要素の短手方向の幅は10μmであり、電極要素間の間隔は20μmであった。各画素を形成する画素電極が、中央部分の屈曲したくの字形状の電極要素を複数配列して構成されているため、各画素の形状は長方形状ではなく、電極要素と同様に中央部分で屈曲する、太字のくの字に似た形状を備えていた。そして、各画素は、その中央の屈曲部分を境にして上下に分割され、屈曲部分の上側の第1領域と下側の第2領域を有した。各画素の第1領域と第2領域とを比較すると、それらを構成する画素電極の電極要素の形成方向が異なるものとなっていた。すなわち、後述する液晶配向膜の配向処理方向を基準とした場合、画素の第1領域では画素電極の電極要素が+15°の角度(時計回り)をなすように形成され、画素の第2領域では画素電極の電極要素が-15°の角度(時計回り)をなすように形成されていた。すなわち、各画素の第1領域と第2領域とでは、画素電極と対向電極との間の電圧印加によって誘起される液晶の、基板面内での回転動作(インプレーン・スイッチング)の方向が互いに逆方向となるように構成されていた。 [Production of liquid crystal cell]
Using the liquid crystal aligning agent (A31) obtained in Example 31, a liquid crystal cell was produced 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 has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width of each electrode element in the short direction was 10 μm, and the distance between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It had a shape that bends and resembles a bold-faced koji. Each pixel was divided vertically with the central bent portion as a boundary, and had a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode were formed so as to form an angle of −15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It was configured to be in the opposite direction.
VHRの評価は、得られた液晶セルに、70℃の温度下で1Vの電圧を印加し、1000ms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として計算した。液晶セル作製後に測定した初期の電圧保持率をVHR1とし、1週間後バックライトエージング試験を行った後に測定した電圧保持率をVHR2とした。
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。 (Voltage holding ratio (VHR) evaluation)
For the evaluation of VHR, a voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 70 ° C., the voltage after 1000 ms was measured, and how much the voltage could be held was calculated as a voltage holding ratio. The initial voltage holding ratio measured after manufacturing the liquid crystal cell was VHR1, and the voltage holding ratio measured after one week after performing the backlight aging test was VHR2.
The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.
As shown in Table 22, Examples 31 to 34 according to the present invention all have high initial voltage holding ratio (VHR1) and voltage holding ratio after backlight aging (VHR2). It can be seen that the voltage holding ratios of Examples 31, 32, and 34 are further improved compared to Example 33 using PUPAA 31 that is the same as PUPAA1.
Claims (16)
- (A)所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、
(B)ジイソシアネート成分及びテトラカルボン酸誘導体から選ばれる少なくとも一種と、ジアミン化合物の2種以上とを用いて製造された重合体、及び
(C)有機溶媒
を含有することを特徴とする重合体組成物。 (A) a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range;
(B) a polymer produced using at least one selected from diisocyanate components and tetracarboxylic acid derivatives and two or more diamine compounds, and (C) a polymer composition comprising an organic solvent object. - (B)成分が、ジイソシアネート成分及びテトラカルボン酸誘導体から選ばれる少なくとも一種と、ジアミン化合物の2種以上とを用いて製造された重合体であって、ジアミン由来の構造として式(Y2-1)で表される構造を有する重合体である、請求項1に記載の重合体。
(但し、Z3はエーテル結合、エステル結合、アミド結合及びウレア結合から選ばれる結合で中断されていてもよい炭素数1~20のアルキレン基であり、Z3とベンゼン環との結合部分は単結合、エーテル結合、エステル結合、ウレア結合又はアミド結合である)。 The component (B) is a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more diamine compounds, and the structure derived from the diamine is represented by the formula (Y2-1) The polymer of Claim 1 which is a polymer which has a structure represented by these.
(However, Z 3 is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bond part between Z 3 and the benzene ring is a single bond. Bond, ether bond, ester bond, urea bond or amide bond). - (B)成分の重合体が、ジイソシアネート成分とジアミン成分とを重合反応させることにより得られるポリウレアである請求項1又は2記載の組成物。 The composition according to claim 1 or 2, wherein the polymer of component (B) is a polyurea obtained by polymerizing a diisocyanate component and a diamine component.
- (B)成分の重合体が、ジイソシアネート成分と、テトラカルボン酸誘導体と、ジアミン成分とを重合反応させることにより得られるポリウレアポリイミド前駆体である請求項1又は2記載の組成物。 3. The composition according to claim 1, wherein the polymer of component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component.
- (B)成分の重合体が、テトラカルボン酸誘導体と、ジアミン成分とを重合反応させることにより得られるポリイミド前駆体である請求項1又は2記載の組成物。 The composition according to claim 1 or 2, wherein the polymer of component (B) is a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.
- (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)ジイソシアネート化合物と、テトラカルボン酸誘導体と、ジアミン化合物とを重合反応させ、次いでイミド化することにより製造されるポリウレアポリイミド、及び
(C)有機溶媒
を含有することを特徴とする重合体組成物。 (A) a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range;
(B) A polyurea polyimide produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound and then imidizing, and (C) a polymer composition comprising an organic solvent object. - (B)成分が、ジアミン由来の構造として式(Y2-1)で表される構造を有する、請求項6に記載の重合体。
(但し、Z3はエーテル結合、エステル結合、アミド結合及びウレア結合から選ばれる結合で中断されていてもよい炭素数1~20のアルキレン基であり、Z3とベンゼン環との結合部分は単結合、エーテル結合、エステル結合、ウレア結合又はアミド結合である)。 The polymer according to claim 6, wherein the component (B) has a structure represented by the formula (Y2-1) as a structure derived from a diamine.
(However, Z 3 is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bond part between Z 3 and the benzene ring is a single bond. Bond, ether bond, ester bond, urea bond or amide bond). - ジイソシアネート成分が、芳香族ジイソシアネート及び/又は脂肪族ジイソシアネートである、請求項1~7のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein the diisocyanate component is an aromatic diisocyanate and / or an aliphatic diisocyanate.
- (A)成分が、光架橋、光異性化、または光フリース転移を起こす感光性側鎖を有する、請求項1~8のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 8, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
- (A)成分が、下記式(1)~(6)
(式中、A、B、Dはそれぞれ独立に、単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、又は-O-CO-CH=CH-を表す;
Sは、炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Tは、単結合または炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Y1は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数5~8の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった2~6の環が結合基Bを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に-COOR0(式中、R0は水素原子又は炭素数1~5のアルキル基を表す)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
Y2は、2価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
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。)
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1~9のいずれか一項に記載の組成物。
(Wherein A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof. )
The composition according to any one of claims 1 to 9, which has any one photosensitive side chain selected from the group consisting of:
- (A)成分が、下記式(21)~(31)
(式中、A及びBは上記と同じ定義を有する;
Y3は、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に-NO2、-CN、ハロゲン基、炭素数1~5のアルキル基、又は炭素数1~5のアルキルオキシ基で置換されても良い;
R3は、水素原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、炭素数5~8の脂環式炭化水素、炭素数1~12のアルキル基、又は炭素数1~12のアルコキシ基を表す;
q1とq2は、一方が1で他方が0である;
lは1~12の整数を表し、mは0から2の整数を表し、但し、式(23)~(24)において、全てのmの合計は2以上であり、式(25)~(26)において、全てのmの合計は1以上であり、m1、m2およびm3は、それぞれ独立に1~3の整数を表す;
R2は、水素原子、-NO2、-CN、ハロゲン基、1価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、窒素含有複素環、及び炭素数5~8の脂環式炭化水素、および、アルキル基、又はアルキルオキシ基を表す;
Z1、Z2は単結合、-CO-、-CH2O-、-CH=N-、-CF2-を表す)
からなる群から選ばれるいずれか1種の液晶性側鎖を有する請求項1~10のいずれか一項に記載の組成物。
Wherein 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. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 represent a single bond, —CO—, —CH 2 O—, —CH═N—, —CF 2 —)
The composition according to any one of claims 1 to 10, which has any one liquid crystalline side chain selected from the group consisting of:
- [I] 請求項1~11のいずれか一項に記載の組成物を、横電界駆動用の導電膜を有する基板上に塗布して塗膜を形成する工程;
[II] [I]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された横電界駆動型液晶表示素子用液晶配向膜を得る、前記液晶配向膜を有する基板の製造方法。 [I] A step of forming a coating film by applying the composition according to any one of claims 1 to 11 onto a substrate having a conductive film for driving a lateral electric field;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having. - 請求項12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。 A substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element manufactured by the method according to claim 12.
- 請求項13記載の基板を有する横電界駆動型液晶表示素子。 A lateral electric field drive type liquid crystal display element comprising the substrate according to claim 13.
- 請求項13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1~11のいずれか一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。 Preparing a substrate (first substrate) according to claim 13;
[I ′] a step of coating the polymer composition according to any one of claims 1 to 11 on a second substrate to form a coating film;
[II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays; and [III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control capability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element. - 請求項15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。
A lateral electric field drive type liquid crystal display device manufactured by the method according to claim 15.
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Also Published As
Publication number | Publication date |
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JP6618043B2 (en) | 2019-12-11 |
CN107109050A (en) | 2017-08-29 |
KR102425044B1 (en) | 2022-07-25 |
TWI685525B (en) | 2020-02-21 |
TW201634590A (en) | 2016-10-01 |
KR20170082560A (en) | 2017-07-14 |
CN107109050B (en) | 2020-09-25 |
JPWO2016076348A1 (en) | 2017-08-31 |
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