Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a novel coating solution for forming a functional polymer film and a method for forming a functional polymer film.
• a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction.
• the main liquid crystal alignment films that are industrially used are polyimide precursors such as polyamic acid (also called polyamic acid), polyamic acid esters, and polyimide-based liquid crystal aligning agents composed of polyimide solutions. It is manufactured by applying and forming a film.
• a surface stretching process is further performed by rubbing after film formation.
• a method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays has been proposed, and in recent years, studies for industrialization have been performed.
• liquid crystal display elements In order to improve the display characteristics of such liquid crystal display elements, methods such as changing the structure of polyamic acid, polyamic acid ester and polyimide, polyamic acid with different characteristics, blend of polyamic acid ester and polyimide, adding additives, etc. As a result, improvements in liquid crystal alignment and electrical characteristics, control of the pretilt angle, and the like are performed.
• the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle in accordance with the proportion of the diamine used, so that the desired pretilt angle is obtained. This is relatively easy and is useful as a means for increasing the pretilt angle.
• Examples of the side chain structure of the diamine that increases the pretilt angle of the liquid crystal include a long-chain alkyl group or a fluoroalkyl group (see, for example, Patent Document 1), a cyclic group, or a combination of a cyclic group and an alkyl group (see, for example, Patent Document 2), A steroid skeleton (see, for example, Patent Document 3) is known.
• the diamine for increasing the pretilt angle of the liquid crystal has been studied for improving the stability and process dependency of the pretilt angle
• the side chain structure used here includes a phenyl group.
• those containing a ring structure such as a cyclohexyl group have been proposed (see, for example, Patent Documents 4 and 5).
• a diamine having such a ring structure in 3 to 4 side chains has also been proposed (see, for example, Patent Document 6).
• a solution of a polyamic acid or a solvent-soluble polyimide When applying a solution of a polyamic acid or a solvent-soluble polyimide to a substrate in the process of producing a liquid crystal alignment film, it is generally industrially performed by flexographic printing.
• N-methyl-2-pyrrolidone and ⁇ -butyrolactone which are solvents with excellent resin solubility (hereinafter also referred to as good solvents)
• the solvent of the coating solution is used to improve the uniformity of the coating film.
• Butyl cellosolve which is a solvent having low solubility (hereinafter also referred to as a poor solvent), is mixed.
• liquid crystal display elements have higher performance, larger area, and power saving of display devices.
• they can be used in various environments, and the characteristics required for liquid crystal alignment films are severe. It has become a thing.
• problems such as occurrence of printing failure due to deposition and separation due to a long tact time, and burn-in due to accumulated charge (RDC) are problems. It is difficult to solve both of these simultaneously.
• polyimide In addition to its liquid crystal alignment film, polyimide is widely used as a protective material and insulating material in the electrical and electronic fields because of its high mechanical strength, heat resistance, and solvent resistance.
• diamine component as a raw material for polyimide is also improved, but the desired diamine component cannot be freely used.
• the desire to improve such desired characteristics is not limited to the above-mentioned polyimide-based liquid crystal alignment film, but also in a polymer film formed by applying a solution such as another polymer to a substrate to form a film, It exists as well.
• JP-A-2-282726 Japanese Patent Laid-Open No. 3-179323 JP-A-4-281427 JP-A-9-278724 International Publication No. 2004/52962 Pamphlet JP 2004-67589 A JP-A-2-37324
• An object of the present invention is to solve the above-mentioned problems of the prior art, and a functional polymer film-forming coating solution capable of obtaining a functional polymer film having various properties improved relatively freely, and an object of the present invention is to provide a functional polymer film forming method using the same.
• the coating solution for forming a polyimide film of the present invention that solves the above-mentioned problems includes the following formulas [A] to [A] having a functional structure portion that imparts functionality and at least one Meldrum's acid structure portion connected thereto. And at least one modifying compound selected from the group represented by D], and a polymer for modification or a monomer for synthesizing the polymer for modification.
• W 1 is .V 1 representing the k 1 monovalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -OR, an -SR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k 1 a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.
• W 2 is .V 2 representing the k 2 divalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -SR, an -OR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k 2 a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.
• W 3 and W 4 represents a k 3 monovalent organic group is a functional structural part that imparts respective functional, W 3 and W 4 are .k 3 may be the same or different are Represents an integer of 1 to 8.
• W 5 is .k 4 representing the 2k 4-valent organic group that is functional structural moiety which imparts functionality is an integer of 1-8.
• the functional polymer film-forming coating solution is applied to a substrate, baked, and the functional structure site is bonded to the modified polymer via the Meldrum's acid structure site. A functional polymer film is obtained.
• the functional polymer film-forming coating solution of the present invention is represented by the following formulas [A] to [D] each having a functional structural portion imparting functionality and at least one meltrum acid structural portion linked thereto. It contains at least one modifying compound selected from the group represented.
• W 1 is .V 1 representing the k 1 monovalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -SR, an -OR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k 1 a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.
• W 2 is .V 2 representing the k 2 divalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -SR, an -OR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k 2 a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.
• W 3 and W 4 represents a k 3 monovalent organic group is a functional structural part that imparts respective functional, W 3 and W 4 are .k 3 may be the same or different are Represents an integer of 1 to 8.
• W 5 is .k 4 representing the 2k 4-valent organic group that is functional structural moiety which imparts functionality is an integer of 1-8.
• modifying compound represented by the formula [A] include modifying compounds represented by the following formulas [i] to [iii].
• the modifying compound represented by the above formula [A] is synthesized using an amine compound having a terminal amino group that is primary or secondary, or a hydrazine compound as a raw material, it is represented by the following formula [i].
• a modifying compound represented by the above formula [A] is synthesized using a thiol compound or carbon disulfide as a raw material, it becomes a modifying compound represented by the following formula [ii].
• Y 1 is the formula [A] terminal amino group which is a raw material of the modifying compound represented by the amine compound is a primary or secondary, hydrazine compounds, or, from carbodiimide compound k 1 monovalent an organic group, for example, a single bond or, .k 1 and a k 1 monovalent organic group heteroatom or ring structure which may have a linear or branched carbon atoms 1-60
• V 1 is the same as k 1 and V 1 in the above formula [A]
• p is 1 when an amine compound or a carbodiimide compound is used as a raw material, and 2 when a hydrazine compound is used as a raw material.
• R j is, -H represented by R 1 ⁇ R 8 or a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, a good number of carbon atoms an amide bond anywhere 1 to 35 monovalent organic group, R 1 ⁇ R 8 may be the same or different. Also, R j is coupled with a portion of the Y 1 may form a ring.
• Y 2 is k 1 monovalent organic group of the thiol compound, or carbon disulfide from a raw material of the modifying compound represented by the formula [A], for example, a single bond or a hetero atom and .k 1 and V 1 ring-like straight-chain or may have a or branched carbon atoms are k 1 monovalent organic group of 1 to 60 above formula [a] in the k 1 and V Same as 1. )
• Y 3 is an aldehyde as a raw material of the modifying compound represented by the formula [A], ketone compound or carboxylic acid derivative or a k 1 monovalent organic group derived from the orthoformate, e.g. a single bond or, .k 1 and V 1 is k 1 monovalent organic group heteroatom or ring structure which may have a linear or branched carbon atoms having 1 to 60 the formula [ The same as k 1 and V 1 in A].
• Y 1 to Y 4 when k 1 is 2 include the following formulas (Y-1) to (Y-120) And a divalent organic group represented.
• Y-1 to (Y-120) a divalent organic group represented.
• the functional polymer film obtained is a liquid crystal alignment film for increasing the pretilt angle of the liquid crystal
• a long chain alkyl group for example, an alkyl group having 10 or more carbon atoms
• an aromatic ring for example, an aromatic ring
• an aliphatic ring A structure using a diamine compound having a group ring, a steroid skeleton, or a combination of these as a raw material is preferable.
• Examples of such Y include (Y-83), (Y-84), (Y-85 ), (Y-86), (Y-87), (Y-88), (Y-89), (Y-90), (Y-91), (Y-92), (Y-93), (Y-94), (Y-95), (Y-96), (Y-97), (Y-98), (Y-99), (Y-100), (Y-101), (Y -102), (Y-103), (Y-104), (Y-105), (Y-106), (Y-107), or (Y-108). It is not something.
• Y 1 to Y 3 when k 1 is 1 include monovalent organic groups represented by the following formulas, [ Examples include, but are not limited to, a structure in which one bond of Y-1] to [Y-120] is bonded to a hydrogen atom.
• Y 1 to Y 4 in the case where k 1 is 3 or more include trivalent or more organic compounds represented by the following formula: And a structure in which a hydrogen atom of [Y-1] to [Y-120] is eliminated, but is not limited thereto.
• Me is a methyl group.
• the method for producing the modifying compound represented by the formula [A] is not particularly limited.
• the modifying compound represented by the formulas [i] and [ii] may be used in trimethyl orthoformate or orthoformate.
• Organic solvents used in general organic synthesis in triethyl for example, ethyl acetate, hexane, toluene, tetrahydrofuran, acetonitrile, methanol, chloroform, 1,4-dioxane, N, N-dimethylformamide, N-methyl- 2-pyrrolidone
• trimethyl orthoformate or triethyl orthoformate with an amine compound represented by the following formula [E1] or a thiol compound represented by the following formula [E2] and Meldrum's acid.
• the reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 60 to 120 ° C. for about 30 minutes to 2 hours.
• the modifying compound represented by the above formula [iii] is pyridine or other organic base compound (for example, triethylamine, tributylamine, diisopropylethylamine), or these organic base compounds and phosphines such as triphenylphosphine. It can be produced by reacting an aldehyde compound represented by the following formula [E3] with Meldrum's acid in an organic solvent used in the above general organic synthesis in the presence of a system compound.
• the reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 0 ° C. to 100 ° C. for about 1 to 24 hours.
• modifying compound represented by the formula [A] include amine compounds such as [E1], thiol compounds such as [E2], and amino groups of aldehyde compounds such as [E3].
• the thiol group and aldehyde group are chemically modified according to various generally known organic synthesis methods to form a compound having an amino group, a thiol group, or an aldehyde group via a spacer. The method of making it react with an acid is mentioned. Of course, this chemical modification may be performed a plurality of times.
• the amino group of the amine compound [E1] is chemically modified according to various generally known organic synthesis methods, and is represented by the following formulas [E4] to [E6].
• the compound can also be produced by reacting it with Meldrum acid by the same synthesis method as the modifying compounds represented by the above formulas [i] to [iii].
• a compound represented by the following formulas [E4] to [E6] is reacted with Meldrum acid as a raw material, a modifying compound represented by the formula [A] of the following formulas [i ′] to [iii ′] Become.
• Q 1 is a single bond or have a hetero atom or ring structure
• R i may be linked to a part of Q 1 to form a ring.
• modifying compound represented by the formula [B] include the modifying compounds represented by the following formulas [iv] and [v].
• Y 4 represents an aldehyde, a ketone compound, a halogenated alkyl compound, or a compound having an electron-deficient unsaturated bond (for example, a compound having an acryloyl group) that is a raw material of the modifying compound represented by the formula [B].
• k 2 divalent organic group derived from, for example, a single bond or a hetero atom and the ring structure or may have a linear or branched carbon atoms of k 2 divalent 1-60 organic (K 2 and V 2 are the same as k 2 and V 2 in the above formula [B].)
• Y 5 is a k 2 divalent organic group derived from a carboxylic acid derivative as a raw material of the modifying compound represented by the formula [B], for example, a single bond or a hetero atom or ring structure have been or may be linear or branched carbon atoms is k 2 monovalent organic group 1 ⁇ 60 .k 2 and V 2 ⁇ are the same as k 2 and V 2 in the formula [B] .
• the method for producing the modifying compound represented by the above formula [B] is not particularly limited.
• the modifying compound represented by the above formula [iv] may be used in an organic solvent used in the general organic synthesis.
• Pyridine, or other organic base compounds eg, triethylamine, tributylamine, diisopropylethylamine
• inorganic bases such as potassium carbonate, sodium bicarbonate, sodium hydroxide, aldehydes, ketone compounds, alkyl halide compounds (halogens)
• reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 0 ° C. to 120 ° C. for about 30 minutes to 2 hours.
• the modifying compound represented by the above formula [B] is prepared by using an aldehyde, a ketone compound, an alkyl halide compound, or a compound having an electron-deficient unsaturated bond (for example, a compound having an acryloyl group) as a raw material.
• the modification represented by the above formula [iv] is carried out directly or once through the compound represented by the above formula [iii] and then reducing the carbon-carbon double bond. Compound.
• the modifying compound represented by the above formula [v] is pyridine, other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine) or the like in the organic solvent used in the general organic synthesis. It can be produced by reacting mellic acid with a carboxylic acid or a carboxylic acid derivative such as carboxylic acid chloride together with an inorganic base such as potassium carbonate, sodium hydrogen carbonate or sodium hydroxide.
• the reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at ⁇ 20 to 120 ° C. for about 30 minutes to 2 hours.
• an aldehyde, a ketone compound, a halogenated alkyl compound, an electron deficiency A compound having a saturated bond, a carboxylic acid, and a carboxylic acid derivative are chemically modified according to various generally known organic synthesis methods, and an aldehyde group, a ketone group, a halogenated alkyl group, an electron through a spacer Examples thereof include a method in which a compound having a deficient unsaturated bond (for example, acryloyl group) and a carboxyl group is used, and this is used as a raw material to react with Meldrum's acid.
• a compound having a deficient unsaturated bond for example, acryloyl group
• this chemical modification may be performed a plurality of times.
• Y 4 of the modification compound represented by the above formula [iv] and the Meldrum's acid structure A structure derived from a compound to be chemically modified (for example, a divalent organic group having 1 to 15 carbon atoms having a chain or branched structure which may have a heteroatom or a ring structure) between the moiety A structure derived from the compound to be chemically modified between Y 5 and the carbonyl group of the modifying compound represented by the formula [B] of the inserted structure or the modifying compound represented by the formula [v] (for example, And a structure represented by the formula [B] having a structure in which a divalent organic group having 1 to 15 carbon atoms and having a chain or branched structure which may have a hetero atom or a ring structure is inserted Become a compound.
• modifying compound represented by the above formula [C] include a modifying compound represented by the following formula [vi].
• Y 6 and Y 7 are each a halogenated alkyl compound as a raw material for modifying compound represented by the formula [C], or represents a k 3 monovalent organic group derived from an alcohol derivative, e.g., single bond or a hetero atom and the ring structure or may have a linear or branched carbon atoms is k 3 monovalent organic group 1 ⁇ 60 .
• Y 6 and Y 7 are either the same or different K 3 is the same as k 3 in the above formula [C].
• the method for producing the modifying compound represented by the formula [C] is not particularly limited.
• the modifying compound represented by the formula [vi] may be used in an organic solvent used in the general organic synthesis. , Pyridine, or other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine) or an inorganic base such as potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, for the modification represented by the above formula [iv] It can be produced by reacting a compound and a halogenated alkyl compound or a compound having a terminal hydroxyl group in the presence of a palladium catalyst.
• pyridine in an organic solvent used in the above general organic synthesis, pyridine, other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine), potassium carbonate, sodium bicarbonate, sodium hydroxide, etc. It can be produced by reacting an alkyl halide compound with an inorganic base, or a compound having a hydroxyl group at the terminal in the presence of a palladium catalyst.
• Y 6 and Y 7 may be the same or different.
• two or more kinds of halogenated alkyl compounds and a compound having a hydroxyl group at the terminal can be coexisted or added stepwise.
• the reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 60 to 120 ° C. for about 30 minutes to 2 hours.
• an alkyl halide compound or an alcohol derivative is generally known.
• a method of chemically modifying a compound having a halogenated alkyl group, an alkoxy group, or a hydroxy group via a spacer and reacting it with Meldrum's acid as a raw material can be mentioned.
• this chemical modification may be performed a plurality of times.
• the modifying compound represented by the above formula [C] is produced by performing chemical modification, for example, Y 6 of the modifying compound represented by the above formula [vi] and the Meldrum's acid structure and between the sites, between the Y 7 and Meldrum's acid structural moiety, compounds derived from the structure of chemically modified (e.g., number of carbon atoms consisting of a good chain or branched structure which may have a hetero atom or ring structure Is a modifying compound represented by the formula [C] having a structure in which 1 to 15 divalent organic groups are inserted.
• chemically modified e.g., number of carbon atoms consisting of a good chain or branched structure which may have a hetero atom or ring structure
• modifying compound represented by the above formula [D] include a modifying compound represented by the following formula [vii].
• Y 8 is a 2k 4 having 1 to 15 carbon atoms derived from a cyclic ketone compound, a cyclic alkoxyimine compound, or a cyclic carbodiimide compound that is a raw material of the modifying compound represented by the above formula [D].
• .k 4 representing an organic group are the same as k 4 in the formula [D].
• Y 8 include a cyclic structure derived from a cyclic ketone such as a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, and ⁇ -pyrone.
• the method for producing the modifying compound represented by the above formula [D] is not particularly limited.
• the modifying compound represented by the above formula [vii] may be used in an organic solvent used in the above general organic synthesis. , Pyridine, or other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine), or an inorganic base such as potassium carbonate, sodium bicarbonate, sodium hydroxide, and cyclic ketone compounds (for example, cyclohexanone derivatives and ⁇ - A pyrone derivative), a cyclic alkoxyimine compound (for example, a 6-position alkoxy-substituted tetrahydropyridine), or a cyclic carbodiimide compound (for example, a 3-diazacyclonona-1,2-diene derivative) and a reaction with Meldrum's acid.
• the reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at
• modifying compounds represented by the above formulas [A] to [D] may be used alone or in combination of two or more.
• the functional polymer film-forming coating solution of the present invention contains a polymer for modification or a monomer for synthesizing these polymers for modification.
• the polymer to be modified is not particularly limited as long as it has a site that reacts with the Meldrum's acid structure.
• at least one tetracarboxylic acid component selected from tetracarboxylic acid and its derivatives and a diamine component are polymerized.
• Polyimide precursor obtained by imidating polyimide obtained by imidizing this polyimide precursor, acrylic polymer, methacrylic polymer, acrylamide polymer, methacrylamide polymer, polystyrene, polyvinyl, polysiloxane and polyamide, polyester, polyurethane, polycarbonate, Examples thereof include polyurea, polyphenol (novolak resin), maleimide polymer, and a polymer in which a compound having an isocyanuric acid skeleton or a triazine skeleton is introduced.
• the polymer may be in the form of, for example, a branched polymer such as a dendrimer, a hyperbranched polymer or a star-like polymer, or a noncovalent polymer such as polycatenan or polyrotaxane.
• a branched polymer such as a dendrimer, a hyperbranched polymer or a star-like polymer, or a noncovalent polymer such as polycatenan or polyrotaxane.
• the polymer to be modified when the polymer to be modified is a polyimide precursor or polyimide, at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof and a diamine component
• the polymer to be modified is an acrylic polymer, acrylic acid and its derivatives, acrylic esters and derivatives thereof
• the polymer to be modified when the polymer to be modified is a methacrylic polymer, methacrylic acid and derivatives thereof, methacrylic esters and derivatives thereof
• the polymer is polyvinyl, a derivative having a vinyl group is selected.
• the polymer to be modified is polysiloxane
• a silane compound having a methoxy group or an ethoxy group is selected.
• the polymer to be modified is polyamide
• the derivative is selected from dicarboxylic acids and derivatives thereof.
• At least one dicarboxylic acid component and a diamine component when the polymer to be modified is a polyester, at least one dicarboxylic acid component and a diol component selected from dicarboxylic acids and derivatives thereof, and when the polymer to be modified is a polyurethane, an isocyanate and
• the polymer to be modified is a polycarbonate, a bisphenol derivative and phosgene, or a phosgene equivalent (for example, trichlorophosgene), diphenyl carbonate, or the polymer to be modified is a polyurea Bisisocyanate derivative and diamine component, if the polymer to be modified is a maleimide polymer, maleimide derivative alone or copolymerized with styrene, if the polymer to be modified is a polymer into which a compound having an isocyanuric acid skeleton or a triazine skeleton is introduced And compounds having an
• the modified polymer contained in the functional polymer film-forming coating solution of the present invention can be produced by a conventional method.
• a polyimide precursor or a polyimide is obtained by polymerizing at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof and a diamine component as described above.
• the diamine component for example, a diamine compound k 1 is represented by the formula [E1] is 2.
• the diamine component currently used when making a polyimide precursor react by making a diamine component and a tetracarboxylic-acid component react can be used.
• the diamine component that is the raw material of the polyimide precursor may be partially or entirely the same as the raw material of the modifying compound represented by the above formula [A], or the diamine component and the above formula [A It is good also as a compound different from the raw material of the compound for a modification represented by these.
• tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof
• a tetracarboxylic acid component that has been used in the past to obtain a polyimide precursor by reacting a diamine component and a tetracarboxylic acid component is used.
• the tetracarboxylic acid derivative include tetracarboxylic acid dihalide, tetracarboxylic dianhydride represented by the following formula [F], tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester.
• a polyamic acid can be obtained by reacting tetracarboxylic acid or a derivative thereof such as tetracarboxylic acid dihalide or tetracarboxylic dianhydride with a diamine component. It is also possible to obtain a polyamic acid ester by reacting a tetracarboxylic acid diester dichloride with a diamine component, or reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or base. it can.
• X in the above formula [F] include tetravalent organic groups represented by the following formulas (X-1) to (X-46). From the viewpoint of availability of compounds, X represents (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X- 8), (X-16), (X-17), (X-19), (X-21), (X-25), (X-26), (X-27), (X-28) , (X-32) and (X-46) are preferable.
• a tetracarboxylic dianhydride having an aliphatic and aliphatic ring structure is (X-1) , (X-2), and (X-25) are more preferred, and (X-1) is more preferred from the viewpoint of reactivity with the diamine component.
• 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 Acid dialkyl ester, 3,4-dicarboxy-1,2, , 4-Tetrahydro-1-naphthalene succinic acid dialkyl este
• each of the diamine component and the tetracarboxylic acid component may be one kind, or two or more kinds may be used in combination.
• a method for synthesizing a polyimide precursor by polymerizing a tetracarboxylic acid component and a diamine component is not particularly limited, and a known synthesis method can be used.
• the reaction of the diamine component and tetracarboxylic dianhydride includes a method of reacting the diamine component and tetracarboxylic dianhydride in an organic solvent.
• the organic solvent used in that case will not be specifically limited if the produced
• the polymerization temperature 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. It becomes. Therefore, it 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 the diamine component to the total number of moles of tetracarboxylic dianhydride is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
• the polyamic acid ester can be obtained by reacting the tetracarboxylic acid diester dichloride with the diamine component as described above, or reacting the tetracarboxylic acid diester with the diamine component in the presence of an appropriate condensing agent or base. it can. Alternatively, it can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxyl group of the polyamic acid using a polymer reaction.
• tetracarboxylic acid diester dichloride and a diamine component in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1
• a polyamic acid ester By reacting for 4 to 4 hours, a polyamic acid ester can be synthesized.
• pyridine triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
• the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
• the reaction proceeds efficiently by adding Lewis acid as an additive.
• Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
• the addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount of the diamine or tetracarboxylic acid diester to be reacted.
• the solvent used in the above reaction can be the same solvent as that used in the synthesis of the polyamic acid shown above.
• N-methyl-2-pyrrolidone, ⁇ -Butyrolactone is preferred, and these may be used alone or in combination of two or more.
• the concentration at the time of synthesis is such that in the reaction solution of a tetracarboxylic acid derivative such as tetracarboxylic acid diester dichloride or tetracarboxylic acid diester and a diamine component, from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
• the total concentration is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.
• the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
• the polyimide contained in the functional polymer film-forming coating solution of the present invention can be obtained by dehydrating and ring-closing the polyimide precursor.
• the dehydration cyclization rate (imidization 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 the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
• the temperature when the polyimide precursor is thermally imidized in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
• the catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a basicity appropriate for advancing 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 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.
• a polyimide precursor that can be used as a polymer to be modified and polymers other than polyimide include acrylic polymer, methacrylic polymer, acrylamide polymer, methacrylamide polymer, polystyrene, polyvinyl, polysiloxane, polyamide, polyester, polyurethane, polycarbonate , Polyurea, polyphenol (novolak resin), maleimide polymer, polymers incorporating isocyanuric acid skeleton and triazine skeleton, branched polymers such as dendrimer, hyperbranched polymer, star-like polymer, and non-covalent polymers such as polycatenan and polyrotaxane
• functional groups capable of reacting with ketene intermediates formed by the thermal decomposition of Meldrum's acid compound for example, , Carboxyl group, hydroxy group, thiol, amino group, imino group, unsaturated bond such as carbon-carbon double bond (alkene) and carbon-carbon
• the polymer to be modified contained in the functional polymer film forming coating liquid of the present invention is in consideration of the strength of the obtained functional polymer film, the workability when forming the functional polymer film, and the uniformity of the functional polymer film.
• the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
• a polymer film for forming a conventional polymer film or the like, for example, by containing at least one modifying compound selected from the above and a polymer to be modified or a monomer for synthesizing the polymer to be modified A functional polymer film in which various properties are relatively freely improved by further containing at least one modifying compound selected from the group represented by the formulas [A] to [D] in the forming coating solution
• the coating liquid for forming a functional polymer film can be obtained.
• the modifying compounds represented by the above formulas [A] to [D] have at least one Meldrum's acid structure, that is, Meldrum's-derived structure at the end.
• Meldrum's acid structure that is, Meldrum's-derived structure at the end.
• carbon dioxide and acetone are eliminated to form ketene (that is, a carbonyl compound having a divalent group> C ⁇ C ⁇ O).
• polyimide Precursor, polyimide, acrylic polymer, methacrylic polymer, acrylamide polymer, methacrylamide polymer, polystyrene, polyvinyl, polysiloxane, polyamide, polyester, polyurethane, polycarbonate, polyurea, polyphenol (novolak resin), maleimide polymer, or isocyanuric acid skeleton And triazine skeleton introduced Functional groups present in non-covalent polymers such as polycatenans and polyrotaxanes (eg carboxyl groups, hydroxy groups, thiols, amino groups) Reaction with an imino group, an unsaturated bond such as a carbon-carbon double bond (alkene) or a carbon-carbon triple bond (alkyne), a nitrile group, a ketone group, an aldehyde group, an ester group, an amide group, an imide group), or It reacts by dimerization with ketene itself.
• non-covalent polymers such
• the modifying compounds represented by the above formulas [A] to [D] are not heated to a high temperature (for example, 100 ° C. or less), and in the state of the functional polymer film forming coating solution, the modifying polymer or modified compound is used. Although it does not react with the monomer for synthesizing the polymer for use, it is introduced into the polymer for modification via the Meldrum's acid structure by heating.
• the modifying compound represented by the above formulas [A] to [D] in which k 1 to k 4 are 2 or more it has two or more Meldrum structures. It is presumed that the polymer has a structure crosslinked with the modifying compounds represented by the above formulas [A] to [D].
• the functional polymer film obtained by applying the functional polymer film-forming coating solution of the present invention to a substrate and baking is used for the W 1 -W possessed by the modifying compounds represented by the above formulas [A]-[D]. structure of W 5 is what is introduced into the modified polymer.
• a polyimide film which is an example of a functional polymer film
• various diamine components are used as a part of raw materials.
• a desired diamine component cannot be used freely.
• various diamine components are used as a part of raw materials in order to improve desired characteristics such as improvement of liquid crystal orientation and pretilt angle.
• the polymerization reactivity between the diamine component and the tetracarboxylic acid component is deteriorated, so the type, combination and amount of the diamine component for obtaining desired properties are limited. May end up.
• a coating solution for forming a polyimide film that can form a uniform polyimide film (a coating solution for forming a functional polymer film)
• the compound to be modified is represented by [D] and is a compound for obtaining desired characteristics at the stage of heating (baking) the functional polymer film-forming coating solution.
• a compound for modification represented by the above formulas [A] to [D] is introduced into a polymer for modification. Therefore, the polymer to be modified contained in the coating liquid for forming the functional polymer film does not need to use a monomer as a raw material for obtaining the desired characteristics, and therefore the problem that the polymerization reactivity of the monomers is deteriorated, the desired characteristics.
• the coating liquid for forming a functional polymer film of the present invention is intended to obtain desired characteristics (functions) without considering the polymerization reactivity of the monomers, the necessity of examining the polymerization reaction conditions, and the solubility of the polymer. Therefore, various properties of the obtained functional polymer film can be improved relatively freely as compared with the conventional coating liquid for forming a polymer film.
• the coating liquid for forming a functional polymer film of the present invention contains a modifying compound represented by the above formulas [A] to [D] having two or more Meldrum structures, Since the polymer is crosslinked with the modifying compounds represented by the above formulas [A] to [D] by heating, the resulting functional polymer film is resistant to an organic solvent and becomes a hard film.
• a polyimide precursor obtained by polymerization reaction of at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof and a diamine component, and a polyimide obtained by imidizing this polyimide precursor.
• a coating solution for forming a functional polymer film containing at least one polymer and a modifying compound represented by the above formula [i] and having two Meldrum's acid structures is used, it is represented by the above formula [i].
• the modifying compound is obtained by introducing a Meldrum's acid structure into each of the two amino groups of the diamine compound.
• diamine compound a diamine component for obtaining the desired properties that have been conventionally studied, that is, tetracarboxylic acid is used.
• Diamine for producing polyimide precursor and polyimide by polymerization reaction with acid component A minute can be applied diamine component for obtaining the desired characteristics. Therefore, various characteristics of the obtained polyimide film can be easily improved.
• the modifying compound represented by the above formulas [A] to [D] is heated as a side chain on the polymer to be modified.
• the polymer to be modified is represented by the above formulas [A] to [D].
• a crosslinked structure is obtained by the modifying compound represented.
• the Meldrum's acid structure of the modifying compound represented by the above formulas [A] to [D] is the polymerization of the monomer.
• the monomer for synthesizing the polymer for modification is first polymerized at a low temperature to synthesize the polymer for modification, and then heated to the above formulas [A] to [[ D] is introduced as a side chain of the polymer to be modified, and in particular, the modifying compounds represented by the above formulas [A] to [D] have two or more Meldrum structures.
• the polymer to be modified has a structure crosslinked with the modifying compounds represented by the above formulas [A] to [D].
• a functional polymer film-forming coating containing a monomer for synthesizing a polymer to be modified and a modifying compound represented by the above formulas [A] to [D] having two or more Meldrum structures In the case of a liquid, by setting the temperature at which both the polymerization reaction of the monomer and the reaction of the Meldrum acid structure occur, the reaction of the Meldrum acid structure is caused simultaneously with the polymerization of the monomer, and the main chain of the polymer to be modified is represented by the above formula [ A modifying compound represented by A] to [D] can also be introduced.
• the method for producing the coating liquid for forming a functional polymer film of the present invention is not particularly limited, and the above formula comprising a functional structural portion imparting functionality and at least one Meldrum's acid structural portion connected thereto [ It is sufficient that at least one modifying compound selected from the group represented by A] to [D] and a polymer to be modified or a monomer for synthesizing the polymer to be modified are dissolved in a solvent.
• the solvent of the coating liquid for forming a functional polymer film of the present invention is a monomer for synthesizing the polymer to be modified or the polymer to be modified, a functional structure site that imparts functionality, and at least one linked thereto.
• Any compound capable of dissolving the modifying compounds represented by the above formulas [A] to [D] having two Meldrum's acid structural sites for example, N, N-dimethylformamide, N, N -Dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone And organic solvent
• the coating solution for forming a functional polymer film of the present invention preferably has an organic solvent content of 70 to 97% by mass from the viewpoint of forming a uniform functional polymer film by coating. This content can be appropriately changed depending on the film thickness of the intended functional polymer film.
• the content of the monomer for synthesizing the polymer to be modified or the polymer to be modified in the coating solution for forming a functional polymer film of the present invention is preferably 3 to 30% by mass. This content can also be appropriately changed depending on the film thickness of the intended functional polymer film.
• the content of the modifying compound represented by the above formulas [A] to [D] in the functional polymer film-forming coating solution of the present invention is not particularly limited as long as it is dissolved, but the content is not limited. It is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of monomers for synthesizing the polymer or the polymer to be modified, and more preferably 1 to 100 parts by mass in order not to lower the orientation of the liquid crystal Particularly preferred is 1 to 50 parts by mass.
• the functional polymer film-forming coating liquid of the present invention has a uniform film thickness and surface of the functional polymer film when the functional polymer film-forming coating liquid of the present invention is applied unless the effects of the present invention are impaired.
• An organic solvent also referred to as a poor solvent
• a compound that improves smoothness can be used.
• a compound that improves the adhesion between the functional polymer film and the substrate can also be used.
• Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like.
• fluorine-based surfactants silicone-based surfactants, nonionic surfactants, and the like.
• EFTOP EF301 , EF303, EF352 manufactured by Tochem Products
• MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
• Florard FC430, FC431 (manufactured by Sumitomo 3M)
• Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass) and the like.
• the ratio of these surfactants to be used is preferably 0.00 with respect to 100 parts by mass of the total amount of monomers for synthesizing the polymer to be modified or the polymer to be modified contained in the functional polymer film-forming coating solution. 01 to 2 parts by mass, more preferably 0.01 to 1 part by mass.
• Specific examples of the compound that improves the adhesion between the functional polymer film and the substrate include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxy.
• the polymer for modification contained in the functional polymer film-forming coating liquid of the present invention or the total amount of monomers for synthesizing the polymer for modification is 100 parts by mass.
• the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected. If the amount exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate when the functional polymer film is used as the liquid crystal alignment film.
• the functional polymer film-forming coating liquid of the present invention has a dielectric material intended to change the electrical properties such as the dielectric constant and conductivity of the functional polymer film as long as the effects of the present invention are not impaired. Or a conductive material may be added.
• the functional polymer film-forming coating solution of the present invention includes a crosslinkable compound having an epoxy group, an isocyanate group or an oxetane group, and further a group consisting of a hydroxyl group or an alkoxyl group, unless the effects of the present invention are impaired.
• a crosslinkable compound having at least one substituent selected from the above and a crosslinkable compound having a polymerizable unsaturated bond may be mixed.
• Such a coating liquid for forming a functional polymer film of the present invention can be used as a liquid crystal aligning agent for forming a liquid crystal aligning film.
• the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction.
• a film can be formed.
• the functional polymer film-forming coating solution of the present invention is used as a liquid crystal aligning agent, it is applied onto a substrate and baked, and then subjected to an alignment treatment such as rubbing treatment or light irradiation, or for vertical alignment use. Then, a liquid crystal alignment film can be formed without alignment treatment.
• the substrate is not particularly limited as long as it can apply the functional polymer film-forming coating solution, but when the liquid crystal alignment film is formed, it is preferably highly transparent. Specific examples include a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process.
• an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate. In this case, a material that reflects light, such as aluminum, can be used.
• a high-performance element such as a TFT-type element, an element in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
• the method for applying the functional polymer film-forming coating liquid to the substrate is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
• the functional polymer film-forming coating solution contains a monomer for synthesizing the polymer to be modified
• the monomer is polymerized when the functional polymer film-forming coating solution is applied on the substrate or when it is dried. It is preferable to do so.
• a functional polymer film-forming coating solution is applied onto the substrate, and if necessary, part or all of the solvent is dried and then baked.
• This calcination is carried out by the carboxyl group, hydroxy group, thiol group, amino group, imino group of the polymer to be modified in which the Meldrum acid structure of the modifying compound represented by the above formulas [A] to [D] is ketene or the like. Reacts with reactive sites such as unsaturated bonds such as carbon-carbon double bond (alkene) and carbon-carbon triple bond (alkyne), nitrile group, ketone group, aldehyde group, ester bond, amide bond, imide bond Heating to such a temperature is possible.
• a heating means such as a hot plate, a hot air circulating furnace, an infrared furnace, etc.
• the solvent is evaporated and the Meldrum's acid structure is reacted with the polymer to be modified.
• the modifying compounds represented by A] to [D] are introduced to form the functional polymer film of the present invention.
• the thickness of the functional polymer film formed after firing is a liquid crystal alignment film, if it is too thick, it is 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 reduced. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 200 nm.
• the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
• the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film by the above-described method and then preparing a liquid crystal cell by a known method. For example, two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a coating solution for forming a functional polymer film of the present invention provided between the substrate and the liquid crystal layer.
• the liquid crystal display element which comprises the liquid crystal cell which has the said liquid crystal aligning film formed with the liquid crystal aligning agent which consists of these.
• various devices such as a twisted nematic (TN) method, a vertical alignment (VA) method, a horizontal alignment (IPS) method, and the like are available. Can be mentioned.
• the substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed.
• a substrate on which a transparent electrode for driving liquid crystal is formed As a specific example, the thing similar to the board
• liquid crystal alignment film is formed by applying a liquid crystal aligning agent comprising the functional polymer film forming coating liquid of the present invention on this substrate and baking it, and the details are as described above.
• the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and conventional liquid crystal materials such as MLC-2003, MLC-6608, MLC-6609 manufactured by Merck & Co., Inc. can be used.
• a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads 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 sealed by injecting liquid crystal under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed.
• Etc. can be exemplified.
• the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
• the liquid crystal display device manufactured as described above is for synthesizing the modifying compound represented by the above formulas [A] to [D] and the polymer to be modified or the polymer to be modified, which can introduce desired characteristics. Since it is produced using the liquid crystal aligning agent containing the monomer, various characteristics can be improved.
• valeric acid [79] (25.0 g, 245 mmol), dichloromethane 200 g) was added, N, N-dimethylaminopyridine (DMAP: 32.6 g, 267 mmol), dicyclohexylcarbidiimide (DCC: 55).
• DMAP N, N-dimethylaminopyridine
• DCC dicyclohexylcarbidiimide
• Meldrum's acid [1] (35.3 g, 245 mmol) were added, and the mixture was stirred at room temperature overnight. After completion of the reaction, the solid content was filtered using Celite, and the filtrate was concentrated with an evaporator.
• the molecular weight of the polymer was determined by using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and a column manufactured by Shodex (KD-803, KD-805). ) And was measured as follows.
• the imidization ratio of polyimide was measured as follows. About 20 mg of polyimide powder was placed in an NMR sample tube, about 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture) was added, and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz by means of NMR measurement.
• the imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and a peak integrated value of this proton and a proton peak integrated value derived from the NH group of the amic acid that appears near 10.0 ppm.
• x is the proton peak integrated value derived from the NH group of the amic acid
• y is the peak integrated value of the reference proton
• PAA-2 a 15% by weight solution of this polyamic acid
• PAA-2 polyamic acid
• the number average molecular weight of this polyamic acid (PAA-2) was 7,609, and the weight average molecular weight was 15,837.
• NMP (98 g) and BCS (90 g) are added to the polyimide powder (SPI-1) (12.0 g) obtained above and dissolved by stirring at 80 ° C. for 40 hours to obtain a soluble polyimide (SPI-1) solution. Produced.
• Example 46 to 57 To the polyamic acid (PAA-2) solution (10.0 g) prepared above, the compounds described in the following Table 3 prepared as the modifying compound in the above synthesis example were respectively added to the solid polyamic acid (PAA-2) solution.
• the coating solution for forming a polyimide film of Examples 46 to 57 was prepared by adding at 10 mol% with respect to the amount (that is, polyamic acid (PAA-2)) and stirring at room temperature until a uniform solution was obtained.
• Example 75 to 90 In the soluble polyimide (SPI-1) solution (10.0 g) prepared above, the compounds described in the following Table 6 prepared as the modifying compound in the above synthesis example were respectively solidified in the soluble polyimide (SPI-1) solution.
• the mixture was added to the minute (ie soluble polyimide (SPI-1)) so as to have the ratio shown in Table 6 below, and stirred at room temperature until a uniform solution was obtained. A coating solution was prepared.
• Examples 91 to 102 and Comparative Example 1> [Confirmation test of crosslinking effect (stripping test)]
• the polyimide film forming coating solutions of Examples 75 to 86 were spin coated (2500 rpm / 30 seconds) on a silicon wafer and baked on a hot plate at 230 ° C. for 30 minutes to form a coating film [a1].
• the film thickness of the obtained coating film [a1] was measured using Surfcorder ET4000M manufactured by Kosaka Laboratory Ltd.
• the silicon wafer on which the coating film [a1] is formed is set again on the spin coater, NMP is dropped until the entire surface of the silicon wafer is covered, and left for 60 seconds, and then NMP is spin-dried (1500 rpm / 30).
• the solvent resistance of the coating film can be improved by using the polyimide film forming coating liquid (liquid crystal alignment treatment agent) to which the modifying compound is added. Therefore, it can be said that the modifying compound was introduced into the soluble polyimide.
• the residual film ratio was particularly high. It is estimated that it was bridge
• liquid crystal alignment film and liquid crystal cell Using the polyimide film forming coating solution (liquid crystal aligning agent) prepared in each of the above examples, a liquid crystal cell was prepared as follows.
• a polyimide film-forming coating solution (liquid crystal aligning agent) is spin-coated on a glass substrate or a glass substrate with an ITO transparent electrode, dried on a hot plate at 80 ° C. for 70 seconds, and then subjected to a predetermined baking condition with a film thickness of 100 nm. A coating film was formed.
• linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm ⁇ 2 ) was changed between 0 mJ and 1000 mJ on the coating surface, and the normal line of the plate was changed. This was performed by irradiating at an angle of 40 °.
• the linearly polarized light UV was prepared by passing a 313 nm band pass filter through the ultraviolet light of a high pressure mercury lamp and then passing it through a 313 nm polarizing plate.
• the substrates are laminated so that the liquid crystal alignment film faces face each other and the rubbing directions are parallel to each other (anti-parallel liquid crystal cells, Examples 103 to 133), or are laminated so as to be perpendicular (twisted nematic liquid crystal cell, implementation) Examples 174 to 206, and Examples 322 to 343 and Examples 344 to 350), or those subjected to UV irradiation were bonded so that the directions of polarized light irradiated were parallel (anti-parallel liquid crystal cell for vertical alignment mode, Examples 207 to 209 and Examples 210 to 321) and the sealing agent were cured to produce empty cells.
• liquid crystal MLC-2003 (manufactured by Merck) is injected in the anti-parallel liquid crystal cell
• liquid crystal MLC-2003 manufactured by Merck
• a chiral agent is injected in the twisted nematic liquid crystal cell
• liquid crystal MLC-6608 manufactured by Merck & Co., Inc.
• liquid crystal cell evaluation The method of measuring the physical properties and evaluating the characteristics of each liquid crystal cell produced is as follows. In addition, the liquid crystal aligning film produced in each measurement and evaluation, the board
• the liquid crystal cell produced using the polyimide film-forming coating solution prepared in each example shown in Table 8 was sandwiched between polarizing plates, and the liquid crystal cell was rotated in a state where the backlight was irradiated from the rear part. It was visually observed whether the liquid crystal was aligned with or without flow alignment. At that time, the following criteria were used for evaluation.
• the liquid crystal cell produced for liquid crystal orientation evaluation uses a glass substrate as a substrate, and baked for 30 minutes on a hot plate heated to 230 ° C. as a baking condition of a coating liquid for forming a polyimide film.
• the liquid crystal cell produced for the pretilt angle measurement of the anti-parallel liquid crystal cell uses a glass substrate with an ITO transparent electrode as a substrate, and the hot air circulation type in which the baking condition of the coating film of the polyimide film forming coating liquid is heated to 200 ° C. The above-described liquid crystal cell was produced without firing the alignment treatment in an oven for 30 minutes.
• a compound with no modifier compound added (Comparative Example 8) was prepared, and the effects were compared. The results are shown in Table 11.
• the pretilt angle can be remarkably increased when the polyimide film-forming coating solution to which the modifying compound is added is used as compared with Comparative Example 8 in which the modifying compound is not added. It was. Therefore, by adding the modifying compound, the base polymer, that is, the polyimide precursor contained in the coating solution for forming the polyimide film or the side chain component that makes the liquid crystal stand up in the polyimide, can be introduced vertically It was confirmed that it can be oriented.
• the liquid crystal was orientated by the presence or absence of change in brightness and the presence or absence of fluid orientation, it was observed visually. Thereafter, an AC voltage of 3 V was applied to the liquid crystal cell, and it was visually observed whether the liquid crystal was aligned. At that time, the following criteria were used for evaluation.
• the liquid crystal cell produced for liquid crystal orientation evaluation was obtained by baking for 30 minutes in a hot-air circulating oven heated to 200 ° C. using a glass substrate as the substrate and the coating condition of the coating liquid for forming the polyimide film was 200 ° C. It produced after performing the above-mentioned photo-alignment process to the obtained glass substrate with a coating film.
• Evaluation criteria Good The orientation of the liquid crystal can be confirmed and there is no fluid orientation.
• Poor The liquid crystal is oriented, but many fluid orientations are observed.
• liquid crystal cell produced using the coating solution for forming a polyimide film prepared in each Example shown in Tables 12-1 to 12-4 was heated at 120 ° C. for 1 hour, and then the pretilt angle was measured.
• the pretilt angle was measured by “Axo Scan” from Axo Metrix using the Mueller matrix method.
• a coating liquid for forming a polyimide film liquid crystal alignment treatment agent
• a modifying compound having a photoreactive side chain a coating liquid for forming a polyimide film (liquid crystal alignment treatment agent) to which a modifying compound having a photoreactive side chain is added
• a good vertical alignment can be obtained even when a photo-alignment treatment is performed.
• the polyimide film-forming coating liquid (liquid crystal alignment treatment agent) of the present invention has the ability to align liquid crystals in a slightly tilted state by irradiating polarized ultraviolet rays. It was also confirmed that the pretilt angle can be finely adjusted by controlling the addition amount and the irradiation amount.
• the coating liquid for forming a polyimide film (liquid crystal alignment treatment agent) of the present invention can be used for a liquid crystal alignment film for a vertical alignment type liquid crystal display element, and also used for a photo alignment method. It can be said that it is also useful.
• VHR voltage holding ratio
• the voltage holding ratio was measured by applying a voltage of 4 V for 60 ⁇ s at a temperature of 90 ° C., measuring the voltage after 16.67 ms, and calculating how much the voltage could be held as the voltage holding ratio.
• a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica Co., Ltd. was used for measuring the voltage holding ratio.
• the liquid crystal cell produced for the measurement of voltage holding ratio uses a glass substrate with an ITO transparent electrode as a substrate, and is on a hot plate heated to 230 ° C. under the baking condition of the coating liquid for forming the polyimide film. Baked for 30 minutes, and the rubbing conditions were set at a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm.
• a compound with no modifier compound added (Comparative Example 9) was prepared, and the effects were compared. The results are shown in Table 13.
• the liquid crystal cell produced for the estimation measurement of the accumulated charge uses a glass substrate with an ITO transparent electrode as a substrate, and is on a hot plate heated to 230 ° C. for the baking condition of the coating liquid for forming the polyimide film. Baked for 30 minutes, and the rubbing conditions were set at a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm.
• a compound with no modifier compound added (Comparative Example 10) was prepared, and the effects were compared. The results are shown in Table 14.
• a liquid crystal cell having a small RDC can be obtained by using a coating solution for forming a polyimide film to which a modifying compound is added.
• the ion density of an initial state (23 degreeC) is measured, and it hold
• the ion density measurement was performed.
• the ion density measurement was measured when a triangular wave having a voltage of ⁇ 10 V and a frequency of 0.01 Hz was applied to the liquid crystal cell.
• the measurement temperature was 80 ° C.
• a 6245 type liquid crystal property evaluation apparatus manufactured by Toyo Technica Co., Ltd. was used for all measurements. The results are shown in Table 15.
• the twisted nematic liquid crystal cell is the same as that of the above twisted nematic liquid crystal cell (Examples 174 to 206) except that the firing condition of the coating film of the polyimide film forming coating solution was fired for 30 minutes on a hot plate heated to 200 ° C. The same operation was performed. In addition, the same operation was performed for those to which no modifier compound was added, and the effects were compared.
• the ionic impurities in the liquid crystal cell can be significantly reduced by appropriately selecting the type and amount of the modifying compound as compared with the case where it is not added.
• the number average molecular weight Mn and the weight average molecular weight Mw of the acrylic polymer and polysiloxane obtained according to the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran. was flowed through the column at a flow rate of 1 ml / min (column temperature 40 ° C.) for elution. Note that both the number average molecular weight Mn and the weight average molecular weight Mw are expressed in terms of polystyrene.
• Polymer-1 Poly [(o-cresyl glycidyl ether) -co-formaldehyde]
• Polymer-2 Poly [N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3, 5-triazine]
• Polymer-3 Poly (Bisphenol A-co-epichlorohydrin)
• Polymer-4 Poly (melamine-co-formaldehyde) acrylated, 80 wt% MEK Solution.
• Polymer-5 Novolak resin, PSM-4326, manufactured by Gunei Chemical Industry Co., Ltd.
• TEOS ⁇ Synthesis of Polymer-7 and preparation of its solution>
• a solution prepared by mixing oxalic acid as a mixed solvent, water and a catalyst in advance was added dropwise to the solution at room temperature over 30 minutes. The solution was stirred for 30 minutes and then heated to reflux for 1 hour and allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12 wt%.
• the obtained polysiloxane solution having a SiO 2 equivalent concentration of 12 wt% was further diluted with the above mixed solvent to obtain a 5 wt% polysiloxane (Polymer-7) solution.
• the anti-parallel liquid crystal cell uses a glass substrate with an ITO transparent electrode as a substrate, and is fired for 30 minutes in a hot-air circulating oven heated to 200 ° C. for the coating conditions of various polymer film forming coating solutions. It was manufactured by performing the same operation as that of the anti-parallel liquid crystal cell for vertical alignment mode (Examples 210 to 321) except that the treatment was not performed. In addition, the same operation was performed for those to which no modifier compound was added, and the effects were compared.
• a coating solution for forming a polyimide film (liquid crystal aligning agent) is spin-coated on a glass substrate, dried on a hot plate at 80 ° C. for 70 seconds, and then baked for 30 minutes in a hot air circulating oven heated to 200 ° C. A coating film having a thickness of 100 nm was formed.
• linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm ⁇ 2 ) was changed between the exposure amount of 0 mJ and 1000 mJ on the surface of the coating film, and irradiated at a tilt of 40 ° with respect to the normal line of the plate.
• the linearly polarized light UV was prepared by passing a 313 nm band pass filter through the ultraviolet light of a high pressure mercury lamp and then passing it through a 313 nm polarizing plate.
• the prepared liquid crystal cell is sandwiched between polarizing plates, and the liquid crystal cell is rotated in a state where the backlight is irradiated from the rear, and it is visually observed whether the liquid crystal is aligned with the presence or absence of change in light and darkness or flow alignment. As a result, good orientation was exhibited. Thereafter, an AC voltage of 3 V was applied to the liquid crystal cell, and it was visually observed whether the liquid crystal was aligned. At that time, the following criteria were used for evaluation. The results are shown in Tables 19-1 to 19-5. Evaluation criteria Good: The orientation of the liquid crystal can be confirmed and there is no fluid orientation. Poor: The liquid crystal is oriented, but many fluid orientations are observed.
• the prepared liquid crystal cell was heated at 120 ° C. for 1 hour, and then the pretilt angle was measured.
• the pretilt angle was measured by “Axo Scan” from Axo Metrix using the Mueller matrix method. The results are shown in Tables 19-1 to 19-5.
• the photo-alignment treatment was performed by using a polyimide film-forming coating liquid (liquid crystal alignment treatment agent) to which a modifying compound having a photoreactive side chain was added. It was confirmed that good vertical alignment could be obtained even in the case of carrying out. It was also confirmed that the polyimide film-forming coating liquid (liquid crystal alignment treatment agent) of the present invention has the ability to align liquid crystals in a slightly tilted state by irradiating polarized ultraviolet rays. It was also confirmed that the pretilt angle can be finely adjusted by controlling the addition amount and the irradiation amount.
• the coating liquid for forming a polyimide film (liquid crystal alignment treatment agent) of the present invention can be used for a liquid crystal alignment film for a vertical alignment type liquid crystal display element, and also used for a photo alignment method. It can be said that it is also useful.
• Examples 537 to 578 In the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compounds described in the following Tables 20-1 to 20-2 prepared in the above synthesis examples as modifying compounds were respectively added to the polyamic acid (PAA). -1) Add to the solid content of the solution (ie, polyamic acid (PAA-1)) so that the ratio is as described in Tables 20-1 to 20-2 below, and stir at room temperature until a uniform solution is obtained.
• the coating solutions for forming a polyimide film of Examples 537 to 578 were prepared.
• a coating solution for forming a polyimide film (liquid crystal aligning agent) is spin-coated on a glass substrate, dried on a hot plate at 80 ° C. for 70 seconds, and then baked for 30 minutes in a hot air circulating oven heated to 200 ° C. A coating film having a thickness of 100 nm was formed.
• linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm ⁇ 2 ) was changed from 0 mJ to 1000 mJ on the coating surface, and the substrate was irradiated from directly above.
• the linearly polarized light UV was prepared by passing a 313 nm band pass filter through the ultraviolet light of a high pressure mercury lamp and then passing it through a 313 nm polarizing plate.
• the prepared anti-parallel liquid crystal cell for horizontal alignment mode is sandwiched between polarizing plates, and the liquid crystal cell is rotated in a state where a backlight is irradiated from the rear portion, and the liquid crystal is aligned with the presence or absence of light / dark change or fluid alignment. It was observed visually. At that time, the following criteria were used for evaluation. The results are shown in Tables 21-1 to 21-2. Evaluation Criteria A: The orientation of the liquid crystal can be confirmed and there is no fluid orientation. ⁇ : The liquid crystal is oriented, but the fluid orientation is slightly observed. ⁇ : The liquid crystal is oriented, but a lot of fluid orientation is observed. ⁇ : Liquid crystal is not aligned at all
• the liquid crystal cell that has not been irradiated with light does not exhibit orientation at all, but in the liquid crystal cell that has been irradiated with light, depending on the amount of the modifying compound added and the amount of light irradiated, It was confirmed that the liquid crystal was aligned.
• the horizontal alignment cell can be easily produced by appropriately selecting the type and amount of the additive.

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