Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
• • 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
  • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
  • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/095—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • 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
• • 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
• • 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
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133723—Polyimide, polyamide-imide

Definitions

• the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display device suitable for coating by an inkjet method (hereinafter, referred to as inkjet coating).
• liquid crystal alignment film As the liquid crystal alignment film, a so-called polyimide-based liquid crystal alignment film is widely used which is obtained by applying and baking a liquid crystal alignment agent containing a polyimide precursor such as polyamic acid or a solution of a soluble polyimide as a main component.
• a method for forming such a liquid crystal alignment film inkjet coating is currently mainstream instead of spin coating, flexo printing, etc. so far.
• Ink jet coating is a method in which fine droplets are dropped on a substrate to form a film by wetting and spreading of a liquid.
• the liquid crystal aligning agent used for inkjet coating is required to have a small film thickness unevenness inside the coating surface and to have a high film forming accuracy in the periphery of the coating. At the same time, it is also important that the organic solvent in the liquid crystal alignment agent does not damage the inkjet head and the peripheral members when the ink is ejected from the inkjet device.
• the present invention aims to provide a liquid crystal aligning agent most suitable for inkjet coating, by improving various properties required for inkjet coating.
• the inventors conducted various studies to achieve the above object, and found that the liquid crystal aligning agent having the following constitution is most suitable for achieving the above object, and completed the present invention.
• a liquid crystal aligning agent containing an organic solvent and at least one polymer selected from a polyimide precursor which is a reaction product of a tetracarboxylic acid derivative and a diamine and a polyimide which is an imidized product thereof, wherein the organic solvent is component A: At least one component B selected from ⁇ -butyrolactone and ⁇ -valerolactone: containing dipropylene glycol dimethyl ether, the content of each of the components A and B is 25% by weight or less, and the content of the components A and B Liquid crystal aligning agent characterized in that the amount difference is 5% by weight or less.
• liquid crystal aligning agent By using the liquid crystal aligning agent according to the present invention, it is possible to obtain a liquid crystal aligning film having a small film thickness unevenness inside the coated surface and a high film forming accuracy in the peripheral portion of the coating when using the liquid crystal aligning agent When the ink is discharged from the ink jet apparatus, the ink jet head and peripheral members are not damaged, and as a result, it is possible to contribute to the stability of the liquid crystal display element production.
• the liquid crystal aligning agent of the present invention contains the following components A and B as an organic solvent.
• Component A At least one selected from ⁇ -butyrolactone and ⁇ -valerolactone B component: Dipropylene glycol dimethyl ether
• the organic solvent of the A component dissolves the polymer contained in the liquid crystal aligning agent of the present invention
• the ink jet head and peripheral members of the ink jet coating apparatus are not easily adversely affected.
• Preferred as the A component is ⁇ -butyrolactone.
• the solvent of component B is one that improves the wetting and spreading properties when the liquid crystal aligning agent of the present invention is applied on a substrate or a film.
• the content of each of the component A and the component B is 25% by weight or less, and the content difference between the component A and the component B is 5% by weight or less. Further, it is preferable from the viewpoint of solubility that the component C further contains at least one selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-butyl-2-pyrrolidone.
• the organic solvent of component C is a component that dissolves the polymer contained in the liquid crystal aligning agent of the present invention. Preferred specific examples include N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.
• the content is 35 weight% or less with respect to the weight of the whole liquid crystal aligning agent, and 30 weight% or less is more preferable.
• the polymer contained in the liquid crystal aligning agent of the present invention is at least one polymer selected from a polyimide precursor which is a reaction product of a tetracarboxylic acid derivative and a diamine and a polyimide which is an imidized product thereof.
• the structure of the polymer is not particularly limited, and the tetracarboxylic acid derivative and the diamine to be described later can be optionally selected according to the characteristics of the liquid crystal aligning agent to be obtained. Among them, the side of the following formula [1-1] A polymer containing a chain structure is preferred from the viewpoint of solubility and the like.
• Y 1 and Y 3 are each independently a single bond,-(CH 2 ) a- (a is an integer of 1 to 15), -O-, -CH 2 O- And at least one selected from the group consisting of -COO- and -OCO-.
• Y 2 represents a single bond or-(CH 2 ) b- (b is an integer of 1 to 15) (provided that Y 1 or Y 3 is a single bond,-(CH 2 ) a- 2 is a single bond, Y 1 is at least one selected from the group consisting of -O-, -CH 2 O-, -COO- and -OCO-, and / or Y 3 is -O-, In the case of at least one member selected from the group consisting of -CH 2 O-, -COO- and -OCO-, Y 2 is a single bond or-(CH 2 ) b- ).
• Y 4 represents at least one kind of divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton
• hydrogen is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms or a fluorine atom It may be substituted.
• Y 5 represents at least one cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, 1 carbon atom It may be substituted by an alkoxy group of to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.
• Y 6 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and a fluorine-containing alkoxy having 1 to 18 carbon atoms
• n is an integer of 0 to 4;
• a process such as ultraviolet irradiation is included in the manufacturing process of the liquid crystal display element, it is preferable to introduce a photoreactive side chain that causes a photoreaction by ultraviolet light of a specific wavelength.
• the photoreactive side chain includes a side chain structure of the following formula [VII].
• the side chain structure of the formula [VII] has a radical generating structure.
• radicals are generated by decomposition upon irradiation with ultraviolet light.
• Ar represents at least one aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, and the hydrogen atom of their ring may be substituted by a halogen atom. Since Ar to which a carbonyl is bound is involved in the absorption wavelength of ultraviolet light, when the wavelength is increased, a structure with a long conjugate length such as naphthylene or biphenylene is preferable. On the other hand, when Ar has a structure such as naphthylene or biphenylene, the solubility may be deteriorated, and in this case, the degree of difficulty of synthesis becomes high. If the wavelength of ultraviolet light is in the range of 250 nm to 380 nm, sufficient characteristics can be obtained even with a phenyl group, so Ar is most preferably a phenyl group.
• the aromatic hydrocarbon group may be provided with a substituent.
• a substituent an electron donative organic group such as an alkyl group, a hydroxyl group, an alkoxy group, an amino group and the like is preferable.
• R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group. In the case of an alkyl group or an alkoxy group, a ring may be formed by R 1 and R 2 .
• T 1 and T 2 each independently represent a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O -, - N (CH 3) -, - CON (CH 3) - or an -N (CH 3) CO- linking group.
• S represents a single bond or an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted by a fluorine atom.
• Q represents a structure selected from the following formula (1d).
• R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 3 represents —CH 2 —, —NR—, —O— or —S—.
• Q is preferably an electron-donating organic group, and is preferably an alkyl group, a hydroxyl group, an alkoxy group, an amino group or the like as mentioned in the example of Ar above.
• Q is an amino derivative, a problem such as a carboxylic acid group generated and an amino group forming a salt may occur during polymerization of a polyamic acid which is a precursor of polyimide, so a hydroxyl group or an alkoxy group is generated. Is more preferred.
• the polymer contained in the liquid crystal aligning agent of the present invention is at least one polymer selected from a polyimide precursor obtained from the reaction of a tetracarboxylic acid derivative and a diamine and a polyimide which is an imidized product thereof.
• a polyimide precursor obtained from the reaction of a tetracarboxylic acid derivative and a diamine
• a polyimide which is an imidized product thereof.
• tetracarboxylic acid dihalide compounds tetracarboxylic acid dialkyl esters and tetracarboxylic acid dialkyl esters are used as tetracarboxylic acid derivatives used for producing polyimide precursors Ester dihalides are mentioned.
• tetracarboxylic acid derivatives those represented by the following formula (3) are preferable.
• X 1 is not particularly limited. Specific examples include the following formulas (X1-1) to (X1-42). Preferred are (X1-1), (X1-2), (X1-5), (X1-7), (X1-8), (X1-10), (X1-11), and (X1-26). And (X1-27), (X1-33), (X1-38) and (X1-40).
• R 3 to R 23 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, It is an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group.
• R 3 to R 23 are preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, and a hydrogen atom or a methyl group is preferable.
• Specific examples of the formula (X1-1) include the following formulas (X1-1-1) to (X1-1-6). From the viewpoint of liquid crystal alignment and polymerization reactivity, (X1-1-1) and (X1-1-2) are particularly preferable.
• the diamine used for manufacture of a polyimide precursor is represented by following formula (4).
• a 1 and A 2 each independently represent a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms is there.
• the structure of the said Formula (4) is not specifically limited.
• the above-mentioned diamine containing the side chain structure of the formula [1-1] can be mentioned. Specific examples thereof include (Y-178), (Y-180) and (Y-181). Besides, it is possible to use diamine having any structure. Specific examples include the following (Y-1) to (Y-177).
• (Y-72), (Y-76), (Y-77), (Y-80), (Y-81), (Y-82), (Y-158), (Y-159), (Y Y-160), (Y-161) and (Y-169) to (Y-188) are preferable.
• Me represents a methyl group
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.
• the polyamic acid which is a polyimide precursor used for this invention can be manufactured by the method shown below. Specifically, a tetracarboxylic dianhydride and a diamine are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized by
• the organic solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of solubility of monomers and polymers, and one or more of these may be mixed You may use.
• the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight polymer is easily obtained.
• the polyamic acid obtained as described above can be recovered by precipitating a polymer by pouring the reaction solution into a poor solvent while well stirring it. Further, precipitation is carried out several times, and after washing with a poor solvent, it is possible to obtain a purified polyamic acid powder by normal temperature or heat drying.
• the poor solvent is not particularly limited, and water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned.
• the polyamic acid ester which is one of the polyimide precursors used for this invention can be manufactured by the method of (I), (II) or (III) shown below.
• the polyamic acid ester can be synthesized by esterification of a polyamic acid obtained from tetracarboxylic acid dianhydride and diamine. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized.
• esterifying agent those which can be easily removed by purification are preferable, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
• the amount of the esterifying agent used is preferably 2 to 6 molar equivalents with respect to 1 mole of the repeating unit of the polyamic acid.
• the solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the polymer, and these may be used alone or in combination of two or more. Good.
• the concentration of the polymer in the reaction solution is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer hardly occurs and a polymer can be easily obtained.
• Polyamic acid ester can be manufactured from tetracarboxylic acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine 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 to 4 hours It can be synthesized by reaction.
• pyridine triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds mildly.
• the amount of the base used 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 solvent used for the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of monomers and polymers, and these may be used alone or in combination of two or more.
• the concentration of the polymer in the reaction solution is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer hardly occurs and a polymer can be easily obtained.
• the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent the mixing of outside air in a nitrogen atmosphere.
• Polyamic acid ester can be manufactured by polycondensing tetracarboxylic acid diester and diamine. Specifically, a tetracarboxylic acid diester and a diamine in the presence of a condensing agent, a base and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 It can be produced by reacting for time.
• the condensing agent examples include triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triadidi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N And N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate and the like can be used.
• the addition amount of the condensing agent is preferably 2 to 3 moles per mol of the tetracarboxylic acid die
• tertiary amines such as pyridine and triethylamine can be used.
• the amount of the base used is preferably 2 to 4 moles per mole of the diamine component from the viewpoint of easy removal and high molecular weight.
• the reaction proceeds efficiently by adding a Lewis acid as an additive.
• a Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
• the addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount with respect to the diamine component.
• the solution of the polyamic acid ester obtained as described above can precipitate the polymer by pouring it into a poor solvent while stirring well. Precipitation is carried out several times, and after washing with a poor solvent, it is possible to obtain a purified polyamic acid ester powder at room temperature or by heating and drying.
• the poor solvent is not particularly limited, and water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned.
• the polyimide used in the present invention can be produced by imidizing the above-mentioned polyamic acid or polyamic acid ester.
• the polyimide imidization rate used in the present invention is not limited to 100%. From the viewpoint of electrical characteristics, 20 to 99% is preferable.
• chemical imidization which adds a basic catalyst to the polyamic acid solution obtained by dissolving the said polyamic acid ester solution or polyamic acid ester resin powder in an organic solvent is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature, and molecular weight reduction of the polymer does not easily occur in the imidization process.
• Chemical imidization can be carried out by stirring the polyamic acid or polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
• a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine and trioctylamine.
• pyridine is preferable because it has a suitable basicity to allow the reaction to proceed.
• acetic anhydride trimellitic anhydride, pyromellitic anhydride and the like can be mentioned, and it is preferable to use acetic anhydride among them because purification after completion of the reaction becomes easy.
• the temperature at which the imidization reaction is carried out is, for example, ⁇ 20 ° C. to 120 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
• the amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles of the amic acid group. It is a double.
• the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature and reaction time.
• the obtained imidized polymer is recovered by the means described below, and redissolved in an organic solvent.
• the liquid crystal aligning agent of the present invention is used.
• the solution of the polyimide obtained as mentioned above can precipitate a polymer by inject
• the poor solvent is not particularly limited, and methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and the like can be mentioned.
• the liquid crystal aligning agent of the present invention has the form of a solution in which a polymer containing a specific polymer is dissolved in an organic solvent containing a specific solvent.
• the molecular weight of the polyimide precursor and the polyimide described in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100, in weight average molecular weight. , 000. Also, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
• the concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but from the point of forming a uniform and defect-free coating film, 1 weight % Or more is preferable, and from the viewpoint of storage stability of the solution, 10% by weight or less is preferable.
• the solvent in the liquid crystal aligning agent of the present invention preferably contains the components A and B and further contains a component C, but may contain other solvents.
• a solvent which dissolves a polyimide precursor and a polyimide also referred to as a good solvent
• a solvent which improves the coating property and surface smoothness of a liquid crystal alignment film when a liquid crystal aligning agent is applied also a poor solvent
• Specific examples of other solvents are listed below, but are not limited to these examples.
• good solvents include 1,3-dimethylimidazolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethyl Propanamide or 4-hydroxy-4-methyl-2-pentanone and the like can be mentioned.
• the poor solvent include 1-butoxy-2-propanol, 2-butoxy-1-propanol, 2-propoxyethanol, 2- (2-propoxyethoxy) ethanol, 1-propoxy-2-propanol ethanol, isopropyl alcohol 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3 -Methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3 -Heptanol, 1-octano , 2-octanol, 2-ethyl-1-hexanol, cyclohe
• R 24 and R 25 are each independently a linear or branched alkyl group having 1 to 8 carbon atoms. However, R 24 + R 25 is an integer greater than 3.
• the solvents represented by the following [D-1] to the formula [D-3] are used Also good.
• D 1 represents an alkyl group having 1 to 3 carbon atoms
• D 2 represents an alkyl group having 1 to 3 carbon atoms
• Formula [D-3] among, D 3 is an alkyl group having 1 to 4 carbon atoms.
• the liquid crystal aligning agent of the present invention is at least one kind of substitution selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group.
• a crosslinkable compound having a group or a crosslinkable compound having a polymerizable unsaturated bond may be included.
• crosslinking compound various known compounds can be used depending on the purpose.
• the crosslinkable compound having an epoxy group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminodiphenylene, tetraglycidyl-m-xylene diamine, tetraglycidyl-1 , 3-Bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trile Fluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphen
• the crosslinkable compound having an oxetane group is represented by the formula [4a] to the formula [4k] published on pages 58 to 59 of International Publication WO 2011/132751 (published on 2011.10.27).
• Crosslinkable compounds may be mentioned.
• Specific examples of the crosslinkable compound having a cyclocarbonate group include those represented by the formulas [5-1] to [5] listed on pages 76 to 82 of International Publication WO 2012/014898 (2012.2.2 published).
• a crosslinkable compound represented by the formula -42 are examples of the formulas [5-1] to [5] listed on pages 76 to 82 of International Publication WO 2012/014898 (2012.2.2 published).
• crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include pages 62 to 66 of International Publication WO 2011/132751 (published on 2011.10.27).
• the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Among these, in order for the crosslinking reaction to proceed and to achieve the desired effect, 0.1 to 100 parts by mass is preferable, and 1 to 50 parts by mass is more preferable.
• the liquid crystal aligning agent of this invention can contain the compound which improves the uniformity of the film thickness of a liquid crystal aligning film at the time of apply
• a fluorine-type surfactant As a compound which improves the uniformity of the film thickness of a liquid crystal aligning film, and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, a nonion type surfactant etc. are mentioned.
• the amount of surfactant used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 parts by mass, with respect to 100 parts by mass of all polymer components contained in the liquid crystal aligning agent.
• the liquid crystal aligning film of this invention is a film
• the substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. At that time, 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 simplification of the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used if it is only on one substrate, and in this case, a material that reflects light such as aluminum can also be used for the electrode.
• the liquid crystal aligning agent is generally applied by screen printing, offset printing, flexographic printing or ink jet method, and as the other coating methods, dip method, roll coater method, slit coater, etc. Methods, spinner methods or spray methods are known.
• the solvent can be evaporated by using a heating means such as a hot plate, a thermal circulation type oven or an IR (infrared) type oven to form a liquid crystal alignment film.
• a heating means such as a hot plate, a thermal circulation type oven or an IR (infrared) type oven to form a liquid crystal alignment film.
• the drying and baking steps after the application of the liquid crystal aligning agent can be performed at any temperature and time. Usually, in order to sufficiently remove the contained solvent, baking is carried out at 50 to 120 ° C. for 1 to 10 minutes, followed by baking at 150 to 300 ° C. for 5 to 120 minutes.
• the thickness of the liquid crystal alignment film after firing is preferably 5 to 300 nm, and more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may decrease.
• the liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film without application of alignment treatment in a vertical alignment application or the like after being coated and baked on a substrate and then subjected to alignment treatment by rubbing treatment or photo alignment treatment.
• a known method or apparatus can be used in alignment treatment such as rubbing treatment or light alignment treatment.
• a liquid crystal display element having a passive matrix structure is described as an example. It may be a liquid crystal display element of an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting an image display.
• TFT Thin Film Transistor
• a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate.
• These electrodes can be, for example, ITO electrodes, and are patterned to provide a desired image display.
• an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
• the insulating film can be, for example, a film of SiO 2 -TiO 2 formed by a sol-gel method.
• a liquid crystal alignment film is formed on each substrate, the other substrate is superimposed on one of the substrates so that the liquid crystal alignment film faces each other, and the periphery is bonded with a sealing agent.
• a spacer in the sealing agent it is usually preferable to mix a spacer in the sealing agent, and to disperse the substrate gap control spacer also in the in-plane portion where the sealing agent is not provided.
• An opening capable of being filled with liquid crystal from the outside is provided in part of the sealing agent.
• a liquid crystal material is injected into the space surrounded by the two substrates and the sealing agent through the opening provided in the sealing agent, and then the opening is sealed with an adhesive.
• the liquid crystal material may be either a positive liquid crystal material or a negative liquid crystal material, preferably a negative liquid crystal material.
• the polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surface of the two substrates opposite to the liquid crystal layer.
• CBDA 1,2,3,4, -cyclobutanetetracarboxylic acid dianhydride
• BODA bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride
• DSDA 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride
• PMDA pyromellitic Acid anhydride
• DA-1 p-phenylenediamine DA-2: 4, 4-diaminodiphenylmethane DA-3: 3,5-diaminobenzoic acid DA-4: 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide DA -5: 4,4 '-[Isopropylidenebis (p-phenyleneoxy)] dianiline DA-6: diamine DA-7 of the following formula DA-6: 1- (4- (2- (2,4-diaminophenoxy) ) Ethoxy) phenyl) -2-hydroxy-2-methylpropanone DA-8: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene DA-9: 1,3 -Diamino-4- [trans-4- [trans-4- (pentylcyclohexyl) -cyclohexyl] phenoxy]
• TM-BIP-A 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane
• the imidation ratio is determined using a proton derived from a structure which does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of amic acid appearing around 9.0 to 11.0 ppm. It calculated
• x is a proton peak integrated value derived from the NH group of the amic acid
• y is a peak integrated value of the reference proton
• ⁇ is the NH group of the amic acid in the case of polyamic acid (imidation ratio is 0%) It is the number ratio of reference protons to one proton.
• NMP is added to this polyamic acid solution (a) (498.13 g) to dilute the content of the polyamic acid solution (a) to 10% by mass, and then acetic anhydride (90.87 g) as an imidization catalyst, And pyridine (28.16 g) were added and reacted at 70 ° C. for 3.5 hours.
• the reaction solution was poured into methanol (5,000 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide (A).
• the imidation ratio of this polyimide (A) was 72%.
• the number average molecular weight of this polyamic acid solution (b) was 17,000, and the weight average molecular weight was 45,000.
• acetic anhydride 93.93 g as an imidation catalyst is carried out.
• pyridine 72.77 g were added and reacted at 75 ° C. for 3.5 hours.
• the reaction solution was poured into methanol (5,000 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide (B).
• the imidation ratio of this polyimide (B) was 74%.
• NMP is added to this polyamic acid solution (c) (450.0 g) to dilute it so that the content of the polyamic acid solution (a) is 10% by mass, then acetic anhydride (103.6 g) as an imidization catalyst, And pyridine (32.11 g) were added and reacted at 70 ° C. for 3.5 hours.
• the reaction solution was poured into methanol (3,600 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide (C).
• the imidation ratio of this polyimide (C) was 69%.
• NMP is added to this polyamic acid solution (d) (450.0 g) to dilute the content of the polyamic acid solution (d) to 10% by mass, and then acetic anhydride (90.9 g) as an imidization catalyst, And pyridine (28.17 g) were added and reacted at 70 ° C. for 3.5 hours.
• the reaction solution was poured into methanol (3,600 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide (D).
• the imidation ratio of this polyimide (D) was 73%.
• the number average molecular weight of this polyamic acid solution (e) was 25,000, and the weight average molecular weight was 65,000.
• NMP is added to this polyamic acid solution (e) (450.0 g) to dilute the content of the polyamic acid solution (d) to 10% by mass, and then acetic anhydride (96.7 g) as an imidization catalyst, And pyridine (29.97 g) were added and reacted at 70 ° C. for 3.5 hours.
• the reaction solution was poured into methanol (3,600 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide (E).
• the imidation ratio of this polyimide (E) was 72%.
• Example 1 NEP (198 g) is added to the polyimide (A) (13.5 g) obtained in Synthesis Example 1 and the polyimide (B) (13.5 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 20 hours I did. NEP (17.91 g), GBL (151.2 g), PB (180 g), DME (144 g), and TM-BIP-A (1.89 g) were added to this solution and stirred at 25 ° C. for 2 hours. This solution was filtered through a filter with a pore size of 1 ⁇ m to prepare a liquid crystal aligning agent [A] of the present invention.
• Example 2 NMP (150.73 g) is added to the polyimide (A) (13.3 g) obtained in Synthesis Example 1 and the polyimide (B) (13.3 g) obtained in Synthesis Example 2 and stirred at 70 ° C. for 20 hours Dissolved. NMP (65.30 g), GBL (115.02 g), BCS (251.6 g), DME (107.8 g), TM-BIP-A (1.86 g) are added to this solution, and 2 hours at 25 ° C. It stirred. This solution was filtered through a filter with a pore size of 1 ⁇ m to prepare a liquid crystal aligning agent [B] of the present invention.
• Example 3 NMP (150.73 g) is added to the polyimide (C) obtained in Synthesis Example 3 (13.3 g) and the polyimide (E) obtained in Synthesis Example 5 (13.3 g) and stirred at 70 ° C. for 20 hours Dissolved. NMP (65.30 g), GBL (115.02 g), BCS (251.6 g), DME (107.8 g), TM-BIP-A (1.86 g) are added to this solution, and 2 hours at 25 ° C. It stirred. This solution was filtered through a filter with a pore size of 1 ⁇ m to prepare a liquid crystal aligning agent [C] of the present invention.
• Example 4 NEP (198 g) is added to the polyimide (D) obtained in Synthesis Example 4 (13.5 g) and the polyimide (E) obtained in Synthesis Example 5 (13.5 g) and dissolved by stirring at 70 ° C. for 20 hours I did. NEP (17.91 g), GBL (151.2 g), PB (180 g), DME (144 g), and TM-BIP-A (1.86 g) were added to this solution and stirred at 25 ° C. for 2 hours. This solution was filtered through a filter with a pore size of 1 ⁇ m to prepare a liquid crystal aligning agent [D] of the present invention.
• Example 5 NEP (150.73 g) is added to the polyimide (A) (13.3 g) obtained in Synthesis Example 1 and the polyimide (E) (13.3 g) obtained in Synthesis Example 5 and stirred at 70 ° C. for 20 hours Dissolved. NEP (65.30 g), GBL (115.02 g), BCS (251.6 g), DME (107.8 g), TM-BIP-A (1.86 g) are added to this solution, and 2 hours at 25 ° C. It stirred. This solution was filtered through a filter with a pore size of 1 ⁇ m to prepare a liquid crystal aligning agent [E] of the present invention.
• the prepared liquid crystal aligning agent was applied to a substrate by an ink jet method, predrying and main baking were performed to form a coating film.
• the evaluation of the ink jet coating was performed using an ink jet apparatus (type IJ-1021) manufactured by Shibaura Mechatronics, Ltd. under the following conditions. Ink jet application conditions: Head: H18, H1A Nozzle No.
• those with an average value of 7 mm or more in color tone change (film thickness unevenness) at the coating film edge at lower, left, and right are marked x, those with 6 mm to 5 mm are marked ⁇ and those less than 5 mm are marked ⁇ .
• the following table shows the evaluation results of the liquid crystal aligning agent obtained in Examples 1 to 5 and Comparative Examples 1 to 3.
• the liquid crystal aligning agent of the present invention can solve display unevenness in the vicinity of the frame by improving the adhesion between the sealing agent and the liquid crystal alignment film in a narrow frame liquid crystal display element capable of securing a large number of display surfaces. It is useful.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Nonlinear Science (AREA)
• Crystallography & Structural Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Mathematical Physics (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Dispersion Chemistry (AREA)
• Liquid Crystal (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=66247430

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (2)

Family Cites Families (17)

• 2018
  • 2018-10-24 CN CN201880069277.6A patent/CN111263913B/zh active Active
  • 2018-10-24 JP JP2019551186A patent/JP7256472B2/ja active Active
  • 2018-10-24 WO PCT/JP2018/039439 patent/WO2019082913A1/ja active Application Filing
  • 2018-10-24 KR KR1020207014312A patent/KR102586311B1/ko active IP Right Grant
  • 2018-10-25 TW TW107137742A patent/TWI772546B/zh active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events