Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
• • 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
• • 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 suitable for application by an inkjet method and a liquid crystal aligning film obtained from the liquid crystal aligning agent.
• liquid crystal alignment film a so-called polyimide-based liquid crystal alignment film, which is obtained by applying and baking a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (also called polyamic acid) or a soluble polyimide solution, is widely used.
• a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (also called polyamic acid) or a soluble polyimide solution
• spin coating, dip coating, flexographic printing, and the like are generally known as methods for forming such a liquid crystal alignment film.
• flexographic printing requires various resin plates due to the different types of liquid crystal panels, the plate replacement in the manufacturing process is complicated, and film formation on a dummy substrate is required to stabilize the film formation process. There are problems such as the necessity of manufacturing the plate and the production cost of the liquid crystal display panel.
• an inkjet method has attracted attention as a new method for applying a liquid crystal alignment film without using a printing plate.
• the ink jet method is a method in which fine droplets are dropped on a substrate and a film is formed by wetting and spreading of the liquid. Not only the printing plate is not used, but also the printing pattern can be set freely, so that the manufacturing process of the liquid crystal display element can be simplified. In addition, there is an advantage that the waste of the coating liquid is reduced because the film formation on the dummy substrate which is necessary for flexographic printing is not necessary.
• the inkjet method is expected to reduce the cost of liquid crystal panels and improve production efficiency.
• the liquid crystal alignment film formed by the ink jet method is required to have small film thickness unevenness inside the coating surface and high film forming accuracy in the peripheral part of the coating.
• a liquid crystal alignment film formed by an ink-jet method has a trade-off relationship between the uniformity of the film thickness in the coating surface and the film forming accuracy in the periphery of the coating.
• a material with high in-plane uniformity has a saw-tooth shape in the periphery of the application instead of being linear.
• the material in which the coating peripheral part is a straight line has poor uniformity in the coated surface.
• Patent Document 1 Patent Document 2, Patent Document 3
• Patent Document 2 Patent Document 3
• Patent Document 3 Patent Document 3
• the present invention provides a polyimide-based liquid crystal aligning agent suitable for the inkjet method and a liquid crystal aligning film using the same, which can form a coating film having excellent uniformity in the thickness of the coating surface and linearity in the peripheral portion of the coating. There is to do.
• a liquid crystal aligning agent comprising: at least one polymer selected from the group consisting of a polyimide and a polyimide precursor; and a solvent containing an alkyl cellosolve acetate compound represented by the following formula (1).
• R 1 is an alkyl group having 1 to 8 carbon atoms.
• the polyimide precursor contains at least one selected from the group consisting of a polyamic acid ester and a polyamic acid.
• the solvent contains at least one selected from the group consisting of N-methylpyrrolidone and ⁇ -butyrolactone. 4).
• the liquid crystal aligning agent according to any one of 1 to 7 above having a viscosity of 5 to 20 mPa ⁇ s. 9.
• a method for forming a liquid crystal alignment film wherein the liquid crystal aligning agent according to any one of 1 to 8 is applied by an inkjet method.
• a liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of 1 to 8 above, drying and baking.
• the conventional liquid crystal aligning agent which is excellent in the uniformity of the film thickness in the coating surface and the linearity in the peripheral portion of the application, is compatible.
• a coating film having excellent characteristics that are difficult to obtain in this way can be obtained.
• the liquid crystal alignment film obtained from such a coating film has excellent characteristics in terms of in-plane uniformity and linearity in the peripheral portion.
• the polyimide precursor contained in the liquid crystal aligning agent of this invention produces
• the polyamic acid ester and the polyamic acid have the following formula (1) and the following formula (2), respectively.
• R 1 is an alkyl group having 1 to 5, preferably 1 to 2 carbon atoms.
• R 1 is particularly preferably a methyl group from the viewpoint of ease of imidization by heat.
• a 1 and A 2 are each independently a hydrogen atom or an alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms that may have a substituent. is there.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a bicyclohexyl group.
• alkenyl group examples include those in which one or more CH 2 —CH 2 structures present in the above alkyl group are replaced with a CH ⁇ CH structure, and more specifically, vinyl groups, allyl groups, 1- Examples include propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like.
• Alkynyl groups include those in which one or more CH 2 —CH 2 structures present in the alkyl group are replaced with C ⁇ C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -Propynyl group and the like.
• the above alkyl group, alkenyl group, or alkynyl group may have a substituent as long as it has 1 to 10 carbon atoms as a whole, and may further form a ring structure by the substituent.
• forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are combined to form a ring structure.
• substituents examples include halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls. Groups, alkenyl groups and alkynyl groups.
• halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• a phenyl group is mentioned as an aryl group which is a substituent.
• This aryl group may be further substituted with the other substituent described above.
• the organooxy group as a substituent can have a structure represented by —O—R.
• the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Specific examples of the organooxy group include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
• the organothio group can have a structure represented by —S—R.
• R include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Specific examples of the organothio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
• the organosilyl group as a substituent can have a structure represented by —Si— (R) 3 .
• the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group.
• the acyl group as a substituent can have a structure represented by —C (O) —R.
• R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above.
• Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
• As the ester group which is a substituent a structure represented by —C (O) O—R or —OC (O) —R can be shown. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
• the thioester group as a substituent can have a structure represented by —C (S) O—R or —OC (S) —R.
• R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
• the phosphate group which is a substituent can have a structure represented by —OP (O) — (OR) 2 .
• the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Examples of the substituent amide group include —C (O) NH 2 , —C (O) NHR, —NHC (O) R, —C (O) N (R) 2 , —NRC (O) R.
• the structure represented by can be shown.
• the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Examples of the aryl group as a substituent include the same aryl groups as described above. This aryl group may be further substituted with the other substituent described above.
• Examples of the alkyl group as a substituent include the same alkyl groups as described above. This alkyl group may be further substituted with the other substituent described above.
• alkenyl group as a substituent examples include the same alkenyl groups as described above. This alkenyl group may be further substituted with the other substituent described above.
• alkynyl group that is a substituent examples include the same alkynyl groups as described above. This alkynyl group may be further substituted with the other substituent described above.
• the reactivity of the amino group and the liquid crystal orientation may be lowered.
• a 1 and A 2 a hydrogen atom or a carbon atom that may have a substituent is 1
• An alkyl group of 1 to 5 is more preferable, and a hydrogen atom, a methyl group, or an ethyl group is particularly preferable.
• X 1 and X 2 are each independently a tetravalent organic group
• Y 1 and Y 2 are each independently a divalent organic group.
• X 1 and X 2 are tetravalent organic groups and are not particularly limited. Two or more kinds of X 1 and X 2 may be mixed in the polyimide precursor. Specific examples of X 1 and X 2 include X-1 to X-46 shown below independently.
• X 1 and X 2 are each independently X-1, X-2, X-3, X-4, X-5, X-6, X-8, X from the availability of monomers. -16, X-19, X-21, X-25, X-26, X-27, X-28 or X-32 are preferred.
• the amount of tetracarboxylic dianhydride having these preferable X 1 and X 2 is preferably 2 to 100 mol%, more preferably 40 to 100 mol% of the total tetracarboxylic dianhydride.
• Y 1 and Y 2 are each independently a divalent organic group and are not particularly limited. When showing a specific example of Y 1 and Y 2, include Y-1 ⁇ Y-103 below. As Y 1 and Y 2 , two or more types may be mixed independently.
• Y 1 is represented by Y-7, Y-10, Y-11, Y- 12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Diamines having Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, or Y-98 are preferred.
• the amount of these diamines preferably used as Y 1 is preferably 1 to 100 mol%, more preferably 50 to 100 mol% of the total diamine.
• Y 1 is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, 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, or Y-97 are more preferred.
• at least 1 sort (s) chosen from the structure represented by the following Formula is especially preferable.
• Y 2 is Y-19, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y-32, Y-33, Y-34, Y- 35, Y-36, Y-40, Y-41Y-42, Y-44, Y-45, Y-49, Y-50, Y-51 or Y-61 are more preferred, Y-31 or Y A diamine of ⁇ 40 is particularly preferred. The amount of these diamines preferably used as Y 2 is preferably 1 to 100 mol%, more preferably 50 to 100 mol% of the total diamine.
• the polyamic acid ester represented by the above formula (1) is obtained by reaction of any of the tetracarboxylic acid derivatives represented by the following formulas (6) to (8) with the diamine compound represented by the formula (9). be able to.
• the polyamic acid ester represented by the above formula (1) can be synthesized by the following methods (1) to (3) using the above monomer.
• a polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic dianhydride and a 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. Can be synthesized.
• the esterifying agent those that can be easily removed by purification are preferable.
• the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
• the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone from the solubility of the polymer, and these may be used alone or in combination. Good.
• the concentration at the time of synthesis 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 product is easily obtained.
• 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 reacting.
• a base 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 solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
• the polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is 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 mixing of outside air in a nitrogen atmosphere.
• the polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine. Specifically, tetracarboxylic acid diester and 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 synthesize
• condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
• Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
• the amount of the condensing agent added is preferably 2 to 3 moles compared to the tetracarboxylic acid diester.
• tertiary amines such as pyridine and triethylamine can be used.
• the addition amount of the base is preferably 2 to 4 times mol with respect to the diamine component 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 to 1.0 times the mole of the diamine component.
• the polyamic acid ester solution obtained as described above can be polymerized by being poured into a poor solvent while being well stirred. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
• the weight average molecular weight of the polyamic acid ester is preferably 5,000 to 300,000, and more preferably 10,000 to 200,000.
• the number average molecular weight is preferably 2,500 to 150,000, and more preferably 5,000 to 100,000.
• the polyamic acid represented by the above formula (2) can be obtained by a reaction between a tetracarboxylic dianhydride represented by the following formula (10) and a diamine compound represented by the formula (11).
• tetracarboxylic dianhydride and 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.
• the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone because of the solubility of the monomer and polymer, and these may be used alone or in combination of two or more. It may be used.
• 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 difficult to occur and a high molecular weight body is easily obtained.
• the polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
• a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
• the weight average molecular weight of the polyamic acid is preferably 10,000 to 305,000, and more preferably 20,000 to 210,000.
• the number average molecular weight is preferably 5,000 to 152,500, and more preferably 10,000 to 105,000.
• the polyimide contained in the liquid crystal aligning agent of the present invention can be obtained by imidizing the above polyimide precursor.
• the method of imide thermal imidization by heating and catalyst imidization using a catalyst are generally used.
• the catalyst imidation in which the imidization reaction proceeds at a relatively low temperature is lower in the molecular weight of the resulting polyimide. Is less likely to occur.
• Catalytic imidation can be carried out in an organic solvent by stirring the polyamic acid in the presence of a basic catalyst and an acid anhydride, or stirring the polyamic acid ester in the presence of a basic catalyst.
• the reaction temperature at this time is ⁇ 20 to 250 ° C., preferably 0 to 180 ° C.
• the higher the reaction temperature the faster the imidization proceeds.
• the molecular weight of the polyimide may decrease.
• the amount of the basic catalyst is 1 to 60 moles, preferably 2 to 40 moles per mole of the repeating unit of the polyamic acid or polyamic acid ester.
• the amount of the acid anhydride for catalytic imidization of the polyamic acid is 2 to 100 moles, preferably 6 to 60 moles per mole of the repeating unit of the polyamic acid. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it becomes difficult to completely remove the reaction after completion of the reaction.
• the basic catalyst used for the catalytic imidation of polyamic acid include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. .
• Examples of the basic catalyst used for the catalytic imidation of the polyamic acid ester include triethylamine, trimethylamine, tributylamine, trioctylamine and the like, and triethylamine is particularly preferable because of its fast reaction.
• Examples of acid anhydrides used for catalytic imidation of polyamic acid include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Among them, use of acetic anhydride facilitates purification after completion of the reaction. preferable.
• the organic solvent is not limited as long as it dissolves polyamic acid or polyamic acid ester. Specific examples thereof include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl- Examples include 2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, dimethyl sulfone, hexamethyl sulfoxide, and ⁇ -butyrolactone.
• the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
• the produced polyimide can be obtained by collecting the reaction solution in a poor solvent and collecting the produced precipitate.
• the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
• the polyimide that has been poured into a poor solvent and precipitated is filtered, and then can be powdered by drying at normal temperature or under reduced pressure at normal temperature or under reduced pressure.
• the polyimide can be purified by repeating the steps of dissolving the polyimide powder in an organic solvent and reprecipitating it 2 to 10 times. When the impurities cannot be removed by a single precipitation recovery operation, it is preferable to perform this purification step.
• the molecular weight of the polyimide is not particularly limited, but is preferably 2,000 to 200,000, more preferably 4,000 to 50,000 in terms of weight average molecular weight from the viewpoint of ease of handling and stability of characteristics when a film is formed. 000.
• the molecular weight is determined by GPC (gel permeation chromatography).
• the terminal of the polyimide or polyamic acid or polyamic acid ester used in the present invention may be modified.
• the terminal modification can be synthesized by adding an acid anhydride, a monoamine compound, an acid chloride compound, a monoisocyanate compound or the like when synthesizing a polyamic acid or a polyamic acid ester.
• the liquid crystal aligning agent of the present invention is in the form of a solution in which at least one polymer selected from the group consisting of the polyimide precursor and polyimide is dissolved in an organic solvent.
• a polyimide precursor such as polyamic acid ester and / or polyamic acid and / or polyimide
• the resulting reaction solution itself may be used.
• the solution may be diluted with an appropriate solvent.
• a polyimide precursor and / or a polyimide is obtained as a powder, it may be dissolved in an organic solvent to form a solution.
• the organic solvent contained in the liquid crystal aligning agent of the present invention needs to contain an alkyl cellosolve acetate compound.
• the alkyl cellosolve acetate compound contained in the organic solvent is preferably a cellosolve acetate compound having an alkyl group having preferably 1 to 10, more preferably 1 to 6 carbon atoms. Preferable examples thereof include at least one selected from the group consisting of methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cellosolve acetate. Of these, butyl cellosolve acetate is preferable from the viewpoint of an appropriate boiling point and volatilization rate. When the alkyl chain length of the alkyl cellosolve acetate is too long, the boiling point becomes high, causing a problem that the liquid crystal alignment film is not dried in the drying step.
• the organic solvent is not particularly limited as long as the polymer is uniformly dissolved.
• Specific examples include ⁇ -butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N -Methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. You may use these 1 type or in mixture of 2 or more types.
• ⁇ -butyrolactone or N-methyl-2-pyrrolidone is preferable from the viewpoint of versatility and solubility.
• the solvent for the liquid crystal aligning agent for ink jet coating contains a large amount of ⁇ -butyrolactone. Specifically, it is desirable to contain 50% by weight or more, more preferably 60% by weight or more of ⁇ -butyrolactone.
• the viscosity of the liquid crystal aligning agent of the present invention is preferably 5 mPa ⁇ s to 20 mPa ⁇ s, particularly preferably 5 mPa ⁇ s to 15 mPa ⁇ s, from the viewpoint of inkjet coating.
• the content of the solvent in the liquid crystal aligning agent of the present invention is selected in consideration of the above viscosity, and is preferably 95 to 99% by mass, and particularly preferably 96 to 98% by mass.
• a concentrated solution of the polymer may be prepared in advance and diluted when the liquid crystal aligning agent is used from the concentrated solution.
• the film thickness of the liquid crystal alignment film becomes too small to obtain a good liquid crystal alignment film.
• the content of the alkyl cellosolve acetate compound in the organic solvent is preferably 1% by mass to 60% by mass, more preferably 2% by mass to 40% by mass.
• the content is small, the in-plane uniformity and the peripheral portion linearity of the inkjet coating film are insufficient, and when the content is too large, the storage stability of the liquid crystal aligning agent during freezing deteriorates.
• the content (concentration) of the polymer in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the polyimide film to be formed, but a uniform and defect-free coating film is formed. Therefore, the content is preferably 1% by mass to 5% by mass, and particularly preferably 2% by mass to 4% by mass.
• the liquid crystal aligning agent of the present invention may contain the following solvent in addition to the organic solvent for dissolving the polymer component and the alkyl cellosolve acetate compound. You may contain the solvent for improving the coating-film uniformity at the time of apply
• a solvent having a surface tension lower than that of the organic solvent is generally used.
• ethyl cellosolve ethyl cellosolve
• butyl cellosolve ethyl carbitol
• butyl carbitol ethyl carbitol
• ethyl carbitol acetate ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, etc. That. Two types of these solvents may be used
• the liquid crystal aligning agent of this invention may contain various additives, such as a silane coupling agent and a crosslinking agent.
• the silane coupling agent is added for the purpose of improving the adhesion between the substrate on which the liquid crystal alignment agent is applied and the liquid crystal alignment film formed thereon.
• Existing silane coupling agents are added. If the addition amount of the silane coupling agent is too large, unreacted ones may adversely affect the liquid crystal orientation. 0.01 to 5.0% by weight is preferable, and 0.1 to 1.0% by weight is more preferable.
• an imidization accelerator may be added to the liquid crystal aligning agent of the present invention in order to efficiently advance imidization of the polyimide precursor when the coating film is baked.
• Existing imidation accelerators are used. When adding an imidization accelerator, since imidation may advance by heating, it is preferable to add after diluting with a good solvent and a poor solvent.
• the liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal aligning agent to a substrate, drying and baking.
• the substrate on 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, an acrylic substrate, a polycarbonate substrate such as a polycarbonate substrate, or the like can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed.
• 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 for the electrode.
• the liquid crystal aligning agent of the present invention As a method for applying the liquid crystal aligning agent of the present invention, a spin coating method, a printing method, or the like can be used. As described above, the liquid crystal aligning agent of the present invention is particularly suitable for the ink jet method. When the liquid crystal aligning agent of the present invention is applied by an ink jet method to form a coating film, a coating film having excellent uniformity of the film thickness within the coating surface and linearity of the coating peripheral portion can be obtained.
• any temperature and time can be selected.
• drying is performed at 50 ° C. to 120 ° C. for 1 minute to 10 minutes, and then baking is performed at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes.
• the thickness of the coating film after baking is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, and therefore it is 5 to 300 nm, preferably 10 to 200 nm.
• the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate, then subjected to alignment treatment by rubbing treatment, photo-alignment treatment, or the like, or without alignment treatment in vertical alignment applications. it can.
• 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 from the liquid crystal aligning agent of the present invention by the above-described method, performing an alignment treatment, and then preparing a liquid crystal cell by a known method. It is.
• the manufacturing method of the liquid crystal cell is not particularly limited, but for example, a pair of substrates on which the liquid crystal alignment film is formed is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m with the liquid crystal alignment film surface inside.
• a method is generally employed in which the spacer is fixed with a sealing agent after the spacer is sandwiched, and liquid crystal is injected and sealed.
• the method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method of injecting liquid crystal after reducing the pressure inside the produced liquid crystal cell, and a dropping method of sealing after dropping the liquid crystal.
• CBDA cyclobutanetetracarboxylic dianhydride
• 1,3DMCBDE-Cl dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate
• TDA 3,4-dicarboxy-1 , 2,3,4-Tetrahydro-1-naphthalene succinic dianhydride
• BDA 1,2,3,4-butanetetracarboxylic dianhydride
• PMDA pyromellitic dianhydride
• ODA 4,4′-oxydianiline
• p-PDA p-phenylenediamine
• C16DAB 4-hexadecyloxy-1,3-diaminobenzene
• C12DAB 4-dodecyloxy-1,3-diaminobenzene
• 4-ABA 4 -Aminobenzylamine
• DA-A Diamine of the following formula
• DA-B Diamine of the following formula DA-B
• the molecular weight of the polyimide, polyamic acid or polyamic acid ester in the synthesis example is measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight as polyethylene glycol and polyethylene oxide equivalent values. (Hereinafter also referred to as Mw) was calculated.
• GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF ) Is 10 mL / L) Flow rate: 1.0 mL / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30000) manufactured by Tosoh Corporation, and polyethylene glycol (peak top molecular weight manufactured by Polymer Laboratories) (Mp) about 12000, 4000, 1000). In order to avoid the overlap of peaks, two samples of 90000, 100000, 12000, 1000 mixed samples and 250,000
• the imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was put into an NMR sample tube, and 0.53 mL of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixed product) was added and completely dissolved. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNM-ECA500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of polyamic acid appearing in the vicinity of 9.5 to 10.0 ppm.
• Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
• x is the proton peak integrated value derived from the NH group of the polyamic acid
• y is the peak integrated value of the reference proton
• ⁇ is one NH group proton of the polyamic acid in the case of the polyamic acid (imidation rate is 0%).
• Example 1 To a 100 mL Erlenmeyer flask containing a stirrer, 1.75 g of the polyamic acid ester obtained in Synthesis Example 1 and 15.75 g of GBL were added and stirred to dissolve. Next, 22.5 g of GBL and 10.00 g of BCA were added to obtain a liquid crystal aligning agent.
• Example 3 1.80 g of the polyimide obtained in Synthesis Example 3 and 16.2 g of GBL were added to a 100 mL Erlenmeyer flask containing a stir bar, and dissolved by stirring. Next, 19.5 g of GBL and 12.5 g of BCA were added to obtain a liquid crystal aligning agent.
• Example 4 1.80 g of the polyimide obtained in Synthesis Example 4 and 16.2 g of GBL were added to a 100 mL Erlenmeyer flask containing a stir bar, and dissolved by stirring. Next, 24.5 g of GBL and 7.5 g of ECA were added to obtain a liquid crystal aligning agent.
• Example 5 To a 100 mL Erlenmeyer flask containing a stir bar, 0.72 g of the polyamic acid ester obtained in Synthesis Example 5 and 6.48 g of GBL were added, and dissolved by stirring. Next, 7.11 g of the polyamic acid solution obtained in Synthesis Example 6, 0.95 g of NMP, 29.7 g of GBL, and 5.00 g of BCA were added to obtain a liquid crystal aligning agent.
• Example 6> To a 100 mL Erlenmeyer flask containing a stir bar, 0.90 g of the polyamic acid ester obtained in Synthesis Example 2 and 8.10 g of GBL were added and stirred to dissolve. Next, 5.00 g of the polyamic acid solution obtained in Synthesis Example 7, 6.82 g of NMP, 19.18 g of GBL, and 10.0 g of ECA were added to obtain a liquid crystal aligning agent.
• ⁇ Comparative Example 1> To a 100 mL Erlenmeyer flask containing a stirrer, 1.75 g of the polyamic acid ester obtained in Synthesis Example 1 and 15.75 g of GBL were added and stirred to dissolve. Next, 22.5 g of GBL and 10.0 g of BCS were added to obtain a liquid crystal aligning agent.
• ⁇ Comparative Example 2> To a 100 mL Erlenmeyer flask containing a stir bar, 1.80 g of the polyamic acid ester obtained in Synthesis Example 2 and 16.2 g of GBL were added and dissolved by stirring. Next, 23.0 g of GBL and 9.0 g of BCS were added to obtain a liquid crystal aligning agent.
• ⁇ Comparative Example 5> To a 100 mL Erlenmeyer flask containing a stir bar, 1.75 g of the polyamic acid ester obtained in Synthesis Example 2 and 15.75 g of GBL were added and stirred to dissolve. Next, 22.5 g of GBL and 10.0 g of DEDnBE were added to obtain a liquid crystal aligning agent.
• ⁇ Comparative Example 7> To a 100 mL Erlenmeyer flask containing a stir bar, 1.75 g of the polyamic acid ester obtained in Synthesis Example 2 and 15.75 g of GBL were added and stirred to dissolve. Next, 22.5 g of GBL and 10.0 g of DEEA were added to obtain a liquid crystal aligning agent.
• ⁇ Comparative Example 9> To a 100 mL Erlenmeyer flask containing a stir bar, 1.75 g of the polyamic acid ester obtained in Synthesis Example 2 and 15.75 g of GBL were added and stirred to dissolve. Next, 22.5 g of GBL and 10.0 g of DEGBEA were added to obtain a liquid crystal aligning agent.
• ⁇ Comparative Example 10> To a 100 mL Erlenmeyer flask containing a stir bar, 1.75 g of the polyamic acid ester obtained in Synthesis Example 2 and 15.75 g of GBL were added and stirred to dissolve. Next, 22.5 g of GBL and 10.0 g of PGDA were added to obtain a liquid crystal aligning agent.
• Fine pattern coating device by inkjet printing (HIS-200-1H, manufactured by Hitachi Plant Technologies, Ltd.) Coating substrate: 100 ⁇ 100 mm ITO substrate Coating area: 72 ⁇ 80 mm
• Application conditions resolution 15 ⁇ m, stage speed 40 mm / sec, frequency 2000 Hz, pulse width 9.6 ⁇ sec, appropriate amount 42 pl, pitch width 60 ⁇ m, pitch length 141 ⁇ m, applied voltage: 15 V, nozzle gap 0.5 mm, standing time 30 sec, drying temperature 50 ° C, drying time 2 minutes (hot plate), main baking temperature 230 ° C, main baking time 30 minutes (IR oven)
• Examples 1 to 4 can obtain films having good in-plane uniformity and peripheral linearity.
• Comparative Examples 1 to 9 the fine droplets applied by the ink jet method were not spread on the substrate and could not be formed.
• Comparative Examples 10 to 12 although film formation was possible, in-plane film thickness unevenness was observed.
• liquid crystal aligning agent of the present invention and the liquid crystal alignment film using the same are widely useful for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-079904 filed on March 31, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

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