WO2009148100A1 - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Liquid crystal aligning agent and liquid crystal display element using same Download PDF

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Publication number
WO2009148100A1
WO2009148100A1 PCT/JP2009/060200 JP2009060200W WO2009148100A1 WO 2009148100 A1 WO2009148100 A1 WO 2009148100A1 JP 2009060200 W JP2009060200 W JP 2009060200W WO 2009148100 A1 WO2009148100 A1 WO 2009148100A1
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WIPO (PCT)
Prior art keywords
liquid crystal
aligning agent
crystal aligning
pyrrolidone
polyimide
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PCT/JP2009/060200
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French (fr)
Japanese (ja)
Inventor
尚士 鉄谷
皇晶 筒井
啓文 志田
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日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to CN200980126798.1A priority Critical patent/CN102084287B/en
Priority to JP2010515903A priority patent/JP5578075B2/en
Publication of WO2009148100A1 publication Critical patent/WO2009148100A1/en

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    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723Polyimide, polyamide-imide

Definitions

  • the present invention relates to a liquid crystal alignment treatment agent used for a liquid crystal display element, a liquid crystal alignment film using the same, and a liquid crystal display element.
  • a liquid crystal display element has a structure in which liquid crystal molecules are sandwiched between liquid crystal alignment films formed on a substrate, and is a display element utilizing the fact that liquid crystal molecules aligned in a certain direction by a liquid crystal alignment film respond with voltage. is there.
  • This liquid crystal alignment film is generally produced by subjecting the surface of a polyimide film formed on a substrate with electrodes to a so-called “rubbing process” in which pressure is applied to the surface with rayon or nylon cloth. .
  • VA abbreviation for Vertical Alignment
  • photo alignment films that align the liquid crystal by applying anisotropy to the film surface by irradiating polarized UV light have attracted attention.
  • a method of creating a coating film using a solution of a polyimide precursor such as polyamic acid and imidizing on the substrate, and a polyimide that has been imidized in advance are used. And a method using a solution containing the same.
  • the method using a polyimide-containing solution was able to form a polyimide film with good characteristics when used as a liquid crystal alignment film, even when firing at a relatively low temperature.
  • the strength of the film is low and the rubbing treatment tends to cause scratches or peeling of the film surface. Scratches and peeling on the surface of the liquid crystal alignment film are important problems because they cause display defects when the liquid crystal display element is formed.
  • polyimide is generally inferior in solubility in organic solvents compared to polyamic acid and the like, so if imidized in advance, it may be difficult to form a uniform coating film.
  • the composition is insolubilized in a solvent commonly used for the agent and cannot be contained in the liquid crystal aligning agent. Therefore, the solubility of the polyimide contained in the liquid crystal aligning agent is also important.
  • a liquid crystal aligning agent containing polyimide when printing on a substrate, the varnish containing polyimide is whitened by moisture absorption, or the varnish is dried on the printing plate and aggregates are generated. The problem was easy to happen.
  • a liquid crystal alignment treatment agent containing a diamine component having a specific structure has been proposed as an excellent liquid crystal alignment film rubbing resistance and polyimide solubility (for example, see Patent Document 1).
  • a method for suppressing the whitening phenomenon of varnish containing polyimide it has been proposed to use N-vinylpyrrolidone or N-cyclohexylpyrrolidone for 50% or more of the solvent (for example, see Patent Document 2).
  • a liquid crystal aligning agent that suppresses aggregates produced by drying of the varnish has not been proposed so far.
  • the present invention is a liquid crystal alignment treatment agent that maintains good electrical characteristics of a polyimide alignment film, has good whitening and printability, and does not generate aggregates that cause gap unevenness in a liquid crystal panel during printing.
  • the purpose is to provide.
  • the liquid crystal alignment treatment agent is also excellent in long-term storage stability, and when used as a liquid crystal alignment film, it has excellent rubbing resistance and a liquid crystal tilt angle.
  • An object of the present invention is to provide a liquid crystal alignment treatment agent that is high and has good alignment properties.
  • the gist of the present invention is as follows. 1.
  • a pyrrolidone compound comprising a resin component containing a polyimide obtained by imidizing a polyamic acid obtained by reacting a diamine component with tetracarboxylic dianhydride, and N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone
  • a solvent component comprising: a liquid crystal aligning agent characterized by comprising: 2.
  • k represents an integer of 1 to 20. 8).
  • 11. 11 A liquid crystal display device having the liquid crystal alignment film as described in 10 above.
  • liquid crystal alignment treatment agent of the present invention a liquid crystal alignment film having good electrical characteristics can be obtained, and the occurrence of aggregates that cause gap unevenness of the liquid crystal panel during printing is suppressed, so that reliability of a narrow gap is improved. LCD panels with high yield can be produced with good yield.
  • the liquid crystal aligning agent of this invention is a processing agent which forms the liquid crystal aligning film used for a liquid crystal display element, and is obtained by imidating the polyamic acid obtained by making a diamine component and tetracarboxylic dianhydride react. It contains polyimide and N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone.
  • a diamine component containing a diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms hereinafter referred to as a specific diamine
  • a polyimide obtained by imidizing a polyamic acid obtained by reacting with a carboxylic dianhydride component is particularly preferred because the solubility in an organic solvent is increased.
  • the diamine component (also simply referred to as diamine) used in the present invention is not particularly limited.
  • the diamine can be used alone or in combination, and the type is not limited.
  • Examples of the diamine include alicyclic diamines, aromatic diamines, heterocyclic diamines, and aliphatic diamines. Specific examples are shown below.
  • alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, and isophorone Examples include diamines.
  • aromatic diamines examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamin
  • heterocyclic diamines examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diamino
  • examples thereof include carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole.
  • aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diaminododecane 1,18-diaminooctadecan
  • a diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms (hereinafter also referred to as a specific diamine) is preferable as the diamine in order to increase the solubility of polyimide in an organic solvent.
  • diaminobenzene having a disubstituted amino group substituted by a 2-propenyl group (hereinafter also referred to as an allyl group) represented by the following formula [1] is preferable.
  • the position of each substituent on the benzene ring is not particularly limited, but the positional relationship between the two amino groups is preferably meta or para.
  • the more preferable specific example of this diamine is given below.
  • the formula [2] is 2,4-diamino-N, N-diallylaniline
  • the formula [3] is 3,5-diamino-N, N-diallylaniline
  • the formula [4] is 2,5-diamino-N, N-diallylaniline.
  • the diaminobenzene is at least one selected from the group consisting of [2], [3] and [4].
  • the diaminobenzene is particularly preferably 2,4-diamino-N, N-diallylaniline.
  • the diamine component used as a raw material for polyimide may be only a specific diamine, or a combination of a specific diamine and one or more of other diamines.
  • the content of the specific diamine in the diamine component is preferably 20 mol (mol)% or more, more preferably 40 mol% or more, particularly 50 mol% or more.
  • the higher the specific diamine content ratio in the diamine component the higher the effect of suppressing scratches on the alignment film surface and the film peeling during the rubbing treatment. Moreover, the solubility with respect to the organic solvent of the polyimide obtained also becomes high.
  • the diamine component may be only the specific diamine, but it is preferable to use a diamine other than the specific diamine because other characteristics required for the liquid crystal alignment film can be imparted. Therefore, the content of the specific diamine is more preferably 90 mol% or less.
  • the solubility of polyimide in an organic solvent increases, and a liquid crystal alignment treatment agent with excellent liquid crystal alignment is obtained. This is particularly preferable.
  • the preferred content of 4-aminobenzylamine, 3-aminobenzylamine, or 4-aminophenethylamine in the diamine component is 10 mol% to 50 mol%.
  • a diamine having a specific substituent can be used in combination.
  • the substituent capable of increasing the pretilt angle of the liquid crystal a long-chain alkyl group, a perfluoroalkyl group, an aromatic cyclic group, an aliphatic cyclic group, a combination of these, or a steroid skeleton group is preferable.
  • the specific example of the diamine which has the said substituent is given to the following, it is not limited to this.
  • j represents an integer of 5 to 20, preferably 9 to 17, and k represents an integer of 1 to 20, preferably 4 to 15.
  • the diamines of the formulas [5] and [32] are preferable because of excellent liquid crystal alignment.
  • the diamines represented by the formulas [12] to [19] have a very high tilting ability, and are therefore suitably used for OCB (Optically mp Compensated Bend) alignment films and VA (Vertical Alignment) alignment films.
  • OCB Optically mp Compensated Bend
  • VA Very Alignment
  • the diamine of formula [5] or [32] is 5 to 40 mol%, preferably 10 to 30 mol in the diamine component.
  • the diamine of formula [12]-[19] may be contained in the diamine component in an amount of 5-60 mol%, preferably 10-40 mol%. It is not limited to this.
  • the diamine of formula [32] is particularly preferable because it has a high tilt angle and is excellent in liquid crystal alignment even when the rubbing conditions are weak when used in combination with the specific diamine. . Furthermore, the effect of increasing the pretilt angle of the liquid crystal as described above tends to be weakened when the liquid crystal aligning agent contains a large amount of N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone.
  • the diamine of the formula [32] has a characteristic that it is not easily affected by the above, and is suitable as a diamine component of the polyimide contained in the liquid crystal aligning agent of the present invention.
  • the tetracarboxylic dianhydride component used as a raw material for polyimide may be one type of tetracarboxylic dianhydride or a mixture of two or more types of tetracarboxylic dianhydrides. good. However, even if it is a polyimide with a high imidization rate, a tetracarboxylic acid having an alicyclic structure or an aliphatic structure can be obtained because it is easy to obtain a polyimide with relatively high solubility and the voltage holding ratio of the liquid crystal cell can be increased. It is preferable to use an acid dianhydride.
  • Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane.
  • Tetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclo
  • tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure examples include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4 Use of tetrahydro-1-naphthalene succinic dianhydride or 1,2,3,4-butanetetracarboxylic dianhydride is particularly preferable because an alignment film excellent in liquid crystal alignment can be obtained.
  • Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4-benzophenonetetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride And 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.
  • Aromatic tetracarboxylic dianhydrides include, among others, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Or 1,4,5,8-naphthalenetetracarboxylic dianhydride is particularly preferred.
  • the ratio with the acid dianhydride is preferably 90/10 to 50/50, more preferably 80/20 to 60/40, as the molar ratio of the former / the latter.
  • the polyimide used for the liquid-crystal aligning agent of this invention is a polyimide which imidized the polyamic acid obtained by making the above-mentioned diamine component and the tetracarboxylic dianhydride component react.
  • the polyamic acid can be obtained by mixing and reacting a tetracarboxylic dianhydride component and a diamine component in an organic solvent.
  • a solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent.
  • a method of adding by dispersing or dissolving in a solvent a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component. The method of adding alternately etc. are mentioned.
  • the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of types of compounds, the plurality of types of components may be preliminarily mixed, or may be individually polymerized sequentially.
  • the temperature at which the tetracarboxylic dianhydride component and the diamine component are subjected to a polymerization reaction in an organic solvent is usually 0 to 150 ° C., preferably 5 to 100 ° C., more preferably 10 to 80 ° C. When the temperature is higher, the polymerization reaction is completed earlier, but when it is too high, a high molecular weight polymer may not be obtained.
  • the polymerization reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. Since it becomes difficult, the concentration of the total amount of the tetracarboxylic dianhydride component and the diamine component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the polymerization reaction may be performed at a high concentration, and then an organic solvent may be added.
  • the organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid can be dissolved, but N-ethyl-2-pyrrolidone or N-cyclohexyl-2 which is an essential component for the liquid crystal aligning agent.
  • -Pyrrolidone or other solvents may be used. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethylimidazolidinone and the like can be mentioned.
  • the solvent may be used alone or in combination.
  • it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
  • water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
  • the ratio of the tetracarboxylic dianhydride component and the diamine component used for the polymerization reaction of the polyamic acid is preferably 1: 0.8 to 1: 1.2 in molar ratio, and this molar ratio is close to 1: 1.
  • the molecular weight of the polyamic acid obtained increases. By controlling the molecular weight of this polyamic acid, the molecular weight of the polyimide obtained after imidation can be adjusted.
  • the molecular weight of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited, but in terms of the strength of the coating film and the ease of handling as a liquid crystal aligning agent, the weight average molecular weight is 2,000 to 200, 000 is preferred, more preferably 5,000 to 50,000.
  • the imidization of the polyamic acid obtained as described above can be performed by stirring in an organic solvent for 1 to 100 hours in the presence of a basic catalyst and an acid anhydride.
  • Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferable because the obtained polyimide can be easily purified after imidization.
  • As an organic solvent the solvent used at the time of the polyamic acid polymerization reaction mentioned above can be used.
  • the imidation ratio of polyimide can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the amount of the basic catalyst at this time is preferably 0.2 to 10 times mol, more preferably 0.5 to 5 times mol of the amic acid group of the starting polyamic acid.
  • the amount of the acid anhydride is preferably 1 to 30 times mol, more preferably 1 to 10 times mol of the amic acid group of the starting polyamic acid.
  • the reaction temperature is preferably ⁇ 20 to 250 ° C., more preferably 0 to 180 ° C.
  • the imidation ratio of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited, it is preferably 40% or more in consideration of electrical characteristics, and 60% or more is more preferable in order to obtain a high voltage holding ratio. More preferably, it is 80% or more. Since the added catalyst or the like remains in the polyimide solution thus obtained, it is preferable to use the liquid crystal alignment treatment agent of the present invention after recovering and washing the specific polyimide.
  • the polyimide can be recovered by putting the solution after imidization into a poor solvent that is being stirred and precipitating the polyimide, followed by filtration.
  • the poor solvent at this time include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
  • the recovered polyimide can also be washed with this poor solvent.
  • the polyimide recovered and washed in this way can be powdered by drying at room temperature or under normal pressure or reduced pressure.
  • the liquid crystal alignment treatment agent of the present invention is a solution containing the above polyimide as a resin component and N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone as a solvent component.
  • N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone it is necessary to use N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone as a solvent component.
  • a pyrrolidone compound for example, when N-methyl-2-pyrrolidone is used.
  • whitening of the coating film and unevenness of the film thickness in the vicinity of the printing edge may occur, and it is difficult to achieve the object of the present invention.
  • the concentration of the solution constituting the liquid crystal alignment treatment agent can be appropriately changed by setting the thickness of the liquid crystal alignment film to be formed.
  • the solvent component is preferably 9 to 99 with respect to 1 part by mass of the nonvolatile component such as the resin component. Part by mass, more preferably 11.5 to 49 parts by mass. When the solvent component is more than 99 parts by mass, it is difficult to form a uniform and defect-free coating film, and when it is less than 9 parts by mass, the storage stability of the solution may be deteriorated.
  • the content of the solvent component in the liquid crystal aligning agent of the present invention is preferably 90 to 99% by mass, more preferably 92 to 98 parts by mass with respect to the entire liquid crystal aligning agent.
  • the resin component in the liquid crystal aligning agent of the present invention may be a mixture of two or more types of polyimides having different structures.
  • polyamic acid and other types of resins are used together to the extent that electrical properties are not impaired, storage stability of the varnish is not deteriorated, and aggregates that cause gap unevenness of the liquid crystal panel are not generated during printing. May be.
  • the amount of the resin used in combination is preferably 0.05 to 7 parts by mass, more preferably 0.1 to 4 parts by mass with respect to 1 part by mass of polyimide.
  • the content of the resin component in the liquid crystal aligning agent of the present invention is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on the entire liquid crystal aligning agent.
  • the solvent component in the liquid crystal aligning agent of the present invention may be only N-ethyl-2-pyrrolidone, but contains other solvents in order to ensure the solubility of the resin component and to control the coating property to the substrate. It is preferable to do.
  • N-cyclohexyl-2-pyrrolidone since the solubility of polyimide is inferior to that of N-ethyl-2-pyrrolidone, its content is determined from the viewpoint of long-term storage stability of the liquid crystal aligning agent. It is preferable to contain a solvent for ensuring the solubility of the resin component as the other solvent component.
  • Solvents for ensuring the solubility of the resin component include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinylpyrrolidone, dimethyl Examples thereof include sulfoxide, tetramethylurea, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone.
  • N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, and ⁇ -butyrolactone are preferably used because of the high solubility of polyimide.
  • ⁇ -butyrolactone is preferably used because it has an effect of suppressing whitening.
  • Examples of the solvent for controlling the coating property to the substrate include a solvent having a low surface tension.
  • a solvent having a low surface tension By appropriately mixing a solvent having a low surface tension with the solvent component, the coating film uniformity can be improved during application to the substrate.
  • Solvents having low surface tension include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, diethylene glycol diethyl ether, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-mono Ethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, ethyl lactate Le, lactate n- propyl ester, lactate n- butyl ester, and the like lactic isoamyl ester.
  • the amount of N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone is 0.5 parts by mass or more with respect to 1 part by mass of the resin component
  • production of the aggregate is seen, Preferably it is 1 to 80 weight part, More preferably, it is 2 to 70 weight part.
  • N-ethyl-2-pyrrolidone is preferably used because it has excellent solubility of the resin component and thus excellent storage stability of the varnish, and varnish is not easily whitened even when moisture is absorbed.
  • N-ethyl-2-pyrrolidone is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the entire solvent component.
  • N-cyclohexyl-2-pyrrolidone is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the entire solvent component.
  • N-ethyl-2-pyrrolidone is preferably 40% by mass or less of the total solvent component.
  • the solvent for ensuring the solubility of the resin component when the amount is too large, whitening of the varnish or generation of foreign matter during printing, the content is preferably 80% by mass or less of the solvent component, more preferably Is 60% by mass or less.
  • a solvent having a low surface tension improves the coating property to the substrate, but if the amount is too large, precipitation of the resin component occurs, so the content is preferably 60% by mass or less, more preferably 50% by mass of the solvent component. It is as follows.
  • the more preferable content of each solvent is 5 to 70% by mass of the solvent for ensuring the solubility of the resin component.
  • the solvent having a low surface tension is 10 to 60% by mass, more preferably the solvent for ensuring the solubility of the resin component is 10 to 45% by mass, and the solvent having a low surface tension is 20 to 50% by mass. %.
  • Examples of the solvent composition in the liquid crystal aligning agent of the present invention include 5 to 80% by mass of N-ethyl-2-pyrrolidone, 5 to 70% by mass of a solvent for ensuring the solubility of the resin component, and a low surface.
  • N-ethyl-2-pyrrolidone is 10 to 40% by mass
  • the solvent for ensuring the solubility of the resin component is 10 to 45% by mass
  • the solvent having a low surface tension is 20 to 50% by mass.
  • the liquid crystal aligning agent of the present invention may contain additives for improving the properties of the coating film.
  • Additives for improving coating properties include 3-aminopropylmethyldiethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane
  • silane coupling agents such as The addition of these silane coupling agents can further improve the adhesion of the coating film to the substrate, but if added too much, the polyimide used in the present invention and the polymer compound used in combination with it will cause aggregation. Therefore, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the resin component used in the present invention.
  • the method for preparing the liquid crystal aligning agent of the present invention is not particularly limited as long as the contained components are in a uniform state in the liquid crystal aligning agent.
  • a polyimide powder is dissolved in an organic solvent to form a polyimide solution, and then diluted by adding an organic solvent to a desired concentration.
  • adjustment of the solvent composition for controlling the coating property to the substrate, addition of an additive for improving the properties of the coating film, and the like can be performed.
  • the solvent for dissolving the polyimide powder include N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, and the solvents described above.
  • the liquid crystal aligning agent obtained as described above is preferably filtered before being applied to the substrate.
  • the liquid crystal alignment treatment agent of the present invention can be applied to a substrate, dried and baked to form a coating film. By rubbing this coating film surface, it is used as a liquid crystal alignment film for rubbing. It is also used as a liquid crystal alignment film for VA or a photo alignment film that is not rubbed.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used, and an ITO electrode for driving a liquid crystal is formed. It is preferable to use a new substrate 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 as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, and ink-jet methods. From the viewpoint of productivity, the flexographic printing method is widely used industrially, and the liquid crystal aligning treatment of the present invention. It is also preferably used in agents.
  • the drying process after applying the liquid crystal alignment treatment agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. Inclusion is preferred.
  • the drying is not particularly limited as long as the solvent is evaporated to such an extent that the shape of the coating film is not deformed by the conveyance of the substrate or the like.
  • a method of drying on a hot plate at 50 to 150 ° C., preferably 80 to 120 ° C., for 0.5 to 30 minutes, preferably 1 to 5 minutes is employed.
  • the substrate coated with the liquid crystal aligning agent can be baked at an arbitrary temperature of 100 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 250 ° C.
  • an amic acid group is present in the liquid crystal aligning agent, it changes from an amic acid to an imide depending on the baking temperature, but the liquid crystal aligning agent of the present invention does not necessarily need to be 100% imidized.
  • the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 10 to 200 nm, more preferably 50 to 100 nm.
  • an existing rubbing apparatus can be used.
  • the material of the rubbing cloth at this time include cotton, rayon, and nylon.
  • 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 method described above, and then preparing a liquid crystal cell by a known method.
  • an alignment treatment direction is 0 to 270 ° with a pair of substrates on which a liquid crystal alignment film is formed, preferably with a spacer of 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • a method is generally used in which the angle is set at an arbitrary angle, the periphery is fixed with a sealant, 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.
  • the liquid crystal display elements thus obtained include various types such as TN liquid crystal display elements, STN liquid crystal display elements, TFT liquid crystal display elements, OCB liquid crystal display elements, lateral electric field type liquid crystal display elements, and VA liquid crystal display elements. It is suitably used for a display element by the above method.
  • ⁇ Tetracarboxylic dianhydride> CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene-2-succinic acid Anhydride ⁇ Diamine> 2,4-DAA: 2,4-Diamino-N, N-diallylaniline
  • p-PDA p-phenylenediamine
  • DDM 4,4′-diaminodiphenylmethane
  • BAPP 1,5-bis (4-aminophenoxy) pentane
  • C12DAB 4-dodecyloxy-1,3-diaminobenzene
  • C14DAB 4-tetradecyl Oxy-1,3-diaminobenzene
  • C18DAB 4-octadecyloxy-1,3-diaminobenzene
  • PCBA-PDA 4- (t-4-pentylcyclohexyl) benzamide-2 ′, 4′-phenylenediamine
  • NMP N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • NCP N-cyclohexyl-2-pyrrolidone
  • ⁇ BL ⁇ -butyrolactone
  • DMI 1,3-dimethylimidazolidinone
  • BC Butyl cellosolve
  • DPM Dipropylene glycol Monomethyl ether
  • the molecular weight of the polyimide was measured with a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight and weight average molecular weight were calculated as polyethylene glycol and polyethylene oxide equivalent values.
  • 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) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10ml / L) Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (weight average molecular weight: about 12,000, manufactured by Polymer Laboratories) 4,000, 1,000).
  • the imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was placed in an NMR sample tube, and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture) 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.
  • JNM-ECA500 deuterated dimethyl sulfoxide
  • the imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, a peak integrated value of this proton, and a proton peak integrated value derived from the NH group of the amic acid that appears around 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 amic acid
  • y is the peak integrated value of the reference proton
  • is one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%).
  • the number ratio of the reference protons is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, a peak integrated value of this proton, and a proton peak integrated value derived from the NH group of the amic acid that appears around 9.5 to 10.0 ppm
  • the number average molecular weight of this polyamic acid was 11,067, and the weight average molecular weight was 26,270.
  • Synthesis Example 11 NEP and BC were added to 50 g of the polyamic acid solution obtained in Synthesis Example 10 to prepare 6% by mass of polyamic acid, 59% by mass of NEP, 20% by mass of ⁇ -BL, and 15% by mass of BC.
  • Example 1 After cooling 20.23 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 8.67 g of ⁇ BL, 4.93 g of NEP and 14.78 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
  • the voltage holding rate of the liquid crystal cell was evaluated as follows.
  • a liquid crystal alignment treatment agent is spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 70 ° C. for 70 seconds, and then baked on a hot plate at 210 ° C. for 10 minutes to form a coating film having a thickness of 100 nm. I let you.
  • the surface of the coating film was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.
  • a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.
  • Prepare two sheets of this substrate spray a 6 ⁇ m spacer on the surface of one liquid crystal alignment film, print a sealant on it, and the other substrate faces the liquid crystal alignment film and the rubbing direction is perpendicular.
  • the sealing agent was cured to produce an empty cell.
  • Liquid crystal MLC-2003 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a twisted nematic liquid crystal cell.
  • a voltage of 4 V was applied to the liquid crystal cell at a temperature of 90 ° C. for 60 ⁇ s, the voltage after 16.67 ms was measured, and how much the voltage could be held was calculated as a voltage holding ratio.
  • the voltage holding ratio was measured using a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica. The evaluation results are shown in Table 2.
  • Printing was performed using the same apparatus as described above. After performing the idling 10 times, the printing machine was stopped for 1 minute and the printing plate was dried. Thereafter, one Cr substrate was printed and fired in the same manner as described above. The fired substrate was observed in the vicinity of the printing edge with a confocal laser microscope ("VL2000" manufactured by Lasertec Co., Ltd.). If there was no foreign material of 3 ⁇ m or less near the printing edge, ⁇ , did. The results are shown in Table 2.
  • Example 2 After cooling 21.00 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 3.87 g of ⁇ BL, 10.21 g of NEP and 15.32 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • the composition of the obtained liquid crystal aligning agent is summarized in Table 1. Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 3 After cooling 18.77 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 7.08 g of ⁇ BL, 4.80 g of NCP and 14.40 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • the composition of the obtained liquid crystal aligning agent is summarized in Table 1. Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 4 After cooling 19.49 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 3.28 g of ⁇ BL, 9.60 g of NCP and 14.40 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • Table 1 shows the composition of the obtained liquid crystal aligning agent. Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 5 After cooling the solution obtained in the same manner as in Synthesis Example 3 to about room temperature, 2.66 g of NEP and 8.00 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • Table 1 shows the composition of the obtained liquid crystal aligning agent.
  • the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 6 After cooling 20 g of the solution obtained in the same manner as in Synthesis Example 7 to about room temperature, 8.8 g of ⁇ BL, 4.8 g of NEP, and 14.4 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • Table 1 shows the composition of the obtained liquid crystal aligning agent. Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 7 After cooling 20 g of the solution obtained in the same manner as in Synthesis Example 7 to about room temperature, 4.0 g of ⁇ BL, 14.4 g of NEP, and 9.6 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • Table 1 shows the composition of the obtained liquid crystal aligning agent. Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 8 20 g of the solution obtained in Synthesis Example 9 and 80 g of the solution obtained in Synthesis Example 11 were stirred at 23 ° C. for 20 hours. After the stirring, a uniform liquid crystal aligning agent was obtained. Table 1 shows the composition of the obtained liquid crystal aligning agent. Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 9 20 g of the solution obtained in Synthesis Example 13 and 80 g of the solution obtained in Synthesis Example 14 were stirred at 23 ° C. for 20 hours. After the stirring, a uniform liquid crystal aligning agent was obtained. Table 1 shows the composition of the obtained liquid crystal aligning agent. Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 10 60 g of the solution obtained in the same manner as in Synthesis Example 16 was cooled to about room temperature, 20 g of DMI and 20 g of EC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • Table 1 shows the composition of the obtained liquid crystal aligning agent.
  • the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 11 60 g of the solution obtained in the same manner as in Synthesis Example 16 was cooled to about room temperature, 10 g of NMP and 30 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • Table 1 shows the composition of the obtained liquid crystal aligning agent.
  • the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 12 The solution obtained in the same manner as in Synthesis Example 18 was cooled to about room temperature, 2.66 g of NEP and 8.00 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • Table 1 shows the composition of the obtained liquid crystal aligning agent.
  • the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • Example 13 The solution obtained in the same manner as in Synthesis Example 5 was cooled to about room temperature, 6.40 g of NCP and 9.60 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
  • Table 1 shows the composition of the obtained liquid crystal aligning agent.
  • the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
  • the liquid crystal display element produced using the liquid crystal aligning agent of the present invention can be a highly reliable liquid crystal display device, such as a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, and an OCB liquid crystal display. It is suitably used for display elements of various systems such as elements, horizontal electric field type liquid crystal display elements, VA liquid crystal display elements. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-146792 filed on June 4, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

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Abstract

Provided are a liquid crystal aligning agent with good whitening and printing performance which generates no aggregate that causes an uneven gap in a liquid crystal panel during printing while maintaining the good electric property of a polyimide alignment film, and a liquid crystal alignment film and a liquid crystal display element which are obtained by using the same. The liquid crystal aligning agent is characterized by containing a resin component containing polyimide obtained by imidizing a polyamic acid obtained by a reaction between a diamine component and a tetracarboxylic dianhydride, and a solvent component containing a pyrrolidone compound composed of N-ethyl-pirrolidone or N-cyclohexyl-2-pyrrolidone, and the liquid crystal alignment film and the liquid crystal display element are obtained by using the same.

Description

液晶配向処理剤及びそれを用いた液晶表示素子Liquid crystal alignment treatment agent and liquid crystal display element using the same
 本発明は、液晶表示素子に用いる液晶配向処理剤、それを用いた液晶配向膜及び液晶表示素子に関するものである。 The present invention relates to a liquid crystal alignment treatment agent used for a liquid crystal display element, a liquid crystal alignment film using the same, and a liquid crystal display element.
 液晶表示素子は、液晶分子が基板に形成された液晶配向膜で挟まれた構造をしており、液晶配向膜によって一定方向に配向した液晶分子が、電圧によって応答することを利用した表示素子である。この液晶配向膜は、一般的には電極付き基板上に形成されたポリイミド膜の表面を、レーヨンやナイロン布によってその表面に圧力をかけてこする、いわゆる“ラビング処理”を行って作製されている。またラビング処理を行わないVA(Vertical Alignmentの略)用配向膜、偏光UVを照射することで膜表面に異方性を付与し液晶を配向させる光配向膜も注目されている。 A liquid crystal display element has a structure in which liquid crystal molecules are sandwiched between liquid crystal alignment films formed on a substrate, and is a display element utilizing the fact that liquid crystal molecules aligned in a certain direction by a liquid crystal alignment film respond with voltage. is there. This liquid crystal alignment film is generally produced by subjecting the surface of a polyimide film formed on a substrate with electrodes to a so-called “rubbing process” in which pressure is applied to the surface with rayon or nylon cloth. . In addition, VA (abbreviation for Vertical Alignment) alignment films that do not undergo rubbing treatment, and photo alignment films that align the liquid crystal by applying anisotropy to the film surface by irradiating polarized UV light have attracted attention.
 電極付き基板上にポリイミド膜を形成させる手段としては、ポリアミック酸などのポリイミド前駆体の溶液を使用して塗膜を作成し、基板上でイミド化させる方法と、あらかじめイミド化させてあるポリイミドを含む溶液を使用する方法とがある。 As a means of forming a polyimide film on a substrate with electrodes, a method of creating a coating film using a solution of a polyimide precursor such as polyamic acid and imidizing on the substrate, and a polyimide that has been imidized in advance are used. And a method using a solution containing the same.
 このうち、ポリイミドを含む溶液を使用する方法は、比較的低温の焼成であっても、液晶配向膜としたときの特性が良好なポリイミド膜を形成させることが可能であるという反面、形成された膜の強度が低く、ラビング処理により膜表面への傷や膜の剥離が起き易いという問題がある。液晶配向膜表面の傷や剥離は、液晶表示素子とした際に表示不良が起こる原因となるため重要な問題である。また、ポリイミドは、ポリアミック酸などと比較して一般的に有機溶媒への溶解性に劣るため、あらかじめイミド化させると、均一な塗膜の形成が困難になる場合があり、更には液晶配向処理剤に常用される溶媒に対して不溶化し、液晶配向処理剤中に含有させることができなくなることも起こりうる。したがって、液晶配向処理剤中に含有させるポリイミドの溶解性も重要となる。また、ポリイミドを含有する液晶配向処理剤を用いると、基板上に印刷するなどの場合、吸湿によりポリイミドを含有するワニスが白化したり、印刷版上でワニスが乾燥して凝集物が発生するという問題が起こりやすかった。 Among them, the method using a polyimide-containing solution was able to form a polyimide film with good characteristics when used as a liquid crystal alignment film, even when firing at a relatively low temperature. There is a problem that the strength of the film is low and the rubbing treatment tends to cause scratches or peeling of the film surface. Scratches and peeling on the surface of the liquid crystal alignment film are important problems because they cause display defects when the liquid crystal display element is formed. In addition, polyimide is generally inferior in solubility in organic solvents compared to polyamic acid and the like, so if imidized in advance, it may be difficult to form a uniform coating film. It may happen that the composition is insolubilized in a solvent commonly used for the agent and cannot be contained in the liquid crystal aligning agent. Therefore, the solubility of the polyimide contained in the liquid crystal aligning agent is also important. In addition, when a liquid crystal aligning agent containing polyimide is used, when printing on a substrate, the varnish containing polyimide is whitened by moisture absorption, or the varnish is dried on the printing plate and aggregates are generated. The problem was easy to happen.
 上記のような課題に対して、液晶配向膜のラビング耐性とポリイミドの溶解性に優れるものとして特定構造を有するジアミン成分を含有する液晶配向処理剤が提案されている(例えは、特許文献1参照)。また、ポリイミドを含有するワニスの白化現象を抑制する方法として、溶媒の50%以上にN-ビニルピロリドンやN-シクロヘキシルピロリドンを用いることが提案されている(例えば、特許文献2参照)。しかしながら、ワニスが乾燥することで生じる凝集物を抑制する液晶配向処理剤は今まで提案されていなかった。 In response to the above problems, a liquid crystal alignment treatment agent containing a diamine component having a specific structure has been proposed as an excellent liquid crystal alignment film rubbing resistance and polyimide solubility (for example, see Patent Document 1). ). As a method for suppressing the whitening phenomenon of varnish containing polyimide, it has been proposed to use N-vinylpyrrolidone or N-cyclohexylpyrrolidone for 50% or more of the solvent (for example, see Patent Document 2). However, a liquid crystal aligning agent that suppresses aggregates produced by drying of the varnish has not been proposed so far.
 ワニスの乾燥による凝集物は、印刷版のへりの部分で発生しやすいという特徴がある。このため、多少の凝集物が発生しても、それが画素内に存在しなければ特に問題とはならなかった。ところが、近年、液晶パネルの高速応答を実現するためにパネルの狭ギャップ化が進んでいる。このように、液晶セルを構成する2枚の基板の間隔が狭くなることで、従来であれば画素内に存在しなければ問題とならなかった上記のような凝集物が、パネルのギャップムラの原因となるケースが増えてきた。 凝集 Agglomerates due to drying of the varnish are characterized by being easily generated at the edge of the printing plate. For this reason, even if some agglomerates are generated, there is no particular problem unless they are present in the pixel. However, in recent years, in order to realize a high-speed response of the liquid crystal panel, the narrowing of the panel is progressing. As described above, since the distance between the two substrates constituting the liquid crystal cell is narrowed, the agglomerates as described above, which were not a problem unless they existed in the pixel in the past, are caused by the gap unevenness of the panel. The number of cases has increased.
国際公開第2006/126555号パンフレットInternational Publication No. 2006/126555 Pamphlet 特開平5-117587号公報Japanese Patent Laid-Open No. 5-117487
 本発明者らが検討した結果、パネルのギャップムラの原因となる凝集物は、ワニスの吸湿による白化現象とは関係なく発生することがわかった。
 本発明は上記の状況を鑑み、ポリイミド配向膜の良好な電気特性を維持しつつ、白化、印刷性が良好でかつ印刷時に液晶パネルのギャップムラの原因となる凝集物を発生させない液晶配向処理剤を提供することを目的とする。更には、白化、印刷性、凝集物などの特性に加えて、液晶配向処理剤の長期保存安定性にも優れ、また、液晶配向膜としたときに、ラビング耐性に優れ、液晶のチルト角が高く、かつ配向性も良好である液晶配向処理剤を提供することを目的とする。
As a result of investigations by the present inventors, it has been found that aggregates that cause panel gap unevenness are generated regardless of the whitening phenomenon caused by moisture absorption of the varnish.
In view of the above situation, the present invention is a liquid crystal alignment treatment agent that maintains good electrical characteristics of a polyimide alignment film, has good whitening and printability, and does not generate aggregates that cause gap unevenness in a liquid crystal panel during printing. The purpose is to provide. Furthermore, in addition to characteristics such as whitening, printability, and aggregates, the liquid crystal alignment treatment agent is also excellent in long-term storage stability, and when used as a liquid crystal alignment film, it has excellent rubbing resistance and a liquid crystal tilt angle. An object of the present invention is to provide a liquid crystal alignment treatment agent that is high and has good alignment properties.
 本発明者は、上記の目的を達成するために鋭意研究を行った結果、本発明を完成するに至った。即ち、本発明は以下を要旨とする。
 1.ジアミン成分とテトラカルボン酸二無水物とを反応させて得られるポリアミック酸をイミド化して得られるポリイミドを含む樹脂成分と、N-エチル-2-ピロリドン又はN-シクロヘキシル-2-ピロリドンからなるピロリドン化合物を含む溶媒成分と、を含有することを特徴とする液晶配向処理剤。
 2.ピロリドン化合物がN-エチル-2-ピロリドンであり、該N-エチル-2-ピロリドンが溶媒成分の5~80質量%である上記1に記載の液晶配向処理剤。
 3.ピロリドン化合物がN-シクロヘキシル-2-ピロリドンであり、該N-シクロヘキシル-2-ピロリドンが溶媒成分の5~40質量%である上記1に記載の液晶配向処理剤。
 4.樹脂成分が1~10質量%含有され、溶媒成分が90~99質量%含有される上記1~3のいずれかに記載の液晶配向処理剤。
 5.ジアミン成分として炭素数2又は3のアルケニル基で置換されたジ置換アミノ基を有するジアミノベンゼンを含む、上記1~4のいずれかに記載の液晶配向処理剤。
 6.炭素数2又は3のアルケニル基で置換されたジ置換アミノ基を有するジアミノベンゼンが、下記式[1]で表されるジアミンである、上記5に記載の液晶配向処理剤。
As a result of intensive studies to achieve the above object, the present inventors have completed the present invention. That is, the gist of the present invention is as follows.
1. A pyrrolidone compound comprising a resin component containing a polyimide obtained by imidizing a polyamic acid obtained by reacting a diamine component with tetracarboxylic dianhydride, and N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone And a solvent component comprising: a liquid crystal aligning agent characterized by comprising:
2. 2. The liquid crystal aligning agent according to 1 above, wherein the pyrrolidone compound is N-ethyl-2-pyrrolidone, and the N-ethyl-2-pyrrolidone is 5 to 80% by mass of the solvent component.
3. 2. The liquid crystal aligning agent according to 1 above, wherein the pyrrolidone compound is N-cyclohexyl-2-pyrrolidone, and the N-cyclohexyl-2-pyrrolidone is 5 to 40% by mass of the solvent component.
4). 4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the resin component is contained in an amount of 1 to 10% by mass and the solvent component is contained in an amount of 90 to 99% by mass.
5). 5. The liquid crystal aligning agent according to any one of the above 1 to 4, comprising diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms as a diamine component.
6). 6. The liquid crystal aligning agent according to 5 above, wherein the diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms is a diamine represented by the following formula [1].
Figure JPOXMLDOC01-appb-C000003
 7.ジアミン成分が、さらに、下記の式で表されるジアミンを含む、上記6に記載の液晶配向処理剤。
Figure JPOXMLDOC01-appb-C000003
7). 7. The liquid crystal aligning agent according to 6 above, wherein the diamine component further contains a diamine represented by the following formula.
Figure JPOXMLDOC01-appb-C000004
(上記式中、kは1~20の整数を表す。)
 8.式[1]で表されるジアミンが、全ジアミン成分中20~90モル%含有される上記6に記載の液晶配向処理剤。
 9.さらに、式[32]で表されるジアミンが、全ジアミン成分中5~40モル%含有される、請求項8に記載の液晶配向処理剤。
 10.上記1~9のいずれかに記載の液晶配向処理剤を電極付き基板上に塗布、焼成して得られる液晶配向膜。
 11.上記10に記載の液晶配向膜を有する液晶表示素子。
Figure JPOXMLDOC01-appb-C000004
(In the above formula, k represents an integer of 1 to 20.)
8). 7. The liquid crystal aligning agent according to 6 above, wherein the diamine represented by the formula [1] is contained in an amount of 20 to 90 mol% in all diamine components.
9. The liquid crystal aligning agent according to claim 8, wherein the diamine represented by the formula [32] is contained in an amount of 5 to 40 mol% in all diamine components.
10. 10. A liquid crystal alignment film obtained by applying and baking the liquid crystal aligning agent according to any one of 1 to 9 above on a substrate with an electrode.
11. 11. A liquid crystal display device having the liquid crystal alignment film as described in 10 above.
 本発明の液晶配向処理剤によれば、電気特性が良好な液晶配向膜が得られ、かつ印刷時に液晶パネルのギャップムラの原因となる凝集物の発生が抑制されるため、狭ギャップの信頼性の高い液晶パネルを歩留り良く生産できる。 According to the liquid crystal alignment treatment agent of the present invention, a liquid crystal alignment film having good electrical characteristics can be obtained, and the occurrence of aggregates that cause gap unevenness of the liquid crystal panel during printing is suppressed, so that reliability of a narrow gap is improved. LCD panels with high yield can be produced with good yield.
 本発明に関して以下に詳細に述べる。
 本発明の液晶配向処理剤は、液晶表示素子に用いられる液晶配向膜を形成する処理剤であり、ジアミン成分とテトラカルボン酸二無水物とを反応させて得られるポリアミック酸をイミド化して得られるポリイミド、及びN-エチル-2-ピロリドンまたはN-シクロへキシル-2-ピロリドンを含有することを特徴とする。本発明に使用されるポリイミドの構造は特に限定されないが、炭素数2又は3のアルケニル基で置換されたジ置換アミノ基を有するジアミノベンゼン(以下、特定ジアミンという。)を含むジアミン成分と、テトラカルボン酸二無水物成分とを反応させて得られるポリアミック酸をイミド化して得られるポリイミドを用いると、有機溶媒に対する溶解性が高くなるために特に好ましい。
The present invention is described in detail below.
The liquid crystal aligning agent of this invention is a processing agent which forms the liquid crystal aligning film used for a liquid crystal display element, and is obtained by imidating the polyamic acid obtained by making a diamine component and tetracarboxylic dianhydride react. It contains polyimide and N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone. Although the structure of the polyimide used in the present invention is not particularly limited, a diamine component containing a diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms (hereinafter referred to as a specific diamine), tetra The use of a polyimide obtained by imidizing a polyamic acid obtained by reacting with a carboxylic dianhydride component is particularly preferred because the solubility in an organic solvent is increased.
[ジアミン成分]
 本発明で用いられるジアミン成分(単に、ジアミンともいう。)は特に限定されない。そのジアミンは一種でも複数種でも併用可能であり、種類は限定されない。ジアミンの種類としては、脂環式ジアミン、芳香族ジアミン類、複素環式ジアミン類または脂肪族ジアミンが例示される。以下にその具体例を示す。
[Diamine component]
The diamine component (also simply referred to as diamine) used in the present invention is not particularly limited. The diamine can be used alone or in combination, and the type is not limited. Examples of the diamine include alicyclic diamines, aromatic diamines, heterocyclic diamines, and aliphatic diamines. Specific examples are shown below.
 脂環式ジアミンの例としては、1,4-ジアミノシクロヘキサン、1,3-ジアミノシクロヘキサン、4,4’-ジアミノジシクロヘキシルメタン、4,4’-ジアミノ-3,3’-ジメチルジシクロヘキシルアミン、およびイソホロンジアミン等が挙げられる。 Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, and isophorone Examples include diamines.
 芳香族ジアミン類の例としては、o-フェニレンジアミン、m-フェニレンジアミン、p-フェニレンジアミン、2,4-ジアミノトルエン、2,5-ジアミノトルエン、3,5-ジアミノトルエン、1,4-ジアミノ-2-メトキシベンゼン、2,5-ジアミノ-p-キシレン、1,3-ジアミノ-4-クロロベンゼン、3,5-ジアミノ安息香酸、1,4-ジアミノ-2,5-ジクロロベンゼン、4,4’-ジアミノ-1,2-ジフェニルエタン、4,4’-ジアミノ-2,2’-ジメチルビベンジル、4,4’-ジアミノジフェニルメタン、3,3’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、4,4’-ジアミノ-3,3’―ジメチルジフェニルメタン、2,2’-ジアミノスチルベン、4,4’-ジアミノスチルベン、4,4’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルスルフィド、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、4,4’-ジアミノベンゾフェノン、1,3-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、3,5-ビス(4-アミノフェノキシ)安息香酸、4,4’-ビス(4-アミノフェノキシ)ビベンジル、2,2-ビス[(4-アミノフェノキシ)メチル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフロロプロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、1,1-ビス(4-アミノフェニル)シクロヘキサン、α、α’-ビス(4-アミノフェニル)-1,4-ジイソプロピルベンゼン、9,9-ビス(4-アミノフェニル)フルオレン、2,2-ビス(3-アミノフェニル)ヘキサフロロプロパン、2,2-ビス(4-アミノフェニル)ヘキサフロロプロパン、4,4’-ジアミノジフェニルアミン、2,4-ジアミノジフェニルアミン、1,8-ジアミノナフタレン、1,5-ジアミノナフタレン、1,5-ジアミノアントラキノン、1,3-ジアミノピレン、1,6-ジアミノピレン、1,8―ジアミノピレン、2,7-ジアミノフルオレン、1,3-ビス(4-アミノフェニル)テトラメチルジシロキサン、ベンジジン、2,2’-ジメチルベンジジン、1,2-ビス(4-アミノフェニル)エタン、1,3-ビス(4-アミノフェニル)プロパン、1,4-ビス(4-アミノフェニル)ブタン、1,5-ビス(4-アミノフェニル)ペンタン、1,6-ビス(4-アミノフェニル)ヘキサン、1,7-ビス(4-アミノフェニル)ヘプタン、1,8-ビス(4-アミノフェニル)オクタン、1,9-ビス(4-アミノフェニル)ノナン、1,10-ビス(4-アミノフェニル)デカン、1,3-ビス(4-アミノフェノキシ)プロパン、1,4-ビス(4-アミノフェノキシ)ブタン、1,5-ビス(4-アミノフェノキシ)ペンタン、1,6-ビス(4-アミノフェノキシ)ヘキサン、1,7-ビス(4-アミノフェノキシ)ヘプタン、1,8-ビス(4-アミノフェノキシ)オクタン、1,9-ビス(4-アミノフェノキシ)ノナン、1,10-ビス(4-アミノフェノキシ)デカン、ジ(4-アミノフェニル)プロパン-1,3-ジオエート、ジ(4-アミノフェニル)ブタン-1,4-ジオエート、ジ(4-アミノフェニル)ペンタン-1,5-ジオエート、ジ(4-アミノフェニル)ヘキサン-1,6-ジオエート、ジ(4-アミノフェニル)ヘプタン-1,7-ジオエート、ジ(4-アミノフェニル)オクタン-1,8-ジオエート、ジ(4-アミノフェニル)ノナン-1,9-ジオエート、ジ(4-アミノフェニル)デカン-1,10-ジオエート、1,3-ビス〔4-(4-アミノフェノキシ)フェノキシ〕プロパン、1,4-ビス〔4-(4-アミノフェノキシ)フェノキシ〕ブタン、1,5-ビス〔4-(4-アミノフェノキシ)フェノキシ〕ペンタン、1,6-ビス〔4-(4-アミノフェノキシ)フェノキシ〕ヘキサン、1,7-ビス〔4-(4-アミノフェノキシ)フェノキシ〕ヘプタン、1,8-ビス〔4-(4-アミノフェノキシ)フェノキシ〕オクタン、1,9-ビス〔4-(4-アミノフェノキシ)フェノキシ〕ノナン、1,10-ビス〔4-(4-アミノフェノキシ)フェノキシ〕デカンなどが挙げられる。 Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamino-3,3′-dimethyldiphenylmethane, 2,2′-diaminostilbene, 4,4′-dia Nostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4- Aminophenoxy) benzoic acid, 4,4'-bis (4-aminophenoxy) bibenzyl, 2,2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4 (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α'-bis (4-aminophenyl)- 1,4-diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) te Lamethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-amino) Phenyl) butane, 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4 -Aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophen Xyl) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, di (4-aminophenyl) Propane-1,3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) hexane-1,6 -Geoate, di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di (4-aminophenyl) nonane-1,9-dioate, di ( 4-aminophenyl) decane-1,10-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4 -Aminophenoxy) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-bis [ 4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] nonane, 1, And 10-bis [4- (4-aminophenoxy) phenoxy] decane.
 複素環式ジアミン類の例としては、2,6-ジアミノピリジン、2,4-ジアミノピリジン、2,4-ジアミノ-1,3,5-トリアジン、2,7-ジアミノジベンゾフラン、3,6-ジアミノカルバゾール、2,4-ジアミノ-6-イソプロピル-1,3,5-トリアジン、2,5-ビス(4-アミノフェニル)-1,3,4-オキサジアゾールなどが挙げられる。 Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diamino Examples thereof include carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole.
 脂肪族ジアミンの例としては、1,2-ジアミノエタン、1,3-ジアミノプロパン、1,4-ジアミノブタン、1,5-ジアミノペンタン、1,6-ジアミノヘキサン、1,7-ジアミノヘプタン、1,8-ジアミノオクタン、1,9-ジアミノノナン、1,10-ジアミノデカン、1,3-ジアミノ-2,2-ジメチルプロパン、1,6-ジアミノ-2,5-ジメチルヘキサン、1,7-ジアミノ-2,5-ジメチルヘプタン、1,7-ジアミノ-4,4-ジメチルヘプタン、1,7-ジアミノ-3-メチルヘプタン、1,9-ジアミノ-5-メチルヘプタン、1,12-ジアミノドデカン、1,18-ジアミノオクタデカン、1,2-ビス(3-アミノプロポキシ)エタンなどが挙げられる。 Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diaminododecane 1,18-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane and the like.
 本発明では、ジアミンとして、ポリイミドの有機溶媒への溶解性を高めるために、炭素数2又は3のアルケニル基で置換されたジ置換アミノ基を有するジアミノベンゼン(以下、特定ジアミンともいう)が好適に用いられる。特に、下記式[1]で表される、2-プロペニル基(以下、アリル基ともいう)で置換されたジ置換アミノ基を有するジアミノベンゼンが好ましい。 In the present invention, a diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms (hereinafter also referred to as a specific diamine) is preferable as the diamine in order to increase the solubility of polyimide in an organic solvent. Used for. In particular, diaminobenzene having a disubstituted amino group substituted by a 2-propenyl group (hereinafter also referred to as an allyl group) represented by the following formula [1] is preferable.
Figure JPOXMLDOC01-appb-C000005
 式[1]で表されるジアミンにおいて、ベンゼン環上の各置換基の位置は特に限定されないが、2つのアミノ基の位置関係はメタまたはパラが好ましい。以下にこのジアミンのより好ましい具体例を挙げる。
Figure JPOXMLDOC01-appb-C000005
In the diamine represented by the formula [1], the position of each substituent on the benzene ring is not particularly limited, but the positional relationship between the two amino groups is preferably meta or para. The more preferable specific example of this diamine is given below.
Figure JPOXMLDOC01-appb-C000006
 前記式[2]は、2,4-ジアミノ-N,N-ジアリルアニリンであり、前記式[3]は、3,5-ジアミノ-N,N-ジアリルアニリンであり、前記式[4]は、2,5-ジアミノ-N,N-ジアリルアニリンである。前記ジアミノベンゼンは、前記[2]、[3]及び[4]からなる群から選ばれる少なくとも一種であるのがより好ましい。なかでも、前記ジアミノベンゼンは、2,4-ジアミノ-N,N-ジアリルアニリンであるのが特に好ましい。
Figure JPOXMLDOC01-appb-C000006
The formula [2] is 2,4-diamino-N, N-diallylaniline, the formula [3] is 3,5-diamino-N, N-diallylaniline, and the formula [4] is 2,5-diamino-N, N-diallylaniline. More preferably, the diaminobenzene is at least one selected from the group consisting of [2], [3] and [4]. Among these, the diaminobenzene is particularly preferably 2,4-diamino-N, N-diallylaniline.
 本発明において、ポリイミドの原料となるジアミン成分は、特定ジアミンのみであってもよく、或いは、特定ジアミンとその他のジアミンの1種または2種以上とを組み合わせでもよい。ポリイミドを得るためのジアミン成分に特定ジアミンを含有させることで、ポリイミドの有機溶媒に対する溶解性が高くなる。さらに、塗膜をラビング処理する際の膜表面への傷や膜の剥離といった問題が改善される。 In the present invention, the diamine component used as a raw material for polyimide may be only a specific diamine, or a combination of a specific diamine and one or more of other diamines. By making a diamine component for obtaining a polyimide contain a specific diamine, the solubility of the polyimide in an organic solvent is increased. Furthermore, problems such as scratches on the film surface and film peeling when the coating film is rubbed are improved.
 ジアミン成分中における特定ジアミンの含有量は、20モル(mol)%以上含有することが好ましく、より好ましくは40モル%以上であり、特には50モル%以上である。ジアミン成分中の特定ジアミン含有比率が高くなるほど、ラビング処理時の配向膜表面の傷や膜の剥離を抑制する効果が高くなる。また、得られるポリイミドの有機溶媒に対する溶解性も高くなる。他方、ジアミン成分が特定ジアミンのみでも良いが、特定ジアミン以外のジアミンを併用することで、液晶配向膜に必要とされるその他の特性を付与できるので好ましい。そのため、特定ジアミンの含有量は90モル%以下がより好ましい。特に特定ジアミンと4-アミノベンジルアミン、3-アミノベンジルアミン、または4-アミノフェネチルアミンを用いると、ポリイミドの有機溶媒への溶解性が高くなり、さらに液晶配向性に優れた液晶配向処理剤が得られるため特に好ましい。4-アミノベンジルアミン、3-アミノベンジルアミン、または4-アミノフェネチルアミンのジアミン成分中の好ましい含有量は10モル%~50モル%である。 The content of the specific diamine in the diamine component is preferably 20 mol (mol)% or more, more preferably 40 mol% or more, particularly 50 mol% or more. The higher the specific diamine content ratio in the diamine component, the higher the effect of suppressing scratches on the alignment film surface and the film peeling during the rubbing treatment. Moreover, the solubility with respect to the organic solvent of the polyimide obtained also becomes high. On the other hand, the diamine component may be only the specific diamine, but it is preferable to use a diamine other than the specific diamine because other characteristics required for the liquid crystal alignment film can be imparted. Therefore, the content of the specific diamine is more preferably 90 mol% or less. In particular, when a specific diamine and 4-aminobenzylamine, 3-aminobenzylamine, or 4-aminophenethylamine are used, the solubility of polyimide in an organic solvent increases, and a liquid crystal alignment treatment agent with excellent liquid crystal alignment is obtained. This is particularly preferable. The preferred content of 4-aminobenzylamine, 3-aminobenzylamine, or 4-aminophenethylamine in the diamine component is 10 mol% to 50 mol%.
 また、液晶のプレチルト角を高める為に、特定の置換基を有するジアミンを組み合わせて使用することもできる。液晶のプレチルト角を高めることができる置換基としては、長鎖アルキル基、パーフルオロアルキル基、芳香族環状基、脂肪族環状基、これらを組み合わせた置換基またはステロイド骨格基などが好ましい。以下にかかる置換基を有するジアミンの具体例を挙げるが、これに限定されるものではない。なお、以下に例示する構造においてjは5~20、好ましくは9~17の整数を表し、kは1~20、好ましくは4~15の整数を表す。 Also, in order to increase the pretilt angle of the liquid crystal, a diamine having a specific substituent can be used in combination. As the substituent capable of increasing the pretilt angle of the liquid crystal, a long-chain alkyl group, a perfluoroalkyl group, an aromatic cyclic group, an aliphatic cyclic group, a combination of these, or a steroid skeleton group is preferable. Although the specific example of the diamine which has the said substituent is given to the following, it is not limited to this. In the structures exemplified below, j represents an integer of 5 to 20, preferably 9 to 17, and k represents an integer of 1 to 20, preferably 4 to 15.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
 上記のジアミンの内、式〔5〕、〔32〕のジアミンは液晶配向性に優れるため好ましい。式〔12〕~〔19〕のジアミンは、チルト発現能が非常に高いため、OCB(Optically Compensated Bend)用配向膜、VA(Vertical Alignment)用配向膜に好適に用いられる。好ましい1例として、TN(Twisted Nematic)用配向膜(プレチルトが3~5°)では、式〔5〕または〔32〕のジアミンをジアミン成分中に5~40モル%、好ましくは10~30モル%、OCB、VA用配向膜(プレチルト10~90°)では、式〔12〕~〔19〕のジアミンをジアミン成分中に5~60モル%、好ましく10~40モル%は含有すると良いが、これに限定されない。 Among the above diamines, the diamines of the formulas [5] and [32] are preferable because of excellent liquid crystal alignment. The diamines represented by the formulas [12] to [19] have a very high tilting ability, and are therefore suitably used for OCB (Optically mp Compensated Bend) alignment films and VA (Vertical Alignment) alignment films. As a preferred example, in a TN (Twisted Nematic) alignment film (pretilt 3 to 5 °), the diamine of formula [5] or [32] is 5 to 40 mol%, preferably 10 to 30 mol in the diamine component. %, OCB, VA alignment film (pretilt 10-90 °), the diamine of formula [12]-[19] may be contained in the diamine component in an amount of 5-60 mol%, preferably 10-40 mol%. It is not limited to this.
 上記のジアミンの中でも、特に、式〔32〕のジアミンは、チルト角が高く、かつ、前記の特定ジアミンと組み合わせて用いた場合には、ラビング条件が弱い場合でも液晶配向性に優れるために好ましい。更には、上記のようなジアミンが液晶のプレチルト角を高める効果は、液晶配向処理剤中にN-エチル-2-ピロリドンまたはN-シクロへキシル-2-ピロリドンを多く含有する場合に弱まる傾向にあるが、式〔32〕のジアミンはこのような影響を受けにくいという特徴があり、本発明の液晶配向処理剤に含有するポリイミドのジアミン成分として好適である。 Among the above diamines, the diamine of formula [32] is particularly preferable because it has a high tilt angle and is excellent in liquid crystal alignment even when the rubbing conditions are weak when used in combination with the specific diamine. . Furthermore, the effect of increasing the pretilt angle of the liquid crystal as described above tends to be weakened when the liquid crystal aligning agent contains a large amount of N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone. However, the diamine of the formula [32] has a characteristic that it is not easily affected by the above, and is suitable as a diamine component of the polyimide contained in the liquid crystal aligning agent of the present invention.
[テトラカルボン酸二無水物成分]
 本発明において、ポリイミドの原料となるテトラカルボン酸二無水物成分は、1種類のテトラカルボン酸二無水物であってもよく、2種類以上のテトラカルボン酸二無水物を混合して用いても良い。
 しかしながら、高イミド化率のポリイミドであっても比較的溶解性の高いポリイミドが得やすい点、及び液晶セルの電圧保持率を高くできる点などから、脂環式構造又は脂肪族構造を有するテトラカルボン酸二無水物を用いることが好ましい。
[Tetracarboxylic dianhydride component]
In the present invention, the tetracarboxylic dianhydride component used as a raw material for polyimide may be one type of tetracarboxylic dianhydride or a mixture of two or more types of tetracarboxylic dianhydrides. good.
However, even if it is a polyimide with a high imidization rate, a tetracarboxylic acid having an alicyclic structure or an aliphatic structure can be obtained because it is easy to obtain a polyimide with relatively high solubility and the voltage holding ratio of the liquid crystal cell can be increased. It is preferable to use an acid dianhydride.
 脂環式構造又は脂肪族構造を有するテトラカルボン酸二無水物としては、1,2,3,4-シクロブタンテトラカルボン酸二無水物、1,2-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸二無水物、1,3-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸二無水物、1,2,3,4-テトラメチル-1,2,3,4-シクロブタンテトラカルボン酸二無水物、1,2,3,4-シクロペンタンテトラカルボン酸二無水物、2,3,4,5-テトラヒドロフランテトラカルボン酸二無水物、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物、3,4-ジカルボキシ-1-シクロヘキシルコハク酸二無水物、3,4-ジカルボキシ-1,2,3,4-テトラヒドロ-1-ナフタレンコハク酸二無水物、1,2,3,4-ブタンテトラカルボン酸二無水物、ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸二無水物、3,3’,4,4’-ジシクロヘキシルテトラカルボン酸二無水物、2,3,5-トリカルボキシシクロペンチル酢酸二無水物、シス-3,7-ジブチルシクロオクタ-1,5-ジエン-1,2,5,6-テトラカルボン酸二無水物、トリシクロ[4.2.1.02,5]ノナン-3,4,7,8-テトラカルボン酸-3,4:7,8-二無水物、ヘキサシクロ[6.6.0.12,7.03,6.19,14.010,13]ヘキサデカン-4,5,11,12-テトラカルボン酸-4,5:11,12-二無水物などが挙げられる。 Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride , Tricyclo [4.2.1.0 2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo [6.6.0.1 2 , 7 . 0 3,6 . 1 9,14 . 0 10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-like dianhydride.
 脂環式構造又は脂肪族構造を有するテトラカルボン酸二無水物としては、特に1,2,3,4-シクロブタンテトラカルボン酸二無水物、3,4-ジカルボキシ-1,2,3,4-テトラヒドロ-1-ナフタレンコハク酸二無水物、または1,2,3,4-ブタンテトラカルボン酸二無水物を用いると液晶配向性に優れた配向膜が得られるために特に好ましい。 Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4 Use of tetrahydro-1-naphthalene succinic dianhydride or 1,2,3,4-butanetetracarboxylic dianhydride is particularly preferable because an alignment film excellent in liquid crystal alignment can be obtained.
 更には、脂環式構造又は脂肪族構造を有するテトラカルボン酸二無水物に加えて芳香族テトラカルボン酸二無水物を併用すると、液晶配向性が向上し、かつ液晶セルの蓄積電荷を低減させることができるので好ましい。芳香族テトラカルボン酸二無水物としては、ピロメリット酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、2,2’,3,3’-ビフェニルテトラカルボン酸二無水物、2,3,3’,4-ビフェニルテトラカルボン酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、2,3,3’,4-ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、ビス(3,4-ジカルボキシフェニル)スルホン二無水物、1,2,5,6-ナフタレンテトラカルボン酸二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物などが挙げられる。 Furthermore, when an aromatic tetracarboxylic dianhydride is used in combination with a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, the liquid crystal alignment is improved and the accumulated charge of the liquid crystal cell is reduced. This is preferable. Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4-benzophenonetetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride And 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.
 芳香族テトラカルボン酸二無水物としては、中でもピロメリット酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、または1,4,5,8-ナフタレンテトラカルボン酸二無水物が特に好ましい。 Aromatic tetracarboxylic dianhydrides include, among others, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Or 1,4,5,8-naphthalenetetracarboxylic dianhydride is particularly preferred.
 ポリイミドの溶解性、液晶の配向性、電圧保持率、蓄積電荷などの各特性のバランスを考慮するならば、脂環式構造又は脂肪族構造を有するテトラカルボン酸二無水物と、芳香族テトラカルボン酸二無水物との比率は、前者/後者のモル比で90/10~50/50が好ましく、より好ましくは80/20~60/40である。 Considering the balance of properties such as polyimide solubility, liquid crystal orientation, voltage holding ratio, accumulated charge, tetracarboxylic dianhydride having an alicyclic structure or aliphatic structure, and aromatic tetracarboxylic The ratio with the acid dianhydride is preferably 90/10 to 50/50, more preferably 80/20 to 60/40, as the molar ratio of the former / the latter.
[ポリイミド及びその製造方法]
 本発明の液晶配向処理剤に用いられるポリイミドは、上記したジアミン成分とテトラカルボン酸二無水物成分とを反応させて得られるポリアミック酸をイミド化したポリイミドである。ここで、ポリアミック酸は、テトラカルボン酸二無水物成分とジアミン成分とを有機溶媒中で混合し、反応させることで得ることができる。
[Polyimide and its production method]
The polyimide used for the liquid-crystal aligning agent of this invention is a polyimide which imidized the polyamic acid obtained by making the above-mentioned diamine component and the tetracarboxylic dianhydride component react. Here, the polyamic acid can be obtained by mixing and reacting a tetracarboxylic dianhydride component and a diamine component in an organic solvent.
 テトラカルボン酸二無水物成分とジアミン成分とを有機溶媒中で混合させる方法としては、ジアミン成分を有機溶媒に分散あるいは溶解させた溶液を攪拌させ、テトラカルボン酸二無水物成分をそのまま、または有機溶媒に分散あるいは溶解させて添加する方法、逆にテトラカルボン酸二無水物成分を有機溶媒に分散あるいは溶解させた溶液にジアミン成分を添加する方法、テトラカルボン酸二無水物成分とジアミン成分とを交互に添加する方法などが挙げられる。また、テトラカルボン酸二無水物成分またはジアミン成分が複数種の化合物からなる場合は、これら複数種の成分をあらかじめ混合した状態で重合反応させても良く、個別に順次重合反応させても良い。 As a method of mixing the tetracarboxylic dianhydride component and the diamine component in an organic solvent, a solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent. A method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component. The method of adding alternately etc. are mentioned. When the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of types of compounds, the plurality of types of components may be preliminarily mixed, or may be individually polymerized sequentially.
 テトラカルボン酸二無水物成分とジアミン成分を有機溶剤中で重合反応させる際の温度は、通常0~150℃、好ましくは5~100℃、より好ましくは10~80℃である。温度が高い方が重合反応は早く終了するが、高すぎると高分子量の重合体が得られない場合がある。 The temperature at which the tetracarboxylic dianhydride component and the diamine component are subjected to a polymerization reaction in an organic solvent is usually 0 to 150 ° C., preferably 5 to 100 ° C., more preferably 10 to 80 ° C. When the temperature is higher, the polymerization reaction is completed earlier, but when it is too high, a high molecular weight polymer may not be obtained.
 また、重合反応は任意の濃度で行うことができるが、濃度が低すぎると高分子量の重合体を得ることが難しくなり、濃度が高すぎると反応液の粘性が高くなり過ぎて均一な攪拌が困難となるので、テトラカルボン酸二無水物成分とジアミン成分との合計量の濃度が、好ましくは1~50質量%、より好ましくは5~30質量%である。重合反応初期は高濃度で行い、その後、有機溶媒を追加しても構わない。 The polymerization reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. Since it becomes difficult, the concentration of the total amount of the tetracarboxylic dianhydride component and the diamine component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the polymerization reaction may be performed at a high concentration, and then an organic solvent may be added.
 上記反応の際に用いられる有機溶媒は、生成したポリアミック酸が溶解するものであれば特に限定されないが、本液晶配向処理剤に必須成分であるN-エチル-2-ピロリドンもしくはN-シクロヘキシル-2-ピロリドン、もしくはその他の溶媒を用いてもよい。その具体例を挙げると、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ-ブチロラクトン、1,3-ジメチルイミダゾリジノン等を挙げることができる。これらは単独でも、また混合して使用してもよい。さらに、ポリアミック酸を溶解させない溶媒であっても、生成したポリアミック酸が析出しない範囲で、上記溶媒に混合して使用してもよい。また、有機溶媒中の水分は重合反応を阻害し、さらには生成したポリアミック酸を加水分解させる原因となるので、有機溶媒はなるべく脱水乾燥させたものを用いることが好ましい。 The organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid can be dissolved, but N-ethyl-2-pyrrolidone or N-cyclohexyl-2 which is an essential component for the liquid crystal aligning agent. -Pyrrolidone or other solvents may be used. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethylimidazolidinone and the like can be mentioned. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyamic acid, it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate. In addition, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
 ポリアミック酸の重合反応に用いるテトラカルボン酸二無水物成分とジアミン成分の比率は、モル比で1:0.8~1:1.2であることが好ましく、このモル比が1:1に近いほど得られるポリアミック酸の分子量は大きくなる。このポリアミック酸の分子量を制御することで、イミド化後に得られるポリイミドの分子量を調整することができる。 The ratio of the tetracarboxylic dianhydride component and the diamine component used for the polymerization reaction of the polyamic acid is preferably 1: 0.8 to 1: 1.2 in molar ratio, and this molar ratio is close to 1: 1. The molecular weight of the polyamic acid obtained increases. By controlling the molecular weight of this polyamic acid, the molecular weight of the polyimide obtained after imidation can be adjusted.
 本発明の液晶配向処理剤に含有されるポリイミドの分子量は特に限定されないが、塗膜の強度と液晶配向処理剤としての取り扱いのしやすさの観点から、重量平均分子量で2,000~200,000が好ましく、より好ましくは5,000~50,000である。
 上記のようにして得られたポリアミック酸のイミド化は、有機溶媒中において、塩基性触媒と酸無水物の存在下で1~100時間攪拌することにより可能である。
The molecular weight of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited, but in terms of the strength of the coating film and the ease of handling as a liquid crystal aligning agent, the weight average molecular weight is 2,000 to 200, 000 is preferred, more preferably 5,000 to 50,000.
The imidization of the polyamic acid obtained as described above can be performed by stirring in an organic solvent for 1 to 100 hours in the presence of a basic catalyst and an acid anhydride.
 塩基性触媒としてはピリジン、トリエチルアミン、トリメチルアミン、トリブチルアミン、トリオクチルアミン等を挙げることができる。中でもピリジンは、反応を進行させるのに適度な塩基性を持つので好ましい。また、酸無水物としては無水酢酸、無水トリメリット酸、無水ピロメリット酸などを挙げることができる。中でも無水酢酸は、イミド化終了後に、得られたポリイミドの精製が容易となるので好ましい。有機溶媒としては前述したポリアミック酸重合反応時に用いる溶媒を使用することができる。 Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferable because the obtained polyimide can be easily purified after imidization. As an organic solvent, the solvent used at the time of the polyamic acid polymerization reaction mentioned above can be used.
 ポリイミドのイミド化率は、触媒量と反応温度、反応時間を調節することにより制御することができる。このときの塩基性触媒の量は、原料のポリアミック酸の有するアミック酸基の0.2~10倍モルが好ましく、より好ましくは0.5~5倍モルである。また、酸無水物の量は、原料のポリアミック酸の有するアミック酸基の1~30倍モルが好ましく、より好ましくは1~10倍モルである。反応温度は-20~250℃が好ましく、より好ましくは0~180℃である。 The imidation ratio of polyimide can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. The amount of the basic catalyst at this time is preferably 0.2 to 10 times mol, more preferably 0.5 to 5 times mol of the amic acid group of the starting polyamic acid. The amount of the acid anhydride is preferably 1 to 30 times mol, more preferably 1 to 10 times mol of the amic acid group of the starting polyamic acid. The reaction temperature is preferably −20 to 250 ° C., more preferably 0 to 180 ° C.
 本発明の液晶配向処理剤に含有されるポリイミドのイミド化率は特に限定されないが、電気特性を考慮すると40%以上であることが好ましく、高い電圧保持率を得るためには60%以上がより好ましく、さらに好ましくは80%以上である。
 このようにして得られたポリイミドの溶液内には、添加した触媒などが残存しているので、特定ポリイミドを回収・洗浄してから本発明の液晶配向処理剤に用いることが好ましい。
Although the imidation ratio of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited, it is preferably 40% or more in consideration of electrical characteristics, and 60% or more is more preferable in order to obtain a high voltage holding ratio. More preferably, it is 80% or more.
Since the added catalyst or the like remains in the polyimide solution thus obtained, it is preferable to use the liquid crystal alignment treatment agent of the present invention after recovering and washing the specific polyimide.
 ポリイミドの回収は、イミド化後の溶液を攪拌している貧溶媒に投入し、ポリイミドを析出させた後にろ過することで可能である。このときの貧溶媒としてはメタノール、アセトン、ヘキサン、ブチルセロソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼンなどを挙げることができる。回収したポリイミドの洗浄も、この貧溶媒で行うことができる。
 このようにして回収・洗浄したポリイミドは、常圧あるいは減圧下で、常温あるいは加熱乾燥して粉末とすることができる
The polyimide can be recovered by putting the solution after imidization into a poor solvent that is being stirred and precipitating the polyimide, followed by filtration. Examples of the poor solvent at this time include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. The recovered polyimide can also be washed with this poor solvent.
The polyimide recovered and washed in this way can be powdered by drying at room temperature or under normal pressure or reduced pressure.
[液晶配向処理剤]
 本発明の液晶配向処理剤は、前記したポリイミドを樹脂成分として、N-エチル-2-ピロリドン又はN-シクロヘキシル-2-ピロリドンを溶媒成分として含有する溶液である。本発明では、溶媒成分として、N-エチル-2-ピロリドン又はN-シクロヘキシル-2-ピロリドンを使用することが必要であり、ピロリドン化合物でも、例えば、N-メチル-2-ピロリドンを使用した場合には、後記する比較例に示されるように、塗膜の白化や印刷エッジ付近の膜厚のムラが発生する場合があり、本発明の目的を達成し難い。
[Liquid crystal aligning agent]
The liquid crystal alignment treatment agent of the present invention is a solution containing the above polyimide as a resin component and N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone as a solvent component. In the present invention, it is necessary to use N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone as a solvent component. Even when a pyrrolidone compound is used, for example, when N-methyl-2-pyrrolidone is used. As shown in a comparative example described later, whitening of the coating film and unevenness of the film thickness in the vicinity of the printing edge may occur, and it is difficult to achieve the object of the present invention.
 液晶配向処理剤を構成する溶液の濃度は、形成する液晶配向膜の厚みの設定によって適宜変更することができるが、樹脂成分等の不揮発成分1質量部に対して溶媒成分が好ましくは9~99質量部、より好ましくは11.5~49質量部である。溶媒成分が99質量部よりも多いと均一で欠陥のない塗膜を形成させることが困難となり、9質量部未満であると溶液の保存安定性が悪くなる場合がある。本発明の液晶配向処理剤における、溶媒成分の含有量は、液晶配向処理剤全体の好ましくは90~99質量%、より好ましくは92~98質量部である。 The concentration of the solution constituting the liquid crystal alignment treatment agent can be appropriately changed by setting the thickness of the liquid crystal alignment film to be formed. The solvent component is preferably 9 to 99 with respect to 1 part by mass of the nonvolatile component such as the resin component. Part by mass, more preferably 11.5 to 49 parts by mass. When the solvent component is more than 99 parts by mass, it is difficult to form a uniform and defect-free coating film, and when it is less than 9 parts by mass, the storage stability of the solution may be deteriorated. The content of the solvent component in the liquid crystal aligning agent of the present invention is preferably 90 to 99% by mass, more preferably 92 to 98 parts by mass with respect to the entire liquid crystal aligning agent.
 本発明の液晶配向処理剤における樹脂成分は、構造の異なる2種類以上のポリイミドの混合物であってもよい。更には、電気特性を損なわず、ワニスの保存安定性を低下させず、そして、印刷時に液晶パネルのギャップムラの原因となる凝集物を発生させない程度に、ポリアミック酸や他の種類の樹脂を併用してもよい。かかる併用する樹脂の使用量は、ポリイミドの1質量部に対して、0.05~7質量部が好ましく、より好ましくは0.1~4質量部である。本発明の液晶配向処理剤における、樹脂成分の好ましい含有量は、液晶配向処理剤全体の好ましくは1~10質量%、より好ましくは2~8質量%である。 The resin component in the liquid crystal aligning agent of the present invention may be a mixture of two or more types of polyimides having different structures. In addition, polyamic acid and other types of resins are used together to the extent that electrical properties are not impaired, storage stability of the varnish is not deteriorated, and aggregates that cause gap unevenness of the liquid crystal panel are not generated during printing. May be. The amount of the resin used in combination is preferably 0.05 to 7 parts by mass, more preferably 0.1 to 4 parts by mass with respect to 1 part by mass of polyimide. The content of the resin component in the liquid crystal aligning agent of the present invention is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on the entire liquid crystal aligning agent.
 本発明の液晶配向処理剤における溶媒成分は、N-エチル-2-ピロリドンのみであっても構わないが、樹脂成分の溶解性確保や基板への塗布性を制御する為に他の溶媒を含有することが好ましい。一方、N-シクロヘキシル-2-ピロリドンの場合は、N-エチル-2-ピロリドンよりもポリイミドの溶解性に劣るため、液晶配向処理剤の長期保存安定性の観点から、その含有量は溶媒成分全体の40質量%以下とし、その他の溶媒成分として樹脂成分の溶解性確保のための溶媒を含有することが好ましい。 The solvent component in the liquid crystal aligning agent of the present invention may be only N-ethyl-2-pyrrolidone, but contains other solvents in order to ensure the solubility of the resin component and to control the coating property to the substrate. It is preferable to do. On the other hand, in the case of N-cyclohexyl-2-pyrrolidone, since the solubility of polyimide is inferior to that of N-ethyl-2-pyrrolidone, its content is determined from the viewpoint of long-term storage stability of the liquid crystal aligning agent. It is preferable to contain a solvent for ensuring the solubility of the resin component as the other solvent component.
 樹脂成分の溶解性確保のための溶媒としては、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-メチルカプロラクタム、2-ピロリドン、N-ビニルピロリドン、ジメチルスルホキシド、テトラメチル尿素、ジメチルスルホン、ヘキサメチルスルホキシド、γ-ブチロラクトン、1,3-ジメチル-イミダゾリジノンなどが挙げられる。なかでもN-メチル-2-ピロリドン、1,3-ジメチルイミダゾリジノン、γ-ブチロラクトンはポリイミドの溶解性が高いために好適に用いられる。またγ-ブチロラクトンは白化を抑制する効果があるために好適に用いられる。 Solvents for ensuring the solubility of the resin component include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinylpyrrolidone, dimethyl Examples thereof include sulfoxide, tetramethylurea, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone. Among these, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, and γ-butyrolactone are preferably used because of the high solubility of polyimide. Γ-butyrolactone is preferably used because it has an effect of suppressing whitening.
 基板への塗布性を制御する為の溶媒としては、低表面張力を有する溶媒が挙げられる。溶媒成分に低表面張力を有する溶媒を適度に混合させることにより、基板への塗布時に塗膜均一性を向上させることができる。 Examples of the solvent for controlling the coating property to the substrate include a solvent having a low surface tension. By appropriately mixing a solvent having a low surface tension with the solvent component, the coating film uniformity can be improved during application to the substrate.
 低表面張力を有する溶媒としては、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、エチレングリコール、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、1-ブトキシ-2-プロパノール、1-フェノキシ-2-プロパノール、ジエチレングリコールジエチルエーテル、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、ジプロピレングリコールモノメチルエーテル、プロピレングリコール-1-モノメチルエーテル-2-アセテート、プロピレングリコール-1-モノエチルエーテル-2-アセテート、ジプロピレングリコール、2-(2-エトキシプロポキシ)プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸n-プロピルエステル、乳酸n-ブチルエステル、乳酸イソアミルエステルなどが挙げられる。この中でも基板への塗布性の観点から、ブチルセロソルブ、エチルカルビトール、ジプロピレングリコールモノメチルエーテル、またはジエチレングリコールジエチルエーテルが特に好ましい。 Solvents having low surface tension include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, diethylene glycol diethyl ether, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-mono Ethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, ethyl lactate Le, lactate n- propyl ester, lactate n- butyl ester, and the like lactic isoamyl ester. Among these, butyl cellosolve, ethyl carbitol, dipropylene glycol monomethyl ether, or diethylene glycol diethyl ether is particularly preferable from the viewpoint of applicability to the substrate.
 溶媒成分に上記した他の溶媒を含有させる場合、N-エチル-2-ピロリドン又はN-シクロヘキシル-2-ピロリドンの量は、樹脂成分の1質量部に対して0.5質量部以上である場合に凝集物の発生を抑制する改善効果がみられ、好ましくは1質量部以上80重量部以下であり、より好ましくは2質量部以上70重量部以下である。特にN-エチル-2-ピロリドンは樹脂成分の溶解性に優れるためワニスの保存安定性に優れ、かつ吸湿してもワニスの白化が起きにくいため好適に用いられる。本発明では、N-エチル-2-ピロリドンは、溶媒成分全体の5~80質量%が好ましく、より好ましくは10~70質量%である。一方、N-シクロヘキシル-2-ピロリドンは、溶媒成分全体の5~40質量%が好ましく、より好ましくは10~30質量%である。また、前記したように、液晶のプレチルト角を高めるジアミンの効果を弱めないといった観点に主眼を置くならば、N-エチル-2-ピロリドンも溶媒成分全体の40質量%以下とすることが好ましい。 When the solvent component contains the above-mentioned other solvent, the amount of N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone is 0.5 parts by mass or more with respect to 1 part by mass of the resin component The improvement effect which suppresses generation | occurrence | production of the aggregate is seen, Preferably it is 1 to 80 weight part, More preferably, it is 2 to 70 weight part. In particular, N-ethyl-2-pyrrolidone is preferably used because it has excellent solubility of the resin component and thus excellent storage stability of the varnish, and varnish is not easily whitened even when moisture is absorbed. In the present invention, N-ethyl-2-pyrrolidone is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the entire solvent component. On the other hand, N-cyclohexyl-2-pyrrolidone is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the entire solvent component. Further, as described above, from the viewpoint of not reducing the effect of the diamine that increases the pretilt angle of the liquid crystal, N-ethyl-2-pyrrolidone is preferably 40% by mass or less of the total solvent component.
 また、樹脂成分の溶解性確保のための溶媒は、量が多すぎるとワニスが白化したり、あるいは印刷時に異物が発生するため、その含有量は溶媒成分の80質量%以下が好ましく、より好ましくは60質量%以下である。低表面張力を有する溶媒は基板への塗布性を改善させるが、量が多すぎると樹脂成分の析出が生じるため、その含有量は溶媒成分の60質量%以下が好ましく、より好ましくは50質量%以下である。樹脂成分の溶解性確保のための溶媒と低表面張力を有する溶媒を組み合わせて用いる場合、それぞれの溶媒のより好ましい含有量は、樹脂成分の溶解性確保のための溶媒が5~70質量%であり、低表面張力を有する溶媒が10~60質量%であり、さらに好ましくは樹脂成分の溶解性確保のための溶媒が10~45質量%であり、低表面張力を有する溶媒が20~50質量%である。 In addition, the solvent for ensuring the solubility of the resin component, when the amount is too large, whitening of the varnish or generation of foreign matter during printing, the content is preferably 80% by mass or less of the solvent component, more preferably Is 60% by mass or less. A solvent having a low surface tension improves the coating property to the substrate, but if the amount is too large, precipitation of the resin component occurs, so the content is preferably 60% by mass or less, more preferably 50% by mass of the solvent component. It is as follows. When a solvent for ensuring the solubility of the resin component is used in combination with a solvent having a low surface tension, the more preferable content of each solvent is 5 to 70% by mass of the solvent for ensuring the solubility of the resin component. The solvent having a low surface tension is 10 to 60% by mass, more preferably the solvent for ensuring the solubility of the resin component is 10 to 45% by mass, and the solvent having a low surface tension is 20 to 50% by mass. %.
 本発明の液晶配向処理剤における溶媒組成の例を挙げるならば、N-エチル-2-ピロリドンが5~80質量%、樹脂成分の溶解性確保のための溶媒が5~70質量%、低表面張力を有する溶媒が10~60質量%の混合溶媒;N-エチル-2-ピロリドンが10~70質量%、樹脂成分の溶解性確保のための溶媒が10~45質量%、低表面張力を有する溶媒が20~50質量%の混合溶媒;N-エチル-2-ピロリドンが5~40質量%、樹脂成分の溶解性確保のための溶媒が5~70質量%、低表面張力を有する溶媒が10~60質量%の混合溶媒;N-エチル-2-ピロリドンが10~40質量%、樹脂成分の溶解性確保のための溶媒が10~45質量%、低表面張力を有する溶媒が20~50質量%の混合溶媒;N-シクロヘキシル-2-ピロリドンが5~40質量%、樹脂成分の溶解性確保のための溶媒が5~70質量%、低表面張力を有する溶媒が10~60質量%の混合溶媒;N-シクロヘキシル-2-ピロリドンが10~40質量%、樹脂成分の溶解性確保のための溶媒が10~45質量%、低表面張力を有する溶媒が20~50質量%の混合溶媒などを例示することができる。
 本発明の液晶配向処理剤には、上記以外に塗膜の特性を改善する為の添加物を含有してもよい。
Examples of the solvent composition in the liquid crystal aligning agent of the present invention include 5 to 80% by mass of N-ethyl-2-pyrrolidone, 5 to 70% by mass of a solvent for ensuring the solubility of the resin component, and a low surface. Mixed solvent with 10-60 mass% of solvent having tension; 10-70 mass% of N-ethyl-2-pyrrolidone, 10-45 mass% of solvent for ensuring the solubility of the resin component, low surface tension Mixed solvent having a solvent of 20 to 50% by mass; 5 to 40% by mass of N-ethyl-2-pyrrolidone, 5 to 70% by mass of a solvent for ensuring the solubility of the resin component, and 10 of a solvent having a low surface tension Mixed solvent of ˜60% by mass; N-ethyl-2-pyrrolidone is 10 to 40% by mass, the solvent for ensuring the solubility of the resin component is 10 to 45% by mass, and the solvent having a low surface tension is 20 to 50% by mass. % Mixed solvent; N-cyclohexyl -2-pyrrolidone in a mixed solvent of 5 to 40% by mass, a solvent for ensuring the solubility of the resin component in a range of 5 to 70% by mass, and a solvent having a low surface tension of 10 to 60% by mass; N-cyclohexyl-2- Examples thereof include a mixed solvent of 10 to 40% by mass of pyrrolidone, 10 to 45% by mass of a solvent for ensuring the solubility of the resin component, and 20 to 50% by mass of a solvent having a low surface tension.
In addition to the above, the liquid crystal aligning agent of the present invention may contain additives for improving the properties of the coating film.
 塗膜の特性を改善する為の添加物としては、3-アミノプロピルメチルジエトキシシラン、3-フェニルアミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、(アミノエチルアミノメチル)フェネチルトリメトキシシランなどのシランカップリング剤が挙げられる。これらシランカップリング剤の添加により、基板に対する塗膜の密着性を更に向上させることができるが、添加しすぎると本発明に用いるポリイミドやそれと併用する高分子化合物が凝集する原因となる。従って、シランカップリング剤の含有量は、好ましくは本発明に用いる樹脂成分の100質量部に対して0.1~20質量部、より好ましくは0.2~10質量部である。 Additives for improving coating properties include 3-aminopropylmethyldiethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane And silane coupling agents such as The addition of these silane coupling agents can further improve the adhesion of the coating film to the substrate, but if added too much, the polyimide used in the present invention and the polymer compound used in combination with it will cause aggregation. Therefore, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the resin component used in the present invention.
[液晶配向処理剤の調製方法]
 本発明の液晶配向処理剤の調製方法は、含有している成分が液晶配向処理剤中で均一な状態となるならば特に限定されない。その一例を挙げると、ポリイミドの粉末を、有機溶媒に溶解させてポリイミド溶液とし、次いで、所望の濃度まで有機溶媒を添加して希釈する方法などである。この希釈工程において、基板への塗布性を制御する為の溶媒組成の調整や、塗膜の特性を改善する為の添加物の追加などを行うことができる。ポリイミドの粉末を溶解させる溶媒としては、N-エチル-2-ピロリドン、もしくはN-シクロヘキシル-2-ピロリドン又は前記した溶媒が挙げられる。上記のようにして得られた液晶配向処理剤は、基板に塗布する前に濾過することが好ましい。
[Method for Preparing Liquid Crystal Alignment Treatment Agent]
The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited as long as the contained components are in a uniform state in the liquid crystal aligning agent. For example, a polyimide powder is dissolved in an organic solvent to form a polyimide solution, and then diluted by adding an organic solvent to a desired concentration. In this dilution step, adjustment of the solvent composition for controlling the coating property to the substrate, addition of an additive for improving the properties of the coating film, and the like can be performed. Examples of the solvent for dissolving the polyimide powder include N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, and the solvents described above. The liquid crystal aligning agent obtained as described above is preferably filtered before being applied to the substrate.
 本発明の液晶配向処理剤は、基板に塗布し、乾燥、焼成することで塗膜とすることができ、この塗膜面をラビング処理することにより、ラビング用の液晶配向膜として使用される。またラビング処理をしないVA用液晶配向膜、または光配向膜としても使用される。 The liquid crystal alignment treatment agent of the present invention can be applied to a substrate, dried and baked to form a coating film. By rubbing this coating film surface, it is used as a liquid crystal alignment film for rubbing. It is also used as a liquid crystal alignment film for VA or a photo alignment film that is not rubbed.
 この際、用いる基板としては透明性の高い基板であれば特に限定されず、ガラス基板、アクリル基板やポリカーボネート基板などのプラスチック基板などを用いることができ、液晶駆動のためのITO電極などが形成された基板を用いることがプロセスの簡素化の観点から好ましい。また、反射型の液晶表示素子では片側の基板のみにならばシリコンウエハー等の不透明な物でも使用でき、この場合の電極はアルミ等の光を反射する材料も使用できる。 At this time, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used, and an ITO electrode for driving a liquid crystal is formed. It is preferable to use a new substrate 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 as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
 液晶配向処理剤の塗布方法としては、スピンコート法、印刷法、インクジェット法などが挙げられるが、生産性の面から工業的にはフレキソ印刷法が広く用いられており、本発明の液晶配向処理剤においても好適に用いられる。 Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, and ink-jet methods. From the viewpoint of productivity, the flexographic printing method is widely used industrially, and the liquid crystal aligning treatment of the present invention. It is also preferably used in agents.
 液晶配向処理剤を塗布した後の乾燥の工程は、必ずしも必要とされないが、塗布後から焼成までの時間が基板ごとに一定していない場合や、塗布後ただちに焼成されない場合には、乾燥工程を含める方が好ましい。この乾燥は、基板の搬送等により塗膜形状が変形しない程度に溶媒が蒸発していれば良く、その乾燥手段については特に限定されない。具体例を挙げるならば、50~150℃、好ましくは80~120℃のホットプレート上で、0.5~30分、好ましくは1~5分乾燥させる方法がとられる。 The drying process after applying the liquid crystal alignment treatment agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. Inclusion is preferred. The drying is not particularly limited as long as the solvent is evaporated to such an extent that the shape of the coating film is not deformed by the conveyance of the substrate or the like. As a specific example, a method of drying on a hot plate at 50 to 150 ° C., preferably 80 to 120 ° C., for 0.5 to 30 minutes, preferably 1 to 5 minutes is employed.
 液晶配向処理剤を塗布した基板の焼成は、100~350℃の任意の温度で行うことができるが、好ましくは150℃~300℃であり、さらに好ましくは180℃~250℃である。液晶配向処理剤中にアミック酸基が存在する場合は、この焼成温度によってアミック酸からイミドへ変化するが、本発明の液晶配向処理剤は、必ずしも100%イミド化させる必要は無い。 The substrate coated with the liquid crystal aligning agent can be baked at an arbitrary temperature of 100 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 250 ° C. When an amic acid group is present in the liquid crystal aligning agent, it changes from an amic acid to an imide depending on the baking temperature, but the liquid crystal aligning agent of the present invention does not necessarily need to be 100% imidized.
 焼成後の塗膜の厚みは、厚すぎると液晶表示素子の消費電力の面で不利となり、薄すぎると液晶表示素子の信頼性が低下する場合があるので、好ましくは10~200nm、より好ましくは50~100nmである。 If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 10 to 200 nm, more preferably 50 to 100 nm.
 上記のようにして基板上に形成された塗膜面のラビング処理は、既存のラビング装置を使用することができる。この際のラビング布の材質としては、コットン、レーヨン、ナイロンなどが挙げられる。 For the rubbing treatment of the coating surface formed on the substrate as described above, an existing rubbing apparatus can be used. Examples of the material of the rubbing cloth at this time include cotton, rayon, and nylon.
 本発明の液晶表示素子は、上記した手法により本発明の液晶配向処理剤から液晶配向膜付き基板を得た後、公知の方法で液晶セルを作製し、液晶表示素子としたものである。液晶セルの作製の一例を挙げるならば、液晶配向膜の形成された1対の基板を、好ましくは1~30μm、より好ましくは2~10μmのスペーサーを挟んで、配向処理方向が0~270°の任意の角度となるように設置して周囲をシール剤で固定し、液晶を注入して封止する方法が一般的である。液晶封入の方法については特に制限されず、作製した液晶セル内を減圧にした後液晶を注入する真空法、液晶を滴下した後封止を行う滴下法などが例示できる。 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 method described above, and then preparing a liquid crystal cell by a known method. As an example of manufacturing a liquid crystal cell, an alignment treatment direction is 0 to 270 ° with a pair of substrates on which a liquid crystal alignment film is formed, preferably with a spacer of 1 to 30 μm, more preferably 2 to 10 μm. A method is generally used in which the angle is set at an arbitrary angle, the periphery is fixed with a sealant, 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.
 このようにして得られた液晶表示素子は、TN液晶表示素子、STN液晶表示素子、TFT液晶表示素子、OCB液晶表示素子、更には、横電界型の液晶表示素子、VA液晶表示素子など、種々の方式による表示素子に好適に用いられる。 The liquid crystal display elements thus obtained include various types such as TN liquid crystal display elements, STN liquid crystal display elements, TFT liquid crystal display elements, OCB liquid crystal display elements, lateral electric field type liquid crystal display elements, and VA liquid crystal display elements. It is suitably used for a display element by the above method.
 以下に実施例を挙げ、本発明を更に詳しく説明するが、本発明はこれらに限定して解釈されるものではない。
実施例及び比較例で使用する略号は以下の通りである。
The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto.
Abbreviations used in Examples and Comparative Examples are as follows.
<テトラカルボン酸二無水物>
 CBDA: 1,2,3,4-シクロブタンテトラカルボン酸二無水物
 PMDA: ピロメリット酸二無水物
 TDA:3,4-ジカルボキシ-1,2,3,4-テトラヒドロ-1-ナフタレンコハク酸二無水物
<ジアミン>
 2,4-DAA: 2,4-ジアミノ-N,N-ジアリルアニリン
<Tetracarboxylic dianhydride>
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene-2-succinic acid Anhydride <Diamine>
2,4-DAA: 2,4-Diamino-N, N-diallylaniline
Figure JPOXMLDOC01-appb-C000011
 p-PDA:p-フェニレンジアミン
 DDM:4,4’-ジアミノジフェニルメタン
 BAPP:1,5-ビス(4-アミノフェノキシ)ペンタン
 C12DAB: 4-ドデシルオキシ-1,3-ジアミノベンゼン
 C14DAB: 4-テトラデシルオキシ-1,3-ジアミノベンゼン
 C18DAB: 4-オクタデシルオキシ-1,3-ジアミノベンゼン
 PCBA-PDA:4-(t-4-ペンチルシクロヘキシル)ベンズアミド-2',4'-フェニレンジアミン
Figure JPOXMLDOC01-appb-C000011
p-PDA: p-phenylenediamine DDM: 4,4′-diaminodiphenylmethane BAPP: 1,5-bis (4-aminophenoxy) pentane C12DAB: 4-dodecyloxy-1,3-diaminobenzene C14DAB: 4-tetradecyl Oxy-1,3-diaminobenzene C18DAB: 4-octadecyloxy-1,3-diaminobenzene PCBA-PDA: 4- (t-4-pentylcyclohexyl) benzamide-2 ′, 4′-phenylenediamine
Figure JPOXMLDOC01-appb-C000012
 3-ABA: 3-アミノベンジルアミン
Figure JPOXMLDOC01-appb-C000012
3-ABA: 3-Aminobenzylamine
<有機溶媒>
 NMP: N-メチル-2-ピロリドン
 NEP: N-エチル-2-ピロリドン
 NCP: N-シクロヘキシル-2-ピロリドン
 γBL: γ-ブチロラクトン
 DMI:1,3-ジメチルイミダゾリジノン
 BC: ブチルセロソルブ
 DPM:ジプロピレングリコールモノメチルエーテル
 EC:エチルカルビトール
<Organic solvent>
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone NCP: N-cyclohexyl-2-pyrrolidone γBL: γ-butyrolactone DMI: 1,3-dimethylimidazolidinone BC: Butyl cellosolve DPM: Dipropylene glycol Monomethyl ether EC: Ethyl carbitol
 <分子量の測定>
 ポリイミドの分子量は、該ポリイミドをGPC(常温ゲル浸透クロマトグラフィー)装置によって測定し、ポリエチレングリコール、ポリエチレンオキシド換算値として数平均分子量と重量平均分子量を算出した。
 GPC装置:Shodex社製 (GPC-101)
 カラム:Shodex社製 (KD803、KD805の直列)
 カラム温度:50℃
 溶離液:N,N-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)
 流速:1.0ml/分
 検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(重量平均分子量 約900,000、150,000、100,000、30,000)、及び、ポリマーラボラトリー社製 ポリエチレングリコール(重量平均分子量 約12,000、4,000、1,000)。
<Measurement of molecular weight>
The molecular weight of the polyimide was measured with a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight and weight average molecular weight were calculated as polyethylene glycol and polyethylene oxide equivalent values.
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) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (weight average molecular weight: about 12,000, manufactured by Polymer Laboratories) 4,000, 1,000).
 <イミド化率の測定>
 ポリイミドのイミド化率は次のようにして測定した。ポリイミド粉末20mgをNMRサンプル管に入れ、重水素化ジメチルスルホキシド(DMSO-d、0.05%TMS混合品)0.53mlを添加し、完全に溶解させた。この溶液を日本電子データム社製NMR測定器(JNM-ECA500)にて500MHzのプロトンNMRを測定した。イミド化率は、イミド化前後で変化しない構造に由来するプロトンを基準プロトンとして決め、このプロトンのピーク積算値と、9.5~10.0ppm付近に現れるアミック酸のNH基に由来するプロトンピーク積算値とを用い次式によって求めた。
イミド化率(%)=(1-α・x/y)×100
 上記式において、xはアミック酸のNH基由来のプロトンピーク積算値、yは基準プロトンのピーク積算値、αはポリアミック酸(イミド化率が0%)の場合におけるアミック酸のNH基プロトン一個に対する基準プロトンの個数割合である。
<Measurement of imidization ratio>
The imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was placed in an NMR sample tube, and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture) 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 by determining a proton derived from a structure that does not change before and after imidation as a reference proton, a peak integrated value of this proton, and a proton peak integrated value derived from the NH group of the amic acid that appears around 9.5 to 10.0 ppm. Was obtained by the following equation.
Imidization rate (%) = (1−α · x / y) × 100
In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%). The number ratio of the reference protons.
(合成例1)
 テトラカルボン酸二無水物成分として、CBDAを13.53g(0.069mol)、PMDAを6.54g(0.030mol)、ジアミン成分として、2,4-DAAを6.10g(0.030mol)、3-ABAを4.89g(0.040mol)、C14DABを9.62g(0.030mol)用い、NMP162.7g中、23℃で24時間反応させポリアミック酸溶液を得た。
 このポリアミック酸溶液142.8gに、NMPを333.2g加えて希釈し、無水酢酸21.5gとピリジン9.2gを加え、温度50℃で3時間反応させてイミド化した。
 この反応溶液を室温程度まで冷却後、メタノール1.8l中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、温度100℃で減圧乾燥して、ポリイミド(SPI)の白色粉末を得た。このポリイミドの数平均分子量は13,472、重量平均分子量は35,859であった。また、イミド化率は89%であった。
(Synthesis Example 1)
As a tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA, 6.54 g (0.030 mol) of PMDA, and 6.10 g (0.030 mol) of 2,4-DAA as a diamine component, Using 3.89 g (0.040 mol) of 3-ABA and 9.62 g (0.030 mol) of C14DAB, the reaction was performed in NMP162.7 g at 23 ° C. for 24 hours to obtain a polyamic acid solution.
331.8 g of NMP was added to 142.8 g of this polyamic acid solution for dilution, 21.5 g of acetic anhydride and 9.2 g of pyridine were added, and the mixture was reacted at a temperature of 50 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 1.8 l of methanol to recover the precipitated solid. The solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI). The number average molecular weight of this polyimide was 13,472, and the weight average molecular weight was 35,859. Further, the imidization ratio was 89%.
(合成例2)
 合成例1と同様にして得られたポリイミド17.9gに、γBLを131.3g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(合成例3)
 合成例1と同様にして得られたポリイミド1.6gに、NEPを14.4g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(合成例4)
 合成例1で得られたポリイミド1.6gに、NMPを14.4g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(合成例5)
 合成例1で得られたポリイミド1.6gに、γBLを8g、NCPを6.4g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(Synthesis Example 2)
131.3 g of γBL was added to 17.9 g of polyimide obtained in the same manner as in Synthesis Example 1, and the mixture was stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(Synthesis Example 3)
14.4 g of NEP was added to 1.6 g of polyimide obtained in the same manner as in Synthesis Example 1, and the mixture was stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(Synthesis Example 4)
14.4 g of NMP was added to 1.6 g of the polyimide obtained in Synthesis Example 1, and the mixture was stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(Synthesis Example 5)
To 1.6 g of the polyimide obtained in Synthesis Example 1, 8 g of γBL and 6.4 g of NCP were added and stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(合成例6)
 テトラカルボン酸二無水物成分として、CBDAを13.53g(0.069mol)、PMDAを6.54g(0.030mol)、ジアミン成分として、2,4-DAAを7.12g(0.035mol)、3-ABAを4.89g(0.040mol)、PCBA-PDAを10.19g(0.025mol)用い、NMP169.1g中、23℃で24時間反応させポリアミック酸溶液を得た。
 このポリアミック酸溶液150gに、NMPを350g加えて希釈し、無水酢酸21.74gとピリジン9.27gを加え、温度50℃で3時間反応させてイミド化した。
 この反応溶液を室温程度まで冷却後、メタノール1.86l中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、温度100℃で減圧乾燥して、ポリイミド(SPI)の白色粉末を得た。このポリイミドの数平均分子量は12,156、重量平均分子量は32,418であった。また、イミド化率は90%であった。
(Synthesis Example 6)
As a tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA, 6.54 g (0.030 mol) of PMDA, and 7.12 g (0.035 mol) of 2,4-DAA as a diamine component, Using 3.89 g (0.040 mol) of 3-ABA and 10.19 g (0.025 mol) of PCBA-PDA, the reaction was carried out in NMP 169.1 g at 23 ° C. for 24 hours to obtain a polyamic acid solution.
To 150 g of this polyamic acid solution, 350 g of NMP was added for dilution, 21.74 g of acetic anhydride and 9.27 g of pyridine were added, and the mixture was reacted at 50 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 1.86 l of methanol to recover the precipitated solid. The solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI). The number average molecular weight of this polyimide was 12,156, and the weight average molecular weight was 32,418. Moreover, the imidation ratio was 90%.
(合成例7)
 合成例6と同様にして得られたポリイミド4.8gに、γBLを35.2g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(合成例8)
 テトラカルボン酸二無水物成分として、TDAを15.01g(0.05mol)、ジアミン成分として、p-PDAを4.87g(0.045mol)、C18DABを1.88g(0.005mol)用い、NMP 123.3g中、50℃で24時間反応させポリアミック酸溶液を得た。
 このポリアミック酸溶液に、NMPを350g加えて希釈し、無水酢酸51.0gとピリジン23.7gを加え、温度40℃で3時間反応させてイミド化した。
 この反応溶液を室温程度まで冷却後、メタノール1.7l中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、温度100℃で減圧乾燥して、ポリイミド(SPI)の白色粉末を得た。このポリイミドの数平均分子量は9,273、重量平均分子量は18,815であった。また、イミド化率は84%であった。
(Synthesis Example 7)
35.2 g of γBL was added to 4.8 g of polyimide obtained in the same manner as in Synthesis Example 6, and the mixture was stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(Synthesis Example 8)
As the tetracarboxylic dianhydride component, 15.1 g (0.05 mol) of TDA, 4.87 g (0.045 mol) of p-PDA and 1.88 g (0.005 mol) of C18DAB were used as the diamine component, and NMP The reaction was carried out in 123.3 g at 50 ° C. for 24 hours to obtain a polyamic acid solution.
To this polyamic acid solution, 350 g of NMP was added for dilution, 51.0 g of acetic anhydride and 23.7 g of pyridine were added, and the mixture was reacted at a temperature of 40 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 1.7 l of methanol, and the precipitated solid was recovered. The solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI). The number average molecular weight of this polyimide was 9,273, and the weight average molecular weight was 18,815. Moreover, the imidation ratio was 84%.
(合成例9)
 合成例8と同様にして得られたポリイミド6.0gに、NEPを94.0g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(合成例10)
 テトラカルボン酸二無水物成分として、CBDAを4.90g(0.025mol)、PMDAを4.80g(0.022mol)、ジアミン成分として、DDMを9.91g(0.05mol)用い、NEP55.5g、γBL55.5g の混合溶媒中、室温で5時間反応させポリアミック酸溶液を得た。このポリアミック酸の数平均分子量は11,067、重量平均分子量が26,270であった。
(合成例11)
 合成例10で得られたポリアミック酸溶液50gにNEP、BCを加え、ポリアミック酸が6質量%、NEPが59質量%、γ-BLが20質量%、BCが15質量%になるよう調製した。
(Synthesis Example 9)
94.0 g of NEP was added to 6.0 g of polyimide obtained in the same manner as in Synthesis Example 8, and the mixture was stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(Synthesis Example 10)
As the tetracarboxylic dianhydride component, 4.90 g (0.025 mol) of CBDA, 4.80 g (0.022 mol) of PMDA, and 9.91 g (0.05 mol) of DDM as the diamine component were used, and 55.5 g of NEP was used. In a mixed solvent of γBL55.5 g, a reaction was performed at room temperature for 5 hours to obtain a polyamic acid solution. The number average molecular weight of this polyamic acid was 11,067, and the weight average molecular weight was 26,270.
(Synthesis Example 11)
NEP and BC were added to 50 g of the polyamic acid solution obtained in Synthesis Example 10 to prepare 6% by mass of polyamic acid, 59% by mass of NEP, 20% by mass of γ-BL, and 15% by mass of BC.
(合成例12)
 テトラカルボン酸二無水物成分として、TDAを15.01g(0.05mol)、ジアミン成分として、p-PDAを2.70g(0.025mol)、2,4-DAAを3.05g(0.015mol)、PCBA-PDAを4.08g(0.01mol)用い、NMP 140.8g中、50℃で24時間反応させポリアミック酸溶液を得た。
 このポリアミック酸溶液に、NMPを331g加えて希釈し、無水酢酸51.0gとピリジン23.7gを加え、温度40℃で3時間反応させてイミド化した。
 この反応溶液を室温程度まで冷却後、メタノール2.0l中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、温度100℃で減圧乾燥して、ポリイミド(SPI)の白色粉末を得た。このポリイミドの数平均分子量は8,579、重量平均分子量は22,319であった。また、イミド化率は87%であった。
(Synthesis Example 12)
As a tetracarboxylic dianhydride component, 15.01 g (0.05 mol) of TDA, 2.70 g (0.025 mol) of p-PDA as a diamine component, and 3.05 g (0.015 mol) of 2,4-DAA ), 4.08 g (0.01 mol) of PCBA-PDA was used and reacted in 140.8 g of NMP at 50 ° C. for 24 hours to obtain a polyamic acid solution.
To this polyamic acid solution, 331 g of NMP was added for dilution, 51.0 g of acetic anhydride and 23.7 g of pyridine were added, and the mixture was reacted at a temperature of 40 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 2.0 l of methanol to recover the precipitated solid. The solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI). The number average molecular weight of this polyimide was 8,579, and the weight average molecular weight was 22,319. The imidation ratio was 87%.
(合成例13)
 合成例12と同様にして得られたポリイミド6.0gに、γBLを94.0g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(合成例14)
 合成例10で得られたポリアミック酸溶液50gにγBL、BCを加え、ポリアミック酸が6質量%、γBLが59質量%、NEPが20質量%、BCが15質量%になるよう調製した。
(合成例15) 
 テトラカルボン酸二無水物成分として、CBDAを19.41g(0.099mol)、ジアミン成分として、BAPPを5.73g(0.02mol)、2,4-DAAを14.23g(0.07mol)、PCBA-PDAを4.08g(0.01mol)用い、NMP 246.2g中、23℃で24時間反応させポリアミック酸溶液を得た。
 このポリアミック酸溶液に、NMPを434g加えて希釈し、無水酢酸25.8gとピリジン11.0gを加え、温度35℃で3時間反応させてイミド化した。
 この反応溶液を室温程度まで冷却後、メタノール2.7l中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、温度100℃で減圧乾燥して、ポリイミド(SPI)の白色粉末を得た。このポリイミドの数平均分子量は12,132、重量平均分子量は26,538であった。また、イミド化率は70%であった。
(Synthesis Example 13)
94.0 g of γBL was added to 6.0 g of polyimide obtained in the same manner as in Synthesis Example 12, and the mixture was stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(Synthesis Example 14)
ΓBL and BC were added to 50 g of the polyamic acid solution obtained in Synthesis Example 10 to prepare 6% by mass of polyamic acid, 59% by mass of γBL, 20% by mass of NEP, and 15% by mass of BC.
(Synthesis Example 15)
As the tetracarboxylic dianhydride component, 19.41 g (0.099 mol) of CBDA, as the diamine component, 5.73 g (0.02 mol) of BAPP, 14.23 g (0.07 mol) of 2,4-DAA, Using 4.08 g (0.01 mol) of PCBA-PDA, the reaction was carried out in 236.2 g of NMP at 23 ° C. for 24 hours to obtain a polyamic acid solution.
To this polyamic acid solution, 434 g of NMP was added for dilution, 25.8 g of acetic anhydride and 11.0 g of pyridine were added, and the mixture was reacted at a temperature of 35 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 2.7 l of methanol to recover the precipitated solid. The solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI). The number average molecular weight of this polyimide was 12,132, and the weight average molecular weight was 26,538. Moreover, the imidation ratio was 70%.
(合成例16)
 合成例15と同様にして得られたポリイミド12.0gに、NEPを108.0g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(合成例17) 
 テトラカルボン酸二無水物成分として、CBDAを19.41g(0.099mol)、ジアミン成分として、2,4-DAAを14.23g(0.07mol)、C12DABを8.77g(0.03mol)用い、NMP 169.7g中、23℃で24時間反応させポリアミック酸溶液を得た。
 このポリアミック酸溶液に、NMPを494.9g加えて希釈し、無水酢酸30.6gとピリジン13.1gを加え、温度50℃で3時間反応させてイミド化した。
 この反応溶液を室温程度まで冷却後、メタノール2.6l中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、温度100℃で減圧乾燥して、ポリイミド(SPI)の白色粉末を得た。このポリイミドの数平均分子量は11,098、重量平均分子量は21,431であった。また、イミド化率は91%であった。
(合成例18) 
 合成例17と同様にして得られたポリイミド1.6gに、NEPを14.4g加え、温度50℃で24時間攪拌した。攪拌終了時点でポリイミドは完全に溶解していた。
(Synthesis Example 16)
108.0 g of NEP was added to 12.0 g of polyimide obtained in the same manner as in Synthesis Example 15, and the mixture was stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(Synthesis Example 17)
As the tetracarboxylic dianhydride component, 19.41 g (0.099 mol) of CBDA, 14.23 g (0.07 mol) of 2,4-DAA and 8.77 g (0.03 mol) of C12DAB were used as the diamine component. , NMP (169.7 g) was reacted at 23 ° C. for 24 hours to obtain a polyamic acid solution.
To this polyamic acid solution, 494.9 g of NMP was added for dilution, 30.6 g of acetic anhydride and 13.1 g of pyridine were added, and the mixture was reacted at a temperature of 50 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 2.6 l of methanol to recover the precipitated solid. The solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI). The number average molecular weight of this polyimide was 11,098, and the weight average molecular weight was 21,431. Moreover, the imidation ratio was 91%.
(Synthesis Example 18)
14.4 g of NEP was added to 1.6 g of polyimide obtained in the same manner as in Synthesis Example 17, and the mixture was stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring.
(実施例1)
 合成例2と同様にして得られた溶液20.23gを23℃まで冷却後、γBLを8.67g、NEPを4.93g、BCを14.78g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
(Example 1)
After cooling 20.23 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 8.67 g of γBL, 4.93 g of NEP and 14.78 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
<電圧保持率の評価>
 上記液晶配向処理剤について、以下のようにして液晶セルの電圧保持率の評価を行った。
液晶配向処理剤を透明電極付きガラス基板にスピンコートし、温度70℃のホットプレート上で70秒乾燥させた後、210℃のホットプレートで10分間焼成を行い、膜厚100nmの塗膜を形成させた。この塗膜面をロール径120mmのラビング装置でレーヨン布を用いて、ロール回転数1000rpm、ロール進行速度50mm/sec、押し込み量0.3mmの条件でラビングし、液晶配向膜付き基板を得た。
 この基板を2枚用意し、その1枚の液晶配向膜面上に6μmのスペーサーを散布し、その上からシール剤を印刷し、もう1枚の基板を液晶配向膜面が向き合いラビング方向が直行するようにして張り合わせた後、シール剤を硬化させて空セルを作製した。この空セルに減圧注入法によって、液晶MLC-2003(メルク・ジャパン社製)を注入し、注入口を封止して、ツイストネマティック液晶セルを得た。
 この液晶セルに、90℃の温度下で4Vの電圧を60μs間印加し、16.67ms後の電圧を測定し、電圧がどのくらい保持できているかを電圧保持率として計算した。なお、電圧保持率の測定には、東陽テクニカ社製のVHR-1電圧保持率測定装置を使用した。評価結果を表2に示す。
<Evaluation of voltage holding ratio>
About the said liquid-crystal aligning agent, the voltage holding rate of the liquid crystal cell was evaluated as follows.
A liquid crystal alignment treatment agent is spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 70 ° C. for 70 seconds, and then baked on a hot plate at 210 ° C. for 10 minutes to form a coating film having a thickness of 100 nm. I let you. The surface of the coating film was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.
Prepare two sheets of this substrate, spray a 6μm spacer on the surface of one liquid crystal alignment film, print a sealant on it, and the other substrate faces the liquid crystal alignment film and the rubbing direction is perpendicular. After the lamination, the sealing agent was cured to produce an empty cell. Liquid crystal MLC-2003 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a twisted nematic liquid crystal cell.
A voltage of 4 V was applied to the liquid crystal cell at a temperature of 90 ° C. for 60 μs, the voltage after 16.67 ms was measured, and how much the voltage could be held was calculated as a voltage holding ratio. The voltage holding ratio was measured using a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica. The evaluation results are shown in Table 2.
<チルト角の測定>
 上記<液晶セルの作製>と同様にして得られた液晶セルを用いて、液晶のチルト角の測定を行った。測定にはAutronic社製のTBA107を用いた。測定は、加熱前(23℃)と、液晶セルを60℃に保持した条件で行った。結果を表3に示す。
<Measurement of tilt angle>
Using the liquid crystal cell obtained in the same manner as in the above <Production of liquid crystal cell>, the tilt angle of the liquid crystal was measured. For the measurement, TBA107 manufactured by Autronic was used. The measurement was performed before heating (23 ° C.) and under the condition that the liquid crystal cell was held at 60 ° C. The results are shown in Table 3.
<弱ラビングにおける液晶配向性の評価>
 上記<電圧保持率の評価>において、ラビングローラーの押し込みを0.2mmに変更し、さらにラビング方向が180°(アンチパラレル)になるようにして基板を張り合わせた以外は同じ条件で液晶セルを作成した。その際、液晶注入後に液晶セルの注入口から液晶の流動配向の有無を観察し、下記の評価を行った。
○:流動配向が観測されない。
△ :わずかに流動配向が観察される。
×:スジ状の流動配向が多数観測される。
評価結果を表3に示す。
<Evaluation of liquid crystal alignment in weak rubbing>
In the above <Evaluation of voltage holding ratio>, the liquid crystal cell was created under the same conditions except that the rubbing roller push-in was changed to 0.2 mm and the substrates were bonded so that the rubbing direction was 180 ° (anti-parallel). did. At that time, after liquid crystal injection, the presence / absence of liquid crystal orientation was observed from the injection port of the liquid crystal cell, and the following evaluation was performed.
○: Flow orientation is not observed.
Δ: Slight flow orientation is observed.
X: Many streaky flow orientations are observed.
The evaluation results are shown in Table 3.
<ラビング耐性の評価>
 上記<電圧保持率の評価>において、ラビングローラーの押し込みを0.5mmに変えた条件でラビングを行い、液晶配向膜付き基板を作成した。この液晶配向膜の表面をレーザー顕微鏡にて観察し、目視にて下記の評価を行った。
○:削れカスやラビング傷がほとんど発生しない。
×:カスが発生する、またはラビング傷がつく。
評価結果を表3に示す。
<Evaluation of rubbing resistance>
In the above <Evaluation of voltage holding ratio>, rubbing was performed under the condition that the indentation of the rubbing roller was changed to 0.5 mm, and a substrate with a liquid crystal alignment film was prepared. The surface of the liquid crystal alignment film was observed with a laser microscope, and the following evaluation was performed visually.
○: Scraping and rubbing scratches hardly occur.
X: Waste or rubbing scratches are generated.
The evaluation results are shown in Table 3.
<乾燥速度の評価>
 上記の液晶配向処理剤をクロム蒸着したガラス基板(以下Cr基板と省略)上(大きさ10cm x 10cm)に膜厚100nmになるようにスピンコートした。その後、温度23℃、湿度45%下で、スピンコート完了直後から膜が均一に乾燥するまでの時間を測定した。その結果340秒となった。
<Evaluation of drying speed>
It spin-coated so that it might become a film thickness of 100 nm on the glass substrate (henceforth Cr board | substrate) which vapor-deposited said liquid crystal aligning agent (it abbreviate | omitted Cr board | substrate) (size 10cm x 10cm). Thereafter, at a temperature of 23 ° C. and a humidity of 45%, the time from when the spin coating was completed until the film was uniformly dried was measured. The result was 340 seconds.
<白化特性の評価>
 上記の液晶配向処理剤を、Cr基板上にそれぞれ約0.1ml滴下し、温度23℃、湿度45%の環境に放置した。この液滴の端近傍及び中央付近を1時間ごとに顕微鏡で観察した。なお、液滴の端近傍は100倍で、液滴の中央付近は50倍の倍率で観察を行った。6h以内に液滴の端及び中央付近に凝集物が見られた場合は×、6h経過しても見られない場合を○とした。結果を表2に記載した。
<Evaluation of whitening characteristics>
About 0.1 ml of each liquid crystal alignment treatment agent was dropped on the Cr substrate and left in an environment at a temperature of 23 ° C. and a humidity of 45%. The vicinity of the end and the center of the droplet were observed with a microscope every hour. The observation was performed at a magnification of 100 times near the edge of the droplet and at a magnification of 50 times near the center of the droplet. The case where aggregates were observed near the edge and center of the droplet within 6 hours was evaluated as x, and the case where the aggregates were not observed after 6 hours was evaluated as ◯. The results are shown in Table 2.
<印刷ムラの評価>
 上記の液晶配向処理剤を洗浄したCr基板上に配向膜印刷機(日本写真印刷社製「オングストローマー」)を用いてフレキソ印刷した(タクトタイム30秒)。最初に空運転を10回実施した後、印刷を開始し、10枚目の印刷基板を観察に用いた。印刷後の基板は80℃のホットプレート上に5分間放置して塗膜の仮乾燥を行った。上記仮乾燥後の印刷エッジ付近を光学顕微鏡(ニコン社製「ECLIPSE ME600」)にて50倍で観察し、膜厚ムラが発生していないものを○、発生したものを×とした。結果を表2に記載した。
<Evaluation of uneven printing>
Flexographic printing was performed on a Cr substrate washed with the above liquid crystal alignment treatment agent using an alignment film printer (“Angstromer” manufactured by Nissha Printing Co., Ltd.) (tact time 30 seconds). First, after performing the idling operation 10 times, printing was started, and the 10th printed board was used for observation. The substrate after printing was allowed to stand on a hot plate at 80 ° C. for 5 minutes, and the coating film was temporarily dried. The vicinity of the printing edge after the temporary drying was observed with an optical microscope ("ECLIPSE ME600" manufactured by Nikon Corporation) at a magnification of 50 times. The results are shown in Table 2.
<印刷時の異物評価>
 上記と同様な装置を用いて、印刷を実施した。空運転を10回実施した後、1分間印刷機を止め、印刷版を乾燥させた。その後Cr基板1枚印刷し、上記と同様に焼成した。焼成した基板は共焦点レーザー顕微鏡(レーザーテック(株)社製「VL2000」) で印刷エッジ付近を観察し、印刷エッジ付近に3μm以下の異物が発生していないものを○、発生したものを×とした。結果を表2に記載した。
<Foreign matter evaluation during printing>
Printing was performed using the same apparatus as described above. After performing the idling 10 times, the printing machine was stopped for 1 minute and the printing plate was dried. Thereafter, one Cr substrate was printed and fired in the same manner as described above. The fired substrate was observed in the vicinity of the printing edge with a confocal laser microscope ("VL2000" manufactured by Lasertec Co., Ltd.). If there was no foreign material of 3 µm or less near the printing edge, ○, did. The results are shown in Table 2.
<保存安定性の評価>
 上記液晶配向処理剤を-20℃で2ヶ月間保存し、析出、ワニスの白濁がないものを○、析出、ワニスの白濁があるものを×とした。
<Evaluation of storage stability>
The liquid crystal aligning agent was stored at −20 ° C. for 2 months, and “O” indicates that there is no precipitation and varnish white turbidity, and “X” indicates that there is precipitation and varnish white turbidity.
(実施例2)
 合成例2と同様にして得られた溶液21.00gを23℃まで冷却後、γBLを3.87g、NEPを10.21g、BCを15.32g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1にまとめた。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 2)
After cooling 21.00 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 3.87 g of γBL, 10.21 g of NEP and 15.32 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. The composition of the obtained liquid crystal aligning agent is summarized in Table 1.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例3)
 合成例2と同様にして得られた溶液18.77gを23℃まで冷却後、γBLを7.08g、NCPを4.80g、BCを14.40g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1にまとめた。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 3)
After cooling 18.77 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 7.08 g of γBL, 4.80 g of NCP and 14.40 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. The composition of the obtained liquid crystal aligning agent is summarized in Table 1.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例4)
 合成例2と同様にして得られた溶液19.49gを23℃まで冷却後、γBLを3.28g、NCPを9.60g、BCを14.40g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
Example 4
After cooling 19.49 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 3.28 g of γBL, 9.60 g of NCP and 14.40 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例5)
 合成例3と同様にして得られた溶液を室温程度まで冷却後、NEPを2.66g、BCを8.00g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 5)
After cooling the solution obtained in the same manner as in Synthesis Example 3 to about room temperature, 2.66 g of NEP and 8.00 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例6)
 合成例7と同様にして得られた溶液20gを室温程度まで冷却後、γBLを8.8g、NEPを4.8g、BCを14.4g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 6)
After cooling 20 g of the solution obtained in the same manner as in Synthesis Example 7 to about room temperature, 8.8 g of γBL, 4.8 g of NEP, and 14.4 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例7)
 合成例7と同様にして得られた溶液20gを室温程度まで冷却後、γBLを4.0g、NEPを14.4g、BCを9.6g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 7)
After cooling 20 g of the solution obtained in the same manner as in Synthesis Example 7 to about room temperature, 4.0 g of γBL, 14.4 g of NEP, and 9.6 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例8)
 合成例9で得られた溶液20gと合成例11で得られた溶液80gを23℃で20時間攪拌した。攪拌終了後、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 8)
20 g of the solution obtained in Synthesis Example 9 and 80 g of the solution obtained in Synthesis Example 11 were stirred at 23 ° C. for 20 hours. After the stirring, a uniform liquid crystal aligning agent was obtained. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例9)
 合成例13で得られた溶液20gと合成例14で得られた溶液80gを23℃で20時間攪拌した。攪拌終了後、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
Example 9
20 g of the solution obtained in Synthesis Example 13 and 80 g of the solution obtained in Synthesis Example 14 were stirred at 23 ° C. for 20 hours. After the stirring, a uniform liquid crystal aligning agent was obtained. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例10)
 合成例16と同様にして得られた溶液60gを室温程度まで冷却後、DMIを20g、ECを20g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 10)
60 g of the solution obtained in the same manner as in Synthesis Example 16 was cooled to about room temperature, 20 g of DMI and 20 g of EC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例11)
 合成例16と同様にして得られた溶液60gを室温程度まで冷却後、NMPを10g、BCを30g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 11)
60 g of the solution obtained in the same manner as in Synthesis Example 16 was cooled to about room temperature, 10 g of NMP and 30 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(実施例12)
 合成例18と同様にして得られた溶液を室温程度まで冷却後、NEPを2.66g、BCを8.00g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
Example 12
The solution obtained in the same manner as in Synthesis Example 18 was cooled to about room temperature, 2.66 g of NEP and 8.00 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
(比較例1)
 合成例4と同様にして得られた溶液を23℃まで冷却後、NMPを2.66g、BCを8.00g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1にまとめた。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。異物は観察されなかったが、白化、膜厚ムラが観察された。
(Comparative Example 1)
After cooling the solution obtained in the same manner as in Synthesis Example 4 to 23 ° C., 2.66 g of NMP and 8.00 g of BC were added and stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. The composition of the obtained liquid crystal aligning agent is summarized in Table 1.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3. No foreign matter was observed, but whitening and film thickness unevenness were observed.
(比較例2)
 合成例2と同様にして得られた溶液19.49gを23℃まで冷却後、γBLを3.28g、NMPを9.60g、BCを14.40g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。白化特性は良好、異物も観察されなかったが、膜厚ムラが観察された。
(Comparative Example 2)
After cooling 19.49 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 3.28 g of γBL, 9.60 g of NMP and 14.40 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3. Although the whitening characteristics were good and no foreign matter was observed, film thickness unevenness was observed.
(比較例3)
 合成例2と同様にして得られた溶液19.49gを23℃まで冷却後、γBLを9.03g、BCを9.13g、DPMを9.13g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。白化特性は良好であったが、膜厚ムラが生じ、異物も観察された。
(Comparative Example 3)
After cooling 19.49 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C., 9.03 g of γBL, 9.13 g of BC and 9.13 g of DPM were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3. Although the whitening characteristics were good, film thickness unevenness occurred and foreign matter was also observed.
(実施例13)
 合成例5と同様にして得られた溶液を室温程度まで冷却後、NCPを6.40g、BCを9.60g加え、温度50℃で20時間攪拌した。攪拌終了後、23℃まで冷却し、均一な液晶配向処理剤を得た。得られた液晶配向処理剤の組成を表1に示す。
 この液晶配向処理剤を用い、実施例1と同様に電圧保持率、チルト角、液晶配向性、ラビング耐性、乾燥速度、白化特性、印刷ムラ、印刷時の異物、保存安定性の評価を行った。結果は表2、表3に記載した。
(Example 13)
The solution obtained in the same manner as in Synthesis Example 5 was cooled to about room temperature, 6.40 g of NCP and 9.60 g of BC were added, and the mixture was stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent. Table 1 shows the composition of the obtained liquid crystal aligning agent.
Using this liquid crystal alignment treatment agent, the voltage holding ratio, tilt angle, liquid crystal alignment property, rubbing resistance, drying speed, whitening characteristics, printing unevenness, foreign matter during printing, and storage stability were evaluated in the same manner as in Example 1. . The results are shown in Tables 2 and 3.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
 本発明の液晶配向処理剤は、電圧保持特性が良好で、印刷時に液晶パネルのギャップムラの原因となる凝集物発生がないため、狭ギャップの液晶パネルを歩留りよく生産できる。そのため、本発明の液晶配向処理剤を用いて作製した液晶表示素子は、信頼性の高い液晶表示デバイスとすることができ、TN液晶表示素子、STN液晶表示素子、TFT液晶表示素子、OCB液晶表示素子、横電界型液晶表示素子、VA液晶表示素子など、種々の方式による表示素子に好適に用いられる。
 なお、2008年6月4日に出願された日本特許出願2008-146792号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Since the liquid crystal aligning agent of the present invention has good voltage holding characteristics and does not generate aggregates that cause gap unevenness of the liquid crystal panel during printing, a narrow gap liquid crystal panel can be produced with high yield. Therefore, the liquid crystal display element produced using the liquid crystal aligning agent of the present invention can be a highly reliable liquid crystal display device, such as a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, and an OCB liquid crystal display. It is suitably used for display elements of various systems such as elements, horizontal electric field type liquid crystal display elements, VA liquid crystal display elements.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-146792 filed on June 4, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (11)

  1.  ジアミン成分とテトラカルボン酸二無水物とを反応させて得られるポリアミック酸をイミド化して得られるポリイミドを含む樹脂成分と、N-エチル-2-ピロリドン又はN-シクロヘキシル-2-ピロリドンからなるピロリドン化合物を含む溶媒成分と、を含有することを特徴とする液晶配向処理剤。 A pyrrolidone compound comprising a resin component containing a polyimide obtained by imidizing a polyamic acid obtained by reacting a diamine component with tetracarboxylic dianhydride, and N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone And a solvent component comprising: a liquid crystal aligning agent characterized by comprising:
  2.  ピロリドン化合物がN-エチル-2-ピロリドンであり、該N-エチル-2-ピロリドンが溶媒成分の5~80質量%である請求項1に記載の液晶配向処理剤。 The liquid crystal aligning agent according to claim 1, wherein the pyrrolidone compound is N-ethyl-2-pyrrolidone, and the N-ethyl-2-pyrrolidone is 5 to 80% by mass of the solvent component.
  3.  ピロリドン化合物がN-シクロヘキシル-2-ピロリドンであり、該N-シクロヘキシル-2-ピロリドンが溶媒成分の5~40質量%である請求項1に記載の液晶配向処理剤。 The liquid crystal aligning agent according to claim 1, wherein the pyrrolidone compound is N-cyclohexyl-2-pyrrolidone, and the N-cyclohexyl-2-pyrrolidone is 5 to 40% by mass of the solvent component.
  4.  樹脂成分が1~10質量%含有され、溶媒成分が90~99質量%含有される請求項1~3のいずれかに記載の液晶配向処理剤。 4. The liquid crystal aligning agent according to claim 1, wherein the resin component is contained in an amount of 1 to 10% by mass and the solvent component is contained in an amount of 90 to 99% by mass.
  5.  ジアミン成分が、炭素数2又は3のアルケニル基で置換されたジ置換アミノ基を有するジアミノベンゼンである、請求項1~4のいずれかに記載の液晶配向処理剤。 5. The liquid crystal aligning agent according to claim 1, wherein the diamine component is diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms.
  6.  炭素数2又は3のアルケニル基で置換されたジ置換アミノ基を有するジアミノベンゼンが、下記の式[1]で表されるジアミンである、請求項5に記載の液晶配向処理剤。
    Figure JPOXMLDOC01-appb-C000001
    The liquid crystal aligning agent of Claim 5 whose diaminobenzene which has a disubstituted amino group substituted by the C2-C3 alkenyl group is diamine represented by following formula [1].
    Figure JPOXMLDOC01-appb-C000001
  7.  ジアミン成分が、さらに、下記の式[32]で表されるジアミンを含む、請求項6に記載の液晶配向処理剤。
    Figure JPOXMLDOC01-appb-C000002
    (上記式中、kは1~20の整数を表す。)
    The liquid-crystal aligning agent of Claim 6 in which a diamine component contains the diamine represented by following formula [32] further.
    Figure JPOXMLDOC01-appb-C000002
    (In the above formula, k represents an integer of 1 to 20.)
  8.  式[1]で表されるジアミンが、全ジアミン成分中20~90モル%含有される請求項6に記載の液晶配向処理剤。 The liquid crystal aligning agent according to claim 6, wherein the diamine represented by the formula [1] is contained in an amount of 20 to 90 mol% in all diamine components.
  9.  さらに、式[32]で表されるジアミンが、全ジアミン成分中5~40モル%含有される、請求項8に記載の液晶配向処理剤。 Furthermore, the liquid crystal aligning agent according to claim 8, wherein the diamine represented by the formula [32] is contained in an amount of 5 to 40 mol% in all diamine components.
  10.  請求項1~9のいずれかに記載の液晶配向処理剤を電極付き基板上に塗布、焼成して得られる液晶配向膜。 A liquid crystal alignment film obtained by applying and baking the liquid crystal aligning agent according to any one of claims 1 to 9 on a substrate with an electrode.
  11.  請求項10に記載の液晶配向膜を有する液晶表示素子。 A liquid crystal display element having the liquid crystal alignment film according to claim 10.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011132751A1 (en) * 2010-04-22 2011-10-27 日産化学工業株式会社 Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element
WO2013035803A1 (en) * 2011-09-08 2013-03-14 日産化学工業株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2013125595A1 (en) * 2012-02-22 2013-08-29 日産化学工業株式会社 Composition, liquid crystal aligninig agent, liquid crystal alighment film, and liquid crystal display element
WO2014115233A1 (en) * 2013-01-28 2014-07-31 日立化成デュポンマイクロシステムズ株式会社 Resin composition, method for manufacturing pattern cured film, and semiconductor element
KR20140113421A (en) 2013-03-14 2014-09-24 제이엔씨 주식회사 Liquid crystal aligning agents and liquid crystal display devices
KR20140117593A (en) 2012-01-26 2014-10-07 닛산 가가쿠 고교 가부시키 가이샤 Method for preparing polyimide varnish, and liquid crystal aligning agent
TWI608278B (en) * 2011-10-13 2017-12-11 Jsr股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device
JP2019174800A (en) * 2018-03-27 2019-10-10 Jnc株式会社 Liquid crystal alignment agent for forming liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element using the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5929565B2 (en) 2011-10-13 2016-06-08 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP5929566B2 (en) * 2011-11-16 2016-06-08 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP5990928B2 (en) * 2012-02-24 2016-09-14 Jsr株式会社 Liquid crystal alignment agent
JP6217937B2 (en) * 2012-08-10 2017-10-25 日産化学工業株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JPWO2014192922A1 (en) * 2013-05-31 2017-02-23 日産化学工業株式会社 Manufacturing method of substrate having liquid crystal alignment film for lateral electric field driving type liquid crystal display element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09230353A (en) * 1996-02-20 1997-09-05 Japan Synthetic Rubber Co Ltd Liquid crystal alignment layer agent
JPH09265096A (en) * 1996-03-27 1997-10-07 Japan Synthetic Rubber Co Ltd Liquid crystal alignment agent
JPH1060275A (en) * 1996-08-13 1998-03-03 Japan Synthetic Rubber Co Ltd Liquid crystal orienting agent
JPH10204437A (en) * 1997-01-24 1998-08-04 Jsr Corp Liquid crystal-orienting agent
JPH11109365A (en) * 1997-09-29 1999-04-23 Jsr Corp Liquid crystal orienting agent

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2526845B2 (en) 1991-10-25 1996-08-21 日産化学工業株式会社 Polyimide varnish composition and use thereof
US5700860A (en) * 1995-03-27 1997-12-23 Japan Synthetic Rubber Co., Ltd. Liquid crystal orienting agent
TWI284147B (en) * 2001-11-15 2007-07-21 Nissan Chemical Ind Ltd Liquid crystal aligning agent for vertical alignment, alignment layer for liquid crystal, and liquid crystal displays made by using the same
KR101166003B1 (en) * 2004-04-28 2012-07-18 닛산 가가쿠 고교 가부시키 가이샤 Liquid-crystal aligning agent, liquid-crystal alignment film comprising the same, and liquid-crystal element
WO2006126555A1 (en) 2005-05-25 2006-11-30 Nissan Chemical Industries, Ltd. Liquid crystal aligning agent and liquid crystal display device using same
TW200801737A (en) * 2006-06-22 2008-01-01 Jsr Corp Liquid crystal alignment agent and liquid crystal display device
KR101446818B1 (en) * 2006-11-24 2014-10-01 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09230353A (en) * 1996-02-20 1997-09-05 Japan Synthetic Rubber Co Ltd Liquid crystal alignment layer agent
JPH09265096A (en) * 1996-03-27 1997-10-07 Japan Synthetic Rubber Co Ltd Liquid crystal alignment agent
JPH1060275A (en) * 1996-08-13 1998-03-03 Japan Synthetic Rubber Co Ltd Liquid crystal orienting agent
JPH10204437A (en) * 1997-01-24 1998-08-04 Jsr Corp Liquid crystal-orienting agent
JPH11109365A (en) * 1997-09-29 1999-04-23 Jsr Corp Liquid crystal orienting agent

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KR101775182B1 (en) 2010-04-22 2017-09-05 닛산 가가쿠 고교 가부시키 가이샤 Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element
KR101775181B1 (en) 2010-04-22 2017-09-05 닛산 가가쿠 고교 가부시키 가이샤 Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element
JP5713009B2 (en) * 2010-04-22 2015-05-07 日産化学工業株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2011132751A1 (en) * 2010-04-22 2011-10-27 日産化学工業株式会社 Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element
JP2016194707A (en) * 2011-09-08 2016-11-17 日産化学工業株式会社 Liquid crystal alignment processing agent, liquid crystal alignment film, and liquid crystal display
WO2013035803A1 (en) * 2011-09-08 2013-03-14 日産化学工業株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
JPWO2013035803A1 (en) * 2011-09-08 2015-03-23 日産化学工業株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI608278B (en) * 2011-10-13 2017-12-11 Jsr股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device
KR20140117593A (en) 2012-01-26 2014-10-07 닛산 가가쿠 고교 가부시키 가이샤 Method for preparing polyimide varnish, and liquid crystal aligning agent
JPWO2013125595A1 (en) * 2012-02-22 2015-07-30 日産化学工業株式会社 Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element
WO2013125595A1 (en) * 2012-02-22 2013-08-29 日産化学工業株式会社 Composition, liquid crystal aligninig agent, liquid crystal alighment film, and liquid crystal display element
JP2018083943A (en) * 2012-02-22 2018-05-31 日産化学工業株式会社 Composition, liquid crystal orientation treatment agent, liquid crystal orientation film and liquid crystal display element
WO2014115233A1 (en) * 2013-01-28 2014-07-31 日立化成デュポンマイクロシステムズ株式会社 Resin composition, method for manufacturing pattern cured film, and semiconductor element
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