WO2022014467A1 - 液晶配向剤、液晶配向膜、及び液晶表示素子 - Google Patents
液晶配向剤、液晶配向膜、及び液晶表示素子 Download PDFInfo
- Publication number
- WO2022014467A1 WO2022014467A1 PCT/JP2021/025826 JP2021025826W WO2022014467A1 WO 2022014467 A1 WO2022014467 A1 WO 2022014467A1 JP 2021025826 W JP2021025826 W JP 2021025826W WO 2022014467 A1 WO2022014467 A1 WO 2022014467A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- crystal alignment
- group
- diamine
- alignment agent
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Definitions
- the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
- liquid crystal displays have been widely used as display units for personal computers, smartphones, mobile phones, television receivers, and the like.
- the liquid crystal display device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, and an alignment film that controls the orientation of liquid crystal molecules in the liquid crystal layer. It is equipped with a thin film transistor (TFT) or the like for switching an electric signal supplied to a pixel electrode.
- TFT thin film transistor
- As the driving method of the liquid crystal molecule a vertical electric field method such as a TN method and a VA method, and a horizontal electric field method such as an IPS method and an FFS (fringe field switching) method are known.
- liquid crystal alignment film in the industry is a film made of polyamic acid and / or a polyimide imidized with a polyamic acid formed on an electrode substrate, and the surface of the film is made of a cloth such as cotton, nylon, or polyester. It is manufactured by performing a so-called rubbing process of rubbing in one direction.
- the rubbing process is a simple and highly productive industrially useful method.
- scratches on the surface of the alignment film generated by the rubbing process, dust generation, the effects of mechanical force and static electricity, and the in-plane alignment process Various problems such as non-uniformity of the above have been clarified.
- Non-Patent Document 1, Patent Document 1, and Patent Document 2). reference a photo-alignment method for imparting a liquid crystal alignment ability by irradiating with polarized radiation.
- a photoalignment method a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photodecomposition reaction, and the like have been proposed (for example, Non-Patent Document 1, Patent Document 1, and Patent Document 2). reference).
- the irradiation amount of light is a factor that affects the energy cost and the production speed, so it is preferable that the orientation treatment can be performed with a small irradiation amount.
- the liquid crystal alignment agent can obtain good liquid crystal alignment under the condition of a large irradiation amount, when the light irradiation amount is reduced, the liquid crystal alignment film surface is covered.
- the liquid crystal orientation of the liquid crystal display tends to vary (non-uniformity), and the twist angle of the liquid crystal display in the surface of the liquid crystal display element also has a large variation. Then, when black display is performed by the liquid crystal display element, there is a concern that the brightness in the plane may vary and the display quality may be deteriorated.
- liquid crystal alignment film used for the liquid crystal display element of the IPS drive system or the FFS drive system is also required to have an orientation regulating force for suppressing the afterimage generated by the long-term AC drive (hereinafter, also referred to as AC afterimage).
- an object of the present invention is a liquid crystal alignment film in which the variation (non-uniformity) of the liquid crystal orientation in the liquid crystal alignment film surface is suppressed even if the light irradiation amount in the alignment treatment by the photoalignment method is reduced. It is an object of the present invention to provide a liquid crystal alignment agent for obtaining the liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment film. Furthermore, it is an object of the present invention to provide a liquid crystal alignment film having an excellent liquid crystal alignment regulating force capable of suppressing AC afterimage, a liquid crystal alignment agent for obtaining the liquid crystal alignment film, and a liquid crystal display element using the liquid crystal alignment film. And.
- the present inventor has conducted diligent research to achieve the above problems, and as a result, a liquid crystal containing a polymer obtained by using a specific amount of a specific diamine and a specific alicyclic tetracarboxylic dianhydride as essential components.
- a liquid crystal alignment film formed by using the aligning agent is extremely effective for achieving the above object, and completed the present invention.
- a characteristic liquid crystal alignment agent is provided.
- X represents a structure selected from the group consisting of the following formulas (x-1) to (x-7).
- R 1 to R 4 each independently contain a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom. It represents a monovalent organic group or a phenyl group having 1 to 6 carbon atoms.
- R 5 and R 6 each independently represent a hydrogen atom or a methyl group. * 1 is bonded to one of the acid anhydride groups. It is a bond, and * 2 is a bond that binds to the other acid anhydride group.)
- the liquid crystal alignment film in which the variation (non-uniformity) of the liquid crystal orientation in the liquid crystal alignment film surface is suppressed even if the light irradiation amount in the alignment treatment by the photoalignment method is reduced, and the liquid crystal. It is possible to provide a liquid crystal alignment agent for obtaining an alignment film and a liquid crystal display element using the liquid crystal alignment film. Further, it is possible to provide a liquid crystal alignment film having an excellent liquid crystal alignment regulating force capable of suppressing AC afterimage, a liquid crystal alignment agent for obtaining the liquid crystal alignment film, and a liquid crystal display element using the liquid crystal alignment film. ..
- the polymer of the present invention has a structure in which a urea bond and a benzene ring are directly connected, and the obtained polymer has a relatively rigid structure, so that the liquid crystal orientation in the liquid crystal alignment film surface varies. It is considered that the amount was reduced and the effect was also effective in suppressing the AC afterimage.
- examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Boc represents a tert-butoxycarbonyl group.
- liquid crystal alignment agent containing a polymer obtained by using a specific amount of a specific diamine and a specific alicyclic tetracarboxylic dianhydride as essential components, and a liquid crystal alignment film formed by using the liquid crystal alignment agent.
- liquid crystal display element having the liquid crystal alignment film will be described in detail, but the description of the constituent requirements described below is an example as an embodiment of the present invention, and is not specified in these contents. ..
- the liquid crystal alignment agent of the present invention contains the polymer (A).
- Preferred embodiments of the liquid crystal alignment agent of the present invention include a liquid crystal alignment agent containing a polymer (A) and an organic solvent. Further, the liquid crystal alignment agent of the present invention can also contain a polymer other than the polymer (A) (for example, the polymer (B) described later).
- the polymer (A) contains a diamine component represented by the above formula (1) (hereinafter, also referred to as a specific diamine) in an amount of 5 mol% or more based on 1 mol of the diamine component used, and the above formula (T). It is selected from the group consisting of a polyimide precursor obtained by using an alicyclic tetracarboxylic acid dianhydride represented by (1) or a tetracarboxylic acid derivative component containing a derivative thereof, and a polyimide which is an imidized product of the polyimide precursor. At least one polymer. Specific examples of such a polymer include a polyimide precursor having an imide precursor structure such as polyamic acid and a polyamic acid ester, and polyimide which is an imidized product of the polyimide precursor.
- the specific diamine used in the present invention is a diamine represented by the following formula (1). (Any hydrogen atom on the benzene ring may be substituted with a monovalent substituent.)
- Examples of the monovalent substituent on the benzene ring include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Fluoroalkyl group, fluoroalkenyl group having 2 to 10 carbon atoms, fluoroalkoxy group having 1 to 10 carbon atoms, carboxy group, alkyloxycarbonyl group having 1 to 10 carbon atoms, cyano group, nitro group and the like.
- preferred specific examples of the specific diamine include, but are not limited to, diamines represented by the following formulas (1-1) to (1-3).
- the diamine component for obtaining the polymer (A) is a substance containing at least one diamine represented by the above formula (1) in an amount of 5 mol% or more based on 1 mol of the diamine component used, and is one kind. It may be composed of diamines, or may be composed of two or more types of diamines. When the diamine component is composed of two or more kinds of diamines, it may contain a diamine other than the diamine represented by the formula (1) together with the diamine represented by the formula (1). As the compound represented by the following formula (1), one kind may be used alone, or two or more kinds may be used in combination.
- the ratio of the diamine represented by the formula (1) in the diamine component for obtaining the polymer (A) is preferably 5 to 100 mol% with respect to 1 mol of the diamine component used, and is preferably 5 to 99. More preferably, it is 5 to 70 mol%. From the viewpoint of enhancing the liquid crystal orientation, it is even more preferably 10 to 60 mol%.
- the diamine component used together with the diamine represented by the formula (1) is not particularly limited as the diamine component for obtaining the polymer (A), and examples thereof include compounds represented by the following formula (2) or formula (2i). Can be done.
- the compounds represented by the following formulas (2) and (2i) may be used alone or in combination of two or more.
- Y 2 represents a divalent organic group represented by the following formula (O).
- Two Rs independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- Two Y 2i are each.
- Independently represents a divalent organic group represented by the following formula (O').
- Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring.
- the two Ars may be the same or different, and any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring is a monovalent substitution. It may be substituted with a group.
- P is an integer of 0 or 1.
- Q 2 is ⁇ (CH 2 ) n ⁇ (n is an integer of 2 to 18), or the ⁇ (CH 2 ) n.
- Examples of the substituent of the benzene ring, biphenyl structure, or naphthalene ring include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number of carbon atoms. Fluoroalkyl group of 1 to 10, fluoroalkenyl group of 2 to 10 carbon atoms, fluoroalkoxy group of 1 to 10 carbon atoms, carboxy group, hydroxy group, alkyloxycarbonyl group of 1 to 10 carbon atoms, cyano group, nitro group And so on.
- the divalent organic group represented by the above formula (O) is preferably a divalent organic group represented by the following formulas (o-1) to (o-16) from the viewpoint of enhancing the liquid crystal orientation.
- * represents a bond.
- the divalent organic group represented by the above formula (O') is preferably a divalent organic group represented by the above formulas (o-7) to (o-16) from the viewpoint of enhancing the liquid crystal orientation.
- Y 2 is a divalent organic group represented by the above formulas (o-1) to (o-14) in the formula (2).
- a combination of a diamine and a diamine of the formula (2) in which Y 2 is a divalent organic group represented by the above formulas (o-15) to (o-16) is preferable.
- Preferred specific examples of the diamine represented by the above formula (2i) include compounds represented by the following formulas (2i-1) to (2i-5).
- the two ns independently represent an integer of 1 to 6.
- the two ns are independent of each other. Represents an integer of 2 to 6)
- the total content of the diamine represented by the formula (2) and the diamine represented by the formula (2i) is 1 mol of the diamine component used for the synthesis of the polymer (A). On the other hand, it is preferably 1 to 95 mol%, more preferably 30 to 95 mol%, still more preferably 40 to 90 mol%.
- Y 2 is a divalent organic group represented by the above formulas (o-1) to (o-14) in the formula (2).
- the sum of the diamine and the diamine of the formula (2) in which Y 2 is a divalent organic group represented by the above formulas (o-15) to (o-16) is used for the synthesis of the polymer (A). It is preferably 1 to 95 mol%, more preferably 30 to 95 mol%, and even more preferably 40 to 90 mol% with respect to 1 mol of the diamine component to be obtained. Further, from the viewpoint of increasing the contrast of the liquid crystal display element, the upper limit of the diamine represented by the formula (2) and each diamine represented by the formula (2i) is the diamine component used for the synthesis of the polymer (A). It may be 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less with respect to 1 mol.
- the polymer (A) having the group "-N (D)-(D represents a carbamate-based protecting group)" has the group "-N (D)-(D represents a carbamate-based protecting group)".
- the carbamate-based protecting group include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.
- diamine having the group "-N (D)-(D represents a carbamate-based protecting group) a diamine having at least one aromatic group such as a benzene ring is preferable, and an aromatic group such as a benzene ring is used.
- a diamine having at least one residue other than the group “(D)” having 6 to 30 carbon atoms is more preferable.
- Specific examples of the diamine having the group “-N (D)-(D represents a carbamate-based protecting group)” include compounds represented by the following formulas (5-1) to (5-10). Can be mentioned.
- the ratio of the diamine having the group "-N (D)-(D represents a carbamate-based protecting group)" is used for the synthesis of the polymer (A) from the viewpoint of increasing the voltage retention rate of the liquid crystal display element.
- 1 mol% or more is preferable with respect to 1 mol of the diamine component, and 2 mol% or more is more preferable.
- the usage ratio is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less.
- diamine component for obtaining the polymer (A) the diamine represented by the above formula (1), the diamine represented by the above formula (2) or the formula (2i), or the group "-N (D)-( D represents a carbamate-based protecting group.) ”,
- diamines other than diamines may be used. Examples of other diamines include the following diamines.
- Diamines having photoorienting groups such as 4,4'-diaminoazobenzene and diamines represented by the following formulas (d T -1) to (d T -3); 2,4-diaminophenol, 3,5-diamino Phenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid and: Diamines having a carboxyl group such as diamine compounds represented by the formulas (3b-1) to (3b-4); 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-Diaminobenzophenone, 1,4-bis (4-aminobenzyl) benzene,
- a diamine having a urea bond such as a diamine to be formed; a diamine having an amide bond represented by the following formulas (h-4) to (h-6); 2- (2,4-diaminophenoxy) ethyl methacrylate and 2, A diamine having a photopolymerizable group such as 4-diamino-N, N-diallylaniline at the end; a diamine having a siloxane bond such as 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; the following formula (Ox) -1)-Diamines having an oxazoline structure such as (Ox-2).
- a 1 is a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, -O-, -CO-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO-, -OCO-, -CON ( CH 3 )-or -N (CH 3 ) CO-, m1 and m2 independently represent an integer of 0 to 4, and m1 + m2 represent an integer of 1 to 4. Equation (3b-2).
- m3 and m4 each independently represent an integer of 1 to 5.
- a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
- m5 represents 1 to 5.
- a 3 and a 4 are each independently a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2- , -C (CF 3 ) 2- , -O-, -CO-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO -, - OCO -, - CON (CH 3) - or -N (CH 3) CO- represents, m6 is an integer of 1-4).
- Tetracarboxylic acid derivative component When the above polymer (A) is produced, the tetracarboxylic acid derivative component to be reacted with the diamine component is not only tetracarboxylic acid dianhydride, but also tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester. Derivatives of tetracarboxylic acid dianhydride such as dihalide can also be used. As the tetracarboxylic acid derivative component, one kind of tetracarboxylic dianhydride or a derivative thereof may be used alone, or two or more kinds thereof may be used in combination.
- the tetracarboxylic dianhydride component for obtaining the polymer (A) includes an alicyclic tetracarboxylic dianhydride represented by the above formula (T) or a derivative thereof.
- the alicyclic tetracarboxylic dianhydride represented by the formula (T) or a derivative thereof may be composed of one kind of tetracarboxylic dianhydride or a derivative thereof, or two or more kinds of tetracarboxylic dianhydrides. (Ii) It may consist of anhydrate or a derivative thereof.
- the alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the alicyclic structure. be. However, none of these four carboxy groups are bonded to the aromatic ring. Further, it does not have to be composed only of an alicyclic structure, and may have a chain hydrocarbon structure or an aromatic ring structure as a part thereof.
- the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the aromatic ring.
- the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure.
- it does not have to be composed only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure as a part thereof.
- the above formula (x-1) is preferably selected from the group consisting of the following formulas (X1-1) to (X1-6). From the viewpoint of enhancing the liquid crystal orientation, the following formula (X1-1) is more preferable. (* 1 is a bond that binds to one acid anhydride group, and * 2 is a bond that binds to the other acid anhydride group.)
- the ratio of the alicyclic tetracarboxylic dianhydride represented by the above formula (T) or a derivative thereof is 10 with respect to 1 mol of the total tetracarboxylic dianhydride component used in the synthesis of the polymer (A). It is preferably ⁇ 100 mol%, more preferably 20-100 mol%, still more preferably 50-100 mol%.
- the tetracarboxylic acid dianhydride and its derivative used for producing the polymer (A) are an alicyclic tetracarboxylic acid dianhydride represented by the above formula (T) or a tetracarboxylic acid dianhydride other than the derivative thereof.
- tetracarboxylic acid dianhydride or a derivative thereof
- other tetracarboxylic dianhydrides or derivatives thereof include tetracarboxylic dianhydrides represented by the following formula (2T) or derivatives thereof.
- 2T tetracarboxylic dianhydrides represented by the following formula (2T) or derivatives thereof.
- the above-mentioned tetracarboxylic dianhydride or a derivative thereof may be used alone or in combination of two or more.
- (X 2 represents a structure selected from the group consisting of the following formulas (x-8) to (x-13) and the following formulas (t-1) to (t-26).)
- (J and k are integers of 0 or 1
- a 1 and A 2 independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amide group, respectively.
- * 1 represents a bond that binds to one acid anhydride group
- * 2 represents a bond that binds to the other acid anhydride group
- * represents a bond that binds to an acid anhydride group.
- R 8 independently contains a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom having 1 to 6 carbon atoms. 6 monovalent organic group, or a phenyl group. liquid crystal alignment of the points, R 8 is a hydrogen atom, a halogen atom, preferably a methyl group or an ethyl group, a hydrogen atom, or a methyl group is more preferable.
- the liquid crystal alignment agent of the present invention is a group consisting of a polyimide precursor obtained by using a tetracarboxylic acid derivative component and a diamine component and a polyimide which is an imidized product of the polyimide precursor, from the viewpoint of reducing the afterimage derived from residual DC.
- the polymer (B) selected from the above (however, excluding the polymer (A)) may be contained.
- examples thereof include polymers selected from.
- Specific examples of the polyimide precursor include polyamic acid and polyamic acid ester.
- the polymer (B) one type may be used alone, or two or more types may be used in combination.
- Examples of the tetracarboxylic dianhydride component for obtaining the polymer (B) include acyclic aliphatic tetocarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride or derivatives thereof. Can be mentioned. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride, the alicyclic tetracarboxylic dianhydride, and the aromatic tetocarboxylic dianhydride include the tetracarboxylic dianhydride exemplified in the polymer (A). Can be mentioned.
- the preferred tetcarboxylic acid derivative component is the alicyclic tetracarboxylic acid dianhydride represented by the above formula (T) or a derivative thereof, and X 2 is a formula of the above formulas (x-8) to (x-13).
- the tetracarboxylic acid dianhydride represented by (2T) or a derivative thereof (hereinafter, these are collectively referred to as a specific tetracarboxylic acid derivative component (b)) is preferable.
- the tetracarboxylic acid derivative component one kind of tetracarboxylic dianhydride or a derivative thereof may be used alone, or two or more kinds thereof may be used in combination.
- Examples of the diamine component for obtaining the polymer (B) include the diamine exemplified in the polymer (A) (however, the specific diamine is excluded), a nitrogen atom-containing heterocycle, a secondary amino group and a tertiary amino.
- Examples thereof include diamines having at least one nitrogen atom-containing structure (hereinafter, also referred to as a specific nitrogen atom-containing structure) selected from the group consisting of groups (however, diamine represented by the above (5-8) is excluded).
- Examples of the nitrogen atom-containing heterocycle that the diamine having the specific nitrogen atom-containing structure may have include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indol, benzimidazole, purine, and quinoline. , Isoquinoline, naphthylidine, quinoxalin, phthalazine, triazine, carbazole, aclysine, piperidine, piperazine, pyrrolidine, hexamethyleneimine and the like. Of these, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine are preferable.
- the secondary amino group and the tertiary amino group that the diamine having the specific nitrogen atom-containing structure may have are represented by, for example, the following formula (n).
- R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group.
- "*" Represents a bond that binds to a hydrocarbon group.
- Examples of the alkyl group of R in the above formula (n) include a methyl group, an ethyl group and a propyl group.
- Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aryl group include a phenyl group and a methylphenyl group.
- R is preferably a hydrogen atom or a methyl group.
- diamine having the specific nitrogen atom-containing structure examples include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, and N-methyl-3.
- 6-Diaminocarbazole, 1,4-bis- (4-aminophenyl) -piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole examples thereof include compounds represented by the following formulas (Dp-1) to (Dp-8) and compounds represented by the following formulas (z-1) to (z-18).
- the polymer (B) is a diamine having a nitrogen atom-containing structure, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-.
- Diamines with carboxyl groups such as the indicated diamine compounds, 4- (2- (methylamino) ethyl) aniline, 4- (2-aminoethyl) aniline, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone. , 4,4'-Diaminodiphenyl ether, and diamines selected from the group consisting of diamines having a urea bond such as diamines represented by the above formulas (h-1) to (h-3) (collectively, diamines (collectively, diamines). It is preferably a polymer obtained by using b).
- the content of diamine (b) is preferably 1 to 100 mol% with respect to 1 mol of the diamine component used for the synthesis of the polymer (B), 5 to 5 to. 100 mol% is more preferable.
- the total content of the diamine (b) is preferably 90 mol% or less, more preferably 80 mol% or less.
- the content ratio of the polymer (A) and the polymer (B) is 10/90 to 90 in terms of the mass ratio of [polymer (A)] / [polymer (B)]. It may be / 10, 20/80 to 90/10, or 20/80 to 80/20.
- the ratio of the specific tetracarboxylic acid derivative component (b) used is preferably 1 to 100 mol% with respect to 1 mol of the total tetracarboxylic acid derivative component used in the synthesis of the polymer (B). It is more preferably 5 to 100 mol%, and even more preferably 10 to 100 mol%.
- the polymer (A) or (B) is produced by reacting the diamine component and the tetracarboxylic acid derivative component in a solvent (condensation).
- a part of the polymer (A) or (B) contains an amic acid structure, for example, a polymer having an amic acid structure (polyamic acid) by reacting a tetracarboxylic acid dianhydride component with a diamine component. Is obtained.
- the solvent is not particularly limited as long as it dissolves the produced polymer.
- the above solvent examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl.
- -2-Imidazolidinone can be mentioned.
- the polymer has high solvent solubility, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3].
- a solvent can be used.
- D 1 represents an alkyl group having 1 to 3 carbon atoms
- D 2 represents an alkyl group having 1 to 3 carbon atoms
- D-3 represents an alkyl group having 1 to 4 carbon atoms.
- the reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
- the initial reaction can be carried out at a high concentration and then the solvent can be added.
- the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid derivative component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weights of the polymer (A) and the polymer (B) produced.
- the polymer containing the amic acid ester structure is, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [II]. III] It can be obtained by a known method such as a method of reacting a tetracarboxylic acid diester dihalide with a diamine.
- the imidized product in the polymer (A) or (B) contained in the liquid crystal alignment agent of the present invention is obtained by ring-closing the polymer obtained above.
- the ring closure rate (also referred to as imidization rate) of the functional group of the amic acid group or its derivative does not necessarily have to be 100%, and the imidized product can be arbitrarily adjusted according to the intended use and purpose.
- the imidization ratio of the polymer (A) is preferably 20 to 100%, preferably 50 to 95%, and even more preferably 60 to 90%.
- Examples of the method for obtaining an imidized product include thermal imidization in which the polymer solution obtained in the above reaction is heated as it is, or catalytic imidization in which a catalyst is added to the polymer solution.
- the temperature for thermal imidization in the solution is preferably 100 to 400 ° C, more preferably 120 to 250 ° C, and it is preferable to remove the water produced by the imidization reaction from the system.
- the catalyst imidization is carried out by adding a basic catalyst and an acid anhydride to a solution of the polymer obtained by the reaction, and stirring the mixture at preferably ⁇ 20 to 250 ° C., more preferably 0 to 180 ° C. be able to.
- the amount of the basic catalyst is preferably 0.5 to 30 mol times, more preferably 2 to 20 mol times, and the amount of acid anhydride is preferably 1 to 50 mol times, more than the amic acid group. It is preferably 3 to 30 mol times.
- the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like, and among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
- Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like, and among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed.
- the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.
- the reaction solution may be added to a solvent for precipitation.
- the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like.
- the polymer put into a solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure.
- impurities in the polymer can be reduced.
- the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these, because the purification efficiency is further improved.
- the polymer (A) or (B) used in the present invention preferably has a solution viscosity of, for example, 10 to 1000 mPa ⁇ s when it is used as a solution having a concentration of 10 to 15% by mass from the viewpoint of workability.
- the solution viscosity (mPa ⁇ s) of the polymer is a polymer having a concentration of 10 to 15% by mass prepared by using a good solvent of the polymer (for example, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.).
- the values of the solution were measured at 25 ° C. using an E-type rotational viscometer.
- the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polymer (A) or (B) is preferably 1,000 to 500,000, more preferably 2,. It is 000 to 500,000.
- the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. Within such a molecular weight range, good orientation and stability of the liquid crystal display element can be ensured.
- an end-sealed polymer is prepared by using an appropriate end-sealing agent together with the tetracarboxylic acid derivative component and the diamine component as described above. It may be synthesized.
- the end-sealed polymer has the effects of improving the film hardness of the liquid crystal alignment film obtained by the coating film and improving the adhesion characteristics between the sealant and the liquid crystal alignment film.
- Examples of the terminal of the polymer (A) and the polymer (B) in the present invention include an amino group, a carboxy group, an acid anhydride group or a derivative thereof.
- Amino groups, carboxy groups, acid anhydride groups or derivatives thereof can be obtained by a usual condensation reaction or by sealing the ends with the following terminal encapsulants, wherein the derivatives are, for example, , Can also be obtained in the same manner using the following terminal encapsulants.
- terminal encapsulant examples include acetic anhydride, maleic anhydride, nagic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-( 3-Trimethoxysilyl) propyl) -3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride, etc.
- Dicarbonate diester compounds such as di-tert-butyl dicarbonate, diallyl dicarbonate
- chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, nicotinic acid chloride
- aniline 2-aminophenol, 3-aminophenol, 4 -Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n -Monoamine compounds such as heptylamine and n-octylamine; monoisocyanate compounds such as ethyl isocyanate, phenylisocyanate and naphthylisocyanate can be mentioned.
- the ratio of the terminal encapsulant to be used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, based on 100 mol parts of the total diamine component used.
- the liquid crystal alignment agent of the present invention contains a polymer (A) and, if necessary, a polymer (B).
- the liquid crystal alignment agent of the present invention may contain other polymers in addition to the polymer (A) and the polymer (B).
- examples of other types of polymers include polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene or its derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like.
- the liquid crystal alignment agent is used for producing a liquid crystal alignment film, and takes the form of a coating liquid from the viewpoint of forming a uniform thin film.
- the liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and an organic solvent.
- the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, 1% by mass or more is preferable, and from the viewpoint of storage stability of the solution, 10% by mass or less is preferable. A particularly preferable concentration of the polymer is 2 to 8% by mass.
- the content of the polymer (A) in the liquid crystal alignment agent can be appropriately changed depending on the application method of the liquid crystal alignment agent and the film thickness of the target liquid crystal alignment film, but it may be 2 to 10% by mass. It is preferable, and particularly preferably 3 to 7% by mass.
- the organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfonate, and ⁇ -butyrolactone.
- ⁇ -Valerolactone 1,3-dimethyl-2-imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropaneamide, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N- (n-pentyl) ) -2-Pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (collectively "good solvent”) Also known as).
- N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide or ⁇ -butyrolactone are preferable.
- the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent.
- the organic solvent contained in the liquid crystal alignment agent is a mixture in which a solvent (also referred to as a poor solvent) for improving the coatability when applying the liquid crystal alignment agent and the surface smoothness of the coating film is used in combination with the above solvent.
- a solvent also referred to as a poor solvent
- the use of solvent is preferred. Specific examples of the poor solvent used in combination are described below, but the present invention is not limited thereto.
- the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.
- the type and content of the poor solvent are appropriately selected according to the liquid crystal alignment agent coating device, coating conditions, coating environment, and the like.
- diisopropyl ether diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol)
- ethylene glycol dimethyl ether ethylene glycol diethyl ether
- ethylene glycol dibutyl ether 1,2-butoxyetan
- diethylene glycol dimethyl ether diethylene glycol diethyl ether.
- diisobutylcarbinol diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene.
- Glycol monobutyl ether acetate or diisobutyl ketone is preferred.
- Preferred combinations of good and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2-.
- Examples thereof include diisobutylketone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone and diisobutylketone, N-ethyl-2-pyrrolidone and N, N-dimethyllactamide and diisobutylketone.
- the liquid crystal alignment agent of the present invention may additionally contain a component other than the polymer component and the organic solvent (hereinafter, also referred to as an additive component).
- additive components include an adhesion aid for enhancing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealant, and a compound for increasing the strength of the liquid crystal alignment film (hereinafter,).
- Also referred to as a crosslinkable compound a compound for promoting imidization, a dielectric for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film, a conductive substance, and the like can be mentioned.
- an oxylanyl group an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, and a meldrum.
- R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or "* -CH 2- OH". * Indicates a bond.
- R is 1 carbon atom. Represents an alkyl group of up to 6; an alkenyl group of 2 to 6 carbon atoms, or an alkynyl group of 2 to 6 carbon atoms.
- Z represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. , Or an alkynyl group having 2 to 6 carbon atoms.
- A represents a (m + n) valent organic group having an aromatic ring.
- R' represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- M represents 1 Represents an integer of ⁇ 6, and n represents an integer of 0 to 4.
- the compound having an oxylanyl group examples include the compound described in paragraph [0037] of JP-A-10-338880 and the compound having a triazine ring as a skeleton described in International Publication No. 2017/170483. Examples thereof include compounds having more than one oxylanyl group.
- the compound having an oxetanyl group include the compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751.
- the compound having a protected isocyanate group include the compounds having two or more protected isocyanate groups described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978, International Publication No. 2015/141598.
- the compounds having three or more protected isocyanate groups described in paragraphs [0119] to [0120] of the above are mentioned, and the compounds represented by the following formulas (bi-1) to (bi-3) may be used. ..
- Specific examples of the compound having a protected isothiocyanate group include the compounds having two or more protected isothiocyanate groups described in Japanese Patent Application Laid-Open No. 2016-2000798.
- Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597.
- Specific examples of the compound having a group containing a Meldrum's acid structure include the compound having two or more Meldrum's acid structures described in International Publication No. 2012/091088.
- Specific examples of the compound having a cyclocarbonate group include the compound described in International Publication No. 2011/155577.
- R 2 an alkyl group having 1 to 3 carbon atoms R 3 group represented by the above formula (d), a methyl group, an ethyl group, a propyl group.
- the compound having a group represented by the above formula (d) include the above formula (d) described in International Publication No. 2015/072554 and paragraph [0058] of Japanese Patent Application Laid-Open No. 2016-118753.
- Examples thereof include compounds having two or more groups represented by (2) and compounds described in Japanese Patent Application Laid-Open No. 2016-209458, which are compounds represented by the following formulas (hd-1) to (hd-8). May be good.
- the compound having a group represented by the above (d1) include the compounds described in International Publication No. 2019/142927, and more preferably the following formulas (hd1-1) to (hd1-4). It may be a compound represented.
- Examples of the (m + n) -valent organic group having an aromatic ring in A of the above formula (e) include an (m + n) -valent aromatic hydrocarbon group having 6 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples thereof include (m + n) valent organic groups bonded directly or via a linking group, and (m + n) valent groups having an aromatic heterocycle.
- Examples of the aromatic hydrocarbon include benzene and naphthalene.
- Examples of the aromatic heterocycle include the aromatic heterocycle exemplified in the above-mentioned specific nitrogen atom-containing structure.
- Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, a group obtained by removing one hydrogen atom from the alkylene group, a divalent or trivalent cyclohexane ring, and the like. Any hydrogen atom of the alkylene group may be substituted with an organic group such as a fluorine atom or a trifluoromethyl group.
- Examples of the alkyl group having 1 to 5 carbon atoms in R'of the above formula (e) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Examples include the n-pentyl group. Specific examples include the compounds described in International Publication No. 2010/074269 and the compounds represented by the following formulas (e-1) to (e-10).
- the above compound is an example of a crosslinkable compound, and is not limited thereto.
- components other than the above disclosed in International Publication No. 2015/060357 on pages 53 [0105] to 55 [0116] can be mentioned.
- two or more kinds of crosslinkable compounds may be combined.
- the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and the crosslinking reaction proceeds. In addition, from the viewpoint of exhibiting good resistance to AC afterimages, it is more preferably 1 to 15 parts by mass.
- adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N.
- silane coupling agent when used, it should be 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent from the viewpoint of exhibiting good resistance to AC afterimage. It is preferable, more preferably 0.1 to 20 parts by mass.
- Examples of the compound for promoting imidization include basic sites (eg, primary amino group, aliphatic heterocycle (eg, pyrrolidine skeleton), aromatic heterocycle (eg, imidazole ring, indole ring), etc.
- a compound having a guanidino group or the like (however, the crosslinkable compound and the adhesion aid are excluded), or a compound in which the basic moiety is generated during firing is preferable. More preferably, it is a compound in which the above-mentioned basic moiety is generated at the time of firing, and a preferable specific example is an amino acid in which a part or all of the basic moiety of the amino acid is protected.
- amino acids include glycine, alanine, cysteine, methionine, asparagine, glutamine, valine, leucine, phenylalanine, tyrosine, tryptophan, proline, hydroxyproline, arginine, histidine, lysine and ornithine.
- More preferred specific examples of the compound for promoting imidization include N- ⁇ - (9-fluorenylmethoxycarbonyl) -N- ⁇ - (tert-butoxycarbonyl) -L-histidine.
- the liquid crystal alignment film of the present invention is obtained from the above liquid crystal alignment agent.
- the liquid crystal alignment film of the present invention can be used for a horizontally oriented type or a vertically oriented type (VA type) liquid crystal alignment film, and among them, a liquid crystal alignment suitable for a horizontally oriented type liquid crystal display element such as an IPS method or an FFS method. It is a membrane.
- the liquid crystal display element of the present invention includes the liquid crystal alignment film.
- the liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (4) or steps (1) to (2) and (4).
- the liquid crystal alignment agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by an appropriate coating method such as a roll coater method, a spin coating method, a printing method, or an inkjet method.
- the substrate is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate.
- a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate.
- an opaque object such as a silicon wafer can be used, and in this case, a material that reflects light such as aluminum can also be used for the electrode.
- a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb tooth shape, and a facing substrate not provided with an electrode Is used.
- Examples of the method of applying the liquid crystal alignment agent to the substrate to form a film include screen printing, offset printing, flexographic printing, inkjet method, spray method and the like. Among them, the coating and film forming methods by the inkjet method can be preferably used.
- Step (2) is a step of firing the liquid crystal alignment agent applied on the substrate to form a film.
- the solvent is evaporated or the polyamic acid or polyamic acid ester is thermally imidized by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. Can be done.
- the drying and firing steps after applying the liquid crystal alignment agent of the present invention can be performed at any temperature and time, and may be performed a plurality of times.
- the drying temperature can be, for example, 40 to 180 ° C. From the viewpoint of shortening the process, it may be carried out at 40 to 150 ° C.
- the drying time is not particularly limited, and examples thereof include 1 to 10 minutes or 1 to 5 minutes.
- a step of firing in a temperature range of, for example, 150 to 300 ° C. or 150 to 250 ° C. can be performed after the drying step.
- the firing time is not particularly limited, and examples thereof include a firing time of 5 to 40 minutes or 5 to 30 minutes. If the film-like material after firing is too thin, the reliability of the liquid crystal display element may decrease, so 5 to 300 nm is preferable, and 10 to 200 nm is more preferable.
- the step (3) is, in some cases, a step of orienting the film obtained in the step (2). That is, in a horizontally oriented liquid crystal display element such as an IPS system or an FFS system, an alignment ability imparting process is performed on the coating film. On the other hand, in a vertically oriented liquid crystal display element such as a VA method or a PSA mode, the formed coating film can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment. Examples of the method for aligning the liquid crystal alignment film include a rubbing treatment method and a photo-alignment treatment method, and the photo-alignment treatment method is more preferable.
- the surface of the film-like material is irradiated with radiation deflected in a certain direction, and in some cases, heat treatment is performed at a temperature of 150 to 250 ° C. to achieve liquid crystal orientation (liquid crystal alignment).
- heat treatment is performed at a temperature of 150 to 250 ° C. to achieve liquid crystal orientation (liquid crystal alignment).
- the radiation ultraviolet rays having a wavelength of 100 to 800 nm or visible light can be used. Among them, ultraviolet rays having a wavelength of preferably 100 to 400 nm, more preferably 200 to 400 nm.
- the dose of the radiation is preferably 1 ⁇ 10,000mJ / cm 2, more preferably 100 ⁇ 5,000mJ / cm 2, more preferably 100 ⁇ 1500mJ / cm 2, particularly preferably 100 ⁇ 1000mJ / cm 2.
- the light irradiation amount in the alignment treatment is 100 to 5000 mJ / cm 2 , but in the liquid crystal alignment agent of the present invention, even if the light irradiation amount in the alignment treatment is reduced. , It is possible to obtain a liquid crystal alignment film in which the variation (non-uniformity) of the liquid crystal orientation in the surface of the liquid crystal alignment film is suppressed.
- the substrate having the film-like substance may be irradiated while being heated at 50 to 250 ° C.
- the liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a certain direction.
- the liquid crystal alignment film irradiated with polarized radiation can be contact-treated with a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.
- the solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves the decomposition product generated from the film-like substance by irradiation with radiation.
- Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3-.
- Examples thereof include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like.
- water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate are preferable from the viewpoint of versatility and solvent safety. More preferred are water, 1-methoxy-2-propanol or ethyl lactate.
- the solvent may be used alone or in combination of two or more.
- the temperature of the heat treatment for the coating film irradiated with the above radiation is more preferably 50 to 300 ° C, further preferably 120 to 250 ° C.
- the heat treatment time is preferably 1 to 30 minutes, respectively.
- Step (4) Step of manufacturing a liquid crystal cell> Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and the liquid crystal is arranged between the two substrates arranged opposite to each other. Specifically, the following two methods can be mentioned. In the first method, first, two substrates are arranged facing each other through a gap (cell gap) so that the liquid crystal alignment films face each other. Next, the peripheral portions of the two substrates are bonded together using a sealant, and the liquid crystal composition is injected and filled into the surface of the substrate and the cell gap partitioned by the sealant to contact the film surface, and then the injection holes are sealed. Stop.
- the second method is a method called an ODF (One Drop Fill) method.
- ODF One Drop Fill
- an ultraviolet light-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is further applied to a predetermined number of places on the liquid crystal alignment film surface. Is dropped. Then, the other substrate is bonded so that the liquid crystal alignment film faces each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant.
- the two substrates are arranged so as to face each other so that the rubbing directions of the coating films are opposite to each other at a predetermined angle, for example, orthogonal or antiparallel.
- the sealing agent for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
- the liquid crystal include a nematic liquid crystal and a smectic liquid crystal, and among them, the nematic liquid crystal is preferable.
- a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell.
- a polarizing plate attached to the outer surface of the liquid crystal cell a polarizing plate called an "H film" in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between a cellulose acetate protective film or the H film itself.
- a polarizing plate made of the above can be mentioned.
- WA-1 A compound represented by the following formula (WA-1)
- (Tetracarboxylic dianhydride) B1 to B3 Compounds represented by the following formulas (B1) to (B3), respectively.
- AD-1 to AD-4 Compounds represented by the following formulas (AD-1) to (AD-4), respectively.
- the molecular weight is measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and a column (KD-803, KD-805) (manufactured by Showa Denko). did.
- GPC room temperature gel permeation chromatography
- N N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr ⁇ H 2 O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L)
- Flow rate 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (Tosoh) and polyethylene glycol (molecular weight; about) 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).
- the viscosity of the solution was measured at a temperature of 25 ° C. using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone rotor TE-1 (1 ° 34', R24). did.
- the ratio of WA-1 in the diamine component was 20 mol% with respect to 1 mol of the diamine component.
- NMP was added to the obtained polyamic acid solution (30.0 g) to dilute it to a solid content concentration of 9.0% by mass, and then acetic anhydride (2.39 g) and pyridine (0.618 g) were added as imidization catalysts. , 65 ° C. for 3 hours.
- This reaction solution was put into methanol (220 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 80 ° C. to obtain a polyimide powder.
- the imidization ratio of this polyimide was 89%, the number average molecular weight was 10,216, and the weight average molecular weight was 43,193.
- NMP (22.0 g) was added to the obtained polyimide powder (3.00 g), and the mixture was stirred and dissolved at 80 ° C. for 15 hours to obtain a polyimide solution (SPI-1).
- NMP was added to the obtained polyamic acid solution (30.0 g) to dilute it to a solid content concentration of 9.0% by mass, and then acetic anhydride (2.33 g) and pyridine (0.602 g) were added as imidization catalysts. , 60 ° C. for 3 hours.
- This reaction solution was put into methanol (210 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 80 ° C. to obtain a polyimide powder.
- the imidization ratio of this polyimide was 88%, the number average molecular weight was 11,829, and the weight average molecular weight was 42,836.
- NMP (22.0 g) was added to the obtained polyimide powder (3.00 g), and the mixture was stirred and dissolved at 80 ° C. for 15 hours to obtain a polyimide solution (SPI-2).
- NMP was added to the obtained polyamic acid solution (30.0 g) to dilute it to a solid content concentration of 9.0% by mass, and then acetic anhydride (2.33 g) and pyridine (0.602 g) were added as imidization catalysts. , 60 ° C. for 3 hours.
- This reaction solution was put into methanol (210 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 80 ° C. to obtain a polyimide powder.
- the imidization ratio of this polyimide was 88%, the number average molecular weight was 11,194, and the weight average molecular weight was 40,838.
- NMP (22.0 g) was added to the obtained polyimide powder (3.00 g), and the mixture was stirred and dissolved at 80 ° C. for 15 hours to obtain a polyimide solution (SPI-3).
- NMP was added to the obtained polyamic acid solution (30.0 g) to dilute it to a solid content concentration of 9.0% by mass, and then acetic anhydride (2.28 g) and pyridine (0.591 g) were added as imidization catalysts. , 60 ° C. for 3.5 hours.
- This reaction solution was put into methanol (220 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 80 ° C. to obtain a polyimide powder.
- the imidization ratio of this polyimide was 86%, the number average molecular weight was 11,191, and the weight average molecular weight was 40,381.
- NMP (22.0 g) was added to the obtained polyimide powder (3.00 g), and the mixture was stirred and dissolved at 80 ° C. for 15 hours to obtain a polyimide solution (SPI-R1).
- Example 2 NMP (1.67 g), GBL (3.00 g) and BCS (2.00 g) were added to the polyimide solution (SPI-2) (3.33 g) obtained in Synthesis Example 2, and the mixture was stirred at room temperature for 2 hours.
- the liquid crystal alignment agent (V-2) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed that the solution was uniform.
- Example 3 A liquid crystal alignment agent (V-3) was obtained in the same manner as in Example 2 except that the polyimide solution (SPI-3) was used instead of the polyimide solution (SPI-2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed that the solution was uniform.
- Example 4 NMP (3.67 g) and BCS (3.00 g) were added to the polyamic acid solution (PAA-4) (3.33 g) obtained in Synthesis Example 4, and the mixture was stirred at room temperature for 2 hours to prepare a liquid crystal alignment agent (V). -4) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed that the solution was uniform.
- Example 5 A liquid crystal alignment agent (V-5) was obtained in the same manner as in Example 4 except that the polyamic acid solution (PAA-5) was used instead of the polyamic acid solution (PAA-4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed that the solution was uniform.
- Example 6 The polyamic acid solution (PAA-5) (1.83 g) obtained in Synthesis Example 5 and the polyamic acid solution (PAA-6) (3.30 g), NMP (0.770 g) obtained in Synthesis Example 6 were added to the polyamic acid solution (PAA-5) (1.83 g). BCS (3.00 g), 10% by mass NMP diluted solution of AD-1 (0.550 g) and 1% by mass NMP diluted solution of AD-4 (0.550 g) were added, and the mixture was stirred at room temperature for 2 hours to form a liquid crystal. An alignment agent (V-6) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed that the solution was uniform.
- the liquid crystal cell for Fringe Field Switching (FFS) mode has a FOP (Finger on Plate) electrode layer formed on the surface of a surface-shaped common electrode-insulating layer-comb-shaped pixel electrode.
- FOP Fringe Field Switching
- the glass substrate of No. 1 and the second glass substrate having a columnar spacer having a height of 4 ⁇ m on the front surface and an ITO film for preventing antistatic formation on the back surface were made into a set.
- the above pixel electrode has a comb-teeth shape in which a plurality of electrode elements having a width of 3 ⁇ m bent at an internal angle of 160 ° are arranged in parallel with an interval of 6 ⁇ m, and one pixel has a comb-teeth shape. It has a first region and a second region with a line connecting the bent portions of the plurality of electrode elements as a boundary.
- the liquid crystal alignment film formed on the first glass substrate is oriented so that the direction in which the inner angle of the pixel bending portion is equally divided and the orientation direction of the liquid crystal are orthogonal to each other, and the liquid crystal alignment film is formed on the second glass substrate. The film is oriented so that the orientation direction of the liquid crystal on the first substrate and the orientation direction of the liquid crystal on the second substrate coincide with each other when the liquid crystal cell is produced.
- a liquid crystal alignment agent filtered through a filter having a pore size of 1.0 ⁇ m was applied to the surface of each of the above sets of glass substrates by spin coating, and dried on a hot plate at 80 ° C. for 2 minutes. Then, the coating film surface is irradiated with ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26: 1 via a polarizing plate, and then baked in a hot air circulation oven at 230 ° C. for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. Obtained a substrate with. The irradiation amount of the ultraviolet rays is as shown in Tables 1 and 2.
- a sealant was printed on one of the above set of glass substrates with a liquid crystal alignment film, the other substrate was bonded so that the liquid crystal alignment film surfaces faced each other, and the sealant was cured to prepare an empty cell.
- a liquid crystal MLC-7026 manufactured by Merck Group
- the obtained liquid crystal cell was heated at 120 ° C. for 1 hour, left overnight, and then the afterimage characteristics were evaluated.
- a liquid crystal cell is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, the backlight is turned on, and the liquid crystal cell is set so that the transmitted light intensity in the first region of the pixel is minimized.
- the rotation angle required when the liquid crystal cell was rotated so that the transmitted light intensity in the second region of the pixel was the smallest was obtained.
- the afterimage characteristics due to long-term AC drive were evaluated by defining them as "good” when the value of this rotation angle was 0.1 ° or less and “poor” when the value was larger than 0.1 °. Table 2 shows the evaluation results of the afterimage characteristics.
- the liquid crystal alignment film obtained from the liquid crystal alignment agent using diamine WA-1 is the liquid crystal alignment agent V-R1 using diamine A5 or the liquid crystal alignment agent V- without diamine WA-1. It was found that there was little variation in the liquid crystal alignment in the surface of the liquid crystal alignment film as compared with the liquid crystal alignment film obtained from R2. Specifically, it is shown in the comparison between Examples 1 to 6 and Comparative Examples 1 and 2 shown in Table 1. Further, as shown in Table 2, the liquid crystal alignment film obtained from the liquid crystal alignment agent using diamine WA-1 showed good afterimage characteristics.
- the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is, for example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcoder, a PDA, a digital camera, a mobile phone, a smartphone, various monitors, a liquid crystal television, and the like. It can be used for various display devices such as information displays.
- the polymer composition contained in the liquid crystal alignment agent is a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmission scattering type liquid crystal photochromic element. Alternatively, it can also be used for applications other than these, such as a protective film for a color filter, a gate insulating film for a flexible display, and a substrate material.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal (AREA)
Abstract
Description
下記式(1)で表されるジアミンを使用されるジアミン成分1モルに対して5モル%以上含むジアミン成分と、下記式(T)で表される脂環式テトラカルボン酸二無水物又はその誘導体を含むテトラカルボン酸誘導体成分と、を用いて得られるポリイミド前駆体、及び該ポリイミド前駆体のイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体(A)を含有することを特徴とする、液晶配向剤。
本発明の上記効果が得られるメカニズムは必ずしも明らかではないが、以下に述べることが一因と考えられる。すなわち、本発明の重合体は、ウレア結合とベンゼン環とが直結した構造を有し、得られる重合体が比較的剛直な構造となるため、液晶配向膜面内での液晶配向性にバラツキが少なくなると共に、AC残像の抑制にも効果があったと考えられる。
本発明の液晶配向剤は、重合体(A)を含有する。
本発明の液晶配向剤の好ましい実施態様としては、重合体(A)、及び有機溶媒を含有する液晶配向剤が挙げられる。
また、本発明の液晶配向剤は、重合体(A)以外の重合体(例えば、後述する重合体(B))も含有することができる。
重合体(A)は、上記式(1)で表されるジアミン(以下、特定ジアミンともいう)を使用されるジアミン成分1モルに対して5モル%以上含むジアミン成分と、上記式(T)で表される脂環式テトラカルボン酸二無水物又はその誘導体を含むテトラカルボン酸誘導体成分とを用いて得られるポリイミド前駆体、及び該ポリイミド前駆体のイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体である。
このような重合体の具体例としては、例えば、ポリアミック酸及びポリアミック酸エステルなどのイミド前駆体構造を有するポリイミド前駆体、該ポリイミド前駆体のイミド化物であるポリイミドが挙げられる。
重合体(A)を得る為のジアミン成分は、上記式(1)で表されるジアミンの少なくとも1種を使用されるジアミン成分1モルに対して5モル%以上含む物であり、1種類のジアミンからなるものであってもよく、2種類以上のジアミンからなるものであってもよい。ジアミン成分が2種類以上のジアミンからなる場合には、式(1)で表されるジアミンと共に式(1)で表されるジアミン以外のジアミンを含んでいてもよい。下記式(1)で表される化合物は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。重合体(A)を得る為のジアミン成分における式(1)で表されるジアミンの割合は、使用されるジアミン成分1モルに対して、5~100モル%であることが好ましく、5~99モル%がより好ましく、更に好ましくは5~70モル%である。液晶配向性を高める観点で、より一層好ましくは10~60モル%である。
上記式(2)で表されるジアミンを2種以上用いる場合は、Y2が上記式(o-1)~(o-14)で表される2価の有機基である式(2)のジアミンと、Y2が上記式(o-15)~(o-16)で表される2価の有機基である式(2)のジアミンとの合計が、重合体(A)の合成に使用されるジアミン成分1モルに対して1~95モル%であることが好ましく、30~95モル%であることがより好ましく、40~90モル%であることがさらに好ましい。
また、液晶表示素子のコントラストを高める観点から、式(2)で表されるジアミン及び式(2i)で表される各ジアミンの上限量は、重合体(A)の合成に使用されるジアミン成分1モルに対して50モル%以下、より好ましくは40モル%以下、更に好ましくは30モル%以下であってもよい。
基「-N(D)-(Dはカルバメート系保護基を表す。)」を有するジアミンの具体例としては、例えば、下記式(5-1)~(5-10)で表される化合物が挙げられる。
4,4’-ジアミノアゾベンゼン及び下記式(dT-1)~(dT-3)で表されるジアミンなどの光配向性基を有するジアミン;2,4-ジアミノフェノール、3,5-ジアミノフェノール、3,5-ジアミノベンジルアルコール、2,4-ジアミノベンジルアルコール、4,6-ジアミノレゾルシノール;2,4-ジアミノ安息香酸、2,5-ジアミノ安息香酸、3,5-ジアミノ安息香酸及び下記式(3b-1)~式(3b-4)で示されるジアミン化合物などのカルボキシル基を有するジアミン;3,3’-ジアミノジフェニルメタン、4,4’-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’-ジアミノベンゾフェノン、1,4-ビス(4-アミノベンジル)ベンゼン、4,4’-ジアミノジフェニルエーテル、1-(4-アミノフェニル)-1,3,3-トリメチル-1H-インダン-5-アミン、1-(4-アミノフェニル)-2,3-ジヒドロ-1,3,3-トリメチル-1H-インデン-6-アミン;下記式(h-1)~(h-3)で表されるジアミン等のウレア結合を有するジアミン;下記式(h-4)~(h-6)で表されるアミド結合を有するジアミン;メタクリル酸2-(2,4-ジアミノフェノキシ)エチル及び2,4-ジアミノ-N,N-ジアリルアニリン等の光重合性基を末端に有するジアミン;1,3-ビス(3-アミノプロピル)-テトラメチルジシロキサン等のシロキサン結合を有するジアミン;下記式(Ox-1)~(Ox-2)等のオキサゾリン構造を有するジアミン等。
上記重合体(A)を製造する場合、ジアミン成分と反応させるテトラカルボン酸誘導体成分は、テトラカルボン酸二無水物だけでなく、テトラカルボン酸ジハライド、テトラカルボン酸ジアルキルエステル、又はテトラカルボン酸ジアルキルエステルジハライドなどのテトラカルボン酸二無水物の誘導体を用いることもできる。テトラカルボン酸誘導体成分は、一種のテトラカルボン酸二無水物又はその誘導体を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
なお、本発明において、脂環式テトラカルボン酸二無水物は、脂環式構造に結合する少なくとも1つのカルボキシ基を含めて4つのカルボキシ基が分子内脱水することにより得られる酸二無水物である。但し、これら4つのカルボキシ基はいずれも芳香環には結合していない。また、脂環式構造のみで構成されている必要はなく、その一部に鎖状炭化水素構造や芳香環構造を有していてもよい。
芳香族テトラカルボン酸二無水物は、芳香環に結合する少なくとも1つのカルボキシ基を含めて4つのカルボキシ基が分子内脱水することにより得られる酸二無水物である。但し、芳香環構造のみで構成されている必要はなく、その一部に鎖状炭化水素構造や脂環式構造を有していてもよい。
非環式脂肪族テトラカルボン酸二無水物は、鎖状炭化水素構造に結合する4つのカルボキシ基が分子内脱水することにより得られる酸二無水物である。但し、鎖状炭化水素構造のみで構成されている必要はなく、その一部に脂環式構造や芳香環構造を有していてもよい。
重合体(A)の製造に用いられるテトラカルボン酸二無水物及びその誘導体は、上記式(T)で表される脂環式テトラカルボン酸二無水物又はその誘導体以外のテトラカルボン酸二無水物又はその誘導体(以下、その他のテトラカルボン酸二無水物又はその誘導体)を含有していてもよい。その他のテトラカルボン酸二無水物またはその誘導体の例として、下記式(2T)で表されるテトラカルボン酸二無水物またはその誘導体が挙げられる。上記テトラカルボン酸二無水物またはその誘導体は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
本発明の液晶配向剤は、残留DC由来の残像を少なくする観点から、テトラカルボン酸誘導体成分とジアミン成分とを用いて得られるポリイミド前駆体及び該ポリイミド前駆体のイミド化物であるポリイミドからなる群から選ばれる重合体(B)(但し、重合体(A)を除く。)を含有してもよい。このような重合体の具体例を挙げると、テトラカルボン酸誘導体成分と、上記特定ジアミンを含まないジアミン成分とを用いて得られるポリイミド前駆体及び該ポリイミド前駆体のイミド化物であるポリイミドからなる群から選ばれる重合体が挙げられる。
上記ポリイミド前駆体の具体例としては、ポリアミック酸、ポリアミック酸エステルなどが挙げられる。
重合体(B)は、一種を単独で使用してもよく、また二種以上を組み合わせて使用してもよい。
重合体(A)又は(B)の製造は、上記ジアミン成分と、テトラカルボン酸誘導体成分と、を溶媒中で(縮重合)反応させることにより行われる。重合体(A)又は(B)の一部にアミック酸構造を含む場合、例えば、テトラカルボン酸二無水物成分とジアミン成分とを反応させることにより、アミック酸構造を有する重合体(ポリアミック酸)が得られる。溶媒としては、生成した重合体が溶解するものであれば特に限定されない。
上記溶媒の具体例としては、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、γ-ブチロラクトン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、ジメチルスルホキシド、1,3-ジメチル-2-イミダゾリジノンが挙げられる。また、重合体の溶媒溶解性が高い場合は、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、4-ヒドロキシ-4-メチル-2-ペンタノン、又は下記式[D-1]~[D-3]で示される溶媒を用いることができる。
ジアミン成分とテトラカルボン酸誘導体成分とを溶媒中で反応させる際には、反応は任意の濃度で行うことができるが、好ましくは1~50質量%、より好ましくは5~30質量%である。反応初期は高濃度で行い、その後、溶媒を追加することもできる。
反応においては、ジアミン成分の合計モル数とテトラカルボン酸誘導体成分の合計モル数の比は0.8~1.2であることが好ましい。通常の縮重合反応同様、このモル比が1.0に近いほど生成する重合体(A)、重合体(B)の分子量は大きくなる。
液晶配向性を高める観点から、重合体(A)のイミド化率は、20~100%が好ましく、50~95%が好ましく、更に好ましくは60~90%である。
本発明に用いられる重合体(A)又は(B)は、これを濃度10~15質量%の溶液としたときに、例えば10~1000mPa・sの溶液粘度を持つものが作業性の観点から好ましいが、特に限定されない。なお、上記重合体の溶液粘度(mPa・s)は、当該重合体の良溶媒(例えばγ-ブチロラクトン、N-メチル-2-ピロリドンなど)を用いて調製した濃度10~15質量%の重合体溶液につき、E型回転粘度計を用いて25℃において測定した値である。
本発明における重合体(A)、重合体(B)を合成するに際して、上記の如きテトラカルボン酸誘導体成分、及びジアミン成分とともに、適当な末端封止剤を用いて末端封止型の重合体を合成することとしてもよい。末端封止型の重合体は、塗膜によって得られる液晶配向膜の膜硬度の向上や、シール剤と液晶配向膜の密着特性の向上という効果を有する。
本発明における重合体(A)、重合体(B)の末端の例としては、アミノ基、カルボキシ基、酸無水物基又はこれらの誘導体が挙げられる。アミノ基、カルボキシ基、酸無水物基又はこれらの誘導体は通常の縮合反応により得るか、又は以下の末端封止剤を用いて末端を封止することにより得ることができ、前記誘導体は、例えば、以下の末端封止剤を用いて、同様に得ることができる。
本発明の液晶配向剤は、重合体(A)及び必要に応じて重合体(B)を含有する。本発明の液晶配向剤は、重合体(A)、重合体(B)に加えて、その他の重合体を含有していてもよい。その他の重合体の種類としては、ポリエステル、ポリアミド、ポリウレア、ポリオルガノシロキサン、セルロース誘導体、ポリアセタール、ポリスチレン又はその誘導体、ポリ(スチレン-フェニルマレイミド)誘導体、ポリ(メタ)アクリレートなどを挙げることができる。
液晶配向剤中の重合体(A)の含有量は、液晶配向剤の塗布方法や目的とする液晶配向膜の膜厚によって、適宜変更することができるが、2~10質量%であることが好ましく、特に、3~7質量%が好ましい。
本発明の液晶配向膜は、上記液晶配向剤から得られる。本発明の液晶配向膜は、水平配向型若しくは垂直配向型(VA型)の液晶配向膜に用いることができるが、中でもIPS方式又はFFS方式等の水平配向型の液晶表示素子に好適な液晶配向膜である。本発明の液晶表示素子は、上記液晶配向膜を具備するものである。本発明の液晶表示素子は、例えば以下の工程(1)~(4)或いは工程(1)~(2)及び(4)を含む方法により製造することができる。
パターニングされた透明導電膜が設けられている基板の一面に、本発明の液晶配向剤を、例えばロールコーター法、スピンコート法、印刷法、インクジェット法などの適宜の塗布方法により塗布する。ここで基板としては、透明性の高い基板であれば特に限定されず、ガラス基板、窒化珪素基板とともに、アクリル基板やポリカーボネート基板等のプラスチック基板等を用いることもできる。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、この場合の電極にはアルミニウム等の光を反射する材料も使用できる。また、IPS型又はFFS型の液晶素子を製造する場合には、櫛歯型にパターニングされた透明導電膜又は金属膜からなる電極が設けられている基板と、電極が設けられていない対向基板とを用いる。
工程(2)は、基板上に塗布した液晶配向剤を焼成し、膜を形成する工程である。液晶配向剤を基板上に塗布した後は、ホットプレート、熱循環型オーブン又はIR(赤外線)型オーブンなどの加熱手段により、溶媒を蒸発させたり、ポリアミック酸又はポリアミック酸エステルの熱イミド化を行ったりすることができる。本発明の液晶配向剤を塗布した後の乾燥、焼成工程は、任意の温度と時間を選択することができ、複数回行ってもよい。乾燥温度としては、例えば40~180℃で行うことができる。プロセスを短縮する観点で、40~150℃で行ってもよい。乾燥時間としては特に限定されないが、1~10分又は、1~5分が挙げられる。ポリアミック酸又はポリアミック酸エステルの熱イミド化を行う場合には、上記乾燥工程の後、例えば150~300℃、又は150~250℃の温度範囲で焼成する工程ができる。焼成時間としては特に限定されないが、5~40分、又は、5~30分の焼成時間が挙げられる。
焼成後の膜状物は、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、5~300nmが好ましく、10~200nmがより好ましい。
工程(3)は、場合により、工程(2)で得られた膜に配向処理する工程である。即ち、IPS方式又はFFS方式等の水平配向型の液晶表示素子では該塗膜に対し配向能付与処理を行う。一方、VA方式又はPSAモード等の垂直配向型の液晶表示素子では、形成した塗膜をそのまま液晶配向膜として使用することができるが、該塗膜に対し配向能付与処理を施してもよい。液晶配向膜の配向処理方法としては、ラビング処理法、光配向処理法が挙げられ、光配向処理法がより好適である。光配向処理法としては、上記膜状物の表面に、一定方向に偏向された放射線を照射し、場合により、好ましくは、150~250℃の温度で加熱処理を行い、液晶配向性(液晶配向能ともいう)を付与する方法が挙げられる。放射線としては、100~800nmの波長を有する紫外線又は可視光線を用いることができる。なかでも、好ましくは100~400nm、より好ましくは、200~400nmの波長を有する紫外線である。
また、放射線を照射する場合、液晶配向性を改善するために、上記膜状物を有する基板を、50~250℃で加熱しながら照射してもよい。このようにして作製した上記液晶配向膜は、液晶分子を一定の方向に安定して配向させることができる。
更に、上記の方法で、偏光された放射線を照射した液晶配向膜に、溶媒を用いて、これらと接触処理するか、放射線を照射した液晶配向膜を加熱処理することもできる。
上記のようにして液晶配向膜が形成された基板を2枚準備し、対向配置した2枚の基板間に液晶を配置する。具体的には以下の2つの方法が挙げられる。第一の方法は、先ず、それぞれの液晶配向膜が対向するように間隙(セルギャップ)を介して2枚の基板を対向配置する。次いで、2枚の基板の周辺部をシール剤を用いて貼り合わせ、基板表面及びシール剤により区画されたセルギャップ内に液晶組成物を注入充填して膜面に接触した後、注入孔を封止する。
なお、塗膜に対してラビング処理を行った場合には、2枚の基板は、各塗膜におけるラビング方向が互いに所定の角度、例えば直交又は逆平行となるように対向配置される。
シール剤としては、例えば硬化剤及びスペーサーとしての酸化アルミニウム球を含有するエポキシ樹脂等を用いることができる。液晶としては、ネマチック液晶及びスメクチック液晶を挙げることができ、その中でもネマチック液晶が好ましい。
NMP:N-メチル-2-ピロリドン
BCS:エチレングリコールモノブチルエーテル
GBL:γ-ブチロラクトン
分子量は、常温ゲル浸透クロマトグラフィー(GPC)装置(GPC-101)(昭和電工社製)、カラム(KD-803,KD-805)(昭和電工社製)を用いて、以下のようにして測定した。
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、臭化リチウム一水和物(LiBr・H2O)が30mmol/L(リットル)、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:TSK 標準ポリエチレンオキサイド(分子量;約900,000、150,000、100,000及び30,000)(東ソー社製)及びポリエチレングリコール(分子量;約12,000、4,000及び1,000)(ポリマーラボラトリー社製)。
溶液の粘度は、E型粘度計TVE-22H(東機産業社製)を用い、サンプル量1.1mL、コーンロータTE-1(1°34’、R24)を用いて、温度25℃で測定した。
(合成例1)
WA-1(1.26g,5.20mmol)、A1(1.27g,5.20mmol)、A3(1.20g,5.20mmol)、A4(1.79g,5.20mmol)、A2(1.23g,5.20mmol)及びB1(5.48g,24.4mmol)をNMP(87.9g)中で混合し、40℃で3時間反応させ、樹脂固形分濃度12質量%のポリアミック酸溶液(粘度:212mPa・s)を得た。なお、ジアミン成分におけるWA-1の割合は、ジアミン成分1モルに対して、20モル%であった。
得られたポリアミック酸溶液(30.0g)に、NMPを加えて固形分濃度9.0質量%に希釈した後、イミド化触媒として無水酢酸(2.39g)及びピリジン(0.618g)を加え、65℃で3時間反応させた。この反応溶液をメタノール(220ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、80℃で減圧乾燥しポリイミド粉末を得た。このポリイミドのイミド化率は89%であり、数平均分子量は10,216であり、重量平均分子量は43,193であった。
得られたポリイミド粉末(3.00g)に、NMP(22.0g)を加え、80℃にて15時間撹拌して溶解させ、ポリイミド溶液(SPI-1)を得た。
WA-1(1.26g,5.20mmol)、A1(2.54g,10.4mmol)、A4(1.79g,5.20mmol)、A2(1.23g,5.20mmol)及びB1(5.48g,24.4mmol)をNMP(87.3g)中で混合し、40℃で3時間反応させ、樹脂固形分濃度12質量%のポリアミック酸溶液(粘度:199mPa・s)を得た。なお、ジアミン成分におけるWA-1の割合は、ジアミン成分1モルに対して、20モル%であった。
得られたポリアミック酸溶液(30.0g)に、NMPを加えて固形分濃度9.0質量%に希釈した後、イミド化触媒として無水酢酸(2.33g)及びピリジン(0.602g)を加え、60℃で3時間反応させた。この反応溶液をメタノール(210ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、80℃で減圧乾燥しポリイミド粉末を得た。このポリイミドのイミド化率は88%であり、数平均分子量は11,829であり、重量平均分子量は42,836であった。
得られたポリイミド粉末(3.00g)に、NMP(22.0g)を加え、80℃にて15時間撹拌して溶解させ、ポリイミド溶液(SPI-2)を得た。
WA-1(2.52g,10.4mmol)、A1(2.54g,10.4mmol)、A2(1.23g,5.20mmol)及びB1(5.48g,24.4mmol)をNMP(86.2g)中で混合し、40℃で3時間反応させ、樹脂固形分濃度12質量%のポリアミック酸溶液(粘度:189mPa・s)を得た。なお、ジアミン成分におけるWA-1の割合は、ジアミン成分1モルに対して、40モル%であった。
得られたポリアミック酸溶液(30.0g)に、NMPを加えて固形分濃度9.0質量%に希釈した後、イミド化触媒として無水酢酸(2.33g)及びピリジン(0.602g)を加え、60℃で3時間反応させた。この反応溶液をメタノール(210ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、80℃で減圧乾燥しポリイミド粉末を得た。このポリイミドのイミド化率は88%であり、数平均分子量は11,194であり、重量平均分子量は40,838であった。
得られたポリイミド粉末(3.00g)に、NMP(22.0g)を加え、80℃にて15時間撹拌して溶解させ、ポリイミド溶液(SPI-3)を得た。
WA-1(1.89g,7.80mmol)、A1(1.91g,7.80mmol)、A6(0.562g,5.20mmol)、A8(2.07g,5.20mmol)及びB1(5.59g,25.0mmol)をNMP(86.2g)中で混合し、40℃で3時間反応させ、樹脂固形分濃度12質量%のポリアミック酸溶液(PAA-4)(粘度:412mPa・s)を得た。なお、ジアミン成分におけるWA-1の割合は、ジアミン成分1モルに対して、30モル%であった。このポリマーの数平均分子量は15,832であり、重量平均分子量は46,829であった。
WA-1(1.26g,5.20mmol)、A1(1.91g,7.80mmol)、A6(0.562g,5.20mmol)、A8(3.11g,7.80mmol)及びB1(5.59g,25.0mmol)をNMP(91.1g)中で混合し、40℃で3時間反応させ、樹脂固形分濃度12質量%のポリアミック酸溶液(PAA-5)(粘度:398mPa・s)を得た。なお、ジアミン成分におけるWA-1の割合は、ジアミン成分1モルに対して、20モル%であった。このポリマーの数平均分子量は16,888であり、重量平均分子量は46,001であった。
A9(4.14g,20.8mmol)、A5(1.55g,5.20mmol)及びB3(4.84g,24.7mmol)をNMP(94.8g)中で混合し、40℃で15時間反応させ、樹脂固形分濃度10質量%のポリアミック酸溶液(PAA-6)(粘度:315mPa・s)を得た。このポリマーの数平均分子量は15,888であり、重量平均分子量は43,741であった。
A9(4.14g,20.8mmol)、A5(1.55g,5.20mmol)及びB2(7.34g,25.0mmol)をNMP(95.6g)中で混合し、70℃で15時間反応させ、樹脂固形分濃度12質量%のポリアミック酸溶液(PAA-7)(粘度:465mPa・s)を得た。このポリマーの数平均分子量は13,182であり、重量平均分子量は42,252であった。
A5(1.55g,5.20mmol)、A1(1.27g,5.20mmol)、A3(1.20g,5.20mmol)、A4(1.79g,5.20mmol)、A2(1.23g,5.20mmol)及びB1(5.48g,24.4mmol)をNMP(91.8g)中で混合し、40℃で3時間反応させ、樹脂固形分濃度12質量%のポリアミック酸溶液(粘度:203mPa・s)を得た。
得られたポリアミック酸溶液(30.0g)に、NMPを加えて固形分濃度9.0質量%に希釈した後、イミド化触媒として無水酢酸(2.28g)及びピリジン(0.591g)を加え、60℃で3.5時間反応させた。この反応溶液をメタノール(220ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、80℃で減圧乾燥しポリイミド粉末を得た。このポリイミドのイミド化率は86%であり、数平均分子量は11,191であり、重量平均分子量は40,381であった。
得られたポリイミド粉末(3.00g)に、NMP(22.0g)を加え、80℃にて15時間撹拌して溶解させ、ポリイミド溶液(SPI-R1)を得た。
A8(2.07g,5.20mmol)、A1(1.91g,7.80mmol)、A7(2.50g,7.80mmol)、A6(0.562g,5.20mmol)、及びB1(5.60g,25.0mmol)をNMP(92.6g)中で混合し、40℃で3時間反応させ、樹脂固形分濃度12質量%のポリアミック酸溶液(PAA-R2)(粘度:423mPa・s)を得た。このポリマーの数平均分子量は14,921であり、重量平均分子量は45,956であった。
(実施例1)
合成例1で得られたポリイミド溶液(SPI-1)(2.08g)に、合成例7で得られたポリアミック酸溶液(PAA-7)(2.08g)、GBL(3.00g)、BCS(2.00g)、AD-1の10質量%NMP希釈溶液(0.500g)、AD-2(0.050g)、AD-3(0.050g)及びAD-4の1質量%GBL希釈溶液(0.500g)を加え、室温で5時間撹拌して、液晶配向剤(V-1)を得た。この液晶配向剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例2で得られたポリイミド溶液(SPI-2)(3.33g)に、NMP(1.67g)、GBL(3.00g)及びBCS(2.00g)を加え、室温で2時間撹拌して、液晶配向剤(V-2)を得た。この液晶配向剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
実施例2において、ポリイミド溶液(SPI-2)の代わりにポリイミド溶液(SPI-3)としたこと以外は、実施例2と同様にして液晶配向剤(V-3)を得た。この液晶配向剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例4で得られたポリアミック酸溶液(PAA-4)(3.33g)にNMP(3.67g)とBCS(3.00g)を加え、室温で2時間撹拌して、液晶配向剤(V-4)を得た。この液晶配向剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
実施例4において、ポリアミック酸溶液(PAA-4)の代わりにポリアミック酸溶液(PAA-5)としたこと以外は、実施例4と同様にして液晶配向剤(V-5)を得た。この液晶配向剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例5で得られたポリアミック酸溶液(PAA-5)(1.83g)に、合成例6で得られたポリアミック酸溶液(PAA-6)(3.30g)、NMP(0.770g)、BCS(3.00g)、AD-1の10質量%NMP希釈溶液(0.550g)及びAD-4の1質量%NMP希釈溶液(0.550g)を加え、室温で2時間撹拌して、液晶配向剤(V-6)を得た。この液晶配向剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
比較合成例1で得られたポリイミド溶液(SPI-R1)(2.08g)に、合成例7で得られたポリアミック酸(PAA-7)(2.08g)、GBL(3.00g)、BCS(2.00g)、AD-1の10質量%NMP希釈溶液(0.500g)、AD-2(0.050g)、AD-3(0.050g)及びAD-4の1質量%GBL希釈溶液(0.500g)を加え、室温で5時間撹拌して、液晶配向剤(V-R1)を得た。この液晶配向剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
比較合成例2で得られたポリアミック酸溶液(PAA-R2)(3.33g)に、NMP(1.67g)、GBL(3.00g)及びBCS(2.00g)を加え、室温で2時間撹拌して、液晶配向剤(V-R2)を得た。この液晶配向剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
<FFS駆動液晶セルの構成>
フリンジフィールドスィッチング(Fringe Field Switching:FFS)モード用の液晶セルは、面形状の共通電極-絶縁層-櫛歯形状の画素電極からなるFOP(Finger on Plate)電極層が表面に形成されている第1のガラス基板と、表面に高さ4μmの柱状スペーサーを有し裏面に帯電防止の為のITO膜が形成されている第2のガラス基板とを、一組とした。上記の画素電極は、中央部分が内角160°で屈曲した幅3μmの電極要素が6μmの間隔を開けて平行になるように複数配列された櫛歯形状を有しており、1つの画素は、複数の電極要素の屈曲部を結ぶ線を境に第1領域と第2領域を有している。
なお、第1のガラス基板に形成する液晶配向膜は、画素屈曲部の内角を等分する方向と液晶の配向方向とが直交するように配向処理し、第2のガラス基板に形成する液晶配向膜は、液晶セルを作製した時に第1の基板上の液晶の配向方向と第2の基板上の液晶の配向方向とが一致するように配向処理する。
上記一組のガラス基板それぞれの表面に、孔径1.0μmのフィルターで濾過した液晶配向剤をスピンコート塗布にて塗布し80℃のホットプレート上で2分間乾燥させた。その後、塗膜面に偏光板を介して消光比26:1の直線偏光した波長254nmの紫外線を照射し、次いで230℃の熱風循環式オーブンで30分間焼成を行い、膜厚100nmの液晶配向膜付き基板を得た。前記紫外線の照射量は表1および2に記載された通りである。
次に、上記一組の液晶配向膜付きガラス基板の一方にシール剤を印刷し、もう一方の基板を液晶配向膜面が向き合うように貼り合わせ、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-7026(メルク社製)を注入し、注入口を封止して、FFS駆動液晶セルを得た。その後、得られた液晶セルを120℃で1時間加熱し、一晩放置してから残像特性の評価を実施した。
シンテック社製OPTIPRO-microを用いて液晶表示素子のツイスト角の評価を行った。上記で作製した液晶セルを測定ステージに設置し、電圧無印加の状態で、第1画素面内を20点測定して標準偏差σの3倍である3σを算出した。ツイスト角のバラツキが小さいことは、液晶配向膜面内での液晶配向性にバラツキが少ないことを示す。評価は、上記3σ値が1.3未満の場合は「良好」とし、1.3以上の場合は「不良」と定義して評価を行った。上記実施例及び比較例の各液晶配向剤を使用する液晶表示素子に関して実施した評価結果を表1に示す。
上記で作製したFFS駆動液晶セルに対し、60℃の恒温環境下、周波数60Hzで±10Vの交流電圧を120時間印加した。その後、液晶セルの画素電極と対向電極との間をショートさせた状態にし、そのまま室温に一日放置した。上記の処理を行った液晶セルに関して、電圧無印加状態における、画素の第1領域の液晶の配向方向と第2領域の液晶の配向方向とのずれを角度として算出した。具体的には、偏光軸が直交するように配置された2枚の偏光板の間に液晶セルを設置し、バックライトを点灯させ、画素の第1領域の透過光強度が最も小さくなるように液晶セルの配置角度を調整し、次に画素の第2領域の透過光強度が最も小さくなるように液晶セルを回転させたときに要する回転角度を求めた。長期交流駆動による残像特性は、この回転角度の値が0.1°以下の場合は「良好」とし、0.1°より大きい場合は「不良」と定義して評価を行った。残像特性の評価結果を表2に示す。
さらに、表2に示されるように、ジアミンWA-1を用いた液晶配向剤から得られる液晶配向膜は、良好な残像特性を示した。
Claims (18)
- 下記式(1)で表されるジアミンを使用されるジアミン成分1モルに対して5モル%以上含むジアミン成分と、下記式(T)で表される脂環式テトラカルボン酸二無水物又はその誘導体を含むテトラカルボン酸誘導体成分と、を用いて得られるポリイミド前駆体、及び該ポリイミド前駆体のイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体(A)を含有することを特徴とする、液晶配向剤。
- 前記ジアミン成分中の10~60モル%が、式(1)で表されるジアミンである、請求項1~2のいずれか一項に記載の液晶配向剤。
- 前記ジアミン成分が、更に下記式(2)又は(2i)で表されるジアミンを含有する請求項1~3のいずれか一項に記載の液晶配向剤。
- 前記重合体(A)が、分子内に基「-N(D)-(Dはカルバメート系保護基を表す。)」を有する、請求項1~5のいずれか一項に記載の液晶配向剤。
- 前記ジアミン成分が、基「-N(D)-(Dはカルバメート系保護基を表す。)」を有するジアミンをさらに含有する、請求項1~6のいずれか一項に記載の液晶配向剤。
- テトラカルボン酸誘導体成分と、前記式(1)で表されるジアミンを含まないジアミン成分とを用いて得られるポリイミド前駆体及び該ポリイミド前駆体のイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体(B)を更に含有する、請求項1~7のいずれか一項に記載の液晶配向剤。
- 前記重合体(B)を得るためのジアミン成分が、窒素原子含有複素環、第二級アミノ基及び第三級アミノ基よりなる群から選ばれる少なくとも一種の窒素原子含有構造を有するジアミンを含む、請求項8に記載の液晶配向剤。
- 架橋性化合物、末端封止剤及び密着助剤からなる群から選ばれる少なくとも1種の添加剤をさらに含有する、請求項1~9のいずれか一項に記載の液晶配向剤。
- 前記Xが式(x-1)で表される構造である、請求項1~10のいずれか一項に記載の液晶配向剤。
- 光配向処理法用の液晶配向膜に用いられる、請求項1~11のいずれか一項に記載の液晶配向剤。
- 請求項1~12のいずれか1項に記載の液晶配向剤から得られる液晶配向膜。
- 請求項13に記載の液晶配向膜を具備する液晶表示素子。
- 下記の工程(1)~(3)を含む、液晶配向膜の製造方法。
工程(1):請求項1~11のいずれか一項に記載の液晶配向剤を基板上に塗布する工程
工程(2):塗布した液晶配向剤を焼成する工程
工程(3):工程(2)で得られた膜に配向処理する工程 - 前記配向処理が、光配向処理である、請求項15に記載の液晶配向膜の製造方法。
- 前記光配向処理における放射線の照射量が、100~1500mJ/cm2である、請求項16に記載の液晶配向膜の製造方法。
- 配向処理された膜に対して50~300℃の加熱処理を更に行う、請求項15~17のいずれか一項に記載の液晶配向膜の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202180063543.6A CN116234857B (zh) | 2020-07-17 | 2021-07-08 | 液晶取向剂、液晶取向膜以及液晶显示元件 |
JP2022536310A JP7302744B2 (ja) | 2020-07-17 | 2021-07-08 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
KR1020237004490A KR20230038512A (ko) | 2020-07-17 | 2021-07-08 | 액정 배향제, 액정 배향막, 및 액정 표시 소자 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-122979 | 2020-07-17 | ||
JP2020122979 | 2020-07-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022014467A1 true WO2022014467A1 (ja) | 2022-01-20 |
Family
ID=79555439
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/025826 WO2022014467A1 (ja) | 2020-07-17 | 2021-07-08 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7302744B2 (ja) |
KR (1) | KR20230038512A (ja) |
CN (1) | CN116234857B (ja) |
TW (1) | TW202206499A (ja) |
WO (1) | WO2022014467A1 (ja) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014157143A1 (ja) * | 2013-03-25 | 2014-10-02 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
WO2017217413A1 (ja) * | 2016-06-14 | 2017-12-21 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
JP2018200439A (ja) * | 2017-05-29 | 2018-12-20 | Jsr株式会社 | 液晶配向剤、液晶配向膜及びその製造方法、液晶素子、重合体並びに化合物 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3893659B2 (ja) | 1996-03-05 | 2007-03-14 | 日産化学工業株式会社 | 液晶配向処理方法 |
JP5879693B2 (ja) * | 2011-02-22 | 2016-03-08 | Jsr株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
WO2016152928A1 (ja) | 2015-03-24 | 2016-09-29 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
JP7131538B2 (ja) * | 2017-02-27 | 2022-09-06 | 日産化学株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
CN114609830A (zh) * | 2017-03-02 | 2022-06-10 | 日产化学株式会社 | 液晶取向剂、液晶取向膜以及液晶表示元件 |
-
2021
- 2021-07-08 CN CN202180063543.6A patent/CN116234857B/zh active Active
- 2021-07-08 KR KR1020237004490A patent/KR20230038512A/ko unknown
- 2021-07-08 JP JP2022536310A patent/JP7302744B2/ja active Active
- 2021-07-08 WO PCT/JP2021/025826 patent/WO2022014467A1/ja active Application Filing
- 2021-07-12 TW TW110125419A patent/TW202206499A/zh unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014157143A1 (ja) * | 2013-03-25 | 2014-10-02 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
WO2017217413A1 (ja) * | 2016-06-14 | 2017-12-21 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
JP2018200439A (ja) * | 2017-05-29 | 2018-12-20 | Jsr株式会社 | 液晶配向剤、液晶配向膜及びその製造方法、液晶素子、重合体並びに化合物 |
Also Published As
Publication number | Publication date |
---|---|
TW202206499A (zh) | 2022-02-16 |
JPWO2022014467A1 (ja) | 2022-01-20 |
KR20230038512A (ko) | 2023-03-20 |
CN116234857A (zh) | 2023-06-06 |
CN116234857B (zh) | 2024-04-26 |
JP7302744B2 (ja) | 2023-07-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022176680A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP7343059B2 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2022234820A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP7302744B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
WO2021177113A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2021210252A1 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
WO2020184373A1 (ja) | 機能性高分子膜形成用塗布液及び機能性高分子膜 | |
WO2022085674A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP7311047B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
JP7544138B2 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2022181311A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2024029576A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2022168722A1 (ja) | 液晶配向剤、液晶配向膜、液晶表示素子の製造方法及び液晶表示素子 | |
WO2024162336A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP7318826B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
WO2024111498A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2022107640A1 (ja) | 重合体組成物、液晶配向剤、樹脂膜、液晶配向膜、液晶表示素子の製造方法及び液晶表示素子 | |
WO2022190896A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP7315106B2 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP2024022213A (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2021206003A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2021246431A1 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
WO2021261281A1 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
JP2024070838A (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
WO2023068084A1 (ja) | 液晶配向剤、液晶配向膜、液晶表示素子、化合物、及び重合体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21843440 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022536310 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20237004490 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21843440 Country of ref document: EP Kind code of ref document: A1 |