Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
• Liquid crystal display elements are widely used from small applications such as mobile phones and smartphones to relatively large applications such as televisions and monitors.
• the liquid crystal display element is generally configured by arranging a pair of electrode substrates so as to face each other with a predetermined gap (several ⁇ m) and enclosing liquid crystal between the electrode substrates. Then, by applying a voltage between the transparent conductive films constituting each electrode of the electrode substrate, the display on the liquid crystal display element is performed.
• These liquid crystal display elements have a liquid crystal alignment film that is indispensable for controlling the arrangement state of liquid crystal molecules.
• a liquid crystal display element various drive methods have been developed in which the electrode structure and the physical characteristics of the liquid crystal molecules used are different.
• various modes such as TN (Twisted Nematic) method, STN (Super Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane Switching) method, and FFS (fringe field switching) method are known.
• TN Transmission Nematic
• STN Super Twisted Nematic
• VA Very Alignment
• IPS In-Plane Switching
• FFS far-Plane Switching
• the VA vertical orientation type liquid crystal display element has a wide viewing angle, a fast response speed, a large contrast, and the rubbing process can be eliminated in the production process. Therefore, there is a particular need for an increase in size. Widely used mainly for expensive TVs and monitors.
• the mainstream of the VA liquid crystal display element is the PSA method, in which a photopolymerizable compound is added to the liquid crystal composition in advance and ultraviolet rays are irradiated while applying a voltage to the liquid crystal cell to increase the response speed of the liquid crystal. (See Patent Document 1 and Patent Document 2).
• the liquid crystal alignment film is required to have various properties in addition to the liquid crystal alignment.
• the accumulated charge affects the display as a disorder of the liquid crystal orientation or an afterimage, and the display quality of the liquid crystal element is significantly deteriorated. There is. For this reason, a liquid crystal alignment film that suppresses the accumulation of static electricity and has a small afterimage is required.
• Patent Document 3 proposes a polyimide-based liquid crystal alignment film having a pyrrole structure.
• the above-mentioned transparent conductive film in the liquid crystal display element is usually formed of a composition (ITO) containing indium oxide as a main component and doped with several% tin oxide, and its refractive index is determined by the liquid crystal alignment film. It has a high value unlike the refractive index of. Therefore, when the light from the display light source is to be transmitted to the electrode substrate, the light is reflected at the interface between the transparent conductive film and the liquid crystal alignment film in each electrode substrate.
• ITO composition
• an object of the present invention is to provide a liquid crystal alignment film having a high refractive index, a high light transmittance, quick relaxation of accumulated charges, and excellent afterimage characteristics.
• An object of the present invention is 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.
• the gist of the present invention is as follows.
• the first repeating unit (a1) selected from the group consisting of the repeating unit represented by the following formula (1) and the imidized structure of the repeating unit represented by the above formula (1), and A polymer component having a repeating unit represented by the following formula (2) and a second repeating unit (a2) selected from the group consisting of an imidized structure of the repeating unit represented by the above formula (2).
• (X 1 and X 2 represent a tetravalent organic group.
• Y 1 represents a divalent organic group having a structure represented by the following formula (S).
• Y 2 is represented by the following formula (2c). Represents a divalent organic group having a partial structure.
• Two R 1 and R 2 independently represent a hydrogen atom or a monovalent organic group.
• Two Z 1 and Z 2 are independent of each other.
• X is a single bond,-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3 )-, -NH-, -O- , -COO-, -OCO- or-((CH 2 ) a1 -A 1 ) m1- (a1 is an integer of 1 to 15, A 1 represents an oxygen atom or -COO-, and m 1 is 1 to It is an integer of 2.
• J represents an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an alicyclic hydrocarbon group.
• At least one of the atoms is a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, and an alkenyl group having 3 to 10 carbon atoms.
• Indicates a bond.) Any hydrogen atom on the benzene ring may be substituted with a monovalent substituent. * Indicates a bond.
• a liquid crystal alignment film having a high refractive index, a high light transmission rate, quick relaxation of accumulated charges, and excellent afterimage characteristics is provided, and the liquid crystal alignment film is provided.
• a liquid crystal aligning agent for obtaining the liquid crystal aligning agent and a liquid crystal display element using the liquid crystal alignment film can also be provided.
• the mechanism by which the above effects of the present invention are obtained is not always clear, but it is considered that the following is one of the causes. That is, it is considered that by using the liquid crystal alignment agent containing the above polymer, the packing property is improved by the hydrogen bond of the urea group, so that the accumulated charge is quickly relaxed and the liquid crystal alignment film having excellent afterimage characteristics can be obtained. .. Further, since the film density is increased, it is considered that a liquid crystal alignment film having a high refractive index and a high light transmittance can be obtained.
• liquid crystal alignment agent of the present invention the liquid crystal alignment film formed by using the liquid crystal alignment agent, and the liquid crystal display element having the liquid crystal alignment film will be described in detail. It is an example as one embodiment of the present invention, and is not specified in these contents.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * Indicates a bond unless otherwise specified.
• the liquid crystal alignment agent of the present invention is a first repeating unit (a1) selected from the group consisting of the repeating unit represented by the above formula (1) and the imidized structure of the repeating unit represented by the above formula (1).
• a polymer component having a repeating unit represented by the above formula (2) and a second repeating unit (a2) selected from the group consisting of an imidized structure of the repeating unit represented by the above formula (2). contains.
• an imidized structure of the repeating unit represented by the above formula (1) can be obtained.
• the ring closure rate of the amic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose. The same applies to the imidized structure of the repeating unit represented by the above formula (2).
• the polymer component include (i) a polyimide precursor having the first repeating unit (a1) and the second repeating unit (a2) in the same molecule, and imidization thereof.
• a polyimide precursor having at least one polymer (hereinafter, also referred to as a copolymer) selected from the group consisting of polyimide having a structure, (ii) the first repeating unit (a1), and an imidized structure thereof.
• a mixture with one kind of polymer (P-a2) (hereinafter, also referred to as a polymer blend) can be mentioned.
• the above-mentioned copolymer or the above-mentioned polymer blend may be used alone or in combination.
• the total of the first repeating unit (a1) and the second repeating unit (a2) is 5 to 100 of all the repeating units constituting the copolymer. It is preferably mol%, more preferably 10 to 100 mol%.
• the content ratio of the repeating unit (a1) is preferably 1 to 90 mol%, more preferably 1 to 85 mol% of the total number of repeating units constituting the copolymer.
• the content ratio of the repeating unit (a1) is 1 mol of the entire repeating unit constituting the polymer (P-a1) in terms of enhancing the liquid crystal orientation. % Or more and 99 mol% or less is preferable, 2 mol% or more and 95 mol% or less is more preferable, and 5 mol% or more and 90 mol% or less is further preferable. Further, the content ratio of the repeating unit (a2) is 5 mol% or more and 90 mol% or less of the entire repeating unit constituting the polymer (P-a2) from the viewpoint of efficiently obtaining the effect of the present invention. Preferably, it is 10 mol% or more and 80 mol% or less, more preferably.
• the mass ratio of the content of the polymer (P-a2) to the content of the polymer (P-a1) is preferably 5/95 to 95/5, more preferably 10/90 to It is 90/10.
• Y 1 represents a divalent organic group having a structure represented by the above formula (S).
• Examples of the alicyclic hydrocarbon group having 4 to 40 carbon atoms in the above formula (S) include monocyclic alicyclic hydrocarbon groups such as cyclobutane, cyclopentane, cyclohexane and cyclodecane; norbornene, adamantan, steroid skeleton and the like. Examples thereof include condensed polycyclic alicyclic hydrocarbon groups in which two or more monocyclic alicyclic hydrocarbon groups are condensed with each other.
• the steroid skeleton is based on the cyclopentano-perhydrophenanthrene nucleus, and may have a double bond in the aliphatic ring of the nucleus or may have a substituent.
• Examples of the substituent that the alicyclic hydrocarbon group may have include a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, and an alkoxy group having 3 to 10 carbon atoms.
• the carbon-carbon bond of the halogen atom-containing alkyl group, the halogen atom-containing alkoxy group, the alkyl group, the alkoxy group, and any methylene group of the alkenyl group is interrupted by the oxygen atom.
• Substituents selected from the group consisting of hetero-atom-containing groups are mentioned, and substituents other than these substituents (alkyl groups having 1 to 2 carbon atoms, alkoxy groups having 1 to 2 carbon atoms, hydroxy groups, cyano) can be mentioned. It may have a group, a vinyl group, a methoxymethyl group, etc.).
• the halogen atom is preferably a fluorine atom, and the fluorine atom-containing alkyl group is preferably a trifluoromethyl group.
• Examples of the aromatic hydrocarbon group having 6 to 40 carbon atoms in the above formula (S) include monocyclic aromatic hydrocarbon groups such as benzene; and two or more monocyclic aromatic hydrocarbons such as naphthalene and anthracene. Examples thereof include condensed polycyclic aromatic hydrocarbon groups in which groups are condensed with each other. Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, and an alkoxy group having 3 to 10 carbon atoms.
• the carbon-carbon bond of the alkenyl group having 3 to 10 carbon atoms and any methylene group of the halogen atom-containing alkyl group, halogen atom-containing alkoxy group, alkyl group, alkoxy group, and alkenyl group is interrupted by an oxygen atom.
• Substituents selected from the group consisting of hetero-atom-containing groups are mentioned, and substituents other than these substituents (alkyl groups having 1 to 2 carbon atoms, alkoxy groups having 1 to 2 carbon atoms, hydroxy groups, cyano groups) can be mentioned. , Vinyl group, methoxymethyl group, etc.).
• the halogen atom is preferably a fluorine atom, and the fluorine atom-containing alkyl group is preferably a trifluoromethyl group.
• the above formula (S) is a monovalent group having at least two or more groups selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms.
• at least one alicyclic hydrocarbon group or aromatic hydrocarbon group is a substituent exemplified above (that is, a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, 3 carbon atoms).
• X 1 is a single bond,-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N (CH 3 )-, -NH-, -O-, -COO-, -OCO- or-((CH 2 ) a1 -A 1 ) m1- (a1 is an integer from 1 to 15, A 1 represents an oxygen atom or -COO-, and m 1 Is an integer of 1 to 2.
• G 1 represents a divalent cyclic group selected from a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms and a divalent alicyclic hydrocarbon group having 4 to 8 carbon atoms. Any hydrogen atom on the cyclic group contains an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom-containing alkyl group having 1 to 3 carbon atoms, and a fluorine atom containing 1 to 3 carbon atoms. It may be substituted with an alkoxy group or a fluorine atom.
• m is an integer of 1 to 4.
• R 1 is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or carbon. Represents an alkoxyalkyl group of number 3-10.
• X 2 represents -CONH-, -NHCO-, -O-, -CH 2 O-, -OCH 2- , -COO- or -OCO-.
• G 2 represents a structure having a steroid skeleton.
• At least one of the hydrogen atoms in the structure having a steroid skeleton is a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, and a carbon number of carbon atoms.
• Heterozygous, in which the carbon-carbon bond of 3 to 10 alkenyl groups and any methylene group of the halogen atom-containing alkyl group, halogen atom-containing alkoxy group, alkyl group, alkoxy group, and alkenyl group is interrupted by an oxygen atom. It is substituted with a substituent selected from the group consisting of atomic-containing groups.
• examples of the divalent cyclic group in G 1 include a cyclopropylene group, a cyclohexylene group, and a phenylene group.
• Any hydrogen atom on these cyclic groups can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. It may be substituted with a contained alkoxy group or a fluorine atom.
• examples of the structure having a steroid skeleton in G 2 include a structure containing a cholestanyl group, a cholesteryl group or a lanostenyl group.
• Preferred embodiments of the formula (S1) include the following formulas (S1-x1) to (S1-x7).
• X p is-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3 )-, -NH-, -O-. , -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-.
• a 1 is an oxygen atom or -COO- * (however, the bond with "*" binds to (CH 2 ) a2 )
• a 2 is an oxygen atom or * -COO- (however, "*”.
• the bond with "" is (CH 2 ) to bond with a2 ), a3 is 0 or 1 , a1 and a2 are independently integers of 1 to 10, and Cy.
• R 1 is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or carbon. Represents an alkoxyalkyl group of number 3-10.
• a preferred embodiment of the above formula (S2) is the following formula (S2-x).
• X is a formula (X1), a formula (X2) or a formula (X3)
• Col is a formula (Col1), a formula (Col2) or a formula (Col3)
• G is an equation (G1), an equation (G2), an equation (G3) or an equation (G4).
• Me represents a methyl group.
• a divalent organic group having a structure represented by the above formula (S) a divalent organic group derived from an aromatic diamine (d) having a structure represented by the above formula (S) in a side chain.
• Organic groups can be mentioned.
• the divalent organic group having the structure represented by the above formula (S) is preferably a group obtained by removing two amino groups from the above aromatic diamine (d).
• the aromatic diamine (d) preferably has at least one benzene ring.
• Specific examples of the aromatic diamine (d) include diamines represented by the following formula (d1) or formula (d2).
• (X is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-,-(CH 2 ) m- , -SO 2- , -O- (CH 2 ) m- O-, -OC (CH 3 ) 2- , -CO- (CH 2 ) m- , -NH- (CH 2 ) m- , -SO 2- (CH 2 ) m- , -CONH- (CH 2) 2 ) represents a divalent organic group of m- , -CONH- (CH 2 ) m -NHCO-, or -COO- (CH 2 ) m -OCO-.
• M is an integer of 1-8.
• Y is an integer of 1-8. ,
• Preferred examples of the diamine represented by the above formula (d1) include the following formulas (d1-1) to (d1-6).
• Preferred examples of the diamine represented by the above formula (d2) include the following formulas (d2-1) to (d2-6).
• (X v1 to X v4 and X p1 to X p8 are independently- (CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, and -CON (CH 3 ).
• X V5 to X V6 and X s1 to X s4 are independent of each other.
• X a to X f are single bonds, -O-, -NH-, or -O- (CH 2 ) m- . It represents O- (m represents an integer of 1 to 8), R v1 to R v4 , and R 1a to R 1h are independently -C n H 2n + 1 (n represents an integer of 3 to 10). , Or -OC n H 2n + 1 (n represents an integer of 3 to 10).
• X 1 represents a tetravalent organic group.
• the tetravalent organic group include a tetravalent organic group derived from an acyclic aliphatic tetcarboxylic acid dianhydride or a derivative thereof, and a tetravalent organic derived from an alicyclic tetracarboxylic acid dianhydride or a derivative thereof.
• examples thereof include a tetravalent organic group derived from a group or aromatic tetracarboxylic acid dianhydride or a derivative thereof, preferably derived from a tetracarboxylic acid dianhydride represented by the following formula (T) or a derivative thereof 4 It is a valent organic group.
• the aromatic tetracarboxylic acid 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 acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not have to be composed of only a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure.
• the alicyclic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group attached to the alicyclic structure. However, none of these four carboxy groups are bonded to the aromatic ring. Further, it is not necessary to have only an alicyclic structure, and a chain hydrocarbon structure or an aromatic ring structure may be partially provided.
• (X represents a structure selected from any of the following formulas (x-1) to (x-13).)
• R 1 to R 4 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.
• R 5 and R 6 independently represent a hydrogen atom or a methyl group.
• J and k are integers of 0 or 1.
• a 1 and A 2 independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl group, or amide group.
• * 1 is for one acid anhydride group. It is a bond that binds, and * 2 is a bond that binds to the other acid anhydride group.
• two A 2s may be the same or different from each other. good.
• X is the above formulas (x-1) to (x-7), (x-11) to (x-13).
• the tetracarboxylic acid dianhydride represented by the formula (3) or a derivative thereof can be mentioned.
• the two R 1s independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group include a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• the two R 1s each independently represent preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• the two Z 1s independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, and a substituent.
• each of X 1 , Y 1 , R 1 , and Z 1 may be of one type or two or more types.
• Y 2 represents a divalent organic group having a partial structure represented by the following formula (2c).
• the divalent organic group include a divalent organic group obtained by removing two amino groups from a diamine having a partial structure represented by the following formula (2c).
• Y 2 may have a partial structure represented by the following formula (2c) in either the main chain direction or the side chain direction. Further, Y 2 may have one, two, or three or more partial structures represented by the following formula (2c).
• Y 2 preferably has one or two partial structures represented by the following formula (2c) in the main chain direction, and more preferably one in the main chain direction.
• Y 2 is even more preferably a divalent organic group represented by the following formula (2c).
• Examples of the monovalent substituent of 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.
• Examples thereof include a fluoroalkyl group, a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxyl group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group and a nitro group.
• Divalent organic groups include, but are not limited to. (Any hydrogen atom on the benzene ring may be substituted with a monovalent substituent.
• the monovalent substituent may be a substituent of an arbitrary hydrogen atom on the benzene ring in the above formula (2c). An illustrated structure can be mentioned.)
• the X 2 in the above formula (2) is the same as the X 1 in the above formula (1).
• the R 2 in the above formula (2) is the same as the R 1 in the above formula (1).
• the Z 2 in the above formula (2) is the same as the Z 1 in the above formula (1).
• X 2 , Y 2 , R 2 , and Z 2 may each have one type or two or more types.
• the polymer component further comprises a third repeating unit (a3) selected from the group consisting of a repeating unit represented by the following formula (3) and an imidized structure of the repeating unit represented by the following formula (3).
• a3 a third repeating unit selected from the group consisting of a repeating unit represented by the following formula (3) and an imidized structure of the repeating unit represented by the following formula (3).
• (X 3 represents a tetravalent organic group.
• Y 3 is a divalent organic group having a structure represented by the above formula (S) and a divalent organic having a partial structure represented by the above formula (2c). Represents a divalent organic group other than a group.
• R 3 independently represents a hydrogen atom or a monovalent organic group.
• Z 3 independently represents a hydrogen atom or a monovalent organic group.)
• polymer component further having the third repeating unit (a3) include copolymers and polymer blends.
• a polyimide precursor having the first repeating unit (a1), the second repeating unit (a2), and the third repeating unit (a3) in the same molecule At least one polymer selected from the group consisting of a body and a polyimide having an imidized structure thereof can be mentioned.
• An example of the polymer blend is a group consisting of a polyimide precursor having the first repeating unit (a1) and the second repeating unit (a2) in the same molecule and a polyimide having an imidized structure thereof.
• Examples thereof include a mixture with at least one polymer (P-a1 + a3) selected from the group consisting of polyimide having a structure.
• the polymer (P-a1 + a3) does not have to have the second repeating unit (a2).
• the above-mentioned copolymer or the above-mentioned polymer blend may be used alone or in combination.
• the content ratio of the above-mentioned repeating unit (a3) is preferably 5 to 90 mol%, more preferably 10 to 80 mol% of the total of the repeating units constituting the above-mentioned copolymer.
• the total of the first repeating unit (a1) and the second repeating unit (a2) is preferably 10 to 95 mol%, preferably 20 to 90 mol% of the total of the repeating units constituting the copolymer. Is more preferable.
• the mass ratio of the content of the polymer (P-a1 + a3) to the content of the polymer (P-a1 + a2) is 5/95 to 95/5. It is preferable, more preferably 10/90 to 90/10.
• divalent organic group of Y3 include , but are not limited to, the following diamines (hereinafter, also referred to as other diamines) excluding two amino groups.
• Diamines having a carboxyl group such as diamine compounds represented by the formulas (3b-1) to (3b-4) and photoorientative groups such as diamines represented by the following formulas (g-1) to (g-6).
• D is preferably a tert-butoxycarbonyl group.
• group "* -L-OD" (* represents a bond with a nitrogen atom.
• L represents an alkylene group having 1 to 5 carbon atoms.
• D represents a protective group that is desorbed by heating and replaced with a hydrogen atom. Represented.
• D is preferably a diamine having a tert-butoxycarbonyl group), 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, diamine represented by the following formula (Ds-1), and the like.
• Diamine having a siloxane bond diamine having an oxazoline structure such as the following formulas (Ox-1) to (Ox-2), 1,1-methaxylylene diamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine , An aliphatic diamine such as hexamethylenediamine; a diamine such as an alicyclic diamine such as 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexane.
• oxazoline structure such as the following formulas (Ox-1) to (Ox-2), 1,1-methaxylylene diamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine , An aliphatic diamine such as hexamethylenediamine; a diamine such as an alicyclic diamine such as
• 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 integers 0-4, and m1 + m2 represent integers 1-4. Equation (3b-2).
• a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
• m5 represents 1 to 5 in an integer of 1 to 5, respectively.
• a 3 and A 4 are independently single-bonded, -CH 2- , -C 2 H 4- , -C (CH 3 ) 2- , -CF.
• L is a single bond, an alkylene group having 1 to 15 carbon atoms, or -O between the carbon-carbon bonds of the alkylene group and at least one of the ends of the alkylene group.
• the divalent organic group is the oxygen atom contained in the ester bond. Bonded with a carbon atom.
• X 1 , G 1 , and R 1 are synonymous with (S1) above.
• M is an integer of 0 to 4. When m is 2 or more, a plurality of X 1 , G 1 Each has the above definition independently.
• the hydrogen atom on the benzene ring is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a fluorine atom-containing alkyl group having 1 to 3 carbon atoms.
• the above 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, the diamine having a photopolymerizable group at the end, the diamine represented by the above formulas (R1) to (R5), the above formula (z-1) to The diamine represented by (z-20) may be used alone or in combination of two or more when producing the above-mentioned polymer component from the viewpoint of increasing the response speed of the liquid crystal display element using the PSA method or the SC-PVA mode. good.
• the X 3 in the above formula (3) is the same as the X 1 in the above formula (1).
• the R 3 in the above formula (3) is the same as the R 1 in the above formula (1).
• the Z 3 in the above formula (3) is the same as the Z 1 in the above formula (1).
• each of X 3 , Y 3 , R 3 , and Z 3 may be one type or two or more types.
• polyimide precursor used in the present invention examples include polyamic acid and polyamic acid ester.
• the polyimide precursor used in the present invention can be synthesized by a known method as described in, for example, International Publication 2013/157586.
• tetracarboxylic acid derivative component examples include tetracarboxylic acid dianhydride and its derivatives (tetracarboxylic acid dihalide, tetracarboxylic acid diester, or tetracarboxylic acid diester dihalide).
• a part of the polymer contains an amic acid structure (for example, when R 1 and R 2 are hydrogen atoms in the above formula (1) or (2)), for example, the tetracarboxylic acid derivative component and the diamine component are reacted.
• the solvent is not particularly limited as long as the produced polymer dissolves.
• Specific examples of the above solvent include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethyl sulfoxide. , 1,3-Dimethyl-2-imidazolidinone.
• methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] can be used.
• the indicated solvents 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.
• solvent represented by the above formulas [D-1] to [D-3] include propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethyl ether such as ethylene glycol, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol.
• examples include monoethyl ether.
• 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 weight of the produced polymer.
• the polyamic acid ester 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, and [III] a method of reacting a tetracarboxylic acid. It can be obtained by a known method such as a method of reacting a diester dihalide with a diamine.
• the polyimide can be obtained by ring-closing (imidizing) the above-mentioned polyimide precursor.
• the ring closure rate (also referred to as imidization rate) of the amic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
• the imidization rate as used herein is the ratio of the imide group to the total amount of the imide group derived from the tetracarboxylic acid dianhydride or its derivative and the carboxyl group (or its derivative).
• Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
• the temperature at which the polyimide precursor is thermally imidized in the solution is preferably 100 to 400 ° C., more preferably 120 to 250 ° C., and it is preferable to remove the water generated by the imidization reaction from the outside of the system. ..
• the catalytic imidization of the polyimide precursor is carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor and stirring at preferably ⁇ 20 to 250 ° C., more preferably 0 to 180 ° C. Can be done.
• 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 and trioctylamine, and among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
• the acid anhydride examples include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, acetic anhydride is preferable because it facilitates purification after completion of the reaction.
• 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 to precipitate.
• 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 which has been 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 increased.
• the molecular weight of the polymer used in the present invention is a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained from the polymer, the workability at the time of film formation, and the coating film property. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
• ⁇ Terminal sealant> When synthesizing the polymer in the present invention, it is also possible to synthesize an end-sealing type polymer using an appropriate end-sealing agent together with the above-mentioned tetracarboxylic acid dianhydride or a derivative thereof and a diamine component. good.
• the end-sealing type 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 in the present invention include an amino group, a carboxyl group, an acid anhydride group or a derivative thereof.
• the amino group, carboxyl group, acid anhydride group, and isocyanate group can be obtained by a usual condensation reaction, or can be obtained by sealing the ends with the following terminal encapsulants, and the derivatives can be obtained, for example, by using the following terminal encapsulants. It can be obtained in the same manner by using the following terminal encapsulants.
• terminal encapsulant examples include acetic anhydride, maleic anhydride, nadic acid 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.
• Acid anhydride dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and 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; ethyl isocyanate, phenylisocyanate, naphthylisocyanate, monoisocyanate compounds having structures represented by the following formulas [1a] to [1d] and the like can
• X 3 represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring
• X 4 represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring
• X 5 represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring
• X 6 represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring.
• the ratio of the end-capping agent 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 blending ratio of the polymer component used in the method for producing the liquid crystal alignment film of the present invention is not particularly limited, but for example, the total amount of the polymer component contained in the liquid crystal alignment agent is 0.1 to 30% by mass, preferably 0.1 to 30% by mass. It is 3 to 10% by mass.
• the liquid crystal alignment agent used for producing the liquid crystal alignment film may be mixed with a polymer other than the polymer component.
• the content of the other polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass, based on the total amount of the polymer components.
• other polymers include polyimide precursors other than the polymer components, polyimides, acrylic polymers, methacrylic polymers, polystyrene, polyamides, polysiloxanes, and the like.
• the solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve the polymer, and is, for example, a lactone solvent such as ⁇ -valerolactone and ⁇ -butyrolactone; ⁇ -butyrolactam and N-methyl.
• N-Pyrrolidone N-ethyl-2-pyrrolidone, 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- Lactam solvents such as 2-pyrrolidone; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyllactoamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N- Amido solvents such as dimethylpropanamide;
• Preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and propylene.
• the liquid crystal alignment agent of the present invention may contain other components other than the above, such as a crosslinkable compound, a functional silane compound, a surfactant, and a compound having a polymerizable group.
• the crosslinkable compound can be used for the purpose of increasing the strength of the liquid crystal alignment film.
• the crosslinkable compound include a compound having at least two or more groups selected from the group consisting of an epoxy group, an isocyanate group, an oxetane ring, an oxazoline ring, and a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group, and a lower alkoxy.
• examples thereof include a compound having at least two or more groups of at least one selected from the group consisting of alkyl groups, and at least one compound selected from the group consisting of compounds having a blocked isocyanate group.
• Examples of the compound having an epoxy group include bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl diamine type epoxy resin, and heterocyclic epoxy resin. , Acrylic resin having an epoxy group and the like.
• Examples of these commercially available products include Epolite 400E, 3002 (manufactured by Kyoeisha Chemical Co., Ltd.), Epicoat 828, 152, and Epoxy Novolac 180S (manufactured by Japan Epoxy Resin Co., Ltd.). Of these, a glycidyl diamine-based epoxy resin is preferable, and the following formula (b E ) is used.
• R is a divalent organic group having an aromatic ring or a cyclohexane ring and having 6 to 40 carbon atoms.
• R is a divalent organic group having an aromatic ring or a cyclohexane ring and having 6 to 40 carbon atoms.
• Specific examples of the compound represented by the above formula (b E ) include compounds represented by the following formulas (b E -1) to (b E -6).
• compounds having two or more oxetane rings include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene (alon oxetane OXT-121 (XDO)) and di [2-.
• BisAOX BisAOX
• Bisphenol F and OXC Bisphenol F and OXC
• PNOX etherified products of phenol novolac and OXC
• CNOX etherified products of cresol novolac and OXC
• OX-SQ oxetanyl silsesquioxane
• OX-SC 3-ethyl -3-Hydroxymethyloxetane Silicon Alcoxene
• Aron Oxetane, OX-SC, OXT-121, OXT-221, PNOX-1009 (manufactured by Toagosei Co., Ltd.) and ETARNACOLL OXBP (manufactured by Ube Kosan Co., Ltd.) are preferable, and OX-SC, OXT-121, OXT- 221 and PNOX-1009 are particularly preferable.
• compounds having two or more oxazoline rings include 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), and 2,2'-bis (5).
• -Methyl-2-oxazoline 2,2'-bis (5,5'-dimethyloxazoline), 2,2'-bis (4,5,4', 4'-tetramethyl-2-oxazoline), 1 , 2-Bis (2-oxazoline-2-yl) ethane, 1,4-bis (2-oxazoline-2-yl) butane, 1,6-bis (2-oxazoline-2-yl) hexane, 1,8 -Bis (2-oxazoline-2-yl), 1,4-bis (2-oxazoline-2-yl) cyclohexane, 1,2-bis (2-oxazoline-2-yl) benzene, 1,3-bis ( 2-Oxazoline-2-yl) Benzene, 1,4-bis (2-ox
• Blocked isocyanate compounds are available as commercial products, for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosoh Corporation), Takenate B-830, B. -815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.) and the like can be preferably used.
• the compound having two or more at least one group selected from the group consisting of the hydroxy group, the hydroxyalkyl group and the lower alkoxyalkyl group is a compound represented by the following formulas (b1-1) to (b1-22). Can be mentioned.
• crosslinkable compound used in the liquid crystal alignment agent of the present invention may be one kind or a combination of two or more kinds.
• the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is 0.1 to 150 parts by mass, 0.1 to 100 parts by mass, or 1 to 50 parts by mass with respect to 100 parts by mass of all the polymer components. It is a department.
• the functional silane compound can be used for the purpose of improving the adhesion between the liquid crystal alignment film and the underlying substrate.
• the silane compound described in paragraph [0019] of International Publication 2014/119682 can be mentioned.
• the content of the functional silane compound is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of all the polymer components.
• the surfactant can be used for the purpose of improving the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film.
• the compound include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. Specific examples of these include the surfactants described in paragraph [0117] of WO 2016/047771.
• the amount of the surfactant used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.
• the compound having a polymerizable group is a compound having one or more polymerizable unsaturated groups in the molecule such as an acrylate group and a methacrylate group, for example, as represented by the following formulas (M-1) to (M-7). Compounds can be mentioned.
• the liquid crystal aligning agent of the present invention is a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of the device, as described in Paragraph of International Publication No. 2011/132751 (Published 2011.10.27) [
• the nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed in 0194] to [0200], more preferably 3-picorylamine and 4-picorylamine can be added.
• This amine compound may be added directly to the liquid crystal alignment agent, but it is preferably added after making a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass.
• This solvent is not particularly limited as long as it dissolves the polymer.
• the liquid crystal alignment agent of the present invention may be added with an imidization accelerator or the like for the purpose of efficiently advancing imidization by heating when firing the coating film.
• the solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. It is in the range of 0.5 to 15% by mass, more preferably 1 to 10% by mass.
• the range of particularly preferable solid content concentration depends on the method used when applying the liquid crystal alignment agent to the substrate. For example, in the case of the spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass.
• the solid content concentration is in the range of 3 to 9% by mass, and the solution viscosity is in the range of 12 to 50 mPa ⁇ s.
• the solid content concentration is in the range of 1 to 5% by mass and the solution viscosity is in the range of 3 to 15 mPa ⁇ s.
• 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 liquid crystal alignment film, and is particularly suitable for a vertically oriented type liquid crystal display element such as a VA method or a PSA mode.
• the liquid crystal display element of the present invention includes the liquid crystal alignment film.
• the liquid crystal alignment agent of the present invention has a liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display element manufactured through a step of arranging an object and polymerizing a polymerizable compound by at least one of irradiation and heating of active energy rays while applying a voltage between electrodes.
• the liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (3) or steps (1) to (4).
• a method including the following steps (1) to (3) or steps (1) to (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, for example, by a roll coater method, a spin coating method, a printing method, or an inkjet. Apply by an appropriate coating method such as the 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.
• the prebake temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C.
• the prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, it is preferable that a heating (post-baking) step is further carried out.
• the post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C.
• the post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
• the film thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.
• the coating film formed in the above step (1) 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.
• the alignment ability-imparting treatment includes a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, and cotton, and photoalignment in which the coating film is irradiated with polarized or unpolarized radiation. Processing etc. can be mentioned.
• the radiation to irradiate the coating film for example, ultraviolet rays including light having a wavelength of 150 to 800 nm and visible light can be used.
• the radiation when the radiation is polarized, it may be linearly polarized or partially polarized.
• the irradiation may be carried out from a direction perpendicular to the substrate surface, may be carried out from an oblique direction, or may be carried out in combination thereof.
• the direction of irradiation is diagonal.
• Step of forming a liquid crystal layer (3-1) In the case of a VA type liquid crystal display element Two substrates on which a liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is formed between the two substrates arranged to face each other. To place. Specifically, the following two methods can be mentioned.
• the first method is a conventionally known method. First, two substrates are arranged facing each other with 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 attached so that the liquid crystal alignment films face 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.
• liquid crystal composition is not particularly limited, and various liquid crystal compositions having at least one liquid crystal compound (liquid crystal molecule) having a positive or negative dielectric anisotropy can be used.
• a liquid crystal composition having a positive dielectric anisotropy will also be referred to as a positive liquid crystal
• a liquid crystal composition having a negative dielectric anisotropy will also be referred to as a negative liquid crystal.
• the liquid crystal composition comprises a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (for example, a trifluoromethyl group), a cyano atom, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, and the like. It may contain a liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring, and a compound having two or more rigid sites (mesogen skeleton) expressing liquidity in the molecule (for example, two rigid biphenyls).
• the liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase.
• additives may be further added from the viewpoint of improving the liquid crystal orientation.
• Such additives are photopolymerizable monomers such as compounds having the following polymerizable groups; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); antioxidants; UV absorbers; Examples include dyes; antifoaming agents; polymerization initiators; or polymerization inhibitors.
• Examples of the positive liquid crystal display include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, and MLC-7081 manufactured by Merck & Co., Inc.
• Examples of the negative liquid crystal display include MLC-6608, MLC-6609, MLC-6610, and MLC-7026-100 manufactured by Merck & Co., Inc.
• MLC-3023 manufactured by Merck & Co., Inc. can be mentioned as a liquid crystal containing a compound having a polymerizable group.
• the compound having a polymerizable group is a compound having one or more polymerizable unsaturated groups in the molecule such as an acrylate group and a methacrylate group as represented by the above formulas (M-1) to (M-7).
• the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of all the polymer components.
• the polymerizable group may be contained in the polymer used as the liquid crystal aligning agent, and as such a polymer, for example, a diamine component containing a diamine having the photopolymerizable group at the terminal is used in the reaction. Examples thereof include the obtained polymer.
• the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in (3-2) or (3-3) above.
• the voltage applied here can be, for example, a direct current or an alternating current of 5 to 50 V.
• the light to be irradiated for example, ultraviolet rays containing light having a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable.
• the light source of the irradiation light for example, a low pressure mercury lamp, a high pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excima laser and the like can be used.
• the irradiation amount of light is preferably 1,000 to 200,000 J / m 2 , and more preferably 1,000 to 100,000 J / m 2 .
• 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 "H film” in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between cellulose acetate protective films or the H film itself.
• a polarizing plate made of the above can be mentioned.
• the liquid crystal display element of the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a cam coder, a PDA, a digital camera, a mobile phone, a smartphone, and the like. It can be used for various display devices such as various monitors, liquid crystal televisions, and 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 dimming element. Alternatively, it can also be used for applications other than these, for example, a protective film for a color filter, a gate insulating film for a flexible display, and a substrate material.
• CA-1 to CA-4 Compounds (diamines) represented by the following formulas (CA-1) to (CA-4), respectively.
• DA-1 to DA-3 Compounds represented by the following formulas (DA-1) to (DA-3), respectively.
• ⁇ Measurement of viscosity> 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.
• ⁇ Measurement of molecular weight> The molecular weight was measured by a room temperature GPC (gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated as polyethylene glycol and polyethylene oxide equivalent values.
• GPC device GPC-101 (manufactured by Showa Denko), column: GPC KD-803, GPC KD-805 (manufactured by Showa Denko) in series, column temperature: 50 ° C, eluent: N, N-dimethylformamide (addition)
• eluent N, N-dimethylformamide
• lithium bromide monohydrate LiBr ⁇ H 2 O
• phosphoric acid / anhydrous crystal o-phosphoric acid
• THF tetrahydrofuran
• flow velocity 1.0 mL / min Standard sample for preparation of calibration line: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Toso) and polyethylene glycol (molecular weight; about 12, 000, 4,000 and 1,000) (manufactured by Polymer Laboratory).
• DA-1 (2.20 g, 9.11 mmol), DA-2 (1.48 g, 3.90 mmol), CA-4 (0.976 g, 0.976 g, in a 50 mL four-necked flask with agitator and nitrogen inlet tube. 3.90 mmol), NMP (22.2 g) and GBL (3.20 g) were added and stirred at 40 ° C. for 3 hours. Then, CA-1 (1.68 g, 8.58 mmol) and NMP (9.54 g) were added, and the mixture was stirred at 40 ° C. for 3 hours to obtain a polyamic acid solution (1) (viscosity: 808 mPa) having a solid content concentration of 15%.
• Example 1 The liquid crystal alignment agent (A-1) was obtained by adding NMP (9.00 g) and BCS (10.8 g) to the polyamic acid solution (1) (7.20 g) obtained in Synthesis Example 1 and stirring at room temperature for 3 hours. Got (Examples 2 and 3) The liquid crystal alignment agents (A-2) and (A-2) of Examples 2 and 3 were used in the same manner as in Example 1 except that the polyamic acid solutions (2) and (3) were used instead of the polyamic acid solution (1), respectively. A-3) was obtained.
• the liquid crystal alignment agents (A-1) to (A-3) and (B-1) to (B-3) obtained as described above did not show any abnormalities such as turbidity or precipitation, and were prepared in a uniform solution. It was confirmed that there was.
• the refractive index and residual DC voltage were evaluated using the obtained liquid crystal alignment agent.
• the liquid crystal alignment agents (A-1) to (A-3) and (B-1) to (B-3) obtained in Examples 1 to 3 and Comparative Examples 1 to 3 are spin-coated on a silicon substrate. After firing for 90 seconds on a hot plate at 70 ° C., firing was performed in an infrared heating furnace at 230 ° C. for 20 minutes to prepare a silicon substrate with a liquid crystal aligning agent having a film thickness of 100 nm. Next, the refractive index was measured with M-2000 manufactured by JA Woolam Japan, and the refractive index at 550 nm was compared. The results are shown in Table 3 below.
• liquid crystal alignment agent (A-1), (A-3), (B-1) and (B-3) obtained in Examples 1 and 3 and Comparative Examples 1 and 3 above.
• a liquid crystal cell was produced according to the procedure.
• the liquid crystal alignment agent was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 70 ° C. for 90 seconds, and then fired in an infrared heating furnace at 230 ° C. for 20 minutes to form a liquid crystal alignment film having a thickness of 100 nm. ..
• thermosetting sealant thermosetting sealant (SW-D1)) is applied.
• XN-1500T manufactured by Kyoritsu Chemical Industry Co., Ltd. was printed.
• the surface of the other substrate on which the liquid crystal alignment film was formed is turned inside, and after bonding with the previous substrate, heat treatment is performed at 150 ° C. for 60 minutes to cure the sealant and empty cell.
• heat treatment is performed at 150 ° C. for 60 minutes to cure the sealant and empty cell.
• a liquid crystal MLC-3023 (negative type liquid crystal, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
• UV was irradiated from the outside of the liquid crystal cell through a cut filter having a wavelength of 325 nm or less at 10 J / cm 2 .
• the illuminance of UV was measured using UV-MO3A manufactured by ORC.
• UV UV lamp: FLR40SUV32 /
• A-1 UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied. A-1) was irradiated for 30 minutes.
• the liquid crystal aligning agent (A-1) of Example 1 containing the polyamic acid solution (1) obtained by using the diamine compound (DA-1) as a raw material is a diamine compound (DA-1).
• the liquid crystal alignment agent (B-1) of Comparative Example 1 containing the polyamic acid solution (4) obtained from the monomer component containing the diamine compound (DA-3) the refractive index of the obtained liquid crystal alignment film. Showed a high value.
• a comparison between the liquid crystal alignment agent (A-2) of Example 2 and the corresponding liquid crystal alignment agent (B-2) of Comparative Example 2 and a comparative example corresponding to the liquid crystal alignment agent (A-3) of Example 3 In the comparison with the liquid crystal alignment agent (B-3) of No.

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• 2022
  • 2022-01-12 JP JP2022575598A patent/JP7819636B2/ja active Active
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