WO2016080458A1 - Liquid crystal aligning agent containing polyamic acid or derivative thereof, liquid crystal alignment film and liquid crystal display element - Google Patents
Liquid crystal aligning agent containing polyamic acid or derivative thereof, liquid crystal alignment film and liquid crystal display element Download PDFInfo
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- WO2016080458A1 WO2016080458A1 PCT/JP2015/082443 JP2015082443W WO2016080458A1 WO 2016080458 A1 WO2016080458 A1 WO 2016080458A1 JP 2015082443 W JP2015082443 W JP 2015082443W WO 2016080458 A1 WO2016080458 A1 WO 2016080458A1
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- 0 **c1ccccc1 Chemical compound **c1ccccc1 0.000 description 26
- OBCSAIDCZQSFQH-UHFFFAOYSA-N Cc(cc(cc1)N)c1N Chemical compound Cc(cc(cc1)N)c1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 3
- HDDQXUDCEIMISH-UHFFFAOYSA-N C(C1OC1)Oc1ccc(C(C(c(cc2)ccc2OCC2OC2)c(cc2)ccc2OCC2OC2)c(cc2)ccc2OCC2OC2)cc1 Chemical compound C(C1OC1)Oc1ccc(C(C(c(cc2)ccc2OCC2OC2)c(cc2)ccc2OCC2OC2)c(cc2)ccc2OCC2OC2)cc1 HDDQXUDCEIMISH-UHFFFAOYSA-N 0.000 description 1
- XDVPTLCPDVDNSP-UHFFFAOYSA-N C(c(c(cc1)c(cc2)c(C3)c1OCN3c1ccccc1)c2OC1)N1c1ccccc1 Chemical compound C(c(c(cc1)c(cc2)c(C3)c1OCN3c1ccccc1)c2OC1)N1c1ccccc1 XDVPTLCPDVDNSP-UHFFFAOYSA-N 0.000 description 1
- OHKJGNSTCPDZOS-UHFFFAOYSA-N C(c(c1c(CN(CO2)c3ccccc3)c2ccc1cc1)c1OC1)N1c1ccccc1 Chemical compound C(c(c1c(CN(CO2)c3ccccc3)c2ccc1cc1)c1OC1)N1c1ccccc1 OHKJGNSTCPDZOS-UHFFFAOYSA-N 0.000 description 1
- KQVVPVCKQVMOTE-UHFFFAOYSA-N C(c(cc(cc1)Oc(cc2)cc(C3)c2OCN3c2ccccc2)c1OC1)N1c1ccccc1 Chemical compound C(c(cc(cc1)Oc(cc2)cc(C3)c2OCN3c2ccccc2)c1OC1)N1c1ccccc1 KQVVPVCKQVMOTE-UHFFFAOYSA-N 0.000 description 1
- BDSYTYPSFUGBLH-UHFFFAOYSA-N C(c(ccc1c2ccc(OC3)c1CN3c1ccccc1)c2OC1)N1c1ccccc1 Chemical compound C(c(ccc1c2ccc(OC3)c1CN3c1ccccc1)c2OC1)N1c1ccccc1 BDSYTYPSFUGBLH-UHFFFAOYSA-N 0.000 description 1
- FMZPVXIKKGVLLV-UHFFFAOYSA-N C(c(cccc1)c1OC1)N1c1ccccc1 Chemical compound C(c(cccc1)c1OC1)N1c1ccccc1 FMZPVXIKKGVLLV-UHFFFAOYSA-N 0.000 description 1
- XQLBRTHCGDSORN-UHFFFAOYSA-N CC(C)(C)OC(N(c(cc1)ccc1N)I)=O Chemical compound CC(C)(C)OC(N(c(cc1)ccc1N)I)=O XQLBRTHCGDSORN-UHFFFAOYSA-N 0.000 description 1
- GEUVTLZSOCUHIF-UHFFFAOYSA-N CC(C)(c1ccc(C(C)(c(cc2)ccc2OCC(COCC2OC2)O)c(cc2)ccc2OCC(COCC2OC2)O)cc1)c(cc1)ccc1OCC(COCC1OC1)O Chemical compound CC(C)(c1ccc(C(C)(c(cc2)ccc2OCC(COCC2OC2)O)c(cc2)ccc2OCC(COCC2OC2)O)cc1)c(cc1)ccc1OCC(COCC1OC1)O GEUVTLZSOCUHIF-UHFFFAOYSA-N 0.000 description 1
- DFATXMYLKPCSCX-UHFFFAOYSA-N CC(CC(O1)=O)C1=O Chemical compound CC(CC(O1)=O)C1=O DFATXMYLKPCSCX-UHFFFAOYSA-N 0.000 description 1
- SFNVCIXHFAIRFG-UHFFFAOYSA-N CN(C1)COc(cc2)c1cc2Oc(cc1)cc(C2)c1OCN2I Chemical compound CN(C1)COc(cc2)c1cc2Oc(cc1)cc(C2)c1OCN2I SFNVCIXHFAIRFG-UHFFFAOYSA-N 0.000 description 1
- ZZLHZRRZJWMQOL-UHFFFAOYSA-N CN(C1)COc2c1cccc2 Chemical compound CN(C1)COc2c1cccc2 ZZLHZRRZJWMQOL-UHFFFAOYSA-N 0.000 description 1
- WJNGKXQGWPKCFZ-UHFFFAOYSA-N COC(CC(C=C1)NCCNc(cc2)cc(OC)c2N)=C1N Chemical compound COC(CC(C=C1)NCCNc(cc2)cc(OC)c2N)=C1N WJNGKXQGWPKCFZ-UHFFFAOYSA-N 0.000 description 1
- BDHGRBRMUAGQRB-UHFFFAOYSA-N NC(CC1)=CC=C1C(CC1)=CC=C1N Chemical compound NC(CC1)=CC=C1C(CC1)=CC=C1N BDHGRBRMUAGQRB-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N Nc(cc1)ccc1N Chemical compound Nc(cc1)ccc1N CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NRHZAVJNUJCQRL-UHFFFAOYSA-N Nc(cc1)ccc1N(CC1)CCN1c(cc1)ccc1N Chemical compound Nc(cc1)ccc1N(CC1)CCN1c(cc1)ccc1N NRHZAVJNUJCQRL-UHFFFAOYSA-N 0.000 description 1
- LZDNJNIYWSZLJX-UHFFFAOYSA-N Nc(ccc(NCCNc(cc1)cc(Cl)c1N)c1)c1Cl Chemical compound Nc(ccc(NCCNc(cc1)cc(Cl)c1N)c1)c1Cl LZDNJNIYWSZLJX-UHFFFAOYSA-N 0.000 description 1
- VNADHGDVFCTMBO-UHFFFAOYSA-N O=C(c(cc1)cc(C2)c1OCN2c1ccccc1)c(cc1)cc(C2)c1OCN2c1ccccc1 Chemical compound O=C(c(cc1)cc(C2)c1OCN2c1ccccc1)c(cc1)cc(C2)c1OCN2c1ccccc1 VNADHGDVFCTMBO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- 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
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- 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 polyamic acid obtained using tetracarboxylic dianhydride or a derivative thereof, a liquid crystal aligning agent containing a specific solvent, a liquid crystal aligning film formed using this liquid crystal aligning agent, and further this liquid crystal aligning film
- the present invention relates to a liquid crystal display element having
- liquid crystal alignment agent in the present invention means a polymer-containing composition used for forming a liquid crystal alignment film.
- liquid crystal display elements are display elements using nematic liquid crystals.
- a TN (Twisted Nematic) mode and an STN (Super Twisted Nematic) mode are well known.
- a TN liquid crystal display device using an optical compensation film MVA (Multi -domain (vertical alignment) mode, IPS (in-plane switching) mode of lateral electric field method, and FFS (fringe field switching) mode have been proposed and put into practical use.
- MVA Multi -domain (vertical alignment) mode
- IPS in-plane switching
- FFS far field switching
- the development of the technology of the liquid crystal display element has been achieved not only by improving these driving methods and element structures but also by improving the components used in the elements.
- the liquid crystal alignment film is one of important materials related to display quality, and the performance of the alignment film can be improved with the improvement in quality of the liquid crystal display element. It is becoming important.
- the liquid crystal alignment film is formed using a liquid crystal aligning agent.
- liquid crystal aligning agents mainly used are resins such as polyamic acid, polyimide, polyamide, polyimide amide, and polyamic acid ester, and are solutions (varnishes) in which these resins are dissolved in an organic solvent. . After this solution is applied to the substrate, it is formed by means such as heating to form a polyimide-based liquid crystal alignment film.
- the rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction using a cloth in which fibers of nylon, rayon, polyester, or the like are planted, and this makes it possible to obtain uniform alignment of liquid crystal molecules.
- the rubbing process has problems such as dust generated by scraping the liquid crystal alignment film, scratches on the liquid crystal alignment film degrading display quality, and generation of static electricity. Development of an alignment treatment method that replaces this has been activated.
- an alignment treatment method that replaces the rubbing method is a photo-alignment treatment method in which alignment treatment is performed by irradiating light.
- Many alignment mechanisms such as a photodecomposition method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed for the photoalignment treatment method (see, for example, Non-Patent Document 1, Patent Documents 1 and 2).
- the photo-alignment method has higher uniformity of alignment than the rubbing method, and it is a non-contact alignment method, so the film is not damaged and causes the display defects of liquid crystal display elements such as dust generation and static electricity. There are advantages such as reduction.
- examples of the alignment film printing method include spin coating, flexographic printing, and inkjet printing.
- a technique suitable for pattern printing is flexographic printing. This method is a method of transferring the varnish on the APR plate to the substrate, and causes film thickness unevenness and disorder of the linearity of the edge portion of the printed alignment film (hereinafter, sometimes referred to as “backlash”). It is hard to do.
- inkjet printing is more suitable for printing on a large-area substrate of the sixth generation or higher.
- An object of the present invention is to provide a liquid crystal aligning agent capable of preventing the coating film from being uneven when printing a coating film for a liquid crystal alignment film by an ink jet method and not causing film shrinkage or edge backlash.
- Another object of the present invention is to provide a liquid crystal alignment film formed using the liquid crystal alignment agent, and further a liquid crystal display element having the liquid crystal alignment film.
- the present inventors have found a solvent that can simultaneously solve the problem of preventing uneven stripes, shrinking of the film, and preventing rattling of the edge by using a solvent of a plurality of components for the resin forming the alignment film described later. Completed the invention.
- a liquid crystal aligning agent comprising at least one polymer selected from the group consisting of polyamic acid and derivatives thereof and a solvent;
- the solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone as the first solvent,
- the second solvent at least one selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether,
- As the third solvent at least one selected from the group consisting of diisobutyl ketone and dipentyl ether, and
- R 1 is alkyl having 2 carbons
- R 2 is alkyl
- the proportion of the first solvent is 20 to 89% by weight with respect to the total solvent weight
- the proportion of the second solvent is 10 to 60% by weight with respect to the total solvent weight
- the proportion of the third solvent is 0.1 to 15% by weight with respect to the total solvent weight
- the liquid crystal aligning agent according to item [1] wherein the proportion of the fourth solvent is 0.1 to 20% by weight based on the total solvent weight.
- the tetracarboxylic dianhydride used for the synthesis of the polymer contains at least one selected from the group of compounds represented by the following formulas (AN-I) to (AN-VII); Diamine does not have a side chain represented by the following formulas (DI-1) to (DI-16), and does not have a side chain represented by any of the following formulas (DIH-1) to (DIH-3)
- X is independently a single bond or —CH 2 —.
- G is a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —.
- Y is independently one selected from the group of the following trivalent groups, and the bond is connected to any carbon.
- At least one hydrogen may be replaced by methyl, ethyl or phenyl;
- the ring A 10 is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, At least one hydrogen of the group may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are the same carbon You may connect to.
- X 10 is alkylene having 2 to 6 carbon atoms, Me represents methyl, Ph represents phenyl;
- G 10 is independently —O—, —COO— or —OCO—, and r is independently 0 or 1;
- G 20 is —CH 2 —, at least one —CH 2 — may be replaced by —NH—, —O—, and m is an integer of 1 to 12 And at least one hydrogen of the alkylene may be replaced by —OH;
- G 21 is independently a single bond, —NH—, —NCH 3 —, —O—, —S—, —S.
- At least one hydrogen of the cyclohexane ring and the benzene ring in formula (DI-2) to formula (DI-7) is —F, —Cl, alkyl having 1 to 3 carbon atoms, —OCH 3 , —OH, —CF 3 , —CO 2 H, —CONH 2 , —NHC 6 H 5 , phenyl, or benzyl, and in Formula (DI-4), at least one hydrogen of the benzene ring is represented by the following formula ( DI-4-a) to (DI-4-e) may be substituted with one selected from the group of groups represented by formula (DI-4-e); the bonding position is fixed to the carbon atom constituting the ring in the above formula An unlabeled group indicates that the position of attachment in the ring is arbitrary; The bonding position of —NH 2 to the cyclohexane ring or the benzene ring is any position except the bonding position of G 21 or G 22
- R 21 and R 22 are independently alkyl or phenyl having 1 to 3 carbon atoms
- G 23 is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms.
- R 23 is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer from 0 to 3, and q is An integer from 0 to 4;
- ring B is a monocyclic heteroaromatic group, R 24 is hydrogen, —F, —Cl, C 1-6 alkyl, alkoxy, vinyl, alkynyl, q is independently an integer of 0 to 4.
- ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group
- G 24 is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1; A group whose bonding position is not fixed to the carbon atom constituting the ring in the above formula indicates that the bonding position in the ring is arbitrary;
- the bonding position of —NH 2 bonded to the ring is an arbitrary position;
- G 25 represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or — C (CF 3 ) 2 —;
- ring D is a cyclohexane ring, a benzene ring
- R 25 is an alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a).
- this alkyl at least one hydrogen is —F.
- At least one —CH 2 — may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—, and the hydrogen of the phenyl is —F, —CH 3 , —OCH 3 , —OCH 2 F, —OCHF 2, —OCF 3, alkyl having 3 to 30 carbon atoms, or alkoxy having 3 to 30 carbon atoms, and —NH 2 bonded to the benzene ring
- the bond position is any position in the ring;
- G 27 , G 28 and G 29 are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbon atoms, and one or more — CH 2 — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH ⁇ CH—, and ring B 21 , ring B 22 , ring B 23 and ring B 24 are independent.
- t and u are each independently an integer of 0 to 2, and their sum is 1 to 5, and when s, t or u is 2, two bonds in each parenthesis
- the groups may be the same or different, and the two rings may be the same or different, and R 26 is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, carbon number 1 to 30 fluorine-substituted alkyl, 1 to 30 carbon alk
- R 31 is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — of the alkyl may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—
- R 32 is alkyl having 6 to 22 carbon atoms
- R 33 is hydrogen or alkyl having 1 to 22 carbon atoms
- ring B 25 is 1,4-phenylene or 1,4-cyclohexylene
- r is 0
- —NH 2 bonded to a benzene ring indicates that the bonding position in the ring is arbitrary.
- the tetracarboxylic dianhydride used for the synthesis of the polymer contains at least one selected from the group of compounds represented by the following formulas (2) to (13);
- X and Y are each independently a single bond, —O—, —NH—, —S—, or alkylene having 1 to 6 carbon atoms;
- a is an integer of 1 to 8;
- Ra is alkyl having 1 to 3 carbons; and At least one hydrogen of the benzene ring in the above formula may be replaced by —CH 3 .
- the polyamic acid and its derivative are polymers (a) obtained by reacting a raw material monomer in which at least one of tetracarboxylic dianhydride and diamine has a photoreactive structure, [1] to [4 ]
- the tetracarboxylic dianhydride used for the synthesis of the polymer (b) contains at least one selected from the group of compounds represented by the following formulas (2) to (13);
- X and Y are each independently a single bond, —O—, —NH—, —S—, or alkylene having 1 to 6 carbon atoms;
- a is an integer of 1 to 8;
- Ra is alkyl having 1 to 3 carbons; and At least one hydrogen of the benzene ring in the above formula may be replaced by —CH 3 .
- liquid crystal alignment according to any one of [1] to [8], further containing at least one selected from the group consisting of an oxazine compound, an oxazoline compound, an epoxy compound, and a silane coupling agent. Agent.
- the liquid crystal aligning agent of the present invention in which a polymer obtained from tetracarboxylic dianhydride and diamine is dissolved in a solvent obtained by mixing the first solvent to the fourth solvent is a coating film for a liquid crystal aligning film by an inkjet method.
- a liquid crystal aligning agent prepared by blending two or more polymers exhibits the same effect.
- 6 is an image obtained by photographing a discharge pattern in an ink jet discharge experiment (Example 1) performed using the polyamic acid solution PC-1.
- 6 is an image obtained by photographing a discharge pattern in an ink jet discharge experiment (Comparative Example 1) performed using a polyamic acid solution PC-27.
- 6 is a photomicrograph of edge roughness measured in edge linearity evaluation (Example 1) performed using the polyamic acid solution PC-1.
- 4 is a photomicrograph of edge roughness measured in edge linearity evaluation (Comparative Example 1) performed using the polyamic acid solution PC-27.
- 6 is a photograph showing in-plane uneven stripes in an in-plane stripe unevenness evaluation (Example 1) performed using the polyamic acid solution PC-1.
- 6 is a photograph showing in-plane uneven stripes in an in-plane stripe unevenness evaluation (Comparative Example 1) performed using a polyamic acid solution PC-27.
- the subject of the present invention is a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid and derivatives thereof and a solvent.
- the solvent used for the liquid crystal aligning agent of this invention is divided into the following four groups.
- the first solvent is selected from the group of polar organic solvents that have good solubility in the polymer forming the alignment film.
- polar organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, Lactones such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, and ⁇ -butyrolactone.
- preferred solvents from the boiling point are N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, and ⁇ -butyrolactone.
- the boiling point of the first solvent is preferably in the range of 190 ° C to 250 ° C.
- the second solvent is characterized by a relatively small surface energy of less than 30 mN / m and good paintability to the substrate.
- Specific examples include alcohols and ethers.
- alcohols include butyl cellosolve (ethylene glycol monobutyl ether), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, 1- Butoxy-2-propanol, ethyl lactate, methyl lactate, propyl lactate.
- butyl cellosolve ethylene glycol monobutyl ether
- ethylene glycol monomethyl ether ethylene glycol monoethyl ether
- propylene glycol monomethyl ether propylene glycol monomethyl ether
- propylene glycol monobutyl ether propylene glycol monopropyl ether
- 1- Butoxy-2-propanol ethyl lactate, methyl lactate, propyl lactate.
- ethers are ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether, propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl.
- preferred solvents from the boiling point are butyl cellosolve (ethylene glycol monobutyl ether), 1-butoxy-2-propanol, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol propyl methyl ether.
- More preferred solvents are butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol ethyl methyl ether, and diethylene glycol propyl methyl ether.
- the boiling point of the second solvent is preferably in the range of 120 ° C. to 200 ° C.
- the third solvent is a solvent that improves the spread of the solution. Mixing this solvent can prevent the coating film from becoming uneven.
- Such solvents specifically include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, methyl-3-methoxypropionate, and the like.
- dipentyl ether preferred solvents are methyl isobutyl ketone, diisobutyl ketone and dipentyl ether. More preferred solvents are diisobutyl ketone and dipentyl ether.
- the fourth solvent has an effect of suppressing film shrinkage and preventing backlash of the coating film. This effect is considered to be due to the fact that the fourth solvent has a boiling point in a temperature range close to that of the first solvent and is higher than the boiling points of the second solvent and the third solvent. That is, it seems that the drying rate when the discharged liquid spreads by the fourth solvent having a high boiling point becomes slow, and in particular, evaporation of the solvent at the edge portion is suppressed.
- the preferred fourth solvent are diethylene glycol ethyl propyl ether, diethylene glycol butyl methyl ether and diethylene glycol butyl ethyl ether.
- the ratio of the first solvent to the total solvent weight is 20 to 89% by weight, preferably 30 to 84% by weight, and more preferably 45 to 75% by weight.
- the first solvent has a ratio of 20% by weight or more with respect to the total solvent weight in order to prevent the precipitation of the polymer in the solution, the clogging of the nozzles and heads of the ink jet apparatus, and the occurrence of in-plane unevenness of the coating film. Used.
- the amount of the second solvent which is a poor solvent, is reduced and does not deteriorate printability, so that it is used in a proportion of 89% by weight or less based on the total solvent weight.
- the ratio of the second solvent to the total solvent weight is 10 to 60% by weight, preferably 15 to 50% by weight, and more preferably 20 to 45% by weight.
- the second solvent is used in a ratio of 10% by weight or more based on the total solvent weight in order to prevent the occurrence of liquid shrinkage due to printing failure or evaporation from the edge portion. On the contrary, the ratio of good solvent is reduced, so that precipitation of the polymer in the solution, clogging of the nozzles and heads of the ink jet device, and in-plane unevenness of the coating film are prevented. And 60% by weight or less.
- the ratio of the third solvent to the total solvent weight is 0.1 to 15% by weight, preferably 0.1 to 10% by weight, and more preferably 0.1 to 5% by weight.
- the third solvent is used at a ratio of 0.1% by weight or more with respect to the total solvent weight in order to prevent deterioration of the liquid spreading property and generation of unevenness in the head running direction.
- it is used at a ratio of 15 wt% or less based on the total solvent weight.
- the ratio of the fourth solvent to the total solvent weight is 0.1 to 20% by weight, preferably 0.1 to 15% by weight, and more preferably 0.1 to 10% by weight.
- the fourth solvent is used at a ratio of 0.1% by weight or more with respect to the total solvent weight in order to exhibit the effect of maintaining the linearity of the edge and the effect of good liquid spreading. On the contrary, in order to prevent the coating film from being poorly dried, causing in-plane unevenness and deterioration of uniformity, it is used at a ratio of 20% by weight or less with respect to the total solvent weight.
- the polyamic acid and derivatives thereof of the present invention will be described.
- the polyamic acid and derivatives thereof of the present invention are reaction products of tetracarboxylic dianhydride and diamine.
- the polyamic acid derivative is a component that dissolves in a solvent when the liquid crystal aligning agent described later containing a solvent is used.
- the liquid crystal aligning agent is used as a liquid crystal aligning film, the liquid crystal alignment is mainly composed of polyimide. It is a component that can form a film. Examples of such a derivative of polyamic acid include soluble polyimide, polyamic acid ester, polyamic acid amide, and the like.
- polyimide in which all amino acids and carboxyl of polyamic acid are subjected to a dehydration ring-closing reaction
- Partially dehydrated ring-closing partial polyimide 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester
- Part of acid dianhydride contained in tetracarboxylic dianhydride compound is organic dicarboxylic Examples thereof include polyamic acid-polyamide copolymers obtained by reacting with an acid, and 5) polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction.
- the polyamic acid and its derivative may be a compound having a structure of a reaction product of tetracarboxylic dianhydride and diamine, and other raw materials may be used except for the reaction of tetracarboxylic dianhydride and diamine. It may contain reaction products from other reactions.
- the tetracarboxylic dianhydride used for producing the polyamic acid and its derivative contained in the liquid crystal aligning agent of the present invention will be described.
- the tetracarboxylic dianhydride used in the present invention can be selected without limitation from known tetracarboxylic dianhydrides.
- Such tetracarboxylic dianhydrides include aromatic systems (including heteroaromatic ring systems) in which dicarboxylic acid anhydrides are directly bonded to aromatic rings, and aliphatic groups in which dicarboxylic acid anhydrides are not directly bonded to aromatic rings. It may belong to any group of systems (including heterocyclic ring systems).
- Tetracarboxylic dianhydride may react one compound with diamine, or may mix two or more compounds and react with diamine.
- “tetracarboxylic dianhydride” refers not only to one compound, but may also include a mixture of two or more compounds in its meaning.
- tetracarboxylic dianhydrides include those represented by the formulas (AN-I) to (AN-VII) from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electrical characteristics of the film.
- the tetracarboxylic dianhydride represented is mentioned.
- X is independently a single bond or —CH 2 —.
- G is a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —.
- Y is independently one selected from the group of the following trivalent groups, and the bond is connected to any carbon. At least one hydrogen may be replaced with methyl, ethyl or phenyl.
- the ring A 10 is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, At least one hydrogen of the group may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are the same carbon You may connect to.
- X 10 is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl.
- G 10 is independently —O—, —COO— or —OCO—, and r is independently 0 or 1.
- tetracarboxylic dianhydrides represented by the following formulas (AN-1) to (AN-16-14) can be mentioned.
- G 11 is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene.
- X 11 is independently a single bond or —CH 2 —.
- G 12 is independently one of the following trivalent groups. When G 12 is> CH—, the hydrogen of> CH— may be replaced with —CH 3 . When G 12 is> N—, G 11 is not a single bond and —CH 2 —, and X 11 is not a single bond.
- R 11 is hydrogen or —CH 3 .
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula. In the formulas (AN-1-2) and (AN-1-14), m is an integer of 1 to 12.
- R 12 is independently hydrogen, —CH 3 , —CH 2 CH 3 , or phenyl.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formula.
- ring A 11 is a cyclohexane ring or a benzene ring.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formula.
- G 13 is a single bond, — (CH 2 ) m —, —O—, —S—, —C (CH 3 ) 2 —, —SO 2 —, —CO—, —C (CF 3 ) 2 — or a divalent group represented by the following formula (G13-1), and m is an integer of 1 to 12.
- Each ring A 11 is independently a cyclohexane ring or a benzene ring.
- G 13 may be bonded to any position of ring A 11 .
- G 13a and G 13b each independently represent a single bond, a divalent group represented by —O— or —NHCO—.
- the phenylene is preferably 1,4-phenylene and 1,3-phenylene.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formula.
- m is an integer of 1 to 12.
- R 11 is hydrogen or —CH 3 .
- R 11 whose bond position is not fixed to the carbon atom constituting the benzene ring indicates that the bond position in the benzene ring is arbitrary.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formula.
- X 11 is independently a single bond or —CH 2 —.
- n is 1 or 2.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formula.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formula.
- X 11 is a single bond or —CH 2 —.
- R 12 is hydrogen, —CH 3 , —CH 2 CH 3 , or phenyl, and ring A 12 is a cyclohexane ring or a cyclohexene ring.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formula.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formula.
- ring A 11 is independently a cyclohexane ring or a benzene ring.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formula.
- each ring A 11 is independently a cyclohexane ring or a benzene ring.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formula.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formula.
- Ph represents phenyl.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formula.
- Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formula.
- Examples of tetracarboxylic dianhydrides other than the above include the following compounds.
- the tetracarboxylic dianhydride more preferably used as a raw material for the polymer contained in the liquid crystal aligning agent of the present invention is at least one selected from the group of compounds represented by the following formulas (2) to (13). It is. At least one of the hydrogens in the above formula may be replaced with —CH 3 , —CH 2 CH 3 or phenyl.
- the unsubstituted compound in formula (2) is the compound of formula (AN-3-2), the unsubstituted compound in formula (3) is the compound of formula (AN-2-1),
- the unsubstituted compound in 4) is the compound of formula (AN-1-1), the unsubstituted compound in formula (5) is the compound of formula (AN-3-1), and the
- the substituted compound is the compound of the formula (AN-1-13), the unsubstituted compound in the formula (7) is the compound of the formula (AN-16-1), and the unsubstituted compound in the formula (8) is
- the diamine and dihydrazide used for producing the polyamic acid and its derivative contained in the liquid crystal aligning agent of the present invention will be described.
- the diamine and dihydrazide used in the present invention can be selected without limitation from known diamines and dihydrazides.
- Diamine may react one compound with tetracarboxylic dianhydride, or may mix two or more compounds and react with tetracarboxylic dianhydride.
- diamine refers not only to one compound but also to a mixture of two or more compounds. In the present specification, dihydrazide is also handled as “diamine”.
- Diamines can be divided into two types according to their structure. That is, when a skeleton connecting two amino groups is viewed as a main chain, a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group.
- This side chain group is a group having an effect of increasing the pretilt angle.
- the side chain group having such an effect needs to be a group having 3 or more carbon atoms. Specific examples include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and A group having a steroid skeleton can be exemplified.
- a diamine having such a side chain group may be referred to as a side chain diamine.
- Such a diamine having no side chain group may be referred to as a non-side chain diamine.
- the side chain diamine is preferably used in combination so as not to impair the properties of the present invention.
- the side chain diamine and the non-side chain diamine are preferably selected and used for the purpose of improving the vertical alignment with respect to the liquid crystal, the voltage holding ratio, the image sticking property, and the alignment.
- the non-side chain diamine will be described.
- diamines having no known side chain include diamines of the following formulas (DI-1) to (DI-16).
- G 20 is —CH 2 —, at least one —CH 2 — may be replaced by —NH—, —O—, and m is an integer of 1 to 12 And at least one hydrogen of the alkylene may be replaced by —OH.
- G 21 is independently a single bond, —NH—, —NCH 3 —, —O—, —S—, —S.
- s is independently an integer of 0 to 2.
- G 22 is independently a single bond, —O—, —S—, —CO—, —C (CH 3 ) 2 —, —C (CF 3 2 ), -NH-, or alkylene having 1 to 10 carbon atoms.
- Formula (DI-2) at least one hydrogen of cyclohexane ring and benzene ring in ⁇ formula (DI-7) is, -F, -Cl, alkyl having 1 to 3 carbon atoms, -OCH 3, -OH, -CF 3 , —CO 2 H, —CONH 2 , —NHC 6 H 5 , phenyl, or benzyl, and in Formula (DI-4), at least one hydrogen of the benzene ring is represented by the following formula ( DI-4-a) to one selected from the group of groups represented by formula (DI-4-e) may be substituted.
- a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.
- the bonding position of —NH 2 to the cyclohexane ring or benzene ring is an arbitrary position excluding the bonding position of G 21 or G 22 .
- R 20 is independently hydrogen or —CH 3 .
- R 21 and R 22 are independently alkyl or phenyl having 1 to 3 carbon atoms
- G 23 is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms.
- w is an integer of 1 to 10.
- R 23 is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl
- p is independently an integer from 0 to 3
- q is It is an integer from 0 to 4.
- ring B is a monocyclic heteroaromatic group
- R 24 is hydrogen, —F, —Cl, C 1-6 alkyl, alkoxy, vinyl, alkynyl
- q is independently an integer of 0 to 4.
- ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group.
- G 24 is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1.
- a group whose bond position is not fixed to the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.
- the bonding position of —NH 2 bonded to the ring is an arbitrary position.
- diamine represented by the formula (DI-1) examples are shown below.
- k is each independently an integer of 1 to 3.
- diamines represented by formula (DI-2) and formula (DI-3) are shown below.
- Examples of the diamine represented by the formula (DI-4) are shown below.
- Examples of the diamine represented by the formula (DI-5) are shown below.
- m is an integer of 1 to 12.
- m is an integer of 1 to 12.
- v is an integer of 1 to 6.
- k is an integer of 1 to 5.
- m is an integer of 1 to 12, and the formula (DI-5-38) and the formula (DI In DI-5-39), k is an integer of 1 to 5, and in Formula (DI-5-40), n is an integer of 1 or 2.
- Examples of the diamine represented by the formula (DI-7) are shown below.
- m is an integer of 1 to 12
- n is independently 1 or 2.
- Examples of the diamine represented by the formula (DI-12) are shown below.
- Examples of the diamine represented by the formula (DI-13) are shown below.
- dihydrazide Describes dihydrazide.
- dihydrazide having no known side chain include the following formulas (DIH-1) to (DIH-3).
- G 25 represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or — C (CF 3 ) 2 —.
- ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl or phenyl.
- each ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl, or phenyl, and Y is a single bond, It is alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —.
- the bonding position of —CONHNH 2 bonded to the ring is an arbitrary position.
- non-side chain diamines and hydrazides have the effect of improving electrical properties, such as reducing the ion density of liquid crystal display elements.
- the proportion of the diamine and dihydrazide in the total amount is 0 to 90 mol. %, Preferably 0 to 50 mol%.
- the side chain type diamine will be described.
- Examples of the side chain group of the side chain type diamine include the following groups.
- alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, Alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like can be mentioned.
- Alkyl, alkenyl and alkynyl in these groups are all groups having 3 or more carbon atoms. However, in alkyloxyalkyl, it is sufficient if the entire group has 3 or more carbon atoms. These groups may be linear or branched.
- phenyl, phenylalkyl, phenylalkyloxy, phenyloxy provided that the terminal ring has alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms or alkoxyalkyl having 2 or more carbon atoms as a substituent.
- a ring assembly group having an alkoxy of several or more or an alkoxyalkyl having two or more carbons can be given.
- a group having a steroid skeleton is also effective as a side chain group.
- Examples of the diamine having a side chain include compounds represented by the following formulas (DI-31) to (DI-35).
- G 26 represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH 2 O—, —OCH 2 —, —CF 2 O—. , —OCF 2 —, or — (CH 2 ) m ′ —, and m ′ is an integer of 1 to 12.
- G 26 are a single bond, —O—, —COO—, —OCO—, —CH 2 O—, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples are a single bond, —O—, — COO -, - OCO -, - CH 2 O -, - CH 2 - and -CH 2 CH 2 -.
- R 25 is an alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a).
- At least one hydrogen may be replaced with —F, and at least one —CH 2 — may be replaced with —O—, —CH ⁇ CH— or —C ⁇ C—.
- the hydrogen of this phenyl is replaced by —F, —CH 3 , —OCH 3 , —OCH 2 F, —OCHF 2, —OCF 3, alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms. Also good.
- the bonding position of —NH 2 bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably meta or para.
- G 27 , G 28 and G 29 are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbon atoms, and one or more — CH 2 — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH ⁇ CH—.
- Ring B 21 , Ring B 22 , Ring B 23 and Ring B 24 are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5 -Diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring B 21 , ring B 22 , ring B 23 and ring in B 24, at least one hydrogen may be replaced by -F, or -CH 3, s, t and u is an integer of 0 to 2 independently, the total is 1 to 5, When s, t or u is 2, the two linking groups in each parenthesis may be the same or different, and the two rings may be the same or different.
- R 26 is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH 2 F, —OCHF 2 , or —OCF 3 and at least one —CH 2 — of the alkyl having 1 to 30 carbon atoms may be replaced with a divalent group represented by the following formula (DI-31-b).
- R 27 and R 28 are independently alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6.
- Preferred examples of R 26 are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.
- G 30 is independently a single bond, —CO— or —CH 2 —, R 29 is independently hydrogen or —CH 3 , R 30 30 is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. At least one hydrogen of the benzene ring in the formula (DI-33) may be replaced with alkyl having 1 to 20 carbons or phenyl. A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.
- One of the two groups “-phenylene-G 30 —O—” in the formula (DI-32) is preferably bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position of the steroid nucleus.
- the bonding position of the two groups “-phenylene-G 30 —O—” in the formula (DI-33) to the benzene ring is preferably a meta position or a para position, respectively, with respect to the bonding position of the steroid nucleus.
- —NH 2 bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.
- G 31 is independently —O— or alkylene having 1 to 6 carbons, and G 32 is a single bond or alkylene having 1 to 3 carbons.
- R 31 is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — of the alkyl may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—.
- R 32 is alkyl having 6 to 22 carbon atoms, and R 33 is hydrogen or alkyl having 1 to 22 carbon atoms.
- Ring B 25 is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1.
- —NH 2 bonded to the benzene ring indicates that the bonding position in the ring is arbitrary, but it is preferably independently of the meta position or the para position with respect to the bonding position of G 31 .
- side chain diamines are illustrated below.
- Examples of the diamine having a side chain of the formula (DI-31) to the formula (DI-35) include compounds represented by the following formulas (DI-31-1) to (DI-35-3). it can.
- R 34 is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 5 to 25 carbons or Alkoxy having 5 to 25 carbon atoms.
- R 35 is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.
- R 36 is alkyl having 4 to 30 carbons, and preferably alkyl having 6 to 25 carbons.
- R 37 is alkyl having 6 to 30 carbon atoms, preferably alkyl having 8 to 25 carbon atoms.
- R 38 is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl having 3 to 20 carbons or Alkoxy having 3 to 20 carbon atoms.
- R 39 is hydrogen, —F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH 2 F, —OCHF 2 or —OCF 3 , preferably having 3 to 25 carbons. Alkyl or alkoxy having 3 to 25 carbon atoms.
- G 33 is alkylene having 1 to 20 carbon atoms.
- R 40 is hydrogen or alkyl having 1 to 20 carbons, preferably hydrogen or alkyl having 1 to 10 carbons, and R 41 is Hydrogen or alkyl having 1 to 12 carbons.
- R 37 is alkyl having 6 to 30 carbons
- R 41 is hydrogen or alkyl having 1 to 12 carbons.
- Examples of the diamine in the present invention include formulas (DI-1-1) to (DI-16-1), formulas (DIH-1-1) to (DIH-3-6), and formula (DI-31-1). ) To diamines other than those represented by the formula (DI-35-3) can also be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13). In the formulas (DI-36-1) to (DI-36-8), R 42 each independently represents an alkyl group having 3 to 30 carbon atoms.
- R 43 each independently represents hydrogen, —NHBoc Or —N (Boc) 2 , at least one of R 43 is —NHBoc or —N (Boc) 2 , and in formula (DI-36-13), R 44 is —NHBoc or —N (Boc) 2 and m is an integer from 1 to 12.
- Boc is a t-butoxycarbonyl group.
- the formula (DI-1-3), the formula (DI-5-1), the formula (DI-5-5), Formula (DI-5-9), Formula (DI-5-12), Formula (DI-5-13), Formula (DI-5-29), Formula (DI-6-7), Formula (DI-7 -3) and a diamine represented by the formula (DI-11-2) are preferred.
- the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), the formula ( It is preferred to use diamines represented by DI-5-5), formula (DI-5-24), and formula (DI-7-3), and diamines represented by (DI-2-1) are particularly preferred.
- a part of the diamine may be replaced with a monoamine in a range where the ratio of the monoamine to the diamine is 40 mol% or less.
- Such replacement can cause termination of the polymerization reaction when the polyamic acid is produced, and further progress of the polymerization reaction can be suppressed.
- the molecular weight of the obtained polymer (polyamic acid or a derivative thereof) can be easily controlled by such replacement, and for example, the coating characteristics of the liquid crystal aligning agent are improved without impairing the effects of the present invention. be able to.
- one or more diamines may be substituted for the monoamine.
- Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Is mentioned.
- the polyamic acid or derivative thereof of the present invention may further contain a monoisocyanate compound in the monomer.
- a monoisocyanate compound in the monomer, the terminal of the resulting polyamic acid or derivative thereof is modified, and the molecular weight is adjusted.
- the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention.
- the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% based on the total amount of diamine and tetracarboxylic dianhydride in the monomer from the above viewpoint.
- the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
- the diamine more preferably used as a raw material for the polymer contained in the liquid crystal aligning agent of the present invention is at least one selected from the group of compounds represented by the following formulas (D-1) to (D-5). is there.
- formula (D-2) and formula (D-4) X and Y are each independently a single bond, —O—, —NH—, —S—, or alkylene having 1 to 6 carbon atoms.
- a is an integer of 1 to 8.
- Ra is alkyl having 1 to 3 carbon atoms.
- at least one hydrogen of the benzene ring in the above formula may be replaced with —CH 3 .
- the unsubstituted compound in formula (D-1) is the compound of formula (DI-4-1), and the unsubstituted compound in formula (D-3) is the compound of formula (DI-13-1). Respectively. Further, the compound represented by the formula (D-2) or the formula (D-5) falls within the category of the formula (DI-5), and the compound represented by the formula (D-4) represents the formula (DI It is included in the category of -7).
- diamines that are more preferably used among the above diamines include the following formulas (D-1), (D-2-1) to (D-2-9), (D-3), (D- 4-1) to (D-4-72) and (D-5-1) to (D-5-3).
- a photoreactive structure In order to give the polymer contained in the liquid crystal aligning agent of the present invention a photoreactive structure, it is preferable to use a diamine having a photoreactive structure or a tetracarboxylic dianhydride having a photoreactive structure as a raw material. .
- a diamine having a photoreactive structure and a tetracarboxylic dianhydride having a photoreactive structure may be used in combination.
- Preferred examples of the monomer having these photoreactive structures are compounds represented by the following formulas (I-1) to (I-4).
- the compound represented by the formula (I-3) is more preferable because it exhibits greater anisotropy when the alignment film is formed.
- the polymer contained in the liquid crystal aligning agent of the present invention can be obtained by reacting the above tetracarboxylic dianhydride and diamine in a solvent. In this synthesis reaction, no special conditions other than the selection of the raw materials are required, and the conditions for normal polyamic acid synthesis can be applied as they are.
- the polymer contained in the liquid crystal aligning agent of the present invention may be one, or a blend of two or more may be used.
- at least one of the polymers is a polymer obtained by reacting a raw material monomer in which at least one of tetracarboxylic dianhydride and diamine has a photoreactive structure (a
- at least one of the other polymers is a polyamic acid obtained by reacting a tetracarboxylic dianhydride having no photoreactive structure and a diamine not having a photoreactive structure, and a derivative thereof.
- the case of at least one polymer (b) selected is included.
- the polymer (a) changes its structure when the photoreactive structure is isomerized, decomposed or dimerized by the irradiation of ultraviolet energy energy rays, and the liquid crystal molecules in contact with the polymer film are moved in a specific direction. It has the ability to align (photo-alignment).
- Such polymers may be used in blends with other polymers that do not contain photoreactive structures.
- the liquid crystal aligning agent of the present invention may further contain other components other than polyamic acid or derivatives thereof.
- the other component may be one type or two or more types. Examples of other components include other polymers and compounds described below.
- the structure and molecular weight of each polymer are controlled, and applied to a substrate and pre-dried as described later, for example,
- the polymer (a) having the photo-alignment function can be separated into the upper layer of the coating film, and the other polymer (b) can be separated into the lower layer of the coating film.
- This can be controlled by using a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer in a mixed polymer. Confirmation of the layer separation can be confirmed by confirming that the surface energy of the formed alignment film is the same as or close to the surface energy of the alignment film formed by the liquid crystal aligning agent containing only the polymer (a).
- tetracarboxylic dianhydride used for synthesizing the polymer (b) tetracarboxylic dianhydride used for synthesizing polyamic acid or a derivative thereof which is an essential component of the liquid crystal aligning agent of the present invention. It can select without limitation from well-known tetracarboxylic dianhydride as a thing, and can mention the same thing illustrated above.
- the tetracarboxylic dianhydride used to synthesize the polymer (b) preferably contains 10% by mole or more of the aromatic tetracarboxylic dianhydride with respect to the total tetracarboxylic dianhydride. 30% or more is more preferable.
- Examples of the diamine and hydrazide used for synthesizing the polymer (b) are the above as other diamines that can be used for synthesizing the polyamic acid or its derivative, which is an essential component of the liquid crystal aligning agent of the present invention. You can list the same ones.
- the formula (DI-1-2), the formula (DI-2-1), the formula (DI-5-1), and the formula The diamine represented by (DI-7-3) is preferably used, and the diamine represented by the formula (DI-2-1) is particularly preferred.
- the formula (DI-4-1), the formula (DI-5-1), and the formula (DI- The diamine represented by 5-12) is particularly preferred.
- the diamine used for synthesizing the polymer (b) preferably contains 30% by mole or more, more preferably 50% or more of the aromatic diamine with respect to the total diamine.
- the ratio of the polymer (a) to the total amount of the polymer (a) and the polymer (b) is preferably 10% by weight to 100% by weight, and 20% by weight to 100% by weight. % Is more preferable.
- polysiloxane examples include JP2009-036966, JP2010-185001, JP2011-109633, JP2011-253175, JP2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication. 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International Publication 2012/165354, etc.
- the polysiloxane may be further contained.
- the liquid crystal aligning agent of the present invention may further contain various additives.
- the various additives include oxazine compounds, oxazoline compounds, epoxy compounds, high molecular compounds other than polyamic acid and its derivatives, and other low molecular compounds, which can be selected and used according to their respective purposes. it can.
- the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time.
- the oxazine compound may be one type of compound or two or more types of compounds.
- the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof. More preferably.
- the oxazine compound will be specifically described below.
- the oxazine compound is soluble in a solvent that dissolves polyamic acid or a derivative thereof, and in addition, an oxazine compound having ring-opening polymerizability is preferable. Further, the number of oxazine structures in the oxazine compound is not particularly limited.
- oxazine compounds Various structures are known for oxazine compounds.
- the structure of oxazine is not particularly limited, but examples of the oxazine structure in the oxazine compound include an oxazine structure having an aromatic group containing a condensed polycyclic aromatic group such as benzoxazine and naphthoxazine.
- Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6).
- the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.
- L 3 and L 4 are organic groups having 1 to 30 carbon atoms.
- L 5 to L 8 is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms
- Q 1 is a single bond, —O—, — S—, —S—S—, —SO 2 —, —CO—, —CONH—, —NHCO—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, — (CH 2 ) v -, -O- (CH 2 ) v -O-, -S- (CH 2 ) v -S-, where v is an integer of 1 to 6, and is represented by formula (OX-5) and formula (OX In ⁇ 6), Q 2 is independently a single bond, —O—, —S—, —CO—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 — or a carbon
- Is alkylene The hydrogen bonded to the benzene ring and naphthalene ring in Q 2 may be independently replaced with —F, —CH 3 , —OH, —COOH, —SO 3 H, —PO 3 H 2. .
- the oxazine compound includes an oligomer or polymer having an oxazine structure in the side chain, and an oligomer or polymer having an oxazine structure in the main chain.
- Examples of the oxazine compound represented by the formula (OX-1) include the following oxazine compounds.
- L 3 is preferably alkyl having 1 to 30 carbons, more preferably alkyl having 1 to 20 carbons.
- Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.
- L 3 is preferably alkyl having 1 to 30 carbons, more preferably alkyl having 1 to 20 carbons.
- Examples of the oxazine compound represented by the formula (OX-3) include an oxazine compound represented by the following formula (OX-3-I).
- L 3 and L 4 are organic groups having 1 to 30 carbon atoms
- L 5 to L 8 are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms
- Q 1 is A single bond, —CH 2 —, —C (CH 3 ) 2 —, —CO—, —O—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —.
- Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.
- L 3 and L 4 are preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms.
- Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.
- Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.
- Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.
- the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), and the formula (OX-3- 7), Formula (OX-3-9), Formula (OX-4-1) to Formula (OX-4-6), Formula (OX-5-3), Formula (OX-5-4), and Formula Oxazine compounds represented by (OX-6-2) to (OX-6-4) are listed.
- the oxazine compound can be produced by the same method as described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-2004-352670.
- the oxazine compound represented by the formula (OX-1) can be obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication 2004/009708).
- the oxazine compound represented by the formula (OX-2) is obtained by reacting by a method in which a primary amine is gradually added to formaldehyde, and then reacting by adding a compound having a naphthol-based hydroxyl group (International Publication 2004 / (See 009708.)
- the oxazine compound represented by the formula (OX-3) is a secondary aliphatic compound in which an organic solvent contains 1 mol of a phenol compound, at least 2 mol or more of an aldehyde per 1 phenolic hydroxyl group, and 1 mol of a primary amine. It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine, or a basic nitrogen-containing heterocyclic compound (see International Publication No. 2004/009708 and JP-A-11-12258).
- the oxazine compounds represented by the formulas (OX-4) to (OX-6) include diamines such as 4,4′-diaminodiphenylmethane and diamines having a plurality of benzene rings and organic groups connecting them, formalin and the like. It can be obtained by subjecting an aldehyde and phenol to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90 ° C. or higher (see JP 2004-352670 A).
- the liquid crystal aligning agent of this invention may further contain the oxazoline compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long term.
- An oxazoline compound is a compound having an oxazoline structure.
- the oxazoline compound may be one type of compound or two or more types of compounds.
- the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof.
- the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted to oxazoline.
- the oxazoline compound will be specifically described below.
- the oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more.
- the oxazoline compound may be a polymer having an oxazoline structure in the side chain, or may be a copolymer.
- the polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be.
- the copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and an oxazoline structure. It may also be a copolymer with a monomer that does not have.
- the oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyamic acid.
- oxazoline compound examples include 2,2′-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H— Oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4- Isopropenyl-2-oxazolin-2-yl) butane, 2,2′-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2,2 ′ -Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline), 2,2'-methylene Scan (4-ter
- polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also included.
- Epocross trade name, manufactured by Nippon Shokubai Co., Ltd.
- 1,3-bis (4,5-dihydro-2-oxazolyl) benzene is more preferable.
- the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time.
- the epoxy compound may be one type of compound or two or more types of compounds.
- the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.
- the epoxy compound will be specifically described below.
- Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule.
- Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxy Propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.
- Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl.
- Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy] phenyl)] ethyl] phenyl] propane (trade name “Techmore VG3101L” (manufactured by Mitsui Chemicals, Inc.)).
- Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, and 3- (N-allyl-N-glycidyl) Aminopropyltrimethoxysilane is mentioned.
- examples of compounds having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring.
- examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.
- monomers that copolymerize with monomers having an epoxy ring include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethyl Styrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.
- the monomer polymer having an epoxy ring include polyglycidyl methacrylate.
- Preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate.
- examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.
- an epoxy compound means the compound which has an epoxy group
- an epoxy resin means resin which has an epoxy group.
- Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.
- Examples of the glycidyl ether include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol.
- glycidyl ester examples include a diglycidyl ester compound and a glycidyl ester epoxy compound.
- glycidylamine examples include polyglycidylamine compounds and glycidylamine type epoxy resins.
- epoxy group-containing acrylic compound examples include homopolymers and copolymers of monomers having oxiranyl.
- glycidyl amide examples include glycidyl amide type epoxy compounds.
- Examples of the chain aliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.
- Examples of the cycloaliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.
- Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER -331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all trade names, manufactured by DIC Corporation), Epomic R-140, Epomic R-301 And Epomic R-304 (both trade names, manufactured by Mitsui Chemicals, Inc.).
- Examples of the bisphenol F type epoxy compound include jER806, jER807, jER4004P (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001 (all trade names, Toto Kasei) DER-354 (trade name, manufactured by Dow Chemical Company), Epicron 830, and Epicron 835 (all trade names, manufactured by DIC Corporation).
- Examples of the bisphenol type epoxy compound include epoxidized products of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.
- Examples of the hydrogenated bisphenol-A type epoxy compound include Santo Tote ST-3000 (trade name, manufactured by Toto Kasei Co., Ltd.), Jamaica Resin HBE-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252. (Trade name, manufactured by Nagase ChemteX Corporation).
- Examples of the hydrogenated bisphenol type epoxy compound include an epoxidized product of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.
- brominated bisphenol-A type epoxy compounds examples include jER5050, jER5051 (both trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YDB-360, Epototo YDB-400 (both trade names, manufactured by Toto Kasei Co., Ltd.) ), DER-530, DER-538 (both trade names, manufactured by The Dow Chemical Company), Epicron 152, and Epicron 153 (all trade names, manufactured by DIC Corporation).
- phenol novolac type epoxy compounds examples include jER152, jER154 (both trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade names, manufactured by Tohto Kasei Co., Ltd.), DEN431, DEN438 (both trade names, The Dow Chemical Company), Epicron N-770 (trade name, manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all trade names, manufactured by Nippon Kayaku Co., Ltd.).
- cresol novolac type epoxy compound examples include jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all trade names, manufactured by Tohto Kasei Co., Ltd.), Epicron N-665, and Epicron N-695. (All trade names, manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) ).
- Examples of the bisphenol A novolak type epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation) and Epicron N-880 (trade name, manufactured by DIC Corporation).
- naphthalene skeleton-containing epoxy compound examples include Epicron HP-4032, Epicron HP-4700, Epicron HP-4770 (all trade names, manufactured by DIC Corporation), and NC-7000 (trade names, manufactured by Nippon Kayaku Co., Ltd.). Is mentioned.
- aromatic polyglycidyl ether compound examples include hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (following formula EP-2), resorcinol diglycidyl ether (following formula EP-3), 2- [4 -(2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (formula EP-4 below) , Tris (4-glycidyloxyphenyl) methane (following formula EP-5), jER1031S, jER1032H60 (all trade names, manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade name, manufactured by The Dow Chemical Company), Denacol EX-201 (trade name, manufactured by Nagase ChemteX Corporation), DPPN-503, DPPN-50 H, DPPN-501H, NC6000 (all trade names
- Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (trade name, manufactured by The Dow Chemical Company) and Epicron HP-7200 (trade name, manufactured by DIC Corporation).
- Examples of the alicyclic diglycidyl ether compound include cyclohexane dimethanol diglycidyl ether compound and licarresin DME-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.).
- Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (following formula EP-8), diethylene glycol diglycidyl ether (following formula EP-9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (following formula EP).
- polysulfide-type diglycidyl ether compound examples include FLDP-50 and FLDP-60 (both trade names, manufactured by Toray Rethiocol Co., Ltd.).
- biphenol type epoxy compound examples include YX-4000, YL-6121H (both trade names, manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). ).
- diglycidyl ester compound examples include diglycidyl terephthalate (following formula EP-17), diglycidyl phthalate (following formula EP-18), bis (2-methyloxiranylmethyl) phthalate (following formula EP-19), di Examples thereof include glycidyl hexahydrophthalate (following formula EP-20), a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and a compound represented by the following formula EP-23.
- Examples of the glycidyl ester epoxy compound include jER871, jER872 (both trade names, manufactured by Mitsubishi Chemical Corporation), Epicron 200, Epicron 400 (all trade names, manufactured by DIC Corporation), Denacol EX-711, and Denacol. EX-721 (both trade names, manufactured by Nagase ChemteX Corporation) can be mentioned.
- polyglycidylamine compound examples include N, N-diglycidylaniline (formula EP-24 below), N, N-diglycidyl-o-toluidine (formula EP-25 below), N, N-diglycidyl-m-toluidine (formula EP-25)
- Examples of the homopolymer of the monomer having oxiranyl include polyglycidyl methacrylate.
- Examples of the copolymer of monomers having oxiranyl include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer.
- Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate.
- Examples of the monomer other than the monomer having oxiranyl in the copolymer of the monomer having oxiranyl include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth).
- Examples of glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (formula EP-50 below), 1,3 -Diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (formula EP-51 below) and glycidyl isocyanurate type epoxy resin.
- chain aliphatic epoxy compound examples include epoxidized polybutadiene and epolide PB3600 (trade name, manufactured by Daicel Corporation).
- cycloaliphatic epoxy compound examples include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Corporation), the following formula EP-52), 2-methyl -3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (formula EP-53 below), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (Formula EP-54), ⁇ -caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (trade name, ( Manufactured by Daicel Corporation), the following formula EP-55), a compound represented by the following formula
- the epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolac type epoxy compound, and a cycloaliphatic type epoxy compound, and N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L” 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak type Epoxy compound And is preferably one or more
- polymer compound examples include polymer compounds that are soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed.
- the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, and poly (styrene-phenylmaleimide).
- Derivatives and poly (meth) acrylates 1 type or 2 types or more may be sufficient. Of these, polysiloxane is preferred.
- low molecular weight compounds include, for example, 1) a surfactant in accordance with the purpose when improvement in coating properties is desired, 2) an antistatic agent when improvement in antistatic properties is required, and 3) adhesion to the substrate.
- a silane coupling agent or a titanium-based coupling agent is desired when improvement of the above is desired, and 4) an imidization catalyst when imidization proceeds at a low temperature.
- silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltri Methoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxy Lan, 3-
- imidization catalyst examples include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline.
- cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole.
- the imidation catalyst may be one or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. preferable.
- the amount of the silane coupling agent added is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or its derivative.
- the amount of the imidation catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or derivative thereof.
- the addition amount of other additives varies depending on the application, but is usually 0 to 100% by weight, preferably 0.1 to 50% by weight, based on the total weight of the polyamic acid or its derivative.
- the polyamic acid or derivative thereof of the present invention can be produced in the same manner as a known polyamic acid or derivative thereof used for forming a polyimide film.
- the total amount of tetracarboxylic dianhydride is preferably approximately equimolar to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).
- the molecular weight of the polyamic acid or derivative thereof contained in the liquid crystal aligning agent of the present invention is preferably 7,000 to 500,000 in terms of polystyrene-equivalent weight average molecular weight (Mw), and is 10,000 to 200,000. More preferably.
- the molecular weight of the polyamic acid or derivative thereof can be determined from measurement by gel permeation chromatography (GPC).
- the presence of the polyamic acid or derivative thereof of the present invention can be confirmed by analyzing the solid content obtained by precipitation with a large amount of poor solvent by IR or NMR.
- the concentration of the polyamic acid in the aligning agent of the present invention is preferably 0.1 to 40% by weight.
- an operation of diluting the contained polyamic acid with a solvent in advance may be required to adjust the film thickness.
- the solid content concentration in the aligning agent of the present invention is not particularly limited, and an optimal value may be selected according to the following various coating methods.
- the amount is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight based on the weight of the varnish in order to suppress unevenness and pinholes during coating.
- the preferred range of the viscosity of the liquid crystal aligning agent of the present invention varies depending on the coating method, the concentration of the polyamic acid or its derivative, the type of polyamic acid or its derivative used, and the type and ratio of the solvent.
- 5 to 50 mPa ⁇ s is suitable.
- it is preferably 5 mPa ⁇ s or more, and in order not to cause printing unevenness, it is preferably 50 mPa ⁇ s or less. More preferably, it is in the range of 5 to 20 mPa ⁇ s.
- the viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measurement method, for example, using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25 ° C.).
- the liquid crystal alignment film of the present invention is a film
- the liquid crystal alignment film of the present invention can be obtained by an ordinary method for producing a liquid crystal alignment film from a liquid crystal aligning agent.
- the liquid crystal alignment film of the present invention can be obtained through a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of drying by heating, and a step of baking by heating.
- the coating film can be formed by applying the liquid crystal aligning agent of the present invention to the substrate in the liquid crystal display element in the same manner as the production of the normal liquid crystal aligning film.
- the substrate include a glass substrate in which electrodes such as ITO (Indium Tin Oxide), IZO (In 2 O 3 —ZnO), and IGZO (In—Ga—ZnO 4 ) electrodes and a color filter may be provided. .
- an ink jet method is preferable, but other generally known methods such as a spinner method, a printing method, a dipping method, and a dropping method are also applicable.
- the heat drying step a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known.
- the heat drying step is preferably performed at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the heat baking step.
- the heat drying temperature is preferably in the range of 30 ° C. to 150 ° C., and more preferably in the range of 50 ° C. to 120 ° C.
- the heating and firing step can be performed under conditions necessary for the polyamic acid or derivative thereof to exhibit dehydration and ring closure reactions.
- a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. In general, it is preferably performed at a temperature of about 100 to 300 ° C. for 1 minute to 3 hours, more preferably 120 to 280 ° C., and still more preferably 150 to 250 ° C.
- a rubbing method, a photo alignment method, or the like is known as a means for imparting anisotropy to the alignment film in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical direction.
- the forming method can be suitably used as a means for imparting anisotropy to the alignment film in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical direction.
- the liquid crystal alignment film of the present invention using the rubbing method includes a step of applying the liquid crystal alignment agent of the present invention to a substrate, a step of heating and drying the substrate coated with the alignment agent, a step of heating and baking the film, Can be formed through a rubbing process.
- the rubbing treatment can be performed in the same manner as the rubbing treatment for the alignment treatment of a normal liquid crystal alignment film, and may be any conditions as long as sufficient retardation is obtained in the liquid crystal alignment film of the present invention.
- the preferable conditions are a push-in amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm / sec, and a roller rotation speed of 500 to 2,000 rpm.
- the method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail.
- the liquid crystal alignment film of the present invention using the photo-alignment method gives the coating film anisotropy by irradiating linearly polarized light or non-polarized light after the coating film is heated and dried, and the film is heated and fired. Can be formed.
- the coating film can be formed by irradiating linearly polarized light or non-polarized light after the coating film is heated and dried and heated and fired. From the viewpoint of orientation, the radiation irradiation step is preferably performed before the heating and baking step.
- the heating and drying temperature in this step is preferably in the range of 30 ° C. to 150 ° C., more preferably in the range of 50 ° C. to 120 ° C.
- the heating and baking temperature in this step is preferably in the range of 30 ° C. to 300 ° C., more preferably in the range of 50 ° C. to 250 ° C.
- ultraviolet rays including light having a wavelength of 150 to 800 nm or visible light can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable.
- linearly polarized light or non-polarized light can be used. These lights are not particularly limited as long as they are capable of imparting liquid crystal alignment ability to the coating film, but linearly polarized light is preferable when it is desired to develop a strong alignment regulating force for liquid crystals.
- the liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even with low energy light irradiation.
- the irradiation amount of linearly polarized light in the radiation irradiation step is preferably 0.05 to 20 J / cm 2, and more preferably 0.5 to 10 J / cm 2.
- the wavelength of linearly polarized light is preferably 200 to 400 nm, and more preferably 300 to 400 nm.
- the irradiation angle with respect to the film surface of linearly polarized light is not particularly limited, it is preferable from the viewpoint of shortening the alignment processing time that it is as perpendicular as possible to the film surface in order to develop a strong alignment regulating force for the liquid crystal.
- the liquid crystal alignment film of the present invention can align liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.
- the light applied to the film may be linearly polarized light or non-polarized light as described above.
- the amount of light irradiated to the film is preferably 0.05 to 20 J / cm 2, particularly preferably 0.5 to 10 J / cm 2, and its wavelength is 250 to 400 nm. It is preferable that the thickness is 300 to 380 nm.
- the irradiation angle of the light applied to the film with respect to the film surface is not particularly limited, but is preferably 30 to 60 degrees from the viewpoint of shortening the alignment processing time.
- the light source used in the process of irradiating linearly polarized light or non-polarized light is ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, deep UV lamp, halogen lamp, metal halide lamp, high power metal halide lamp, xenon lamp, mercury.
- a xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave excitation electrodeless lamp, and the like can be used without limitation.
- the liquid crystal alignment film of the present invention can be suitably obtained by a method further including other steps than the steps described above.
- the liquid crystal alignment film of the present invention does not require a process of cleaning the film after baking or radiation irradiation with a cleaning liquid, but a cleaning process can be provided for convenience of other processes.
- the cleaning liquid is pure water, various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone. Although it can be used, it is not limited to these. Of course, these cleaning liquids are sufficiently purified and have few impurities. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.
- annealing treatment with heat or light can be used before or after the heating and baking step, before or after the rubbing step, or before or after irradiation with polarized or non-polarized radiation.
- the annealing temperature is 30 to 180 ° C., preferably 50 to 150 ° C., and the time is preferably 1 minute to 2 hours.
- the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp.
- the amount of light irradiation is preferably 0.3 to 10 J / cm 2 .
- the thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, and more preferably 30 to 150 nm.
- the film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a step meter or an ellipsometer.
- the liquid crystal alignment film of the present invention is characterized by a particularly large alignment anisotropy.
- the magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364. Further, as shown in the following examples, evaluation can also be made by a method using ellipsometry.
- the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of alignment, and when used as a liquid crystal alignment film, an alignment film having a greater anisotropy is considered to have a large alignment regulating force on the liquid crystal composition.
- the liquid crystal alignment film of the present invention can be used for alignment control of an optical compensation material and all other liquid crystal materials, in addition to the alignment use of a liquid crystal composition for liquid crystal displays. Further, since the alignment film of the present invention has large anisotropy, it can be used alone for an optical compensator application.
- liquid crystal display element of the present invention will be described in detail.
- a pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces facing each of the pair of substrates, and a surface facing each of the pair of substrates are formed.
- a liquid crystal display element having a liquid crystal alignment film formed and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the alignment film of the present invention.
- the electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate.
- Examples of such electrodes include ITO and metal vapor deposition films.
- the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape that is patterned, for example. Examples of the desired shape of the electrode include a comb shape or a zigzag structure.
- the electrode may be formed on one of the pair of substrates, or may be formed on both substrates.
- the form of electrode formation varies depending on the type of liquid crystal display element. For example, in the case of an IPS liquid crystal display element, an electrode is disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrodes of the pair of substrates are arranged. Electrodes are arranged on both sides.
- the liquid crystal alignment film is formed on the substrate or electrode.
- the liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates facing each other on which the liquid crystal alignment film is formed.
- a spacer such as fine particles or a resin sheet that is interposed between the pair of substrates to form an appropriate interval can be used as necessary.
- the liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used.
- Preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, JP-A-5-501735, JP-A-8-157826, JP-A-8-231960, JP-A-9-241644 (EP8827272A1), Kaihei 9-302346 (EP806466A1); -204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, and the like.
- a liquid crystal composition having a negative dielectric anisotropy will be described.
- the negative dielectric anisotropy liquid crystal composition include a composition containing at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1) as the first component.
- R 1a and R 2a are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine.
- 2-12 alkenyl, ring A 2 and ring B 2 are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1 , 4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4 - phenylene, a 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalene-diyl or 7,8-difluoro-chroman-2,6-diyl, wherein the ring a 2 Contact At least one 2,3-difluoro-1,4-phenylene fine ring B 2, 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phen
- Preferred ring A 2 and ring B 2 are each 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and 1,2 for decreasing the viscosity. 4-cyclohexylene.
- Desirable Z 1 is —CH 2 O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.
- Preferred j is 1 for decreasing the lower limit temperature and 2 for increasing the upper limit temperature.
- liquid crystal compound of the above formula (NL-1) include compounds represented by the following formulas (NL-1-1) to (NL-1-32).
- R 1a and R 2a independently represent an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine.
- 2-12 alkenyl, ring A 21 , ring A 22 , ring A 23 , ring B 21 , and ring B 22 are independently 1,4-cyclohexylene or 1,4-phenylene;
- 11 and Z 12 are each independently a single bond, — (CH 2 ) 2 —, —CH 2 O—, or —COO—.
- Desirable R 1a and R 2a are alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, or alkoxy having 1 to 12 carbons for increasing the absolute value of dielectric anisotropy.
- Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing the viscosity.
- Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.
- Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity.
- the preferred configuration of —CH ⁇ CH— in these alkenyls depends on the position of the double bond.
- Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity.
- Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.
- linear alkenyl is preferable to branching.
- alkenyl in which at least one hydrogen is replaced by fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4 -Pentenyl, and 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.
- Desirable ring A 21 , ring A 22 , ring A 23 , ring B 21 , and ring B 22 are each 1,4-cyclohexylene for decreasing the viscosity.
- Desirable Z 11 and Z 12 are —CH 2 O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.
- a compound (NL-1) in which a liquid crystal composition having a negative dielectric anisotropy is preferably used as the first component is the compounds (NL-1-1), (NL-1-4), (NL-1-7). ) Or (NL-1-32).
- liquid crystal composition having a negative dielectric anisotropy are disclosed in JP-A-57-114532, JP-A-2-4725, JP-A-4-224858, JP-A-8-40953, JP-A-8-104869, JP-A-8-104869.
- JP-A-10-168453 JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10-236993, JP-A-10-236994, JP-A-10-237000, JP-A-10- 237,004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076, JP-A-10-237448 (EP967261A1), JP-A-10-287874, JP-A-10-287875, JP-A-10-287875 -291945, JP-A-11-029581, JP 11-080049, JP 2000-256307, JP 2001-019965, JP 2001-072626, JP 2001-192657, JP 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Special Table 2010. -537010, JP2012-0777
- the liquid crystal composition used in the device of the present invention may further contain an additive from the viewpoint of improving the orientation, for example.
- additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.
- the photopolymerizable monomer or oligomer is desirably 0.01% by weight or more in order to exhibit the effect of determining the tilt direction of the liquid crystal after polymerization. Further, in order to make the orientation effect of the polymer after polymerization appropriate, or in order to avoid the unreacted monomer or oligomer from eluting into the liquid crystal after ultraviolet irradiation, the content is preferably 30% by weight or less.
- An optically active compound is mixed with the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle.
- examples of such compounds are from compound (PAC-1-1) to compound (PAC-1-4).
- a desirable ratio of the optically active compound is 5% by weight or less. A more desirable ratio is in the range of 0.01% to 2% by weight.
- an antioxidant is added to the liquid crystal composition. Mixed.
- a preferred example of the antioxidant is a compound (AO-1) where w is an integer of 1 to 10.
- preferred w is 1, 3, 5, 7, or 9. Further preferred w is 1 or 7.
- the compound (AO-1) in which w is 1 has high volatility, it is effective in preventing a decrease in specific resistance due to heating in the atmosphere.
- the compound (AO-1) in which w is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a high temperature after the device has been used for a long time.
- a desirable ratio of the antioxidant is 50 ppm or more for achieving its effect, and is 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature.
- a more desirable ratio is in the range of 100 ppm to 300 ppm.
- the ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines.
- a desirable ratio in these absorbents and stabilizers is 50 ppm or more for obtaining the effect thereof, and 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 10,000 ppm.
- a dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition so as to be adapted to a GH (Guest host) mode element.
- a preferred ratio of the dye is in the range of 0.01% by weight to 10% by weight.
- an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed with the composition.
- a desirable ratio of the antifoaming agent is 1 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display.
- a more desirable ratio is in the range of 1 ppm to 500 ppm.
- a polymerizable compound can be mixed into the composition in order to adapt it to a PSA (polymer-sustained-alignment) mode device.
- Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Particularly preferred examples are acrylate or methacrylate derivatives. Examples of such compounds are compound (PM-2-1) to compound (PM-2-9).
- a desirable ratio of the polymerizable compound is approximately 0.05% by weight or more for obtaining the effect thereof, and approximately 10% by weight or less for preventing a display defect. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.
- R 3a , R 4a , R 5a , and R 6a are independently acryloyl or methacryloyl
- R 7a and R 8a are independently hydrogen, halogen, or alkyl having 1 to 10 carbons
- Z 13 , Z 14 , Z 15 , and Z 16 are each independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH 2 — is replaced by —O— or —CH ⁇ CH—.
- S, t, and u are each independently 0, 1, or 2.
- a polymerization initiator can be mixed as a substance necessary for easily generating radicals or ions and initiating a chain polymerization reaction.
- Irgacure 651 registered trademark
- Irgacure 184 registered trademark
- Darocure 1173 registered trademark
- the polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1% to 5% by weight.
- the photopolymerization initiator is contained in the range of 1% by weight to 3% by weight.
- a polymerization inhibitor In a radical polymerization system, a polymerization inhibitor is mixed for the purpose of rapidly reacting with a radical generated from a polymerization initiator or monomer to change to a stable radical or neutral compound, and as a result, stop the polymerization reaction. Can do.
- Polymerization inhibitors are classified into several structures. One is a radical that is itself stable, such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine, and the other is a radical that is easily reacted with radicals present in the polymerization system. Typical examples include nitro, nitriso, amino, and polyhydroxy compounds. Representative examples of the latter include hydroquinone and dimethoxybenzene.
- a desirable ratio of the polymerization inhibitor is 5 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display. A more desirable ratio is in the range of 5 ppm to 500 ppm.
- Contrast The contrast of the liquid crystal element described later was evaluated using a luminance meter (YOKOGAWA 3298F).
- a liquid crystal display element was placed under a polarizing microscope in a crossed Nicol state, and the element was rotated and fixed at an angle at which transmitted light intensity, that is, luminance was minimized.
- the luminance value in this state was defined as “black luminance”.
- an arbitrary rectangular wave voltage was applied to the element, and the numerical value at which the luminance became maximum was defined as “white luminance”. This white luminance / black luminance value was defined as contrast. Contrast is less than 2500, poor, 2500 or more is good, and 3000 or more is judged to be the best.
- DAAB 4,4′-diaminoazobenzene (compound of formula (I-3))
- DDE 4,4′-diaminodiphenyl ether (unsubstituted compound in which X in formula (D-2) is —O—)
- APDA 4,4′-N, N′-bis (4-aminophenyl) piperazine (unsubstituted compound of formula (D-3))
- DDBU 4,4′-diaminodiphenylbutane (an unsubstituted compound in which X in formula (D-2) is — (CH 2 ) 4 —)
- PDA 1,4-phenylenediamine (formula (D-1))
- BABZP3 4,4 ′-((propane-1,3-diylbis (4,1-phenylene)) bis (methylene)) dianiline (formula (D-4-3))
- NMP N-methyl-2-pyrrolidone
- GBL ⁇ -butyrolactone
- BC butyl cellosolve
- BP 1-butoxy-2-propanol
- EDM diethylene glycol ethyl methyl ether
- DIBK diisobutyl ketone
- DPE dipentyl ether
- BDM diethylene glycol butyl methyl ether
- EDP diethylene glycol ethyl Propyl ether
- BDE Diethylene glycol butyl ethyl ether
- PB-1 The weight average molecular weight of the polyamic acid contained in PB-1 was 50,000.
- composition ratio (weight ratio) of the solvent used for dilution is NMP 0.067 g, BP 2.667 g, GBL 13.60 g, EDM 15.00 g, BDM 1.00 g, and DIBK 1.00 g.
- Example 1 ⁇ Evaluation of ink jet discharge properties> Using a polyamic acid solution (PC-1) with a blended polymer solid concentration of 4% by weight as a liquid crystal aligning agent, an ink jet apparatus DMP-2831 manufactured by FUJIFILM Dimatix was used for a continuous discharge experiment for 60 minutes. Five nozzles were confirmed on the monitor, and nozzle clogging could not be confirmed for 60 minutes continuously (see FIG. 1).
- this liquid crystal aligning agent was apply
- Examples 2 to 28, Comparative Examples 1 to 8 Except that the polyamic acid solutions shown in Table 3 and Table 4 were used as the liquid crystal aligning agent, the ejection properties, in-plane unevenness and edge linearity were evaluated by the method according to Example 1. The results are shown in Table 5 together with Example 1.
- Example 29 A polyamic acid solution (PC-1) having a polymer solid content concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a substrate with SiNx / ITO comb-teeth electrodes with a spinner. It applied to the attached glass substrate (height of spacer: 4 micrometers) with the inkjet coating apparatus (inkjet apparatus EB100XY100 made from Konica Minolta). The liquid crystal alignment film was adjusted to the following film thickness by adjusting the droplet interval and the cartridge applied voltage.
- PC-1 polyamic acid solution having a polymer solid content concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a substrate with SiNx / ITO comb-teeth electrodes with a spinner. It applied to the attached glass substrate (height of spacer: 4 micrometers) with the inkjet coating apparatus (inkjet apparatus EB
- the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate.
- the exposure energy at this time is 1.0 ⁇ 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC.
- the exposure time was adjusted.
- heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form a liquid crystal alignment film having a thickness of 100 ⁇ 10 nm.
- the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate.
- the exposure energy at this time is 1.0 ⁇ 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC.
- the exposure time was adjusted.
- the film was heat-treated at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form an alignment film having a thickness of 100 ⁇ 10 nm.
- Example 30 A polyamic acid solution (PD-1) having a polymer solid concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a substrate with SiNx / ITO comb-teeth electrodes with a spinner. It applied to the attached glass substrate (height of spacer: 4 micrometers) with the inkjet coating apparatus (inkjet apparatus EB100XY100 made from Konica Minolta). The liquid crystal alignment film was adjusted to the following film thickness by adjusting the droplet interval and the cartridge applied voltage. After the application, it was heated and dried at 70 ° C.
- the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate.
- the exposure energy at this time is 1.0 ⁇ 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC.
- the exposure time was adjusted.
- heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form a liquid crystal alignment film having a thickness of 100 ⁇ 10 nm.
- the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate.
- the exposure energy at this time is 1.0 ⁇ 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC.
- the exposure time was adjusted.
- the film was heat-treated at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form an alignment film having a thickness of 100 ⁇ 10 nm.
- the same liquid crystal aligning agent as the FFS liquid crystal display element having the liquid crystal aligning film formed by drying, irradiating with ultraviolet rays, and heat-treating the coating film obtained by printing the liquid crystal aligning agent of the present invention on the substrate by the inkjet method is spin
- an FFS liquid crystal display element having a liquid crystal alignment film formed by coating, coating, drying, ultraviolet irradiation, and heat treatment was compared in terms of the presence / absence of flow alignment, contrast, and AC afterimage, it was determined by the inkjet method.
- the performance of the photo-alignment film obtained from the coating film was no different from that of the photo-alignment film obtained from the spin-coating coating film, and showed good cell characteristics.
- BP20.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained.
- This polyamic acid solution is designated as PB-7.
- the weight average molecular weight of the polyamic acid contained in PB-7 was 48,000.
- Table 7 shows the composition of the raw materials and the solvent.
- composition ratio (weight ratio) of the solvent used for dilution is NMP 0.067 g, BP 2.667 g, GBL 13.60 g, EDM 15.00 g, BDM 1.00 g, and DIBK 1.00 g.
- polyamic acids (PC-37) to (PC-40) one polyamic acid solution selected from polyamic acids (PA-6) to (PA-9) is used, and the polymer solid content concentration is as shown in Table 8. Dilution was carried out with various solvents so as to achieve a weight% of 5%.
- the composition ratio of the polyamic acid solution and the solvent is shown in Table 8 together with PC-33.
- Example 31 ⁇ Evaluation of ink jet discharge properties> Using a polyamic acid solution (PC-33) having a blended polymer solid concentration of 4% by weight as a liquid crystal aligning agent, a continuous discharge experiment was conducted for 60 minutes using an inkjet apparatus DMP-2831 manufactured by FUJIFILM Dimatix. Five nozzles were confirmed on the monitor, and clogging of the nozzles could not be confirmed for 60 minutes continuously.
- PC-33 polyamic acid solution having a blended polymer solid concentration of 4% by weight
- this liquid crystal aligning agent was apply
- Example 32-42 Except that the polyamic acid solutions shown in Table 8 and Table 9 were used as the liquid crystal aligning agent, the ejection properties, in-plane unevenness and edge linearity were evaluated by the method according to Example 29. The results are shown in Table 10 together with Example 31.
- liquid crystal aligning agent of the present invention can form a liquid crystal aligning film having good ejection properties, in-plane unevenness and edge linearity.
- the liquid crystal aligning agent of this invention can be applied suitably in the model which requires a narrow frame.
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Abstract
Description
[1] ポリアミック酸およびその誘導体からなる群から選ばれる少なくとも1つの重合体および溶剤を含有する液晶配向剤であって;
前記溶剤が、第1溶剤として、N-メチル-2-ピロリドン、γ-ブチロラクトン、1,3-ジメチル-2-イミダゾリジノン、N-エチル-2-ピロリドンからなる群から選ばれる少なくとも1つ、
第2溶剤として、ブチルセロソルブ、1-ブトキシ-2-プロパノ-ル、ジエチレングリコ-ルエチルメチルエ-テル、ジエチレングリコールプロピルメチルエーテルからなる群から選ばれる少なくとも1つ、
第3溶剤として、ジイソブチルケトン、ジペンチルエーテルからなる群から選ばれる少なくとも1つ、そして、
第4溶剤として、下記式(1)で表される化合物の群から選ばれる少なくとも1つを含有する、液晶配向剤;
[1] A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of polyamic acid and derivatives thereof and a solvent;
The solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone as the first solvent,
As the second solvent, at least one selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether,
As the third solvent, at least one selected from the group consisting of diisobutyl ketone and dipentyl ether, and
A liquid crystal aligning agent containing at least one selected from the group of compounds represented by the following formula (1) as the fourth solvent;
第2溶剤の割合が全溶剤重量に対して10~60重量%であり、
第3溶剤の割合が全溶媒重量に対して0.1~15重量%であり、そして、
第4溶剤の割合が全溶剤重量に対して0.1~20重量%である、[1]項に記載の液晶配向剤。 [2] The proportion of the first solvent is 20 to 89% by weight with respect to the total solvent weight,
The proportion of the second solvent is 10 to 60% by weight with respect to the total solvent weight,
The proportion of the third solvent is 0.1 to 15% by weight with respect to the total solvent weight, and
The liquid crystal aligning agent according to item [1], wherein the proportion of the fourth solvent is 0.1 to 20% by weight based on the total solvent weight.
ジアミンが下記式(DI-1)~(DI-16)で表される側鎖を有さないジアミン、下記式(DIH-1)~(DIH-3)で表される側鎖を有さないジヒドラジドおよび下記式(DI-31)~(DI-35)で表される側鎖を有するジアミンの群から選択される少なくとも1つを含有する、[1]項または[2]項に記載の液晶配向剤;
式(AN-VII)において、G10は独立して-O-、-COO-または-OCO-であり、rは独立して0または1であり;
式(DI-3)および式(DI-5)~式(DI-7)において、G21は独立して単結合、-NH-、-NCH3-、-O-、-S-、-S-S-、-SO2-、-CO-、-COO-、-CONCH3-、-CONH-、-C(CH3)2-、-C(CF3)2-、-(CH2)m-、-O-(CH2)m-O-、-N(-Ra)-(CH2)k-N(-Ra)-、-(O-C2H4)m-O-、-O-CH2-C(CF3)2-CH2-O-、-O-CO-(CH2)m-CO-O-、-CO-O-(CH2)m-O-CO-、-(CH2)m-NH-(CH2)m-、-CO-(CH2)k-NH-(CH2)k-、-(NH-(CH2)m) k-NH-、-CO-C3H6-(NH-C3H6)n-CO-、または-S-(CH2)m-S-であり、Raは炭素数1~3のアルキルであり、mは独立して1~12の整数であり、kは1~5の整数であり、nは1または2であり;
式(DI-4)において、sは独立して0~2の整数であり;
式(DI-6)および式(DI-7)において、G22は独立して単結合、-O-、-S-、-CO-、-C(CH3)2-、-C(CF3)2-、-NH-、または炭素数1~10のアルキレンである。式(DI-2)~式(DI-7)中のシクロヘキサン環およびベンゼン環の少なくとも1つの水素は、-F、-Cl、炭素数1~3のアルキル、-OCH3、-OH、-CF3、-CO2H、-CONH2、-NHC6H5、フェニル、またはベンジルで置き換えられてもよく、加えて式(DI-4)においては、ベンゼン環の少なくとも1つの水素は下記式(DI-4-a)~式(DI-4-e)で表される基の群から選ばれる1つで置き換えられていてもよく;上記式中の環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し;
シクロヘキサン環またはベンゼン環への-NH2の結合位置は、G21またはG22の結合位置を除く任意の位置であり;
式(DI-13)において、R23は独立して炭素数1~5のアルキル、炭素数1~5のアルコキシまたは-Clであり、pは独立して0~3の整数であり、qは0~4の整数であり;
式(DI-14)において、環Bは単環の複素環式芳香族基であり、R24は水素、-F、-Cl、炭素数1~6のアルキル、アルコキシ、ビニル、アルキニルであり、qは独立して0~4の整数である。式(DI-15)において、環Cは複素環式芳香族基または複素環式脂肪族基であり;
式(DI-16)において、G24は単結合、炭素数2~6のアルキレンまたは1,4-フェニレンであり、rは0または1であり;
上記式中の環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し;
式(DI-13)~式(DI-16)において、環に結合する-NH2の結合位置は、任意の位置であり;
式(DIH-2)において、環Dはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この基の少なくとも1つの水素はメチル、エチル、またはフェニルで置き換えられてもよく;
式(DIH-3)において、環Eはそれぞれ独立してシクロヘキサン環、またはベンゼン環であり、この基の少なくとも1つの水素はメチル、エチル、またはフェニルで置き換えられてもよく、Yは単結合、炭素数1~20のアルキレン、-CO-、-O-、-S-、-SO2-、-C(CH3)2-、または-C(CF3)2-であり;
式(DIH-2)および式(DIH-3)において、環に結合する-CONHNH2の結合位置は、任意の位置であり;
R25は炭素数3~30のアルキル、フェニル、ステロイド骨格を有する基、または下記の式(DI-31-a)で表される基であり、このアルキルにおいて、少なくとも1つの水素は-Fで置き換えられてもよく、そして少なくとも1つの-CH2-は-O-、-CH=CH-または-C≡C-で置き換えられていてもよく、このフェニルの水素は、-F、-CH3、-OCH3、-OCH2F、-OCHF2、-OCF3、炭素数3~30のアルキルまたは炭素数3~30のアルコキシで置き換えられていてもよく、ベンゼン環に結合する-NH2の結合位置はその環において任意の位置であることを示し、
式(DI-33)におけるベンゼン環の少なくとも1つの水素は、炭素数1~20のアルキルまたはフェニルで置き換えられてもよく;
上記式中の環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し;
式(DI-32)および式(DI-33)において、ベンゼン環に結合する-NH2はその環における結合位置が任意であることを示し;
Diamine does not have a side chain represented by the following formulas (DI-1) to (DI-16), and does not have a side chain represented by any of the following formulas (DIH-1) to (DIH-3) The liquid crystal according to item [1] or [2], comprising dihydrazide and at least one selected from the group of diamines having side chains represented by the following formulas (DI-31) to (DI-35) An alignment agent;
In formula (AN-VII), G 10 is independently —O—, —COO— or —OCO—, and r is independently 0 or 1;
In Formula (DI-3) and Formula (DI-5) to Formula (DI-7), G 21 is independently a single bond, —NH—, —NCH 3 —, —O—, —S—, —S. —S—, —SO 2 —, —CO—, —COO—, —CONCH 3 —, —CONH—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, — (CH 2 ) m —, —O— (CH 2 ) m —O—, —N (—Ra) — (CH 2 ) k —N (—Ra) —, — (O—C 2 H 4 ) m —O—, —O —CH 2 —C (CF 3 ) 2 —CH 2 —O—, —O—CO— (CH 2 ) m —CO—O—, —CO—O— (CH 2 ) m —O—CO—, — (CH 2 ) m —NH— (CH 2 ) m —, —CO— (CH 2 ) k —NH— (CH 2 ) k —, — (NH— (CH 2 ) m ) k —NH—, —CO -C 3 H 6- ( NH—C 3 H 6 ) n —CO—, or —S— (CH 2 ) m —S—, Ra is alkyl having 1 to 3 carbon atoms, and m is independently an integer of 1 to 12 And k is an integer from 1 to 5 and n is 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In the formula (DI-6) and the formula (DI-7), G 22 is independently a single bond, —O—, —S—, —CO—, —C (CH 3 ) 2 —, —C (CF 3 2 ), -NH-, or alkylene having 1 to 10 carbon atoms. At least one hydrogen of the cyclohexane ring and the benzene ring in formula (DI-2) to formula (DI-7) is —F, —Cl, alkyl having 1 to 3 carbon atoms, —OCH 3 , —OH, —CF 3 , —CO 2 H, —CONH 2 , —NHC 6 H 5 , phenyl, or benzyl, and in Formula (DI-4), at least one hydrogen of the benzene ring is represented by the following formula ( DI-4-a) to (DI-4-e) may be substituted with one selected from the group of groups represented by formula (DI-4-e); the bonding position is fixed to the carbon atom constituting the ring in the above formula An unlabeled group indicates that the position of attachment in the ring is arbitrary;
The bonding position of —NH 2 to the cyclohexane ring or the benzene ring is any position except the bonding position of G 21 or G 22 ;
In the formula (DI-13), R 23 is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer from 0 to 3, and q is An integer from 0 to 4;
In the formula (DI-14), ring B is a monocyclic heteroaromatic group, R 24 is hydrogen, —F, —Cl, C 1-6 alkyl, alkoxy, vinyl, alkynyl, q is independently an integer of 0 to 4. In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group;
In the formula (DI-16), G 24 is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1;
A group whose bonding position is not fixed to the carbon atom constituting the ring in the above formula indicates that the bonding position in the ring is arbitrary;
In formula (DI-13) to formula (DI-16), the bonding position of —NH 2 bonded to the ring is an arbitrary position;
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this group may be replaced by methyl, ethyl or phenyl;
In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl, or phenyl, and Y is a single bond, Alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —;
In Formula (DIH-2) and Formula (DIH-3), the bonding position of —CONHNH 2 bonded to the ring is an arbitrary position;
R 25 is an alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen is —F. And at least one —CH 2 — may be replaced by —O—, —CH═CH— or —C≡C—, and the hydrogen of the phenyl is —F, —CH 3 , —OCH 3 , —OCH 2 F, —OCHF 2, —OCF 3, alkyl having 3 to 30 carbon atoms, or alkoxy having 3 to 30 carbon atoms, and —NH 2 bonded to the benzene ring The bond position is any position in the ring;
At least one hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl or phenyl having 1 to 20 carbon atoms;
A group whose bonding position is not fixed to any carbon atom constituting the ring in the above formula indicates that the bonding position in the ring is arbitrary;
In formula (DI-32) and formula (DI-33), —NH 2 bonded to the benzene ring indicates that the bonding position in the ring is arbitrary;
ジアミンが下記式(D-1)~(D-5)で表される化合物の群から選択される少なくとも1つを含有する、[1]項または[2]項に記載の液晶配向剤;
式(D-4)において、aは1~8の整数であり;
式(D-5)において、Raは炭素数1~3のアルキルであり;そして、
上記式中のベンゼン環の少なくとも1つの水素は-CH3で置き換えられていてもよい。 [4] The tetracarboxylic dianhydride used for the synthesis of the polymer contains at least one selected from the group of compounds represented by the following formulas (2) to (13);
The liquid crystal aligning agent according to item [1] or [2], wherein the diamine contains at least one selected from the group of compounds represented by the following formulas (D-1) to (D-5);
In the formula (D-4), a is an integer of 1 to 8;
In formula (D-5), Ra is alkyl having 1 to 3 carbons; and
At least one hydrogen of the benzene ring in the above formula may be replaced by —CH 3 .
ジアミンが下記式(D-1)~(D-5)で表される化合物の群から選択される少なくとも1つを含有する、[1]~[7]のいずれか1項に記載の液晶配向剤;
式(D-4)において、aは1~8の整数であり;
式(D-5)において、Raは炭素数1~3のアルキルであり;そして、
上記式中のベンゼン環の少なくとも1つの水素は-CH3で置き換えられていてもよい。 [8] The tetracarboxylic dianhydride used for the synthesis of the polymer (b) contains at least one selected from the group of compounds represented by the following formulas (2) to (13);
The liquid crystal alignment according to any one of [1] to [7], wherein the diamine contains at least one selected from the group of compounds represented by the following formulas (D-1) to (D-5): Agent;
In the formula (D-4), a is an integer of 1 to 8;
In formula (D-5), Ra is alkyl having 1 to 3 carbons; and
At least one hydrogen of the benzene ring in the above formula may be replaced by —CH 3 .
本発明のポリアミック酸およびその誘導体はテトラカルボン酸二無水物とジアミンとの反応生成物である。前記ポリアミック酸の誘導体とは、溶剤を含有する後述する液晶配向剤としたときに溶剤に溶解する成分であり、その液晶配向剤を液晶配向膜としたときに、ポリイミドを主成分とする液晶配向膜を形成することができる成分である。このようなポリアミック酸の誘導体としては、例えば可溶性ポリイミド、ポリアミック酸エステル、およびポリアミック酸アミド等が挙げられ、より具体的には1)ポリアミック酸の全てのアミノとカルボキシルとが脱水閉環反応したポリイミド、2)部分的に脱水閉環反応した部分ポリイミド、3)ポリアミック酸のカルボキシルがエステルに変換されたポリアミック酸エステル、4)テトラカルボン酸二無水物化合物に含まれる酸二無水物の一部を有機ジカルボン酸に置き換えて反応させて得られたポリアミック酸-ポリアミド共重合体、さらに5)該ポリアミック酸-ポリアミド共重合体の一部または全部を脱水閉環反応させたポリアミドイミドが挙げられる。前記ポリアミック酸およびその誘導体は、1種の化合物であってもよいし、2種以上であってもよい。また前記ポリアミック酸およびその誘導体は、テトラカルボン酸二無水物とジアミンとの反応生成物の構造を有する化合物であればよく、他の原料を用い、テトラカルボン酸二無水物とジアミンとの反応以外の他の反応による反応生成物を含有してもよい。 The polyamic acid and derivatives thereof of the present invention will be described.
The polyamic acid and derivatives thereof of the present invention are reaction products of tetracarboxylic dianhydride and diamine. The polyamic acid derivative is a component that dissolves in a solvent when the liquid crystal aligning agent described later containing a solvent is used. When the liquid crystal aligning agent is used as a liquid crystal aligning film, the liquid crystal alignment is mainly composed of polyimide. It is a component that can form a film. Examples of such a derivative of polyamic acid include soluble polyimide, polyamic acid ester, polyamic acid amide, and the like. More specifically, 1) polyimide in which all amino acids and carboxyl of polyamic acid are subjected to a dehydration ring-closing reaction, 2) Partially dehydrated ring-closing partial polyimide, 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) Part of acid dianhydride contained in tetracarboxylic dianhydride compound is organic dicarboxylic Examples thereof include polyamic acid-polyamide copolymers obtained by reacting with an acid, and 5) polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction. One kind of compound may be sufficient as the said polyamic acid and its derivative (s), and 2 or more types may be sufficient as it. The polyamic acid and its derivative may be a compound having a structure of a reaction product of tetracarboxylic dianhydride and diamine, and other raw materials may be used except for the reaction of tetracarboxylic dianhydride and diamine. It may contain reaction products from other reactions.
式(DIH-2)において、環Dはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この基の少なくとも1つの水素はメチル、エチル、またはフェニルで置き換えられてもよい。式(DIH-3)において、環Eはそれぞれ独立してシクロヘキサン環、またはベンゼン環であり、この基の少なくとも1つの水素はメチル、エチル、またはフェニルで置き換えられてもよく、Yは単結合、炭素数1~20のアルキレン、-CO-、-O-、-S-、-SO2-、-C(CH3)2-、または-C(CF3)2-である。式(DIH-2)および式(DIH-3)において、環に結合する-CONHNH2の結合位置は、任意の位置である。
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl or phenyl. In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl, or phenyl, and Y is a single bond, It is alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —. In formula (DIH-2) and formula (DIH-3), the bonding position of —CONHNH 2 bonded to the ring is an arbitrary position.
本発明の液晶配向剤は、液晶表示素子における電気特性を長期に安定させる目的から、オキサジン化合物をさらに含有していてもよい。オキサジン化合物は1種の化合物であってもよいし、2種以上の化合物であってもよい。オキサジン化合物の含有量は、上記の目的から、ポリアミック酸またはその誘導体に対して0.1~50重量%であることが好ましく、1~40重量%であることがより好ましく、1~20重量%であることがさらに好ましい。以下にオキサジン化合物について具体的に説明する。 <Oxazine compound>
The liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be one type of compound or two or more types of compounds. For the above purpose, the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof. More preferably. The oxazine compound will be specifically described below.
本発明の液晶配向剤は、液晶表示素子における電気特性を長期に安定させる目的から、オキサゾリン化合物をさらに含有していてもよい。オキサゾリン化合物はオキサゾリン構造を有する化合物である。オキサゾリン化合物は1種の化合物であってもよいし、2種以上の化合物であってもよい。オキサゾリン化合物の含有量は、上記の目的から、ポリアミック酸またはその誘導体に対して0.1~50重量%であることが好ましく、1~40重量%であることがより好ましく、1~20重量%であることが好ましい。または、オキサゾリン化合物の含有量は、オキサゾリン化合物中のオキサゾリン構造をオキサゾリンに換算したときに、ポリアミック酸またはその誘導体に対して0.1~40重量%であることが、上記の目的から好ましい。以下にオキサゾリン化合物について具体的に説明する。 <Oxazoline compound>
The liquid crystal aligning agent of this invention may further contain the oxazoline compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long term. An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one type of compound or two or more types of compounds. For the above purpose, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof. It is preferable that Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted to oxazoline. The oxazoline compound will be specifically described below.
本発明の液晶配向剤は、液晶表示素子における電気特性を長期に安定させる目的から、エポキシ化合物をさらに含有していてもよい。エポキシ化合物は1種の化合物であってもよいし、2種以上の化合物であってもよい。エポキシ化合物の含有量は、上記の目的から、ポリアミック酸またはその誘導体に対して0.1~50重量%であることが好ましく、1~40重量%であることがより好ましく、1~20重量%であることがさらに好ましい。以下にエポキシ化合物について具体的に説明する。 <Epoxy compound>
The liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be one type of compound or two or more types of compounds. The content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably. The epoxy compound will be specifically described below.
本発明は、対向配置されている一対の基板と、前記一対の基板それぞれの対向している面の一方または両方に形成されている電極と、前記一対の基板それぞれの対向している面に形成された液晶配向膜と、前記一対の基板間に形成された液晶層とを有する液晶表示素子において、前記液晶配向膜が本発明の配向膜である液晶表示素子を提供する。 The liquid crystal display element of the present invention will be described in detail.
According to the present invention, a pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces facing each of the pair of substrates, and a surface facing each of the pair of substrates are formed. A liquid crystal display element having a liquid crystal alignment film formed and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the alignment film of the present invention.
光学活性な化合物の好ましい割合は5重量%以下である。さらに好ましい割合は0.01重量%から2重量%の範囲である。
A desirable ratio of the optically active compound is 5% by weight or less. A more desirable ratio is in the range of 0.01% to 2% by weight.
1.重量平均分子量(Mw)
ポリアミック酸の重量平均分子量は、2695セパレーションモジュール・2414示差屈折計(Waters製)を用いてGPC法により測定し、ポリスチレン換算することにより求めた。得られたポリアミック酸をリン酸-DMF混合溶液(リン酸/DMF=0.6/100:重量比)で、ポリアミック酸濃度が約2重量%になるように希釈した。カラムはHSPgel RT MB-M(Waters製)を使用し、前記混合溶液を展開剤として、カラム温度50℃、流速0.40mL/minの条件で測定を行った。標準ポリスチレンは東ソー(株)製TSK標準ポリスチレンを用いた。 <Evaluation method>
1. Weight average molecular weight (Mw)
The weight average molecular weight of the polyamic acid was measured by GPC method using a 2695 separation module / 2414 differential refractometer (manufactured by Waters) and calculated by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 2% by weight. The column was HSPgel RT MB-M (manufactured by Waters), and the measurement was performed under the conditions of a column temperature of 50 ° C. and a flow rate of 0.40 mL / min using the mixed solution as a developing agent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.
FUJIFILM Dimatix社製インクジェット装置DMP-2831を用いて、60分間の連続吐出を実施。モニターに映る5つのノズルから液滴の吐出を、42μ秒毎にカメラで撮影して確認した。図1のように大きさの揃った液滴が60分間連続で吐出できた液晶配向剤を合格とした。ノズル詰まりを起こして、図2のようにノズル付近にインクだまりができたり、斜め方向に吐出する現象が観察された場合を不合格とした。
ヘッド:DMC-11610(ノズル数:16 液滴10pL)
ヘッド温度:28℃
印加電圧:22V
周波数:10kHz 2. Inkjet ejection property Continuous ejection for 60 minutes was performed using an inkjet device DMP-2831 manufactured by FUJIFILM Dimatix. The discharge of droplets from the five nozzles displayed on the monitor was confirmed by photographing with a camera every 42 μs. As shown in FIG. 1, a liquid crystal aligning agent in which droplets having a uniform size could be continuously discharged for 60 minutes was regarded as acceptable. A case where nozzle clogging occurred and ink was clogged in the vicinity of the nozzle as shown in FIG.
Head: DMC-11610 (Nozzle number: 16 droplets 10pL)
Head temperature: 28 ° C
Applied voltage: 22V
Frequency: 10kHz
コニカミノルタ社製インクジェット装置EB100XY100を用いてITO付き基板に塗布した配向膜の、面内観察および顕微鏡におけるエッジのガタツキを確認した。図3のように塗布膜のエッジのガタツキが0.2mm以下である液晶配向剤を合格とした。図4ではエッジのガタツキが0.2mm以上であり、不合格である。
ヘッド:KM512MH(ノズル数:512 液滴14pL)
ヘッド温度:25℃
印加電圧:19V
周波数:709Hz
解像度:360dpi
搬送速度:50mm/sec
ヘッド/ガラス基板間隔28mm 3. In-plane unevenness and edge linearity in inkjet printing In-plane observation of the alignment film applied to the substrate with ITO using an inkjet device EB100XY100 manufactured by Konica Minolta Co., Ltd. and edge roughness in a microscope were confirmed. As shown in FIG. 3, a liquid crystal aligning agent having an edge roughness of the coating film of 0.2 mm or less was accepted. In FIG. 4, the backlash of the edge is 0.2 mm or more, which is unacceptable.
Head: KM512MH (No. of nozzles: 512 droplets 14pL)
Head temperature: 25 ° C
Applied voltage: 19V
Frequency: 709Hz
Resolution: 360 dpi
Conveyance speed: 50mm / sec
Head / glass substrate spacing 28mm
後述する液晶素子のコントラストは、輝度計(YOKOGAWA 3298F)を用いて評価を行った。クロスニコル状態の偏光顕微鏡下に液晶表示素子を配置し、素子を回転させて透過光強度、すなわち輝度が最小となる角度に固定した。この状態での輝度の値を「黒輝度」とした。次に素子に任意の矩形波電圧を印加し、輝度が最大となった数値を「白輝度」とした。この白輝度/黒輝度の値をコントラストとした。コントラストは2500未満で不良、2500以上で良、3000以上で最良と判断する。 4). Contrast The contrast of the liquid crystal element described later was evaluated using a luminance meter (YOKOGAWA 3298F). A liquid crystal display element was placed under a polarizing microscope in a crossed Nicol state, and the element was rotated and fixed at an angle at which transmitted light intensity, that is, luminance was minimized. The luminance value in this state was defined as “black luminance”. Next, an arbitrary rectangular wave voltage was applied to the element, and the numerical value at which the luminance became maximum was defined as “white luminance”. This white luminance / black luminance value was defined as contrast. Contrast is less than 2500, poor, 2500 or more is good, and 3000 or more is judged to be the best.
後述する液晶表示素子の輝度-電圧特性(B-V特性)を測定した。これをストレス印加前の輝度-電圧特性:B(before)とする。次に、素子に4.5V、60Hzの交流を20分間印加した後、1秒間ショートし、再び輝度-電圧特性(B-V特性)を測定した。これをストレス印加後の輝度-電圧特性:B(after)とする。これらの値をもとに、輝度変化率ΔB(%)を下記式(AC1)を用いて見積もった。
ΔB(%)=[B(after)-B(before)]/B(before) (AC1)
これらの測定は国際公開2000/43833号パンフレットを参考に行った。電圧0.75VにおけるΔB(%)の値が小さいほど、AC残像の発生を抑制できるといえ、3.0%以下が好ましい。 5. AC Afterimage Measurement Luminance-voltage characteristics (BV characteristics) of a liquid crystal display element to be described later were measured. This is the luminance-voltage characteristic before stress application: B (before). Next, an alternating current of 4.5 V and 60 Hz was applied to the device for 20 minutes, and then shorted for 1 second, and the luminance-voltage characteristics (BV characteristics) were measured again. This is the luminance-voltage characteristic after application of stress: B (after). Based on these values, the luminance change rate ΔB (%) was estimated using the following formula (AC1).
ΔB (%) = [B (after) −B (before)] / B (before) (AC1)
These measurements were performed with reference to International Publication No. 2000/43833 pamphlet. It can be said that the smaller the value of ΔB (%) at the voltage of 0.75 V, the more the generation of AC afterimage can be suppressed, and 3.0% or less is preferable.
<テトラカルボン酸二無水物>
(2): ピロメリット酸二無水物
(4): 1,2,3,4-ブタンテトラカルボン酸二無水物
(10): 1,8-ビス(3,4-ジカルボン酸フェニル)オクタン二無水物
(11): 4,4’-オキシジフタル酸無水物
実施例に用いた化合物はいずれも無置換である。 Polymer raw material monomers, solvents and additives used in the examples are shown below.
<Tetracarboxylic dianhydride>
(2): Pyromellitic dianhydride (4): 1,2,3,4-butanetetracarboxylic dianhydride (10): 1,8-bis (3,4-dicarboxylic acid phenyl) octane dianhydride Product (11): 4,4′-Oxydiphthalic anhydride The compounds used in the examples are all unsubstituted.
DAAB: 4,4’-ジアミノアゾベンゼン (式(I-3)の化合物)
DDE: 4,4’-ジアミノジフェニルエーテル (式(D-2)のXが-O-である無置換の化合物)
APDA: 4,4’-N,N’-ビス(4-アミノフェニル)ピペラジン (式(D-3)の無置換の化合物)
DDBU: 4,4’-ジアミノジフェニルブタン (式(D-2)のXが-(CH2)4-である無置換の化合物)
PDA: 1,4-フェニレンジアミン(式(D-1))
BABZP3: 4,4’-((プロパン-1,3-ジイルビス(4,1-フェニレン))ビス(メチレン))ジアニリン(式(D-4-3)) <Diamine>
DAAB: 4,4′-diaminoazobenzene (compound of formula (I-3))
DDE: 4,4′-diaminodiphenyl ether (unsubstituted compound in which X in formula (D-2) is —O—)
APDA: 4,4′-N, N′-bis (4-aminophenyl) piperazine (unsubstituted compound of formula (D-3))
DDBU: 4,4′-diaminodiphenylbutane (an unsubstituted compound in which X in formula (D-2) is — (CH 2 ) 4 —)
PDA: 1,4-phenylenediamine (formula (D-1))
BABZP3: 4,4 ′-((propane-1,3-diylbis (4,1-phenylene)) bis (methylene)) dianiline (formula (D-4-3))
NMP: N-メチル-2-ピロリドン
GBL: γ-ブチロラクトン
BC: ブチルセロソルブ
BP: 1-ブトキシ-2-プロパノール
EDM: ジエチレングリコールエチルメチルエーテル
DIBK: ジイソブチルケトン
DPE: ジペンチルエーテル
BDM: ジエチレングリコールブチルメチルエーテル
EDP: ジエチレングリコールエチルプロピルエーテル
BDE: ジエチレングリコールブチルエチルエーテル <Solvent>
NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BC: butyl cellosolve BP: 1-butoxy-2-propanol EDM: diethylene glycol ethyl methyl ether DIBK: diisobutyl ketone DPE: dipentyl ether BDM: diethylene glycol butyl methyl ether EDP: diethylene glycol ethyl Propyl ether BDE: Diethylene glycol butyl ethyl ether
Add.1: 1,3-ビス(4,5-ジヒドロ-2-オキサゾリル)ベンゼン
Add.2: 2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン <Additives>
Add. 1: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene Add. 2: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
[合成例A-1]
温度計、攪拌機、原料投入仕込み口および窒素ガス導入口を備えた200mLの褐色四つ口フラスコにDAAB1.8434g、DDBU0.2087g、APDA0.0259gと脱水NMP54.0gを入れ、乾燥窒素気流下攪拌溶解した。次いで、式(10)のテトラカルボン酸二無水物3.9220gさらに脱水NMP20.0gを入れ、室温で24時間攪拌を続けた。この反応溶液にBP20.0gを加えて、ポリマー固形分濃度が6重量%のポリアミック酸溶液を得た。このポリアミック酸溶液をPA-1とする。PA-1に含まれるポリアミック酸の重量平均分子量は10,300であった。 <Synthesis of polyamic acid>
[Synthesis Example A-1]
DAAB1.8434g, DDBU0.2087g, APDA0.0259g and dehydrated NMP 54.0g were placed in a 200mL brown four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, and stirred and dissolved under a dry nitrogen stream. did. Next, 3.9220 g of tetracarboxylic dianhydride of the formula (10) and 20.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BP20.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained. This polyamic acid solution is designated as PA-1. The weight average molecular weight of the polyamic acid contained in PA-1 was 10,300.
テトラカルボン酸二無水物、ジアミン、および溶剤組成を変更した以外は、合成例A-1に準拠してポリマー固形分濃度が6重量%のポリアミック酸溶液(PA-2)~(PA-4)を調製した。原料および溶剤の組成をPA-1と共に表1に示す。 [Synthesis Examples A-2 to A-4]
Except for changing the tetracarboxylic dianhydride, diamine, and solvent composition, polyamic acid solutions (PA-2) to (PA-4) having a polymer solid content concentration of 6% by weight according to Synthesis Example A-1 Was prepared. The composition of the raw materials and the solvent is shown in Table 1 together with PA-1.
温度計、攪拌機、原料投入仕込み口および窒素ガス導入口を備えた200mLの褐色四つ口フラスコにAPDA1.8321g、DDE1.3670g、および脱水NMP54.0gを入れ、乾燥窒素気流下攪拌溶解した。次いで式(2)のテトラカルボン酸二無水物1.0424g、式(4)のテトラカルボン酸二無水物1.7585g、さらに脱水NMP20.0gを入れ、室温で24時間攪拌を続けた。この反応溶液にBP20.0gを加えて、ポリマー固形分濃度が6重量%のポリアミック酸溶液を得た。このポリアミック酸溶液をPB-1とする。PB-1に含まれるポリアミック酸の重量平均分子量は50,000であった。 [Synthesis Example B-1]
APDA 1.8321 g, DDE 1.3670 g, and dehydrated NMP 54.0 g were placed in a 200 mL brown four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, and dissolved under stirring in a dry nitrogen stream. Next, 1.0424 g of tetracarboxylic dianhydride of formula (2), 1.7585 g of tetracarboxylic dianhydride of formula (4) and 20.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BP20.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained. This polyamic acid solution is designated as PB-1. The weight average molecular weight of the polyamic acid contained in PB-1 was 50,000.
溶剤組成を変更した以外は、合成例B-1に準拠してポリマー固形分濃度が6重量%のポリアミック酸溶液(PB-2)~(PB-6)を調製した。原料および溶剤の組成をPB-1と共に表2に示す。 [Synthesis Examples B-2 to B-6]
Except for changing the solvent composition, polyamic acid solutions (PB-2) to (PB-6) having a polymer solid concentration of 6% by weight were prepared according to Synthesis Example B-1. The composition of the raw material and the solvent is shown in Table 2 together with PB-1.
[合成例PC-1]
[A]合成例A-1で調製したポリマー固形分濃度6重量%のポリアミック酸溶液(PA-1)と、[B]合成例B-1で調製したポリマー固形分濃度6重量%のポリアミック酸溶液(PB-1)とを、[A]/[B]=3.0/7.0(重量比)で混合した。この混合溶液をさらにNMP/BP/GBL/EDM/BDM/DIBKの溶液にて希釈し、ポリマー固形分濃度4重量%のポリアミック酸溶液をPC-1とした。このとき、希釈に用いた溶剤の組成比(重量比)は、NMP0.067g、BP2.667g、GBL13.60g、EDM15.00g、BDM1.00g、およびDIBK1.00gである。 <Polymer blend>
[Synthesis Example PC-1]
[A] A polyamic acid solution (PA-1) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example A-1 and a polyamic acid having a polymer solid content concentration of 6% by weight prepared in [B] Synthesis Example B-1 The solution (PB-1) was mixed at [A] / [B] = 3.0 / 7.0 (weight ratio). This mixed solution was further diluted with a solution of NMP / BP / GBL / EDM / BDM / DIBK, and a polyamic acid solution having a polymer solid concentration of 4% by weight was designated as PC-1. At this time, the composition ratio (weight ratio) of the solvent used for dilution is NMP 0.067 g, BP 2.667 g, GBL 13.60 g, EDM 15.00 g, BDM 1.00 g, and DIBK 1.00 g.
[A]ポリアミック酸溶液(PA-1)~(PA-4)から選ばれる1つのポリアミック酸溶液と、[B]ポリアミック酸溶液(PB-1)~(PB-6)からなるポリアミック酸溶液を、重量比[A]/[B]で混合して、さらにポリマー固形分濃度が表3の記載の重量%となるように、各種溶剤により希釈を実施して、ポリアミック酸溶液(PC-1)~(PC-32)を調整した。ポリアミック酸溶液および溶剤の組成比をPC-1と共に表3に示す。 [Synthesis Examples PC-2 to PC-32]
[A] One polyamic acid solution selected from polyamic acid solutions (PA-1) to (PA-4), and [B] a polyamic acid solution comprising polyamic acid solutions (PB-1) to (PB-6) The polyamic acid solution (PC-1) was mixed at various weight ratios [A] / [B] and further diluted with various solvents so that the polymer solids concentration would be the weight% shown in Table 3. To (PC-32) were adjusted. The composition ratio of the polyamic acid solution and the solvent is shown in Table 3 together with PC-1.
ポリマー固形分濃度4重量%のポリアミック酸溶液(PC-1)に、添加剤(Add.1)をポリマー重量当たり15重量%、添加剤(Add.2)をポリマー重量当たり10重量%の割合で添加した。得られたポリアミック酸溶液をPD-1とする。 [Synthesis Example PD-1]
In a polyamic acid solution (PC-1) having a polymer solid content concentration of 4% by weight, the additive (Add.1) is 15% by weight per polymer weight and the additive (Add.2) is 10% by weight per polymer weight. Added. The resulting polyamic acid solution is designated PD-1.
ポリマー固形分濃度3.5重量%のポリアミック酸溶液(PC-23)に、添加剤(Add.1)をポリマー重量当たり15重量%、添加剤(Add.2)をポリマー重量当たり10重量%の割合で添加した。得られたポリアミック酸溶液をPD-2とする。 [Synthesis Example PD-2]
In a polyamic acid solution (PC-23) having a polymer solid concentration of 3.5% by weight, 15% by weight of the additive (Add.1) and 10% by weight of the additive (Add.2) per weight of the polymer were added. Added in proportions. The resulting polyamic acid solution is designated PD-2.
ポリマー固形分濃度3.5重量%のポリアミック酸溶液(PC-29)および(PC-31)に、添加剤(Add.1)をポリマー重量当たり15重量%、添加剤(Add.2)をポリマー重量当たり10重量%の割合で添加した。得られたポリアミック酸溶液をPD-3およびPD-4とする。ポリアミック酸溶液、添加剤および溶剤の組成比をPD-1およびPD-2と共に表4に示す。
In polyamic acid solutions (PC-29) and (PC-31) having a polymer solid concentration of 3.5% by weight, 15% by weight of the additive (Add.1) per polymer weight and the additive (Add.2) were polymerized. It was added at a rate of 10% by weight per weight. The obtained polyamic acid solutions are designated PD-3 and PD-4. Table 4 shows the composition ratio of the polyamic acid solution, the additive and the solvent together with PD-1 and PD-2.
<インクジェット吐出性の評価>
ブレンド調整したポリマー固形分濃度4重量%のポリアミック酸溶液(PC-1)を液晶配向剤として、FUJIFILM Dimatix社製インクジェット装置DMP-2831を用いて、60分間連続吐出実験を行った。5本のノズルをモニターで確認し、60分間の連続でノズルの詰りは確認できなった(図1を参照。)。 [Example 1]
<Evaluation of ink jet discharge properties>
Using a polyamic acid solution (PC-1) with a blended polymer solid concentration of 4% by weight as a liquid crystal aligning agent, an ink jet apparatus DMP-2831 manufactured by FUJIFILM Dimatix was used for a continuous discharge experiment for 60 minutes. Five nozzles were confirmed on the monitor, and nozzle clogging could not be confirmed for 60 minutes continuously (see FIG. 1).
さらに、コニカミノルタ製インクジェット装置EB100XY100を用いて、この液晶配向剤をITO付きガラス基板に塗布した。塗布後、180秒間静置し、60℃ホットプレート上で80秒間乾燥させた。その後、塗布基板の観察を行った。面内スジムラは目視確認、エッジの直線性は顕微鏡観察にて、エッジのガタツキを測定することで判断した。その結果、面内スジムラは見られず、均一であった。さらに、顕微鏡で観察したところ、エッジのガタツキは0.2mm以下で、直線性は良好であった(図3を参照。)。 <In-plane linearity and edge linearity in inkjet printing>
Furthermore, this liquid crystal aligning agent was apply | coated to the glass substrate with ITO using the inkjet apparatus EB100XY100 made from Konica Minolta. After coating, the solution was allowed to stand for 180 seconds and dried on a 60 ° C. hot plate for 80 seconds. Thereafter, the coated substrate was observed. In-plane unevenness was visually confirmed, and edge linearity was determined by measuring edge roughness by microscopic observation. As a result, no in-plane unevenness was observed and it was uniform. Further, when observed with a microscope, the edge roughness was 0.2 mm or less, and the linearity was good (see FIG. 3).
表3および表4に示すポリアミック酸溶液を液晶配向剤として用いた以外は、実施例1に準じた方法で吐出性、面内スジムラおよびエッジの直線性を評価した。結果を実施例1と共に表5に示す。 [Examples 2 to 28, Comparative Examples 1 to 8]
Except that the polyamic acid solutions shown in Table 3 and Table 4 were used as the liquid crystal aligning agent, the ejection properties, in-plane unevenness and edge linearity were evaluated by the method according to Example 1. The results are shown in Table 5 together with Example 1.
<セル注入時の流動配向の有無、コントラストおよびAC残像の評価>
[実施例29]
ブレンド調製したポリマー固形分濃度4重量%のポリアミック酸溶液(PC-1)を液晶配向剤とし、この液晶配向剤をSiNx/ITO櫛歯電極付き基板にスピンナーで塗布し、対向側には、スペーサー付きガラス基板(スペーサーの高さ:4μm)にインクジェット塗布装置(コニカミノルタ製インクジェット装置EB100XY100)にて塗布した。なお、液滴間隔、カートリッジ印加電圧を調整し、液晶配向膜が下記の膜厚になるようにした。塗布後、ホットプレート(アズワン株式会社製、ECホットプレート(EC-1200N))上で70℃にて80秒間加熱乾燥した。次いで、ウシオ電機(株)製マルチライトML-501C/Bを用い、基板に対して鉛直方向から、偏光板を介して紫外線の直線偏光を照射した。この時の露光エネルギーは、ウシオ電機(株)製紫外線積算光量計UIT-150(受光器UVD-S365)を用いて光量を測定し、波長365nmで1.0±0.1J/cm2になるよう、露光時間を調整した。続いて、クリーンオーブン(エスペック株式会社、PVHC-231)中で、230℃にて15分間加熱処理して、膜厚100±10nmの液晶配向膜を形成した。 [Examples 29 and 30, and Reference Examples 1 and 2]
<Evaluation of presence / absence of flow orientation during cell injection, contrast and AC afterimage>
[Example 29]
A polyamic acid solution (PC-1) having a polymer solid content concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a substrate with SiNx / ITO comb-teeth electrodes with a spinner. It applied to the attached glass substrate (height of spacer: 4 micrometers) with the inkjet coating apparatus (inkjet apparatus EB100XY100 made from Konica Minolta). The liquid crystal alignment film was adjusted to the following film thickness by adjusting the droplet interval and the cartridge applied voltage. After the application, it was heated and dried at 70 ° C. for 80 seconds on a hot plate (manufactured by AS ONE, EC hot plate (EC-1200N)). Next, using a multi-light ML-501C / B manufactured by Ushio Electric Co., Ltd., the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate. The exposure energy at this time is 1.0 ± 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. Subsequently, heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form a liquid crystal alignment film having a thickness of 100 ± 10 nm.
基板上に液晶配向膜が形成された基板2枚の配向膜が形成されている面を対向させ、それぞれの液晶配向膜に照射された紫外線の偏光方向が平行になるように、さらに対向する配向膜の間にポジ型液晶組成物を注入させるための空隙を形成して貼り合わせ、セル厚4μmの空FFSセルを組み立てた。作製した空FFSセルに上記ポジ型液晶組成物1を真空注入して、FFS液晶表示素子を作製した。得られた液晶表示素子中の液晶の配向を確認したところ、流動配向は見られなかった。コントラストの値を測定したところ3080であり、AC残像を測定したところΔBは1.8%であった。 <FFS cell preparation, flow orientation confirmation, contrast and AC afterimage measurement>
Two substrates on which a liquid crystal alignment film is formed on the substrate are opposed to each other, and the opposite alignment is performed so that the polarization directions of ultraviolet rays irradiated to the respective liquid crystal alignment films are parallel to each other. A gap for injecting the positive liquid crystal composition was formed between the films and bonded together to assemble an empty FFS cell having a cell thickness of 4 μm. The positive
ブレンド調製したポリマー固形分濃度4重量%のポリアミック酸溶液(PC-1)を液晶配向剤として、SiNx/ITO櫛歯電極付き基板にスピンナーで塗布し、対向側には、スペーサー付きガラス基板(スペーサーの高さ:4μm)にスピンナー(ミカサ株式会社製、スピンコーター(1H-DX2))にて塗布した。なお、以降の実施例、比較例をも含めて、液晶配向剤の粘度に応じてスピンナーの回転速度を調整し、配向膜が下記の膜厚になるようにした。塗布後、ホットプレート(アズワン株式会社製、ECホットプレート(EC-1200N))上で70℃にて80秒間加熱乾燥した。次いで、ウシオ電機(株)製マルチライトML-501C/Bを用い、基板に対して鉛直方向から、偏光板を介して紫外線の直線偏光を照射した。この時の露光エネルギーは、ウシオ電機(株)製紫外線積算光量計UIT-150(受光器UVD-S365)を用いて光量を測定し、波長365nmで1.0±0.1J/cm2になるよう、露光時間を調整した。続いて、クリーンオーブン(エスペック株式会社、PVHC-231)中で、230℃にて15分間加熱処理して、膜厚100±10nmの配向膜を形成した。 [Reference Example 1]
The blended
基板上に配向膜が形成された基板2枚の配向膜が形成されている面を対向させ、それぞれの配向膜に照射された紫外線の偏光方向が平行になるように、さらに対向する配向膜の間にポジ型液晶組成物を注入させるための空隙を形成して貼り合わせ、セル厚4μmの空FFSセルを組み立てた。作製した空FFSセルに前記ポジ型液晶組成物1を真空注入して、FFS液晶表示素子を作製した。得られた液晶表示素子中の液晶の配向を確認したところ、流動配向は見られなかった。コントラストの値を測定したところ3050であり、AC残像を測定したところΔBは1.9%であった。 <FFS cell preparation, flow orientation confirmation, contrast and AC afterimage measurement>
Two substrates having alignment films formed on the substrates are opposed to each other so that the surfaces on which the alignment films are formed are opposed to each other so that the polarization directions of ultraviolet rays irradiated to the respective alignment films are parallel to each other. A gap for injecting the positive type liquid crystal composition was formed between them and bonded together to assemble an empty FFS cell having a cell thickness of 4 μm. The positive
ブレンド調製したポリマー固形分濃度4重量%のポリアミック酸溶液(PD-1)を液晶配向剤とし、この液晶配向剤をSiNx/ITO櫛歯電極付き基板にスピンナーで塗布し、対向側には、スペーサー付きガラス基板(スペーサーの高さ:4μm)にインクジェット塗布装置(コニカミノルタ製インクジェット装置EB100XY100)にて塗布した。なお、液滴間隔、カートリッジ印加電圧を調整し、液晶配向膜が下記の膜厚になるようにした。塗布後、ホットプレート(アズワン株式会社製、ECホットプレート(EC-1200N))上で70℃にて80秒間加熱乾燥した。次いで、ウシオ電機(株)製マルチライトML-501C/Bを用い、基板に対して鉛直方向から、偏光板を介して紫外線の直線偏光を照射した。この時の露光エネルギーは、ウシオ電機(株)製紫外線積算光量計UIT-150(受光器UVD-S365)を用いて光量を測定し、波長365nmで1.0±0.1J/cm2になるよう、露光時間を調整した。続いて、クリーンオーブン(エスペック株式会社、PVHC-231)中で、230℃にて15分間加熱処理して、膜厚100±10nmの液晶配向膜を形成した。 [Example 30]
A polyamic acid solution (PD-1) having a polymer solid concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a substrate with SiNx / ITO comb-teeth electrodes with a spinner. It applied to the attached glass substrate (height of spacer: 4 micrometers) with the inkjet coating apparatus (inkjet apparatus EB100XY100 made from Konica Minolta). The liquid crystal alignment film was adjusted to the following film thickness by adjusting the droplet interval and the cartridge applied voltage. After the application, it was heated and dried at 70 ° C. for 80 seconds on a hot plate (manufactured by AS ONE, EC hot plate (EC-1200N)). Next, using a multi-light ML-501C / B manufactured by Ushio Electric Co., Ltd., the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate. The exposure energy at this time is 1.0 ± 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. Subsequently, heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form a liquid crystal alignment film having a thickness of 100 ± 10 nm.
基板上に液晶配向膜が形成された基板2枚の配向膜が形成されている面を対向させ、それぞれの液晶配向膜に照射された紫外線の偏光方向が平行になるように、さらに対向する配向膜の間に液晶組成物を注入させるための空隙を形成して貼り合わせ、セル厚4μmの空FFSセルを組み立てた。作製した空FFSセルに前記ポジ型液晶組成物1を真空注入して、FFS液晶表示素子を作製した。得られた液晶表示素子中の液晶の配向を確認したところ、流動配向は見られなかった。コントラストの値を測定したところ3010であり、AC残像を測定したところΔBは2.2%であった。 <FFS cell preparation, flow orientation confirmation, contrast and AC afterimage measurement>
Two substrates on which a liquid crystal alignment film is formed on the substrate are opposed to each other, and the opposite alignment is performed so that the polarization directions of ultraviolet rays irradiated to the respective liquid crystal alignment films are parallel to each other. A gap for injecting the liquid crystal composition was formed between the films and bonded together to assemble an empty FFS cell having a cell thickness of 4 μm. The positive
ブレンド調製したポリマー固形分濃度4重量%のポリアミック酸溶液(PD-1)を液晶配向剤として、SiNx/ITO櫛歯電極付き基板にスピンナーで塗布し、対向側には、スペーサー付きガラス基板(スペーサーの高さ:4μm)にスピンナー(ミカサ株式会社製、スピンコーター(1H-DX2))にて塗布した。なお、以降の実施例、比較例をも含めて、液晶配向剤の粘度に応じてスピンナーの回転速度を調整し、配向膜が下記の膜厚になるようにした。塗布後、ホットプレート(アズワン株式会社製、ECホットプレート(EC-1200N))上で70℃にて80秒間加熱乾燥した。次いで、ウシオ電機(株)製マルチライトML-501C/Bを用い、基板に対して鉛直方向から、偏光板を介して紫外線の直線偏光を照射した。この時の露光エネルギーは、ウシオ電機(株)製紫外線積算光量計UIT-150(受光器UVD-S365)を用いて光量を測定し、波長365nmで1.0±0.1J/cm2になるよう、露光時間を調整した。続いて、クリーンオーブン(エスペック株式会社、PVHC-231)中で、230℃にて15分間加熱処理して、膜厚100±10nmの配向膜を形成した。 [Reference Example 2]
The blended polymer
基板上に配向膜が形成された基板2枚の配向膜が形成されている面を対向させ、それぞれの配向膜に照射された紫外線の偏光方向が平行になるように、さらに対向する配向膜の間にポジ型液晶組成物を注入させるための空隙を形成して貼り合わせ、セル厚4μmの空FFSセルを組み立てた。作製した空FFSセルに前記ポジ型液晶組成物1を真空注入して、FFS液晶表示素子を作製した。得られた液晶表示素子中の液晶の配向を確認したところ、流動配向は見られなかった。コントラストの値を測定したところ3000であり、AC残像を測定したところΔBは2.3%であった。 <FFS cell preparation, flow orientation confirmation, contrast and AC afterimage measurement>
Two substrates having alignment films formed on the substrates are opposed to each other so that the surfaces on which the alignment films are formed are opposed to each other so that the polarization directions of ultraviolet rays irradiated to the respective alignment films are parallel to each other. A gap for injecting the positive type liquid crystal composition was formed between them and bonded together to assemble an empty FFS cell having a cell thickness of 4 μm. The positive
[合成例A-5]
温度計、攪拌機、原料投入仕込み口および窒素ガス導入口を備えた200mLの褐色四つ口フラスコにDAAB1.4209g、DDBU0.6666g、APDA0.0257gと脱水NMP54.0gを入れ、乾燥窒素気流下攪拌溶解した。次いで、式(10)のテトラカルボン酸二無水物3.8869gさらに脱水NMP20.0gを入れ、室温で24時間攪拌を続けた。この反応溶液にBP20.0gを加えて、ポリマー固形分濃度が6重量%のポリアミック酸溶液を得た。このポリアミック酸溶液をPA-5とする。PA-5に含まれるポリアミック酸の重量平均分子量は11,300であった。 <Synthesis of polyamic acid>
[Synthesis Example A-5]
DAAB1.4209g, DDBU0.6666g, APDA0.0257g and dehydrated NMP54.0g were placed in a 200mL brown four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, and stirred and dissolved under a dry nitrogen stream. did. Next, 3.8869 g of tetracarboxylic dianhydride of the formula (10) and 20.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BP20.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained. This polyamic acid solution is designated as PA-5. The weight average molecular weight of the polyamic acid contained in PA-5 was 11,300.
テトラカルボン酸二無水物、ジアミン、および溶剤組成を変更した以外は、合成例A-5に準拠してポリマー固形分濃度が6重量%のポリアミック酸溶液(PA-6)~(PA-10)を調製した。原料および溶剤の組成をPA-5と共に表6に示す。 [Synthesis Examples A-6 to A-10]
Except for changing the tetracarboxylic dianhydride, diamine, and solvent composition, polyamic acid solutions (PA-6) to (PA-10) having a polymer solids concentration of 6% by weight according to Synthesis Example A-5 Was prepared. Table 6 shows the composition of the raw materials and the solvent together with PA-5.
温度計、攪拌機、原料投入仕込み口および窒素ガス導入口を備えた200mLの褐色四つ口フラスコにAPDA1.9123g、DDE0.8561g、PDA0.3082gおよび脱水NMP54.0gを入れ、乾燥窒素気流下攪拌溶解した。次いで式(2)のテトラカルボン酸二無水物1.0424g、式(4)のテトラカルボン酸二無水物1.7585g、さらに脱水NMP20.0gを入れ、室温で24時間攪拌を続けた。この反応溶液にBP20.0gを加えて、ポリマー固形分濃度が6重量%のポリアミック酸溶液を得た。このポリアミック酸溶液をPB-7とする。PB-7に含まれるポリアミック酸の重量平均分子量は48,000であった。原料および溶剤の組成を表7に示す。 [Synthesis Example B-7]
APDA 1.9123 g, DDE 0.8561 g, PDA 0.3082 g and dehydrated NMP 54.0 g were placed in a 200 mL brown four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, and stirred and dissolved in a dry nitrogen stream. did. Next, 1.0424 g of tetracarboxylic dianhydride of formula (2), 1.7585 g of tetracarboxylic dianhydride of formula (4) and 20.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BP20.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained. This polyamic acid solution is designated as PB-7. The weight average molecular weight of the polyamic acid contained in PB-7 was 48,000. Table 7 shows the composition of the raw materials and the solvent.
[合成例PC-33]
[A]合成例A-5で調製したポリマー固形分濃度6重量%のポリアミック酸溶液(PA-5)と、[B]合成例B-7で調製したポリマー固形分濃度6重量%のポリアミック酸溶液(PB-7)とを、[A]/[B]=3.0/7.0(重量比)で混合した。この混合溶液をさらにNMP/BP/GBL/EDM/BDM/DIBKの溶液にて希釈し、ポリマー固形分濃度4重量%のポリアミック酸溶液をPC-33とした。このとき、希釈に用いた溶剤の組成比(重量比)は、NMP0.067g、BP2.667g、GBL13.60g、EDM15.00g、BDM1.00g、およびDIBK1.00gである。 <Polymer blend>
[Synthesis Example PC-33]
[A] Polyamic acid solution (PA-5) having a polymer solid concentration of 6% by weight prepared in Synthesis Example A-5 and [B] Polyamic acid having a polymer solid concentration of 6% by weight prepared in Synthesis Example B-7 The solution (PB-7) was mixed at [A] / [B] = 3.0 / 7.0 (weight ratio). This mixed solution was further diluted with a solution of NMP / BP / GBL / EDM / BDM / DIBK, and a polyamic acid solution having a polymer solid concentration of 4% by weight was designated as PC-33. At this time, the composition ratio (weight ratio) of the solvent used for dilution is NMP 0.067 g, BP 2.667 g, GBL 13.60 g, EDM 15.00 g, BDM 1.00 g, and DIBK 1.00 g.
[A]ポリアミック酸溶液(PA-5)および(PA-10)から選ばれる1つのポリアミック酸溶液と、[B]ポリアミック酸溶液(PB-7)からなるポリアミック酸溶液を、重量比[A]/[B]=3.0/7.0(重量比)で混合して、さらにポリマー固形分濃度が表8の記載の重量%となるように、各種溶剤により希釈を実施して、ポリアミック酸溶液(PC-34)~(PC-36)を調整した。また、ポリアミック酸(PC-37)~(PC-40)については、ポリアミック酸(PA-6)~(PA-9)から選ばれる1つのポリアミック酸溶液を、ポリマー固形分濃度が表8の記載の重量%となるように、各種溶剤により希釈を実施して、調整した。ポリアミック酸溶液および溶剤の組成比をPC-33と共に表8に示す。 [Synthesis Examples PC-34 to PC-40]
[A] A polyamic acid solution selected from one polyamic acid solution selected from polyamic acid solutions (PA-5) and (PA-10) and a polyamic acid solution consisting of [B] polyamic acid solution (PB-7) are mixed in a weight ratio [A]. /[B]=3.0/7.0 (weight ratio), and further diluted with various solvents so that the polymer solids concentration becomes the weight% shown in Table 8, and polyamic acid Solutions (PC-34) to (PC-36) were prepared. For polyamic acids (PC-37) to (PC-40), one polyamic acid solution selected from polyamic acids (PA-6) to (PA-9) is used, and the polymer solid content concentration is as shown in Table 8. Dilution was carried out with various solvents so as to achieve a weight% of 5%. The composition ratio of the polyamic acid solution and the solvent is shown in Table 8 together with PC-33.
ポリマー固形分濃度4重量%のポリアミック酸溶液(PC-33)に、添加剤(Add.2)をポリマー重量当たり10重量%の割合で添加した。得られたポリアミック酸溶液をPD-5とする。 [Synthesis Example PD-5]
To the polyamic acid solution (PC-33) having a polymer solid concentration of 4% by weight, the additive (Add. 2) was added at a rate of 10% by weight per polymer weight. The resulting polyamic acid solution is designated PD-5.
ポリマー固形分濃度4.0重量%のポリアミック酸溶液(PC-34)~(PC-36)に、添加剤(Add.2)をポリマー重量当たり10重量%の割合で添加した。得られたポリアミック酸溶液をPD-6~PD-8とする。 [Synthesis Examples PD-6 to PD-8]
To the polyamic acid solutions (PC-34) to (PC-36) having a polymer solid concentration of 4.0% by weight, the additive (Add. 2) was added at a ratio of 10% by weight per polymer weight. The obtained polyamic acid solutions are designated PD-6 to PD-8.
ポリマー固形分濃度4.0重量%のポリアミック酸溶液(PC-37)~(PC-40)に添加剤(Add.2)をポリマー重量当たり5重量%の割合で添加した。得られたポリアミック酸溶液をPD-9~PD-12とする。
ポリアミック酸溶液、添加剤および溶剤の組成比をPD-5~PD-8と共に表9に示す。 [Synthesis Examples PD-9 to PD-12]
The additive (Add.2) was added to the polyamic acid solutions (PC-37) to (PC-40) having a polymer solid concentration of 4.0% by weight at a ratio of 5% by weight per polymer weight. The obtained polyamic acid solutions are designated PD-9 to PD-12.
Table 9 shows the composition ratio of the polyamic acid solution, the additive, and the solvent together with PD-5 to PD-8.
<インクジェット吐出性の評価>
ブレンド調整したポリマー固形分濃度4重量%のポリアミック酸溶液(PC-33)を液晶配向剤として、FUJIFILM Dimatix社製インクジェット装置DMP-2831を用いて、60分間連続吐出実験を行った。5本のノズルをモニターで確認し、60分間の連続でノズルの詰りは確認できなった。 [Example 31]
<Evaluation of ink jet discharge properties>
Using a polyamic acid solution (PC-33) having a blended polymer solid concentration of 4% by weight as a liquid crystal aligning agent, a continuous discharge experiment was conducted for 60 minutes using an inkjet apparatus DMP-2831 manufactured by FUJIFILM Dimatix. Five nozzles were confirmed on the monitor, and clogging of the nozzles could not be confirmed for 60 minutes continuously.
さらに、コニカミノルタ製インクジェット装置EB100XY100を用いて、この液晶配向剤をITO付きガラス基板に塗布した。塗布後、180秒間静置し、60℃ホットプレート上で80秒間乾燥させた。その後、塗布基板の観察を行った。面内スジムラは目視確認、エッジの直線性は顕微鏡観察にて、エッジのガタツキを測定することで判断した。その結果、面内スジムラは見られず、均一であった。さらに、顕微鏡で観察したところ、エッジのガタツキは0.2mm以下で、直線性は良好であった。 <In-plane linearity and edge linearity in inkjet printing>
Furthermore, this liquid crystal aligning agent was apply | coated to the glass substrate with ITO using the inkjet apparatus EB100XY100 made from Konica Minolta. After coating, the solution was allowed to stand for 180 seconds and dried on a 60 ° C. hot plate for 80 seconds. Thereafter, the coated substrate was observed. In-plane unevenness was visually confirmed, and edge linearity was determined by measuring edge roughness by microscopic observation. As a result, no in-plane unevenness was observed and it was uniform. Furthermore, when observed with a microscope, the edge roughness was 0.2 mm or less, and the linearity was good.
表8および表9に示すポリアミック酸溶液を液晶配向剤として用いた以外は、実施例29に準じた方法で吐出性、面内スジムラおよびエッジの直線性を評価した。結果を実施例31と共に表10に示す。 [Examples 32-42]
Except that the polyamic acid solutions shown in Table 8 and Table 9 were used as the liquid crystal aligning agent, the ejection properties, in-plane unevenness and edge linearity were evaluated by the method according to Example 29. The results are shown in Table 10 together with Example 31.
2 インク液滴
3 鏡の反射像
4 ノズル詰まりによる不吐出
5 ノズル詰まりによる斜め吐出
6 塗布膜
7 基板
8 エッジのガタツキ DESCRIPTION OF
Claims (11)
- ポリアミック酸およびその誘導体からなる群から選ばれる少なくとも1つの重合体および溶剤を含有する液晶配向剤であって;
前記溶剤が、第1溶剤として、N-メチル-2-ピロリドン、γ-ブチロラクトン、1,3-ジメチル-2-イミダゾリジノン、N-エチル-2-ピロリドンからなる群から選ばれる少なくとも1つ、
第2溶剤として、ブチルセロソルブ、1-ブトキシ-2-プロパノ-ル、ジエチレングリコ-ルエチルメチルエ-テル、ジエチレングリコールプロピルメチルエーテルからなる群から選ばれる少なくとも1つ、
第3溶剤として、ジイソブチルケトン、ジペンチルエーテルからなる群から選ばれる少なくとも1つ、そして、
第4溶剤として、下記式(1)で表される化合物の群から選ばれる少なくとも1つを含有する、液晶配向剤;
The solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone as the first solvent,
As the second solvent, at least one selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether,
As the third solvent, at least one selected from the group consisting of diisobutyl ketone and dipentyl ether, and
A liquid crystal aligning agent containing at least one selected from the group of compounds represented by the following formula (1) as the fourth solvent;
- 第1溶剤の割合が全溶剤重量に対して20~89重量%であり、
第2溶剤の割合が全溶剤重量に対して10~60重量%であり、
第3溶剤の割合が全溶媒重量に対して0.1~15重量%であり、そして、
第4溶剤の割合が全溶剤重量に対して0.1~20重量%である、請求項1に記載の液晶配向剤。 The proportion of the first solvent is 20 to 89% by weight with respect to the total solvent weight,
The proportion of the second solvent is 10 to 60% by weight with respect to the total solvent weight,
The proportion of the third solvent is 0.1 to 15% by weight with respect to the total solvent weight, and
The liquid crystal aligning agent according to claim 1, wherein the ratio of the fourth solvent is 0.1 to 20% by weight based on the total weight of the solvent. - 重合体の合成に用いられるテトラカルボン酸二無水物が、下記式(AN-I)~(AN-VII)で表される化合物の群から選択される少なくとも1つを含有し;
ジアミンが下記式(DI-1)~(DI-16)で表される側鎖を有さないジアミン、下記式(DIH-1)~(DIH-3)で表される側鎖を有さないジヒドラジドおよび下記式(DI-31)~(DI-35)で表される側鎖を有するジアミンの群から選択される少なくとも1つを含有する、請求項1または2に記載の液晶配向剤;
式(AN-VII)において、G10は独立して-O-、-COO-または-OCO-であり、rは独立して0または1であり;
式(DI-3)および式(DI-5)~式(DI-7)において、G21は独立して単結合、-NH-、-NCH3-、-O-、-S-、-S-S-、-SO2-、-CO-、-COO-、-CONCH3-、-CONH-、-C(CH3)2-、-C(CF3)2-、-(CH2)m-、-O-(CH2)m-O-、-N(-Ra)-(CH2)k-N(-Ra)-、-(O-C2H4)m-O-、-O-CH2-C(CF3)2-CH2-O-、-O-CO-(CH2)m-CO-O-、-CO-O-(CH2)m-O-CO-、-(CH2)m-NH-(CH2)m-、-CO-(CH2)k-NH-(CH2)k-、-(NH-(CH2)m) k-NH-、-CO-C3H6-(NH-C3H6)n-CO-、または-S-(CH2)m-S-であり、Raは炭素数1~3のアルキルであり、mは独立して1~12の整数であり、kは1~5の整数であり、nは1または2であり;
式(DI-4)において、sは独立して0~2の整数であり;
式(DI-6)および式(DI-7)において、G22は独立して単結合、-O-、-S-、-CO-、-C(CH3)2-、-C(CF3)2-、-NH-、または炭素数1~10のアルキレンである。式(DI-2)~式(DI-7)中のシクロヘキサン環およびベンゼン環の少なくとも1つの水素は、-F、-Cl、炭素数1~3のアルキル、-OCH3、-OH、-CF3、-CO2H、-CONH2、-NHC6H5、フェニル、またはベンジルで置き換えられてもよく、加えて式(DI-4)においては、ベンゼン環の少なくとも1つの水素は下記式(DI-4-a)~式(DI-4-e)で表される基の群から選ばれる1つで置き換えられていてもよく;上記式中の環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し;
シクロヘキサン環またはベンゼン環への-NH2の結合位置は、G21またはG22の結合位置を除く任意の位置であり;
式(DI-13)において、R23は独立して炭素数1~5のアルキル、炭素数1~5のアルコキシまたは-Clであり、pは独立して0~3の整数であり、qは0~4の整数であり;
式(DI-14)において、環Bは単環の複素環式芳香族基であり、R24は水素、-F、-Cl、炭素数1~6のアルキル、アルコキシ、ビニル、アルキニルであり、qは独立して0~4の整数である。式(DI-15)において、環Cは複素環式芳香族基または複素環式脂肪族基であり;
式(DI-16)において、G24は単結合、炭素数2~6のアルキレンまたは1,4-フェニレンであり、rは0または1であり;
上記式中の環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し;
式(DI-13)~式(DI-16)において、環に結合する-NH2の結合位置は、任意の位置であり;
式(DIH-2)において、環Dはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この基の少なくとも1つの水素はメチル、エチル、またはフェニルで置き換えられてもよく;
式(DIH-3)において、環Eはそれぞれ独立してシクロヘキサン環、またはベンゼン環であり、この基の少なくとも1つの水素はメチル、エチル、またはフェニルで置き換えられてもよく、Yは単結合、炭素数1~20のアルキレン、-CO-、-O-、-S-、-SO2-、-C(CH3)2-、または-C(CF3)2-であり;
式(DIH-2)および式(DIH-3)において、環に結合する-CONHNH2の結合位置は、任意の位置であり;
R25は炭素数3~30のアルキル、フェニル、ステロイド骨格を有する基、または下記の式(DI-31-a)で表される基であり、このアルキルにおいて、少なくとも1つの水素は-Fで置き換えられてもよく、そして少なくとも1つの-CH2-は-O-、-CH=CH-または-C≡C-で置き換えられていてもよく、このフェニルの水素は、-F、-CH3、-OCH3、-OCH2F、-OCHF2、-OCF3、炭素数3~30のアルキルまたは炭素数3~30のアルコキシで置き換えられていてもよく、ベンゼン環に結合する-NH2の結合位置はその環において任意の位置であることを示し、
式(DI-33)におけるベンゼン環の少なくとも1つの水素は、炭素数1~20のアルキルまたはフェニルで置き換えられてもよく;
上記式中の環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し;
式(DI-32)および式(DI-33)において、ベンゼン環に結合する-NH2はその環における結合位置が任意であることを示し;
Diamine does not have a side chain represented by the following formulas (DI-1) to (DI-16), and does not have a side chain represented by any of the following formulas (DIH-1) to (DIH-3) The liquid crystal aligning agent according to claim 1 or 2, comprising at least one selected from the group of dihydrazide and a diamine having a side chain represented by the following formulas (DI-31) to (DI-35);
In formula (AN-VII), G 10 is independently —O—, —COO— or —OCO—, and r is independently 0 or 1;
In Formula (DI-3) and Formula (DI-5) to Formula (DI-7), G 21 is independently a single bond, —NH—, —NCH 3 —, —O—, —S—, —S. —S—, —SO 2 —, —CO—, —COO—, —CONCH 3 —, —CONH—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, — (CH 2 ) m —, —O— (CH 2 ) m —O—, —N (—Ra) — (CH 2 ) k —N (—Ra) —, — (O—C 2 H 4 ) m —O—, —O —CH 2 —C (CF 3 ) 2 —CH 2 —O—, —O—CO— (CH 2 ) m —CO—O—, —CO—O— (CH 2 ) m —O—CO—, — (CH 2 ) m —NH— (CH 2 ) m —, —CO— (CH 2 ) k —NH— (CH 2 ) k —, — (NH— (CH 2 ) m ) k —NH—, —CO -C 3 H 6- ( NH—C 3 H 6 ) n —CO—, or —S— (CH 2 ) m —S—, Ra is alkyl having 1 to 3 carbon atoms, and m is independently an integer of 1 to 12 And k is an integer from 1 to 5 and n is 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In the formula (DI-6) and the formula (DI-7), G 22 is independently a single bond, —O—, —S—, —CO—, —C (CH 3 ) 2 —, —C (CF 3 2 ), -NH-, or alkylene having 1 to 10 carbon atoms. At least one hydrogen of the cyclohexane ring and the benzene ring in formula (DI-2) to formula (DI-7) is —F, —Cl, alkyl having 1 to 3 carbon atoms, —OCH 3 , —OH, —CF 3 , —CO 2 H, —CONH 2 , —NHC 6 H 5 , phenyl, or benzyl, and in Formula (DI-4), at least one hydrogen of the benzene ring is represented by the following formula ( DI-4-a) to (DI-4-e) may be substituted with one selected from the group of groups represented by formula (DI-4-e); the bonding position is fixed to the carbon atom constituting the ring in the above formula An unlabeled group indicates that the position of attachment in the ring is arbitrary;
The bonding position of —NH 2 to the cyclohexane ring or the benzene ring is any position except the bonding position of G 21 or G 22 ;
In the formula (DI-13), R 23 is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer from 0 to 3, and q is An integer from 0 to 4;
In the formula (DI-14), ring B is a monocyclic heteroaromatic group, R 24 is hydrogen, —F, —Cl, C 1-6 alkyl, alkoxy, vinyl, alkynyl, q is independently an integer of 0 to 4. In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group;
In the formula (DI-16), G 24 is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1;
A group whose bonding position is not fixed to the carbon atom constituting the ring in the above formula indicates that the bonding position in the ring is arbitrary;
In formula (DI-13) to formula (DI-16), the bonding position of —NH 2 bonded to the ring is an arbitrary position;
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this group may be replaced by methyl, ethyl or phenyl;
In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl, or phenyl, and Y is a single bond, Alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —;
In Formula (DIH-2) and Formula (DIH-3), the bonding position of —CONHNH 2 bonded to the ring is an arbitrary position;
R 25 is an alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen is —F. And at least one —CH 2 — may be replaced by —O—, —CH═CH— or —C≡C—, and the hydrogen of the phenyl is —F, —CH 3 , —OCH 3 , —OCH 2 F, —OCHF 2, —OCF 3, alkyl having 3 to 30 carbon atoms, or alkoxy having 3 to 30 carbon atoms, and —NH 2 bonded to the benzene ring The bond position is any position in the ring;
At least one hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl or phenyl having 1 to 20 carbon atoms;
A group whose bonding position is not fixed to any carbon atom constituting the ring in the above formula indicates that the bonding position in the ring is arbitrary;
In formula (DI-32) and formula (DI-33), —NH 2 bonded to the benzene ring indicates that the bonding position in the ring is arbitrary;
- 重合体の合成に用いられるテトラカルボン酸二無水物が、下記式(2)~(13)で表される化合物の群から選択される少なくとも1つを含有し;
ジアミンが下記式(D-1)~(D-5)で表される化合物の群から選択される少なくとも1つを含有する、請求項1または2に記載の液晶配向剤。
式(D-4)において、aは1~8の整数であり;
式(D-5)において、Raは炭素数1~3のアルキルであり;そして、
ベンゼン環の少なくとも1つの水素は-CH3で置き換えられていてもよい。 The tetracarboxylic dianhydride used in the synthesis of the polymer contains at least one selected from the group of compounds represented by the following formulas (2) to (13);
3. The liquid crystal aligning agent according to claim 1, wherein the diamine contains at least one selected from the group of compounds represented by the following formulas (D-1) to (D-5).
In the formula (D-4), a is an integer of 1 to 8;
In formula (D-5), Ra is alkyl having 1 to 3 carbons; and
At least one hydrogen of the benzene ring may be replaced with —CH 3 . - ポリアミック酸およびその誘導体が、テトラカルボン酸二無水物およびジアミンの少なくとも1つが光反応性構造を有する原料モノマーを反応させて得られる重合体(a)である、請求項1~4のいずれか1項に記載の液晶配向剤。 5. The polymer according to claim 1, wherein the polyamic acid and its derivative are a polymer (a) obtained by reacting a raw material monomer having at least one of a tetracarboxylic dianhydride and a diamine having a photoreactive structure. A liquid crystal aligning agent according to item.
- ジアミンが4,4’-ジアミノアゾベンゼンを含む、請求項5に記載の液晶配向剤。 6. The liquid crystal aligning agent according to claim 5, wherein the diamine contains 4,4′-diaminoazobenzene.
- 重合体(a)と共に、光反応性構造を有さないテトラカルボン酸二無水物および光反応性構造を有さないジアミンを反応させて得られるポリアミック酸およびその誘導体から選択される少なくとも1つの重合体(b)をさらに含有する、請求項5または6に記載の液晶配向剤。 At least one heavy selected from a polyamic acid obtained by reacting a polymer (a) with a tetracarboxylic dianhydride having no photoreactive structure and a diamine having no photoreactive structure, and a derivative thereof. The liquid crystal aligning agent of Claim 5 or 6 which further contains a union (b).
- 重合体(b)の合成に用いられるテトラカルボン酸二無水物が、下記式(2)~(13)で表される化合物の群から選択される少なくとも1つを含有し;
ジアミンが下記式(D-1)~(D-5)で表される化合物の群から選択される少なくとも1つを含有する、請求項1~7のいずれか1項に記載の液晶配向剤;
式(D-4)において、aは1~8の整数であり;
式(D-5)において、Raは炭素数1~3のアルキルであり;そして、
上記式中のベンゼン環の少なくとも1つの水素は-CH3で置き換えられていてもよい。 The tetracarboxylic dianhydride used for the synthesis of the polymer (b) contains at least one selected from the group of compounds represented by the following formulas (2) to (13);
The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the diamine contains at least one selected from the group of compounds represented by the following formulas (D-1) to (D-5);
In the formula (D-4), a is an integer of 1 to 8;
In formula (D-5), Ra is alkyl having 1 to 3 carbons; and
At least one hydrogen of the benzene ring in the above formula may be replaced by —CH 3 . - オキサジン化合物、オキサゾリン化合物、エポキシ化合物、およびシランカップリング剤からなる化合物の群から選ばれる少なくとも1つをさらに含有する、請求項1~8のいずれか1項に記載の液晶配向剤。 The liquid crystal aligning agent according to any one of claims 1 to 8, further comprising at least one selected from the group consisting of an oxazine compound, an oxazoline compound, an epoxy compound, and a silane coupling agent.
- 請求項1~9のいずれか1項に記載の液晶配向剤によって形成された液晶配向膜。 A liquid crystal alignment film formed of the liquid crystal aligning agent according to any one of claims 1 to 9.
- 請求項10に記載の液晶配向膜を有する液晶表示素子。 A liquid crystal display element having the liquid crystal alignment film according to claim 10.
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WO2018155355A1 (en) * | 2017-02-24 | 2018-08-30 | シャープ株式会社 | Liquid crystal alignment agent, alignment film, and liquid crystal display device |
KR20200058281A (en) | 2018-11-19 | 2020-05-27 | 제이엔씨 주식회사 | Liquid crystal aligning agents for forming liquid crystal alignment films, liquid crystal alignment films and liquid crystal display devices using the same |
KR20220066246A (en) | 2019-09-24 | 2022-05-24 | 닛산 가가쿠 가부시키가이샤 | A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element |
KR20220166817A (en) | 2020-04-10 | 2022-12-19 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
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JP7188381B2 (en) * | 2017-03-31 | 2022-12-13 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009063797A (en) * | 2007-09-06 | 2009-03-26 | Seiko Epson Corp | Composition for forming alignment layer and method for manufacturing liquid crystal device |
JP2009080454A (en) * | 2007-09-06 | 2009-04-16 | Seiko Epson Corp | Composition for forming alignment film and method for manufacturing liquid crystal device |
JP2009080156A (en) * | 2007-09-25 | 2009-04-16 | Seiko Epson Corp | Composition for forming liquid crystal alignment layer, and method of manufacturing liquid crystal display device |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2009093709A1 (en) * | 2008-01-25 | 2009-07-30 | Nissan Chemical Industries, Ltd. | Liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element |
JP6056187B2 (en) * | 2012-05-09 | 2017-01-11 | Jnc株式会社 | Liquid crystal alignment agent, liquid crystal alignment film for forming liquid crystal alignment film for photo-alignment, and liquid crystal display element using the same |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009063797A (en) * | 2007-09-06 | 2009-03-26 | Seiko Epson Corp | Composition for forming alignment layer and method for manufacturing liquid crystal device |
JP2009080454A (en) * | 2007-09-06 | 2009-04-16 | Seiko Epson Corp | Composition for forming alignment film and method for manufacturing liquid crystal device |
JP2009080156A (en) * | 2007-09-25 | 2009-04-16 | Seiko Epson Corp | Composition for forming liquid crystal alignment layer, and method of manufacturing liquid crystal display device |
Cited By (7)
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WO2018062353A1 (en) * | 2016-09-29 | 2018-04-05 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
JPWO2018062353A1 (en) * | 2016-09-29 | 2019-07-25 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display device |
JP7063270B2 (en) | 2016-09-29 | 2022-05-09 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
WO2018155355A1 (en) * | 2017-02-24 | 2018-08-30 | シャープ株式会社 | Liquid crystal alignment agent, alignment film, and liquid crystal display device |
KR20200058281A (en) | 2018-11-19 | 2020-05-27 | 제이엔씨 주식회사 | Liquid crystal aligning agents for forming liquid crystal alignment films, liquid crystal alignment films and liquid crystal display devices using the same |
KR20220066246A (en) | 2019-09-24 | 2022-05-24 | 닛산 가가쿠 가부시키가이샤 | A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element |
KR20220166817A (en) | 2020-04-10 | 2022-12-19 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
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