WO2013073636A1 - Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- WO2013073636A1 WO2013073636A1 PCT/JP2012/079700 JP2012079700W WO2013073636A1 WO 2013073636 A1 WO2013073636 A1 WO 2013073636A1 JP 2012079700 W JP2012079700 W JP 2012079700W WO 2013073636 A1 WO2013073636 A1 WO 2013073636A1
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- 0 *C(CC1)CCC1c(cc1)ccc1-c(cc1)ccc1O* Chemical compound *C(CC1)CCC1c(cc1)ccc1-c(cc1)ccc1O* 0.000 description 4
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Definitions
- the present invention relates to a liquid crystal alignment agent containing polysiloxane obtained by hydrolysis and polycondensation of alkoxysilane, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
- the VA method includes an MVA method (Multi Vertical Alignment) in which protrusions for controlling the direction in which the liquid crystal is tilted are formed on the TFT substrate or the color filter substrate, and a direction in which the liquid crystal is tilted by an electric field by forming a slit in the ITO electrode of the substrate.
- MVA method Multi Vertical Alignment
- a PVA (Patterned Vertical Alignment) system to be controlled is known.
- PSA Polymer Sustained Alignment
- the PSA system is a technology that has attracted attention in recent years.
- a photopolymerizable compound is added to a liquid crystal, and after the liquid crystal panel is produced, an electric field is applied to irradiate the liquid crystal panel with UV in a state where the liquid crystal falls down.
- the polymerizable compound is photopolymerized to fix the alignment direction of the liquid crystal, causing a pretilt and improving the response speed. It is possible to operate with a structure in which a slit is made in one electrode constituting the liquid crystal panel, and the electrode pattern on the opposite side is not provided with a protrusion such as MVA or a slit such as PVA, and the manufacturing is simplified and excellent.
- a liquid crystal alignment agent using a polymer in which a photoreactive side chain is introduced into a polymer molecule is applied to a substrate, and a liquid crystal layer in contact with the liquid crystal alignment film obtained by baking is provided.
- a technique capable of obtaining a liquid crystal display element having a high response speed without adding a polymerizable compound to the liquid crystal by producing a liquid crystal display element by irradiating ultraviolet rays while applying a voltage.
- inorganic liquid crystal alignment film materials are also known along with conventionally used organic liquid crystal alignment film materials such as polyimide.
- Japanese Unexamined Patent Publication No. 2004-302061 Japanese Unexamined Patent Publication No. 2011-95697 Japanese Unexamined Patent Publication No. 09-281502
- the object of the present invention is to use a liquid crystal to which no polymerizable compound is added, and also in a liquid crystal display element of a method that improves the response speed after UV irradiation by treating in the same manner as the PSA method, without reducing the vertical alignment force,
- a liquid crystal alignment agent capable of forming a liquid crystal alignment film capable of improving the response speed after UV irradiation, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. is there.
- R 1 Si (OR 2 ) 3 (1) R 1 represents the structure of the following formula (2), and R 2 represents an alkyl group having 1 to 5 carbon atoms.
- Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—.
- Y 2 is a single bond, a divalent hydrocarbon radical straight or branched double bonds to 3 carbon atoms containing 8 or (CR 17 R 18) b - (b is 1 to 15
- each of R 17 and R 18 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- Y 3 is a single bond, — (CH 2 ) c — (c is 1 to 3 ).
- Y 4 is a divalent group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a heterocyclic ring.
- a cyclic group or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and any hydrogen atom on these cyclic groups has 1 to Substituted with one selected from the group consisting of 3 alkyl groups, 1 to 3 carbon alkoxy groups, 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxy groups, and fluorine atoms.
- Y 5 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 to 3 carbon atoms.
- Y 6 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.
- R 3 Si (OR 4 ) 3 (3) (R 3 is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group. R 4 represents an alkyl group having 1 to 5 carbon atoms.)
- Si (OR 15 ) 4 (5) R 15 represents an alkyl group having 1 to 5 carbon atoms.
- [3] The liquid crystal alignment according to the above [2], wherein the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (3). Agent.
- the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (6).
- the liquid crystal aligning agent of description R 16 Si (OR 17 ) 3 (6) (R 16 is an alkyl group having 1 to 5 carbon atoms. R 17 represents an alkyl group having 1 to 5 carbon atoms.)
- At least one of polysiloxane (A) and polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (4):
- the liquid crystal aligning agent according to any one of the above [2] to [4].
- R 13 represents a carbon atom having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group.
- R 14 is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.
- the alkoxysilane represented by the formula (1) is contained in an amount of 2 to 20 mol% in the total alkoxysilane used in the polysiloxane (A), and the alkoxysilane represented by the formula (3)
- [7] The liquid crystal alignment according to any one of [1] to [6], further containing a solvent and having a total polysiloxane content of 0.5 to 15% by weight in terms of SiO 2 Agent.
- a liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of [1] to [7] to a substrate, drying and baking.
- a liquid crystal display device having the liquid crystal alignment film according to [8].
- the liquid crystal aligning agent according to any one of the above [1] to [7] is applied, and UV is irradiated in a state where a voltage is applied to a liquid crystal cell in which the liquid crystal is sandwiched between two baked substrates. Liquid crystal display element.
- a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film can be provided.
- polysiloxane (A) Polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (3).
- R 1 Si (OR 2 ) 3 (1) R 1 represents a structure of the following formula (2), R 2 represents an alkyl group having 1 to 5 carbon atoms.
- R 3 Si (OR 4 ) 3 (3) (R 3 is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group. R 4 represents an alkyl group having 1 to 5 carbon atoms.)
- this invention is invention about the liquid crystal aligning agent containing polysiloxane (A) and the following polysiloxane (B).
- Si (OR 15 ) 4 (5) (R 15 represents an alkyl group having 1 to 5 carbon atoms.)
- the polysiloxane (A) contained in the liquid crystal aligning agent of the present invention hydrolyzes and polycondenses the alkoxysilane containing the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3). It is a polysiloxane obtained.
- R 1 Si (OR 2 ) 3 (1) R 1 represents the structure of the following formula (2), and R 2 represents an alkyl group having 1 to 5 carbon atoms.
- R 3 Si (OR 4 ) 3 (3) (R 3 is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group.
- R 4 represents an alkyl group having 1 to 5 carbon atoms.
- R 1 (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by the formula (1) represents a structure represented by the above formula (2).
- Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. Either. Of these, Y 1 is a single bond, - (CH 2) a - (a is an integer of 1 ⁇ 15), - O - , - CH 2 O- or COO- selecting any of the Is preferable from the viewpoint of facilitating the synthesis of the side chain structure. Y 1 can be selected from a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O—, or COO—. More preferred. Y 1 is particularly preferably a single bond or (CH 2 ) a- (a is an integer of 1 to 10).
- Y 2 is a straight or branched divalent hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or (CR 17 R 18 ) b- (b is R is an integer of 1 to 15, and R 17 and R 18 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- Y 2 is preferably — (CH 2 ) b — (b is an integer of 1 to 10) from the viewpoint of significantly improving the response speed of the liquid crystal display element.
- Y 2 is also preferable a single bond.
- Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. Either. Among them, Y 3 is a single bond, — (CH 2 ) c — (where c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. It is preferable to select from the viewpoint of facilitating the synthesis of the side chain structure. Y 3 represents a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO— or OCO—. More preferably, it is selected. Y 3 is particularly preferably a single bond or O—.
- Y 4 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 to May be substituted by any one of an alkyl group having 3 atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom .
- Y 4 may be a divalent organic group selected from an organic group having a carbon number of 12 to 25 having a steroid skeleton.
- Y 4 is preferably an organic group having 12 to 25 carbon atoms having any one of a benzene ring, a cyclohexyl ring, and a steroid skeleton.
- Y 4 is particularly preferably a divalent cyclic group consisting of a benzene ring.
- Y 5 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has a carbon number of 1 to May be substituted with any one of an alkyl group having 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom .
- Y 5 is particularly preferably a divalent cyclic group consisting of a cyclohexyl ring.
- n is an integer of 0-4.
- it is an integer of 0 to 2, and 1 is particularly preferable.
- Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.
- Y 6 represents any of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 10 carbon atoms.
- Y 6 is more preferably any one of an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Y 6 is more preferably any one of an alkyl group having 1 to 9 carbon atoms and an alkoxy group having 1 to 9 carbon atoms. Y 6 is particularly preferably an alkyl group having 1 to 9 carbon atoms.
- R 2 of the alkoxysilane represented by the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, R 2 is a methyl group or an ethyl group.
- Such an alkoxysilane represented by the formula (1) can be synthesized by a known synthesis method (Japanese Patent Laid-Open No. 61-286393). Although the specific example is given to the following, it is not limited to this.
- R 5 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or CH 2 OCO—
- R 6 represents carbon.
- R 7 represents a single bond, -COO -, - OCO -, - COOCH 2 -, - CH 2 OCO -, - (CH 2) n O- ( n represents an integer of 1 to 5), represents —OCH 2 — or CH 2 —, and R 8 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
- R 9 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, — CH 2 -or O- represents R 10 is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.
- R 11 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
- R 12 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
- B 4 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
- B 3 is a 1,4-cyclohexylene group or a 1,4-phenylene group.
- B 2 is an oxygen atom or COO- * (where a bond marked with "*" is bonded to B 3 )
- B 1 is an oxygen atom or COO- * (where "*" is The bond attached is bonded to (CH 2 ) a 2 ).
- a 1 is an integer of 0 or 1
- a 2 is an integer of 2 to 10
- a 3 is an integer of 0 or 1.
- One or two of the above compounds may be used depending on properties such as solubility in a solvent when used as a siloxane polymer, alignment properties of liquid crystal when used as a liquid crystal alignment film, pretilt angle characteristics, voltage holding ratio, accumulated charge, and the like.
- a mixture of more than one can also be used. Further, it can be used in combination with an alkoxysilane containing a long-chain alkyl group having 10 to 18 carbon atoms.
- the alkoxysilane represented by the formula (1) having the specific organic group described above can be produced by a known method.
- the alkoxysilane represented by the formula (1) having the specific organic group described above is preferably 2 mol% or more in order to obtain good liquid crystal alignment in all alkoxysilanes used for obtaining polysiloxane. More preferably, the alkoxysilane represented by Formula (1) is 3 mol% or more. Further, the alkoxysilane represented by the formula (1) is preferably 20 mol% or less in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed. More preferably, it is 15 mol% or less.
- R 3 of the alkoxysilane represented by the formula (3) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
- the alkoxysilane represented by the formula (3) is preferably 5 mol% or more in order to obtain a good liquid crystal response speed in all alkoxysilanes used for obtaining the polysiloxane.
- the alkoxysilane represented by the formula (3) is more preferably 10 mol% or more, still more preferably 20 mol% or more, preferably 70 mol% or less, more preferably 50 mol% or less.
- the effects of the present invention are intended for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules.
- one or more alkoxysilanes represented by the following formula (4) may be used. Since the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, one or more types can be selected and used according to the required properties.
- R 13 represents a carbon atom having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group.
- R 14 is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 and n is 0 to 3 and preferably represents an integer of 0 to 2.
- R 13 of the alkoxysilane represented by the formula (4) is a hydrogen atom or an organic group having 1 to 10 carbon atoms (hereinafter also referred to as a third organic group).
- the third organic group include aliphatic hydrocarbons; ring structures such as aliphatic rings, aromatic rings and heterocycles; unsaturated bonds; and heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms.
- the organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.
- alkoxysilane represented by the formula (4) are given below, but are not limited thereto.
- 3- (2-aminoethylaminopropyl) trimethoxysilane 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) Triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethy
- the alkoxysilane in which n is 0 is tetraalkoxysilane.
- Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formulas (1) and (3).
- tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
- the alkoxysilane represented by the formula (1) is preferably contained in 2 to 20 mol%, particularly preferably 3 to 15 mol% in the total alkoxysilane used in the production of the polysiloxane (A).
- the alkoxysilane represented by the formula (3) is preferably contained in an amount of 5 to 70 mol%, particularly preferably 10 to 50 mol%, based on the total alkoxysilane used in the production of the polysiloxane (A).
- the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing 50 to 100 mol% of the alkoxysilane represented by the formula (5).
- Si (OR 15 ) 4 (5) (R 15 represents an alkyl group having 1 to 5 carbon atoms.)
- R 15 represents an alkyl group having 1 to 5 carbon atoms.
- tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
- the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (3) in addition to the alkoxysilane represented by the formula (5). There may be.
- the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (6) in addition to the alkoxysilane represented by the formula (5).
- R 16 Si (OR 17 ) 3 (6) R 16 is an alkyl group having 1 to 5 carbon atoms.
- R 17 represents an alkyl group having 1 to 5 carbon atoms.
- R 16 of the alkoxysilane represented by the formula (6) is an alkyl group having 1 to 5 carbon atoms.
- the alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.
- R 17 of the alkoxysilane represented by the formula (6) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
- the specific example of the alkoxysilane represented by Formula (6) is given, it is not limited to these.
- methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxysilane in addition to the alkoxysilane represented by the formula (5), it further contains a polysiloxane (B) obtained by hydrolysis and polycondensation of an alkoxysilane containing the alkoxysilane represented by the formula (6).
- a liquid crystal aligning agent is desirable because it has a high vertical alignment force.
- the alkoxysilane to be used is preferably 10 mol% or more in all alkoxysilanes used for obtaining the polysiloxane. More preferably, it is 20 mol% or more. More preferably, it is 30 mol% or more. Moreover, in order to fully harden the liquid crystal aligning film formed, 75 mol% or less is preferable.
- the production of the polysiloxane (B) is intended to improve adhesion with the substrate and affinity with the liquid crystal molecules.
- one or more alkoxysilanes represented by the above formula (4) can be used. Since the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, one or more types can be selected and used according to the required properties.
- liquid crystal aligning agent which mixed polysiloxane (A) and polysiloxane (B)
- about the mixing ratio of polysiloxane (A) and polysiloxane (B), (A) and ( The weight ratio of B) is preferably 10:90 to 50:50.
- the method for obtaining the polysiloxane used in the present invention is not particularly limited.
- the polysiloxane (A) of the present invention is obtained by condensing an alkoxysilane having the above-described formulas (1) and (3) as essential components in an organic solvent.
- polysiloxane is obtained as a solution in which such alkoxysilane is hydrolyzed and polycondensed to be uniformly dissolved in an organic solvent.
- Examples of the method for hydrolyzing and polycondensing polysiloxane include a method for hydrolyzing and polycondensing alkoxysilane in a solvent such as alcohol or glycol.
- the hydrolysis / polycondensation reaction may be either partial hydrolysis or complete hydrolysis.
- complete hydrolysis theoretically, it is sufficient to add 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water more than 0.5 times mole.
- the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
- acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc.
- Catalysts such as alkali; metal salts of acids such as hydrochloric acid, sulfuric acid, and nitric acid; are used.
- a method of heating and hydrolyzing / polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the alkoxysilane is mixed while the solution is heated. In that case, the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C.
- it is a method of heating for several tens of minutes to several tens of hours under reflux so that evaporation or volatilization of the liquid does not occur.
- obtaining multiple types of alkoxysilane when obtaining polysiloxane you may mix as a mixture which mixed alkoxysilane beforehand, and may mix multiple types of alkoxysilane sequentially.
- the solvent used when hydrolyzing and polycondensing alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it dissolves alkoxysilane.
- Such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1 , 5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, and other glycols: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether Ethylene glycol monobutyl ether
- the polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). ) Is preferably 20% by weight or less, more preferably 5 to 15% by weight. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
- the polymerization solution obtained by the above method may be used as a polysiloxane solution as it is, or if necessary, the solution obtained by the above method may be concentrated or diluted by adding a solvent. Or may be substituted with another solvent to form a polysiloxane solution.
- the solvent to be used hereinafter also referred to as additive solvent
- the additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used.
- Such an additive solvent include, in addition to the solvents mentioned as examples of the polymerization solvent described above, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate. Can be mentioned. These solvents can improve the applicability when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, ink jetting or the like.
- other components other than polysiloxane such as inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, and surfactants are included as long as the effects of the present invention are not impaired. May be.
- the inorganic fine particles fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in the state of a colloidal solution are particularly preferable.
- This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution.
- the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions.
- the inorganic fine particles preferably have an average particle size of 0.001 to 0.2 ⁇ m, more preferably 0.001 to 0.1 ⁇ m. When the average particle diameter of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured film formed using the prepared coating liquid may be lowered.
- the dispersion medium for the inorganic fine particles include water and organic solvents.
- the colloidal solution it is preferable that the pH or pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating solution for forming a film. More preferably, it is 2-7.
- organic solvent used for the dispersion medium of the colloidal solution examples include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion
- metalloxane oligomer and metalloxane polymer single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used.
- the metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, or carboxylate by a conventional method such as hydrolysis.
- metalloxane oligomers and metalloxane polymers include siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, SS-101 manufactured by Colcoat Co.
- examples thereof include titanoxane oligomers such as polymers and titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
- a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.
- the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.
- the liquid crystal aligning agent of the present invention is a solution containing the above-described polysiloxane and, if necessary, other components.
- the solvent a solvent selected from the group consisting of the above-mentioned polysiloxane polymerization solvent and additive solvent is used.
- the content of polysiloxane in the liquid crystal aligning agent is preferably 0.5 to 15% by weight, more preferably 1 to 6% by weight in terms of SiO 2 concentration. Be in the range of such terms of SiO 2 concentration, easy to obtain a desired film thickness by a single coating, easy pot life sufficient solution is obtained.
- the method for preparing the liquid crystal aligning agent of the present invention is not particularly limited.
- the polysiloxane used in the present invention may be in a state where other components added as necessary are uniformly mixed. Since polysiloxane is usually hydrolyzed and polycondensed in a solvent, it is convenient to use the polysiloxane solution as it is or to add other components to the polysiloxane solution as necessary. Furthermore, the most convenient method is to use the polysiloxane polymerization solution as it is. Moreover, when adjusting content of polysiloxane in a liquid crystal aligning agent, the solvent chosen from the group which consists of the polymerization solvent and addition solvent of the polysiloxane mentioned above can be used.
- the liquid crystal aligning film of this invention is obtained using the liquid crystal aligning agent of this invention.
- the cured film obtained by drying and baking can also be used as a liquid crystal aligning film as it is.
- the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, processed with an ion beam, etc., or irradiated with UV in a state where a voltage is applied to the liquid crystal display element after filling the liquid crystal. It is also possible.
- the substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate is preferable.
- glass plate polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, tri
- a substrate in which a transparent electrode is formed on a plastic plate such as acetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose.
- Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, ink jet, spraying, roll coating, and the like.In terms of productivity, the transfer printing method is widely used industrially.
- the present invention is also preferably used.
- the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, a drying process is included. Is preferred.
- the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.
- the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
- the firing temperature can be any temperature of 100 ° C. to 350 ° C., preferably 140 ° C. to 300 ° C., more preferably 150 ° C. to 230 ° C., and further preferably 160 ° C. to 220 ° C. It is. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. The time is preferably 10 to 90 minutes, more preferably 20 to 80 minutes.
- a generally known method such as a hot plate, a hot air circulation oven, an IR oven, a belt furnace, or the like can be used.
- the polysiloxane in the liquid crystal alignment film undergoes polycondensation in the firing step.
- firing is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the liquid crystal cell production process, such as curing of the sealant.
- the thickness of the cured film can be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more, because the reliability of the liquid crystal display element can be easily obtained.
- the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is suitable.
- the liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then preparing a liquid crystal cell by a known method.
- a method is generally employed in which a pair of substrates on which a liquid crystal alignment film is formed are fixed with a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed.
- the size of the spacer used is 1 to 30 ⁇ m, preferably 2 to 10 ⁇ m.
- the method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting liquid crystal after the inside of the manufactured liquid crystal cell is decompressed, and a dropping method for sealing after dropping the liquid crystal.
- the voltage to be applied is AC 5 to 50 Vp-p or DC 5 to 30 V, but is preferably 5 to 30 Vp-p or DC 5 to 20 V.
- the UV irradiation amount to be irradiated is 1 to 60 J using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp or the like, but is preferably 40 J or less, and a smaller UV irradiation amount constitutes a liquid crystal display. It is preferable because a reduction in reliability due to the destruction of the member can be suppressed, and the manufacturing tact can be increased by reducing the UV irradiation time.
- the substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate.
- a specific example is the same as the substrate described in [Liquid crystal alignment film].
- Standard electrode patterns such as PVA and MVA and protrusion patterns can also be used. Similar to the PSA type liquid crystal display, it can be operated even in a structure in which a line / slit electrode pattern of 1 to 10 ⁇ m is formed on one side substrate and no slit pattern or protrusion pattern is formed on the opposite substrate.
- the liquid crystal display can simplify the manufacturing process and provide high transmittance.
- a high-performance element such as a TFT element
- an element in which a transistor element is formed between an electrode for driving a liquid crystal and a substrate is used.
- a transmissive liquid crystal element it is common to use a substrate as described above.
- a reflective liquid crystal display element a material such as aluminum that reflects light only on one substrate may be used. It is possible to use an opaque substrate such as a silicon wafer.
- TEOS tetraethoxysilane
- C18 octadecyltriethoxysilane
- MPMS 3-methacryloxypropyltrimethoxysilane
- M8MS 3-methacryloxyoctyltrimethoxysilane
- MTES methyltriethoxysilane
- HG 2-methyl-2,4-pentanediol ( (Alternative name: hexylene glycol)
- BCS 2-butoxyethanol UPS: 3-ureidopropyltriethoxysilane
- a solution of alkoxysilane monomer was prepared by mixing 4.2 g of HG 22.6 g, BCS 7.5 g, TEOS 39.2 g, and C18 in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube.
- a solution prepared by previously mixing 11.3 g of HG, 3.8 g of BCS, 10.8 g of water and 0.2 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes.
- Example 1 The liquid crystal aligning agent [K1] obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ 300 microns and a line / space of 5 microns was formed. did. After drying for 2 minutes on an 80 ° C. hot plate, baking was performed in a hot air circulation oven at 200 ° C. or 220 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. The liquid crystal aligning agent [K1] obtained in Example Synthesis Example 1 was spin-coated on the ITO surface on which no electrode pattern was formed, dried on a hot plate at 80 ° C. for 2 minutes, and then 200 ° C.
- a liquid crystal cell was prepared by injecting the liquid crystal MLC-6608 (trade name, manufactured by Merck) into the empty cell by vacuum injection. The response speed characteristics of these liquid crystal cells were measured by the method described later.
- Example 2> A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K2] obtained in Example of Synthesis Example 2, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
- Example 3> A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K3] obtained in Example Synthesis Example 3, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
- ⁇ Comparative Example 1> A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L1] obtained in Comparative Synthesis Example 1, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
- ⁇ Comparative example 2> A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L2] obtained in Comparative Synthesis Example 2, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
- the liquid crystal display element produced using the liquid crystal aligning agent of the present invention is a liquid crystal display element of a system that improves the response speed after UV irradiation by using a liquid crystal to which a polymerizable compound is not added and treating in the same manner as the PSA system.
- a liquid crystal alignment agent capable of forming a liquid crystal alignment film capable of improving the response speed after UV irradiation without reducing the vertical alignment force, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and the liquid crystal alignment film The liquid crystal display element which has can be provided. Therefore, it is useful for a TFT liquid crystal display device, a TN liquid crystal display device, a VA liquid crystal display device and the like manufactured by the above method. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-251377 filed on November 17, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.
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Abstract
Description
しかし、この方式の液晶表示素子においては、液晶に添加する重合性化合物の溶解性が低く、その添加量を増やすと低温時に析出するという問題がある。またその一方で、重合性化合物の添加量を減らすと良好な配向状態、応答速度が得られなくなる。また、液晶中に残留する未反応の重合性化合物は液晶中の不純物となり、液晶表示素子の信頼性を低下させるという問題もある。 In recent years, among liquid crystal display element display methods, vertical (VA) liquid crystal display elements are widely used for large-screen liquid crystal televisions and high-definition mobile applications (display units of digital cameras and mobile phones). . The VA method includes an MVA method (Multi Vertical Alignment) in which protrusions for controlling the direction in which the liquid crystal is tilted are formed on the TFT substrate or the color filter substrate, and a direction in which the liquid crystal is tilted by an electric field by forming a slit in the ITO electrode of the substrate. A PVA (Patterned Vertical Alignment) system to be controlled is known. As another orientation method, there is a PSA (Polymer Sustained Alignment) method. Among VA systems, the PSA system is a technology that has attracted attention in recent years. In this method, a photopolymerizable compound is added to a liquid crystal, and after the liquid crystal panel is produced, an electric field is applied to irradiate the liquid crystal panel with UV in a state where the liquid crystal falls down. As a result, the polymerizable compound is photopolymerized to fix the alignment direction of the liquid crystal, causing a pretilt and improving the response speed. It is possible to operate with a structure in which a slit is made in one electrode constituting the liquid crystal panel, and the electrode pattern on the opposite side is not provided with a protrusion such as MVA or a slit such as PVA, and the manufacturing is simplified and excellent. The panel transmittance is obtained. (See Patent Document 1.)
However, in this type of liquid crystal display element, the solubility of the polymerizable compound added to the liquid crystal is low, and there is a problem that when the addition amount is increased, it precipitates at a low temperature. On the other hand, when the addition amount of the polymerizable compound is reduced, a good alignment state and response speed cannot be obtained. Further, the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity in the liquid crystal, and there is a problem that the reliability of the liquid crystal display element is lowered.
一方、従来から用いられているポリイミド等の有機系の液晶配向膜材料と共に、無機系の液晶配向膜材料も知られている。例えば、塗布型の無機系配向膜の材料として、テトラアルコキシシランと、トリアルコキシシランと、アルコール及び蓚酸との反応生成物を含有する配向剤組成物が提案され、液晶表示素子の電極基板上で垂直配向性、耐熱性及び均一性に優れる液晶配向膜を形成することが報告されている。(特許文献3参照。) Therefore, a liquid crystal alignment agent using a polymer in which a photoreactive side chain is introduced into a polymer molecule is applied to a substrate, and a liquid crystal layer in contact with the liquid crystal alignment film obtained by baking is provided. There has been proposed a technique capable of obtaining a liquid crystal display element having a high response speed without adding a polymerizable compound to the liquid crystal by producing a liquid crystal display element by irradiating ultraviolet rays while applying a voltage. (See Patent Document 2)
On the other hand, inorganic liquid crystal alignment film materials are also known along with conventionally used organic liquid crystal alignment film materials such as polyimide. For example, as a material for a coating-type inorganic alignment film, an alignment agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid has been proposed. It has been reported that a liquid crystal alignment film excellent in vertical alignment, heat resistance and uniformity is formed. (See Patent Document 3)
〔1〕下記のポリシロキサン(A)を含有する液晶配向剤。
ポリシロキサン(A):式(1)で表されるアルコキシシラン及び式(3)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサン。
R1Si(OR2)3 (1)
(R1は下記式(2)の構造を表し、R2は炭素数1~5のアルキル基を表す。) The gist of the present invention is as follows.
[1] A liquid crystal aligning agent containing the following polysiloxane (A).
Polysiloxane (A): Polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (3).
R 1 Si (OR 2 ) 3 (1)
(R 1 represents the structure of the following formula (2), and R 2 represents an alkyl group having 1 to 5 carbon atoms.)
R3Si(OR4)3 (3)
(R3は、アクリル基、アクリロキシ基、メタクリル基、メタクリロキシ基、又はスチリル基で置換された炭素数5~10のアルキル基である。R4は炭素数1~5のアルキル基を表す。)
R 3 Si (OR 4 ) 3 (3)
(R 3 is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group. R 4 represents an alkyl group having 1 to 5 carbon atoms.)
ポリシロキサン(B):式(5)で表されるアルコキシシランを50~100モル%含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサン。
Si(OR15)4 (5)
(R15は炭素数1~5のアルキル基を表す。)
〔3〕ポリシロキサン(B)が、さらに式(3)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサンである、上記〔2〕に記載の液晶配向剤。
〔4〕ポリシロキサン(B)が、さらに式(6)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサンである、上記〔2〕又は〔3〕に記載の液晶配向剤。
R16Si(OR17)3 (6)
(R16は、炭素数1~5のアルキル基である。R17は炭素数1~5のアルキル基を表す。) [2] The liquid crystal aligning agent according to the above [1], further comprising a polysiloxane (B).
Polysiloxane (B): polysiloxane obtained by hydrolysis and polycondensation of alkoxysilane containing 50 to 100 mol% of alkoxysilane represented by formula (5).
Si (OR 15 ) 4 (5)
(R 15 represents an alkyl group having 1 to 5 carbon atoms.)
[3] The liquid crystal alignment according to the above [2], wherein the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (3). Agent.
[4] In the above [2] or [3], the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (6). The liquid crystal aligning agent of description.
R 16 Si (OR 17 ) 3 (6)
(R 16 is an alkyl group having 1 to 5 carbon atoms. R 17 represents an alkyl group having 1 to 5 carbon atoms.)
(R13)nSi(OR14)4-n (4)
(式(4)中、R13は、水素原子、又はヘテロ原子、ハロゲン原子、アミノ基、グリシドキシ基、メルカプト基、イソシアネート基、ウレイド基で置換されていてもよい、炭素数1~10の炭化水素基である。R14は炭素数1~5のアルキル基である。nは0~3の整数を表す。)
〔6〕前記式(1)で表されるアルコキシシランが、ポリシロキサン(A)に用いられる全アルコキシシラン中、2~20モル%含まれ、かつ前記式(3)で表されるアルコキシシランが、ポリシロキサン(A)に用いられる全アルコキシシラン中、5~70モル%含まれる上記〔1〕~〔5〕のいずれかに記載の液晶配向剤。
〔7〕さらに、溶媒を含有し、かつ全ポリシロキサンの含有量が、SiO2換算で、0.5~15重量%である、上記〔1〕~〔6〕のいずれかに記載の液晶配向剤。
〔8〕上記〔1〕~〔7〕のいずれかに記載の液晶配向剤を基板に塗布し、乾燥、焼成して得られる液晶配向膜。
〔9〕上記〔8〕に記載の液晶配向膜を有する液晶表示素子。
〔10〕上記〔1〕~〔7〕のいずれかに記載の液晶配向剤を塗布し、焼成された2枚の基板で液晶が挟持された液晶セルに、電圧を印加した状態でUVを照射した液晶表示素子。
〔11〕上記〔1〕~〔7〕のいずれかに記載の液晶配向剤を塗布し、焼成した2枚の基板で液晶を挟持し、電圧を印加した状態でUVを照射する液晶表示素子の製造方法。 [5] At least one of polysiloxane (A) and polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (4): The liquid crystal aligning agent according to any one of the above [2] to [4].
(R 13 ) n Si (OR 14 ) 4-n (4)
(In the formula (4), R 13 represents a carbon atom having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. A hydrogen group, R 14 is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.)
[6] The alkoxysilane represented by the formula (1) is contained in an amount of 2 to 20 mol% in the total alkoxysilane used in the polysiloxane (A), and the alkoxysilane represented by the formula (3) The liquid crystal aligning agent according to any one of the above [1] to [5], which is contained in 5 to 70 mol% in all alkoxysilanes used in the polysiloxane (A).
[7] The liquid crystal alignment according to any one of [1] to [6], further containing a solvent and having a total polysiloxane content of 0.5 to 15% by weight in terms of SiO 2 Agent.
[8] A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of [1] to [7] to a substrate, drying and baking.
[9] A liquid crystal display device having the liquid crystal alignment film according to [8].
[10] The liquid crystal aligning agent according to any one of the above [1] to [7] is applied, and UV is irradiated in a state where a voltage is applied to a liquid crystal cell in which the liquid crystal is sandwiched between two baked substrates. Liquid crystal display element.
[11] A liquid crystal display element in which the liquid crystal aligning agent according to any one of [1] to [7] is applied, the liquid crystal is sandwiched between two baked substrates, and UV is irradiated in a state where a voltage is applied. Production method.
本発明は、下記のポリシロキサン(A)を含有する液晶配向剤についての発明である。
ポリシロキサン(A):式(1)で表されるアルコキシシラン及び式(3)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサン。
R1Si(OR2)3 (1)
(R1は下記式(2)の構造を表し、R2は炭素数1~5のアルキル基を表す。) The present invention is described in detail below.
This invention is invention about the liquid crystal aligning agent containing the following polysiloxane (A).
Polysiloxane (A): Polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (3).
R 1 Si (OR 2 ) 3 (1)
(R 1 represents a structure of the following formula (2), R 2 represents an alkyl group having 1 to 5 carbon atoms.)
(R3は、アクリル基、アクリロキシ基、メタクリル基、メタクリロキシ基、又はスチリル基で置換された炭素数5~10のアルキル基である。R4は炭素数1~5のアルキル基を表す。)
また、本発明は、ポリシロキサン(A)及び下記のポリシロキサン(B)を含有する液晶配向剤についての発明である。
ポリシロキサン(B):式(5)で表されるアルコキシシランを50~100モル%含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサン。
Si(OR15)4 (5)
(R15は炭素数1~5のアルキル基を表す。)
(R 3 is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group. R 4 represents an alkyl group having 1 to 5 carbon atoms.)
Moreover, this invention is invention about the liquid crystal aligning agent containing polysiloxane (A) and the following polysiloxane (B).
Polysiloxane (B): polysiloxane obtained by hydrolysis and polycondensation of alkoxysilane containing 50 to 100 mol% of alkoxysilane represented by formula (5).
Si (OR 15 ) 4 (5)
(R 15 represents an alkyl group having 1 to 5 carbon atoms.)
本発明の液晶配向剤に含有されるポリシロキサン(A)は、式(1)で表されるアルコキシシラン及び式(3)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサンである。
R1Si(OR2)3 (1)
(R1は下記式(2)の構造を表し、R2は炭素数1~5のアルキル基を表す。) <Polysiloxane (A)>
The polysiloxane (A) contained in the liquid crystal aligning agent of the present invention hydrolyzes and polycondenses the alkoxysilane containing the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3). It is a polysiloxane obtained.
R 1 Si (OR 2 ) 3 (1)
(R 1 represents the structure of the following formula (2), and R 2 represents an alkyl group having 1 to 5 carbon atoms.)
(R3は、アクリル基、アクリロキシ基、メタクリル基、メタクリロキシ基又はスチリル基で置換された炭素数5~10のアルキル基である。R4は炭素数1~5のアルキル基を表す。)
式(1)で表されるアルコキシシランのR1(以下、特定有機基ともいう)は、上記式(2)で表す構造を表す。
(R 3 is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group. R 4 represents an alkyl group having 1 to 5 carbon atoms.)
R 1 (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by the formula (1) represents a structure represented by the above formula (2).
式(2)中、nは0~4の整数である。好ましくは、0~2の整数であり、1であるのが特に好ましい。 In the formula (2), Y 5 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has a carbon number of 1 to May be substituted with any one of an alkyl group having 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom . Y 5 is particularly preferably a divalent cyclic group consisting of a cyclohexyl ring.
In the formula (2), n is an integer of 0-4. Preferably, it is an integer of 0 to 2, and 1 is particularly preferable.
このような式(1)で表されるアルコキシシランは、公知の合成方法(特開昭61-286393)によって合成することが出来る。以下にその具体例を挙げるが、これに限定されるものではない。 R 2 of the alkoxysilane represented by the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, R 2 is a methyl group or an ethyl group.
Such an alkoxysilane represented by the formula (1) can be synthesized by a known synthesis method (Japanese Patent Laid-Open No. 61-286393). Although the specific example is given to the following, it is not limited to this.
上記の化合物は、シロキサンポリマーとした際の溶媒への溶解性、液晶配向膜とした場合における液晶の配向性、プレチルト角特性、電圧保持率、蓄積電荷などの特性に応じて、1種類又は2種類以上を混合して使用することもできる。また、炭素数10~18の長鎖アルキル基を含有するアルコキシシランとの併用も可能である。
One or two of the above compounds may be used depending on properties such as solubility in a solvent when used as a siloxane polymer, alignment properties of liquid crystal when used as a liquid crystal alignment film, pretilt angle characteristics, voltage holding ratio, accumulated charge, and the like. A mixture of more than one can also be used. Further, it can be used in combination with an alkoxysilane containing a long-chain alkyl group having 10 to 18 carbon atoms.
上述した特定有機基を有する式(1)で表されるアルコキシシランは、ポリシロキサンを得るために用いる全アルコキシシラン中において、良好な液晶配向性を得るため、2モル%以上が好ましい。式(1)で表されるアルコキシシランは、より好ましくは3モル%以上である。また、式(1)で表されるアルコキシシランは、形成される液晶配向膜の充分な硬化特性を得るためには、20モル%以下が好ましい。より好ましくは15モル%以下である。
式(3)で表されるアルコキシシランのR3は、炭素数1~5のアルキル基であり、好ましくは炭素数1~3であり、特に好ましくは炭素数1~2である。
式(3)で表されるアルコキシシランは、ポリシロキサンを得るために用いる全アルコキシシラン中において、良好な液晶応答速度を得るため、5モル%以上が好ましい。式(3)で表されるアルコキシシランは、より好ましくは10モル%以上であり、更に好ましくは20モル%以上であるが、70モル%以下が好ましく、50モル%以下がより好ましい。 The alkoxysilane represented by the formula (1) having the specific organic group described above can be produced by a known method.
The alkoxysilane represented by the formula (1) having the specific organic group described above is preferably 2 mol% or more in order to obtain good liquid crystal alignment in all alkoxysilanes used for obtaining polysiloxane. More preferably, the alkoxysilane represented by Formula (1) is 3 mol% or more. Further, the alkoxysilane represented by the formula (1) is preferably 20 mol% or less in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed. More preferably, it is 15 mol% or less.
R 3 of the alkoxysilane represented by the formula (3) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
The alkoxysilane represented by the formula (3) is preferably 5 mol% or more in order to obtain a good liquid crystal response speed in all alkoxysilanes used for obtaining the polysiloxane. The alkoxysilane represented by the formula (3) is more preferably 10 mol% or more, still more preferably 20 mol% or more, preferably 70 mol% or less, more preferably 50 mol% or less.
(R13)nSi(OR14)4-n (4)
(式(4)中、R13は、水素原子、又はヘテロ原子、ハロゲン原子、アミノ基、グリシドキシ基、メルカプト基、イソシアネート基、ウレイド基で置換されていてもよい、炭素数1~10の炭化水素基である。R14は炭素数1~5であり、好ましくは1~3のアルキル基である。nは0~3であり、好ましくは0~2の整数を表す。)
式(4)で表されるアルコキシシランのR13は水素原子又は炭素数が1~10の有機基(以下、第三の有機基ともいう)である。第三の有機基の例としては、脂肪族炭化水素;脂肪族環、芳香族環及びヘテロ環のような環構造;不飽和結合;及び酸素原子、窒素原子、硫黄原子等のヘテロ原子等を含んでいてもよく、分岐構造を有していてもよい、炭素数が1~6の有機基である。加えて、この有機基はハロゲン原子、アミノ基、グリシドキシ基、メルカプト基、イソシアネート基、ウレイド基などで置換されていてもよい。 For the production of polysiloxane (A), in addition to the alkoxysilanes represented by the formulas (1) and (3), the effects of the present invention are intended for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules. As long as the above is not impaired, one or more alkoxysilanes represented by the following formula (4) may be used. Since the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, one or more types can be selected and used according to the required properties.
(R 13 ) n Si (OR 14 ) 4-n (4)
(In the formula (4), R 13 represents a carbon atom having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. R 14 is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 and n is 0 to 3 and preferably represents an integer of 0 to 2.)
R 13 of the alkoxysilane represented by the formula (4) is a hydrogen atom or an organic group having 1 to 10 carbon atoms (hereinafter also referred to as a third organic group). Examples of the third organic group include aliphatic hydrocarbons; ring structures such as aliphatic rings, aromatic rings and heterocycles; unsaturated bonds; and heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms. An organic group having 1 to 6 carbon atoms, which may be included and may have a branched structure. In addition, the organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.
このような式(4)においてnが0であるアルコキシシランとしては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン又はテトラブトキシシランがより好ましく、特に、テトラメトキシシラン又はテトラエトキシシランが好ましい。
本発明では、式(1)で表されるアルコキシシランが、ポリシロキサン(A)の製造に使用される全アルコキシシラン中、好ましくは2~20モル%、特に好ましくは3~15モル%含まれ、かつ式(3)で表されるアルコキシシランが、ポリシロキサン(A)の製造に使用される全アルコキシシラン中、5~70モル%、特に好ましくは10~50モル%含まれるのが好ましい。 In the alkoxysilane represented by the formula (4), the alkoxysilane in which n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formulas (1) and (3).
As such alkoxysilane in which n is 0 in the formula (4), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
In the present invention, the alkoxysilane represented by the formula (1) is preferably contained in 2 to 20 mol%, particularly preferably 3 to 15 mol% in the total alkoxysilane used in the production of the polysiloxane (A). In addition, the alkoxysilane represented by the formula (3) is preferably contained in an amount of 5 to 70 mol%, particularly preferably 10 to 50 mol%, based on the total alkoxysilane used in the production of the polysiloxane (A).
ポリシロキサン(B)は、式(5)で表されるアルコキシシランを50~100モル%含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサンである。
Si(OR15)4 (5)
(R15は炭素数1~5のアルキル基を表す。)
このような式(5)で表されるアルコキシシランの具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン又はテトラブトキシシランがより好ましく、特に、テトラメトキシシラン又はテトラエトキシシランが好ましい。 <Polysiloxane (B)>
The polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing 50 to 100 mol% of the alkoxysilane represented by the formula (5).
Si (OR 15 ) 4 (5)
(R 15 represents an alkyl group having 1 to 5 carbon atoms.)
As specific examples of the alkoxysilane represented by the formula (5), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
ポリシロキサン(B)は、式(5)で表されるアルコキシシランの他に、さらに式(6)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサンであっても良い。
R16Si(OR17)3 (6)
(R16は、炭素数1~5のアルキル基である。R17は炭素数1~5のアルキル基を表す。)
式(6)で表されるアルコキシシランのR16は、炭素数1~5のアルキル基である。アルキル基の炭素数は1~4が好ましく、より好ましくは1~3である。
式(6)で表されるアルコキシシランのR17は、炭素数1~5のアルキル基であり、好ましくは炭素数1~3であり、特に好ましくは炭素数1~2である。
式(6)で表されるアルコキシシランの具体例を挙げるが、これらに限定されるものではでない。例えば、メチルトリエトキシシラン、メチルトリメトキシシラン、ジメチルトリメトキシシラン、ジメチルトリエトキシシラン、n-プロピルトリメトキシシラン、n-プロピルトリエトキシシランである。
特に、式(5)で表されるアルコキシシランの他に、さらに式(6)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサン(B)を含有する液晶配向剤は、垂直配向力が高く、望ましい。 The polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (3) in addition to the alkoxysilane represented by the formula (5). There may be.
The polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (6) in addition to the alkoxysilane represented by the formula (5). There may be.
R 16 Si (OR 17 ) 3 (6)
(R 16 is an alkyl group having 1 to 5 carbon atoms. R 17 represents an alkyl group having 1 to 5 carbon atoms.)
R 16 of the alkoxysilane represented by the formula (6) is an alkyl group having 1 to 5 carbon atoms. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.
R 17 of the alkoxysilane represented by the formula (6) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
Although the specific example of the alkoxysilane represented by Formula (6) is given, it is not limited to these. For example, methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxysilane.
In particular, in addition to the alkoxysilane represented by the formula (5), it further contains a polysiloxane (B) obtained by hydrolysis and polycondensation of an alkoxysilane containing the alkoxysilane represented by the formula (6). A liquid crystal aligning agent is desirable because it has a high vertical alignment force.
ポリシロキサン(A)及びポリシロキサン(B)を混合した液晶配向剤を製造する場合、ポリシロキサン(A)とポリシロキサン(B)の混合割合については、同固形分換算にて(A)と(B)の重量比が10:90~50: 50であることが好ましい。 In addition to the alkoxysilanes represented by the formulas (3), (5), and (6), the production of the polysiloxane (B) is intended to improve adhesion with the substrate and affinity with the liquid crystal molecules. As long as the effects of the present invention are not impaired, one or more alkoxysilanes represented by the above formula (4) can be used. Since the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, one or more types can be selected and used according to the required properties.
When manufacturing the liquid crystal aligning agent which mixed polysiloxane (A) and polysiloxane (B), about the mixing ratio of polysiloxane (A) and polysiloxane (B), (A) and ( The weight ratio of B) is preferably 10:90 to 50:50.
本発明に用いるポリシロキサンを得る方法は特に限定されない。本発明のポリシロキサン(A)においては、上記した式(1)及び式(3)を必須成分とするアルコキシシランを、有機溶媒中で縮合させて得られる。通常、ポリシロキサンは、このようなアルコキシシランを加水分解・重縮合して、有機溶媒に均一に溶解した溶液として得られる。
ポリシロキサンを加水分解・重縮合する方法として、例えば、アルコキシシランをアルコール又はグリコールなどの溶媒中で加水分解・重縮合する方法が挙げられる。その際、加水分解・重縮合反応は、部分加水分解及び完全加水分解のいずれであってもよい。完全加水分解の場合は、理論上、アルコキシシラン中の全アルコキシ基の0.5倍モルの水を加えればよいが、通常は0.5倍モルより過剰量の水を加えるのが好ましい。
本発明においては、上記反応に用いる水の量は、所望により適宜選択することができるが、通常、アルコキシシラン中の全アルコキシ基の0.5~2.5倍モルであるのが好ましい。 <Method for producing polysiloxane>
The method for obtaining the polysiloxane used in the present invention is not particularly limited. The polysiloxane (A) of the present invention is obtained by condensing an alkoxysilane having the above-described formulas (1) and (3) as essential components in an organic solvent. Usually, polysiloxane is obtained as a solution in which such alkoxysilane is hydrolyzed and polycondensed to be uniformly dissolved in an organic solvent.
Examples of the method for hydrolyzing and polycondensing polysiloxane include a method for hydrolyzing and polycondensing alkoxysilane in a solvent such as alcohol or glycol. At that time, the hydrolysis / polycondensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water more than 0.5 times mole.
In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
ポリシロキサンを得る際に、アルコキシシランを複数種用いる場合は、アルコキシシランをあらかじめ混合した混合物として混合してもよいし、複数種のアルコキシシランを順次混合してもよい。
アルコキシシランを加水分解・重縮合する際に用いられる溶媒(以下、重合溶媒ともいう)は、アルコキシシランを溶解するものであれば特に限定されない。また、アルコキシシランが溶解しない場合でも、アルコキシシランの加水分解・重縮合反応の進行とともに溶解するものであればよい。一般的には、アルコキシシランの加水分解・重縮合反応によりアルコールが生成するため、アルコール類、グリコール類、グリコールエーテル類、又はアルコール類と相溶性の良好な有機溶媒が用いられる。 As another method, for example, a method of heating and hydrolyzing / polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the alkoxysilane is mixed while the solution is heated. In that case, the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. Preferably, it is a method of heating for several tens of minutes to several tens of hours under reflux so that evaporation or volatilization of the liquid does not occur.
When obtaining multiple types of alkoxysilane when obtaining polysiloxane, you may mix as a mixture which mixed alkoxysilane beforehand, and may mix multiple types of alkoxysilane sequentially.
The solvent used when hydrolyzing and polycondensing alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it dissolves alkoxysilane. Moreover, even when alkoxysilane does not melt | dissolve, what melt | dissolves with the progress of hydrolysis and polycondensation reaction of alkoxysilane should just be used. In general, since alcohol is generated by hydrolysis / polycondensation reaction of alkoxysilane, alcohols, glycols, glycol ethers, or organic solvents having good compatibility with alcohols are used.
上記の方法で得られたポリシロキサンの重合溶液(以下、重合溶液ともいう。)は、原料として仕込んだ全アルコキシシランのケイ素原子をSiO2に換算した濃度(以下、SiO2換算濃度と称す。)を好ましくは20重量%以下、さらには5~15重量%とすることがより好ましい。この濃度範囲において任意の濃度を選択することにより、ゲルの生成を抑え、均質な溶液を得ることができる。 In the present invention, a plurality of the above polymerization solvents may be mixed and used.
The polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). ) Is preferably 20% by weight or less, more preferably 5 to 15% by weight. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
本発明においては、上記の方法で得られた重合溶液をそのままポリシロキサンの溶液としてもよいし、必要に応じて、上記の方法で得られた溶液を、濃縮したり、溶媒を加えて希釈したり又は他の溶媒に置換して、ポリシロキサンの溶液としてもよい。
その際、用いる溶媒(以下、添加溶媒ともいう)は、重合溶媒と同じでもよいし、別の溶媒でもよい。この添加溶媒は、ポリシロキサンが均一に溶解している限りにおいて特に限定されず、一種でも複数種でも任意に選択して用いることができる。
このような添加溶媒の具体例としては、上記した重合溶媒の例として挙げた溶媒のほかに、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類;酢酸メチル、酢酸エチル、乳酸エチル等のエステル類が挙げられる。
これらの溶媒は、液晶配向剤の粘度の調整、又はスピンコート、フレキソ印刷、インクジェット等で液晶配向剤を基板上に塗布する際の塗布性を向上できる。 <Polysiloxane solution>
In the present invention, the polymerization solution obtained by the above method may be used as a polysiloxane solution as it is, or if necessary, the solution obtained by the above method may be concentrated or diluted by adding a solvent. Or may be substituted with another solvent to form a polysiloxane solution.
In that case, the solvent to be used (hereinafter also referred to as additive solvent) may be the same as the polymerization solvent, or may be another solvent. The additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used.
Specific examples of such an additive solvent include, in addition to the solvents mentioned as examples of the polymerization solvent described above, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate. Can be mentioned.
These solvents can improve the applicability when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, ink jetting or the like.
本発明においては、本発明の効果を損なわない限りにおいて、ポリシロキサン以外のその他の成分、例えば、無機微粒子、メタロキサンオリゴマー、メタロキサンポリマー、レベリング剤、更に界面活性剤等の成分が含まれていてもよい。
無機微粒子としては、シリカ微粒子、アルミナ微粒子、チタニア微粒子、又はフッ化マグネシウム微粒子等の微粒子が好ましく、特にコロイド溶液の状態であるものが好ましい。このコロイド溶液は、無機微粒子を分散媒に分散したものでもよいし、市販品のコロイド溶液であってもよい。本発明においては、無機微粒子を含有させることにより、形成される硬化被膜の表面形状及びその他の機能を付与することが可能となる。無機微粒子としては、その平均粒子径が0.001~0.2μmであることが好ましく、更に好ましくは0.001~0.1μmである。無機微粒子の平均粒子径が0.2μmを超える場合には、調製される塗布液を用いて形成される硬化被膜の透明性が低下する場合がある。
無機微粒子の分散媒としては、水及び有機溶剤を挙げることができる。コロイド溶液としては、被膜形成用塗布液の安定性の観点から、pH又はpKaが1~10に調整されていることが好ましい。より好ましくは2~7である。 <Other ingredients>
In the present invention, other components other than polysiloxane, such as inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, and surfactants are included as long as the effects of the present invention are not impaired. May be.
As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in the state of a colloidal solution are particularly preferable. This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution. In the present invention, the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions. The inorganic fine particles preferably have an average particle size of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid may be lowered.
Examples of the dispersion medium for the inorganic fine particles include water and organic solvents. As the colloidal solution, it is preferable that the pH or pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating solution for forming a film. More preferably, it is 2-7.
市販品のメタロキサンオリゴマー、メタロキサンポリマーの具体例としては、コルコート社製の、メチルシリケート51、メチルシリケート53A、エチルシリケート40、エチルシリケート48、EMS-485、SS-101等のシロキサンオリゴマー又はシロキサンポリマー、関東化学社製のチタニウム-n-ブトキシドテトラマー等のチタノキサンオリゴマーが挙げられる。これらは単独又は2種以上混合して使用してもよい。
また、レベリング剤及び界面活性剤等は、公知のものを用いることができ、特に市販品は入手が容易なので好ましい。
また、ポリシロキサンに、上記したその他の成分を混合する方法は、ポリシロキサンと同時でも、後であってもよく、特に限定されない。 As the metalloxane oligomer and metalloxane polymer, single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used. The metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, or carboxylate by a conventional method such as hydrolysis.
Specific examples of commercially available metalloxane oligomers and metalloxane polymers include siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, SS-101 manufactured by Colcoat Co. Examples thereof include titanoxane oligomers such as polymers and titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
Moreover, a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.
Moreover, the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.
本発明の液晶配向剤は上述したポリシロキサン、必要に応じてその他の成分を含有する溶液である。その際、溶媒としては、上述したポリシロキサンの重合溶媒及び添加溶媒からなる群から選ばれる溶媒が用いられる。液晶配向剤におけるポリシロキサンの含有量は、SiO2換算濃度が好ましくは0.5~15重量%、より好ましくは1~6重量%である。このようなSiO2換算濃度の範囲であれば、一回の塗布で所望の膜厚を得やすく、充分な溶液のポットライフが得られ易い。
本発明の液晶配向剤を調製する方法は特に限定されない。本発明に用いるポリシロキサン、必要に応じて加えられるその他の成分が均一に混合した状態であればよい。通常、ポリシロキサンは、溶媒中で加水分解・重縮合されるので、ポリシロキサンの溶液をそのまま用いるか、ポリシロキサンの溶液に必要に応じてその他の成分を添加することが簡便である。更に、ポリシロキサンの重合溶液をそのまま用いる方法が最も簡便である。
また、液晶配向剤中におけるポリシロキサンの含有量を調整する際には、上述したポリシロキサンの重合溶媒及び添加溶媒からなる群から選ばれる溶媒を用いることができる。 <Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is a solution containing the above-described polysiloxane and, if necessary, other components. In this case, as the solvent, a solvent selected from the group consisting of the above-mentioned polysiloxane polymerization solvent and additive solvent is used. The content of polysiloxane in the liquid crystal aligning agent is preferably 0.5 to 15% by weight, more preferably 1 to 6% by weight in terms of SiO 2 concentration. Be in the range of such terms of SiO 2 concentration, easy to obtain a desired film thickness by a single coating, easy pot life sufficient solution is obtained.
The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. The polysiloxane used in the present invention may be in a state where other components added as necessary are uniformly mixed. Since polysiloxane is usually hydrolyzed and polycondensed in a solvent, it is convenient to use the polysiloxane solution as it is or to add other components to the polysiloxane solution as necessary. Furthermore, the most convenient method is to use the polysiloxane polymerization solution as it is.
Moreover, when adjusting content of polysiloxane in a liquid crystal aligning agent, the solvent chosen from the group which consists of the polymerization solvent and addition solvent of the polysiloxane mentioned above can be used.
本発明の液晶配向膜は、本発明の液晶配向剤を用いて得られる。例えば、本発明の液晶配向剤を、基板に塗布した後、乾燥・焼成を行うことで得られる硬化膜を、そのまま液晶配向膜として用いることもできる。また、この硬化膜をラビングしたり、偏光又は特定の波長の光等を照射したり、イオンビーム等の処理をしたり、液晶充填後の液晶表示素子に電圧を印加した状態でUVを照射することも可能である。
液晶配向剤を塗布する基板としては、透明性の高い基板であれば特に限定されないが、基板上に液晶を駆動するための透明電極が形成された基板が好ましい。 <Liquid crystal alignment film>
The liquid crystal aligning film of this invention is obtained using the liquid crystal aligning agent of this invention. For example, after applying the liquid crystal aligning agent of this invention to a board | substrate, the cured film obtained by drying and baking can also be used as a liquid crystal aligning film as it is. In addition, the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, processed with an ion beam, etc., or irradiated with UV in a state where a voltage is applied to the liquid crystal display element after filling the liquid crystal. It is also possible.
The substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate is preferable.
液晶配向剤を塗布した後の乾燥の工程は、必ずしも必要とされないが、塗布後から焼成までの時間が基板ごとに一定していない場合、又は塗布後ただちに焼成されない場合には、乾燥工程を含める方が好ましい。この乾燥は、基板の搬送等により塗膜形状が変形しない程度に溶媒が除去されていればよく、その乾燥手段については特に限定されない。例えば、温度40℃~150℃、好ましくは60℃~100℃のホットプレート上で、0.5~30分、好ましくは1~5分乾燥させる方法が挙げられる。 Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, ink jet, spraying, roll coating, and the like.In terms of productivity, the transfer printing method is widely used industrially. The present invention is also preferably used.
The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, a drying process is included. Is preferred. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.
この硬化膜の厚みは必要に応じて選択することができるが、好ましくは5nm以上、より好ましくは10nm以上の場合、液晶表示素子の信頼性が得られ易いので好適である。また、硬化膜の厚みが好ましくは300nm以下、より好ましくは150nm以下の場合は、液晶表示素子の消費電力が極端に大きくならないので好適である。 The polysiloxane in the liquid crystal alignment film undergoes polycondensation in the firing step. However, in the present invention, it is not necessary to completely polycondense unless the effects of the present invention are impaired. However, firing is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the liquid crystal cell production process, such as curing of the sealant.
The thickness of the cured film can be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more, because the reliability of the liquid crystal display element can be easily obtained. Moreover, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is suitable.
本発明の液晶表示素子は、上記の方法により、基板に液晶配向膜を形成した後、公知の方法で液晶セルを作製して得ることができる。液晶セル作製の一例を挙げると、液晶配向膜が形成された1対の基板を、スペーサーを挟んで、シール剤で固定し、液晶を注入して封止する方法が一般的である。その際、用いるスペーサーの大きさは1~30μmであるが、好ましくは2~10μmである。
液晶を注入する方法は特に制限されず、作製した液晶セル内を減圧にした後、液晶を注入する真空法、液晶を滴下した後に封止を行う滴下法などを挙げることができる。 <Liquid crystal display element>
The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then preparing a liquid crystal cell by a known method. As an example of manufacturing a liquid crystal cell, a method is generally employed in which a pair of substrates on which a liquid crystal alignment film is formed are fixed with a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed. In this case, the size of the spacer used is 1 to 30 μm, preferably 2 to 10 μm.
The method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting liquid crystal after the inside of the manufactured liquid crystal cell is decompressed, and a dropping method for sealing after dropping the liquid crystal.
また、TFT型の素子のような高機能素子においては、液晶駆動のための電極と基板の間にトランジスタ素子が形成されたものが用いられる。
透過型の液晶素子の場合は、上記のような基板を用いることが一般的であるが、反射型の液晶表示素子では、片側の基板のみに光を反射するアルミニウムのような材料を用いることも可能であり、シリコンウエハー等の不透明な基板も用いることが可能である。 The substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. A specific example is the same as the substrate described in [Liquid crystal alignment film]. Standard electrode patterns such as PVA and MVA and protrusion patterns can also be used. Similar to the PSA type liquid crystal display, it can be operated even in a structure in which a line / slit electrode pattern of 1 to 10 μm is formed on one side substrate and no slit pattern or protrusion pattern is formed on the opposite substrate. The liquid crystal display can simplify the manufacturing process and provide high transmittance.
As a high-performance element such as a TFT element, an element in which a transistor element is formed between an electrode for driving a liquid crystal and a substrate is used.
In the case of a transmissive liquid crystal element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, a material such as aluminum that reflects light only on one substrate may be used. It is possible to use an opaque substrate such as a silicon wafer.
マグネチックスターラーを備えた500ml四口フラスコに、金属マグネシウムを1.71g仕込み、容器内を窒素置換し密閉した。THF(脱水)2mlを加えた後、強攪拌させた状態で、20.68gの化合物7をTHF(脱水)155mlに溶かした溶液を1時間かけて滴下した。その後、55℃に昇温し、2時間攪拌させ、金属マグネシウムが消失していることを確認した。次に、氷冷下(内温4℃)、テトラメトキシシランを30.53g一括で加えた後、加熱還流し、3時間攪拌した。反応液を室温まで冷却した後、飽和塩化アンモニウム水溶液を210ml加え、生成した不溶物を減圧濾過にて除去した。さらに、260mlのn-ヘキサンで濾物を洗浄した。ろ液の水相部分を除去し、有機相を純水 200mlで洗浄した。有機相を濃縮乾燥し、粗物 21.65gを得た。これを減圧蒸留し、外温220~230℃/圧力0.8torrの条件で留出させ、化合物8を5.74g得た(収率25%)。
1H-NMR(400MHz) in CDCl3: 0.90ppm(t, J = 7.2 Hz, 3H), 1.00-1.09ppm(m, 2H), 1.20-1.34ppm(m, 9H), 1.40-1.52ppm(m, 2H), 1.83-1.91ppm(m, 4H), 2.41-2.51ppm(m, 1H), 3.62ppm(s, 9H), 7.23ppm(d, J = 8.2 Hz, 2H), 7.56ppm(d, J = 8.2 Hz, 2H) <Synthesis Example 1 of Compound 8>
A 500 ml four-necked flask equipped with a magnetic stirrer was charged with 1.71 g of metallic magnesium, and the inside of the container was purged with nitrogen and sealed. After 2 ml of THF (dehydrated) was added, a solution prepared by dissolving 20.68 g of compound 7 in 155 ml of THF (dehydrated) was added dropwise over 1 hour with vigorous stirring. Then, it heated up at 55 degreeC and made it stir for 2 hours, and confirmed that the magnesium metal was lose | disappeared. Next, under ice-cooling (internal temperature 4 ° C.), 30.53 g of tetramethoxysilane was added all at once, and then heated to reflux and stirred for 3 hours. After cooling the reaction solution to room temperature, 210 ml of a saturated aqueous ammonium chloride solution was added, and the insoluble matter produced was removed by filtration under reduced pressure. Further, the filtrate was washed with 260 ml of n-hexane. The aqueous phase portion of the filtrate was removed, and the organic phase was washed with 200 ml of pure water. The organic phase was concentrated and dried to obtain 21.65 g of a crude product. This was distilled under reduced pressure and distilled under the conditions of an external temperature of 220 to 230 ° C./pressure of 0.8 torr to obtain 5.74 g of Compound 8 (yield 25%).
1 H-NMR (400 MHz) in CDCl 3 : 0.90 ppm (t, J = 7.2 Hz, 3H), 1.00-1.09 ppm (m, 2H), 1.20-1.34 ppm (m, 9H), 1.40-1.52 ppm (m , 2H), 1.83-1.91ppm (m, 4H), 2.41-2.51ppm (m, 1H), 3.62ppm (s, 9H), 7.23ppm (d, J = 8.2 Hz, 2H), 7.56ppm (d, (J = 8.2 Hz, 2H)
マグネチックスターラーを備えた500ml四口フラスコに、化合物9を30.00g、炭酸カリウムを25.24g、及びDMFを120g仕込み、室温下、臭化アリルを22.10g滴下した。その後、50℃にて11時間攪拌した。反応液を500gの酢酸エチルで希釈し、有機相を200gの純水で3回洗浄した。有機相を硫酸ナトリウムで乾燥させ、これを濾過した後、濾液を濃縮乾燥し、化合物10を34.80g得た(収率100%)。
1H-NMR(400MHz) in CDCl3: 0.90ppm(t, J = 7.2 Hz, 3H), 0.99-1.09ppm(m, 2H), 1.18-1.46ppm(m, 11H), 1.84-1.89ppm(m, 4H), 2.37-2.44ppm(m, 1H), 4.51ppm(dt, J = 5.4 Hz, 1.6 Hz, 2H), 5.26ppm(dq, J = 10.6 Hz, 1.6 Hz, 1H), 5.40ppm(dq, J = 17.2 Hz, 1.6 Hz, 1H), 6.07ppm(ddd, J = 17.2 Hz, 10.6 Hz, 5.4 Hz, 1H), 6.83ppm(dd, J = 8.8 Hz, 2.9 Hz, 2H), 7.10ppm(dd, J = 8.8 Hz, 2.9 Hz, 2H) <Synthesis Example 2 of Compound 10>
A 500 ml four-necked flask equipped with a magnetic stirrer was charged with 30.00 g of compound 9, 25.24 g of potassium carbonate, and 120 g of DMF, and 22.10 g of allyl bromide was added dropwise at room temperature. Then, it stirred at 50 degreeC for 11 hours. The reaction solution was diluted with 500 g of ethyl acetate, and the organic phase was washed 3 times with 200 g of pure water. The organic phase was dried over sodium sulfate and filtered, and then the filtrate was concentrated and dried to obtain 34.80 g of compound 10 (yield 100%).
1 H-NMR (400MHz) in CDCl 3: 0.90ppm (t, J = 7.2 Hz, 3H), 0.99-1.09ppm (m, 2H), 1.18-1.46ppm (m, 11H), 1.84-1.89ppm (m , 4H), 2.37-2.44 ppm (m, 1H), 4.51 ppm (dt, J = 5.4 Hz, 1.6 Hz, 2H), 5.26 ppm (dq, J = 10.6 Hz, 1.6 Hz, 1H), 5.40 ppm (dq , J = 17.2 Hz, 1.6 Hz, 1H), 6.07 ppm (ddd, J = 17.2 Hz, 10.6 Hz, 5.4 Hz, 1H), 6.83 ppm (dd, J = 8.8 Hz, 2.9 Hz, 2H), 7.10 ppm ( (dd, J = 8.8 Hz, 2.9 Hz, 2H)
マグネチックスターラーを備えた300ml四口フラスコに、化合物10を20.00g、トルエンを120g仕込み、室温にて攪拌した。次に、karstedt触媒(白金(0)-1,1,3,3-テトラメチルジシロキサン錯体 0.1mol/L キシレン溶液) 700μlを添加した後、トリメトキシシランを12.4ml滴下した。室温にて29時間攪拌後、反応液を濃縮乾燥し、粗物を得た。これを減圧蒸留し、外温245℃/圧力0.8torrの条件で留出させ、化合物11を12.15g得た(収率43%)。
1H-NMR(400MHz) in CDCl3: 0.76-0.82ppm(m, 2H), 0.89ppm(t, J = 7.2 Hz, 3H), 0.98-1.08ppm(m, 2H), 1.18-1.45ppm(m, 11H), 1.84-1.93ppm(m, 6H), 2.36-2.43ppm(m, 1H), 3.58ppm(s, 9H), 3.91ppm(t, J = 6.8 Hz, 2H), 6.81ppm(d, J = 8.8 Hz, 2H), 7.08ppm(d, J = 8.8 Hz, 2H) <Synthesis Example 3 of Compound 11>
A 300 ml four-necked flask equipped with a magnetic stirrer was charged with 20.00 g of compound 10 and 120 g of toluene and stirred at room temperature. Next, 700 μl of karstedt catalyst (platinum (0) -1,1,3,3-tetramethyldisiloxane complex 0.1 mol / L xylene solution) was added, and 12.4 ml of trimethoxysilane was added dropwise. After stirring at room temperature for 29 hours, the reaction solution was concentrated and dried to obtain a crude product. This was distilled under reduced pressure and distilled under conditions of an external temperature of 245 ° C./pressure of 0.8 torr to obtain 12.15 g of Compound 11 (43% yield).
1 H-NMR (400 MHz) in CDCl 3 : 0.76-0.82 ppm (m, 2H), 0.89 ppm (t, J = 7.2 Hz, 3H), 0.98-1.08 ppm (m, 2H), 1.18-1.45 ppm (m , 11H), 1.84-1.93ppm (m, 6H), 2.36-2.43ppm (m, 1H), 3.58ppm (s, 9H), 3.91ppm (t, J = 6.8 Hz, 2H), 6.81ppm (d, J = 8.8 Hz, 2H), 7.08 ppm (d, J = 8.8 Hz, 2H)
本実施例で用いた化合物における略語は以下のとおりである。
TEOS:テトラエトキシシラン
C18:オクタデシルトリエトキシシラン
MPMS:3-メタクリロキシプロピルトリメトキシシラン
M8MS:3-メタクリロキシオクチルトリメトキシシラン
MTES:メチルトリエトキシシラン
HG:2-メチル-2,4-ペンタンジオール(別名:ヘキシレングリコール)
BCS:2-ブトキシエタノール
UPS:3-ウレイドプロピルトリエトキシシラン Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention should not be construed as being limited thereto.
Abbreviations in the compounds used in the examples are as follows.
TEOS: tetraethoxysilane C18: octadecyltriethoxysilane MPMS: 3-methacryloxypropyltrimethoxysilane M8MS: 3-methacryloxyoctyltrimethoxysilane MTES: methyltriethoxysilane HG: 2-methyl-2,4-pentanediol ( (Alternative name: hexylene glycol)
BCS: 2-butoxyethanol UPS: 3-ureidopropyltriethoxysilane
温度計、還流管を備え付けた200mLの四つ口反応フラスコ中でHGを20.5g、BCS6.8g、TEOS22.5g、化合物合成例3で得られた化合物11を4.1g、及びMPMSを19.9g混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、予めHG10.2g、BCS3.4g、水10.8g及び触媒として蓚酸1.3gを混合した溶液を、室温下で30分かけて滴下し、さらに室温で30分間撹拌した。その後オイルバスを用いて加熱して30分間還流させた後、予めUPS含有量92重量%のメタノール溶液0.6g、0.3gのHG及び0.1gのBCSの混合液を加えた。更に30分間還流させてから放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。
得られたポリシロキサン溶液10.0g、及びBCS20.0gを混合し、SiO2換算濃度が4重量%の液晶配向剤中間体[S1]を得た。
温度計、還流管を備え付けた200mLの四つ口反応フラスコ中でHGを23.8g、BCS7.9g、TEOS37.1g、及びMTES3.6gを混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、予めHG11.9g、BCS4.0g、水10.8g及び触媒として蓚酸0.4gを混合した溶液を、室温下で30分かけて滴下し、さらに室温で30分間撹拌した。その後オイルバスを用いて加熱して30分間還流させた後、予めUPS含有量92重量%のメタノール溶液0.6g、HG0.3g及びBCS0.1gの混合液を加えた。更に30分間還流させてから放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。
得られたポリシロキサン溶液10.0g、BCS20.0gを混合し、SiO2換算濃度が4重量%の液晶配向剤中間体(U1)を得た。
得られた液晶配向剤中間体(S1)と液晶配向剤中間体(U1)を、2:8の重量比率で混合し、SiO2換算濃度が4重量%の液晶配向剤[K1]を得た。 <Execution synthesis example 1>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 20.5 g of HG, 6.8 g of BCS, 22.5 g of TEOS, 4.1 g of compound 11 obtained in Compound Synthesis Example 3, and 19 of MPMS .9 g was mixed to prepare an alkoxysilane monomer solution. To this solution, a solution prepared by previously mixing 10.2 g of HG, 3.4 g of BCS, 10.8 g of water and 1.3 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 wt%, 0.3 g of HG and 0.1 g of BCS was previously added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, and mixed BCS20.0g, SiO 2 conversion concentration was obtained 4 wt% liquid crystal aligning agent intermediates [S1].
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 23.8 g of HG, 7.9 g of BCS, 37.1 g of TEOS, and 3.6 g of MTES were mixed to prepare an alkoxysilane monomer solution. A solution prepared by previously mixing 1.9 g of HG, 4.0 g of BCS, 10.8 g of water and 0.4 g of oxalic acid as a catalyst was added dropwise to the solution over 30 minutes, and the mixture was further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by weight, 0.3 g of HG and 0.1 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO 2 concentration of 4 wt% liquid crystal aligning agent intermediates of (U1).
The obtained liquid crystal aligning agent intermediate (S1) and liquid crystal aligning agent intermediate (U1) were mixed at a weight ratio of 2: 8 to obtain a liquid crystal aligning agent [K1] having a SiO 2 equivalent concentration of 4% by weight. .
温度計、還流管を備え付けた200mLの四つ口反応フラスコ中でHGを17.9g、BCS6.0g、TEOS25.0g、化合物合成例3で得られた化合物11を8.2g、及びM8MSを19.1g混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、予めHG9.0g、BCS3.0g、水10.8g及び触媒として蓚酸1.1gを混合した溶液を、室温下で30分かけて滴下し、さらに室温で30分間撹拌した。その後オイルバスを用いて加熱して60分間還流させてから放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。
得られたポリシロキサン溶液10.0g、BCS20.0gを混合し、SiO2換算濃度が4重量%の液晶配向剤中間体[S2]を得た。
得られた液晶配向剤中間体(S2)と合成例1で得られた液晶配向剤中間体(U1)を、2:8の重量比率で混合し、SiO2換算濃度が4重量%の液晶配向剤[K2]を得た。 <Execution synthesis example 2>
In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 17.9 g of HG, 6.0 g of BCS, 25.0 g of TEOS, 8.2 g of compound 11 obtained in Compound Synthesis Example 3, and 19 of M8MS 0.1 g was mixed to prepare an alkoxysilane monomer solution. A solution prepared by mixing 9.0 g of HG, 3.0 g of BCS, 10.8 g of water and 1.1 g of oxalic acid as a catalyst in advance over 30 minutes was added dropwise to this solution over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 60 minutes, and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0g, SiO 2 conversion concentration was obtained 4 wt% liquid crystal aligning agent intermediates [S2].
The obtained liquid crystal aligning agent intermediate (S2) and the liquid crystal aligning agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 8, and the liquid crystal aligning concentration was 4% by weight in terms of SiO 2. Agent [K2] was obtained.
温度計、還流管を備え付けた200mLの四つ口反応フラスコ中でHGを19.4g、BCS6.5g、TEOS22.5g、化合物合成例3で得られた化合物11を8.2g、MPMSを14.9g、及びM8MSを3.2g混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、予めHG9.7g、BCS3.2g、水10.8g及び触媒として蓚酸1.1gを混合した溶液を、室温下で30分かけて滴下し、さらに室温で30分間撹拌した。その後オイルバスを用いて加熱して30分間還流させた後、予めUPS含有量92重量%のメタノール溶液0.6g、HG0.3g及びBCS0.1gの混合液を加えた。更に30分間還流させてから放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。
得られたポリシロキサン溶液10.0g、BCS20.0gを混合し、SiO2換算濃度が4重量%の液晶配向剤中間体(S3)を得た。
得られた液晶配向剤中間体(S3)と合成例1で得られた液晶配向剤中間体(U1)を、2:8の重量比率で混合し、SiO2換算濃度が4重量%の液晶配向剤[K3]を得た。 <Execution synthesis example 3>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 19.4 g of HG, 6.5 g of BCS, 22.5 g of TEOS, 8.2 g of Compound 11 obtained in Compound Synthesis Example 3, and 14.14 of MPMS. 9 g and 3.2 g of M8MS were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution in which 9.7 g of HG, 3.2 g of BCS, 10.8 g of water and 1.1 g of oxalic acid as a catalyst were mixed dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by weight, 0.3 g of HG and 0.1 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO 2 concentration of 4 wt% liquid crystal aligning agent intermediate of (S3).
The obtained liquid crystal aligning agent intermediate (S3) and the liquid crystal aligning agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 8, and the liquid crystal alignment having a SiO 2 equivalent concentration of 4% by weight. Agent [K3] was obtained.
温度計、還流管を備え付けた200mLの四つ口反応フラスコ中でHG22.6g、BCS7.5g、TEOS39.2g、及びC18を4.2g混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、予めHG11.3g、BCS3.8g、水10.8g及び触媒として蓚酸0.2gを混合した溶液を、室温下で30分かけて滴下し、さらに室温で30分間撹拌した。その後オイルバスを用いて加熱して30分間還流させた後、予めUPS含有量92重量%のメタノール溶液0.6g、HG0.3g及びBCS0.1gの混合液を加えた。更に30分間還流させてから放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。
得られたポリシロキサン溶液10.0g、BCS20.0gを混合し、SiO2換算濃度が4重量%の液晶配向剤中間体(S4)を得た。
得られた液晶配向剤中間体(S4)と合成例1で得られた液晶配向剤中間体(U1)を、2:8の重量比率で混合し、SiO2換算濃度が4重量%の液晶配向剤[L1]を得た。 <Comparative Synthesis Example 1>
A solution of alkoxysilane monomer was prepared by mixing 4.2 g of HG 22.6 g, BCS 7.5 g, TEOS 39.2 g, and C18 in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. A solution prepared by previously mixing 11.3 g of HG, 3.8 g of BCS, 10.8 g of water and 0.2 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by weight, 0.3 g of HG and 0.1 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO 2 concentration of 4 wt% liquid crystal aligning agent intermediates of (S4).
The obtained liquid crystal aligning agent intermediate (S4) and the liquid crystal aligning agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 8, and the liquid crystal aligning concentration was 4% by weight in terms of SiO 2. Agent [L1] was obtained.
温度計、還流管を備え付けた200mLの四つ口反応フラスコ中でHG20.4g、BCS6.8g、TEOS22.5g、C18を4.2g、及びMPMSを19.9g混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、予めHG10.2g、BCS3.4g、水10.8g及び触媒として蓚酸1.3gを混合した溶液を、室温下で30分かけて滴下し、さらに室温で30分間撹拌した。その後オイルバスを用いて加熱して30分間還流させた後、予めUPS含有量92重量%のメタノール溶液0.6g、HG0.3g及びBCS0.1gの混合液を加えた。更に30分間還流させてから放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。
得られたポリシロキサン溶液10.0g、BCS20.0gを混合し、SiO2換算濃度が4重量%の液晶配向剤中間体(S5)を得た。
得られた液晶配向剤中間体(S5)と合成例1で得られた液晶配向剤中間体(U1)を、2:8の重量比率で混合し、SiO2換算濃度が4重量%の液晶配向剤[L2]を得た。 <Comparative Synthesis Example 2>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 20.4 g of HG, 6.8 g of BCS, 22.5 g of TEOS, 4.2 g of C18, and 19.9 g of MPMS are mixed to obtain a solution of an alkoxysilane monomer. Was prepared. To this solution, a solution prepared by previously mixing 10.2 g of HG, 3.4 g of BCS, 10.8 g of water and 1.3 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by weight, 0.3 g of HG and 0.1 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO 2 concentration of 4 wt% liquid crystal aligning agent intermediates of (S5).
The obtained liquid crystal aligning agent intermediate (S5) and the liquid crystal aligning agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 8, and the liquid crystal alignment having a SiO 2 equivalent concentration of 4% by weight. Agent [L2] was obtained.
実施合成例1で得られた液晶配向剤[K1]を、画素サイズが100×300ミクロンで、ライン/スペースがそれぞれ5ミクロンのITO電極パターンが形成されているITO電極基板のITO面にスピンコートした。80℃のホットプレートで2分間乾燥した後、200℃若しくは220℃の熱風循環式オーブンで30分間焼成を行い、膜厚100nmの液晶配向膜を形成した。実施合成例1で得られた液晶配向処理剤[K1]を、電極パターンが形成されていないITO面にスピンコートし、80℃のホットプレートで2分間乾燥した後、上記基板同様に200℃若しくは220℃の熱風循環式オーブンで30分間焼成を行い、膜厚100nmの液晶配向膜を形成した。これらの2枚の基板を用意し、一方の基板の液晶配向膜面上に4μmのビーズスペーサーを散布した後、その上からシール剤を印刷した。他方の基板の液晶配向膜面を内側にし、張り合わせた後、シール剤を硬化させて空セルを作製した。液晶MLC-6608(メルク社製商品名)を、空セルに減圧注入法によって、前記液晶を注入した液晶セルを作製した。
これら液晶セルの応答速度特性を、後述する方法により測定した。
その後、この液晶セルに20VのDC電圧を印加した状態で、この液晶セルの外側から超高圧水銀ランプを用いて365nm換算にてUVを20J照射した。その後、再び応答速度特性を測定し、UV照射前後での応答速度を比較した。その結果を表1に示した。
その後、得られた液晶セルを100℃の循環式オーブンで30分のアニールを行った。取り出したセルを、偏光板をクロスニコルにした状態で、顕微鏡観察を行い、液晶の配向乱れであるドメインの状態を観察した。その結果も表1に合わせて示した。 <Example 1>
The liquid crystal aligning agent [K1] obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 × 300 microns and a line / space of 5 microns was formed. did. After drying for 2 minutes on an 80 ° C. hot plate, baking was performed in a hot air circulation oven at 200 ° C. or 220 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. The liquid crystal aligning agent [K1] obtained in Example Synthesis Example 1 was spin-coated on the ITO surface on which no electrode pattern was formed, dried on a hot plate at 80 ° C. for 2 minutes, and then 200 ° C. or Firing was performed in a hot air circulation oven at 220 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. These two substrates were prepared, 4 μm bead spacers were sprayed on the liquid crystal alignment film surface of one substrate, and a sealant was printed thereon. The liquid crystal alignment film surface of the other substrate was placed inside and bonded together, and then the sealing agent was cured to produce an empty cell. A liquid crystal cell was prepared by injecting the liquid crystal MLC-6608 (trade name, manufactured by Merck) into the empty cell by vacuum injection.
The response speed characteristics of these liquid crystal cells were measured by the method described later.
After that, in the state where a DC voltage of 20 V was applied to the liquid crystal cell, 20 J of UV was irradiated from the outside of the liquid crystal cell in terms of 365 nm using an ultrahigh pressure mercury lamp. Thereafter, the response speed characteristic was measured again, and the response speed before and after UV irradiation was compared. The results are shown in Table 1.
Thereafter, the obtained liquid crystal cell was annealed in a circulation oven at 100 ° C. for 30 minutes. The extracted cell was observed with a microscope in a state where the polarizing plate was in a crossed Nicol state, and the state of the domain, which was an alignment disorder of the liquid crystal, was observed. The results are also shown in Table 1.
液晶配向剤[K1]を実施合成例2で得られた液晶配向剤[K2]に変更した以外は、実施例1と同様にして液晶セルを作製し、応答速度を測定し、アニール後の配向乱れであるドメインを観察した。その結果を表1に示した。
<実施例3>
液晶配向剤[K1]を実施合成例3で得られた液晶配向剤[K3]に変更した以外は、実施例1と同様にして液晶セルを作製し、応答速度を測定し、アニール後の配向乱れであるドメインを観察した。その結果を表1に示した。 <Example 2>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K2] obtained in Example of Synthesis Example 2, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
<Example 3>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K3] obtained in Example Synthesis Example 3, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
液晶配向剤[K1]を比較合成例1で得られた液晶配向剤[L1]に変更した以外は、実施例1と同様にして液晶セルを作製し、応答速度を測定し、アニール後の配向乱れであるドメインを観察した。その結果を表1に示した。
<比較例2>
液晶配向剤[K1]を比較合成例2で得られた液晶配向剤[L2]に変更した以外は、実施例1と同様にして液晶セルを作製し、応答速度を測定し、アニール後の配向乱れであるドメインを観察した。その結果を表1に示した。
[応答速度特性]
液晶セルに、±5VのAC電圧、周波数1kHzの矩形波を印加した際の、液晶パネルの輝度の時間変化をオシロスコープにて取り込んだ。電圧を印加していない時の輝度を0%、±5Vの電圧を印加し、飽和した輝度の値を100%として、輝度が10%~90%まで変化する時間を立ち上がりの応答速度とした。 <Comparative Example 1>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L1] obtained in Comparative Synthesis Example 1, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
<Comparative example 2>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L2] obtained in Comparative Synthesis Example 2, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
[Response speed characteristics]
The change in luminance of the liquid crystal panel over time when an AC voltage of ± 5 V and a rectangular wave with a frequency of 1 kHz was applied to the liquid crystal cell was captured with an oscilloscope. When no voltage was applied, the luminance was 0%, a voltage of ± 5 V was applied, the saturated luminance value was 100%, and the time for the luminance to change from 10% to 90% was defined as the response speed of the rise.
アニール後のドメイン観察結果
×:ドメインが多数観察される
○:良好
◎:非常に良好
表1からわかるように、実施例1ではUV照射後の応答速度が速く、かつアニール後のドメイン観察結果でも、良好な結果であった。一方比較例1においては、アニール後のドメイン観察結果は非常に良好であるが、応答速度が遅かった。比較例2においては、応答速度は速かったが、アニール後にドメインが多数観察された。更に実施例2、3においても、UV照射後の応答速度が速く、且つアニール後のドメイン観察結果でも非常に良好な結果を示した。
Domain observation result after annealing ×: Many domains are observed ○: Good ◎: Very good As can be seen from Table 1, in Example 1, the response speed after UV irradiation is high, and the domain observation result after annealing is also It was a good result. On the other hand, in Comparative Example 1, the domain observation result after annealing was very good, but the response speed was slow. In Comparative Example 2, the response speed was fast, but many domains were observed after annealing. Furthermore, in Examples 2 and 3, the response speed after UV irradiation was fast, and the results of domain observation after annealing showed very good results.
なお、2011年11月17日に出願された日本特許出願2011-251377号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The liquid crystal display element produced using the liquid crystal aligning agent of the present invention is a liquid crystal display element of a system that improves the response speed after UV irradiation by using a liquid crystal to which a polymerizable compound is not added and treating in the same manner as the PSA system. , A liquid crystal alignment agent capable of forming a liquid crystal alignment film capable of improving the response speed after UV irradiation without reducing the vertical alignment force, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and the liquid crystal alignment film The liquid crystal display element which has can be provided. Therefore, it is useful for a TFT liquid crystal display device, a TN liquid crystal display device, a VA liquid crystal display device and the like manufactured by the above method.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-251377 filed on November 17, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.
Claims (11)
- 下記のポリシロキサン(A)を含有することを特徴とする液晶配向剤。
ポリシロキサン(A):式(1)で表されるアルコキシシラン及び式(3)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサン。
R1Si(OR2)3 (1)
(R1は下記式(2)の構造を表し、R2は炭素数1~5のアルキル基を表す。)
R3Si(OR4)3 (3)
(R3は、アクリル基、アクリロキシ基、メタクリル基、メタクリロキシ基、又はスチリル基で置換された炭素数5~10のアルキル基である。R4は炭素数1~5のアルキル基を表す。) A liquid crystal aligning agent comprising the following polysiloxane (A).
Polysiloxane (A): Polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (3).
R 1 Si (OR 2 ) 3 (1)
(R 1 represents the structure of the following formula (2), and R 2 represents an alkyl group having 1 to 5 carbon atoms.)
R 3 Si (OR 4 ) 3 (3)
(R 3 is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group. R 4 represents an alkyl group having 1 to 5 carbon atoms.) - さらに、ポリシロキサン(B)を含有する請求項1に記載の液晶配向剤。
ポリシロキサン(B):式(5)で表されるアルコキシシランを50~100モル%含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサン。
Si(OR15)4 (5)
(R15は炭素数1~5のアルキル基を表す。) Furthermore, the liquid crystal aligning agent of Claim 1 containing polysiloxane (B).
Polysiloxane (B): polysiloxane obtained by hydrolysis and polycondensation of alkoxysilane containing 50 to 100 mol% of alkoxysilane represented by formula (5).
Si (OR 15 ) 4 (5)
(R 15 represents an alkyl group having 1 to 5 carbon atoms.) - ポリシロキサン(B)が、さらに式(3)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサンである、請求項2に記載の液晶配向剤。 The liquid crystal aligning agent of Claim 2 whose polysiloxane (B) is polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane further represented by Formula (3).
- ポリシロキサン(B)が、さらに式(6)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサンである、請求項2又は3に記載の液晶配向剤。
R16Si(OR17)3 (6)
(R16は、炭素数1~5のアルキル基である。R17は炭素数1~5のアルキル基を表す。) The liquid crystal aligning agent of Claim 2 or 3 whose polysiloxane (B) is polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane further represented by Formula (6).
R 16 Si (OR 17 ) 3 (6)
(R 16 is an alkyl group having 1 to 5 carbon atoms. R 17 represents an alkyl group having 1 to 5 carbon atoms.) - ポリシロキサン(A)及びポリシロキサン(B)の少なくとも一つが、さらに、下記式(4)で表されるアルコキシシランを含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサンである、請求項2~4のいずれかに記載の液晶配向剤。
(R13)nSi(OR14)4-n (4)
(式(4)中、R13は、水素原子、又はヘテロ原子、ハロゲン原子、アミノ基、グリシドキシ基、メルカプト基、イソシアネート基、ウレイド基で置換されていてもよい、炭素数1~10の炭化水素基である。R14は炭素数1~5のアルキル基である。nは0~3の整数を表す。) At least one of the polysiloxane (A) and the polysiloxane (B) is a polysiloxane obtained by further hydrolyzing and polycondensing an alkoxysilane containing an alkoxysilane represented by the following formula (4): Item 5. The liquid crystal aligning agent according to any one of Items 2 to 4.
(R 13 ) n Si (OR 14 ) 4-n (4)
(In the formula (4), R 13 represents a carbon atom having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. A hydrogen group, R 14 is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.) - 前記式(1)で表されるアルコキシシランが、ポリシロキサン(A)に用いられる全アルコキシシラン中、2~20モル%含まれ、かつ前記式(3)で表されるアルコキシシランが、ポリシロキサン(A)に用いられる全アルコキシシラン中、5~70モル%含まれる請求項1~5のいずれかに記載の液晶配向剤。 The alkoxysilane represented by the formula (1) is contained in 2 to 20 mol% in the total alkoxysilane used in the polysiloxane (A), and the alkoxysilane represented by the formula (3) is a polysiloxane. 6. The liquid crystal aligning agent according to claim 1, which is contained in an amount of 5 to 70 mol% in all alkoxysilanes used in (A).
- さらに、溶媒を含有し、かつ全ポリシロキサンの含有量が、SiO2換算で、0.5~15重量%である、請求項1~6のいずれかに記載の液晶配向剤。 7. The liquid crystal aligning agent according to claim 1, further comprising a solvent and having a total polysiloxane content of 0.5 to 15% by weight in terms of SiO 2 .
- 請求項1~7のいずれかに記載の液晶配向剤を基板に塗布し、乾燥、焼成して得られる液晶配向膜。 A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of claims 1 to 7 to a substrate, drying and baking.
- 請求項8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 8.
- 請求項1~7のいずれかに記載の液晶配向剤を塗布し、焼成された2枚の基板で液晶が挟持された液晶セルに、電圧を印加した状態でUVを照射した液晶表示素子。 A liquid crystal display element in which UV is applied in a state where a voltage is applied to a liquid crystal cell in which the liquid crystal is sandwiched between two substrates that have been coated with the liquid crystal aligning agent according to claim 1 and baked.
- 請求項1~7のいずれかに記載の液晶配向剤を塗布し、焼成した2枚の基板で液晶を挟持し、電圧を印加した状態でUVを照射する液晶表示素子の製造方法。 A method for producing a liquid crystal display element, wherein the liquid crystal aligning agent according to any one of claims 1 to 7 is applied, the liquid crystal is sandwiched between two baked substrates, and UV is irradiated while a voltage is applied.
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