Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.
• 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).
• a slit is formed in the ITO (indium tin oxide) electrode of the MVA method (Multi Vertical Alignment) in which protrusions for controlling the direction in which the liquid crystal falls are formed on the TFT substrate or the color filter substrate.
• MVA method Multi Vertical Alignment
• PVA Plasma Vertical Alignment
• PSA Polymer sustained Alignment
• the PSA method is a technology that has attracted attention in recent years.
• a photopolymerizable compound is added to a liquid crystal, an electric field is applied after the liquid crystal panel is manufactured, and ultraviolet light (UV) is irradiated to the liquid crystal panel in a state where the liquid crystal is tilted.
• UV ultraviolet light
• the polymerizable compound is photopolymerized to fix the alignment direction of the liquid crystal, cause a pretilt, and improve the response speed.
• a slit is made in one electrode constituting the liquid crystal panel, and the structure on the opposite electrode pattern can be operated even without a protrusion such as MVA or a slit such as PVA. Panel transmittance can be obtained.
• a liquid crystal layer is provided in which a liquid crystal alignment treatment agent using a polymer having a photoreactive side chain introduced into a polymer molecule is applied to a substrate and brought into contact with a liquid crystal alignment film obtained by baking.
• a technology has been proposed in which a liquid crystal display element can be obtained by irradiating ultraviolet rays while applying a voltage to a liquid crystal display element without producing a polymerizable compound in the liquid crystal without adding a polymerizable compound. Yes. (See Patent Document 2.)
• an inorganic liquid crystal alignment film material is also known together with an organic liquid crystal alignment film material such as polyimide which has been conventionally used.
• an organic liquid crystal alignment film material such as polyimide which has been conventionally used.
• a liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid has been proposed as a coating-type inorganic liquid crystal alignment film material. It has been reported that a liquid crystal alignment film having excellent vertical alignment properties, heat resistance and uniformity is formed on a substrate. (See Patent Document 3)
• Japanese Unexamined Patent Publication No. 2004-302061 Japanese Unexamined Patent Publication No. 2011-95967 Japanese Unexamined Patent Publication No. 09-281502 Japanese Unexamined Patent Publication No. 2005-250244
• An object of the present invention is to use a liquid crystal to which a polymerizable compound is not added and treat the same as in the PSA method to improve the response speed after UV irradiation without reducing the vertical alignment force.
• the present inventor conducted extensive research to achieve the above object, and as a result, at least one polymer (component (A)) selected from the group consisting of polyamic acid and polyimide and a specific polysiloxane ((B The present invention has been completed by finding that the above-mentioned object can be achieved by a liquid crystal aligning agent containing component)).
• component (A) selected from the group consisting of polyamic acid and polyimide and a specific polysiloxane
• the liquid crystal aligning agent characterized by containing the following (A) component and (B) component.
• Component (A) at least one polymer selected from the group consisting of polyamic acid and polyimide.
• R 1 Si (OR 2 ) 3 (1) (R 1 is a structure of the following formula (2), and R 2 is 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 linear or branched hydrocarbon group having 3 to 8 carbon atoms containing a double bond, or — (CR 17 R 18 ) b — (b is an integer of 1 to 15, R 17 and R 18 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
• Y 4 is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms.
• Y 4 may be a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton.
• 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 is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
• Y 6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
• n is an integer of 0-4.
• R 3 Si (OR 4 ) 3 (3) R 3 is an alkyl group having 1 to 30 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R 4 is an alkyl group having 1 to 5 carbon atoms.
• the liquid-crystal aligning agent of said 1 which is a polysiloxane obtained by polycondensing alkoxysilane which further contains the alkoxysilane represented by following formula (4).
• R 5 is a hydrogen atom or a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, or a ureido group, which has 1 to 10 carbon atoms.
• R 6 is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3.) 3.
• the liquid crystal aligning agent according to 2 above wherein the alkoxysilane represented by the formula (4) is tetramethoxysilane or tetraethoxysilane. 4). Of all the alkoxysilanes used in the production of the polysiloxane (B), 2 to 20 mol% of the alkoxysilane represented by the formula (1) is used, and 5 alkoxysilanes represented by the formula (3) are used. 2. The liquid crystal aligning agent according to the above 1, which is used at ⁇ 80 mol%. 5. 4.
• the component (B) is contained in an amount of 0.5 to 80 parts by mass, based on 100 parts by mass of the component (A), in which the component (B) is equivalent to the SiO 2 of the silicon atom contained in the component (B).
• a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film capable of improving the response speed after UV irradiation without decreasing the vertical alignment force, and a liquid crystal alignment obtained from the liquid crystal alignment treatment agent
• a liquid crystal display element having a film and a liquid crystal alignment film which has a liquid crystal alignment film and is treated in the same manner as the PSA system using a liquid crystal to which no polymerizable compound is added, thereby improving the response speed after UV irradiation.
• the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of polyamic acid and polyimide.
• Specific structures of the polyamic acid and the polyimide are not particularly limited, and may be, for example, a polyamic acid or a polyimide contained in a known liquid crystal aligning agent.
• the polyamic acid can be easily obtained by a (polycondensation) reaction between tetracarboxylic acid or a tetracarboxylic acid derivative and a diamine.
• the manufacturing method of the polyamic acid and polyimide which are (A) component used for this invention is not specifically limited.
• a polyamic acid is obtained by reacting one or more tetracarboxylic acid components selected from the group consisting of tetracarboxylic acids or derivatives thereof with a diamine component consisting of one or more diamine compounds. Get.
• a method for obtaining polyimide a method of imidizing polyamic acid is used.
• the polyamic acid obtained can be made into a homopolymer or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component as raw materials.
• the tetracarboxylic acid or a derivative thereof is tetracarboxylic acid, tetracarboxylic acid dihalide, or tetracarboxylic dianhydride.
• tetracarboxylic dianhydrides are preferred because of their high reactivity with diamine compounds.
• pyromellitic acid 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-di Carboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,
• alicyclic tetracarboxylic acids are preferred from the viewpoint of the transparency of the coating film.
• 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [ 3,3,0] octane-2,4,6,8-tetracarboxylic acid, dihalides of these tetracarboxylic acids, or dianhydrides of these tetracarboxylic acids are preferred.
• the above-mentioned tetracarboxylic acids or derivatives thereof can be used alone or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when formed into a liquid crystal alignment film.
• the diamine used for production of the polyamic acid is not particularly limited.
• p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m- Phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4- Diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3, , 3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,4
• Bis (3-aminopropyl) tetramethyldisiloxane is preferably used.
• diamine which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the macrocyclic substituent which consists of them in a diamine side chain
• diamines represented by the following formulas [A1] to [A20] can be exemplified.
• R 1 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• R 2 is —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—
• R 3 is a hydrogen atom, carbon number 1 or more and 22 or less alkyl group or fluorine-containing alkyl group.
• R 4 is —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
• R 5 is an alkyl group, alkoxy, having 1 to 22 carbon atoms. Group, fluorine-containing alkyl group or fluorine-containing alkoxy group.
• R 6 is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2 —.
• R 7 is an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group having 1 to 22 carbon atoms.
• R 8 is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O — Or —NH—
• R 9 is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, a hydroxyl group, or a carboxyl group.
• the diamines described above can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed. If the diamine which has a hydroxyl group or a carboxyl group is used in the above-mentioned raw material of polyamic acid, the reaction efficiency of a polyamic acid or a polyimide and the crosslinkable compound mentioned later can be improved.
• diamines include 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 3,3 '-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, formula [A22] to [ And diamines represented by A25].
• R 10 is —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
• R 11 is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O -Or -NH-, R 12 is a hydroxyl group or a carboxyl group.
• the solvent used for producing the polyamic acid is not particularly limited as long as the produced polyamic acid can be dissolved.
• Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, Pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl Cellosolve acetate, ethyl cellosolve acetate, butyl car
• the solvent may be used alone or in combination.
• it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
• water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
• a method of adding a dispersion or solution in an organic solvent or a method of adding a diamine to a solution in which a tetracarboxylic acid or a derivative thereof is dispersed or dissolved in an organic solvent, or a tetracarboxylic acid or a derivative thereof and a diamine.
• the method of adding alternately etc. are mentioned. Any of these methods may be used.
• tetracarboxylic acid or a derivative thereof, or diamine is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed to form a high molecular weight product.
• the temperature for synthesizing the polyamic acid can be selected from -20 to 150 ° C, but is preferably in the range of -5 to 100 ° C.
• reaction can be performed by arbitrary density
• the initial reaction may be carried out at a high concentration, and then an organic solvent may be added.
• the ratio of the number of moles of the diamine component to the number of moles of tetracarboxylic acid or its derivative is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. preferable. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
• thermal imidization by heating and catalyst imidization using a catalyst are generally used, but the catalyst imidation in which the imidization reaction proceeds at a relatively low temperature is obtained. It is preferable that the molecular weight does not decrease.
• the catalyst imidization can be performed by stirring the polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride.
• the reaction temperature at this time is ⁇ 20 to 250 ° C., preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but if it is too high, the molecular weight of the polyimide may decrease.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it becomes difficult to completely remove the reaction after completion of the reaction.
• Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
• Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
• the organic solvent for the catalyst imidation is not limited as long as the polyamic acid dissolves. Specific examples thereof include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl Urea, dimethyl sulfone, hexamethyl sulfoxide, ⁇ -butyrolactone, and the like.
• the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
• the produced polyimide can be obtained by collecting the reaction solution into a poor solvent and collecting the produced precipitate.
• the poor solvent to be used is not specifically limited.
• methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like can be mentioned.
• the polyimide that has been poured into a poor solvent and precipitated is filtered, and then can be powdered by drying at normal temperature or under reduced pressure at normal temperature or under reduced pressure.
• the polyimide can be purified by repeating the steps of dissolving the polyimide powder in an organic solvent and reprecipitating it 2 to 10 times. When the impurities cannot be removed by a single precipitation recovery operation, it is preferable to perform this purification step.
• the molecular weight of the polyimide used in the present invention is not particularly limited, but is preferably 2,000 to 200,000 in terms of weight average molecular weight, more preferably 4, from the viewpoint of ease of handling and stability of characteristics when a film is formed. 000 to 50,000.
• the molecular weight is determined by GPC (gel permeation chromatography).
• ⁇ (B) component polysiloxane> (B) component contained in the liquid-crystal aligning agent of this invention is obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1), and the alkoxysilane represented by Formula (3). Polysiloxane.
• R 1 Si (OR 2 ) 3 (1) (R 1 is a structure of the following formula (2), and R 2 is an alkyl group having 1 to 5 carbon atoms.)
• R 3 Si (OR 4 ) 3 (3) (R 3 is an alkyl group having 1 to 30 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group, and R 4 is 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) has 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—. .
• selecting a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO— It is preferable from the viewpoint of facilitating.
• Y 2 is a straight or branched hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or — (CR 17 R 18 ) b — (b is an integer of 1 to 15, R 17 and R 18 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Of these, — (CH 2 ) b — (b is an integer of 1 to 10) is preferable from the viewpoint of significantly improving the response speed of the liquid crystal display element.
• Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
• Y 4 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted by an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
• Y 4 may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. Among these, an organic group having 12 to 25 carbon atoms having any one of a benzene ring, a cyclohexane ring, and a steroid skeleton is preferable.
• Y 5 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, It may be substituted with 3 alkoxyl groups, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
• n is an integer of 0-4.
• it is an integer of 0-2.
• Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
• an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
• liquid crystal alignment treatment agent using polysiloxane introduced with such side chains and photoreactive groups can achieve both response speed characteristics and good vertical alignment, it is similar to the liquid crystal skeleton.
• a side chain having a structure it is presumed that the response speed and the vertical alignment, which are normally in a trade-off relationship, are compatible.
• Preferable combinations of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n in the formula (2) are pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27).
• the same combinations as (2-1) to (2-629) listed in Tables 6 to 47 of the above are listed.
• Y 1 to Y 6 in the present invention are indicated as Y 1 to Y 6, but Y 1 to Y 6 should be read as Y 1 to Y 6 .
• 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 produced by a known method (Japanese Patent Laid-Open No. 61-28639). Although the specific example is given to the following, it is not limited to this.
• R 5 is —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—
• R 6 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or a fluorine-containing alkyl group. Group or fluorine-containing alkoxy group.
• R 7 is a single bond, —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, — (CH 2 ) n O— (n is an integer of 1 to 5), —OCH 2 — or — CH 2 — and R 8 is 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 is —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 — or —O—
• R 10 is a fluorine group , Cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or 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, and 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 with “*” is bonded to B 3 ), and B 1 is an oxygen atom or —COO— * (where “*” is attached).
• the resulting bond 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.
• the above-mentioned alkoxysilane is one kind or the like depending on the solubility in the solvent when the siloxane polymer is used, the orientation of the liquid crystal when the liquid crystal alignment film is used, the pretilt angle characteristics, the voltage holding ratio, the accumulated charge, etc. Two or more types can be mixed and 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 is preferably 1 mol% or more in order to obtain good liquid crystal alignment in all alkoxysilanes used for obtaining polysiloxane. More preferably, it is 1.5 mol% or more.
• the liquid crystal alignment film More preferably, it is 2 mol% or more. Further, in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed, 30 mol% or less is preferable. More preferably, it is 25 mol% or less. More preferably, it is 20 mol% or less.
• R 3 (hereinafter also referred to as a second specific organic group) of the alkoxysilane represented by the formula (3) is an alkyl group substituted with an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group.
• the number of substituted hydrogen atoms is one or more, preferably one.
• the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. More preferably, it is 1-10.
• R 4 of the alkoxysilane represented by the formula (3) is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.
• alkoxysilane represented by Formula (3) is not limited to these.
• 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, or styrylethyltrimethoxysilane is preferable.
• the polysiloxane which is the component (B) is improved in adhesion to the substrate and affinity with liquid crystal molecules.
• one or more alkoxysilanes represented by the following formula (4) can be used for the purpose of improving the properties.
• the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, and one or more types can be selected and used depending on the required properties.
• R 5 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group.
• R 6 is an alkyl group having 1 to 5, preferably 1 to 3 carbon atoms, and n is an integer of 0 to 3, preferably 0 to 2.
• R 5 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; 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. Further, this 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 Formula (4) is not limited to this.
• 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).
• the alkoxysilane represented by the formula (1) is preferably 2 to 20 mol%, particularly preferably 3 to 15 mol%, based on the total alkoxysilane used in the production of the polysiloxane of the component (B).
• the alkoxysilane represented by the formula (3) is used in an amount of 5 to 80 mol%, particularly preferably 10 to 70 mol%, based on the total alkoxysilane used for the production of the polysiloxane of the component (B). Is desirable.
• the alkoxysilane represented by the formula (4) is preferably 10 to 90 mol%, particularly preferably 20 to 20% of the total alkoxysilane used when used for the production of the polysiloxane of the component (B). It is desirable to use 90 mol%.
• the method for obtaining the polysiloxane used in the present invention is not particularly limited, and can be obtained by polycondensation of an alkoxysilane having the above-mentioned alkoxysilane of formula (1) as an essential component in an organic solvent. Therefore, the polysiloxane is obtained as a solution uniformly dissolved in an organic solvent.
• the method of hydrolyzing and condensing the alkoxysilane of the said Formula (1) in solvents, such as alcohol or glycol is mentioned.
• the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 moles of water of all alkoxide groups in the alkoxysilane, but it is usually preferable to add an excess amount of water over 0.5 moles.
• the amount of water used in the above reaction can be appropriately selected as desired, but it is usually within a range of 0.5 to 2.5 moles of all alkoxy groups in the alkoxysilane.
• the amount is preferably 0.5 to 2.5 times mol, more preferably 0.5 to 1.5 times mol.
• acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid;
• a metal salt such as hydrochloric acid, sulfuric acid or nitric acid;
• a method of heating and polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding succinic acid to alcohol in advance to make an alcohol solution of succinic acid, 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. A method of heating for several tens of minutes to several tens of hours under reflux is preferred so that the liquid does not evaporate or volatilize.
• the plurality of alkoxysilanes may be mixed and reacted in advance, or a plurality of alkoxysilanes may be mixed and reacted in sequence.
• the solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even when alkoxysilane does not melt
• the polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, 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 -Glycols such as pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Tylene glycol monobutyl ether, ethylene glycol mono
• 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 also referred to as SiO 2 conversion concentration). ) Is preferably 20% by mass or less, particularly preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
• the polysiloxane polymerization solution obtained by the above method may be used as the solution of the component (B) as it is, or if necessary, the solution obtained by the above method may be concentrated or solvent It is good also as a solution of (B) component by adding and diluting or substituting with another solvent.
• 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.
• the additive solvent examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, and ethyl lactate in addition to the solvents mentioned as examples of the polymerization solvent. .
• ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
• esters such as methyl acetate, ethyl acetate, and ethyl lactate in addition to the solvents mentioned as examples of the polymerization solvent.
• solvents can improve the applicability when applying the liquid crystal aligning agent on the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, inkjet, or the like.
• the solvent used in the solution of the component (B) is N, N′-dimethylformamide, N, N′-dimethylacetamide.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, dimethyl sulfone, hexamethyl sulfoxide, ⁇ -butyrolactone, and ethylene glycol monobutyl ether are preferred.
• [Liquid crystal aligning agent] Content of (B) component (polysiloxane) in the liquid-crystal aligning agent of this invention is SiO of the silicon atom which (B) component has with respect to 100 mass parts of (A) component containing polyamic acid and / or a polyimide.
• the value in terms of 2 is 0.5 to 80 parts by mass, preferably 0.5 to 50 parts by mass.
• the content of the component (B) (polysiloxane) is more preferably 10 to 80 on the same basis in order not to deteriorate the vertical alignment of the liquid crystal. Part by mass, more preferably 20 to 70 parts by mass.
• the liquid crystal aligning agent of the present invention is not particularly limited, it is usually necessary to form a uniform thin film of 0.01 to 1.0 ⁇ m on the substrate when producing the liquid crystal alignment film.
• a coating solution containing an organic solvent for dissolving these components is preferable.
• the content of the organic solvent is 90 to 99% by mass in the liquid crystal aligning agent from the viewpoint of forming a uniform thin film by coating. It is preferably 92 to 97% by mass. These contents can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.
• organic solvent used in the liquid crystal aligning agent of the present invention include organic solvents used in the above-described polyamic acid or polyimide synthesis reaction. Particularly preferred are N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone and the like. These organic solvents may be used alone or in combination of two or more.
• the amount is preferably 80% by mass or less, more preferably 60% by mass or less in the organic solvent. Moreover, if the improvement of the uniformity of a coating film is anticipated, 5 mass% or more in an organic solvent is preferable, More preferably, it is 20 mass% or more.
• the liquid crystal alignment treatment agent of the present invention can contain a compound for improving the adhesion between the coating film and the substrate, a surfactant for enhancing the flatness of the coating film, and the like.
• the compound for improving the adhesion between the coating film and the substrate include the following functional silane-containing compounds.
• the amount of these compounds added is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint that the effect of improving adhesion can be obtained and the orientation of the liquid crystal is not lowered. More preferred is 1 to 20 parts by mass, and particularly 1 to 10 parts by mass.
• the surfactant for improving the flatness of the coating film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
• F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).
• the content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of component (A).
• the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied onto a substrate and baked, and then subjected to alignment treatment by rubbing treatment, light irradiation, or the like, or without alignment treatment in vertical alignment applications.
• the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate; a plastic substrate such as an acrylic substrate or a polycarbonate substrate; Furthermore, it is preferable from the viewpoint of simplification of the process to use a substrate on which an ITO electrode or an IZO (indium zinc oxide) electrode for driving a liquid crystal is formed.
• an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as metal aluminum can be used as the electrode.
• a method for applying the liquid crystal alignment treatment agent is not particularly limited, but a method of performing screen printing, offset printing, flexographic printing, ink jet, or the like is common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
• the substrate after applying the liquid crystal aligning agent is placed on a hot plate at 70 to 100 ° C. for about 1 to 3 minutes to evaporate the solvent and then dried, and then fired.
• the calcination can be performed at an arbitrary temperature of 100 to 350 ° C., preferably 120 to 300 ° C., more preferably 150 to 250 ° C. This baking can be performed with a hot plate, a hot-air circulating furnace, an infrared furnace, or the like.
• the thickness of the coating film after baking is preferably 5 to 300 nm, more preferably The thickness is 10 to 150 nm, more preferably 50 to 100 nm.
• the liquid crystal display element of the present invention is a display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention and then preparing a liquid crystal cell by a known method.
• a pair of substrates on which a liquid crystal alignment film is formed are prepared, column spacers are formed on the liquid crystal alignment film on one substrate, or bead spacers are scattered on the liquid crystal alignment film.
• the other side is bonded so that the surface is on the inside, and the liquid crystal is injected under reduced pressure to seal, or the liquid crystal is dropped on the liquid crystal alignment film surface where column spacers are formed or beads spacers are dispersed
• the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
• TEOS tetraethoxysilane
• C18 octadecyltriethoxysilane
• C12 dodecyltriethoxysilane
• UPS 3-ureidopropyltriethoxysilane
• MPMS 3-methacryloxypropyltrimethoxysilane
• VTMS vinyltrimethoxysilane
• STMS styrylethyltrimethoxysilane
• MTES Methyltriethoxysilane
• CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
• BDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
• PMDA pyromellitic dianhydride
• BODA bicyclo [3,3 0] octane-2,4,6,8-tetracarboxylic dianhydride
• the production of the liquid crystal cell and the evaluation of electrical characteristics, vertical alignment, reworkability, whitening characteristics, response speed, etc. were performed as follows.
• liquid crystal alignment film surface of one of the substrates was turned inside and the two substrates were bonded together, and then the sealing agent was cured to produce an empty cell.
• liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into the empty cell by vacuum injection to produce a liquid crystal cell.
• the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
• the liquid crystal aligning agent was spin-coated on the ITO electrode substrate on which the solid ITO electrode was formed. Then, after drying for 2 minutes with an 80 degreeC hotplate, it baked for 30 minutes in 200 degreeC or 220 degreeC hot-air circulation type oven, and formed the liquid crystal aligning film with a film thickness of 100 nm.
• the substrate was immersed in NMD-3 manufactured by Tokyo Ohka Kogyo Co., Ltd. at 50 ° C. for 10 minutes, washed with water, and dried in an 80 ° C. hot air circulation oven for 10 minutes. Thereafter, the state before and after the immersion is visually observed and the contact angle is measured. If the contact angle returns to the state before application of the liquid crystal alignment treatment agent, it can be reworked: ⁇ . went.
• a liquid crystal alignment treatment agent is spin-coated on a chromium substrate (a glass substrate on which chromium is deposited), and is allowed to stand for 10 minutes in an atmosphere at a temperature of 23 ° C. and a relative humidity of 60%. It was visually observed whether or not this occurred.
• [Evaluation of response speed] 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.
• the luminance When the voltage is not applied, the luminance is 0%, ⁇ 5V voltage is applied, the saturated luminance value is 100%, the time when the luminance changes from 10 to 90% is the rising response speed, and the liquid crystal
• the response speed after irradiating heat or ultraviolet rays was evaluated while applying an AC or DC voltage to the cell obtained according to the cell manufacturing method.
• Example 1 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A1) were mixed to obtain a liquid crystal aligning agent (8). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Table 7.
• Example 2 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A2) were mixed to obtain a liquid crystal aligning agent (9). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Table 7.
• Example 3 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A3) were mixed to obtain a liquid crystal aligning agent (10). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Table 7.
• Example 4 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A4) were mixed to obtain a liquid crystal aligning agent (11). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Table 7.
• Example 5 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A5) were mixed to obtain a liquid crystal aligning agent (12). Using this liquid crystal aligning agent, [Evaluation of response speed], [Evaluation of vertical alignment] and [Evaluation of reworkability] were performed. The results are shown in Table 7, Table 8, and Table 10. Furthermore, voltage holding ratio and ion density were evaluated according to [Evaluation of electrical characteristics]. The results are shown in Table 9.
• Example 6 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A6) were mixed to obtain a liquid crystal aligning agent (13). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Table 7.
• Example 7 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A7) were mixed to obtain a liquid crystal aligning agent (14). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Table 7.
• Example 8 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A8) were mixed to obtain a liquid crystal aligning agent (15). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Table 7. Furthermore, voltage holding ratio and ion density were evaluated according to [Evaluation of electrical characteristics]. The results are shown in Table 9.
• Example 9 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A9) were mixed to obtain a liquid crystal aligning agent (16). Using this liquid crystal aligning agent, [Evaluation of response speed], [Evaluation of vertical alignment] and [Evaluation of reworkability] were performed. The results are shown in Table 7 and Table 10.
• Example 10 3.0 g of polysiloxane solution (B5) and 7.0 g of polyamic acid solution (A10) were mixed to obtain a liquid crystal aligning agent (17). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Table 7.
• Example 11 3.0 g of polysiloxane solution (B6) and 7.0 g of polyamic acid solution (A1) were mixed to obtain a liquid crystal aligning agent (18). [Evaluation of response speed] and [Evaluation of vertical alignment] were performed using this liquid crystal alignment treatment agent. The results are shown in Tables 7 and 8.
• the liquid crystal alignment treatment agent containing ureido group (Reference Example 1) has a VHR (voltage holding ratio) as compared with the liquid crystal alignment treatment agent not containing ureido group (Comparative Example 2). High and low ion density.
• the liquid crystal alignment treatment agent containing at least one polymer selected from the group consisting of polyamic acid and polyimide is compared with the liquid crystal alignment treatment agent containing only the polysiloxane component. It was found that reworkability is high.
• Example 7 In Table 7, in Example 1, the response speed after UV irradiation was fast, and the domain observation result after annealing was also good. On the other hand, in Comparative Example 8, the domain observation result after annealing was very good, but the response speed after UV irradiation was slow. In Comparative Example 7, the response speed was fast, but many domains were observed after annealing. Further, in Examples 2 to 11 and Comparative Examples 9 and 10, the response speed after UV irradiation was high, and the domain observation results after annealing showed very good results.
• the response speed with respect to the UV irradiation amount is at least one polymer selected from the group consisting of polyamic acid and polyimide, compared with the liquid crystal alignment treatment agent consisting of polysiloxane alone in Comparative Example 11 and Comparative Example 12. It was found that the liquid crystal alignment treatment agent contained has a wider range of improved response speed to UV irradiation.
• the liquid crystal aligning agent containing a ureido group has a higher VHR and ion density than the liquid crystal aligning agent containing no ureido group. was found to be low.
• the liquid crystal alignment treatment agent containing at least one polymer selected from the group consisting of polyamic acid and polyimide is reworked compared to the liquid crystal alignment treatment agent composed of inorganic alone. It was found that the nature is high.
• the liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention does not have a reduced vertical alignment force and has an excellent response speed after UV irradiation, and the liquid crystal display element having the liquid crystal alignment film of the present invention is It is useful for TFT liquid crystal display elements, TN liquid crystal display elements, VA liquid crystal display elements, and the like.
• the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2012-190328 filed on August 30, 2012 are incorporated herein as the disclosure of the specification of the present invention. Is.

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