CN105899615B - Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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Abstract
The present invention provides a composition containing (a) component: the following formula [1](formula [1]]In, X1And X2Each independently represents an alkyl group having 1 to 3 carbon atoms, X3And X4Each independently represents an alkyl group having 1 to 3 carbon atoms); and (B) component (A): a polysiloxane.
Description
Technical Field
The present invention relates to a composition for forming a resin coating film, a liquid crystal aligning agent for producing a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal alignment film.
Background
Attention has been paid to ease of forming a resin coating film made of an organic material such as a polymer material, insulating performance, and the like, and the resin coating film is widely used as an interlayer insulating film, a protective film, and the like in electronic devices. Among them, in a liquid crystal display element widely known as a display device, a resin coating film formed of an organic material or an inorganic material is used as a liquid crystal alignment film.
At present, for compositions for forming resin coatings used in industry, compositions containing polyimide polymers having excellent durability and polysiloxane polymers obtained by polycondensation of alkoxysilanes have been used.
In recent years, inorganic resin coatings formed from a composition containing a polysiloxane polymer have been used for interlayer insulating films and protective films, and further, for liquid crystal alignment films. Among them, in order to improve the liquid crystal alignment properties with respect to heat in a liquid crystal display element (for example, patent document 1), or to improve the film hardness of a liquid crystal alignment film and to improve the printing coatability of a liquid crystal alignment treatment agent (for example, patent document 2), a liquid crystal alignment treatment agent and a liquid crystal alignment film using a polysiloxane-based polymer have been proposed.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2001-27761
Patent document 2: international publication No. 2008/044644
Disclosure of Invention
Problems to be solved by the invention
Resin-coated films obtained from polysiloxane polymers are widely used as interlayer insulating films and protective films in electronic devices, and further, as liquid crystal alignment films for liquid crystal display elements. Further, it is required to improve the film coatability of the resin coating film, the protective film and the liquid crystal alignment film. That is, it is effective to improve the film coatability of these films for suppressing defects of electronic devices and liquid crystal display elements caused by poor film coatability.
In recent years, liquid crystal display elements have been widely used for large-screen liquid crystal televisions and high-definition mobile applications (display parts of digital cameras and cellular phones). Accordingly, the size of the substrate used is increased and the unevenness of the height difference of the substrate is gradually increased as compared with the conventional substrate. Under such circumstances, it is required to uniformly apply a liquid crystal alignment film to a large substrate or a level difference in order to improve the display characteristics of the liquid crystal display element and suppress defects. In particular, it is required to apply a liquid crystal alignment film to the unevenness of the substrate height difference in a uniform film thickness (also referred to as improvement of the height difference following property).
In the composition and the liquid crystal alignment treatment agent obtained from the polysiloxane polymer, the polysiloxane polymer has a low molecular weight, and therefore, the level difference following property between the resin coating film and the liquid crystal alignment film (also collectively referred to as the resin coating film) is low. That is, a resin coating having a uniform thickness cannot be obtained on the irregularities of the substrate height difference. Specifically, the resin coating is not applied to the projections having a difference in substrate height or the film thickness thereof is easily reduced. Accordingly, the functions as an interlayer insulating film, a protective film, and a liquid crystal alignment film of a liquid crystal display element in an electronic device cannot be expressed, and the defects are likely to occur.
In addition, the liquid crystal alignment film is also used to control the angle of liquid crystal with respect to the substrate, i.e., the pretilt angle of liquid crystal. In particular, in VA (Vertical Alignment) mode, PSA (Polymer stabilized Alignment) mode, and the like, it is necessary to vertically align liquid crystal, and therefore, a liquid crystal Alignment film is required to have a capability of vertically aligning liquid crystal (also referred to as Vertical Alignment, high pretilt angle). Further, the liquid crystal alignment film is important not only for high vertical alignment properties but also for stability. In particular, liquid crystal display elements such as car navigation systems and large televisions, which use backlights having a large amount of heat generation and a large amount of light irradiation in order to obtain high luminance, are sometimes used or left in an environment exposed to high temperatures and light irradiation for a long time. Under such severe conditions, when the vertical alignment property is lowered, problems such as failure to obtain the initial expression characteristics and occurrence of unevenness in expression occur.
Accordingly, an object of the present invention is to provide a composition having the above-mentioned properties. That is, an object of the present invention is to provide a composition that can suppress the occurrence of pinholes associated with shrinkage when forming a resin coating film, and that has high level difference following properties with respect to irregularities of a level difference substrate.
Further, the liquid crystal aligning agent using the composition of the present invention can suppress the occurrence of pin holes accompanying shrinkage when forming a liquid crystal alignment film, and further can provide a liquid crystal aligning agent having high level difference following properties with respect to unevenness of a level difference substrate. Further, a liquid crystal alignment treatment agent which forms a liquid crystal alignment film capable of exhibiting a stable pretilt angle even after long-term exposure to high temperature and light irradiation is provided.
It is another object of the present invention to provide a resin coating film obtained from the composition, 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.
Means for solving the problems
The inventors of the present invention conducted extensive studies and found that: the present inventors have completed the present invention by finding that a composition comprising a solvent having a specific structure and a polysiloxane obtained by polycondensing an alkoxysilane having a specific structure is extremely effective for achieving the above object.
That is, the present invention has the following gist.
(1) A composition comprising:
(A) the components: a solvent represented by the following formula [1 ]; and
(B) the components: a polysiloxane obtained by polycondensing an alkoxysilane containing at least 1 selected from alkoxysilanes represented by the following formulae [2a ], [2b ] and [2c ],
(in the formula, X1And X2Each independently represents an alkyl group having 1 to 3 carbon atoms, X3And X4Each independently represents an alkyl group having 1 to 3 carbon atoms)
{ formula (I), wherein A1Is represented by a formula [2a-1] selected from]And formula [2a-2]At least 1 of the structures shown; a. the2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; a. the3Each independently represents an alkyl group having 1 to 5 carbon atoms; m is1Represents an integer of 1 or 2; n is1Represents an integer of 0 to 2; p is a radical of1Represents an integer of 0 to 3; wherein m is1+n1+p1Which represents the integer 4, represents the number of atoms,
(in the formula, Y1Represents a group selected from a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from CO-, -COO-and-OCO-; y is2Represents a single bond or- (CH)2)b- (b is an integer of 1 to 15); y is3Represents a group selected from a single bond, - (CH)2)c- (c is an integer of 1 to 15), -O-, -CH2At least 1 bonding group selected from O-, -COO-and-OCO-; y is4At least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 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 is5Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom on the cyclic groups is optionally substituted by alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms, fluorine-containing alkyl with 1 to 3 carbon atoms, fluorine-containing alkoxy with 1 to 3 carbon atoms or fluorine atom; n represents an integer of 0 to 4; y is6Represents at least 1 selected from alkyl group having 1 to 22 carbon atoms, alkenyl group having 2 to 22 carbon atoms, fluorine-containing alkyl group having 1 to 22 carbon atoms, alkoxy group having 1 to 22 carbon atoms and fluorine-containing alkoxy group having 1 to 22 carbon atoms)
-Y7-Y8 [2a-2]
(in the formula, Y7Represents a group selected from a single bond, -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from CO-, -COO-and-OCO-; y is8Alkyl having 8 to 22 carbon atoms or fluoroalkyl having 6 to 18 carbon atoms);
(in the formula, B1Each independently represents an organic group having 2 to 12 carbon atoms and at least 1 selected from vinyl, epoxy, amino, mercapto, isocyanate, methacryloyl, acryloyl, ureido, and cinnamoyl groups; b is2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; b is3Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms; m is2Represents an integer of 1 or 2; n is2Represents an integer of 0 to 2; p is a radical of2Represents an integer of 0 to 3; wherein m is2+n2+p2Represents an integer of 4);
(in the formula, D1Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; d2Each independently represents an alkyl group having 1 to 5 carbon atoms; n is3Represents an integer of 0 to 3).
(2) The composition according to the above (1), wherein the solvent of the component (A) is a solvent represented by the following formula [1a ].
(3) The composition as set forth in the above (1) or (2), wherein the alkoxysilane represented by the formula [2B ] of the component (B) is at least 1 alkoxysilane selected from the group consisting of allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate.
(4) The composition according to the above (1) or (2), wherein the alkoxysilane represented by the formula [2B ] of the component (B) is at least 1 alkoxysilane selected from the group consisting of 3-glycidoxypropyl (dimethoxy) methylsilane, 3-glycidoxypropyl (diethoxy) methylsilane, 3-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
(5) The composition according to any one of the above (1) to (4), wherein the polysiloxane of the component (B) is a polysiloxane containing 1 polysiloxane out of polysiloxanes obtained by polycondensing alkoxysilanes represented by the formulas [2a ] and [2B ] or polysiloxanes obtained by polycondensing alkoxysilanes represented by the formulas [2a ] and [2c ].
(6) The composition according to any one of the above (1) to (5), wherein the polysiloxane of the component (B) is a polysiloxane obtained by polycondensation of alkoxysilanes represented by the formula [2a ], the formula [2B ] and the formula [2c ].
(7) The composition according to any one of the above (1) to (6), wherein the composition contains at least 1 solvent selected from the group consisting of methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and furfuryl alcohol.
(8) The composition according to any one of the above (1) to (7), wherein the composition contains at least 1 solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone and 1, 3-dimethylimidazolidinone.
(9) The composition according to any one of the above (1) to (8), wherein the composition contains at least 1 crosslinkable compound selected from the following crosslinkable compounds: a crosslinkable compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclocarbonate group; a crosslinkable compound having at least 1 substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group; and a crosslinkable compound having a polymerizable unsaturated bond.
(10) The composition according to any one of the above (1) to (9), wherein the component (A) is 20 to 80% by mass of the entire solvent contained in the composition.
(11) The composition according to any one of the above (1) to (10), wherein the component (B) is 0.1 to 30% by mass in the composition.
(12) A resin coating film obtained from the composition according to any one of the above (1) to (11).
(13) A liquid crystal aligning agent obtained from the composition according to any one of the above (1) to (11).
(14) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to the above (13).
(15) A liquid crystal alignment film obtained by an ink jet method using the liquid crystal alignment treatment agent according to (13) above.
(16) A liquid crystal display element comprising the liquid crystal alignment film according to the above (14) or (15).
(17) The liquid crystal alignment film according to the above (14) or (15), which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and manufactured through the following steps: a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the polymerizable compound is polymerized while applying a voltage between the electrodes.
(18) A liquid crystal display element comprising the liquid crystal alignment film according to (17) above.
(19) The liquid crystal alignment film according to the above (14) or (15), which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and manufactured through the following steps: a liquid crystal alignment film including a polymerizable group that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the polymerizable group is polymerized while applying a voltage between the electrodes.
(20) A liquid crystal display element comprising the liquid crystal alignment film according to (19) above.
ADVANTAGEOUS EFFECTS OF INVENTION
The composition of the present invention containing a solvent having a specific structure and a polysiloxane obtained from an alkoxysilane having a specific structure can be provided as a composition which can suppress the occurrence of pinholes when forming a resin coating film and further has high level difference following properties with respect to the unevenness of a level difference substrate.
Further, by using the composition of the present invention as a liquid crystal alignment treatment agent, it is possible to provide a liquid crystal alignment film which can suppress the occurrence of pinholes and has high level difference following properties with respect to the unevenness of a level difference substrate. Further, the liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after long-term exposure to high temperature and light irradiation. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for large-screen and high-definition liquid crystal televisions, medium-and small-sized car navigation systems, smart phones, and the like.
Drawings
Fig. 1 is a schematic view of a step substrate having a resin coating film obtained by applying the composition of the present invention.
Detailed Description
The present inventors have conducted extensive studies and, as a result, have obtained the following findings, thereby completing the present invention.
The present invention relates to a composition containing the following component (a) and component (B), a liquid crystal alignment treatment agent, a resin coating film obtained using the composition, a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.
(A) The components: a solvent represented by the following formula [1] (also referred to as a specific solvent).
(formula [1]]In, X1And X2Each independently represents an alkyl group having 1 to 3 carbon atoms, X3And X4Each independently represents an alkyl group having 1 to 3 carbon atoms).
(B) The components: a polysiloxane (also referred to as a specific polysiloxane) obtained by polycondensation of alkoxysilanes containing at least 1 kind selected from alkoxysilanes represented by the following formulae [2a ], [2b ] and [2c ].
(formula [2a ]]In (A)1Is represented by a formula [2a-1] selected from]And formula [2a-2]At least 1 of the structures shown (also collectively referred to as particular side chain structures); a. the2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; a. the3Each independently represents an alkyl group having 1 to 5 carbon atoms; m is1Represents an integer of 1 or 2; n is1Represents an integer of 0 to 2; p is a radical of1Represents an integer of 0 to 3. Wherein m is1+n1+p1Representing the integer 4).
(formula [2a-1]]In, Y1Represents a group selected from a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from CO-, -COO-and-OCO-; y is2Represents a single bond or- (CH)2)b- (b is an integer of 1 to 15); y is3Represents a group selected from a single bond, - (CH)2)c- (c is an integer of 1 to 15), -O-, -CH2At least 1 bonding group selected from O-, -COO-and-OCO-; y is4At least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 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 is5Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom on the cyclic groups is optionally substituted by alkyl with 1-3 carbon atoms, alkoxy with 1-3 carbon atoms, fluorine-containing alkyl with 1-3 carbon atoms, fluorine-containing alkoxy with 1-3 carbon atoms or fluorine atom, and n represents an integer of 0-4; y is6Represents at least 1 kind selected from alkyl with 1-22 carbon atoms, alkenyl with 2-22 carbon atoms, fluorine-containing alkyl with 1-22 carbon atoms, alkoxy with 1-22 carbon atoms and fluorine-containing alkoxy with 1-22 carbon atoms).
-Y7-Y8 [2a-2]
(formula [2 a-2)]In, Y7Represents a group selected from a single bond, -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from CO-, -COO-and-OCO-; y is8Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms).
(formula [2b ]]In (B)1Each independently represents an organic group having 2 to 12 carbon atoms and at least 1 selected from vinyl, epoxy, amino, mercapto, isocyanate, methacryloyl, acryloyl, ureido, and cinnamoyl groups; b is2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; b is3Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms; m is2Represents an integer of 1 or 2; n is2Represents an integer of 0 to 2; p is a radical of2Represents an integer of 0 to 3. Wherein m is2+n2+p2Representing the integer 4).
(formula [2c ]]In (D)1Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; d2Each independently represents an alkyl group having 1 to 5 carbon atoms; n is3Represents an integer of 0 to 3).
The specific solvent of the present invention has a higher viscosity as a solvent than alcohol-based or glycol-based solvents generally used for silicone polymers. Therefore, when the composition and the liquid crystal alignment treatment agent (also collectively referred to as a coating solution) using the specific solvent of the present invention are coated on a substrate, the coverage of foreign matter having nuclei present on the substrate is increased, and a resin coating film and a liquid crystal alignment film in which the occurrence of pinholes can be suppressed can be obtained. Further, for the above reasons, the coating solution using the specific solvent of the present invention has improved level difference following properties with respect to the unevenness of the substrate level difference, and can also obtain a resin coating film or a liquid crystal alignment film having a uniform film thickness.
The specific solvent of the present invention has a low surface tension as compared with N-methyl-2-pyrrolidone (also referred to as NMP) and γ -butyrolactone (also referred to as γ -BL) which have high viscosity as solvents. Therefore, the coating solution using the specific solvent of the present invention has high wet spreadability against non-nuclear foreign substances (for example, oily stains) and can provide a resin coating film and a liquid crystal alignment film which can suppress the occurrence of shrinkage.
The component (B) of the present invention is a compound selected from the group consisting of the compounds represented by the formula [2a ]]Is of the formula [2b]And formula [2c]Polysiloxane obtained by condensation polymerization of at least 1 alkoxysilane among the alkoxysilanes shown. Among them, when the composition of the present invention is used in a liquid crystal alignment treatment agent to prepare a liquid crystal alignment film, it is preferable to use the formula [2a ]]A in (A)1Is the aforementioned formula [2a-1]The polysiloxane of the alkoxy silane with a specific side chain structure is shown. The specific side chain structure comprises a benzene ring, a cyclohexyl ring or a heterocyclic divalent cyclic group or a divalent organic group with a steroid skeleton and a carbon number of 17-51 in the side chain part. The divalent cyclic group of benzene ring, cyclohexyl ring or heterocycle, or divalent organic group having steroid skeleton and having 17-51 carbon atoms is compared with the long-chain alkyl group of the prior artShowing a rigid structure. This improves the thermal stability and ultraviolet stability of the side chain site, and forms a liquid crystal alignment film having a stable pretilt angle even with heat and light.
From the above viewpoint, the composition containing the specific solvent and the specific polysiloxane of the present invention is a composition capable of forming a resin coating film having excellent film coatability.
The liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film having excellent film coatability, and can form a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. Therefore, by using the liquid crystal alignment film, a liquid crystal display element having excellent display characteristics and high reliability can be obtained.
Hereinafter, embodiments of the present invention will be described in more detail.
< specific solvent >
The specific solvent of the present invention is a solvent represented by the following formula [1 ].
Formula [1]In, X1And X2Each independently represents an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl or isopropyl), preferably represents a methyl group or an ethyl group, and particularly preferably represents a methyl group.
Formula [1]In, X3And X4Each independently represents an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl or isopropyl), preferably represents a methyl group or an ethyl group, and particularly preferably represents a methyl group.
Specifically, the compound represented by the following formula [1a ] is preferable.
In order to improve the effect of the coating solution on the level difference following property of the substrate unevenness and the wet spreading property, the specific solvent of the present invention is preferably 10 to 90% by mass of the entire solvent contained in the composition and the liquid crystal alignment treatment agent. Among them, the amount is preferably 15 to 80% by mass. More preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass.
The effect of the present invention is higher as the amount of the specific solvent of the present invention is larger in the composition and the whole solvent in the liquid crystal alignment treatment agent, and a resin coating film and a liquid crystal alignment film having excellent coatability can be obtained.
< specific polysiloxane >
The specific polysiloxane as the component (B) in the present invention is a polysiloxane obtained by polycondensing alkoxysilane containing at least 1 selected from alkoxysilanes represented by the following formulae [2a ], [2B ] and [2c ].
The alkoxysilane represented by the formula [ A1] of the present invention is an alkoxysilane having a structure represented by the following formula [ A1 ].
Formula [2a ]]In (A)1Is represented by a formula [2a-1] selected from]And formula [2a-2]At least 1 particular side chain structure of the structures shown.
Formula [2a-1]In, Y1Represents a group selected from a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from CO-, -COO-and-OCO-. Among them, a single bond, - (CH) is preferable from the viewpoint of raw material availability and ease of synthesis2)a- (a is an integer of 1 to 15), -O-, -CH2O-or-COO-. More preferably a single bond, - (CH)2)a- (a is an integer of 1 to 10), -O-, -CH2O-or-COO-.
Formula [2a-1]In, Y2Represents a single bond or- (CH)2)b- (b is an integer of 1 to 15). Among them, preferred is a single bond or-(CH2)b- (b is an integer of 1 to 10).
Formula [2a-1]In, Y3Represents a group selected from a single bond, - (CH)2)c- (c is an integer of 1 to 15), -O-, -CH2At least 1 bonding group selected from O-, -COO-and-OCO-. Among them, a single bond, - (CH) is preferable from the viewpoint of ease of synthesis2)c- (c is an integer of 1 to 15), -O-, -CH2O-or-COO-. More preferably a single bond, - (CH)2)c- (c is an integer of 1 to 10), -O-, -CH2O-or-COO-.
Formula [2a-1]In, Y4Is at least 1 divalent cyclic group selected from benzene ring, cyclohexane ring and heterocycle, any hydrogen atom on the cyclic group is optionally substituted by C1-3 alkyl, C1-3 alkoxy, C1-3 fluorine-containing alkyl, C1-3 fluorine-containing alkoxy or fluorine atom. Further, Y4The organic group may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms and having a steroid skeleton. Among them, from the viewpoint of ease of synthesis, a divalent cyclic group of a benzene ring or a cyclohexane ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton is preferable.
Formula [2a-1]In, Y5Represents at least 1 divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic groups is optionally substituted by an alkyl group having 1 to 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. Among them, preferred is a benzene ring or a cyclohexane ring.
In the formula [2a-1], n represents an integer of 0 to 4. Among them, from the viewpoint of raw material availability and ease of synthesis, 0 to 3 is preferable. More preferably 0 to 2.
Formula [2a-1]In, Y6Represents at least 1 kind selected from alkyl with 1-22 carbon atoms, alkenyl with 2-22 carbon atoms, fluorine-containing alkyl with 1-22 carbon atoms, alkoxy with 1-22 carbon atoms and fluorine-containing alkoxy with 1-22 carbon atoms. Among them, preferred is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluoroalkoxy group having 1 to 10 carbon atoms. More excellentThe alkyl group has 1 to 12 carbon atoms, the alkenyl group has 2 to 12 carbon atoms, or the alkoxy group has 1 to 12 carbon atoms. Particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
As formula [2a-1]Y in (1)1～Y6Preferable combinations with n include the same combinations as (2-1) to (2-629) disclosed in tables 6 to 47 on pages 13 to 34 of International patent publication No. 2011/132751 (published 2011.10.27). In the tables of International publication, Y in the present invention1～Y6Are shown as Y1-Y6, but Y1-Y6 are understood to be Y1～Y6. In addition, (2-605) to (2-629) disclosed in each table of the international publication, the organic group having 17 to 51 carbon atoms of the steroid skeleton in the present invention is shown as the organic group having 12 to 25 carbon atoms of the steroid skeleton, but the organic group having 12 to 25 carbon atoms of the steroid skeleton can be understood as the organic group having 17 to 51 carbon atoms of the steroid skeleton.
-Y7-Y8 [2a-2]
Formula [2a-2]In, Y7Represents a group selected from a single bond, -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from CO-, -COO-and-OCO-. Among them, a single bond, -O-, -CH is preferable2O-、-CONH-、-CON(CH3) -or-COO-. More preferably a single bond, -O-, -CONH-or-COO-.
Formula [2a-2]In, Y8Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms. Among them, preferred is an alkyl group having 8 to 18 carbon atoms.
The specific side chain structure of the present invention is preferably a structure represented by the formula [2a-1] from the viewpoint of obtaining a high and stable vertical alignment property of liquid crystal.
Formula [2a ]]In (A)2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, preferred is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Formula [2a ]]In (A)3Each independently is an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of the polycondensation reactivity.
Formula [2a ]]M in1Is an integer of 1 or 2. Among them, 1 is preferable from the viewpoint of synthesis.
Formula [2a ]]In, n1Is an integer of 0 to 2.
Formula [2a ]]In, p1Is an integer of 0 to 3. Among them, from the viewpoint of the polycondensation reactivity, an integer of 1 to 3 is preferable. More preferably 2 or 3.
Formula [2a ]]M in1+n1+p1Is an integer 4.
Specific examples of the specific alkoxysilane (a) represented by the formula [2a ] include alkoxysilanes represented by the following formulae [ a-1] to [ a-32 ].
(formula [ a-1]]-formula [ a-4]In, R1、R3、R5And R7Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-1]-formula [ a-4]In, R2、R4、R6And R8Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-1]-formula [ a-4]Wherein m each independently represents 2 or 3, formula [ a-1]]-formula [ a-4]Wherein n each independently represents 0 or 1, wherein m + n is 3).
(formula [ a-5 ]]-formula [ a-8]In, R1、R3、R5And R7Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-5 ]]-formula [ a-8]In, R2、R4、R6And R8Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-5 ]]-formula [ a-8]Wherein m independently represents 2 or 3, formula [ a-5 ]]-formula [ a-8]Wherein n each independently represents 0 or 1, wherein m + n is 3).
(formula [ a-9)]-formula [ a-12]In, R1、R3、R5And R7Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-9 ]]-formula [ a-12]In, R2、R4、R6And R8Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-9 ]]-formula [ a-12]Wherein m independently represents 2 or 3, formula [ a-9 ]]-formula [ a-12]Wherein n each independently represents 0 or 1, wherein m + n is 3).
(formula [ a-13)]-formula [ a-16]In, R1、R3、R5And R7Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-13]-formula [ a-16]In, R2、R4、R6And R8Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-13]-formula [ a-16]Wherein m independently represents 2 or 3, formula [ a-13 ]]-formula [ a-16]Wherein n each independently represents 0 or 1, wherein m + n is 3).
(formula [ a-17)]And formula [ a-18]In, R1And R3Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-17]And formula [ a-18]In, R2And R4Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-17]And formula [ a-18]Wherein m independently represents 2 or 3, formula [ a-17]And formula [ a-18]Wherein n each independently represents 0 or 1, wherein m + n is 3).
(formula [ a-19 ]]-formula [ a-22]In, R1、R5、R9And R13Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-19]-formula [ a-22]In, R2、R6、R10And R14Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-19]-formula [ a-22]In, R3、R7、R11And R15Each independently represents a group selected from-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH)3)-、-N(CH3)CO-、-OCH2-、-CH2O-、-COOCH2-and-CH2At least 1 bonding group of OCO-, formula [ a-19]-formula [ a-22]In, R4、R8、R12And R16Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroalkoxy group having 1 to 12 carbon atoms, and is represented by the formula [ a-19]-formula [ a-22]Wherein m independently represents 2 or 3, formula [ a-19]-formula [ a-22]Wherein n independently represents 0 or 1, wherein m + n is 3, formula [ a-20]-formula [ a-22]Cis-trans isomers of 1, 4-cyclohexylidene in (a) respectively represent trans isomers).
(formula [ a-23)]And formula [ a-24]In, R1And R5Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-23]And formula [ a-24]In, R2And R6Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-23]And formula [ a-24]In, R3And R7Each independently represents a group selected from-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH)3)-、-N(CH3)CO-、-OCH2-、-CH2O-、-COOCH2-and-CH2At least 1 bonding group of OCO-, formula [ a-23]And formula [ a-24]In, R4And R8Each independently represents at least 1 organic group selected from alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, fluorine-containing alkyl group having 1 to 12 carbon atoms, fluorine-containing alkoxy group having 1 to 12 carbon atoms, fluorine group, cyano group, trifluoromethyl group, nitro group, azo group, formyl group, acetyl group, acetoxy group and hydroxyl group, and is represented by the formula [ a-23]And formula [ a-24]Wherein m independently represents 2 or 3, formula [ a-23 ]]And formula [ a-24]Wherein n each independently represents 0 or 1, wherein m + n is 3).
(formula [ a-25)]-formula [ a-28]In, R1、R5、R9And R13Each independently represents an alkyl group having 1 to 3 carbon atoms of the formula [ a-25]-formula [ a-28]In, R2、R6、R10And R14Each independently represents an alkyl group having 1 to 3 carbon atoms of the formula [ a-25]-formula [ a-28]In, R3、R7、R11And R15Each independently represents a group selected from-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH)3)-、-N(CH3)CO-、-OCH2-、-CH2O-、-COOCH2-and-CH2At least 1 bonding group of OCO-, formula [ a-25]-formula [ a-28]In, R4、R8、R12And R16Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroalkoxy group having 1 to 12 carbon atoms, and is represented by the formula [ a-25]-formula [ a-28]Wherein m independently represents 2 or 3, formula [ a-25 ]]-formula [ a-28]Wherein n independently represents 0 or 1, wherein m + n is 3, formula [ a-26]-formula [ a-28]Cis-trans isomers of 1, 4-cyclohexylidene in (a) respectively represent trans isomers).
(formula [ a-29)]-formula [ a-31]In, R1、R5And R9Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-29]-formula [ a-31]In, R2、R6And R10Each independently represents an alkyl group having 1 to 3 carbon atoms, formula [ a-29]-formula [ a-31]In, R3、R7And R11Each independently represents a group selected from-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH)3)-、-N(CH3)CO-、-OCH2-、-CH2O-、-COOCH2-and-CH2At least 1 bonding group of OCO-, formula [ a-29]-formula [ a-31]In, R4、R8And R12Each of which isIndependently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroalkoxy group having 1 to 12 carbon atoms, and is represented by the formula [ a-29]-formula [ a-31]Wherein m independently represents 2 or 3, formula [ a-29 ]]-formula [ a-31]Wherein n independently represents 0 or 1, wherein m + n is 3, formula [ a-29]-formula [ a-31]Cis-trans isomers of 1, 4-cyclohexylidene in (a) respectively represent trans isomers).
(formula [ a-32)]In, R1Each represents an alkyl group having 1 to 3 carbon atoms, R2Respectively represent alkyl with 1-3 carbon atoms, m represents 2 or 3, n represents 0 or 1, wherein m + n is 3, B14Represents an alkyl group having 3 to 20 carbon atoms optionally substituted with a fluorine atom, B13Represents 1, 4-cyclohexylidene or 1, 4-phenylene, B12Represents an oxygen atom or COO- ("wherein" marked chemical bond with B3And bonding is carried out. ) B, B11Is oxygen atom or COO- ("marked") and (CH)2)a2And bonding is carried out. ). In addition, a1Represents an integer of 0 or 1, a2Represents an integer of 2 to 10, a3Represents an integer of 0 or 1).
Further, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, pentyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, isooctyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, triethoxy-1H, 1H,2H, 2H-tridecafluorooctylsilane and the like can be mentioned.
The alkoxysilane represented by the formula [2a ] of the present invention can be used in 1 kind or 2 or more kinds by mixing depending on the solubility of the specific polysiloxane of the present invention in a solvent, the coating properties of the composition and the liquid crystal alignment treatment agent, and the characteristics such as liquid crystal alignment property, voltage holding ratio, and accumulated charge when a liquid crystal alignment film is formed.
The alkoxysilane represented by the formula [2b ] in the present invention is an alkoxysilane having a structure represented by the following formula [2b ].
Formula [2b]In (B)1Each independently represents an organic group having 2 to 12 carbon atoms and at least 1 selected from a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryloyl group, an acryloyl group, a ureido group and a cinnamoyl group. Among them, from the viewpoint of easy availability, a vinyl group, an epoxy group, an amino group, a methacryloyl group, an acryloyl group, or a ureido group is preferable. More preferably a methacryloyl, acryloyl or ureido group.
Formula [2b]In (B)2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, preferred is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Formula [2b]In (B)3Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of the polycondensation reactivity.
Formula [2b]M in2Represents an integer of 1 or 2. Among them, 1 is preferable from the viewpoint of synthesis.
Formula [2b]In, n2Represents an integer of 0 to 2.
Formula [2b]In, p2Represents an integer of 0 to 3. Among them, from the viewpoint of the polycondensation reactivity, an integer of 1 to 3 is preferable. More preferably 2 or 3.
Formula [2b]M in2+n2+p2Represents the integer 4.
Specific examples of the alkoxysilane represented by the formula [2b ] include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxymethylethylvinylethyltriethoxysilane, and the like, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl ] silane, 3-mercaptopropyl (dimethoxy) methylsilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl ester, 3- (amino) propyl ester, 3- (2-amino) propyl-trimethoxysilane, 3- (2-amino) propyl-dimethoxymethylsilane, 3- (aminopropyl) triethoxysilane, 3-aminopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, and the like, 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 2- (triethoxysilyl) ethyl methacrylate, 2- (trimethoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) ethyl acrylate, 2- (trimethoxysilyl) ethyl acrylate, (triethoxysilyl) methyl methacrylate, (trimethoxysilyl) methyl methacrylate, (triethoxysilyl) methyl acrylate, (trimethoxysilyl) methyl acrylate, (. gamma. -ureidopropyltriethoxysilane,. gamma. -ureidopropyltrimethoxysilane,. gamma. -ureidopropyltripropoxysilane, (. gamma. -ureidopropyltriethoxysilane, (. gamma. -ureidopropyltrimethoxysilane,. gamma. -ureidopropyltripropoxysilane, (. gamma. -ureidopropyltrimethoxysilane,. gamma. -n-ethylsilyl) ethyl acrylate, (R) -N-1-phenylethyl-N '-triethoxysilylpropylurea, (R) -N-1-phenylethyl-N' -trimethoxysilylpropylurea, and the like.
Among them, preferred is allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl 3-glycidoxypropyl (dimethoxy) methylsilane, 3-glycidoxypropyl (diethoxy) methylsilane, 3-glycidoxypropyltrimethoxysilane or 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
The alkoxysilane represented by the formula [2b ] of the present invention can be used in 1 kind or 2 or more kinds by mixing depending on the solubility of the specific polysiloxane of the present invention in a solvent, the coating properties of the composition and the liquid crystal alignment treatment agent, and the characteristics such as liquid crystal alignment property, voltage holding ratio, and accumulated charge when a liquid crystal alignment film is formed.
The alkoxysilane represented by the formula [2c ] in the present invention is an alkoxysilane having a structure represented by the following formula [2c ].
Formula [2c ]]In (D)1Each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which is optionally substituted with a halogen atom, a nitrogen atom, an oxygen atom or a sulfur atom. Wherein D is1Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Formula [2c ]]In (D)2Each represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of the polycondensation reactivity.
In the formula [2c ], n represents an integer of 0 to 3.
Specific examples of the alkoxysilane represented by the formula [2c ] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dibutoxydimethylsilane, (chloromethyl) triethoxysilane, 3-chloropropyldimethoxymethylsilane, 3-chloropropyltriethoxysilane, 2-cyanoethyltriethoxysilane, trimethoxy (3,3, 3-trifluoropropyl) silane, 3-trimethoxysilylpropyl chloride and the like.
Further, examples of the alkoxysilane having n of 0 in the formula [2c ] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, and the alkoxysilane represented by the formula [2c ] is preferably used.
The alkoxysilane represented by the formula [2c ] of the present invention can be used in 1 kind or 2 or more kinds by mixing depending on the solubility of the specific polysiloxane of the present invention in a solvent, the coating properties of the composition and the liquid crystal alignment treatment agent, and the characteristics such as liquid crystal alignment property, voltage holding ratio, and accumulated charge when a liquid crystal alignment film is formed.
The specific polysiloxane of the present invention is a polysiloxane obtained by polycondensing alkoxysilanes containing at least 1 kind selected from alkoxysilanes represented by the above formula [2a ], formula [2b ] or formula [2c ], and is preferably a polysiloxane obtained by polycondensing alkoxysilanes containing a plurality of kinds of these alkoxysilanes. Namely, a polysiloxane obtained by polycondensation of two kinds of alkoxysilanes represented by the above formulas [2a ] and [2b ]; a polysiloxane obtained by polycondensation of two alkoxysilanes represented by the above formulas [2a ] and [2c ]; a polysiloxane obtained by polycondensation of two alkoxysilanes represented by the above formulae [2b ] and [2c ]; and a polysiloxane obtained by polycondensation of three kinds of alkoxysilanes represented by the above formulae [2a ], [2b ] and [2c ]. Among them, preferred is a polysiloxane obtained by polycondensation of two alkoxysilanes represented by the formula [2a ] and the formula [2b ]; a polysiloxane obtained by polycondensation of two alkoxysilanes represented by the formula [2a ] and the formula [2c ]; and a polysiloxane obtained by polycondensation of three kinds of alkoxysilanes represented by the formulae [2a ], [2b ] and [2c ].
When the resin coating film obtained from the composition of the present invention is to have improved hydrophobicity, and when the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is used for a liquid crystal display element in which liquid crystal is vertically aligned, among the above combinations, polysiloxane using the alkoxysilane of the formula [2a ] is preferably used.
When a plurality of alkoxysilanes are used to produce the specific polysiloxane of the present invention, the alkoxysilane represented by the formula [2a ] is preferably 1 to 40 mol%, more preferably 1 to 30 mol%, based on the total alkoxysilanes. The alkoxysilane represented by the formula [2b ] is preferably 1 to 70 mol%, more preferably 1 to 60 mol%, based on the total alkoxysilane. Further, the alkoxysilane represented by the formula [2c ] is preferably 1 to 99 mol%, more preferably 1 to 80 mol% in the total alkoxysilane.
The method for obtaining the specific polysiloxane used in the present invention is not particularly limited. The specific polysiloxane of the present invention can be obtained by polymerizing an alkoxysilane containing any 1 of the alkoxysilanes represented by the above formula [2a ], formula [2b ] or formula [2c ] in a solvent, or can be obtained by polymerizing a plurality of alkoxysilanes among the alkoxysilanes represented by the above formula [2a ], formula [2b ] and formula [2c ] in a solvent. The specific polysiloxane of the present invention can be obtained by polycondensing an alkoxysilane to prepare a solution uniformly dissolved in a solvent.
The method of polycondensation of the specific polysiloxane of the present invention is not particularly limited. For example, a method of subjecting alkoxysilane to hydrolysis/polycondensation reaction in a specific solvent, an alcohol-based solvent or a glycol-based solvent of the present invention can be mentioned. In this case, the hydrolysis/polycondensation reaction may be partially hydrolyzed or may be completely hydrolyzed. When the hydrolysis is completed, theoretically, water may be added in an amount of 0.5 times the molar amount of all alkoxy groups in the alkoxysilane, and it is generally preferable to add water in an excess amount of 0.5 times the molar amount. The amount of water used in the hydrolysis/polycondensation reaction may be appropriately selected depending on the purpose of obtaining the specific polysiloxane of the present invention, but is preferably 0.5 to 2.5 times the molar amount of all alkoxy groups in the alkoxysilane.
In addition, in order to promote the hydrolysis/polycondensation reaction, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, fumaric acid, and the like; ammonia, methylamine, ethylamine, ethanolamine, triethylamine or other basic compounds; or a catalyst such as a metal salt of hydrochloric acid, nitric acid or the like. Further, the hydrolysis/polycondensation reaction can be accelerated by heating the solution in which the alkoxysilane is dissolved. At this time, the heating temperature and the heating time may be appropriately selected according to the purpose. For example, the reaction mixture may be heated and stirred at 50 ℃ for 24 hours, and then heated and stirred under reflux for 1 hour.
Further, another example of the polycondensation method is a method in which a mixture of alkoxysilane, a solvent and oxalic acid is heated to cause a polycondensation reaction. Specifically, the method comprises adding oxalic acid to the specific solvent, alcohol solvent or glycol solvent of the present invention to prepare an oxalic acid solution, and then mixing the resulting solution with alkoxysilane while heating. In this case, the amount of oxalic acid used in the reaction is preferably 0.2 to 2.0 moles per 1 mole of all alkoxy groups in the alkoxysilane. The reaction may be carried out at a solution temperature of 50 to 180 ℃, and is preferably carried out under reflux for several tens of minutes to several tens of hours so as not to cause evaporation or volatilization of the solvent.
In the polycondensation reaction for obtaining the specific polysiloxane of the present invention, when a plurality of alkoxysilanes represented by the above formulae [2a ], [2b ] and [2c ] are used, the reaction may be carried out using a mixture obtained by mixing a plurality of alkoxysilanes in advance, or the reaction may be carried out while adding a plurality of alkoxysilanes in sequence.
The solvent used for the polycondensation reaction of alkoxysilane is not particularly limited as long as it dissolves alkoxysilane, including the specific solvent of the present invention. In addition, even in the case of a solvent which does not dissolve the alkoxysilane, the alkoxysilane may be dissolved while advancing the polycondensation reaction. As the solvent used in the polycondensation reaction, in general, an alcohol is generated by the polycondensation reaction of the alkoxysilane, and therefore an alcohol-based solvent, a glycol ether-based solvent, or a solvent having good compatibility with an alcohol can be used. Specific examples of the solvent used in the polycondensation reaction include alcohol solvents such as methanol, ethanol, propanol, butanol, and diacetone alcohol; glycol solvents such as 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, and 1, 6-hexanediol; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether; and solvents having good compatibility with alcohols, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, and m-cresol.
In the present invention, 1 kind of these solvents or 2 or more kinds of solvents mixed may be used in the polycondensation reaction.
With respect to the polymerization solution of the specific polysiloxane obtained by the above method, silicon atoms of all alkoxysilanes charged as raw materials are converted to SiO2Concentration of (also referred to as SiO)2Reduced concentration) is preferably 20% by mass or less. Among them, it is preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, the occurrence of gel in the solution can be suppressed, and a uniform polycondensation solution of the specific polysiloxane can be obtained.
In the present invention, the polycondensation solution of the specific polysiloxane obtained by the above-mentioned method may be used as it is as the solution of the specific polysiloxane of the component (B) of the present invention, or the polycondensation solution of the specific polysiloxane obtained by the above-mentioned method may be concentrated, diluted with a solvent or replaced with another solvent as a solution of the specific polysiloxane of the component (B) as needed.
The solvent used for dilution by adding the solvent (also referred to as an additive solvent) may be a solvent used in the polycondensation reaction or another solvent. The solvent to be added is not particularly limited as long as it uniformly dissolves the specific polysiloxane, and 1 or 2 or more kinds thereof can be arbitrarily selected and used. Examples of such an additive solvent include, in addition to the solvent used in the polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, and the like.
< composition & liquid Crystal alignment treatment agent >
The composition of the present invention and the liquid crystal alignment treatment agent using the same are coating solutions for forming a resin coating film and a liquid crystal alignment film (also collectively referred to as a resin coating film), and are coating solutions for forming a resin coating film containing a specific solvent and a specific polysiloxane.
All of the polymer components in the composition and the liquid crystal aligning agent of the present invention may be the specific polysiloxane of the present invention, or other polymers may be mixed. Examples of the other polymers include acrylic polymers, methacrylic polymers, polystyrene, polyamic acids, and polyimides. In this case, the content of the other polymer is 0.5 to 30 parts by mass based on 100 parts by mass of the specific polysiloxane of the present invention. Among them, it is preferably 1 to 20 parts by mass.
The solvent in the composition and the liquid crystal alignment treatment agent of the present invention is preferably contained in an amount of 70 to 99.9% by mass from the viewpoint of forming a uniform resin coating film by coating. The content may be appropriately changed depending on the target film thickness of the resin coating film and the coating method.
In addition, the solvent used in this case may be all the specific solvents of the present invention, and any solvent (also referred to as other solvent) that dissolves the specific polysiloxane of the present invention may be used together. Specific examples of other solvents are listed below, but the solvents are not limited to these examples.
Examples thereof include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ -butyrolactone, 1, 3-dimethylimidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentanol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, and the like, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1, 2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, butyl ether ethylene glycol monoethyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol, Propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol monoethyl ether acetate, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, or isoamyl lactate.
Among them, preferred is N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, 1, 3-dimethylimidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, or furfuryl alcohol.
The other solvent of the present invention is preferably 10 to 90% by mass of the total solvent contained in the composition and the liquid crystal alignment treatment agent. Among them, the amount is preferably 15 to 80% by mass. More preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass.
The other solvents of the present invention may be used in a mixture of 1 or 2 or more depending on the solubility of the specific polysiloxane of the present invention in the solvent and the coatability of the composition and the liquid crystal alignment treatment agent.
The composition and the liquid crystal alignment treatment agent of the present invention preferably incorporate the following crosslinkable compounds: a crosslinkable compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclocarbonate group; a crosslinkable compound having at least 1 substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group; or a crosslinkable compound having a polymerizable unsaturated bond. These substituents and polymerizable unsaturated bonds need to be present in the crosslinkable compound in an amount of 2 or more.
Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminobiphenyl, tetraglycidyl m-xylylenediamine, tetraglycidyl-1, 3-bis (aminoethyl) cyclohexane, tetraphenylglycidylethane, triphenylglycidylethane, bisphenol hexafluoroacetyl diglycidyl ether, 1, 3-bis (1- (2, 3-epoxypropoxy) -1-trifluoromethyl-2, 2, 2-trifluoromethyl) benzene, 4-bis (2, 3-epoxypropoxy) octafluorobiphenyl, triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine, and the like, 2- (4- (2, 3-epoxypropoxy) phenyl) -2- (4- (1, 1-bis (4- (2, 3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1, 3-bis (4- (1- (4- (2, 3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol, etc.
The crosslinkable compound having an oxetanyl group is a crosslinkable compound having at least 2 oxetanyl groups represented by the following formula [4A ].
Specifically, examples thereof include crosslinkable compounds represented by the formulae [4a ] to [4k ] disclosed in 58 to 59 of International patent publication No. 2011/132751 (2011.10.27).
The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least 2 cyclocarbonate groups represented by the following formula [5A ].
Specifically, there can be mentioned crosslinkable compounds represented by the formulae [5-1] to [5-42] disclosed in the international patent application laid-open No. 2012/014898 (published 2012.2.2) at items 76 to 82.
Examples of the crosslinkable compound having at least 1 substituent selected from the group consisting of a hydroxyl group and an alkoxy group include amino resins having a hydroxyl group or an alkoxy group, such as melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinamide-formaldehyde resin, ethyleneurea-formaldehyde resin, and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a hydroxymethyl group, an alkoxymethyl group, or both of them can be used. The melamine derivative or benzoguanamine derivative may also be present in the form of a dimer or trimer. They preferably have an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per 1 triazine ring.
Examples of such melamine derivatives or benzoguanamine derivatives include commercially available methoxymethylated melamines such as MX-750 substituted with an average of 3.7 methoxymethyl groups per 1 triazine ring, MW-30 substituted with an average of 5.8 methoxymethyl groups per 1 triazine ring (Sanhe chemical Co., Ltd.), CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc.; methoxymethylated butoxymethylated melamines such as CYMEL 235, 236, 238, 212, 253, 254; butoxymethylated melamines such as CYMEL 506, 508; carboxy-containing methoxymethylated isobutoxymethylated melamines such as CYMEL 1141; methoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1123; methoxymethylated butoxymethylated benzoguanamine such as CYMEL 1123-10; butoxymethylated benzoguanamine such as CYMEL 1128; carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1125-80 (manufactured by Mitsui Cytec Ltd.). Examples of glycolurils include butoxymethylated glycolurils such as CYMEL 1170, hydroxymethylated glycolurils such as CYMEL 1172, and methoxyhydroxymethylated glycolurils such as Powder link 1174.
Examples of the benzene or phenol compound having a hydroxyl group or an alkoxy group include 1,3, 5-tris (methoxymethyl) benzene, 1,2, 4-tris (isopropoxymethyl) benzene, 1, 4-bis (sec-butoxymethyl) benzene, 2, 6-dihydroxymethyl-p-tert-butylphenol, and the like.
More specifically, the crosslinkable compounds represented by the formulae [6-1] to [6-48] disclosed on pages 62 to 66 of International patent publication No. 2011/132751 (publication No. 2011.10.27) are exemplified.
Examples of the crosslinkable compound having a polymerizable unsaturated bond include crosslinkable compounds having 3 polymerizable unsaturated groups in the molecule, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tris (meth) acryloyloxyethoxytrimethylpropane, or glycerol polyglycidyl ether poly (meth) acrylate; further, the acrylic resin composition may further contain a crosslinking group having 2 polymerizable unsaturated groups in the molecule, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethyleneglycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol a type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, or hydroxypivalyl hydroxypivalate di (meth) acrylate A sex compound; and crosslinkable compounds having 1 polymerizable unsaturated group in the molecule, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, and N-methylol (meth) acrylamide.
Further, a compound represented by the following formula [7A ] can also be used.
(formula [7A ]]In, E1Represents at least 1 selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring and a phenanthrene ring, E2Is represented by a formula [7a ] selected from]Or formula [7b]Wherein n represents an integer of 1 to 4. )
The above-mentioned compound is an example of a crosslinkable compound, but is not limited thereto. The number of the crosslinkable compounds used in the composition and the liquid crystal aligning agent of the present invention may be 1, or 2 or more.
The content of the crosslinkable compound in the composition and the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass per 100 parts by mass of the entire polymer components. Among them, in order to promote the crosslinking reaction and to exhibit the desired effect, it is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the entire polymer components. More preferably 1 to 50 parts by mass.
In the composition and the liquid crystal aligning agent of the present invention, a compound which improves the film thickness uniformity and surface smoothness of the resin coating film when the composition and the liquid crystal aligning agent are applied can be used within a range not impairing the effects of the present invention.
Examples of the compound for improving the uniformity of the film thickness and the surface smoothness of the resin coating film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
More specifically, for example, Eftop EF301, EF303, and EF352 (see above, manufactured by Tohkem products Corporation); megafac F171, F173 and R-30 (manufactured by Dainippon ink Co., Ltd.); fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited, supra); asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi glass Co., Ltd.).
The amount of the surfactant to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total polymer components contained in the composition and the liquid crystal aligning agent.
Further, as a compound for promoting charge transfer in the resin coating film and for promoting element charge removal, a nitrogen-containing heterocyclic amine compound represented by the formulae [ M1] to [ M156] disclosed on pages 69 to 73 of International publication No. 2011/132751 (published 2011.10.27) may be added to the composition and the liquid crystal aligning agent of the present invention. The amine compound may be added directly to the composition and the liquid crystal alignment treatment agent, and is preferably added after being made into a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, with an appropriate solvent. The solvent is not particularly limited as long as it dissolves the specific polysiloxane.
In the composition and the liquid crystal alignment treatment agent of the present invention, in addition to the above-mentioned other solvents, crosslinkable compounds, compounds for improving the film thickness uniformity and/or surface smoothness of the resin film, and compounds for promoting charge removal, a dielectric material or conductive material for changing electrical characteristics such as dielectric constant, conductivity, etc. of the resin film may be added within a range not impairing the effects of the present invention.
< resin coating >
The composition of the present invention may be coated on a substrate and fired, and then used as a resin coating film. As the substrate used at this time, a glass substrate, a silicon wafer, an acrylic substrate, a plastic substrate such as a polycarbonate substrate or a PET (polyethylene terephthalate) substrate, or the like may be used depending on the target device. In addition, the resin coating film may be used as it is as a thin film substrate. The method of applying the composition is not particularly limited, and a method using a dipping method, a roll coating method, a slit coating method, a spin coating method, a spray coating method, a screen printing method, an offset printing method, a flexographic printing method, an ink jet method, or the like is generally industrially used. They may use these methods according to purposes.
After the composition is coated on a substrate, the solvent is evaporated at a temperature of 30 to 300 ℃, preferably 30 to 250 ℃ depending on the solvent used in the composition by a heating means such as a hot plate, a thermal cycle oven or an IR (infrared ray) oven, thereby forming a resin coating film. The thickness of the resin coating after firing can be adjusted to 0.01 to 100 μm according to the purpose.
< liquid Crystal alignment film/liquid Crystal display device >
The liquid crystal aligning agent using the composition of the present invention can be applied to a substrate, fired, and then subjected to alignment treatment such as brushing or light irradiation, thereby being used as a liquid crystal alignment film. In addition, a liquid crystal display element in which liquid crystal is vertically aligned and displayed can be used as a liquid crystal alignment film without alignment treatment. The substrate used in this case is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate, or the like can be used. From the viewpoint of simplifying the process, a substrate on which an ITO (indium tin oxide) electrode or the like for driving a liquid crystal is formed is preferably used. In the case of a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used as long as it is a single-sided substrate, and a material that reflects light such as aluminum may be used as an electrode in this case.
The method of applying the liquid crystal aligning agent is not particularly limited, and a method of applying the liquid crystal aligning agent by screen printing, offset printing, flexo printing, ink jet method, or the like is generally industrially used. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spin coating method, a spray coating method, and the like, and these methods can be used according to the purpose.
After coating the liquid crystal alignment treatment agent on the substrate, the solvent is evaporated at a temperature of 30 to 300 ℃, preferably 30 to 250 ℃ depending on the solvent used in the liquid crystal alignment treatment agent by a heating means such as a hot plate, a thermal cycle oven or an IR (infrared ray) oven, thereby forming a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after firing is too large, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when the thickness is too small, the reliability of the liquid crystal display element may be lowered, and therefore, it is preferably 5 to 300nm, more preferably 10 to 150 nm. When the liquid crystal is aligned horizontally or obliquely, the fired liquid crystal alignment film is treated by brushing, polarized ultraviolet irradiation, or the like.
The liquid crystal display element of the present invention is produced by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and then producing a liquid crystal cell by a known method.
As a method for manufacturing a liquid crystal cell, the following method can be exemplified: a method of preparing a pair of substrates on which liquid crystal alignment films are formed, spreading spacers on the liquid crystal alignment films of the individual substrates, attaching the substrates to each other with the liquid crystal alignment films facing inward, injecting liquid crystal under reduced pressure, and sealing the substrates; or a method of dropping liquid crystal onto the liquid crystal alignment film surface on which the spacers are dispersed, and then attaching and sealing the substrate.
Further, the liquid crystal aligning agent of the present invention is preferably used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and manufactured through the following steps: a liquid crystal composition is disposed between a pair of substrates, the liquid crystal composition including a polymerizable compound that is polymerized by at least one of active energy rays and heat, and the polymerizable compound is polymerized by applying a voltage between electrodes and irradiating at least one of the active energy rays and heat. Here, the active energy ray is preferably ultraviolet ray. The ultraviolet ray has a wavelength of 300 to 400nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ℃, preferably 60 to 80 ℃. In addition, the irradiation of ultraviolet rays and the heating may be performed simultaneously.
The liquid crystal display device uses a psa (polymer suspended alignment) method to control the pretilt of the liquid crystal molecules. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed into a liquid crystal material in advance, a liquid crystal cell is assembled, and then the photopolymerizable compound is irradiated with ultraviolet light or the like while a predetermined voltage is applied to the liquid crystal layer, whereby the pretilt of liquid crystal molecules is controlled by the generated polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is memorized even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling an electric field or the like formed in the liquid crystal layer. In addition, since the PSA method does not require a rubbing process, it is suitable for forming a vertical alignment liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.
That is, in the liquid crystal display element of the present invention, after a substrate with a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention by the method described above, a liquid crystal cell is produced, and the polymerizable compound is polymerized by at least one of irradiation with ultraviolet rays and heating, whereby the alignment of liquid crystal molecules can be controlled.
As an example of manufacturing a PSA liquid crystal cell, the following method can be cited: a method of preparing a pair of substrates on which liquid crystal alignment films are formed, spreading spacers on the liquid crystal alignment films of the individual substrates, attaching the substrates to each other with the liquid crystal alignment films facing inward, injecting liquid crystal under reduced pressure, and sealing the substrates; or a method of dropping a liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and then attaching and sealing the substrate.
A polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed into the liquid crystal. Examples of the polymerizable compound include compounds having 1 or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled, and when the amount is more than 10 parts by mass, the amount of unreacted polymerizable compound increases and the afterimage characteristics of the liquid crystal display element deteriorate.
After the liquid crystal cell is produced, the polymerizable compound is polymerized by heating and irradiating with ultraviolet light while applying an alternating-current or direct-current voltage to the liquid crystal cell. This enables control of the alignment of the liquid crystal molecules.
The liquid crystal aligning agent of the present invention is also preferably used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and manufactured through the following steps: a liquid crystal alignment film including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes. Here, the active energy ray is preferably ultraviolet ray. The ultraviolet ray has a wavelength of 300 to 400nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ℃, preferably 60 to 80 ℃. In addition, ultraviolet rays and heat may be applied simultaneously.
In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat, examples of the liquid crystal alignment film include: a method of adding a compound containing the polymerizable group to a liquid crystal aligning agent, and a method of using a polymer component containing the polymerizable group. The liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bond site that reacts by heat or irradiation of ultraviolet rays, and therefore, alignment of liquid crystal molecules can be controlled by at least one of irradiation and heating of ultraviolet rays.
As an example of manufacturing a liquid crystal cell, the following method can be cited: a method of preparing a pair of substrates on which liquid crystal alignment films are formed, spreading spacers on the liquid crystal alignment films of the individual substrates, attaching the other substrate so that the liquid crystal alignment film faces inward, injecting liquid crystal under reduced pressure, and sealing; or a method of dropping liquid crystal onto the liquid crystal alignment film surface on which the spacers are dispersed, and then attaching and sealing the substrate.
After the liquid crystal cell is produced, the liquid crystal cell is heated and irradiated with ultraviolet rays while applying an ac or dc voltage to the liquid crystal cell, whereby the alignment of liquid crystal molecules can be controlled.
As described above, the liquid crystal alignment treatment agent of the present invention forms a liquid crystal alignment film having excellent film coatability, and further, a liquid crystal alignment film capable of exhibiting a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for large-screen and high-definition liquid crystal televisions, medium-and small-sized car navigation systems, smart phones, and the like.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
"abbreviations used in Synthesis examples, examples and comparative examples of the present invention"
Abbreviations used in the synthesis examples, examples and comparative examples are as follows.
< monomers for producing the polysiloxane Polymer of the present invention >
B1: an alkoxysilane monomer represented by the following formula [ B1] (an alkoxysilane monomer represented by the formula [2a ] having a specific side chain structure represented by the formula [2a-1] of the present invention)
B2: octadecyltriethoxysilane (alkoxysilane monomer represented by the formula [2a ] having a specific side chain structure represented by the formula [2a-2] of the present invention)
B3: 3-methacryloxypropyltrimethoxysilane (alkoxysilane monomer represented by the formula [2b ] of the present invention)
B4: 3-ureidopropyltriethoxysilane (the alkoxysilane monomer represented by the formula [2b ] of the present invention)
B5: tetraethoxysilane (alkoxysilane monomer represented by the formula [2c ] of the present invention)
< crosslinkable Compound used in the present invention >
K1: a crosslinkable compound represented by the following formula [ K1]
< specific solvent of the present invention >
S1: a solvent represented by the following formula [ S1] (the solvent represented by the formula [1a ] of the present invention)
< other solvents >
EC: diethylene glycol monoethyl ether
BCS: ethylene glycol monobutyl ether
PB: propylene glycol monobutyl ether
DME: dipropylene glycol dimethyl ether
NMP: n-methyl-2-pyrrolidone
NEP: n-ethyl-2-pyrrolidone
gamma-BL: gamma-butyrolactone
Synthesis of polysiloxane Polymer of the present invention "
< Synthesis example 1>
In a 200ml four-necked reaction beaker equipped with a thermometer and a reflux tube, EC (29.8g), B1(4.10g) and B5(39.6g) were mixed to prepare a solution of alkoxysilane monomer. To this solution, a solution prepared by mixing EC (14.9g), water (10.8g) and oxalic acid (0.90g) as a catalyst in advance was added dropwise over 30 minutes at 25 ℃, and further stirred at 25 ℃ for 30 minutes at room temperature. Thereafter, the mixture was refluxed for 60 minutes by heating in an oil bath, and then naturally cooled to obtain SiO2Polysiloxane solution (1) having a concentration of 12% by mass as converted.
< Synthesis example 2>
In a 200ml four-necked reaction beaker equipped with a thermometer and a reflux tube, EC (29.7g), B2(4.20g) and B5(39.6g) were mixed to prepare a solution of alkoxysilane monomer. To this solution, a solution prepared by mixing EC (14.9g), water (10.8g) and oxalic acid (0.90g) as a catalyst in advance was added dropwise over 30 minutes at 25 ℃, and further stirred at 25 ℃ for 30 minutes at room temperature. Thereafter, the mixture was refluxed for 60 minutes by heating in an oil bath, and then naturally cooled to obtain SiO2A polysiloxane solution (2) having a concentration of 12% by mass as converted.
< Synthesis example 3>
In a 200ml four-necked reaction beaker equipped with a thermometer and a reflux tube, EC (28.2g), B1(4.10g), B3(14.9g) and B5(27.1g) were mixed to prepare a solution of alkoxysilane monomer. To this solution, a solution prepared by mixing EC (14.1g), water (10.8g) and oxalic acid (0.90g) as a catalyst in advance was added dropwise over 30 minutes at 25 ℃, and further stirred at 25 ℃ for 30 minutes. Thereafter, the mixture was refluxed for 60 minutes by heating in an oil bath, and then naturally cooled to obtain SiO2A polysiloxane solution (3) having a concentration of 12% by mass as converted.
< Synthesis example 4>
In a 200ml four-necked reaction beaker equipped with a thermometer and a reflux tube, S was placed1(28.1g), B2(4.20g), B3(14.9g) and B5(27.1g) were mixed to prepare a solution of alkoxysilane monomer. To this solution, a solution prepared by mixing S1(14.1g), water (10.8g) and oxalic acid (0.90g) as a catalyst in advance was added dropwise over 30 minutes at 25 ℃ and further stirred for 30 minutes at 25 ℃. Thereafter, the mixture was refluxed for 60 minutes by heating in an oil bath, and then naturally cooled to obtain SiO2A polysiloxane solution (4) having a concentration of 12% by mass as converted.
< Synthesis example 5>
In a 200ml four-necked reaction beaker equipped with a thermometer and a reflux tube, EC (27.4g), B1(4.10g), B3(14.9g) and B5(26.3g) were mixed to prepare a solution of alkoxysilane monomer. To this solution, a solution prepared by mixing EC (13.7g), water (10.8g) and oxalic acid (0.90g) as a catalyst in advance was added dropwise over 30 minutes at 25 ℃, and further stirred at 25 ℃ for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes by heating with an oil bath, and then a previously prepared mixed solution of a methanol solution (1.15g) having a B4 content of 92 mass% and EC (0.90g) was added. Further refluxing the mixture for 30 minutes, and naturally cooling the mixture to obtain SiO2A polysiloxane solution (5) having a concentration of 12% by mass as converted.
< Synthesis example 6>
In a 200ml four-necked reaction beaker equipped with a thermometer and a reflux tube, EC (29.5g), B3(14.9g) and B5(29.2g) were mixed to prepare a solution of alkoxysilane monomer. To this solution, a solution prepared by mixing EC (14.7g), water (10.8g) and oxalic acid (0.90g) as a catalyst in advance was added dropwise over 30 minutes at 25 ℃, and further stirred at 25 ℃ for 30 minutes. Thereafter, the mixture was refluxed for 60 minutes by heating in an oil bath, and then naturally cooled to obtain SiO2A polysiloxane solution (6) having a concentration of 12% by mass as converted.
< Synthesis example 7>
In a 200ml four-necked reaction beaker equipped with a thermometer and a reflux tube, S1(30.3g) and B5(40.8g) were mixed to prepare a solution of alkoxysilane monomer. To the solution, a solution prepared by mixing S1(15.2g), water (10.8g) and oxalic acid (0.90g) as a catalyst in advance was added dropwise at 25 ℃ over 30 minutes, and the mixture was further stirred at 25 ℃ for 30 minutesA clock. Thereafter, the mixture was refluxed for 30 minutes by heating with an oil bath, and then a mixed solution of a methanol solution (1.15g) having a B4 content of 92 mass% and S1(0.90g) which had been prepared in advance was added. Further refluxing the mixture for 30 minutes, and naturally cooling the mixture to obtain SiO2A polysiloxane solution (7) having a concentration of 12% by mass as converted.
< Synthesis example 8>
In a 200ml four-necked reaction beaker equipped with a thermometer and a reflux tube, EC (28.7g), B3(14.9g) and B5(28.3g) were mixed to prepare a solution of alkoxysilane monomer. To this solution, a solution prepared by mixing EC (14.4g), water (10.8g) and oxalic acid (0.90g) as a catalyst in advance was added dropwise over 30 minutes at 25 ℃, and further stirred at 25 ℃ for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes by heating with an oil bath, and then a previously prepared mixed solution of a methanol solution (1.15g) having a B4 content of 92 mass% and EC (0.90g) was added. Further refluxing the mixture for 30 minutes, and naturally cooling the mixture to obtain SiO2A polysiloxane solution (8) having a concentration of 12% by mass as converted.
The polysiloxane of the present invention (polysiloxane solution) is shown in table 1.
[ Table 1]
Production of the composition and liquid Crystal alignment treatment agent of the present invention "
Examples of producing the compositions described in examples 1 to 13 and comparative examples 1 to 3 are described below. In addition, these compositions were also used for evaluation of liquid crystal aligning agents.
The compositions and the liquid crystal aligning agents of the present invention are shown in tables 2 to 4.
The compositions and the liquid crystal alignment treatment agents obtained in the examples and comparative examples of the present invention were used to perform "evaluation of printability of the compositions and the liquid crystal alignment treatment agents (evaluation of pinholes)", "evaluation of printability of the compositions and the liquid crystal alignment treatment agents (evaluation of level difference following performance)", "evaluation of production of liquid crystal cells and pretilt angles (normal cells)", "evaluation of ink jet coatability of the liquid crystal alignment treatment agents", "production of liquid crystal cells and evaluation of liquid crystal alignment properties (PSA cells)", and "production of liquid crystal cells and evaluation of liquid crystal alignment properties (SC-PVA cells)".
Evaluation of printability of composition and liquid Crystal alignment treatment agent (evaluation of pinhole) "
Using the compositions obtained by the methods of the examples of the present invention and the comparative examples, the pinhole of the resin coating was evaluated. Specifically, these compositions were subjected to pressure filtration using a membrane filter having a pore size of 1 μm, and an unwashed Cr vapor-deposited substrate (100 mm in the vertical direction X100 mm in the horizontal direction, 1.0mm in thickness) was printed. The printing press used a simple printing press model S15 (manufactured by Nippon Kaisha) and was carried out under conditions that the printing area was in the range of 80X 80mm with respect to the center of the substrate, the printing pressure was 0.2mm, 5 sheets of disposable substrates were used, the time from printing to pre-drying was 90 seconds, and the pre-drying was carried out on a hot plate at 70 ℃ for 5 minutes.
Thereafter, the number of pinholes in the resulting resin-coated substrate was checked. Specifically, the substrate with the resin film was visually observed under a sodium lamp, and the number of pinholes in the resin film was counted. The smaller the number of pinholes, the less precipitates in the composition, and this evaluation was regarded as excellent.
Tables 5 to 7 show the numbers of pinholes obtained in examples and comparative examples.
The compositions obtained in examples and comparative examples of the present invention can be used as a liquid crystal alignment treatment agent. Therefore, the pinhole evaluation of the resin coating films of the compositions obtained in the examples of the present invention and the comparative examples was also performed as the pinhole evaluation of the liquid crystal alignment film.
Evaluation of printability of the composition and the liquid Crystal alignment treating agent (evaluation of level Difference following Property) "
Using the compositions obtained by the methods of the examples and comparative examples of the present invention, the printability of the resin coating film on the level difference substrate was evaluated. Specifically, these compositions were subjected to pressure filtration using a membrane filter having a pore size of 1 μm, and a glass substrate (100 mm in length × 100mm in width, 0.7mm in thickness) having a dot pattern of 100 × 100 μm (dot pitch of 50 μm and dot thickness of 0.5 μm) was printed in a range of 70 × 70mm with respect to the center of the substrate. The printing press used a simple printing press model S15 (manufactured by Nippon Kaisha) and was carried out under conditions that the printing area was in the range of 80X 80mm with respect to the center of the substrate, the printing pressure was 0.2mm, 5 sheets of disposable substrates were used, the time from printing to pre-drying was 90 seconds, and the pre-drying was carried out on a hot plate at 70 ℃ for 5 minutes.
With respect to the obtained resin coating, the followability of the resin coating to the level difference substrate was evaluated. Specifically, the cross section of the obtained substrate with a resin coating was observed with a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation), and the film thickness of the resin coating above the dots and the film thickness of the resin coating between the dots were confirmed. More specifically, it was confirmed that the smaller the difference between the film thickness of (1) (the film thickness of the resin coating on the upper portion of the dot, that is, the film thickness of the center portion of the dot) and the film thickness of (2) (the film thickness of the resin coating between the dots, that is, the film thickness of the center portion between the dots) in fig. 1, the more excellent the followability of the resin coating to the level difference substrate.
Tables 5 to 7 show the results of the film thickness of (1) and the film thickness of (2) in fig. 1 and the film thickness ratio (((1) film thickness/(2) film thickness) × 100) obtained in the examples and comparative examples.
The compositions obtained in examples and comparative examples of the present invention can be used as a liquid crystal alignment treatment agent. Therefore, the evaluation of the level difference followability of the compositions obtained in the examples of the present invention and the comparative examples can also be used as the evaluation of the level difference followability of the liquid crystal alignment film.
"production of liquid Crystal cell and evaluation of Pre-Tilt Angle (ordinary cell)"
The liquid crystal alignment treatment agents obtained by the methods of the examples and comparative examples of the present invention were used to prepare liquid crystal cells and evaluate pretilt angles. Specifically, these liquid crystal aligning agents were pressure-filtered through a membrane filter having a pore diameter of 1 μm, and were spin-coated on an ITO surface of an ITO electrode-equipped substrate (40 mm in length by 30mm in width, 0.7mm in thickness) cleaned with pure water and IPA (isopropyl alcohol), and were heat-treated on a hot plate at 80 ℃ for 5 minutes and in a thermal cycle type cleaning oven at 220 ℃ for 30 minutes, thereby obtaining an ITO substrate having a polyimide liquid crystal alignment film with a film thickness of 100 nm. The coating surface of the ITO substrate was brushed using rayon cloth at a roller speed of 1000rpm, a roller advancing speed of 50 mm/sec and a pressing amount of 0.1mm using a brushing device having a roller diameter of 120 mm.
2 pieces of the ITO substrates with liquid crystal alignment films were prepared, and the substrates were combined with a 6 μm spacer interposed between the liquid crystal alignment films, and the periphery was bonded with a sealant to prepare an empty cell. Nematic liquid crystal (MLC-6608) (manufactured by MERCK CORPORATION) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (normal cell).
Using the obtained liquid crystal cell, the pretilt angle was evaluated. The pretilt angle is determined as follows: the liquid crystal cell was irradiated with light at 95 ℃ for 5 minutes after the isotropic treatment at 95 ℃ after the injection of the liquid crystal (also referred to as just after the production of the liquid crystal cell), after the heat treatment at 120 ℃ for 5 hours (also referred to as after the storage in a high temperature bath), and after the isotropic treatment at 95 ℃ for 5 minutes after the injection of the liquid crystal, at a wavelength of 10J/cm in terms of 365nm2After the ultraviolet light (also referred to as after ultraviolet light irradiation), measurement is performed.
The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Further, irradiation of ultraviolet rays was performed using a desk-top UV curing apparatus (HCT3B28HEX-1) (SEN LIGHT Co., Ltd.).
As for the evaluation, it was said that the change of the pretilt angle after storage in the high-temperature tank or after irradiation with ultraviolet light was small as compared with the pretilt angle immediately after the production of the liquid crystal cell, that is, the pretilt angle was high in stability against heat and ultraviolet light.
Tables 8 and 9 show the values of pretilt angles obtained in examples and comparative examples.
"evaluation of ink-jet coatability of liquid Crystal alignment treatment agent"
The liquid crystal alignment treatment agent (4) obtained by the method of example 4 of the present invention, the liquid crystal alignment treatment agent (7) obtained by the method of example 7, and the liquid crystal alignment treatment agent (10) obtained by the method of example 10 were used to evaluate the ink jet coatability. Specifically, these liquid crystal alignment agents were pressure-filtered through a membrane filter having a pore size of 1 μm, and applied onto an ITO vapor-deposited substrate cleaned with pure water and IPA by using an ink jet coater using HIS-200 (manufactured by Hitachi Plant Technologies, Ltd.) under conditions of a coating area of 70X 70mm, a nozzle pitch of 0.423mm, a scanning pitch of 0.5mm, a coating speed of 40 mm/sec, a time from coating to predrying of 60 seconds, and predrying on a hot plate at 70 ℃ for 5 minutes.
The substrate with the liquid crystal alignment film obtained was visually observed under a sodium lamp, and the number of pinholes in the liquid crystal alignment film was counted, and as a result, the number of pinholes in the liquid crystal alignment film obtained in any of the examples was 5 or less. In any of the examples, a liquid crystal alignment film having excellent coating film uniformity was obtained.
Further, using the obtained substrate with the liquid crystal alignment film, the production of the liquid crystal cell and the evaluation of the pretilt angle (normal cell) were performed under the conditions of the "production of the liquid crystal cell and the evaluation of the pretilt angle (normal cell)" described above.
"production of liquid Crystal cell and evaluation of liquid Crystal alignment Property (PSA cell)"
The liquid crystal cell was produced and the liquid crystal alignment properties were evaluated (PSA cell) using the liquid crystal alignment treatment agent (3) obtained by the method of example 3 of the present invention and the liquid crystal alignment treatment agent (6) obtained by the method of example 6. Specifically, these liquid crystal alignment agents were subjected to pressure filtration using a membrane filter having a pore size of 1 μm, and ITO surfaces of a substrate (40 mm in length × 30mm in width, thickness 0.7mm) having ITO electrodes of 10 × 10mm in center and having a pattern interval of 20 μm and a substrate (40 mm in length × 30mm in width, thickness 0.7mm) having ITO electrodes of 10 × 40mm in center were spin-coated with pure water and IPA, and were heat-treated on a hot plate at 100 ℃ for 5 minutes and a heat-circulation type cleaning oven at 230 ℃ for 30 minutes, thereby obtaining a substrate having a liquid crystal alignment film with a film thickness of 100 nm.
These substrates with liquid crystal alignment films were combined with a 6 μm spacer interposed between the liquid crystal alignment film surfaces, and the periphery was bonded with a sealant to prepare an empty cell. The liquid crystal cell was obtained by injecting a liquid crystal into the empty cell by a reduced pressure injection method, the liquid crystal being obtained by mixing a polymerizable compound (1) represented by the following formula into a nematic liquid crystal (MLC-6608) so that the polymerizable compound (1) is 0.3 mass% with respect to 100 mass% of the nematic liquid crystal (MLC-6608) (manufactured by MERCK CORPORATION), and sealing the injection port.
While applying an AC 5V voltage to the obtained liquid crystal cell, a metal halide lamp with an illuminance of 60mW was used, and the wavelength of 350nm or less was cut off, and the irradiation was converted to 20J/cm in terms of 365nm2The alignment direction of the liquid crystal is controlled by the ultraviolet ray of (1). The temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was 50 ℃.
The response speed of the liquid crystal before and after the ultraviolet irradiation of the liquid crystal cell was measured. Response speed was measured from transmission 90% to transmission 10% T90 → T10.
The PSA units obtained in any of the examples showed a faster response speed of the liquid crystal cells after uv irradiation than the liquid crystal cells before uv irradiation, and thus it was confirmed that the alignment direction of the liquid crystal was controlled. Further, it was confirmed by observation using a polarized light microscope (ECLIPSE E600WPOL) (manufactured by nikon corporation) that: the liquid crystals of any liquid crystal cell are uniformly aligned.
"production of liquid Crystal cell and evaluation of liquid Crystal alignment Properties (SC-PVA cell)"
The liquid crystal cell was produced and the liquid crystal alignment property was evaluated (SC-PVA cell) using the liquid crystal alignment treatment agent (3) obtained by the method of example 3 of the present invention and the liquid crystal alignment treatment agent (6) obtained by the method of example 6. Specifically, the polymerizable compound (1) shown above was added to these liquid crystal aligning agents in an amount of 2 mass% based on 100 mass% of the total polymer components in the liquid crystal aligning agents, and the mixture was stirred at 25 ℃ for 4 hours. Thereafter, the obtained liquid crystal alignment treatment agent was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and ITO surfaces of a substrate (40 mm in length × 30mm in width, thickness 0.7mm) having ITO electrodes of 10 × 10mm in center and having a pattern interval of 20 μm and a substrate (40 mm in length × 30mm in width, thickness 0.7mm) having ITO electrodes of 10 × 40mm in center were spin-coated with pure water and IPA, and the substrate was heat-treated on a hot plate at 100 ℃ for 5 minutes and 200 ℃ for 30 minutes in a heat-circulation-type cleaning oven, to thereby obtain a substrate having a liquid crystal alignment film with a film thickness of 100 nm.
These substrates with liquid crystal alignment films were combined with a 6 μm spacer interposed between the liquid crystal alignment film surfaces, and the periphery was bonded with a sealant to prepare an empty cell. Nematic liquid crystal (MLC-6608) (manufactured by MERCK CORPORATION) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.
While applying an AC 5V voltage to the obtained liquid crystal cell, a metal halide lamp with an illuminance of 60mW was used, and the wavelength of 350nm or less was cut off, and the irradiation was converted to 20J/cm in terms of 365nm2The alignment direction of the liquid crystal is controlled by the ultraviolet ray of (2) to obtain a liquid crystal cell (SC-PVA cell). The temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was 50 ℃.
The response speed of the liquid crystal before and after the ultraviolet irradiation of the liquid crystal cell was measured. Response speed was measured from transmission 90% to transmission 10% T90 → T10.
The SC-PVA cells obtained in any of the examples showed a higher response speed in the liquid crystal cell after the ultraviolet irradiation than the liquid crystal cell before the ultraviolet irradiation, and thus it was confirmed that the alignment direction of the liquid crystal was controlled. Further, it was confirmed by observation using a polarized light microscope (ECLIPSE E600WPOL) (manufactured by nikon corporation) that: the liquid crystals of any liquid crystal cell are uniformly aligned.
< example 1>
To the polysiloxane solution (1) (15.0g) obtained by the method of synthesis example 1, EC (0.90g), S1(8.46g) and BCS (5.64g) were added, and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (1). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (1) was also used for evaluation as a liquid crystal alignment treatment agent (1).
Using the obtained composition (1) and the liquid crystal alignment treatment agent (1), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pin hole)", "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of step following property)" and "evaluation of production of liquid crystal cell and pretilt angle (ordinary cell)" were carried out.
< example 2>
To the polysiloxane solution (2) (15.0g) obtained by the method of Synthesis example 2 were added EC (0.90g), S1(8.46g) and PB (5.64g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (2). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (2) was also used as the liquid crystal alignment treatment agent (2) for evaluation.
Using the obtained composition (2) and the liquid crystal alignment treatment agent (2), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pin hole)", "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of step following property)" and "evaluation of production of liquid crystal cell and pretilt angle (ordinary cell)" were carried out.
< example 3>
To the polysiloxane solution (3) (15.5g) obtained by the method of Synthesis example 3 were added EC (0.93g), S1(11.7g) and PB (2.91g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (3). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (3) was also used as the liquid crystal alignment treatment agent (3) for evaluation.
Using the obtained composition (3) and the liquid crystal alignment treatment agent (3), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pinhole)", "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of height difference following property)", "evaluation of production of liquid crystal cell and pretilt angle (normal cell)", "evaluation of production of liquid crystal cell and liquid crystal alignment property (PSA cell)", and "evaluation of production of liquid crystal cell and liquid crystal alignment property (SC-PVA cell)", were carried out.
< example 4>
To the polysiloxane solution (3) (10.0g) obtained by the method of Synthesis example 3, EC (7.74g), S1(9.93), PB (3.31g) and γ -BL (3.31g) were added, and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (4). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (4) was also used as a liquid crystal alignment treatment agent (4) for evaluation.
Using the obtained liquid crystal alignment treatment agent (4), the "evaluation of the ink jet coatability of the liquid crystal alignment treatment agent" and the "production of liquid crystal cell and evaluation of pretilt angle (ordinary cell)" were carried out.
< example 5>
To the polysiloxane solution (4) (15.0g) obtained by the method of Synthesis example 4 were added S1(3.72g), BCS (8.46g) and NMP (2.82g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (5). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (5) was also used as a liquid crystal alignment treatment agent (5) for evaluation.
Using the obtained composition (5) and the liquid crystal alignment treatment agent (5), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pin hole)", "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of step following property)" and "evaluation of production of liquid crystal cell and pretilt angle (ordinary cell)" were carried out.
< example 6>
To the polysiloxane solution (4) (15.5g) obtained by the method of Synthesis example 4 were added S1(0.93g), BCS (5.83g), and PB (8.74g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (6). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (6) was also used as a liquid crystal alignment treatment agent (6) for evaluation.
Using the obtained composition (6) and the liquid crystal alignment treatment agent (6), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pinhole)", "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of height difference following property)", "evaluation of production of liquid crystal cell and pretilt angle (normal cell)", "evaluation of production of liquid crystal cell and liquid crystal alignment property (PSA cell)", and "evaluation of production of liquid crystal cell and liquid crystal alignment property (SC-PVA cell)", were carried out.
< example 7>
To the polysiloxane solution (4) (11.0g) obtained by the method of Synthesis example 4 were added S1(8.52g), PB (10.9g) and γ -BL (7.28g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (7). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (7) was used as the liquid crystal alignment treatment agent (7) for evaluation.
Using the obtained liquid crystal alignment treatment agent (7), the "evaluation of the ink jet coatability of the liquid crystal alignment treatment agent" and the "production of liquid crystal cell and evaluation of pretilt angle (ordinary cell)" were carried out.
< example 8>
To the polysiloxane solution (5) (15.0g) obtained by the method of Synthesis example 5 were added EC (0.90g), S1(11.3g) and NEP (2.82g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (8). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (8) was also used as a liquid crystal alignment treatment agent (8) for evaluation.
Using the obtained composition (8) and the liquid crystal alignment treatment agent (8), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pin hole)", "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of step following property)" and "evaluation of production of liquid crystal cell and pretilt angle (ordinary cell)" were carried out.
< example 9>
To the polysiloxane solution (5) (15.0g) obtained by the method of Synthesis example 5 were added K1(0.09g), EC (0.90g), S1(8.46g), DME (2.82g) and γ -BL (2.82g), and the mixture was stirred at 25 ℃ for 6 hours to obtain composition (9). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (9) was also used as a liquid crystal alignment treatment agent (9) for evaluation.
Using the obtained composition (9) and the liquid crystal alignment treatment agent (9), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pin hole)", "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of step following property)" and "evaluation of production of liquid crystal cell and pretilt angle (ordinary cell)" were carried out.
< example 10>
To the polysiloxane solution (5) (11.0g) obtained by the method of Synthesis example 5 were added EC (8.52g), S1(12.7g), DME (1.82g) and γ -BL (3.64g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (10). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (10) was used for evaluation as a liquid crystal alignment treatment agent (10).
Using the obtained liquid crystal aligning agent (10), the "evaluation of the ink jet coatability of the liquid crystal aligning agent" and the "production of liquid crystal cell and evaluation of pretilt angle (ordinary cell)" were carried out.
< example 11>
To the polysiloxane solution (6) (16.0g) obtained by the method of Synthesis example 6 were added EC (0.96g), S1(12.0g) and PB (3.01g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (11). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution.
Using the obtained composition (11), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pinhole)" and the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of level difference following property)" were carried out.
< example 12>
To the polysiloxane solution (7) (16.0g) obtained by the method of Synthesis example 7 were added S1(6.98g), BCS (6.02g), and PB (3.01g), and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (12). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution.
Using the obtained composition (12), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pinhole)" and the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of level difference following property)" were carried out.
< example 13>
To the polysiloxane solution (8) (15.0g) obtained by the method of Synthesis example 8, EC (0.90g), S1(11.3g), DME (1.41g) and NEP (1.41g) were added, and the mixture was stirred at 25 ℃ for 3 hours to obtain composition (13). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution.
Using the obtained composition (13), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pinhole)" and the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of level difference following property)" were carried out.
< comparative example 1>
To the polysiloxane solution (1) (16.0g) obtained by the method of synthesis example 1, EC (9.98g) and BCS (6.02g) were added, and the mixture was stirred at 25 ℃ for 3 hours to obtain a composition (14). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (14) was also used as a liquid crystal alignment treatment agent (14) for evaluation.
Using the obtained composition (14) and liquid crystal alignment treatment agent (14), the "evaluation of printability of the composition and liquid crystal alignment treatment agent (evaluation of pinhole)", "evaluation of printability of the composition and liquid crystal alignment treatment agent (evaluation of step following property)" and "evaluation of production of liquid crystal cell and pretilt angle (ordinary cell)" were carried out.
< comparative example 2>
To the polysiloxane solution (2) (16.0g) obtained by the method of synthesis example 2, EC (9.98g) and BCS (6.02g) were added, and the mixture was stirred at 25 ℃ for 3 hours to obtain a composition (15). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution. The composition (15) was also used as a liquid crystal alignment treatment agent (15) for evaluation.
Using the obtained composition (15) and the liquid crystal alignment treatment agent (15), the "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of pin hole)", "evaluation of printability of the composition and the liquid crystal alignment treatment agent (evaluation of step following property)" and "evaluation of production of liquid crystal cell and pretilt angle (ordinary cell)" were carried out.
< comparative example 3>
To the polysiloxane solution (6) (15.0g) obtained by the method of Synthesis example 6, EC (12.2g) and PB (2.82g) were added, and the mixture was stirred at 25 ℃ for 3 hours to obtain a composition (16). No abnormality such as turbidity and precipitates was observed in the composition, and it was confirmed that the composition was a homogeneous solution.
Using the obtained composition (16), the "evaluation of printability by composition and liquid crystal alignment treatment agent (evaluation of pinhole)" and the "evaluation of printability by composition and liquid crystal alignment treatment agent (evaluation of level difference following property)" were carried out.
[ Table 2]
And 1 represents the ratio of the specific solvent to 100 of the entire solvent.
*2: the ratio of the other solvents is shown when the total solvent is 100.
And 3, the ratio of the polymer in the composition and the liquid crystal alignment treatment agent.
[ Table 3]
And 1 represents the ratio of the specific solvent to 100 of the entire solvent.
And 2, the ratio of other solvents when the total solvent is 100.
And 3, the ratio of the polymer in the composition and the liquid crystal alignment treatment agent.
[ Table 4]
And 1 represents the ratio of the specific solvent to 100 of the entire solvent.
*2: the ratio of the other solvents is shown when the total solvent is 100.
*3: the ratio of the polymer in the composition and the liquid crystal aligning agent is shown.
[ Table 5]
[ Table 6]
[ Table 7]
[ Table 8]
[ Table 9]
From the above results, it can be seen that: the polyimide films obtained from the compositions of examples of the present invention showed uniform film coatability without occurrence of pin holes, as compared to the polyimide films obtained from the compositions of comparative examples. Further, a resin coating having high level difference following properties with respect to the unevenness of the level difference substrate can be obtained.
Specifically, the present invention is a comparison between a composition using a specific solvent which is the component (a) of the present invention and a composition not using a specific solvent, that is, a comparison between example 1 and comparative example 1, a comparison between example 2 and comparative example 2, and a comparison between example 11 and comparative example 3. In these comparative examples, the number of pinholes in the resin coating was larger than in the corresponding examples, and the level difference following property with respect to the unevenness of the level difference substrate was also lower. Further, the compositions of the examples were also used for evaluation as a liquid crystal aligning agent, and therefore, the results of the examples using these compositions were also regarded as the results of the liquid crystal aligning agent.
Further, the change in the pretilt angle between the liquid crystal alignment agent using the component (a) after storage in a high-temperature tank and after ultraviolet irradiation is smaller than the change in the pretilt angle immediately after the liquid crystal cell is manufactured, as compared with the liquid crystal alignment agent not using the component (a) of the present invention. That is, the pretilt angle has high stability against high temperature and ultraviolet light. Specifically, the results are a comparison between example 1 and comparative example 1, and a comparison between example 2 and comparative example 2.
Further, when the specific side chain structure of the present invention is the structure represented by the above formula [2a-1], the change in the pretilt angle between after storage in a high temperature tank and after ultraviolet irradiation becomes smaller than the change in the pretilt angle immediately after the production of the liquid crystal cell. Specifically, example 1 is compared with example 2.
Industrial applicability
The composition of the present invention can suppress the occurrence of pinholes when forming a resin coating, and can further obtain a resin coating having high level difference following properties with respect to irregularities of a level difference substrate.
Further, by using the composition of the present invention as a liquid crystal alignment treatment agent, it is possible to suppress the occurrence of pinholes, and further, it is possible to obtain a liquid crystal alignment film having high level difference following properties with respect to the unevenness of a level difference substrate. Further, the liquid crystal aligning agent of the present invention forms a liquid crystal alignment film capable of exhibiting a stable pretilt angle even after exposure to high temperature and light irradiation for a long time.
Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability, can be suitably used for large-screen and high-definition liquid crystal televisions, medium-and small-sized car navigation systems, smart phones, and the like, and is useful for TN elements, STN elements, TFT liquid crystal elements, and particularly vertical alignment type liquid crystal display elements such as VA mode, PSA mode, SC-PVA mode, and the like.
Claims (17)
1. A composition comprising:
(A) the components: a solvent represented by the following formula [1a ]; and
(B) the components: a polysiloxane obtained by polycondensing an alkoxysilane containing at least 1 selected from alkoxysilanes represented by the following formulae [2a ], [2b ] and [2c ],
(A1)m1Si(A2)n1(OA3)p1 [2a]
formula [2a ]]In (A)1Is represented by a formula [2a-1] selected from]And formula [2a-2]At least 1 of the structures shown; a. the2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; a. the3Each independently represents an alkyl group having 1 to 5 carbon atoms; m is1Represents an integer of 1 or 2; n is1Represents an integer of 0 to 2; p is a radical of1Represents an integer of 0 to 3; wherein m is1+n1+p1Which represents the integer 4, represents the number of atoms,
formula [2a-1]In, Y1Represents a group selected from a single bond, - (CH)2)a-、-O-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from CO-, -COO-and-OCO-, wherein a is an integer of 1-15; y is2Represents a single bond or- (CH)2)b-, wherein b is an integer of 1 to 15; y is3Represents a group selected from a single bond, - (CH)2)c-、-O-、-CH2At least 1 bonding group of O-, -COO-and-OCO-, wherein c is an integer of 1 to 15; y is4Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, orA C17-51 divalent organic group having a steroid skeleton, wherein any hydrogen atom in the cyclic group is optionally substituted by a C1-3 alkyl group, a C1-3 alkoxy group, a C1-3 fluoroalkyl group, a C1-3 fluoroalkoxy group, or a fluorine atom; y is5Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom on the cyclic groups is optionally substituted by alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms, fluorine-containing alkyl with 1 to 3 carbon atoms, fluorine-containing alkoxy with 1 to 3 carbon atoms or fluorine atom; n represents an integer of 0 to 4; y is6Represents at least 1 kind selected from alkyl with 1-22 carbon atoms, alkenyl with 2-22 carbon atoms, fluorine-containing alkyl with 1-22 carbon atoms, alkoxy with 1-22 carbon atoms and fluorine-containing alkoxy with 1-22 carbon atoms,
-Y7-Y8 [2a-2]
formula [2a-2]In, Y7Represents a group selected from a single bond, -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from CO-, -COO-and-OCO-; y is8Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms,
(B1)m2Si(B2)n2(OB3)p2 [2b]
formula [2b]In (B)1Each independently represents an organic group having 2 to 12 carbon atoms and at least 1 selected from vinyl, epoxy, amino, mercapto, isocyanate, methacryloyl, acryloyl, ureido, and cinnamoyl groups; b is2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; b is3Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms; m is2Represents an integer of 1 or 2; n is2Represents an integer of 0 to 2; p is a radical of2Represents an integer of 0 to 3; wherein m is2+n2+p2Which represents the integer 4, represents the number of atoms,
(D1)n3Si(OD2)4-n3 [2c]
formula [2c ]]In (D)1Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; d2Each independently represents a carbon number of 1 to 5An alkyl group; n is3Represents an integer of 0 to 3,
wherein the component (A) accounts for 20-80% by mass of the total solvent in the composition, and the component (B) accounts for 0.1-30% by mass of the composition.
2. The composition according to claim 1, wherein the alkoxysilane represented by the formula [2B ] of the component (B) is at least 1 alkoxysilane selected from the group consisting of allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate.
3. The composition according to claim 1, wherein the alkoxysilane represented by the formula [2B ] of the component (B) is at least 1 alkoxysilane selected from the group consisting of 3-glycidoxypropyl (dimethoxy) methylsilane, 3-glycidoxypropyl (diethoxy) methylsilane, 3-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
4. The composition according to claim 1, wherein the polysiloxane of the component (B) is a polysiloxane containing 1 polysiloxane of polysiloxanes consisting of a polysiloxane obtained by polycondensing an alkoxysilane represented by the formula [2a ] and a formula [2B ] or a polysiloxane obtained by polycondensing an alkoxysilane represented by the formula [2a ] and a formula [2c ].
5. The composition according to claim 1, wherein the polysiloxane of component (B) is a polysiloxane obtained by polycondensation of alkoxysilanes represented by formula [2a ], formula [2B ] and formula [2c ].
6. The composition according to claim 1, wherein the composition contains at least 1 solvent selected from the group consisting of methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and furfuryl alcohol.
7. The composition of claim 1, wherein the composition comprises at least 1 solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, and 1, 3-dimethylimidazolidinone.
8. The composition according to claim 1, wherein the composition comprises at least 1 crosslinkable compound selected from the following crosslinkable compounds: a crosslinkable compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclocarbonate group; a crosslinkable compound having at least 1 substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group; and a crosslinkable compound having a polymerizable unsaturated bond.
9. A resin coating film obtained from the composition according to any one of claims 1 to 8.
10. A liquid crystal aligning agent obtained from the composition according to any one of claims 1 to 8.
11. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to claim 10.
12. A liquid crystal alignment film obtained by an ink jet method using the liquid crystal alignment treatment agent according to claim 10.
13. A liquid crystal display element having the liquid crystal alignment film according to claim 11 or claim 12.
14. The liquid crystal alignment film according to claim 11 or 12, which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and manufactured through the following steps: a liquid crystal composition is disposed between the pair of substrates, the liquid crystal composition including a polymerizable compound that is polymerized by at least one of active energy rays and heat, and the polymerizable compound is polymerized while applying a voltage between the electrodes.
15. A liquid crystal display element comprising the liquid crystal alignment film according to claim 14.
16. The liquid crystal alignment film according to claim 11 or 12, which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and manufactured through the following steps: a liquid crystal alignment film is disposed between the pair of substrates, the liquid crystal alignment film including a polymerizable group that is polymerized by at least one of active energy rays and heat, and the polymerizable group is polymerized while applying a voltage between the electrodes.
17. A liquid crystal display element comprising the liquid crystal alignment film according to claim 16.
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| CN102414605A (en) * | 2009-05-01 | 2012-04-11 | 日产化学工业株式会社 | Silicon-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
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| CN104140826A (en) * | 2013-05-09 | 2014-11-12 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, retardation film and methods for producing same, and liquid crystal display element |
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| CN102414605A (en) * | 2009-05-01 | 2012-04-11 | 日产化学工业株式会社 | Silicon-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN102713744A (en) * | 2009-12-01 | 2012-10-03 | 日产化学工业株式会社 | Silicon-containing liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN104140826A (en) * | 2013-05-09 | 2014-11-12 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, retardation film and methods for producing same, and liquid crystal display element |
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