CN108349917B - Diamine compound having ability to generate radical and base, and imide polymer using same as raw material - Google Patents

Diamine compound having ability to generate radical and base, and imide polymer using same as raw material Download PDF

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CN108349917B
CN108349917B CN201680063316.2A CN201680063316A CN108349917B CN 108349917 B CN108349917 B CN 108349917B CN 201680063316 A CN201680063316 A CN 201680063316A CN 108349917 B CN108349917 B CN 108349917B
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川野勇太
芦泽亮一
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
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    • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
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    • G02F1/1333—Constructional arrangements; Manufacturing methods
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Abstract

The present invention provides a novel diamine having an ability to generate radicals and an ability to generate a base upon irradiation with ultraviolet rays, and a novel imide polymer using the diamine as a raw material. Disclosed is a diamine represented by the formula (1), and an imide polymer comprising a polyimide precursor obtained by imidizing a polyimide precursor and/or a diamine precursor obtained by imidizing a polyimide precursor. Formula (1) (T1, T2 are single bond, -O-, -COO-and other bonding groups; G is 2-valent heterocyclic group having 2 nitrogen atoms; R1, R2 are C1-10 alkyl, etc.; Q is the following group) formula (2) (R is hydrogen atom, etc.; R3 is nitrogen atom, etc.)

Description

Diamine compound having ability to generate radical and base, and imide polymer using same as raw material
Technical Field
The present invention relates to a novel diamine compound having an ability to generate radicals and an ability to generate a base, and an imide polymer used for a liquid crystal aligning agent, a photosensitive resin material, and the like, which uses the diamine compound as a raw material.
Background
A liquid crystal display element of a type (referred to as a Vertical Alignment (VA) type) in which liquid crystal molecules aligned vertically with respect to a substrate are caused to respond to an electric field may include a step of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules in a manufacturing process thereof.
For such a liquid crystal display element of the vertical alignment type, there are known: a PSA (Polymer stabilized Alignment) type element (patent document 1 and non-patent document 1) in which a photopolymerizable compound is added to a liquid crystal composition in advance, and ultraviolet rays are irradiated to a liquid crystal cell while applying a voltage thereto, thereby increasing the response speed of the liquid crystal, using a vertical Alignment film such as a polyimide-based one.
In the PSA type element, the tilt direction of the liquid crystal molecules responding to the electric field is generally controlled by a protrusion provided on the substrate, a slit provided in the display electrode, or the like. In this case, since the photopolymerizable compound is added to the liquid crystal composition and the polymer structure that memorizes the tilt direction of the liquid crystal molecules is formed on the liquid crystal alignment film by irradiating the liquid crystal cell with ultraviolet rays while applying a voltage, the response speed of the liquid crystal display element can be said to be increased as compared with a method of controlling the tilt direction of the liquid crystal molecules only by the protrusions and slits.
On the other hand, in the PSA type element, there is a problem that the polymerizable compound added to the liquid crystal has low solubility and precipitates at low temperature when the amount of addition is increased, but a good alignment state cannot be obtained when the amount of addition of the polymerizable compound is decreased. Further, the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity (contamination) in the liquid crystal, and thus there is also a problem that the reliability of the liquid crystal display element is lowered. In addition, when the UV irradiation treatment required for the PSA method is performed at a large dose, components in the liquid crystal are decomposed, which leads to a decrease in reliability.
Further, it has been reported that the response speed of the liquid crystal display element is increased by adding a photopolymerizable compound to the liquid crystal alignment film without adding it to the liquid crystal composition (SC-PVA type liquid crystal display, non-patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-307720
Non-patent document
Non-patent document 1: k. Hanaoka, SID 04DIGEST, P.1200-1202
Non-patent document 2: K.H Y. -J.Lee, SID 09DIGEST, P.666-668
Disclosure of Invention
Problems to be solved by the invention
In recent years, as the quality of liquid crystal display elements has improved, it has been desired to further improve the response speed of liquid crystal with respect to voltage application. Therefore, it is required that the polymerizable compound efficiently reacts and exhibits an alignment fixing ability under irradiation with ultraviolet rays having a long wavelength without accompanying decomposition of components in the liquid crystal. Further, it is also necessary that the polymerizable compound does not remain unreacted after the irradiation of ultraviolet rays, and the reliability of the liquid crystal display element is not adversely affected.
The present invention addresses the problem of providing an imide polymer that is suitably used as a liquid crystal aligning agent, particularly a liquid crystal aligning agent for PSA elements having a high response speed, a material for photosensitive resins, and the like, and a novel diamine compound that is a raw material for the imide polymer.
Means for solving the problems
The present application has the following gist.
(1) A diamine compound represented by the following formula (1).
Figure GDA0003174005900000031
(T1、T2Independently represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-、-N(CH3)-、-CON(CH3)-、-N(CH3) A bonding group of CO-or-S-. G is a 2-valent heterocyclic group having 2 nitrogen atoms. R1、R2Each independently is an alkyl group having 1 to 10 carbon atoms, a benzyl group or an alkoxy group. Q is a group selected from the following. )
Figure GDA0003174005900000032
(R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3Is a nitrogen atom or an oxygen atom. )
(2) An imide-based polymer which is at least 1 selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing the diamine compound described in the above (1) with a tetracarboxylic dianhydride component, and a polyimide obtained by imidizing the precursor.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present application, a novel diamine compound which can generate a radical and a base by irradiation with ultraviolet rays is provided. Also provided is a novel imide polymer comprising a polyimide precursor obtained by reacting a diamine component containing the novel diamine compound with a tetracarboxylic dianhydride component and/or a polyimide obtained by imidizing the precursor.
The imide polymer of the present application is used for a liquid crystal aligning agent, a material for a photosensitive resin, and the like. For example, in the liquid crystal aligning agent containing the imide polymer of the present application, since the diamine which is a raw material of the imide polymer generates radicals and bases by irradiation of ultraviolet rays and reacts with the polymerizable compound used in the liquid crystal display element, a liquid crystal display element, particularly a PSA element, of a vertical alignment system which efficiently provides a tilt angle and a high response speed can be obtained.
Detailed Description
< imide-based Polymer of the present application >
(specific diamine)
The imide-based polymer of the present application uses, as a raw material, a novel diamine compound (hereinafter, referred to as a specific diamine) represented by the following formula (1) that can generate radicals and a base by irradiation with ultraviolet light.
Figure GDA0003174005900000041
The specific diamine has a side chain (hereinafter referred to as a specific side chain) represented by the formula (1a) that generates a radical and a base by irradiation with ultraviolet light having a wavelength of 365nm to 420nm, preferably 300 to 380nm as the general light.
Figure GDA0003174005900000042
In the above formulae (1), (1a), T1、T2、G、Ar、R1、R2And Q are each as defined above. Wherein, T1、T2A single bond is preferred from the viewpoint of ease of synthesis, and a piperazine structure is preferred for G from the viewpoint of ease of synthesis and availability of raw materials.
In addition, since Ar bonded to a carbonyl group is related to the absorption wavelength of ultraviolet light, a long structure having a long conjugation such as naphthylene group or biphenylene group is preferable in the case of a long wavelength.
In addition, Ar is optionally substituted with a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, or an amino group.
Ar is most preferably a phenylene group from the viewpoint of ease of synthesis and solubility, as compared with a naphthylene group and a biphenylene group. Sufficient characteristics can be obtained when the wavelength of ultraviolet light is in the range of 250nm to 380nm, and phenylene is most preferable from the viewpoint of availability of raw materials and ease of synthesis.
Furthermore, R1、R2Each independently is an alkyl group, alkoxy group, benzyl group or phenethyl group having 1 to 10 carbon atoms, and in the case of the alkyl group or the alkoxy group, R is optionally substituted1、R2Forming a ring.
In the formula (I), Q is preferably any of the following groups which are decomposed by ultraviolet rays to generate radicals and bases.
Figure GDA0003174005900000051
R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R3Is a nitrogen atom and/or an oxygen atom.
From the viewpoint of availability of raw materials, strength of generated base, and ease of handling, R is preferably methyl or ethyl, and R is preferably methyl or ethyl3Preferably an oxygen atom or a nitrogen atom.
From the viewpoints of ease of synthesis, high versatility, and characteristics, the following are preferable examples of the specific amine.
Figure GDA0003174005900000052
< Synthesis of specific diamine >
Specific diamines can be obtained by: the dinitro compound obtained through each step, or the mononitro group compound having an amino group to which a protecting group removable in the reduction step is added, or the diamine is synthesized, and the nitro group is converted into an amino group or the protecting group is deprotected by a reduction reaction generally used.
The synthesis of specific diamines is shown below, for example: a method of synthesizing a dinitrobenzene-bonded structure by irradiating a radical-generating site with ultraviolet rays, introducing a spacer bond site, and then bonding dinitrobenzene thereto.
Figure GDA0003174005900000061
The base to be used is not particularly limited, but is preferably an inorganic base such as potassium carbonate, sodium carbonate or cesium carbonate, or an organic base such as pyridine, dimethylaminopyridine, trimethylamine, triethylamine or tributylamine.
The method for reducing the dinitro compound is not particularly limited, and the following methods are generally used: reduction is carried out using palladium on carbon, platinum oxide, raney nickel, platinum on carbon, rhodium-alumina, platinum on carbon sulfide, or the like as a catalyst in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, an alcohol, or the like, with hydrogen gas, hydrazine, hydrogen chloride, or the like. If necessary, an autoclave or the like may be used.
On the other hand, when the dinitro compound contains an unsaturated bond site in its structure, there is a concern that the unsaturated bond site is reduced to become a saturated bond when palladium carbon, platinum carbon or the like is used, and therefore, a reduction method using a transition metal such as reduced iron, tin chloride or the like, palladium carbon, platinum carbon doped with iron, or the like poisoned by a catalyst is preferable.
The specific diamine can be obtained by deprotecting a diaminobenzene derivative protected with a benzyl group or the like in the same manner as in the above-mentioned reduction step.
(vertical orientation side chain diamine)
When the imide-based polymer of the present application is used as a liquid crystal aligning agent, a diamine compound represented by the following formula [2] (hereinafter referred to as a vertically aligned side chain diamine) having a side chain for vertically aligning a liquid crystal can be used as a raw material in addition to the specific diamine.
Figure GDA0003174005900000062
In the formula [2], X represents a structure represented by the following formula [ II-1] or formula [ II-2], and n represents an integer of 1 to 4, particularly preferably 1.
Figure GDA0003174005900000071
In the formula [ II-1]In (X)1Represents a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O-, -COO-or OCO-. X2Represents a single bond or (CH)2)b- (b is an integer of 1 to 15). X3Represents a single bond, - (CH)2)c- (c is an integer of 1 to 15), -O-, -CH2O-, -COO-or OCO-, X4Represented by a 2-valent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom of these cyclic groups being optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom, or X4Optionally a 2-valent organic group selected from organic groups having 17 to 51 carbon atoms and having a steroid skeleton. X5Represents a 2-valent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom on 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 or a fluoroalkyl group having 1 to 3 carbon atomsAnd a C1-3 fluoroalkoxy group or a fluorine atom. n represents an integer of 0 to 4. X6Represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.
Wherein, X1From the viewpoint of availability of raw materials and ease of synthesis, a single bond, - (CH) is preferred2) 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-. Wherein, X2Preferably a single bond or (CH)2)b- (b is an integer of 1 to 10). For X3Among them, from the viewpoint of ease of synthesis, a single bond, - (CH) is preferred2)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-.
Wherein, X4From the viewpoint of ease of synthesis, a benzene ring, a cyclohexane ring, or a C17-51 organic group having a steroid skeleton is preferable. For X5Among them, preferred is a benzene ring or a cyclohexane ring. Among them, from the viewpoint of availability of raw materials and ease of synthesis, 0 to 3 is preferable, and 0 to 2 is more preferable.
For X6Among them, preferred is an alkyl group having 1 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 preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
As formula [ II-1]X in (1)1、X2、X3、X4、X5、X6And n are preferably the same as (2-1) to (2-629) described in tables 6 to 47 on pages 13 to 34 of International publication WO2011/132751 (published 2011.10.27). In the tables of WO2011/132751, X in the present application1～X6Y1 to Y6 are shown as Y1 to Y6Is solved as X1～X6。
In addition, (2-605) to (2-629) described in each table of WO2011/132751, the organic group having 17 to 51 carbon atoms and having a steroid skeleton in the present application is represented by an organic group having 12 to 25 carbon atoms and having 12 to 25 carbon atoms, respectively, of the steroid skeleton, and the organic group having 12 to 25 carbon atoms and having a steroid skeleton is understood to be an organic group having 17 to 51 carbon atoms and having a steroid skeleton.
Among them, preferred is a combination of (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315), (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615). Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2-606), (2-607) to (2-609), (2-611), (2-612), or (2-624).
-X7-X8 [II-2]
Formula [ II-2]]In, X7Represents a single bond, -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3) -、-N(CH3) CO-, -COO-or OCO-. X8Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms. Wherein, X7Preferably a single bond, -O-, -CH2O-、-CONH-、-CON(CH3) -or COO-, more preferably a single bond, -O-, -CONH-or COO-. For X8Among them, an alkyl group having 8 to 18 carbon atoms is preferable.
The diamine represented by the formula [2] is preferably a diamine represented by the following formula [2-1] from the viewpoint of high vertical alignment properties, which can provide a stable liquid crystal.
Figure GDA0003174005900000081
The above formula [2-1]X in (1)1、X2、X3、X4、X5And n is the same as the above formula [ II-1]Wherein each of the definitions is the same, and each of the preferred embodiments is the same as the above formula [ II-1]]Are defined identically.
In the formula [2-1], m is an integer of 1 to 4. Preferably an integer of 1.
The diamine represented by the formula [2-1] includes, for example, those represented by the following formulae [2a-1] to [2a-31 ].
Figure GDA0003174005900000091
(R1represents-O-, -OCH2-、-CH2O-、-COOCH2-or CH2OCO-，R2Is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, a linear or branched fluoroalkyl group or fluoroalkoxy group having 1 to 22 carbon atoms. )
Figure GDA0003174005900000092
(R3represents-COO-, -OCO-, -CONH-, -NHCO-, -COOCH2-、-CH2OCO-、 -CH2O-、-OCH2-or CH2-，R4A linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, a linear or branched fluoroalkyl group or fluoroalkoxy group having 1 to 22 carbon atoms).
Figure GDA0003174005900000093
(R5represents-COO-, -OCO-, -CONH-, -NHCO-, -COOCH2-、-CH2OCO-、 -CH2O-、-OCH2-、-CH2-, -O-or NH-, R6Is fluoro, cyano, trifluoromethyl, nitro, azo, formyl, acetyl, acetoxy or hydroxy).
Figure GDA0003174005900000101
(R7Is a linear or branched alkyl group having 3 to 12 carbon atoms, a1, 4-ylidene groupCis-trans isomers of cyclohexyl groups are trans isomers, respectively).
Figure GDA0003174005900000102
(R8Is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of the 1, 4-cyclohexylene group are trans isomers, respectively).
Figure GDA0003174005900000103
(A4Is a linear or branched alkyl group having 3 to 20 carbon atoms optionally substituted with a fluorine atom, A3Is 1, 4-cyclohexylene or 1, 4-phenylene, A2Is oxygen atom or COO-onium (wherein, the connecting bond with the onium) and A3Bonding) A1Is oxygen atom or COO-onium (wherein, the connecting bond with the onium) and (CH)2)a2) Bonding). In addition, a1Is an integer of 0 or 1, a2Is an integer of 2 to 10, a3An integer of 0 or 1).
Figure GDA0003174005900000104
Figure GDA0003174005900000111
Among the above formulas [2a-1] to [2a-31], the formulas [2a-1] to [2a-6], the formulas [2a-9] to [2a-13], or the formulas [2a-22] to [2a-31] are particularly preferable.
Further, as the diamine represented by the above formula [ II-2], there can be mentioned diamines represented by the following formulae [2b-1] to [2b-10 ].
Figure GDA0003174005900000121
(A1Represents an alkyl group having 1 to 22 carbon atoms or a group containingFluoroalkyl groups).
Figure GDA0003174005900000122
The above formula [2b-5]-formula [2b-10]In (A)1represents-COO-, -OCO-, -CONH-, -NHCO-, -CH2-, -O-, -CO-or NH-, A2Represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluoroalkyl group having 1 to 22 carbon atoms.
(other diamines)
As the diamine used as a raw material of the imide-based polymer of the present invention, diamines other than the above-mentioned diamines may be used in combination as a diamine component. Specifically, for example, diamines described in paragraph 0063 of International publication WO2015/033921A1 (2015.3.12), such as p-phenylenediamine, m-phenylenediamine, 3, 5-diaminobenzoic acid, and 4, 4' -diaminobenzophenone, can be used.
< production of imide-based Polymer of the present application >
The imide polymer of the present application is produced by polycondensing a diamine component containing a specific diamine and, if necessary, a diamine having a side chain for vertically aligning a liquid crystal, and the other diamine described above, with a tetracarboxylic dianhydride component.
Specific examples of the tetracarboxylic dianhydride component include diamines described in paragraph 0065 of International publication WO2015/033921A1 (2015.3.12), such as pyromellitic acid, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride, and 2,3, 5-tricarboxycyclopentylacetic acid-1, 4,2, 3-dianhydride. The tetracarboxylic dianhydride may be used in combination of 1 or 2 or more.
When the diamine component is reacted with the tetracarboxylic dianhydride component, the specific diamine is preferably 10 to 100 mol%, more preferably 20 to 60 mol%, and particularly preferably 30 to 50 mol% of the diamine component used for the synthesis of the polyamic acid.
The vertically oriented side chain diamine is preferably 5 to 50 mol% of the diamine component, more preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol% of the diamine component.
When the polyamic acid is obtained by the reaction of the diamine component and the tetracarboxylic dianhydride component, a known synthesis method can be used. In general, a method of reacting a diamine component with a tetracarboxylic dianhydride component in an organic solvent is used. The reaction of the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is produced.
The organic solvent used in the above reaction is not particularly limited as long as the produced polyamic acid is dissolved. Further, even if the organic solvent is an organic solvent in which the polyamic acid is not dissolved, the solvent may be mixed and used in a range where the produced polyamic acid is not precipitated. It is preferable that the organic solvent is dehydrated and dried for use because moisture in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the polyamic acid to be produced.
Examples of the organic solvent used in the above reaction include N, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropionamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, γ -butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, and the like, Ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, methyl cellosolve, butyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, and the like, Diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used alone or in combination.
The method of reacting a diamine component with a tetracarboxylic dianhydride component in an organic solvent may optionally be a method comprising: a method of stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and adding a tetracarboxylic dianhydride component as it is or in a state of being dispersed or dissolved in an organic solvent; a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent; a method of alternately adding a tetracarboxylic dianhydride component and a diamine component. When the diamine component or the tetracarboxylic dianhydride component is formed of a plurality of compounds, they may be reacted in a state of being mixed in advance, or they may be reacted in sequence, or low-molecular-weight materials obtained by the respective reactions may be mixed and reacted to produce a high-molecular-weight material.
The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted is, for example, in the range of-20 to 150 ℃, preferably-5 to 100 ℃. In addition, the total concentration of the diamine component and the tetracarboxylic dianhydride component in the reaction is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the reaction solution, for example.
The ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in the polymerization reaction can be selected according to the desired molecular weight of the polyamic acid. Similarly to the ordinary polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0, and the preferable range is 0.8 to 1.2.
The temperature for thermal imidization of the polyamic acid in the solution is 100 to 400 ℃, preferably 120 to 250 ℃, and is preferably carried out while discharging water produced by the imidization reaction to the outside of the system.
The catalytic imidization of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid and stirring at-20 to 250 ℃, preferably 0 to 180 ℃. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times, by mole the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 times, preferably 3 to 30 times, by mole the amount of the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among these, pyridine is preferable because it has a suitable basic property for promoting the reaction. Examples of the acid anhydride include: acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among them, acetic anhydride is preferred because purification after completion of the reaction becomes easy when acetic anhydride is used. The imidization rate based on the catalytic imidization can be controlled by adjusting the amount of the catalyst and the reaction temperature, reaction time.
< liquid Crystal Aligning agent >
The liquid crystal aligning agent contains an imide polymer having a structure represented by the formula (1) in a side chain, and the content of the imide polymer is preferably 1 to 20 mass%, more preferably 3 to 15 mass%, and particularly preferably 3 to 10 mass%.
The molecular weight of the imide polymer contained in the liquid crystal aligning agent is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000, in terms of the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method, in consideration of the strength of the liquid crystal alignment film obtained by applying the liquid crystal aligning agent, the workability in forming a coating film, and the uniformity of the coating film.
The solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve or disperse in a component containing a polymer having a structure represented by the above formula (1) in a side chain and a polymerizable compound having a group which is photopolymerizable or photocrosslinkable at 2 or more terminals, which is contained as necessary. For example, the organic solvent exemplified in the synthesis of the polyamic acid can be mentioned. Among them, N-methyl-2-pyrrolidone, γ -butyrolactone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropionamide and the like are preferable from the viewpoint of solubility. Naturally, a mixed solvent of 2 or more kinds may be used.
Further, it is preferable to use a solvent that improves the uniformity and smoothness of the coating film by mixing the solvent with a solvent having high solubility in the components contained in the liquid crystal aligning agent.
As the solvent, for example, a solvent described in paragraph 0094 of International publication WO2015/033921A1(2015.3.12 publication) can be used.
< polymerizable Compound >
The liquid crystal aligning agent of the present application may contain a polymerizable compound having 2 or more groups at the end for photopolymerization or photocrosslinking, as necessary. The polymerizable compound is a compound having 2 or more terminals having a group which is photopolymerized or photocrosslinked. Here, the polymerizable compound having a group that undergoes photopolymerization refers to a compound having a functional group that undergoes polymerization upon irradiation with light. The compound having a group which is photocrosslinkable means a compound having a functional group which can be crosslinked by reacting with at least one polymer selected from the group consisting of a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor by irradiation with light. In addition, as for the compounds having a group which undergoes photocrosslinking, the compounds having a group which undergoes photocrosslinking also undergo reaction with each other.
When the polymerizable compound is contained, the content thereof is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the imide polymer.
By using the liquid crystal aligning agent containing the polymerizable compound in a vertical alignment type liquid crystal display element such as an SC-PVA type liquid crystal display, the response speed can be remarkably improved, and the response speed can be sufficiently improved even with a small amount of the polymerizable compound, as compared with the case where the polymerizable compound is used alone and a polymer having a side chain for vertically aligning the liquid crystal and a photoreactive side chain is used.
Examples of the group to be photopolymerized or photocrosslinked include monovalent groups represented by the following formula (IV).
Figure GDA0003174005900000161
(R12Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z1Represents a 2-valent aromatic ring or heterocyclic ring optionally substituted by a C1-12 alkyl group or a C1-12 alkoxy group. Z2Represents a 1-valent aromatic ring or heterocyclic ring optionally substituted by a C1-12 alkyl group or a C1-12 alkoxy group. )
Specific examples of the polymerizable compound include a compound having a group which is photopolymerizable at each of 2 terminals represented by the following formula (V), a compound having a group which is photopolymerizable and a group which is photocrosslinkable at each of 2 terminals represented by the following formula (VI), and a compound having a group which is photocrosslinkable at each of 2 terminals represented by the following formula (VII).
In the following formulae (V) to (VII), R12、Z1And Z2And R in the above formula (IV)12、Z1And Z2Are as defined, Q1Is a 2-valent organic group. Q1Preferably having a phenylene (-C)6H4-) and biphenylene (-C)6H4-C6H4-) cyclohexylene (-C)6H10-) isocyclic structure. This is because the interaction with the liquid crystal tends to become large.
Figure GDA0003174005900000171
Specific examples of the polymerizable compound represented by the formula (V) include polymerizable compounds represented by the following formula (4). In the following formula (4), V, W is a single bond or is represented by the formula-R1O-represents, R1Is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by the formula-R1O-represents, R1Is a straight-chain or branched alkylene group having 2 to 6 carbon atoms. V, W may be the same or different, but they are easy to synthesize when they are the same.
Figure GDA0003174005900000181
Even if the polymerizable compound has an acrylate group or a methacrylate group as a group to be photopolymerized or photocrosslinked instead of the α -methylene- γ -butyrolactone group, the polymerizable compound having a structure in which the acrylate group or the methacrylate group is bonded to a phenylene group via an oxyalkylene-like spacer bond can significantly improve the response speed particularly in the same manner as the polymerizable compound having the α -methylene- γ -butyrolactone group at both ends. Further, a polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group via an oxyalkylene group or the like spacer bond improves stability against heat, and can sufficiently withstand a high temperature, for example, a firing temperature of 200 ℃.
The method for producing the polymerizable compound is not particularly limited, and the production method described in paragraphs 0076 to 0082 of International publication WO2015/033921A1 (2015.3.12) can be used.
The liquid crystal aligning agent may contain components other than those described above. Examples thereof include a compound which improves the uniformity of film thickness and surface smoothness when the liquid crystal alignment agent is applied, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like.
The liquid crystal alignment agent is applied to a substrate and fired to form a liquid crystal alignment film for vertically aligning liquid crystals. By using the liquid crystal aligning agent of the present application, the response speed of a liquid crystal display element using the obtained liquid crystal alignment film can be increased. In addition, the polymerizable compound optionally contained in the liquid crystal aligning agent of the present invention is contained in the liquid crystal without being contained in the liquid crystal aligning agent, or is contained in the liquid crystal together with the liquid crystal aligning agent, so that the sensitivity of photoreaction is increased in the so-called PSA mode, and a tilt angle can be imparted even with a small amount of ultraviolet irradiation.
For example, the liquid crystal alignment agent of the present application may be applied to a substrate, dried and fired as necessary to obtain a cured film, and the cured film may be used as it is as a liquid crystal alignment film. The cured film may be subjected to brushing, irradiation with polarized light, light of a specific wavelength, or the like, or treatment with an ion beam or the like to prepare an alignment film for PSA, and the liquid crystal display element filled with the liquid crystal may be irradiated with UV in a state where a voltage is applied. Particularly useful as an alignment film for PSA.
In this case, the substrate used is not particularly limited as long as it is a substrate having high transparency, and a glass plate, polycarbonate, poly (meth) acrylate, or the like can be used. In addition, the use of a substrate on which an ITO electrode or the like for driving liquid crystal is formed is preferable from the viewpoint of simplification of the process. In the reflective liquid crystal display element, an opaque material 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 examples thereof include printing methods such as screen printing, gravure printing, and flexographic printing; ink-jet methods, spray methods, roll coating methods, dipping, roll coaters, slit coaters, spin coaters, and the like. In terms of productivity, the transfer printing method is widely used industrially, and can be suitably used in the present application.
The coating film formed by applying the liquid crystal aligning agent by the above-mentioned method may be fired to form a cured film. The drying step after the application of the liquid crystal aligning agent is not essential, and when the time from the application to the firing of each substrate is not constant or the firing is not performed immediately after the application, the drying step is preferably performed. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by conveyance of the substrate or the like. For example, the drying may be performed for 0.5 to 30 minutes, preferably 1 to 5 minutes, on a hot plate at a temperature of 40 to 150 ℃, preferably 60 to 100 ℃.
The firing temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and is, for example, 100 to 350 ℃, preferably 120 to 300 ℃, and more preferably 150 to 250 ℃. The firing time is 5 to 240 minutes, preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. The heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace, or the like.
The thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300nm, more preferably 10 to 100 nm.
< liquid crystal display element >
The liquid crystal display element of the present application can be produced by forming a liquid crystal alignment film on a substrate by the above-described method and then fabricating a liquid crystal cell by a known method. A specific example of the liquid crystal display element is a vertical alignment type liquid crystal display element including a liquid crystal cell having: 2 substrates disposed in an opposing manner, a liquid crystal layer provided between the substrates, and the liquid crystal alignment film formed of the liquid crystal alignment agent of the present application provided between the substrates and the liquid crystal layer. Specifically, the liquid crystal display element of the vertical alignment type is provided with a liquid crystal cell manufactured as follows: the liquid crystal alignment agent of the present application is applied to 2 substrates and fired to form a liquid crystal alignment film, the 2 substrates are arranged so that the liquid crystal alignment film faces each other, a liquid crystal layer composed of a liquid crystal is sandwiched between the 2 substrates, that is, the liquid crystal layer is provided so as to be in contact with the liquid crystal alignment film, and ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, thereby producing a liquid crystal cell.
By using the liquid crystal alignment film formed from the liquid crystal aligning agent of the present application, the polymerizable compound is polymerized by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and the photoreactive side chains of the polymer are reacted with each other and the photoreactive side chains of the polymer are reacted with the polymerizable compound, whereby the alignment of the liquid crystal is more effectively fixed, and a liquid crystal display element having a remarkably excellent response speed is formed.
The substrate used in the liquid crystal display element of the present application is not particularly limited as long as it is a substrate having high transparency, and is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples thereof include the same substrates as those described in the liquid crystal alignment film. The conventional substrate provided with an electrode pattern or a protrusion pattern may be used, but the liquid crystal display element of the present invention can be operated even in a structure in which a line/slit electrode pattern of, for example, 1 to 10 μm is formed on one side substrate and no slit pattern or protrusion pattern is formed on the counter substrate because the liquid crystal alignment agent of the present invention is used.
In addition, in a high-functional element such as a TFT-type element, a product in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate can be used.
In the case of a transmissive liquid crystal display element, the above-described substrate is generally used, but in the case of a reflective liquid crystal display element, if the substrate is a single-sided substrate, an opaque substrate such as a silicon wafer may be used. In this case, a material such as aluminum that reflects light may be used for the electrodes formed on the substrate.
The liquid crystal material of the liquid crystal layer constituting the liquid crystal display element of the present application is not particularly limited, and a liquid crystal material used in a conventional vertical alignment system, for example, a negative-type liquid crystal such as MLC-6608, MLC-6609, or the like, manufactured by MERCK Corporation, can be used. In the PSA mode, for example, a liquid crystal containing a polymerizable compound represented by the following formula can be used.
Figure GDA0003174005900000211
In the present application, a known method can be used as a method of sandwiching a liquid crystal layer between 2 substrates. Examples of the method include the following methods: the method includes preparing 1 pair of substrates on which liquid crystal alignment films are formed, spreading spacers such as beads on the liquid crystal alignment film of one substrate, attaching the other substrate so that the surface on which the liquid crystal alignment film is formed is the inner side, injecting liquid crystal under reduced pressure, and sealing. In addition, a liquid crystal cell can also be produced by the following method: the method includes preparing 1 pair of substrates on which liquid crystal alignment films are formed, dispersing spacers such as beads on the liquid crystal alignment film of one substrate, dropping liquid crystal, and then attaching the other substrate so that the surface on which the liquid crystal alignment film is formed is the inner side, and sealing. The thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm.
Examples of the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer include a method of applying an electric field to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes provided on the substrate, and irradiating ultraviolet rays while maintaining the electric field. The voltage applied between the electrodes is, for example, 5 to 30Vp-p, preferably 5 to 20 Vp-p. As the ultraviolet ray, it is possible to use a general light having a wavelength of 250 to 420nm, preferably 300 to 380nm, inclusive of 365 nm. The irradiation dose is, for example, 1 to 60J/cm2Preferably 40J/cm2Hereinafter, it is preferable that the smaller the amount of ultraviolet irradiation, the lower the reliability due to destruction of the member constituting the liquid crystal display element, and the shorter the ultraviolet irradiation time, the higher the manufacturing efficiency.
As described above, when ultraviolet rays are irradiated to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, the polymerizable compound reacts to form a polymer, and the polymer memorizes the tilt direction of the liquid crystal molecules, thereby increasing the response speed of the obtained liquid crystal display element. When ultraviolet rays are irradiated to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, photoreactive side chains of at least one polymer selected from a polyimide precursor having a side chain for vertically aligning a liquid crystal and a photoreactive side chain and a polyimide obtained by imidizing the polyimide precursor react with each other, and the photoreactive side chains of the polymer react with the polymerizable compound, so that the response speed of the obtained liquid crystal display element can be increased.
Examples
The present application will be specifically described below with reference to examples, but the present application is not limited to these examples.
Synthesis of amines "
The analytical equipment and analytical conditions used for the synthesis are as follows.
(1Measurement of H-NMR
The device comprises the following steps: varian NMR System 400NB (400MHz) (manufactured by Varian)
And (3) determination of a solvent: CDCl3(deuterated chloroform), DMSO-d6(deuterated dimethyl sulfoxide)
Reference substance: TMS (tetramethylsilane) (δ: 0.0ppm,1H)，CDCl3(δ：77.0ppm，13C)
< synthetic example >
DA-1 was synthesized by the method described below according to the method described in International patent publication WO2011/001928A 1.
Figure GDA0003174005900000221
To a solution (960g) of fluorobenzene (96.1g, 1000mmol) and aluminum chloride (240g, 1800mmol) in dichloroethane was added dropwise butyryl chloride (128g, 1200mmol) under ice-cooling conditions over a period of 2 hours. After stirring overnight at room temperature, the reaction mixture was poured into a large amount of ice water and stirred for 2 hours. Thereafter, the aqueous layer was removed, and the organic phase was further washed 3 times with pure water (1000g), followed by concentration, thereby obtaining M1. (yield: 133g, yield: 80%)
1H-NMR(CDCl3，δppm)：8.01-7.97(m，2H)，7.16-7.11(m，2H)，3.55-3.48(m，1H)，1.23-1.21(m，6H).
Figure GDA0003174005900000231
To a chloroform solution (166g) to which M1(83.1g, 500mmol) was added, bromine (95.9g, 600mmol) was added dropwise at room temperature over 2 hours, and the mixture was stirred overnight. To the resulting reaction solution was added a saturated sodium bicarbonate solution (160g) and stirred for 2 hours. After that, the aqueous layer was removed, and the organic phase was washed 3 times with pure water (160g), concentrated, and subjected to silica gel column chromatography (ethyl acetate: hexane: 1: 10) to obtain M2. (yield: 55.0g, yield: 45%)
1H-NMR(CDCl3，δppm)：8.23-8.18(m，2H)，7.12-7.08(m，2H)， 2.02(s，6H).
Figure GDA0003174005900000232
To a methanol solution (95.0g) to which sodium methoxide (15.7g, 291mmol) was added, M2(15.7g, 194mmol) was added dropwise over 4 hours at 40 ℃ and the mixture was stirred overnight. Thereafter, insoluble matter was removed by filtration, and the filtrate was diluted with ethyl acetate (500g), and then the organic phase was washed with water (200g) 3 times and concentrated to obtain M3. (yield: 17.3g, yield: 45%)
1H-NMR(CDCl3，δppm)：7.42-7.39(m，2H)，7.06-7.02(m，2H)， 3.17(t，3H),1.51(s，3H)，0.97(s，3H).
Figure GDA0003174005900000233
Morpholine (11.5g, 133mmol) was added to M3(17.3g, 88.2mmol), and stirring was carried out overnight at 130 ℃. The obtained reaction solution was diluted with ethyl acetate (115g), and the organic phase was washed 3 times with pure water (115 g). The organic phase was concentrated, and the obtained crude product was purified by silica gel column chromatography to obtain M4.
1H-NMR(CDCl3，δppm)：8.62-8.58(m，2H)，7.08-7.04(m，2H)， 3.67(t，4H),2.55(t，4H)，1.29(s，6H).
Figure GDA0003174005900000241
Piperazine was added to M4 and stirred overnight at 150 ℃. The obtained reaction solution was diluted with chloroform, and the organic phase was washed with pure water 3 times. The organic phase was concentrated to give M5.
1H-NMR(CDCl3，δppm)：8.55-8.51(m，2H)，6.83-6.80(m，2H)， 3.68-3.66(m，4H),3.32-3.29(m，4H)，3.02-2.99(m，4H)，2.56-2.54(m， 4H)，1.29(s，6H).
Figure GDA0003174005900000242
To a solution (450g) of M5(41.6g, 131mmol) and triethylamine (18.6g, 183mmol) in THF was added dropwise dinitrofluorobenzene (29.2g, 157mmol), and the mixture was reacted at room temperature for 18 hours. The solution was poured into pure water (2500g), and the precipitated solid was collected by filtration, followed by recrystallization from acetonitrile (400g) to give M6 (yield: 39.1g, yield: 61%)
1H-NMR(CDCl3，δppm)：8.73(d，1H)，8.57(d，1H)，8.29(dd， 1H)，7.13(d，1H)，6.81(d，2H)，3.69-3.66(m，4H)，3.60-3.57(m， 4H)，3.49-3.46(m，4H)，2.56(t，4H)，1.23(s，6H).
Figure GDA0003174005900000251
A THF solution (100g) to which M6(20.0g, 41.3mmol) and 3% platinum carbon (2.0g) were added was reacted under a hydrogen atmosphere of 0.4MPa at 40 ℃ for 4 hours. The obtained reaction solution was filtered using a membrane filter to remove platinum and carbon. The filtrate was concentrated, THF was removed, and recrystallization was carried out with IPA (200g) to obtain DA-1 (yield: 16.4g, yield: 93%).
1H-NMR(CDCl3，δppm)：8.73(d，1H)，8.57(d，1H)，8.29(dd， 1H)，7.13(d，1H)，6.81(d，2H)，3.69-3.66(m，4H)，3.60-3.57(m， 4H)，3.49-3.46(m，4H)，2.56(t，4H)，1.23(s，6H).
< production of liquid Crystal Aligning agent >
NMP: n-methyl-2-pyrrolidone
BCS: butyl cellosolve
BODA: bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride
CBDA: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
PDA: p-phenylenediamine
3-AMP: 3-pyridylmethylamines
3-AMPDA: 3, 5-diamino-N- (pyridin-3-ylmethyl) benzamide
Figure GDA0003174005900000252
Figure GDA0003174005900000261
[ measurement of molecular weight of polyimide ]
The device comprises the following steps: manufactured by Senshu Kagaku Co., Ltd., Normal temperature Gel Permeation Chromatography (GPC) apparatus (SSC-7200),
Column: shodex column (KD-803, KD-805)
Column temperature: 50 deg.C
Eluent: n, N' -dimethylformamide (as additive, lithium bromide monohydrate (LiBr. H)2O) 30mmol/L, phosphoric acid anhydrous crystal (orthophosphoric acid) 30mmol/L, Tetrahydrofuran (THF) 10ml/L)
Flow rate: 1.0 ml/min
Standard sample for standard curve preparation: TSK standard polyethylene oxide (molecular weight: 9000,000, 150,000, 100,000, 30,000) manufactured by Tosoh corporation, and polyethylene glycol (molecular weight: 12,000, 4,000, 1,000) manufactured by Polymer Laboratories Ltd.
[ measurement of imidization ratio of polyimide ]
20mg of polyimide powder was put into an NMR sample tube (NMR sample tube Standard. phi.5, manufactured by Softgrass scientific Co., Ltd.), and deuterated dimethyl sulfoxide (DMSO-d) was added thereto60.05% TMS mixture) 1.0ml, and ultrasonic waves were applied thereto to completely dissolve the TMS mixture. The solution was subjected to proton NMR measurement at 500MHz using an NMR measuring instrument (JNW-ECA500, Japan Electronics Co., Ltd.). The imidization ratio is determined using a proton derived from a structure which does not change before and after imidization as a reference proton, and is obtained by using the peak integral value of the proton and the peak integral value of a proton derived from an NH group of amic acid appearing in the vicinity of 9.5 to 10.0ppm, according to the following formula. In the following formula, x is a peak integrated value of a proton derived from an NH group of amic acid, y is a peak integrated value of a reference proton, and α is a ratio of the number of protons of the reference proton to 1 NH group of amic acid in the case of polyamic acid (imidization ratio of 0%).
Imidization ratio (%) - (1-. alpha.x/y). times.100
(example 1)
BODA (1.30g, 5.2mmol), 3AMPDA (0.63g, 2.6mmol), DA-1(2.20g, 5.2mmol) and DA-2(1.98g, 5.2mmol) were dissolved in NMP (22.8g), reacted at 60 ℃ for 5 hours, then CBDA (1.50g, 7.7mmol) and NMP (7.6g) were added, and reacted at 40 ℃ for 10 hours to obtain a polyamic acid solution.
NMP was added to the polyamic acid solution (34g) and the mixture was diluted to 6.5 mass%, and then acetic anhydride (5.9g) and pyridine (1.8g) were added as an imidization catalyst to conduct a reaction at 70 ℃ for 3 hours. The reaction solution was poured into methanol (500ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain a polyimide powder (A). The polyimide had an imidization rate of 76%, a number average molecular weight of 13000, and a weight average molecular weight of 48000.
NMP (22.0g) was added to the obtained polyimide powder (A) (3.0g), and the mixture was stirred at 70 ℃ for 20 hours to dissolve the powder. To the solution were added 3.0g of 3AMP (1 mass% NMP solution), NMP (2.0g) and BCS (20.0g), and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (A1).
< production of liquid Crystal cell >
Using the liquid crystal aligning agent (a1) obtained in example 1, a liquid crystal cell was produced in the following procedure. The liquid crystal aligning agent (A1) obtained in example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100. mu. m × 300. mu.m and a line/space of 5 μm was formed, dried on a hot plate at 80 ℃ for 90 seconds, and then fired in a hot-air circulation oven at 200 ℃ for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.
Further, the liquid crystal aligning agent (A1) was spin-coated on the ITO surface on which no electrode pattern was formed, dried on a hot plate at 80 ℃ for 90 seconds, and then baked in a hot air circulating oven at 200 ℃ for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.
For the 2-piece substrate described above, after a bead spacer of 4 μm was spread on the liquid crystal alignment film of one substrate, a sealant (solvent-based thermosetting epoxy resin) was printed thereon. Next, the other substrate was bonded to the substrate with the surface of the other substrate on which the liquid crystal alignment film was formed as the inner side, and then the sealant was cured to prepare an empty cell. The void cell was filled with a polymerizable compound for PSA containing liquid crystal MLC-3023 (trade name manufactured by MERCK Corporation) by a reduced pressure injection method to prepare a liquid crystal cell.
The response speed of the obtained liquid crystal cell was measured by the following method. Then, the liquid crystal cell was irradiated with a DC voltage of 15V from the outside thereof to 6J/cm2UV passing through a band-pass filter with a wavelength of 365 nm. The UV illuminance was measured by using UV-MO3A manufactured by ORC. Thereafter, Toshiba Lighting was used in a state where no voltage was applied in order to deactivate the unreacted polymerizable compound remaining in the liquid crystal cell&UV-FL irradiation apparatus manufactured by Technology Corporation irradiated UV for 30 minutes (UV lamp: FLR40SUV 32/A-1). After that, the response speed was measured again, and the response speeds before and after UV irradiation were compared. In addition, the pretilt angle of the pixel portion was measured for the cell after UV irradiation.
The results are shown in the table.
Method for measuring response speed "
First, in a measuring apparatus comprising a backlight, a pair of polarizing plates in a crossed nicols state, and a light quantity detector in this order, a liquid crystal cell is disposed between the pair of polarizing plates. At this time, the pattern of the ITO electrodes formed with the lines/spaces was angled at 45 ° with respect to the crossed nicols. Then, a rectangular wave of voltage ± 7V and a frequency of 1kHz was applied to the liquid crystal cell, and a change until the luminance observed by the light amount detector was saturated was received with an oscilloscope, and the luminance when no voltage was applied was set to 0%, the value of the luminance saturated by applying a voltage of ± 7V was set to 100%, and the time taken for the luminance to change from 10% to 90% was set as the response speed.
Measurement of Pre-Tilt Angle "
An LCD analyzer LCA-LUV42A manufactured by Meiryo technical Corporation was used.
Comparative example 1
BODA (1.3g, 5.2mmol), 3AMPDA (0.63g, 2.6mmol), PDA (0.56g, 5.2mmol) and DA-2(1.98g, 5.2mmol) were dissolved in NMP (17.9g), and after reaction at 60 ℃ for 5 hours, CBDA (1.48g, 7.5mmol) and NMP (6.g) were added and reacted at 40 ℃ for 10 hours to obtain a polyamic acid solution.
NMP was added to the polyamic acid solution (25g) and the mixture was diluted to 6.5 mass%, and then acetic anhydride (4.64g) and pyridine (1.44g) were added as an imidization catalyst to conduct a reaction at 70 ℃ for 3 hours. The reaction solution was poured into methanol (330ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain a polyimide powder (B). The polyimide had an imidization rate of 71%, a number average molecular weight of 12000 and a weight average molecular weight of 32000.
NMP (22.0g) was added to the obtained polyimide powder (B) (3.0g), and the mixture was stirred at 70 ℃ for 20 hours to dissolve the powder. To the solution were added 3.0g of 3AMP (1 mass% NMP solution), NMP (2.0g) and BCS (20.0g), and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (B1).
The response speed and pretilt angle were measured in the same manner as in example 1 except that the liquid crystal aligning agent (B1) was used as the liquid crystal aligning agent.
TABLE 1
Figure GDA0003174005900000291
From the above results, it was found that the liquid crystal aligning agent (A1) containing DA-1 can impart a tilt angle efficiently even when irradiated with ultraviolet light having a long wavelength of 365 nm. This is considered to be because the polymerizable compound contained in the liquid crystal efficiently reacts based on the radical generated from DA-1. On the other hand, in the liquid crystal aligning agent B1 containing no DA-1, no tilt angle was imparted, and the response speed was hardly improved. This is considered because the ultraviolet rays used for irradiation have a long wavelength, and therefore polymerization of the polymerizable compound hardly proceeds.
(example 2)
Glycidyl Methacrylate (GMA) (7.11g, 50.0mmol) and Methyl Methacrylate (MMA) (5.01g, 50.0mmol) were dissolved in NMP (116.4g), degassed with a diaphragm pump for 5 minutes, then Azobisisobutyronitrile (AIBN) (0.82g, 5.0mmol) was added, and degassed again for 5 minutes. This was then allowed to react at 60 ℃ for 30 hours to give 1: 1 copolymer. Butyl Cellosolve (BCS) (86.2g) was added to the polymer solution to obtain a 6 mass% polymethacrylate solution (C). The polymer had a number average molecular weight of 6800 and a weight average molecular weight of 10800.
DA-1(42.3mg, 0.1mmol) was added to and dissolved in this solution (C) (10.0g), to give a polymethacrylate solution (C1).
"confirmation of the ability to photogenerate base"
The obtained polymethacrylate solution (C1) was spin-coated on the ITO surface of an ITO electrode substrate, and dried on a hot plate at 80 ℃ for 90 seconds to prepare an ITO electrode substrate having a polymethacrylate thin film with a thickness of 100 nm.
The film surface of the substrate was irradiated with light at 3J/cm2Ultraviolet rays having a wavelength of 313nm passed through a band-pass filter of (1)UV), firing was carried out for 5 minutes with a hot plate at 140 ℃. Next, the obtained substrate was immersed in tetrahydrofuran for 30 seconds, and then washed with pure water for 10 seconds, and it was visually checked whether or not the polymethacrylate on the substrate surface was insoluble.
Further, coated substrates not irradiated with UV and not fired, coated substrates irradiated with UV only, and coated substrates fired only were prepared, and whether polymethacrylate was insoluble or not was judged by the same method as described above. The evaluation results are shown in table 2.
Comparative example 2
The same operation as in example 2 was carried out except that DA-1 was not added, and whether or not the polymethacrylate was insoluble was judged.
Comparative example 3
The same operation as in example 2 was carried out except that DA-2(38.1mg, 0.1mmol) was added instead of DA-1, to determine whether or not polymethacrylate was insoluble.
TABLE 2
Figure GDA0003174005900000301
As shown in comparative example 2, it was confirmed that DA-1 or DA-2 was dissolved in THF in any case in comparative example 2. This means that the glycidyl groups in the polymer do not undergo a crosslinking reaction.
In addition, in comparative example 3 and example 2, when only DA-1 or DA-2 was added without UV irradiation, it was confirmed that the polymethacrylate was not insoluble. In this case, it is shown that the isolated electron pair on the nitrogen atom is delocalized by the benzene ring, steric hindrance of the side chain, or the like, and therefore, the nucleating property of the diamine site is weak, and the glycidyl group in the polymer cannot be crosslinked.
On the other hand, in example 2 using DA-1, it was confirmed that the polymethacrylate film was not dissolved by UV irradiation and subsequent firing. This is considered to be because morpholine is generated from DA-1 by UV irradiation, and glycidyl groups contained in polymethacrylate are crosslinked by subsequent heating.
From the results of examples 1 and 2 described above, it was confirmed that DA-1 has the ability to generate radicals and the ability to generate bases by light irradiation.
Industrial applicability
The imide-based polymer using the novel diamine compound of the present application as a raw material can be widely used for a liquid crystal aligning agent, particularly a liquid crystal aligning agent for a PSA-type liquid crystal display element, a photosensitive resin composition, a highly sensitive photocurable material, a resist material, and the like.
The entire contents of the specification, claims, drawings and abstract of japanese patent application 2015-169557, filed on 8/28/2015, are incorporated herein as the contents of the specification of the present application.

Claims (10)

1. A diamine compound represented by the following formula (1),
Figure FDA0003389294340000011
T1、T2each independently is a single bond, G is
Figure FDA0003389294340000012
R1、R2Each independently an alkyl group, benzyl group or alkoxy group having 1 to 10 carbon atoms, Q is a group selected from the group consisting of,
Figure FDA0003389294340000013
r is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3Is a nitrogen atom or an oxygen atom,
ar is phenylene, naphthylene or biphenylene.
2. The diamine compound according to claim 1, wherein the diamine compound represented by the formula (1) is any of diamines,
Figure FDA0003389294340000014
3. an imide-based polymer which is at least 1 selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing the diamine compound according to claim 1 or 2 with a tetracarboxylic dianhydride component, and a polyimide obtained by imidizing the precursor.
4. The imide-based polymer according to claim 3, wherein the diamine component contains a diamine represented by the following formula [2] in addition to the diamine compound represented by the formula (1),
Figure FDA0003389294340000021
x is an integer of 1 to 4 represented by the following formula [ II-1] or formula [ II-2],
Figure FDA0003389294340000022
X1represents a single bond, - (CH)2)a-、-O-、-CH2O-, -COO-or OCO-, wherein a is an integer of 1 to 15, X2Represents a single bond or (CH)2)b-, wherein b is an integer of 1 to 15, X3Represents a single bond, - (CH)2)c-、-O-、-CH2O-, -COO-or OCO-, wherein c is an integer of 1 to 15, X4Represents a 2-valent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom of 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, or X4Optionally with steroidsA 2-valent organic group of an organic group having 17 to 51 carbon atoms in the skeleton, X5Represents a 2-valent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom on 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, n represents an integer of 0 to 4, X represents6Represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms,
-X7-X8 [II-2]
X7represents a single bond, -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or OCO-, X8Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms.
5. A liquid crystal aligning agent comprising the imide-based polymer as claimed in claim 3 or 4.
6. The liquid crystal aligning agent according to claim 5, which comprises a polymerizable compound having a group that is photopolymerized or photocrosslinked.
7. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to claim 5 or 6.
8. A liquid crystal display element comprising the liquid crystal alignment film according to claim 7.
9. The liquid crystal display element according to claim 8, which is a PSA type element.
10. A photosensitive material obtained from the imide-based polymer according to claim 3 or 4.
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