KR101737122B1 - Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same - Google Patents
Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same Download PDFInfo
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- KR101737122B1 KR101737122B1 KR1020107015818A KR20107015818A KR101737122B1 KR 101737122 B1 KR101737122 B1 KR 101737122B1 KR 1020107015818 A KR1020107015818 A KR 1020107015818A KR 20107015818 A KR20107015818 A KR 20107015818A KR 101737122 B1 KR101737122 B1 KR 101737122B1
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
A liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film in which the residual charge accumulated by the direct current voltage is rapidly alleviated even after a long voltage holding ratio and a long time under high temperature are exposed to the liquid crystal alignment treatment agent and a polyamide acid and / (Hereinafter also referred to as a polymer), a diamine compound usable as a raw material of the polyamic acid and polyimide, and a liquid crystal alignment film having the liquid crystal alignment film, which can withstand long-term use in a severe use environment.
A diamine compound represented by the following formula [1].
[Chemical Formula 1]
(In the formula [1], X 1 represents at least one kind selected from the group consisting of -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, -CH 2 O- and -OCO- A divalent organic group, Q 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 2 is a single bond, or a group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group and at least one kind of divalent organic group of selected, X 3 is a single bond, or -O-, -NQ 2 -, -CONQ 2 -, -NQ 2 CO-, -COO-, -OCO-, and -O (CH 2 ) m - (m is an integer of 1 to 5), Q 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 4 is at least one selected from the group consisting of nitrogen Containing aromatic heterocyclic ring, and n is an integer of 1 to 4).
Description
The present invention relates to a diamine compound useful as a raw material for a polymer used in a liquid crystal alignment film, a polyamic acid and a polyimide obtained using the same, and a liquid crystal alignment treatment agent. Further, the present invention relates to a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent.
At present, as a liquid crystal alignment film of a liquid crystal display element, a liquid crystal alignment treatment agent (also referred to as a liquid crystal aligning agent) containing a solution of a polyimide precursor or a soluble polyimide as a main component is applied to a glass substrate or the like, A liquid crystal alignment layer of the system is mainly used.
The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, in order to suppress the lowering of the contrast of the liquid crystal display element and to reduce the afterimage phenomenon with the liquid crystal display element becoming finer (high definition), the liquid crystal alignment film used also has a high voltage holding ratio, The residual charge is small and / or the residual charge accumulated by the direct-current voltage is relieved rapidly.
In the polyimide-based liquid crystal alignment film, the time taken for the after-image generated by the DC voltage to disappear is short, and the liquid crystal alignment containing a tertiary amine having a specific structure is added to the polyamic acid or the imide- (See, for example, Patent Document 1) or a liquid crystal aligning agent containing a soluble polyimide in which a specific diamine having a pyridine skeleton or the like is used as a raw material (see, for example, Patent Document 2) have. In addition, a compound having a high voltage holding ratio and a short time to disappearance of a residual image caused by a direct current voltage and containing one carboxylic acid group in the molecule by being added to a polyamic acid or an imidized polymer thereof, A liquid crystal aligning agent containing a carboxylic acid anhydride group in one molecule and a compound containing a tertiary amine group in the molecule in a very small amount is known (see, for example, Patent Document 3).
However, in recent years, a liquid crystal television with a large screen and a large size has been widely put to practical use. In comparison with a display for mainly displaying characters or still images in a liquid crystal display device for such a purpose, There is a demand for a characteristic that can withstand long-term use in a severe use environment. Therefore, the liquid crystal alignment film to be used needs to have higher reliability than that of the conventional liquid crystal alignment film, and the electrical properties of the liquid crystal alignment film are required not only to have good initial characteristics but also to maintain good properties even after prolonged exposure, for example, have.
An object of the present invention is to provide a liquid crystal alignment film for use in the following liquid crystal display device, a liquid crystal alignment treatment agent for forming the liquid crystal alignment film, a polyamic acid and / or a polyimide (hereinafter also referred to as a polymer) contained in the liquid crystal alignment treatment agent, And a diamine compound usable as a raw material of the polyamic acid and the polyimide.
It is also an object of the present invention to provide a liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film in which the residual charge rapidly accumulated by a direct current voltage is rapidly alleviated even after a long time under a high voltage maintaining ratio and exposed at a high temperature, And an object of the present invention is to provide a highly reliable liquid crystal display element having an orientation film and capable of enduring long-term use in a severe use environment.
The inventor of the present invention has conducted intensive research to achieve the above object, and as a result, found a novel diamine compound that achieves this. The present invention is based on this finding, and has the following points.
(1) A diamine compound represented by the following formula [1].
[Chemical Formula 1]
(In the formula [1], X 1 represents at least one kind selected from the group consisting of -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, -CH 2 O- and -OCO- A divalent organic group, Q 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 2 is a single bond, or a group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group and at least one kind of divalent organic group of selected, X 3 is a single bond, or -O-, -NQ 2 -, -CONQ 2 -, -NQ 2 CO-, -COO-, -OCO-, and -O (CH 2 ) m - (m is an integer of 1 to 5), Q 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 4 is at least one selected from the group consisting of nitrogen Containing aromatic heterocyclic ring, and n is an integer of 1 to 4).
(2) The diamine compound according to the above (1), wherein the diamine compound of the formula [1] is at least one selected from the group consisting of the compounds represented by the following formulas [1a] to [1f].
(2)
(Wherein Q 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X 2 is a single bond or a group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group At least one bivalent organic group and X 3 is a single bond or a group selected from the group consisting of -O-, -NQ 2 -, -CONQ 2 -, -NQ 2 CO-, -COO-, -OCO-, and -O (CH 2 ) m - (m is an integer of 1 to 5), Q 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 4 is a nitrogen-containing aromatic group Lt; / RTI > is a heterocyclic ring and n is an integer from 1 to 4).
3 formula [1a] to formula [1f] in X 2 is a single bond, a diamine compound described in straight-chain alkylene group, or a benzene ring of the above-mentioned (2) of 1 to 3 carbon atoms.
(4) The diamine compound according to (2) or (3), wherein X 3 in formulas [1a] to [1f] is a single bond, -OCO-, or -OCH 2 -.
(5) The diamine compound according to any one of (2) to (4), wherein X 4 in formulas (1a) to (1f) is an imidazole ring, a pyridine ring or a pyrimidine ring.
(6) The diamine compound according to any one of (2) to (5), wherein n in the formulas (1a) to (1f) is an integer of 1 or 2.
(7) The compound according to any one of (1) to (1), wherein X 2 in the formula (1a) to formula (1f) is at least one member selected from the group consisting of a straight chain or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring and a naphthalene ring, 3 is selected from the group consisting of -O-, -CONH-, -NHCO-, -COO-, -OCO-, and -O (CH 2 ) m - (m is an integer of 1 to 5) at least one member and, X 4 is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and benzo-imidazole (1) or (2), wherein n is an integer of 1 or 2. The diamine compound according to the above (1) or (2), wherein at least one member selected from the group consisting of rings,
8 formula [1a] to formula [1f] in X 2 is that at least one member selected from a single bond, the group consisting of straight-chain or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring, X 3 is only coupled At least one group selected from the group consisting of -O-, -CONH-, -NHCO-, -COO-, -OCO- and -O (CH 2 ) m - (m is an integer of 1 to 5) , X 4 is a pyrrole ring, and at least one member selected from the group consisting of an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, n defined in integer (1) or (2) a is 1 or 2 Diamine compound.
9 formula [1a] to formula [1f] in X 2 is a single bond, and at least one member selected from the group consisting of a straight-chain alkylene group, and the benzene ring having 1 to 3, X 3 is only a bond, - OCO-, and -OCH 2 -, X 4 is at least one member selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring, and n is 1 or 2 The diamine compound according to (1) or (2) which is an integer.
(10) A polyamic acid obtained by reacting a diamine component containing a diamine compound described in any one of (1) to (9) above with a tetracarboxylic acid dianhydride, or a polyimide obtained by dehydrating and ring- .
(11) The polyamic acid or polyimide according to (10), wherein the diamine compound represented by the formula (1) is 1 to 80% by mole of the diamine component.
(12) A liquid crystal alignment treatment agent comprising at least one of polyamic acid and polyimide described in (10) or (11) above, and a solvent.
(13) The liquid crystal alignment treating agent according to (12), wherein 5 to 80 mass% of the liquid crystal alignment treatment agent is a poor solvent.
(14) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to (12) or (13) above.
(15) A liquid crystal display element having the liquid crystal alignment film according to (14) above.
The diamine compound of the present invention can be obtained by a comparatively simple method. When the diamine compound is used as a raw material for the polymer constituting the liquid crystal alignment film, the voltage holding ratio is high and even after being exposed for a long time at a high temperature, It is possible to obtain a liquid crystal alignment film in which the residual charge is rapidly relaxed. 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, and can be preferably used for a liquid crystal television having a large screen and a high definition.
Hereinafter, the present invention will be described in detail.
The present invention relates to a polymer obtained by using a diamine compound represented by the formula [1], a diamine compound represented by the formula [1] as a raw material, a liquid crystal alignment treatment agent containing the polymer, a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, A liquid crystal display device having a liquid crystal alignment film.
The diamine compound of the present invention is a diamine compound having a nitrogen-containing aromatic heterocyclic ring in the side chain (hereinafter sometimes referred to as a specific diamine compound). Since this nitrogen-containing aromatic heterocyclic ring functions as an electron hopping site due to its conjugated structure, in the liquid crystal alignment film produced from a liquid crystal alignment treatment agent containing a polymer obtained from a specific diamine compound, the movement of charges in the liquid crystal alignment film is promoted .
From the above, it can be seen that the liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film in which the liquid crystal alignment film has a high voltage holding ratio and can relieve the residual charges rapidly accumulated by the DC voltage even after being exposed at a high temperature for a long time.
≪ Specific diamine compound &
The specific diamine compound of the present invention is a diamine compound represented by the following formula [1].
(3)
In formula [1], X 1 represents at least one kind of 2 selected from the group consisting of -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, -CH 2 O- and -OCO- Wherein Q 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X 2 is selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group And X 3 is a single bond or a single bond or a group selected from the group consisting of -O-, -NQ 2 -, -CONQ 2 -, -NQ 2 CO-, -COO-, -OCO-, and -O ( CH 2 ) m - (m is an integer of 1 to 5), Q 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 4 is a nitrogen-containing Aromatic heterocyclic ring, and n is an integer of 1 to 4.
The bonding position of two amino groups (-NH 2 ) in the formula [1] is not limited. Concretely, when n is an integer of 1 , with respect to the linking group (X 1 ) of the side chain, the position of 2,3, 2,4, 2,5, 2,6, 3 , The position of 4, and the position of 3, 5. When n is an integer of 2, the following positions can be mentioned. Side relative to the coupler (X 1) of the chain, if the position in the benzene ring with two couplers (X 1) of the side chain, two binding positions of the two amino groups in the 3,4 position, the 3,5 position, 3 , 6 position, and 4, 5 position. Further, with respect to the coupler (X 1) of the side chain, a benzene case of the 3-position on the ring with a coupler (X 1) of the side chain, a combination of two amino groups lies in the 2,4, 2,5 position , Positions 4 and 5, positions 4 and 6, respectively. Further, with respect to the coupler (X 1) of the side chain, a benzene case in the 4 position on the ring to which the combiner (X 1) of the side chain, a combination of two amino groups lies in the 2,3, 2,5 position , 2,6 positions, and 3,5 positions. When n is an integer of 3, the following position can be mentioned. With respect to the coupler side (X 1) of the chain, if there is a combiner (X 1) of the side chain in position 2, 3 on the benzene ring, and second coupling position of the two amino groups in the 4,5 position, the 4,6 position . The side with respect to the coupler (X 1) of the chain, if there is a combiner (X 1) of the side chain in position 2,4 on the benzene ring, a combination of the two amino groups are located in the 3,5 position, the 3,6 And positions of 5 and 6, respectively. Further, the side with respect to the coupler (X 1) of the chain, if there is a combiner (X 1) of the side chains in the 3,5 position on the benzene ring, a combination of two amino groups may be located in the position of the 2,4 . When n is an integer of 4, the following position can be mentioned. With respect to the bonding group (X 1 ) of the side chain, when the side chain bonding unit (X 1 ) is present at the 2,3,4 position on the benzene ring, the bonding positions of the two amino groups are 5,6 positions . In addition, the side chain of the coupler with respect to the (X 1), if the position of the 2,4,5 on the benzene ring with a coupler (X 1) of the side chain, the binding position of the two amino groups is the position of the 3,6 . Further, the side chain of the coupler with respect to the (X 1), if the position of the 2, 4, 6 on the benzene ring with a coupler (X 1) of the side chain, the binding position of the two amino groups is the position of the 3,5 . Among them, from the viewpoints of the reactivity in the synthesis of the polyamic acid and the easiness in the synthesis of the diamine compound, when the n is an integer of 1, the bonding positions of the two amino groups are at the positions of 2, , the 5-position, in the case where the 3,5 position, or n is an integer of 2, if the coupler of the position of the on the benzene ring 3 with respect to the coupler (X 1) of the side chain-side chain of the (X 1) is , It is particularly preferable that the bonding position of the two amino groups is 4,6.
In formula [1], X 1 represents at least one kind of 2 selected from the group consisting of -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, -CH 2 O- and -OCO- Is an organic device. Among them, -O-, -NQ 1 -, -CONQ 1 -, and -NQ 1 CO- are preferable. Q 1 has the same meaning as in formula [1].
More specific structures of X 1 include the following formulas [1a] to [1f].
[Chemical Formula 4]
Among them, the formula [1a], the formula [1b], the formula [1c], and the formula [1d] are preferable. Q 1 has the same meaning as in formula [1].
In the formula [1], X 2 is at least one divalent organic group selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. It may also have an unsaturated bond. Preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
Specific examples of the non-aromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctadecane ring, a tricyclohexane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, A tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring and the like.
Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring and a phenalene ring.
Preferred X 2 in the formula [1] include a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, A cyclopentene ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring and an anthracene ring, more preferably a single bond, A benzene ring, a naphthalene ring, a fluorene ring, and an anthracene ring, more preferably a single bond, or a branched or unbranched alkylene group having 1 to 10 carbon atoms, A straight chain or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring and a naphthalene ring, particularly preferably a single bond, A straight chain or branched alkylene group having 1 to 5 carbon atoms, or a benzene ring. Most preferably a single bond, a straight chain alkylene group having 1 to 3 carbon atoms, or a benzene ring.
Formula [1], X 3 is a single bond, or -O-, -NQ 2 -, -CONQ 2 -, -NQ 2 CO -, - COO-, -OCO-, and -O (CH 2) m - (m is an integer of 1 to 5), and preferably at least one divalent organic group selected from the group consisting of a single bond, -O-, -CONQ 2 -, -NQ 2 CO-, -COO- , -OCO-, -O (CH 2 ) m - (m is an integer of 1 to 5). And most preferably a single bond, -OCO-, or -OCH 2 - is. Q 2 has the same meaning as in formula [1].
In formula [1], X 4 is a nitrogen-containing aromatic heterocyclic ring and is a nitrogen-containing aromatic heterocyclic ring containing at least one structure selected from the group consisting of the following formulas [2a], [2b] to be.
[Chemical Formula 5]
In the formula [2c], Y1 is a linear or branched alkyl group having 1 to 5 carbon atoms.
Preferred X 4 in the formula [1] include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, A thiophene ring, a thiophene ring, a thiophene ring, a thiophene ring, a thiadiazole ring, a thiadiazole ring, a thiadiazole ring, a thiadiazole ring, a pyridazine ring, a pyrazoline ring, An imidazole ring, a pyrazole ring, a pyridine ring, an imidazole ring, an imidazole ring, an imidazole ring, an imidazole ring, an imidazole ring, a pyrimidine ring, Pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring More preferred are pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, Particularly preferred are pyrrole rings, imidazole rings, pyrazole rings, pyridine rings and pyrimidine rings. Most preferably, it is an imidazole ring, a pyridine ring, or a pyrimidine ring.
It is preferable that X 3 is bonded to a substituent not adjacent to the formula [2a], the formula [2b] and the formula [2c] contained in X 4 .
In the formula [1], n is an integer of 1 to 4, preferably an integer of 1 to 3 in terms of reactivity with the tetracarboxylic acid dianhydride. Most preferably, n is an integer of 1 or 2.
Preferred combinations of X 1 , X 2 , X 3 , X 4 and n in the formula [1] are those wherein X 1 is -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, -CH 2 O-, and -OCO-, X 2 is a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring At least one member selected from the group consisting of a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, and an anthracene ring and, X 3 is only coupled, -O-, -NQ 2 -, -CONQ 2 -, -NQ 2 CO-, -COO-, -OCO-, and -O (CH 2) m - ( m is from 1 to X 4 is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyridine ring, A thiadiazole ring, a pyrazoline ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a pyrazoline ring, a pyrazoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, A group consisting of a benzimidazole ring, a benzimidazole ring, a thinoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring At least one kind selected, and n is an integer of 1 or 2.
More preferred combinations of X 1 , X 2 , X 3 , X 4 and n in the formula [1] are those wherein X 1 is -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, -CH 2 O-, X 2 is a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, Provided that at least one member selected from the group consisting of a carbon ring, a benzene ring, a naphthalene ring, a fluorene ring, and an anthracene ring, and X 3 is a single bond, -O-, -NQ 2 -, -CONQ 2 - 2 CO-, -COO-, -OCO-, and -O (CH 2) m - and at least one member selected from the group consisting of (m is an integer from 1 to 5), X 4 is a pyrrole ring, an imidazole A pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, Lee, benz imidazole ring, and a benzo are at least one and, integer n is 1 or 2 already selected from the group consisting of the imidazole ring.
More preferred combinations of X 1 , X 2 , X 3 , X 4 and n in the formula [1] are those wherein X 1 is -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, CH 2 O-, and -OCO-, X 2 is selected from the group consisting of a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring and at least one member, X 3 is only coupled, -O-, -CONQ 2 -, -NQ 2 CO-, -COO-, -OCO-, and -O (CH 2) m - ( m is 1 to 5 And X 4 is at least one member selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring , Benzimidazole ring, and benzimidazole ring, and n is an integer of 1 or 2.
Especially preferred combinations of X 1 , X 2 , X 3 , X 4 and n in the formula [1] are those wherein X 1 is -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, -CH 2 O-, X 2 is at least one member selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring, and X 3 In the group consisting of -O-, -CONQ 2 -, -NQ 2 CO-, -COO-, -OCO-, and -O (CH 2 ) m - (m is an integer of 1 to 5) X 4 is at least one member selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring and a pyrimidine ring, and n is an integer of 1 or 2.
The most preferable combination of X 1 , X 2 , X 3 , X 4 and n in the formula [1] is X 1 is -O-, -NQ 1 -, -CONQ 1 -, and -NQ 1 CO- X 2 is a single bond, a straight chain alkylene group having 1 to 3 carbon atoms, and a benzene ring, X 3 is a single bond, -OCO-, And -OCH 2 -, X 4 is at least one member selected from the group consisting of an imidazole ring, a pyridine ring and a pyrimidine ring, and n is an integer of 1 or 2.
Particularly preferable combinations of X 1 , X 2 , X 3 , X 4 and n in the formula [1] are as shown in Tables 1 to 3 below. Q 1 and Q 2 have the same meanings as defined in formula [1].
≪ Synthesis method of specific diamine compound >
The method for producing the specific diamine compound represented by the formula [1] of the present invention is not particularly limited, but preferred methods include the following methods.
[Chemical Formula 6]
The specific diamine compound of the present invention can be obtained by synthesizing a dinitro compound represented by the formula [4], further reducing the nitro group and converting it into an amino group. There is no particular limitation on the method for reducing the dinitro compound. The method for reducing the dinitro compound is usually carried out in the presence of a catalyst such as palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium- Dioxane, and alcohol-based solvents in the presence of hydrogen gas, hydrazine, hydrogen chloride, or the like. X 1 , X 2 , X 3 , X 4 and n in the formula [4] have the same meanings as defined in the formula [1].
Equation [4] D. knitted Roche is via the X 3 and combining the X 2 and X 4 a, then the dinitrophenyl portions, via the method of bonding via the X 1, dinitrophenyl portion, connecting portion X 1 X 2 And then, bonding X < 4 > through X < 3 & gt ;, or the like.
X 1 represents -O- (ether bond), -NQ 1 - (amino bond), -CONQ 1 - (amide bond), -NQ 1 CO- (reverse amide bond), -CH 2 O- (methylene ether bond) , And -OCO- (reverse ester linkage). These linking groups can be formed by a conventional organic synthetic method. Q 1 of each coupler is the same as defined in formula [1].
For example, when X 1 is an ether or a methylene ether bond, the corresponding dinitro group-containing halogen derivative and a hydroxyl group derivative including X 2 , X 3 and X 4 are reacted in the presence of an alkali, Containing hydroxyl group derivative and a halogen-substituted derivative containing X 2 , X 3 and X 4 in the presence of an alkali.
In the case of an amino bond, there can be mentioned a method in which a corresponding dinitro group-containing halogen derivative is reacted with an amino group-substituted derivative containing X 2 , X 3 and X 4 in the presence of an alkali.
In the case of a reverse ester bond, there is a method of reacting the corresponding dinitro group-containing hydroxyl group derivative and an acid chloride compound containing X 2 , X 3 and X 4 in the presence of an alkali.
In the amide bond, there can be mentioned a method in which an amino group substituent containing X 2 , X 3 and X 4 is reacted in the presence of an alkali in the corresponding dinitro group-containing acid chloride body.
In the case of the reverse amide bond, there can be mentioned a method of reacting a corresponding dinitro group-containing amino group substituent with an acid chloride containing X 2 , X 3 and X 4 in the presence of an alkali.
Specific examples of the dinitro group-containing halogen derivative and the dinitro group-containing derivative include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene, 3,5-di Nitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5-dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, 3,5 Dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5 - dinitrophenol, 2,6-dinitrophenol, 2,4-dinitrophenylacetic acid and the like. One or more species may be selected and used in consideration of the availability of raw materials and the reaction surface.
<Polymer>
The polymer of the present invention is a polyamic acid obtained by the reaction of a diamine component containing a specific diamine compound and a tetracarboxylic acid dianhydride and a polyimide obtained by dehydrocondylating the polyamic acid. All of these polyamic acids and polyimides are useful as polymers for obtaining liquid crystal alignment films.
The liquid crystal alignment film obtained by using the polymer of the present invention has a high voltage retaining ratio and a high residual voltage due to the residual charge accumulated by the direct current voltage even after a long period of exposure at a high temperature as the content ratio of the specific diamine compound in the diamine component increases, Is quickly relieved.
For the purpose of enhancing the above characteristics, it is preferable that 1 mol% or more of the diamine component is a specific diamine compound. Further, it is preferable that 5 mol% or more of the diamine component is a specific diamine compound, more preferably 10 mol% or more.
100 mol% of the diamine component may be a specific diamine compound. However, from the viewpoint of uniform application when applying the liquid crystal alignment treatment agent, the specific diamine compound is preferably 80 mol% or less, more preferably 40 mol% or less of the diamine component .
In the present invention, diamines other than specific diamine compounds (hereinafter, also referred to as other diamine compounds) can be used in combination, and other diamine compounds are not particularly limited. Specific examples thereof are given below.
p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'- Phenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'- Phenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'- Diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Tetramethyldiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, Phenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Aminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'- Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'- Diaminobenzophe , 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 2,6-diaminonaphthalene, 2,6-diaminonaphthalene, Bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, ) Butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, (4-aminophenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '- [1,4-phenylenebis (methylene)] dianiline, 4,4' - [ Phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenanthrene 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone] Phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3- (3-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, bis , N, N '- (1,4-phenylene) bis (4-aminobenzamide) (4-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- ) Terephthalamide, N, N'-bis (3-aminophenyl) (4-aminophenyl) anthracene, N, N'-bis (3-aminophenyl) isophthalamide, N, N'- , 4'-bis (4-aminophenoxy) diphenyl sulfone, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'- (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis Bis (3-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, Bis (4-aminophenoxy) propane, 1,3-bis (4-aminophenoxy) Bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6- Aminophenoxy) hexane, 1,6-bis (3-aminophe (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9- 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.
Examples of the diamine side chain include alkyl groups, fluorine-containing alkyl groups, aromatic rings, aliphatic rings, heterocyclic rings, and diamines having a large ring substituent composed of the same. Specific examples thereof include the following formulas [DA1] to [ ] Can be exemplified.
(7)
(Wherein [DA1]) to ([DA5] of, R 1 is an alkyl group or fluorine-containing alkyl group having a carbon number of less than 1 22)
[Chemical Formula 8]
(Wherein [DA6]) to ([DA9] of, R 2 is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, represents a -CO-, or -NH- , And R 3 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)
[Chemical Formula 9]
(Wherein R 4 represents -O-, -OCH 2 -, -CH 2 O-, -COOCH 2 -, or -CH 2 OCO-, and R 5 represents a C 1 or more An alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)
[Chemical formula 10]
(Wherein [DA12]) to ([DA14] of, R 6 is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH 2 -, or -CH 2 -, and R 7 is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms)
(11)
(Wherein [DA15] and formula [DA16] of, R 8 is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH 2 -, -CH 2 -, -O- , or represents -NH-, R 9 is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or Lt; / RTI >
[Chemical Formula 12]
[Chemical Formula 13]
[Chemical Formula 14]
Further, a diaminosiloxane represented by the following formula [DA27] may be mentioned.
[Chemical Formula 15]
(In the formula [DA27], m is an integer of 1 to 10)
The other diamine compounds may be used alone or in combination of two or more thereof depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
The tetracarboxylic acid dianhydride to be reacted with the diamine component in order to obtain the polyamic acid of the present invention is not particularly limited. Specific examples thereof are given below.
Pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid anhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,5,6-anthracene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracar (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid Bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2- Bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis Phenyl silane, 2,3,4,5-pyridine tetracarboxylic acid dianhydride, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid complex Acid dianhydrides, 3,4,9,10-perylenetetracarboxylic acid dianhydrides, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydrides, oxydipthaletracar 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetra Carboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cycloheptanetetracarboxylic acid dianhydride, 2,3 , 4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,4-dicarboxy -1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracar Tetracarboxylic dianhydride, bicyclo [4,4,0] decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo [4,3,0] Tetracarboxylic acid dianhydride, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid dianhydride, tricyclo [6.3.0.0 <2,6>] undecane- 5,9,11-tetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2 , 3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, Methyl-3-cyclohexane 1,2-dicarboxylic acid dianhydride, tetracyclo [6,2,1,1,0,2,7] -naphthalenesulfonic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) Tetradecarboxylic acid dianhydride, 3,5,6-tricarboxy norbornane-2: 3,5: 6 dicarboxylic acid dianhydride, 1,2,4,4- 5-cyclohexanetetracarboxylic acid dianhydride, and the like.
The tetracarboxylic acid dianhydride may be used alone or in combination of two or more, depending on the properties such as liquid crystal alignability, voltage holding characteristics, and accumulated charge when the liquid crystal alignment film is used.
When the polyamic acid of the present invention is obtained by the reaction of the tetracarboxylic acid dianhydride and the diamine component, known synthesis techniques can be used. Generally, the tetracarboxylic acid dianhydride and the diamine component are reacted in an organic solvent. The reaction of the tetracarboxylic acid dianhydride with the diamine is advantageous in that it proceeds comparatively easily in an organic solvent and does not generate any by-products.
The organic solvent used for the reaction of the tetracarboxylic acid dianhydride and the diamine is not particularly limited as long as it dissolves the produced polyamic acid. Specific examples thereof are given below.
N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve, ethyl cellosolve, methyl cellosolve, But are not limited to, sorbose, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate , Propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethyl Diethylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoacetate Methyl ethyl ketone, ethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3- methoxypropionic acid, Butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination. Further, a solvent in which the polyamic acid is not dissolved may be mixed with the solvent in the range where the produced polyamic acid is not precipitated.
In addition, the water content in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyamic acid. Therefore, it is preferable to use an organic solvent that is dehydrated and dried as much as possible.
When the tetracarboxylic acid dianhydride and the diamine component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid dianhydride is dispersed or dissolved in the organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride and a diamine component, and the like. Method may be used. When the tetracarboxylic acid dianhydride or the diamine component is composed of a plurality of compounds, the reaction may be carried out in a preliminarily mixed state, or may be carried out individually or sequentially, and the low molecular weight compounds reacted individually may be mixed and reacted, .
The polymerization temperature at that time can be selected from any of -20 DEG C to 150 DEG C, preferably from -5 DEG C to 100 DEG C. If the concentration is excessively low, it is difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to perform uniform stirring. Therefore, when the concentration of the tetracarboxylic acid The total concentration of the dianhydrides and diamine components in the reaction solution is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. It is possible to carry out the reaction at a high concentration at the beginning of the reaction and then add an organic solvent.
In the polymerization reaction of the polyamic acid, the ratio of the total number of moles of the tetracarboxylic acid dianhydride to the total number of the moles of the diamine component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyamic acid.
The polyimide of the present invention is useful as a polymer for obtaining a liquid crystal alignment film as a polyimide obtained by dehydrocondylating the above polyamic acid.
In the polyimide of the present invention, the dehydration / removal rate (imidization rate) of the amidic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose.
Examples of the method for imidizing a polyamic acid include thermal imidization in which a solution of a polyamic acid is heated as it is, and catalyst imidization in which a catalyst is added to a solution of a polyamic acid.
The temperature at which the polyamic acid is thermally imidized in a solution is preferably 100 ° C to 400 ° C, and more preferably 120 ° C to 250 ° C. It is preferable to carry out the removal while removing the water generated by the imidization reaction out of the system.
The catalyst imidation of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferred because it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Of these, use of acetic anhydride is preferable since the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.
In the case of recovering the resulting polyamic acid or polyimide from the reaction solution of polyamic acid or polyimide, the reaction solution may be put into a poor solvent and precipitated. Examples of the poor solvent used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. In addition, by repeating the operation of re-dissolving the precipitated and recovered polymer in an organic solvent to reprecipitate and recover it 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further increased, which is preferable.
The molecular weights of the polyamides and polyimides contained in the liquid crystal alignment treatment agent of the present invention are determined by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the coating film obtained therefrom, the workability at the time of forming the coating film and the uniformity of the coating film The weight average molecular weight measured is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
≪ Liquid crystal alignment treatment agent &
The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing at least one kind of polymer selected from the above-mentioned polymers of the present invention. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
In the present invention, all of the above resin components may be a copolymer used in the present invention, and other polymers may be mixed in the polymer of the present invention. At that time, the content of the polymer other than the polymer of the present invention in the resin component is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.
Such another polymer may be, for example, a polyamic acid or polyimide obtained by using a diamine compound other than a specific diamine compound as a diamine component to be reacted with a tetracarboxylic acid dianhydride component.
The organic solvent used in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the resin component. Specific examples thereof are given below.
N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N- Dimethyl sulfoxide, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl Isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination.
The liquid crystal alignment treatment agent of the present invention may contain components other than those described above. Examples thereof include a solvent or a compound that improves film thickness uniformity and surface smoothness when the liquid crystal alignment treatment agent is applied, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, and the like.
Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness or the surface smoothness include the following.
Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, 1-hexanol, n-pentane, n-pentane, n-octane, diethyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, Propoxy Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol , A solvent having a low surface tension such as 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, have.
These poor solvents may be used alone or in combination. When such a solvent is used, the amount of the solvent contained in the liquid crystal alignment treatment agent is preferably 5 to 80 mass%, more preferably 20 to 60 mass%. Examples of the compound that improves film thickness uniformity and surface smoothness include fluorinated surfactants, silicone surfactants, and nonionic surfactants.
More specifically, it is possible to use, for example, EF Top EF301, EF303, EF352 (manufactured by TOKEMO PRODUCTS CO., LTD.), Mega Park F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals Inc.), FLORAD FC430 and FC431 SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Kagaku Co., Ltd.), and the like. The proportion of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent.
Specific examples of the compound improving the adhesion between the liquid crystal alignment layer and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.
When a compound for improving adhesion with a substrate is used, its amount to be used is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass based on 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent. If the amount is less than 0.1 part by mass, the adhesion improving effect can not be expected. If the amount is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.
In the liquid crystal alignment treatment agent of the present invention, a liquid crystal alignment treatment agent may be added to the liquid crystal alignment treatment agent in order to change electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effect of the present invention is not impaired. A crosslinkable compound for the purpose of increasing the hardness or density of the film may be added.
<Liquid Crystal Alignment Film / Liquid Crystal Display Device>
The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without rubbing treatment, light irradiation or the like, or without orientation treatment in a vertical alignment application, after coating and baking on a substrate. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. It is also preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed from the viewpoint of simplifying the process. In a reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used only for a single side substrate. In this case, a material for reflecting light such as aluminum can also be used as the electrode in this case.
The method of applying the liquid crystal alignment treatment agent is not particularly limited, but is generally industrially carried out by screen printing, offset printing, flexographic printing, inkjet or the like. As other coating methods, there are dip, roll coater, slit coater, spinner and the like, and they may be used depending on the purpose.
The baking after coating the liquid crystal alignment treatment agent on the substrate can be carried out by a heating means such as a hot plate at 50 to 300 ° C, preferably 80 to 250 ° C, and the solvent can be evaporated to form a coating film. When the thickness of the coating film formed after firing is too large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may be deteriorated. Therefore, the thickness is preferably 5 to 300 nm, 10 to 100 nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like.
In the liquid crystal display element of the present invention, a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention is obtained by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.
For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared. Spacers are dispersed on the liquid crystal alignment film of the substrate of the single chamber to make the liquid crystal alignment film surface inward, and the substrates of the other substrate are bonded A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is sealed by sealing. The thickness of the spacer at this time is preferably 1 to 30 mu m, more preferably 2 to 10 mu m.
As described above, the liquid crystal display device manufactured by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a liquid crystal television having a large screen and a high definition.
Example
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the interpretation of the present invention is not limited to these examples.
[Synthesis of diamine compound]
≪ Example 1 >
Synthesis of diamine compound (4)
[Chemical Formula 16]
A solution of compound (2) (29.92 g, 277 mmol) and triethylamine (28.03 g, 277 mmol) in tetrahydrofuran (300 g) 263 mmol) of tetrahydrofuran (150 g) was added dropwise with caution to exotherm. After completion of dropwise addition, the reaction temperature was raised to 23 DEG C and the reaction was carried out again. After completion of the reaction was confirmed by HPLC (high performance liquid chromatography), the reaction solution was poured into distilled water (2 L). The precipitated solid was filtered and washed with water and then dispersed and washed with ethanol (450 g) (Yield: 72.91 g, yield: 92%).
Then a mixture of compound (3) (72.00 g, 238 mmol), 5% palladium carbon (hydrated, 7.2 g, 10 wt%), and 1,4-dioxane (720 g) Stir at 60 < 0 > C. After completion of the reaction, the catalyst was filtered through a celite, and then the solvent was distilled off by an evaporator to obtain an amorphous product. The resulting amorphous substance was dispersed and washed with ethanol (360 g) to obtain a diamine compound (4) (yield: 43.62 g, yield: 76%).
≪ Example 2 >
Synthesis of diamine compound (7)
[Chemical Formula 17]
A solution of compound (5) (40.00 g, 328 mmol) and triethylamine (33.18 g, 328 mmol) in tetrahydrofuran (400 g) 312 mmol) in tetrahydrofuran (176 g) was added dropwise with caution to exotherm. After completion of dropwise addition, the reaction temperature was raised to 23 DEG C and the reaction was carried out again. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (3.5 L). The precipitated solid was filtered and washed with water and then dispersed and washed with methanol (200 g) to obtain Compound (6) (Yield: 81.4 g, yield: 82%).
Then a mixture of compound (6) (80.00 g, 253 mmol), palladium hydroxide (hydrated, 8.0 g, 10 wt%) and 1,4-dioxane (1200 g) Lt; 0 > C. After completion of the reaction, the catalyst was filtered through a celite, and then the solvent was distilled off by an evaporator to obtain an amorphous product. The resulting crude product was uniformly dissolved in tetrahydrofuran (150 g), and a solution was added dropwise to hexane (660 g) at -20 ° C to precipitate a solid. Thereafter, the diamine compound (7) (yield: 74.98 g, yield: 98%) was obtained by filtration and washing with cold hexane.
≪ Example 3 >
Synthesis of diamine compound (10)
[Chemical Formula 18]
A solution of compound (8) (16.69 g, 137 mmol) and triethylamine (13.82 g, 137 mmol) in tetrahydrofuran (200 g) 130 mmol) in tetrahydrofuran (150 g) was added dropwise with caution to exotherm. After completion of dropwise addition, the reaction temperature was raised to 23 DEG C and the reaction was carried out again. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2.8 L). The precipitated solid was filtered and washed with water and then dispersed and washed with ethanol (200 g) to obtain Compound (9) (Yield: 34.53 g, yield: 84%).
Then a mixture of compound (9) (32.00 g, 101 mmol), 5% palladium carbon (aqueous, 3.2 g, 10 wt%), and 1,4-dioxane (320 g) Stir at 60 < 0 > C. After completion of the reaction, the catalyst was filtered through a celite, and then the solvent was distilled off by an evaporator to obtain an amorphous product. The resulting amorphous substance was dispersively washed with tetrahydrofuran (150 g) to obtain a diamine compound (10) (Yield: 19.21 g, yield: 74%).
<Example 4>
Synthesis of diamine compound (14)
[Chemical Formula 19]
To a solution of compound (11) (29.84 g, 160 mmol) in tetrahydrofuran (240 g) in a solution of compound (12) (35.00 g, 321 mmol) and triethylamine (97.39 g, 962 mmol) Hydrofuran (60 g) was added dropwise. After completion of the dropwise addition, the reaction was followed by HPLC to confirm the completion of the reaction. Dichloromethane (1 L) was added thereto, followed by washing three times with distilled water (600 mL). The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvent was distilled off to obtain an amorphous substance of the compound (13). The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 L) to obtain compound (13) (Yield: 38.74 g, yield: 88%).
(20.00 g, 72.7 mmol), platinum oxide (IV) (2.0 g, 10 wt%), and ethyl acetate / ethanol (200 g, 100/50 (v / v%)) Was stirred at 40 < 0 > C in the presence of hydrogen. After completion of the reaction, the catalyst was filtered off through celite, and then the solvent was distilled off using an evaporator to obtain an amorphous substance of the compound (14). The obtained amorphous substance was purified by silica gel column chromatography (eluent: hexane / ethyl acetate (100/50 v / v%)) to obtain diamine compound (14) (yield: 15.27 g, yield: 98% .
≪ Example 5 >
Synthesis of diamine compound (16)
[Chemical Formula 20]
To a mixed solution of compound (2) (29.98 g, 277 mmol), sodium hydrogencarbonate (29.12 g, 347 mmol) and distilled water (630 g), compound (11) (43.00 g, 231 mmol ) In ethanol (830 g) was added dropwise. After completion of the dropwise addition, completion of the reaction was confirmed by HPLC, and then dichloromethane (2 L) was added to remove the aqueous layer. Thereafter, the organic layer was washed three times with saturated brine (500 ml), the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 L) to obtain compound (15) (Yield: 55.28 g, yield: 87%).
A mixture of 15 (3.0 g, 10.9 mmol), platinum oxide (IV) (0.3 g, 10 wt%) and 1,4-dioxane (30 g) was then added in the presence of hydrogen 0.0 > 23 C. < / RTI > After completion of the reaction, the catalyst was filtered off with celite, and the solvent was distilled off using an evaporator to obtain a diamine compound (16) (yield: 2.30 g, yield: 98%).
≪ Example 6 >
Synthesis of diamine compound (19)
[Chemical Formula 21]
A solution of compound 17 (50.00 g, 170 mmol), potassium carbonate (47.01 g, 340 mmol), copper (I) iodide (6.48 g, 34.0 mmol), N-methylglycine (6.06 g, 68.0 mmol) (2) (36.78 g, 340 mmol) was added dropwise at 40 占 폚 to a mixed solution of dimethyl sulfoxide (DMSO) and dimethyl sulfoxide (1 L) at 40 占 폚. After completion of the dropwise addition, completion of the reaction was confirmed by HPLC, ethyl acetate (4 L) / distilled water (5 L) was added, and insolubles were removed by filtration. Thereafter, the aqueous layer removed by the liquid separation was extracted twice with ethyl acetate (500 g), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off using an evaporator to obtain an amorphous product. The product was recrystallized from ethyl acetate (700 ml) / hexane (2 L) to obtain a compound (18) (yield: 23.04 g, yield: 49% ).
Then a mixture of compound (18) (1.0 g, 3.65 mmol), platinum oxide (IV) (0.1 g, 10 wt%) and methanol (10 g) was stirred in the presence of hydrogen Respectively. After completion of the reaction, the catalyst was filtered off through celite, and the solvent was distilled off using an evaporator to obtain a diamine compound (19) (yield: 0.97 g, yield: 97%).
≪ Example 7 >
Synthesis of diamine compound (23)
[Chemical Formula 22]
A solution of compound (20) (50.00 g, 281 mmol), triethylamine (28.0 mmol) was added to a solution of compound (21) (51.43 g, 281 mmol) in tetrahydrofuran (300 g) 170.5 g, 1.69 mol) and DMAP (4-dimethylaminopyridine) (6.87 g, 56.2 mmol) in tetrahydrofuran (500 g). After completion of dropwise addition, the reaction temperature was raised to 23 캜 and stirred for 1 hour, followed by further heating and refluxing. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (6.4 L), filtered, and washed to obtain an amorphous substance. The obtained non-purified product was recrystallized from tetrahydrofuran (243 g) / hexane (1458 g) to obtain Compound (22) (Yield: 72.58 g, yield: 89%).
Then a mixture of compound (22) (20.00 g, 69.4 mmol), 5% palladium carbon (hydrated, 2.0 g, 10 wt%) and 1,4-dioxane (400 g) 90 C < / RTI > After completion of the reaction, the catalyst was filtered through a celite, and then the solvent was distilled off by an evaporator to obtain an amorphous product. The obtained amorphous substance was dispersed and washed with ethanol (75 g) to obtain a diamine compound (23) (Yield: 10.14 g, yield: 64%).
≪ Example 8 >
Synthesis of diamine compound (26)
(23)
Under a nitrogen atmosphere, a tetrahydrofuran (120 g) solution of compound (21) (20.00 g, 112 mmol) was cooled to 10 ° C or lower and compound 24 (20.57 g, 112 mmol), triethylamine 68.18 g, 674 mmol) and DMAP (2.74 g, 22.5 mmol) in tetrahydrofuran (200 g) was added dropwise with caution to exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 캜 and stirred for 1 hour, and further heating and refluxing was carried out for 17 hours. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (2.6 L), filtered and washed with water to obtain an amorphous substance. The resultant crude product was dispersed and washed with ethanol (40 g), filtered and dried to obtain a compound (25) (yield: 16.45 g, yield: 51%).
Then a mixture of 25 (15.00 g, 52.0 mmol), 5% palladium carbon (55 g, 10 wt%) and 1,4-dioxane (150 g) Stir at 60 < 0 > C. After the completion of the reaction, the catalyst was filtered off through celite, and the solvent was distilled off using an evaporator to obtain an amorphous product of the compound (26). The obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate (100/50 v / v%)) and further recrystallized from tetrahydrofuran (400 g) / hexane (600 g) To obtain the diamine compound (26) (Yield: 6.11 g, yield: 51%).
≪ Example 9 >
Synthesis of diamine compound (29)
≪ EMI ID =
To a solution of compound (27) (10.00 g, 49.0 mmol) and triethylamine (59.50 g, 588 mmol) in tetrahydrofuran (100 g) in a nitrogen atmosphere, compound 12 (21.39 g, 196 m ㏖) was slowly added dropwise. After completion of the reaction, the reaction solution was added to distilled water (1 L), followed by filtration and washing with water to obtain an amorphous substance of Compound (28). The obtained crude product was recrystallized from acetonitrile (200 g) / ethyl acetate (300 g) to obtain compound (28) (Yield: 11.35 g, yield: 61%).
A mixture of compound (28) (8.00 g, 20.1 mmol), platinum oxide (IV) (0.8 g, 10 wt%) and 1,4-dioxane (80 g) , And stirred at 60 ° C. After completion of the reaction, the catalyst was filtered through a celite, and then the solvent was distilled off by an evaporator to obtain an amorphous product. The obtained amorphous substance was recrystallized from tetrahydrofuran (200 g) / hexane (600 g) to obtain a diamine compound (29) (yield: 4.66 g, yield: 72%).
≪ Example 10 >
Synthesis of diamine compound (34)
(25)
A mixture of compound 31 (81.60 g, 74.1 mmol), calcium hydroxide (18.29 g, 24.7 mmol) and DMSO (375 g) was heated to 50 占 폚 and 50.00 g , 24.7 mmol) in DMSO (125 g) was added dropwise. After completion of the dropwise addition, completion of the reaction was confirmed by HPLC, and the reaction solution was poured into 5 mass% hydrochloric acid ice water (4 L). The solid was filtered and washed with water to obtain a wetting material of the compound (32). Thereafter, recrystallization was performed with 2-propanol (205 g) / hexane (335 g) to obtain a compound (32) (Yield: 49.0 g, yield: 72%).
Then, a solution of compound (21) (19.34 g, 109 mmol) in tetrahydrofuran (180 g) was cooled to 10 占 폚 or lower and a solution of compound (31) (30.0 g, 109 mmol) Amine (33.0 g, 324 mmol) and DMAP (2.65 g, 21.7 mmol) in DMSO (300 g) was added dropwise with caution to exotherm. After completion of dropwise addition, the reaction temperature was raised to 23 DEG C and the mixture was stirred for 1 hour, followed by further heating and refluxing for 19 hours. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (3.9 L), filtered, washed with water, and washed with methanol to obtain an amorphous substance. The obtained amorphous substance was dissolved in chloroform, and the insoluble matter was filtered. Thereafter, the filtrate was concentrated and purified by silica gel column chromatography (eluent: 1,2-dichloroethane / ethyl acetate (100/40 v / v%)) to obtain compound (33) : 35.8 g, yield: 86%).
Subsequently, a solution of compound (33) (30.00 g, 78.7 mmol) and iron (26.36 g, 472 mmol) in toluene (170 g) was heated to 70 ° C and then ammonium chloride (12.63 g, 236 mmol) in 10 mass% aqueous solution was added dropwise. After completion of the reaction, the solid was filtered with Celite. Thereafter, the aqueous layer was removed from the filtrate, and then the organic layer was concentrated by using an evaporator to obtain an amorphous substance. Next, the obtained amorphous substance was dissolved in ethyl acetate (1 L) and washed with distilled water (500 mL) three times. The organic layer was dried over anhydrous magnesium sulfate and then the solvent was distilled off. The obtained amorphous substance of Compound (34) was recrystallized from methanol (100 g) / 2-propanol (100 g) to obtain a diamine compound (Yield: 15.4 g, yield: 61%).
≪ Example 11 >
Synthesis of diamine compound (37)
(26)
Under nitrogen atmosphere, a solution of 340 g of compound (32) (17.00 g, 61.6 mmol), compound 35 (6.57 mL, 67.7 mmol), and triphenylphosphine (20.99 g, 80.0 mmol) in tetrahydrofuran ) Solution was cooled in an ice bath, and a solution of DEAD (diazodicarboxylate diethyl) (40 mass% toluene solution, 34.84 ml, 80.0 mmol) was slowly added dropwise. After completion of the dropwise addition, the reaction temperature was gradually raised to 23 deg. After completion of the reaction was confirmed by HPLC, the solvent was distilled off by an evaporator to obtain an amorphous substance. Thereafter, recrystallization was performed twice with 2-propanol (450 g) to obtain a compound (36) (Yield: 17.77 g, yield: 79%).
Subsequently, a mixture of compound (36) (15.00 g, 40.8 mmol), platinum oxide (IV) (1.5 g, 10 wt%) and 1,4-dioxane (230 g) Was stirred at 23 < 0 > C in the presence of hydrogen. After completion of the reaction, the catalyst was filtered through a celite, and then the solvent was distilled off by an evaporator to obtain an amorphous product. The resulting amorphous substance was recrystallized from 2-propanol (60 g) to obtain a diamine compound (37) (yield: 9.66 g, yield: 77%).
≪ Synthesis Example 1 &
Synthesis of diamine compound (40)
(27)
A solution of 230 mg of compound (38) (23.45 g, 190 mmol) and triethylamine (19.23 g, 277 mmol) in tetrahydrofuran (230 g) 180 mmol) in tetrahydrofuran (110 g) was added dropwise with caution to exotherm. After completion of dropwise addition, the reaction temperature was raised to 23 DEG C and the reaction was carried out again. After completion of the reaction was confirmed by HPLC (high performance liquid chromatography), the reaction solution was poured into distilled water (1.5 L), and the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (380 g) to obtain a compound (39) (Yield: 50.82 g, yield: 89%).
Then a mixture of 39 (48.00 g, 151 mmol), 5% palladium carbon (water, 4.8 g, 10 wt%), and 1,4-dioxane (490 g) Stir at 60 < 0 > C. After completion of the reaction, the catalyst was filtered through a celite, and then the solvent was distilled off by an evaporator to obtain an amorphous product. The resultant amorphous substance was dispersively washed with ethanol (300 g) to obtain a diamine compound (40) (Yield: 27.20 g, yield: 70%).
≪ Synthesis Example 2 &
Synthesis of diamine compound (43)
(28)
A solution of compound (41) (15.22 g, 142 mmol) and triethylamine (15.09 g, 149 mmol) in tetrahydrofuran (150 g) 135 mmol) in tetrahydrofuran (50 g) was added dropwise with caution to exotherm. After completion of dropwise addition, the reaction temperature was raised to 23 DEG C and the reaction was carried out again. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (1 L), and the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (300 g) to obtain Compound (42) (Yield: 36.92 g, yield: 90%).
Then a mixture of 42 (36.00 g, 119 mmol), 5% palladium carbon (water, 3.6 g, 10 wt%) and 1,4-dioxane (300 g) Stir at 60 < 0 > C. After completion of the reaction, the catalyst was filtered through a celite, and then the solvent was distilled off by an evaporator to obtain an amorphous product. The resulting amorphous substance was recrystallized from methanol (200 g) to obtain a diamine compound (43) (yield: 21.5 g, yield: 72%).
[Synthesis of polyamic acid and polyimide]
The following abbreviations are used for tetracarboxylic acid dianhydrides and the like.
(Tetracarboxylic acid dianhydride)
CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride
BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride
[Chemical Formula 29]
(Diamine)
p-PDA: p-phenylenediamine
AP18: 1,3-diamino (4-n-octadecanoyl) benzene
PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene
(30)
(Organic solvent)
NMP: N-methyl-2-pyrrolidone
BCS: butyl cellosolve
≪ Measurement of molecular weight of polyimide &
The molecular weight of the polyimide in the synthesis example was measured using a room temperature gel permeation chromatography (GPC-101) manufactured by Showa Denko K.K. and a column (KD-803, KD-805) Respectively.
Column temperature: 50 ° C
Eluent: N, N'- dimethylformamide (lithium bromide as an additive-hydrate (LiBr · H 2 O) is 30 m㏖ / ℓ, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, tetrahydrofuran (THF) of 10 ml / l)
Flow rate: 1.0 ml / min
Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (molecular weight: approximately 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.
≪ Measurement of imidization rate &
The imidization rate of the polyimide in the synthesis example was measured as follows.
20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Scientific Co., Ltd.), 0.53 ml of deuterated dimethylsulfoxide (DMSO-d6, 0.05% TMS mixture) was added and ultrasonic waves were completely dissolved . This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring device (JNW-ECA500) manufactured by Nippon Denshi Co., Ltd. A proton originating from a structure in which imidization does not change before and after imidization is determined as a reference proton and the peak value of the proton is compared with the proton peak derived from the NH group of the amide acid appearing in the vicinity of 9.5 to 10.0 ppm And was obtained by the following formula using the integrated value.
Imidization ratio (%) = (1 -? X / y) x 100
Wherein x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH group of the amide acid when the polyamide acid (imidization rate is 0%) The ratio of the number of reference protons to one proton.
≪ Example 12 >
(0.64 g, 2.66 mmol) was added to NMP (15.0 g, 8.66 mmol), BHO (3.33 g, 13.3 mmol), p-PDA (0.67 g, 6.21 mmol), PCH7DAB and reacted at 40 DEG C for 6 hours to obtain a resin composition in which the content of the resin component was 24 mass% To obtain a polyamic acid solution (A). The polyamic acid had a number average molecular weight of 17,900 and a weight average molecular weight of 51,800.
≪ Example 13 >
NMP was added to the polyamic acid solution (A) (20.0 g) obtained in Example 12 to dilute it to 6 mass%, acetic anhydride (2.63 g) and pyridine (2.03 g) Lt; 0 > C for 2 hours. The reaction solution was poured into methanol (250 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (B). The imidization rate of the polyimide was 40%, the number average molecular weight was 16,400, and the weight average molecular weight was 44,800.
≪ Example 14 >
(0.64 g, 2.63 mmol) was reacted with NMP (8.10 g, 1.43 mmol), BODA (2.33 g, 9.33 mmol), p-PDA (0.94 g, 8.71 mmol), AP18 g) and reacted at 80 ° C for 5 hours. Then, CBDA (0.61 g, 3.11 mmol) and NMP (6.51 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.
NMP was added to the resultant polyamic acid solution (10.0 g) to dilute it to 6 mass%, acetic anhydride (1.33 g) and pyridine (1.04 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (120 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (C). The imidization ratio of the polyimide was 41%, the number average molecular weight was 17,500, and the weight average molecular weight was 46,400.
≪ Example 15 >
(0.67 g, 2.60 mmol) was reacted with NMP (14.7 g, 8.7 mmol), BHO 3 (3.25 g, 13.0 mmol), p-PDA (0.66 g, 6.07 mmol), PCH7DAB (0.85 g, 4.33 mmol) and NMP (12.0 g) were added and reacted at 40 占 폚 for 6 hours to obtain a resin composition having a content of 25 mass% A polyamic acid solution (D) was obtained. The polyamic acid had a number average molecular weight of 18,800 and a weight average molecular weight of 51,800
≪ Example 16 >
NMP was added to the polyamic acid solution (D) (20.0 g) obtained in Example 15 to dilute it to 6 mass%, acetic anhydride (2.61 g) and pyridine (2.07 g) Lt; 0 > C for 2 hours. The reaction solution was poured into methanol (220 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (E). The imidization ratio of the polyimide was 42%, the number average molecular weight was 17,400, and the weight average molecular weight was 45,800.
≪ Example 17 >
(0.32 g, 2.96 mmol) was added to a solution of NMP (8.10 g, 5.96 mmol), BHOAc (2.22 g, 8.87 mmol), p-PDA (0.58 g, 5.32 mmol), PCH7DAB (1.35 g, 3.55 mmol) g) and reacted at 80 ° C for 5 hours. Then, CBDA (0.58 g, 2.96 mmol) and NMP (6.30 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.
NMP was added to the resulting polyamic acid solution (10.1 g) to dilute to 6 mass%, acetic anhydride (1.34 g) and pyridine (1.04 g) were added as an imidization catalyst and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (140 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (F). The imidization ratio of the polyimide was 41%, the number average molecular weight was 18,100, and the weight average molecular weight was 47,300.
≪ Example 18 >
(0.69 g, 3.49 mmol) was dissolved in NMP (10.0 mmol), BODA (2.18 g, 8.72 mmol), p-PDA (0.69 g, 6.39 mmol), AP18 (0.66 g, 1.74 mmol) g) and reacted at 80 ° C for 5 hours. Then, CBDA (0.57 g, 2.91 mmol) and NMP (8.30 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.
To the resulting polyamic acid solution (10.1 g) was added NMP and diluted to 6 mass%. Acetic anhydride (1.35 g) and pyridine (1.07 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (140 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (G). The imidization rate of the polyimide was 40%, the number average molecular weight was 17,500, and the weight average molecular weight was 46,000.
≪ Example 19 >
(0.39 g, 1.84 mmol) was dissolved in NMP (10.5 mL), and the mixture was stirred at -78 [deg.] C. for 30 minutes. BODA (2.30 g, 9.18 mmol), p-PDA (0.46 g, 4.28 mmol), PCH7DAB g) and reacted at 80 ° C for 5 hours. Then, CBDA (0.57 g, 2.91 mmol) and NMP (8.00 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.
NMP was added to the resultant polyamic acid solution (10.0 g) to dilute to 6 mass%, acetic anhydride (1.31 g) and pyridine (1.04 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (140 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (H). The imidization ratio of the polyimide was 40%, the number average molecular weight was 18,900, and the weight average molecular weight was 49,100.
≪ Example 20 >
(0.43 g, 1.87 mmol) was dissolved in NMP (10.50 mL) at -78 [deg.] C with BODA (2.33 g, 9.33 mmol), p-PDA (0.47 g, 4.35 mmol), PCH7DAB (2.37 g, 6.22 mmol), and diamine compound g) and reacted at 80 ° C for 5 hours. Then, CBDA (0.61 g, 3.11 mmol) and NMP (8.10 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.
NMP was added to the resultant polyamic acid solution (10.2 g) to dilute to 6 mass%, acetic anhydride (1.37 g) and pyridine (1.04 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (150 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (I). The imidization ratio of the polyimide was 42%, the number average molecular weight was 19,900, and the weight average molecular weight was 52,100.
≪ Example 21 >
(0.96 g, 4.21 mmol) was reacted with NMP (8.10 g, 1.20 mmol), BODA (2.26 g, 9.03 mmol), p-PDA (0.72 g, 6.62 mmol), AP18 g) and reacted at 80 ° C for 5 hours. Then, CBDA (0.59 g, 3.01 mmol) and NMP (6.10 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.
NMP was added to the resultant polyamic acid solution (10.0 g) to dilute to 6 mass%, acetic anhydride (1.34 g) and pyridine (1.04 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (150 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (J). The imidization ratio of the polyimide was 40%, the number average molecular weight was 17,900, and the weight average molecular weight was 45,800.
≪ Example 22 >
(0.38 g, 1.18 mmol) was reacted with NMP (7.00 g, 1.18 mmol), BODA (2.22 g, 8.87 mmol), p-PDA (1.02 g, 9.46 mmol), AP18 (0.58 g, 2.96 mmol) and NMP (6.50 g) were added and reacted at 40 DEG C for 6 hours to obtain a resin composition having a resin content of 26 mass% To obtain a polyamic acid solution (K). The polyamic acid had a number average molecular weight of 17,500 and a weight average molecular weight of 45,100.
≪ Example 23 >
PCH7DAB (3.30 g, 8.67 mmol), and diamine compound 34 (1.11 g, 3.47 mmol) were dissolved in NMP (15.0 mmol), BODA (3.25 g, 13.0 mmol), p-PDA (0.56 g, 5.20 mmol) g) and reacted at 80 ° C for 5 hours. Then, CBDA (0.85 g, 4.33 mmol) and NMP (12.5 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.
NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (2.65 g) and pyridine (2.07 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (310 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (L). The imidization ratio of the polyimide was 40%, the number average molecular weight was 20,100, and the weight average molecular weight was 53,400.
≪ Example 24 >
PCH7DAB (3.30 g, 8.67 mmol) and diamine compound 37 (0.80 g, 2.60 mmol) were dissolved in NMP (14.8 g, (0.85 g, 4.33 mmol) and NMP (12.0 g) were added and reacted at 40 占 폚 for 6 hours to obtain a resin composition having a content of 25 mass% To obtain a polyamic acid solution (M). This polyamic acid had a number average molecular weight of 19,400 and a weight average molecular weight of 52,800.
≪ Example 25 >
NMP was added to the polyamic acid solution (M) (20.2 g) obtained in Example 24 to dilute it to 6 mass%, acetic anhydride (2.68 g) and pyridine (2.07 g) Lt; 0 > C for 2 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (N). The imidization ratio of the polyimide was 41%, the number average molecular weight was 18,100, and the weight average molecular weight was 48,100.
≪ Synthesis Example 3 &
PCH7DAB (3.34 g, 8.77 mmol), and diamine compound (40) (0.68 g, 2.63 mmol) were dissolved in NMP (15.0 mmol), BODA (3.29 g, 13.2 mmol), p-PDA (0.67 g, 6.14 mmol) (0.86 g, 4.39 mmol) and NMP (11.5 g) were added and reacted at 40 占 폚 for 6 hours to obtain a resin composition having a resin content of 25 mass% To obtain a polyamic acid solution (O). This polyamic acid had a number average molecular weight of 22,600 and a weight average molecular weight of 54,900.
≪ Synthesis Example 4 &
NMP was added to the polyamic acid solution (O) (20.0 g) obtained in Synthesis Example 3 to dilute it to 6 mass%, acetic anhydride (2.65 g) and pyridine (2.08 g) Lt; 0 > C for 2 hours. The reaction solution was poured into methanol (320 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (P). The imidization ratio of the polyimide was 40%, the number average molecular weight was 18,900, and the weight average molecular weight was 49,200.
≪ Synthesis Example 5 &
(0.62 g, 2.57 mmol) and NMP (15.2 mmol) of BODA (3.22 g, 12.9 mmol), p-PDA (0.65 g, 6.00 mmol), PCH7DAB (3.26 g, 8.57 mmol) and reacted at 40 DEG C for 6 hours to obtain a resin composition having a resin content of 25 mass% (hereinafter referred to as " curing agent ") and reacted at 80 DEG C for 5 hours. Then, CBDA (0.84 g, 4.28 mmol) and NMP To obtain a polyamic acid solution (Q). The polyamic acid had a number average molecular weight of 22,100 and a weight average molecular weight of 53,200.
≪ Synthesis Example 6 &
NMP was added to the polyamide acid solution (Q) (20.1 g) obtained in Synthetic Example 5 to dilute it to 6 mass%, then acetic anhydride (2.68 g) and pyridine (2.04 g) Lt; 0 > C for 2 hours. The reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (R). The imidization ratio of the polyimide was 41%, the number average molecular weight was 18,400, and the weight average molecular weight was 49,100.
[Preparation and evaluation of liquid crystal alignment treatment agent]
≪ Example 26 >
NMP (10.2 g) and BCS (20.0 g) were added to a polyamic acid solution [A] (10.0 g) having a resin component content of 24% by mass obtained in Example 12 and stirred at 25 캜 for 2 hours, To obtain a treating agent [1]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
[Production of liquid crystal cell]
The liquid crystal alignment treatment agent [1] obtained above was spin-coated on the ITO surface of a 3 cm × 4 cm (length × width) ITO electrode-formed substrate and fired at 80 ° C. for 5 minutes in a hot air circulating oven at 210 ° C. for 1 hour A polyimide coating film having a thickness of 100 nm was produced.
The liquid crystal alignment film formation substrate was rubbed under the conditions of a roll diameter of 120 mm, a rubbing apparatus of rayon cloth, a rotation speed of 300 rpm, a roll advancing speed of 20 mm / sec, and an insertion amount of 0.3 mm.
Two liquid crystal alignment film formation substrates were prepared, and 6 mu m of bead spacers were dispersed on the liquid crystal alignment film surface of one liquid crystal alignment film, and then a sealant was printed thereon. One other substrate was cured by aligning the liquid crystal orientation film face inward and the rubbing direction in the reverse direction, and then the sealant was cured to prepare an empty cell. A liquid crystal MLC-6608 (manufactured by Merck & Jacquard) was injected into this vacant cell by a reduced pressure injection method to obtain a nematic liquid crystal cell of an anti-parallel orientation.
[Evaluation of voltage holding ratio]
A voltage of 4 V was applied to the liquid crystal cell obtained above at a temperature of 80 占 폚 for 60 占 퐏 and the voltage after 16.67 ms and after 1667 ms was measured and the voltage holding rate was calculated as the voltage holding ratio. The results are shown in Table 7 below.
[Evaluation of residual charge relaxation]
After applying the DC voltage 10 V for 30 minutes to the liquid crystal cell after the measurement of the voltage holding ratio and short-circuiting for 1 second, the potential generated in the liquid crystal cell was measured for 1800 seconds. Then, residual charges after 50 seconds and after 1000 seconds were measured. For the measurement, a 6254-type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica Co., Ltd. is used. The results are shown in Table 8 below.
[Evaluation after leaving at high temperature]
The liquid crystal cell after the residual charge measurement was left in a high-temperature bath set at 100 占 폚 for 7 days, and then the voltage holding ratio and residual charge were measured. The results are shown in Tables 7 and 8 below.
≪ Example 27 >
NMP (36.3 g) was added to the polyimide powder [B] (5.1 g) obtained in Example 13 and dissolved by stirring at 70 ° C for 40 hours. NMP (18.1 g) and BCS (25.6 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treating agent [2]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [2], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 28 >
NMP (32.8 g) was added to the polyimide powder [C] (5.0 g) obtained in Example 14 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (16.4 g) and BCS (29.2 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treating agent [3]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [3], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were performed. The results are shown in Tables 7 and 8 below.
≪ Example 29 >
NMP (8.9 g) and BCS (23.6 g) were added to a polyamic acid solution [D] (10.5 g) having a resin component content of 25% by mass obtained in Example 15 and stirred at 25 캜 for 2 hours, To obtain an orientation treatment agent [4]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [4], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 30 >
NMP (34.1 g) was added to the polyimide powder [E] (5.2 g) obtained in Example 16 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (17.1 g) and BCS (30.4 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [5]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [5], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 31 >
NMP (35.6 g) was added to the polyimide powder [F] (5.0 g) obtained in Example 17 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (17.8 g) and BCS (25.1 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [6]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [6], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 32 >
NMP (30.1 g) was added to the polyimide powder [G] (5.0 g) obtained in Example 18 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (15.2 g) and BCS (33.2 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [7]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [7], a liquid crystal cell was prepared in the same manner as in Example 26, evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 33 >
NMP (42.2 g) was added to the polyimide powder [H] (5.5 g) obtained in Example 19 and dissolved by stirring at 70 ° C for 40 hours. NMP (20.8 g) and BCS (22.9 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [8]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [8], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 34 >
NMP (30.3 g) was added to the polyimide powder [I] (5.0 g) obtained in Example 20 and dissolved by stirring at 70 ° C for 40 hours. NMP (14.8 g) and BCS (33.8 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [9]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [9], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 35 >
NMP (33.0 g) was added to the polyimide powder [J] (5.1 g) obtained in Example 21 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (17.1 g) and BCS (29.8 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [10]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [10], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 36 >
NMP (15.6 g) and BCS (17.1 g) were added to a polyamic acid solution [K] (10.0 g) having a resin component content of 26% by mass obtained in Example 22 and stirred at 25 캜 for 2 hours, To obtain an orientation treatment agent [11]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [11], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 37 >
NMP (34.5 g) was added to the polyimide powder [L] (5.2 g) obtained in Example 23 and dissolved by stirring at 70 ° C for 40 hours. NMP (16.5 g) and BCS (30.3 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [12]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [12], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 38 >
NMP (9.5 g) and BCS (17.3 g) were added to a polyamic acid solution [M] (8.5 g) having a resin component content of 25% by mass obtained in Example 24 and stirred at 25 캜 for 2 hours, To obtain an orientation treatment agent [13]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [13], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Example 39 >
NMP (35.5 g) was added to the polyimide powder [N] (5.0 g) obtained in Example 25 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (17.8 g) and BCS (25.1 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [14]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [14], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Comparative Example 1 &
NMP (17.5 g) and BCS (15.3 g) were added to a polyamic acid solution [O] (10.4 g) having a resin component content of 25% by mass obtained in Synthesis Example 3 and stirred at 25 占 폚 for 2 hours, To obtain an orientation treatment agent [15]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [15], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Comparative Example 2 &
NMP (34.5 g) was added to the polyimide powder [P] (4.5 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 캜 for 40 hours. NMP (17.2 g) and BCS (18.8 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [16]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [16], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Comparative Example 3 &
NMP (18.8 g) and BCS (12.2 g) were added to a polyamic acid solution [Q] (10.0 g) having a resin component content of 25% by mass obtained in Synthesis Example 5 and stirred at 25 占 폚 for 2 hours, To obtain an orientation treatment agent [17]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [17], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
≪ Comparative Example 4 &
NMP (38.6 g) was added to the polyimide powder [R] (4.7 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (19.4 g) and BCS (15.8 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent [18]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [18], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of the voltage holding ratio, evaluation of residual charge relaxation, and evaluation at high temperature were carried out. The results are shown in Tables 7 and 8 below.
The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film in which the voltage holding ratio is high when the liquid crystal alignment film is used and the charge accumulated by the DC voltage is quickly alleviated even after a long time exposure at a high temperature. It is possible to provide a highly reliable liquid crystal display element capable of enduring long-term use in a severe use environment. As a result, it is useful for TN devices, STN devices, TFT liquid crystal devices, and liquid crystal display devices of vertical alignment type and horizontal alignment type (IPS). The entire contents of the specification, claims, and summary of Japanese Patent Application No. 2008-014965 filed on January 25, 2008 are hereby incorporated herein by reference as the disclosure of the specification of the present invention.
Claims (15)
[Chemical Formula 1]
(Wherein X 1 represents at least one divalent organic group selected from the group consisting of -O-, -NQ 1 -, -CONQ 1 -, -NQ 1 CO-, -CH 2 O-, and -OCO- And Q 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X 2 is a single bond or an alkylene group having at least 1 carbon atom selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group the two kinds of the organic group X 3 is a single bond, or -O-, -NQ 2 -, -CONQ 2 -, -NQ 2 CO-, -COO-, -OCO-, and -O (CH 2) m - (m is an integer of 1 to 5), Q 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 4 is a pyridine ring, or a pyridine ring And X 3 is bonded to a carbon atom not adjacent to the nitrogen atom in the pyridine ring or the pyrimidine ring, and n is an integer of 1 to 4) .
Formula (1) in X 2 is a single bond, C 1 -C 3 straight-chain alkylene group, or a benzene ring of the liquid crystal alignment treating agent of.
X 3 in the formula [1] is a single bond, -OCO-, or -OCH 2 -.
Wherein n in the formula [1] is an integer of 1 or 2.
X 1 in the formula [1] is at least 1 selected from the group consisting of -O-, -NH-, -CONH-, -NHCO-, -CON (CH 3 ) -, -CH 2 O- and -OCO- X 2 is at least one member selected from the group consisting of a straight chain or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring and a naphthalene ring, X 3 is a single bond, -O-, At least one group selected from the group consisting of CONH-, -NHCO-, -COO-, -OCO- and -O (CH 2 ) m - (m is an integer of 1 to 5), X 4 is a pyridine ring , Or a pyrimidine ring, and n is an integer of 1 or 2.
Formula (1) of X 1 is -O-, -NH-, -CONH-, -NHCO-, -CON (CH 3) -, and and at least one member selected from the group consisting of -CH 2 O-, X 2 is a single bond, and at least one member selected from the group consisting of straight-chain or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring, X 3 is only a bond, -O-, -CONH-, -NHCO-, - COO-, -OCO-, and -O (CH 2) m - and at least one member selected from the group consisting of (m is an integer from 1 to 5), wherein X 4 is a pyridine ring, or a pyrimidine ring, n Wherein the liquid crystal alignment treatment agent is an integer of 1 or 2.
Formula (1) of X 1 is -O-, -NH-, -CONH-, -NHCO-, and -CON (CH 3) - and at least one member selected from the group consisting of, X 2 is a single bond, carbon atoms straight-chain alkylene group of 1 to 3, and said at least one member selected from the group consisting of benzene ring, X 3 is only coupled, -OCO-, and -OCH 2 - and at least one member selected from the group consisting of, X A tetravalent pyridine ring, or a pyrimidine ring, and n is an integer of 1 or 2.
The diamine compound represented by the formula [1] is contained in an amount of 1 to 80 mol% of the diamine component.
And 5 to 80 mass% of the solvent contained in the liquid crystal alignment treatment agent is a poor solvent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008014965 | 2008-01-25 | ||
| JPJP-P-2008-014965 | 2008-01-25 | ||
| PCT/JP2009/051107 WO2009093704A1 (en) | 2008-01-25 | 2009-01-23 | Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020177001198A Division KR101738330B1 (en) | 2008-01-25 | 2009-01-23 | Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same |
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| KR20100103606A KR20100103606A (en) | 2010-09-27 |
| KR101737122B1 true KR101737122B1 (en) | 2017-05-17 |
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| KR1020177001198A KR101738330B1 (en) | 2008-01-25 | 2009-01-23 | Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same |
| KR1020107015818A KR101737122B1 (en) | 2008-01-25 | 2009-01-23 | Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same |
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| KR1020177001198A KR101738330B1 (en) | 2008-01-25 | 2009-01-23 | Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same |
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| Country | Link |
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| JP (1) | JP5663876B2 (en) |
| KR (2) | KR101738330B1 (en) |
| CN (1) | CN101925634B (en) |
| TW (1) | TWI490207B (en) |
| WO (1) | WO2009093704A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011010619A1 (en) * | 2009-07-21 | 2011-01-27 | 日産化学工業株式会社 | Diamine compound, polyamic acid, polyimide, and liquid crystal aligning agent |
| CN102858850B (en) * | 2010-02-26 | 2014-12-10 | 日产化学工业株式会社 | Diamine compound, liquid crystal aligning agent and liquid crystal display element |
| JP5998931B2 (en) * | 2010-06-10 | 2016-09-28 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| JP5643985B2 (en) * | 2010-08-19 | 2014-12-24 | Jnc株式会社 | Diamine, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
| CN102346338A (en) * | 2011-10-20 | 2012-02-08 | 深圳市华星光电技术有限公司 | Liquid crystal panel and alignment film thereof |
| WO2013081064A1 (en) * | 2011-11-29 | 2013-06-06 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
| WO2013108854A1 (en) * | 2012-01-18 | 2013-07-25 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| TWI520985B (en) * | 2012-07-18 | 2016-02-11 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liguid crystal display element |
| CN104969123B (en) * | 2012-12-13 | 2019-03-15 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element |
| KR102218510B1 (en) * | 2013-05-23 | 2021-02-19 | 닛산 가가쿠 가부시키가이샤 | Treatment agent for liquid crystal orientation, liquid crystal orientation film, and liquid crystal display device |
| JP6361168B2 (en) * | 2013-06-17 | 2018-07-25 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, method for producing liquid crystal display element, polymer and compound |
| TWI527844B (en) * | 2014-06-06 | 2016-04-01 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| TWI534203B (en) * | 2014-07-24 | 2016-05-21 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| TWI687457B (en) * | 2016-08-24 | 2020-03-11 | 奇美實業股份有限公司 | Liquid crystal alignment agent and use thereof |
| CN114958393B (en) * | 2022-06-16 | 2023-09-05 | 长沙道尔顿电子材料有限公司 | Polyamic acid liquid crystal orientation agent with nitrogen-containing aromatic ring structure, liquid crystal orientation film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005002346A (en) * | 2003-12-25 | 2005-01-06 | Tetsuya Nishio | Diamino compound, vinyl compound, polymer compound, alignment film, organic semiconductor device using the alignment film, conductive polymer, electroluminescent element using the conductive polymer, liquid crystal alignment film, and optical element using the liquid crystal alignment film |
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| JPH03239725A (en) * | 1990-02-16 | 1991-10-25 | Japan Carlit Co Ltd:The | New polyimide |
| JP3430705B2 (en) * | 1994-04-28 | 2003-07-28 | 日産化学工業株式会社 | Novel diaminobenzene derivative and polyimide using it |
| TW290558B (en) * | 1994-04-28 | 1996-11-11 | Nissan Chemical Ind Ltd | |
| JP3201172B2 (en) | 1994-09-08 | 2001-08-20 | ジェイエスアール株式会社 | Liquid crystal alignment agent |
| JP3613421B2 (en) | 1996-05-31 | 2005-01-26 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| JP3650982B2 (en) * | 1996-10-02 | 2005-05-25 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| JPH11149099A (en) * | 1997-09-11 | 1999-06-02 | Sagami Chem Res Center | Compound having pyridyl group, betaine compound, polymer and high molecular nonlinear optical material |
| US6238752B1 (en) * | 1998-07-29 | 2001-05-29 | Chisso Corporation | Diamino compounds, polyamic acids, polyimides, liquid crystal aligning films using said polyimide films and liquid crystal display devices using said aligning films |
| TWI291065B (en) * | 2000-12-26 | 2007-12-11 | Nissan Chemical Ind Ltd | Diamines, polyimide precursors and polyimides produced by using the diamines, and liquid crystal aligning agents |
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| JP2005002346A (en) * | 2003-12-25 | 2005-01-06 | Tetsuya Nishio | Diamino compound, vinyl compound, polymer compound, alignment film, organic semiconductor device using the alignment film, conductive polymer, electroluminescent element using the conductive polymer, liquid crystal alignment film, and optical element using the liquid crystal alignment film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2009093704A1 (en) | 2011-05-26 |
| TW200940506A (en) | 2009-10-01 |
| WO2009093704A1 (en) | 2009-07-30 |
| KR20170010899A (en) | 2017-02-01 |
| JP5663876B2 (en) | 2015-02-04 |
| CN101925634A (en) | 2010-12-22 |
| CN101925634B (en) | 2013-01-02 |
| KR20100103606A (en) | 2010-09-27 |
| TWI490207B (en) | 2015-07-01 |
| KR101738330B1 (en) | 2017-05-19 |
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