WO2012091089A1

WO2012091089A1 - Coating solution for forming functional polymer film, and method for forming functional polymer film

Info

Publication number: WO2012091089A1
Application number: PCT/JP2011/080379
Authority: WO
Inventors: 悟志南
Original assignee: 日産化学工業株式会社
Priority date: 2010-12-28
Filing date: 2011-12-28
Publication date: 2012-07-05
Also published as: TW201240981A; CN103403113B; JP5896164B2; TWI588139B; KR20130143633A; KR101916976B1; JPWO2012091089A1; CN103403113A

Abstract

Provided is a coating solution for forming a functional polymer film, said coating solution containing: at least one type of modifying compound selected from the group represented by formula A-D and having at least one Meldrum's acid structural site and a functional structural site which imparts functionality; and a polymer for modification or a monomer for the synthesis of said polymer for modification. Also provided is a functional polymer film obtained by firing a substrate coated using said coating. (In the formulae, the symbols are groups as defined in claim 1.)

Description

Functional polymer film forming coating solution and functional polymer film forming method

The present invention relates to a novel coating solution for forming a functional polymer film and a method for forming a functional polymer film.

In a liquid crystal display element, a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction. At present, the main liquid crystal alignment films that are industrially used are polyimide precursors such as polyamic acid (also called polyamic acid), polyamic acid esters, and polyimide-based liquid crystal aligning agents composed of polyimide solutions. It is manufactured by applying and forming a film. When the liquid crystal is aligned in parallel or inclined with respect to the substrate surface, a surface stretching process is further performed by rubbing after film formation. As an alternative to the rubbing treatment, a method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays has been proposed, and in recent years, studies for industrialization have been performed.

In order to improve the display characteristics of such liquid crystal display elements, methods such as changing the structure of polyamic acid, polyamic acid ester and polyimide, polyamic acid with different characteristics, blend of polyamic acid ester and polyimide, adding additives, etc. As a result, improvements in liquid crystal alignment and electrical characteristics, control of the pretilt angle, and the like are performed.

Among the techniques for controlling the pretilt angle depending on the structure of the polyimide, the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle in accordance with the proportion of the diamine used, so that the desired pretilt angle is obtained. This is relatively easy and is useful as a means for increasing the pretilt angle. Examples of the side chain structure of the diamine that increases the pretilt angle of the liquid crystal include a long-chain alkyl group or a fluoroalkyl group (see, for example, Patent Document 1), a cyclic group, or a combination of a cyclic group and an alkyl group (see, for example, Patent Document 2), A steroid skeleton (see, for example, Patent Document 3) is known.

In addition, the diamine for increasing the pretilt angle of the liquid crystal has been studied for improving the stability and process dependency of the pretilt angle, and the side chain structure used here includes a phenyl group. And those containing a ring structure such as a cyclohexyl group have been proposed (see, for example, Patent Documents 4 and 5). Furthermore, a diamine having such a ring structure in 3 to 4 side chains has also been proposed (see, for example, Patent Document 6).

In recent years, with the widespread use of liquid crystal display elements in large-screen liquid crystal televisions and high-definition mobile applications (display parts of digital cameras and mobile phones), the size of substrates used in comparison with conventional devices has increased. The unevenness of the step of the substrate is getting larger. Even in such a situation, it has been demanded that the liquid crystal alignment film be uniformly applied to a large substrate or a step due to display characteristics.

When applying a solution of a polyamic acid or a solvent-soluble polyimide to a substrate in the process of producing a liquid crystal alignment film, it is generally industrially performed by flexographic printing. In addition to N-methyl-2-pyrrolidone and γ-butyrolactone, which are solvents with excellent resin solubility (hereinafter also referred to as good solvents), the solvent of the coating solution is used to improve the uniformity of the coating film. Butyl cellosolve, which is a solvent having low solubility (hereinafter also referred to as a poor solvent), is mixed. However, since a poor solvent is inferior in the ability to dissolve a polyamic acid and a polyimide, when it mixes abundantly, precipitation will generate | occur | produce (for example, refer patent document 7). In particular, this problem appears remarkably in a solvent-soluble polyimide solution. Moreover, since the polyimide obtained by using a diamine having a side chain as described above tends to reduce the coating uniformity of the solution, it is necessary to increase the amount of poor solvent mixed. Mixing tolerance is also an important characteristic of polyimide.

In addition, liquid crystal display elements have higher performance, larger area, and power saving of display devices. In addition, they can be used in various environments, and the characteristics required for liquid crystal alignment films are severe. It has become a thing. In particular, when a liquid crystal aligning agent is applied to a substrate, problems such as occurrence of printing failure due to deposition and separation due to a long tact time, and burn-in due to accumulated charge (RDC) are problems. It is difficult to solve both of these simultaneously.

As described above, in the polyimide-based liquid crystal alignment film, various diamine components are used as a part of raw materials in order to improve desired characteristics. However, in relation to other characteristics, desired diamine components are used. In some cases, it cannot be used freely.

In addition to its liquid crystal alignment film, polyimide is widely used as a protective material and insulating material in the electrical and electronic fields because of its high mechanical strength, heat resistance, and solvent resistance. In the same manner, the diamine component as a raw material for polyimide is also improved, but the desired diamine component cannot be freely used.

And the desire to improve such desired characteristics is not limited to the above-mentioned polyimide-based liquid crystal alignment film, but also in a polymer film formed by applying a solution such as another polymer to a substrate to form a film, It exists as well.

JP-A-2-282726 Japanese Patent Laid-Open No. 3-179323 JP-A-4-281427 JP-A-9-278724 International Publication No. 2004/52962 Pamphlet JP 2004-67589 A JP-A-2-37324

An object of the present invention is to solve the above-mentioned problems of the prior art, and a functional polymer film-forming coating solution capable of obtaining a functional polymer film having various properties improved relatively freely, and An object of the present invention is to provide a functional polymer film forming method using the same.

The coating solution for forming a polyimide film of the present invention that solves the above-mentioned problems includes the following formulas [A] to [A] having a functional structure portion that imparts functionality and at least one Meldrum's acid structure portion connected thereto. And at least one modifying compound selected from the group represented by D], and a polymer for modification or a monomer for synthesizing the polymer for modification.

(Wherein, _{W 1} is _.V 1 representing the _{k 1} monovalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -OR, an -SR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k ₁ a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.)

(Wherein, _{W 2} is _.V 2 representing the _{k 2} divalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -SR, an -OR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k ₂ a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.)

(Wherein, W ₃ and W ₄ represents a k ₃ monovalent organic group is a functional structural part that imparts respective functional, W ₃ and W ₄ are .k ₃ may be the same or different are Represents an integer of 1 to 8.)

(Wherein, _{W 5} is .k ₄ representing the 2k _4-valent organic group that is functional structural moiety which imparts functionality is an integer of 1-8.)

In the method for forming a functional polymer film of the present invention, the functional polymer film-forming coating solution is applied to a substrate, baked, and the functional structure site is bonded to the modified polymer via the Meldrum's acid structure site. A functional polymer film is obtained.

According to the present invention, selected from the group represented by the above formulas [A] to [D], which includes a functional structural portion imparting functionality and at least one meldrum acid structural portion linked thereto. By using a coating solution for forming a functional polymer film containing the modifying compound represented by at least one kind, it is possible to obtain a functional polymer film having various properties improved relatively freely.

Hereinafter, the present invention will be described in detail.
The functional polymer film-forming coating solution of the present invention is represented by the following formulas [A] to [D] each having a functional structural portion imparting functionality and at least one meltrum acid structural portion linked thereto. It contains at least one modifying compound selected from the group represented.

(Wherein, _{W 1} is _.V 1 representing the _{k 1} monovalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -SR, an -OR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k ₁ a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.)

Specific examples of the modifying compound represented by the formula [A] include modifying compounds represented by the following formulas [i] to [iii]. In addition, when the modifying compound represented by the above formula [A] is synthesized using an amine compound having a terminal amino group that is primary or secondary, or a hydrazine compound as a raw material, it is represented by the following formula [i]. When a modifying compound represented by the above formula [A] is synthesized using a thiol compound or carbon disulfide as a raw material, it becomes a modifying compound represented by the following formula [ii]. Alternatively, when a modifying compound represented by the above formula [A] is synthesized using a ketone compound or a carboxylic acid derivative as a raw material, the modifying compound represented by the following formula [iii] is obtained. Further, when a carbodiimide compound is used as a raw material, the compound is represented by the following formula [i], and in this case, R _j is —H.

(Wherein, Y ₁ is the formula [A] terminal amino group which is a raw material of the modifying compound represented by the amine compound is a primary or secondary, hydrazine compounds, or, from carbodiimide compound k ₁ monovalent an organic group, for example, a single bond or, .k ₁ and a k ₁ monovalent organic group heteroatom or ring structure which may have a linear or branched carbon atoms 1-60 V ₁ is the same as k ₁ and V ₁ in the above formula [A], p is 1 when an amine compound or a carbodiimide compound is used as a raw material, and 2 when a hydrazine compound is used as a raw material. R _j is, -H represented by R 1 _~ R ₈ or a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, a good number of carbon atoms an amide bond anywhere 1 to 35 monovalent organic group, R 1 _~ R ₈ may be the same or different. Also, R _j is coupled with a portion of the Y ₁ may form a ring.)

(Wherein, Y ₂ is k ₁ monovalent organic group of the thiol compound, or carbon disulfide from a raw material of the modifying compound represented by the formula [A], for example, a single bond or a hetero atom and .k ₁ and V ₁ ring-like straight-chain or may have a or branched carbon atoms are k ₁ monovalent organic group of 1 to 60 above formula [a] in the k ₁ and V Same as _1. )

(Wherein, Y ₃ is an aldehyde as a raw material of the modifying compound represented by the formula [A], ketone compound or carboxylic acid derivative or a k ₁ monovalent organic group derived from the orthoformate, e.g. a single bond or, .k ₁ and V ₁ is k ₁ monovalent organic group heteroatom or ring structure which may have a linear or branched carbon atoms having 1 to 60 the formula [ The same as k ₁ and V ₁ in A].

In the modifying compounds represented by the above formulas [i] to [iii], specific examples of Y ₁ to Y ₄ when k ₁ is 2 include the following formulas (Y-1) to (Y-120) And a divalent organic group represented. Especially, when using the obtained functional polymer film as a liquid crystal alignment film, in order to obtain favorable liquid crystal alignment, it is preferable that it is a structure which uses a highly linear diamine compound as a raw material. (Y-7), (Y-10), (Y-11), (Y-12), (Y-13), (Y-21), (Y-22), (Y-23) , (Y-25), (Y-26), (Y-27), (Y-41), (Y-42), (Y-43), (Y-44), (Y-45), ( Y-46), (Y-48), (Y-61), (Y-63), (Y-64), (Y-65), (Y-66), (Y-67), (Y- 68), (Y-69), (Y-70), (Y-71), (Y-78), (Y-79), (Y-80), (Y-81), (Y-82) And (Y-109). When the functional polymer film obtained is a liquid crystal alignment film for increasing the pretilt angle of the liquid crystal, a long chain alkyl group (for example, an alkyl group having 10 or more carbon atoms) in the side chain, an aromatic ring, an aliphatic ring A structure using a diamine compound having a group ring, a steroid skeleton, or a combination of these as a raw material is preferable. Examples of such Y include (Y-83), (Y-84), (Y-85 ), (Y-86), (Y-87), (Y-88), (Y-89), (Y-90), (Y-91), (Y-92), (Y-93), (Y-94), (Y-95), (Y-96), (Y-97), (Y-98), (Y-99), (Y-100), (Y-101), (Y -102), (Y-103), (Y-104), (Y-105), (Y-106), (Y-107), or (Y-108). It is not something. When it is desired to improve the electrical characteristics of the liquid crystal display element, (Y-31), (Y-40), (Y-64), (Y-65), (Y-66), (Y-67) , (Y-109), (Y-110), and the like. When it is desired to impart photoreactivity to the liquid crystal alignment film, (Y-17), (Y-18), (Y-111), (Y-112), (Y-113), (Y-114) ), (Y-115), (Y-116), (Y-117), (Y-118), (Y-119) and the like.

In the modifying compounds represented by the above formulas [i] to [iii], specific examples of Y ₁ to Y ₃ when k ₁ is 1 include monovalent organic groups represented by the following formulas, [ Examples include, but are not limited to, a structure in which one bond of Y-1] to [Y-120] is bonded to a hydrogen atom.

In the modifying compounds represented by the above formulas [i] to [iii], specific examples of Y ₁ to Y _{4 in} the case where k ₁ is 3 or more include trivalent or more organic compounds represented by the following formula: And a structure in which a hydrogen atom of [Y-1] to [Y-120] is eliminated, but is not limited thereto. In the present specification, Me is a methyl group.

The method for producing the modifying compound represented by the formula [A] is not particularly limited. For example, the modifying compound represented by the formulas [i] and [ii] may be used in trimethyl orthoformate or orthoformate. Organic solvents used in general organic synthesis in triethyl (for example, ethyl acetate, hexane, toluene, tetrahydrofuran, acetonitrile, methanol, chloroform, 1,4-dioxane, N, N-dimethylformamide, N-methyl- 2-pyrrolidone), by reacting trimethyl orthoformate or triethyl orthoformate with an amine compound represented by the following formula [E1] or a thiol compound represented by the following formula [E2] and Meldrum's acid. Can do. The reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 60 to 120 ° C. for about 30 minutes to 2 hours.

_(Wherein, Y _1, _{R j} and _{k 1} is the same as _Y 1, _{R j} and _{k 1} in the above formula [i].)

(Wherein, _{Y 2} and _{k 1} is the same as _{Y 2} and _{k 1} in the formula [ii].)

In addition, the modifying compound represented by the above formula [iii] is pyridine or other organic base compound (for example, triethylamine, tributylamine, diisopropylethylamine), or these organic base compounds and phosphines such as triphenylphosphine. It can be produced by reacting an aldehyde compound represented by the following formula [E3] with Meldrum's acid in an organic solvent used in the above general organic synthesis in the presence of a system compound. The reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 0 ° C. to 100 ° C. for about 1 to 24 hours.

(Wherein, _{Y 3} and _{k 1} are the same as _{Y 3,} and _{k 1} in the above formula [iii].)

Other methods for producing the modifying compound represented by the formula [A] include amine compounds such as [E1], thiol compounds such as [E2], and amino groups of aldehyde compounds such as [E3]. The thiol group and aldehyde group are chemically modified according to various generally known organic synthesis methods to form a compound having an amino group, a thiol group, or an aldehyde group via a spacer. The method of making it react with an acid is mentioned. Of course, this chemical modification may be performed a plurality of times.

Specifically, for example, the amino group of the amine compound [E1] is chemically modified according to various generally known organic synthesis methods, and is represented by the following formulas [E4] to [E6]. The compound can also be produced by reacting it with Meldrum acid by the same synthesis method as the modifying compounds represented by the above formulas [i] to [iii]. When a compound represented by the following formulas [E4] to [E6] is reacted with Meldrum acid as a raw material, a modifying compound represented by the formula [A] of the following formulas [i ′] to [iii ′] Become.

_(Wherein, Y 1, _{R j} and _{k 1} is the same as _Y 1, _{R j} and _{k 1} in the above formula [i] .Q ₁ is a single bond or have a hetero atom or ring structure A linear or branched divalent organic group having 1 to 15 carbon atoms, where R _i is —H represented by R ₁ to R ₈ , or a benzene ring, cyclohexane ring, hetero ring; A monovalent organic group having 1 to 35 carbon atoms which may contain a ring, fluorine, ether bond, ester bond or amide bond at any position, and R ₁ to R ₈ may be the same or different. R _i may be linked to a part of Q ₁ to form a ring.

_{_{_{(Wherein, Y 1, R j, R}}} i, Q 1 and _{k 1} are _{_{_{Y 1, R j, R i}}} , the same as _{Q 1} and _{k 1} in the above formula [E4] ~ [E6], V 1 Is the same as V ₁ in the above formula [A].)

Specific examples of the modifying compound represented by the formula [B] include the modifying compounds represented by the following formulas [iv] and [v].

(In the formula, Y ₄ represents an aldehyde, a ketone compound, a halogenated alkyl compound, or a compound having an electron-deficient unsaturated bond (for example, a compound having an acryloyl group) that is a raw material of the modifying compound represented by the formula [B]. ) and k ₂ divalent organic group derived from, for example, a single bond or a hetero atom and the ring structure or may have a linear or branched carbon atoms of k ₂ divalent 1-60 organic (K ₂ and V ₂ are the same as k ₂ and V ₂ in the above formula [B].)

(Wherein, Y ₅ is a k ₂ divalent organic group derived from a carboxylic acid derivative as a raw material of the modifying compound represented by the formula [B], for example, a single bond or a hetero atom or ring structure have been or may be linear or branched carbon atoms is k ₂ monovalent organic group 1 ~ 60 .k ₂ and V ₂及are the same as k ₂ and V ₂ in the formula [B] .)

In the modifying compounds represented by the above formulas [iv] and [v], specific examples of Y ₄ and Y ₅ are the same as those of Y ₁ to Y ₃ above.

The method for producing the modifying compound represented by the above formula [B] is not particularly limited. For example, the modifying compound represented by the above formula [iv] may be used in an organic solvent used in the general organic synthesis. , Pyridine, or other organic base compounds (eg, triethylamine, tributylamine, diisopropylethylamine) or inorganic bases such as potassium carbonate, sodium bicarbonate, sodium hydroxide, aldehydes, ketone compounds, alkyl halide compounds (halogens) Can be any of —Cl, —Br, and —I) or a compound having an electron-deficient unsaturated bond (for example, a compound having an acryloyl group) and Meldrum's acid. The reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 0 ° C. to 120 ° C. for about 30 minutes to 2 hours. In addition, the modifying compound represented by the above formula [B] is prepared by using an aldehyde, a ketone compound, an alkyl halide compound, or a compound having an electron-deficient unsaturated bond (for example, a compound having an acryloyl group) as a raw material. In the case of synthesis, the modification represented by the above formula [iv] is carried out directly or once through the compound represented by the above formula [iii] and then reducing the carbon-carbon double bond. Compound.

Further, the modifying compound represented by the above formula [v] is pyridine, other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine) or the like in the organic solvent used in the general organic synthesis. It can be produced by reacting mellic acid with a carboxylic acid or a carboxylic acid derivative such as carboxylic acid chloride together with an inorganic base such as potassium carbonate, sodium hydrogen carbonate or sodium hydroxide. The reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at −20 to 120 ° C. for about 30 minutes to 2 hours.

As other methods for producing the modifying compound represented by the formula [B], as in the method for producing the compound represented by the formula [A], an aldehyde, a ketone compound, a halogenated alkyl compound, an electron deficiency A compound having a saturated bond, a carboxylic acid, and a carboxylic acid derivative are chemically modified according to various generally known organic synthesis methods, and an aldehyde group, a ketone group, a halogenated alkyl group, an electron through a spacer Examples thereof include a method in which a compound having a deficient unsaturated bond (for example, acryloyl group) and a carboxyl group is used, and this is used as a raw material to react with Meldrum's acid. Of course, this chemical modification may be performed a plurality of times. In addition, when the modification compound represented by the above formula [B] is produced by performing chemical modification in this way, for example, Y ₄ of the modification compound represented by the above formula [iv] and the Meldrum's acid structure A structure derived from a compound to be chemically modified (for example, a divalent organic group having 1 to 15 carbon atoms having a chain or branched structure which may have a heteroatom or a ring structure) between the moiety A structure derived from the compound to be chemically modified between Y ₅ and the carbonyl group of the modifying compound represented by the formula [B] of the inserted structure or the modifying compound represented by the formula [v] (for example, And a structure represented by the formula [B] having a structure in which a divalent organic group having 1 to 15 carbon atoms and having a chain or branched structure which may have a hetero atom or a ring structure is inserted Become a compound.

Specific examples of the modifying compound represented by the above formula [C] include a modifying compound represented by the following formula [vi].

(Wherein, Y ₆ and Y ₇ are each a halogenated alkyl compound as a raw material for modifying compound represented by the formula [C], or represents a k ₃ monovalent organic group derived from an alcohol derivative, e.g., single bond or a hetero atom and the ring structure or may have a linear or branched carbon atoms is k ₃ monovalent organic group 1 ~ 60 .Y ₆ and Y ₇ are either the same or different K ₃ is the same as k ₃ in the above formula [C].)

In the modifying compound represented by the above formula [vi], specific examples of Y ₆ and Y ₇ are the same as those of Y ₁ to Y ₃ .

The method for producing the modifying compound represented by the formula [C] is not particularly limited. For example, the modifying compound represented by the formula [vi] may be used in an organic solvent used in the general organic synthesis. , Pyridine, or other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine) or an inorganic base such as potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, for the modification represented by the above formula [iv] It can be produced by reacting a compound and a halogenated alkyl compound or a compound having a terminal hydroxyl group in the presence of a palladium catalyst. Alternatively, in an organic solvent used in the above general organic synthesis, pyridine, other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine), potassium carbonate, sodium bicarbonate, sodium hydroxide, etc. It can be produced by reacting an alkyl halide compound with an inorganic base, or a compound having a hydroxyl group at the terminal in the presence of a palladium catalyst. In this case, Y ₆ and Y ₇ may be the same or different. When Y ₆ and Y ₇ are different, in the production method described above, two or more kinds of halogenated alkyl compounds and a compound having a hydroxyl group at the terminal can be coexisted or added stepwise. The reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 60 to 120 ° C. for about 30 minutes to 2 hours.

As other methods for producing the modifying compound represented by the formula [C], as in the method for producing the compound represented by the formula [A], an alkyl halide compound or an alcohol derivative is generally known. In accordance with various organic synthesis methods that have been used, a method of chemically modifying a compound having a halogenated alkyl group, an alkoxy group, or a hydroxy group via a spacer and reacting it with Meldrum's acid as a raw material can be mentioned. Of course, this chemical modification may be performed a plurality of times. In this way, when the modifying compound represented by the above formula [C] is produced by performing chemical modification, for example, Y ₆ of the modifying compound represented by the above formula [vi] and the Meldrum's acid structure and between the sites, between the Y ₇ and Meldrum's acid structural moiety, compounds derived from the structure of chemically modified (e.g., number of carbon atoms consisting of a good chain or branched structure which may have a hetero atom or ring structure Is a modifying compound represented by the formula [C] having a structure in which 1 to 15 divalent organic groups are inserted.

Specific examples of the modifying compound represented by the above formula [D] include a modifying compound represented by the following formula [vii].

(Wherein Y ₈ is a 2k ₄ having 1 to 15 carbon atoms derived from a cyclic ketone compound, a cyclic alkoxyimine compound, or a cyclic carbodiimide compound that is a raw material of the modifying compound represented by the above formula [D]. .k ₄ representing an organic group are the same as _{k 4} in the formula [D].)

In the modifying compound represented by the above formula [vii], specific examples of Y ₈ include a cyclic structure derived from a cyclic ketone such as a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, and γ-pyrone.

The method for producing the modifying compound represented by the above formula [D] is not particularly limited. For example, the modifying compound represented by the above formula [vii] may be used in an organic solvent used in the above general organic synthesis. , Pyridine, or other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine), or an inorganic base such as potassium carbonate, sodium bicarbonate, sodium hydroxide, and cyclic ketone compounds (for example, cyclohexanone derivatives and γ- A pyrone derivative), a cyclic alkoxyimine compound (for example, a 6-position alkoxy-substituted tetrahydropyridine), or a cyclic carbodiimide compound (for example, a 3-diazacyclonona-1,2-diene derivative) and a reaction with Meldrum's acid. be able to. The reaction temperature and reaction time of this reaction are not particularly limited, but for example, the reaction may be performed at 60 to 120 ° C. for about 30 minutes to 2 hours.

Of course, the modifying compounds represented by the above formulas [A] to [D] may be used alone or in combination of two or more.

The functional polymer film-forming coating solution of the present invention contains a polymer for modification or a monomer for synthesizing these polymers for modification. The polymer to be modified is not particularly limited as long as it has a site that reacts with the Meldrum's acid structure. For example, at least one tetracarboxylic acid component selected from tetracarboxylic acid and its derivatives and a diamine component are polymerized. Polyimide precursor obtained by imidating, polyimide obtained by imidizing this polyimide precursor, acrylic polymer, methacrylic polymer, acrylamide polymer, methacrylamide polymer, polystyrene, polyvinyl, polysiloxane and polyamide, polyester, polyurethane, polycarbonate, Examples thereof include polyurea, polyphenol (novolak resin), maleimide polymer, and a polymer in which a compound having an isocyanuric acid skeleton or a triazine skeleton is introduced. The polymer may be in the form of, for example, a branched polymer such as a dendrimer, a hyperbranched polymer or a star-like polymer, or a noncovalent polymer such as polycatenan or polyrotaxane. Moreover, as a monomer for synthesizing these polymers to be modified, when the polymer to be modified is a polyimide precursor or polyimide, at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof and a diamine component When the polymer to be modified is an acrylic polymer, acrylic acid and its derivatives, acrylic esters and derivatives thereof, and when the polymer to be modified is a methacrylic polymer, methacrylic acid and derivatives thereof, methacrylic esters and derivatives thereof Acrylamide and its derivatives when the polymer to be modified is an acrylamide polymer, methacrylamide and its derivatives when the polymer to be modified is a methacrylamide polymer, styrene and its derivatives when the polymer to be modified is polystyrene, Qualified When the polymer is polyvinyl, a derivative having a vinyl group is selected. When the polymer to be modified is polysiloxane, a silane compound having a methoxy group or an ethoxy group is selected. When the polymer to be modified is polyamide, the derivative is selected from dicarboxylic acids and derivatives thereof. At least one dicarboxylic acid component and a diamine component, when the polymer to be modified is a polyester, at least one dicarboxylic acid component and a diol component selected from dicarboxylic acids and derivatives thereof, and when the polymer to be modified is a polyurethane, an isocyanate and When the compound and the compound having a hydroxyl group, the polymer to be modified is a polycarbonate, a bisphenol derivative and phosgene, or a phosgene equivalent (for example, trichlorophosgene), diphenyl carbonate, or the polymer to be modified is a polyurea Bisisocyanate derivative and diamine component, if the polymer to be modified is a maleimide polymer, maleimide derivative alone or copolymerized with styrene, if the polymer to be modified is a polymer into which a compound having an isocyanuric acid skeleton or a triazine skeleton is introduced And compounds having an isocyanuric acid skeleton or a triazine skeleton. Of course, the polymer for modification or the monomer for synthesizing these polymers for modification may be one kind, and may use two or more kinds together. The polyimide precursor refers to polyamic acid and polyamic acid ester.

The modified polymer contained in the functional polymer film-forming coating solution of the present invention can be produced by a conventional method. For example, a polyimide precursor or a polyimide is obtained by polymerizing at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof and a diamine component as described above.

The diamine component, for example, a diamine compound k ₁ is represented by the formula [E1] is 2. Moreover, the diamine component currently used when making a polyimide precursor react by making a diamine component and a tetracarboxylic-acid component react can be used. The diamine component that is the raw material of the polyimide precursor may be partially or entirely the same as the raw material of the modifying compound represented by the above formula [A], or the diamine component and the above formula [A It is good also as a compound different from the raw material of the compound for a modification represented by these.

In addition, as at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof, a tetracarboxylic acid component that has been used in the past to obtain a polyimide precursor by reacting a diamine component and a tetracarboxylic acid component is used. Can be used. Examples of the tetracarboxylic acid derivative include tetracarboxylic acid dihalide, tetracarboxylic dianhydride represented by the following formula [F], tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester. For example, a polyamic acid can be obtained by reacting tetracarboxylic acid or a derivative thereof such as tetracarboxylic acid dihalide or tetracarboxylic dianhydride with a diamine component. It is also possible to obtain a polyamic acid ester by reacting a tetracarboxylic acid diester dichloride with a diamine component, or reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or base. it can.

(X is a tetravalent organic group.)

Specific examples of X in the above formula [F] include tetravalent organic groups represented by the following formulas (X-1) to (X-46). From the viewpoint of availability of compounds, X represents (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X- 8), (X-16), (X-17), (X-19), (X-21), (X-25), (X-26), (X-27), (X-28) , (X-32) and (X-46) are preferable. When it is desired to improve the transparency of the resulting functional polymer film (polyimide film), it is preferable to use a tetracarboxylic dianhydride having an aliphatic and aliphatic ring structure, and X is (X-1) , (X-2), and (X-25) are more preferred, and (X-1) is more preferred from the viewpoint of reactivity with the diamine component.

Specific examples of the tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4 -Cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl Acid dialkyl ester, 3,4-dicarboxy-1,2, , 4-Tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester Ester, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1, 2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dialkyl ester, Hexacyclo [6.6.0.1 ^2,7 . 0 ^3,6 . 1 ^9,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-di-oxo-tetrahydrofuran-3-yl) -1,2, Aliphatic tetracarboxylic acid diesters such as 3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester, pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ', 3,3'-biphenyltetracarboxylic acid dialkyl ester, 2,3,3', 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dialkyl ester, 2,3 , 3 ′, 4-Benzophenonetetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphene) Nyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, etc. And aromatic tetracarboxylic acid dialkyl esters.

Of course, each of the diamine component and the tetracarboxylic acid component may be one kind, or two or more kinds may be used in combination.

A method for synthesizing a polyimide precursor by polymerizing a tetracarboxylic acid component and a diamine component is not particularly limited, and a known synthesis method can be used.

For example, the reaction of the diamine component and tetracarboxylic dianhydride includes a method of reacting the diamine component and tetracarboxylic dianhydride in an organic solvent. The organic solvent used in that case will not be specifically limited if the produced | generated polyimide precursor melt | dissolves. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ -Butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol , Ethyl carbitol, 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, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol Methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3- Tokishipuropion acid, 3-methoxy propionic acid propyl, 3-methoxy propionic acid butyl, and the like diglyme or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction, and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

When the diamine component and the tetracarboxylic dianhydride are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent. Dispersed or dissolved and added, reversely tetracarboxylic dianhydride dispersed or dissolved in an organic solvent, diamine component added, tetracarboxylic dianhydride and diamine component alternately The method of adding etc. is mentioned, You may use any of these methods. In addition, when a plurality of types of diamine components or tetracarboxylic dianhydrides are used for reaction, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. A molecular weight body may be mixed and reacted to form a polymer. In this case, the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of tetracarboxylic dianhydride is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.

The polyamic acid ester can be obtained by reacting the tetracarboxylic acid diester dichloride with the diamine component as described above, or reacting the tetracarboxylic acid diester with the diamine component in the presence of an appropriate condensing agent or base. it can. Alternatively, it can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxyl group of the polyamic acid using a polymer reaction.

Specifically, for example, tetracarboxylic acid diester dichloride and a diamine component in the presence of a base and an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 By reacting for 4 to 4 hours, a polyamic acid ester can be synthesized.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

Further, when polycondensation of tetracarboxylic acid diester and diamine component in the presence of a condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium Tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxa Zolyl) phosphonic acid diphenyl, 4- (4,6-dimethoxy-1,3,5-triazine-2-y ) And 4-methoxy mol ho potassium chloride n- hydrate can be used.

In the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount of the diamine or tetracarboxylic acid diester to be reacted.

The solvent used in the above reaction can be the same solvent as that used in the synthesis of the polyamic acid shown above. However, N-methyl-2-pyrrolidone, γ -Butyrolactone is preferred, and these may be used alone or in combination of two or more. The concentration at the time of synthesis is such that in the reaction solution of a tetracarboxylic acid derivative such as tetracarboxylic acid diester dichloride or tetracarboxylic acid diester and a diamine component, from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained. The total concentration is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass. Moreover, in order to prevent hydrolysis of tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.

The polyimide contained in the functional polymer film-forming coating solution of the present invention can be obtained by dehydrating and ring-closing the polyimide precursor. In this polyimide, the dehydration cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.

The temperature when the polyimide precursor is thermally imidized in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.

The catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a basicity appropriate for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

In addition, what is necessary is just to throw a reaction solution into a solvent and to precipitate, when collect | recovering the produced | generated polyimide precursor or a polyimide from the reaction solution of a polyimide precursor or a polyimide. Examples of the solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.

In addition, a polyimide precursor that can be used as a polymer to be modified, and polymers other than polyimide include acrylic polymer, methacrylic polymer, acrylamide polymer, methacrylamide polymer, polystyrene, polyvinyl, polysiloxane, polyamide, polyester, polyurethane, polycarbonate , Polyurea, polyphenol (novolak resin), maleimide polymer, polymers incorporating isocyanuric acid skeleton and triazine skeleton, branched polymers such as dendrimer, hyperbranched polymer, star-like polymer, and non-covalent polymers such as polycatenan and polyrotaxane In these polymers, functional groups capable of reacting with ketene intermediates formed by the thermal decomposition of Meldrum's acid compound (for example, , Carboxyl group, hydroxy group, thiol, amino group, imino group, unsaturated bond such as carbon-carbon double bond (alkene) and carbon-carbon triple bond (alkyne), nitrile, ketone, aldehyde, ester, amide, imide ) And the like, these polymers may be commercially available or known.

The polymer to be modified contained in the functional polymer film forming coating liquid of the present invention is in consideration of the strength of the obtained functional polymer film, the workability when forming the functional polymer film, and the uniformity of the functional polymer film. The weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

The group represented by the above formulas [A] to [D], comprising functional structural portions W ₁ to W ₅ that impart functionality, and at least one meldrum acid structural portion linked thereto. A polymer film for forming a conventional polymer film or the like, for example, by containing at least one modifying compound selected from the above and a polymer to be modified or a monomer for synthesizing the polymer to be modified A functional polymer film in which various properties are relatively freely improved by further containing at least one modifying compound selected from the group represented by the formulas [A] to [D] in the forming coating solution The coating liquid for forming a functional polymer film can be obtained.

More specifically, the modifying compounds represented by the above formulas [A] to [D] have at least one Meldrum's acid structure, that is, Meldrum's-derived structure at the end. When heated (for example, 180 to 250 ° C. or higher), carbon dioxide and acetone are eliminated to form ketene (that is, a carbonyl compound having a divalent group> C═C═O). For example, polyimide Precursor, polyimide, acrylic polymer, methacrylic polymer, acrylamide polymer, methacrylamide polymer, polystyrene, polyvinyl, polysiloxane, polyamide, polyester, polyurethane, polycarbonate, polyurea, polyphenol (novolak resin), maleimide polymer, or isocyanuric acid skeleton And triazine skeleton introduced Functional groups present in non-covalent polymers such as polycatenans and polyrotaxanes (eg carboxyl groups, hydroxy groups, thiols, amino groups) Reaction with an imino group, an unsaturated bond such as a carbon-carbon double bond (alkene) or a carbon-carbon triple bond (alkyne), a nitrile group, a ketone group, an aldehyde group, an ester group, an amide group, an imide group), or It reacts by dimerization with ketene itself. Therefore, the modifying compounds represented by the above formulas [A] to [D] are not heated to a high temperature (for example, 100 ° C. or less), and in the state of the functional polymer film forming coating solution, the modifying polymer or modified compound is used. Although it does not react with the monomer for synthesizing the polymer for use, it is introduced into the polymer for modification via the Meldrum's acid structure by heating. In the case of the modifying compound represented by the above formulas [A] to [D] in which k ₁ to k ₄ are 2 or more, it has two or more Meldrum structures. It is presumed that the polymer has a structure crosslinked with the modifying compounds represented by the above formulas [A] to [D].

Therefore, the functional polymer film obtained by applying the functional polymer film-forming coating solution of the present invention to a substrate and baking is used for the W ₁ -W possessed by the modifying compounds represented by the above formulas [A]-[D]. structure of W ₅ is what is introduced into the modified polymer.

Here, a polyimide film, which is an example of a functional polymer film, is a liquid crystal alignment film, a protective material in the electric / electronic field, and an insulating material because of its high mechanical strength, heat resistance, and solvent resistance. In order to improve desired characteristics, various diamine components are used as a part of raw materials. However, there are cases where a desired diamine component cannot be used freely. For example, in a liquid crystal alignment film, various diamine components are used as a part of raw materials in order to improve desired characteristics such as improvement of liquid crystal orientation and pretilt angle. Depending on the type, combination and amount of the diamine component used, the polymerization reactivity between the diamine component and the tetracarboxylic acid component is deteriorated, so the type, combination and amount of the diamine component for obtaining desired properties are limited. May end up. Moreover, it is necessary to examine the polymerization reaction conditions between the diamine component and the tetracarboxylic acid component for each type and combination of diamine components used for obtaining desired characteristics. Moreover, in order to obtain a coating solution for forming a polyimide film that can form a uniform polyimide film (a coating solution for forming a functional polymer film), it is necessary to use a solution in which the components are dissolved in a solvent. Depending on the type, combination and amount of the diamine component used to obtain the polyimide, there is a problem that the solubility of the polyimide precursor and polyimide contained in the polyimide film-forming coating solution is deteriorated. In addition, not only in polyimide films, but also in various polymer films, when various monomers are used as a part of raw materials in order to improve desired characteristics, the problem that polymerization reactivity deteriorates as well as desired characteristics There is a problem that it is necessary to examine polymerization reaction conditions for each kind and combination of monomers used to obtain a polymer, and there is a problem that the solubility of the polymer contained in the functional polymer film forming coating solution is deteriorated.

In the present invention, at the stage of the functional polymer film forming coating solution, the polymer to be modified or the monomer for synthesizing the polymer to be modified and the above-mentioned formula [A] to The compound to be modified is represented by [D] and is a compound for obtaining desired characteristics at the stage of heating (baking) the functional polymer film-forming coating solution. A compound for modification represented by the above formulas [A] to [D] is introduced into a polymer for modification. Therefore, the polymer to be modified contained in the coating liquid for forming the functional polymer film does not need to use a monomer as a raw material for obtaining the desired characteristics, and therefore the problem that the polymerization reactivity of the monomers is deteriorated, the desired characteristics. There is no problem that it is necessary to examine the polymerization reaction conditions for each kind and combination of monomers used for obtaining, and the problem that the solubility of the polymer contained in the functional polymer film forming coating solution is deteriorated. Therefore, the coating liquid for forming a functional polymer film of the present invention is intended to obtain desired characteristics (functions) without considering the polymerization reactivity of the monomers, the necessity of examining the polymerization reaction conditions, and the solubility of the polymer. Therefore, various properties of the obtained functional polymer film can be improved relatively freely as compared with the conventional coating liquid for forming a polymer film.

Further, when the coating liquid for forming a functional polymer film of the present invention contains a modifying compound represented by the above formulas [A] to [D] having two or more Meldrum structures, Since the polymer is crosslinked with the modifying compounds represented by the above formulas [A] to [D] by heating, the resulting functional polymer film is resistant to an organic solvent and becomes a hard film.

Further, it is selected from a polyimide precursor obtained by polymerization reaction of at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof and a diamine component, and a polyimide obtained by imidizing this polyimide precursor. When a coating solution for forming a functional polymer film containing at least one polymer and a modifying compound represented by the above formula [i] and having two Meldrum's acid structures is used, it is represented by the above formula [i]. The modifying compound is obtained by introducing a Meldrum's acid structure into each of the two amino groups of the diamine compound. As this diamine compound, a diamine component for obtaining the desired properties that have been conventionally studied, that is, tetracarboxylic acid is used. Diamine for producing polyimide precursor and polyimide by polymerization reaction with acid component A minute can be applied diamine component for obtaining the desired characteristics. Therefore, various characteristics of the obtained polyimide film can be easily improved.

In the case of a functional polymer film-forming coating solution containing a polymer to be modified, the modifying compound represented by the above formulas [A] to [D] is heated as a side chain on the polymer to be modified. In particular, when the modifying compound represented by the above formulas [A] to [D] has two or more Meldrum structures, the polymer to be modified is represented by the above formulas [A] to [D]. A crosslinked structure is obtained by the modifying compound represented. In the case of a functional polymer film-forming coating solution containing a monomer for synthesizing the polymer to be modified, the Meldrum's acid structure of the modifying compound represented by the above formulas [A] to [D] is the polymerization of the monomer. Therefore, the monomer for synthesizing the polymer for modification is first polymerized at a low temperature to synthesize the polymer for modification, and then heated to the above formulas [A] to [[ D] is introduced as a side chain of the polymer to be modified, and in particular, the modifying compounds represented by the above formulas [A] to [D] have two or more Meldrum structures. In this case, the polymer to be modified has a structure crosslinked with the modifying compounds represented by the above formulas [A] to [D]. However, a functional polymer film-forming coating containing a monomer for synthesizing a polymer to be modified and a modifying compound represented by the above formulas [A] to [D] having two or more Meldrum structures In the case of a liquid, by setting the temperature at which both the polymerization reaction of the monomer and the reaction of the Meldrum acid structure occur, the reaction of the Meldrum acid structure is caused simultaneously with the polymerization of the monomer, and the main chain of the polymer to be modified is represented by the above formula [ A modifying compound represented by A] to [D] can also be introduced.

The method for producing the coating liquid for forming a functional polymer film of the present invention is not particularly limited, and the above formula comprising a functional structural portion imparting functionality and at least one Meldrum's acid structural portion connected thereto [ It is sufficient that at least one modifying compound selected from the group represented by A] to [D] and a polymer to be modified or a monomer for synthesizing the polymer to be modified are dissolved in a solvent.

The solvent of the coating liquid for forming a functional polymer film of the present invention is a monomer for synthesizing the polymer to be modified or the polymer to be modified, a functional structure site that imparts functionality, and at least one linked thereto. Any compound capable of dissolving the modifying compounds represented by the above formulas [A] to [D] having two Meldrum's acid structural sites, for example, N, N-dimethylformamide, N, N -Dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone And organic solvents such as methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

The coating solution for forming a functional polymer film of the present invention preferably has an organic solvent content of 70 to 97% by mass from the viewpoint of forming a uniform functional polymer film by coating. This content can be appropriately changed depending on the film thickness of the intended functional polymer film.

Further, the content of the monomer for synthesizing the polymer to be modified or the polymer to be modified in the coating solution for forming a functional polymer film of the present invention is preferably 3 to 30% by mass. This content can also be appropriately changed depending on the film thickness of the intended functional polymer film.

The content of the modifying compound represented by the above formulas [A] to [D] in the functional polymer film-forming coating solution of the present invention is not particularly limited as long as it is dissolved, but the content is not limited. It is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of monomers for synthesizing the polymer or the polymer to be modified, and more preferably 1 to 100 parts by mass in order not to lower the orientation of the liquid crystal Particularly preferred is 1 to 50 parts by mass.

The functional polymer film-forming coating liquid of the present invention has a uniform film thickness and surface of the functional polymer film when the functional polymer film-forming coating liquid of the present invention is applied unless the effects of the present invention are impaired. An organic solvent (also referred to as a poor solvent) or a compound that improves smoothness can be used. Furthermore, a compound that improves the adhesion between the functional polymer film and the substrate can also be used.

Specific examples of poor solvents that improve film thickness uniformity and surface smoothness include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl Carbitol, ethyl carbitol acetate, 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 No acetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclo Hexene, propyl ether, dihexyl ether n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3- Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether 2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n- And organic solvents having a low surface tension such as butyl ester or isoamyl lactate. These poor solvents may be used alone or in combination. When the poor solvent as described above is used, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the entire organic solvent contained in the functional polymer film forming coating solution.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like. Specifically, for example, EFTOP EF301 , EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass) and the like. The ratio of these surfactants to be used is preferably 0.00 with respect to 100 parts by mass of the total amount of monomers for synthesizing the polymer to be modified or the polymer to be modified contained in the functional polymer film-forming coating solution. 01 to 2 parts by mass, more preferably 0.01 to 1 part by mass.

Specific examples of the compound that improves the adhesion between the functional polymer film and the substrate include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxy. Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 0-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-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3- Aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, Propylene glycol diglycid Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl 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-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) ) Functional silane-containing compounds such as cyclohexane or N, N, N ′, N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane, and epoxy group-containing compounds.

When using these compounds to be in close contact with the substrate, the polymer for modification contained in the functional polymer film-forming coating liquid of the present invention or the total amount of monomers for synthesizing the polymer for modification is 100 parts by mass. The amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected. If the amount exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate when the functional polymer film is used as the liquid crystal alignment film.

In addition, the functional polymer film-forming coating liquid of the present invention has a dielectric material intended to change the electrical properties such as the dielectric constant and conductivity of the functional polymer film as long as the effects of the present invention are not impaired. Or a conductive material may be added.

Further, the functional polymer film-forming coating solution of the present invention includes a crosslinkable compound having an epoxy group, an isocyanate group or an oxetane group, and further a group consisting of a hydroxyl group or an alkoxyl group, unless the effects of the present invention are impaired. A crosslinkable compound having at least one substituent selected from the above and a crosslinkable compound having a polymerizable unsaturated bond may be mixed.

Such a coating liquid for forming a functional polymer film of the present invention can be used as a liquid crystal aligning agent for forming a liquid crystal aligning film. The liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction.

The functional polymer having a function derived from the functional structural site of the compound represented by the above formulas [A] to [D] by applying the coating liquid for forming a functional polymer film of the present invention to a substrate and baking it. A film can be formed. When the functional polymer film-forming coating solution of the present invention is used as a liquid crystal aligning agent, it is applied onto a substrate and baked, and then subjected to an alignment treatment such as rubbing treatment or light irradiation, or for vertical alignment use. Then, a liquid crystal alignment film can be formed without alignment treatment.

The substrate is not particularly limited as long as it can apply the functional polymer film-forming coating solution, but when the liquid crystal alignment film is formed, it is preferably highly transparent. Specific examples include a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate. In this case, a material that reflects light, such as aluminum, can be used. As a high-performance element such as a TFT-type element, an element in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.

The method for applying the functional polymer film-forming coating liquid to the substrate is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.

¡Apply a functional polymer film-forming coating solution on the substrate, and dry part or all of the solvent as necessary. When the functional polymer film-forming coating solution contains a monomer for synthesizing the polymer to be modified, the monomer is polymerized when the functional polymer film-forming coating solution is applied on the substrate or when it is dried. It is preferable to do so.

Then, a functional polymer film-forming coating solution is applied onto the substrate, and if necessary, part or all of the solvent is dried and then baked. This calcination is carried out by the carboxyl group, hydroxy group, thiol group, amino group, imino group of the polymer to be modified in which the Meldrum acid structure of the modifying compound represented by the above formulas [A] to [D] is ketene or the like. Reacts with reactive sites such as unsaturated bonds such as carbon-carbon double bond (alkene) and carbon-carbon triple bond (alkyne), nitrile group, ketone group, aldehyde group, ester bond, amide bond, imide bond Heating to such a temperature is possible. For example, it is carried out at 180 to 250 ° C. by a heating means such as a hot plate, a hot air circulating furnace, an infrared furnace, etc., and the solvent is evaporated and the Meldrum's acid structure is reacted with the polymer to be modified. The modifying compounds represented by A] to [D] are introduced to form the functional polymer film of the present invention.

When the thickness of the functional polymer film formed after firing is a liquid crystal alignment film, if it is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 200 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film by the above-described method and then preparing a liquid crystal cell by a known method. For example, two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a coating solution for forming a functional polymer film of the present invention provided between the substrate and the liquid crystal layer. The liquid crystal display element which comprises the liquid crystal cell which has the said liquid crystal aligning film formed with the liquid crystal aligning agent which consists of these. As such a liquid crystal display element of the present invention, various devices such as a twisted nematic (TN) method, a vertical alignment (VA) method, a horizontal alignment (IPS) method, and the like are available. Can be mentioned.

The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. As a specific example, the thing similar to the board | substrate described with the said functional polymer film can be mentioned.

Further, the liquid crystal alignment film is formed by applying a liquid crystal aligning agent comprising the functional polymer film forming coating liquid of the present invention on this substrate and baking it, and the details are as described above.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and conventional liquid crystal materials such as MLC-2003, MLC-6608, MLC-6609 manufactured by Merck & Co., Inc. can be used.

To give an example of a liquid crystal cell manufacturing method, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. In such a manner, the other substrate is bonded and sealed by injecting liquid crystal under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed. Etc. can be exemplified. The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

The liquid crystal display device manufactured as described above is for synthesizing the modifying compound represented by the above formulas [A] to [D] and the polymer to be modified or the polymer to be modified, which can introduce desired characteristics. Since it is produced using the liquid crystal aligning agent containing the monomer, various characteristics can be improved.

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 Modification Compounds Represented by Formulas [A] to [D] above]
<Synthesis Example 1>
Compound 5,5 ′-(1,4-phenylenebis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane represented by the following formula [4] -4,6-dione)

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 mL four-necked flask and heated under reflux for 1 hour. Thereafter, paraphenylenediamine [3] (5.0 g, 46 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 15.8 g of Compound [4] (yield 82%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.29 (2H, d), 8.56 (2H, d), 7.64 (4H, s), 1.68 (12H, s).

<Synthesis Example 2>
Compound 5,5 ′-(1,3-phenylenebis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane represented by the following formula [6] -4,6-dione)

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 mL four-necked flask and heated under reflux for 1 hour. Thereafter, metaphenylenediamine [5] (5.0 g, 46 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 14.1 g of Compound [6] (yield 72%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.28 (2H, s), 8.74 (2H, s), 7.98 (1H, s), 7.44 (3H, s), 1.68 (12H, s).

<Synthesis Example 3>
Compound 5,5 ′-(pyridine-2,6-diylbis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3 represented by the following formula [8] -dioxane-4,6-dione)

Meldrum acid [1] (16.0 g, 111 mmol) and trimethyl orthoformate [2] (160 g) were added to a 300 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 2,6-diaminopyridine [7] (5.5 g, 50 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 16.7 g of Compound [8] (yield 80%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.42 (2H, d), 9.15 (2H, d), 7.96 (1H, t), 7.52 (2H, d), 1.67 (12H, s).

<Synthesis Example 4>
Compound 5,5 ′, 5 ″-(benzene-1,3,5-triyltris (azanediyl)) tris (methan-1-yl-1-ylidene) tris (2,2 -dimethyl-1,3-dioxane-4,6-dione)

A mixture of 3,5-dinitroaniline [9] (32.6 g, 178 mmol), 5% palladium carbon (3.75 g, 10 wt%), and 1,4-dioxane (375 g) in a 1 L four neck flask Was stirred at room temperature under hydrogen atmosphere. After completion of the reaction, palladium carbon was filtered through celite, and the filtrate was concentrated with an evaporator to obtain 21.7 g of Compound [10] (yield 99%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 5.11 (3H, s), 4.28 (6H, s).

Meldrum acid [1] (83.8 g, 582 mmol) and trimethyl orthoformate [2] (660 g) were added to a 1 L four-necked flask and heated under reflux for 1 hour. Thereafter, compound [10] (21.7 g, 176 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 73.0 g of Compound [11] (yield 71%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.22 (3H, s), 8.26 (3H, s), 7.70 (3H, s), 1.65 (18H, s).

<Synthesis Example 5>
Compound 5,5 ′-(4,4′-methylenebis (4,1-phenylene) bis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2, represented by the following formula [13] 2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 4,4′-diaminodiphenylmethane [12] (5.0 g, 46 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 14.1 g of Compound [13] (yield 72%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.23 (2H, d), 8.54 (2H, d), 7.50-7.48 (4H, m), 7.31-7.29 (4H, m), 3.96 (2H, m), 1.66 (12H, s).

<Synthesis Example 6>
Compound 5,5 ′-(4,4′-oxybis (4,1-phenylene) bis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2, represented by the following formula [15] 2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (7.92 g, 54.9 mmol) and trimethyl orthoformate [2] (78 g) were added to a 200 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, 4,4′-diaminodiphenyl ether [14] (5.0 g, 25.0 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 11.7 g of Compound [15] (yield 92%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.30 (2H, d), 8.51 (2H, d), 7.62 (4H, d), 7.08 (4H, d), 1.67 (12H, s).

<Synthesis Example 7>
Compound 5,5 ′-(4,4′-azanediylbis (4,1-phenylene) bis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2, represented by the following formula [17] 2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (7.96 g, 55.2 mmol) and trimethyl orthoformate [2] (79 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 4,4′-diaminodiphenylamine [16] (5.0 g, 25.1 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 10.1 g of Compound [17] (yield 79%).
¹ H-NMR (400MHz, DMSO-d6, δppm): 11.29 (2H, d), 8.51 (2H, d), 7.62 (4H, d), 7.08 (4H, d), 4.97 (1H, s), 1.67 (12H, s).

<Synthesis Example 8>
Compound 5,5 ′-(4,4 ′-(methylazanediyl) bis (4,1-phenylene) bis (azanediyl)) bis (methan-1-yl-1-ylidene) bis represented by the following formula [19] Synthesis of (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum's acid [1] (14.9 g, 103 mmol) and trimethyl orthoformate [2] (100 g) were added to a 500 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 4,4′-diaminodiphenylmethylamine [18] (10.0 g, 46.9 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 21.7 g of Compound [19] (yield 86%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.21 (2H, d), 8.44 (2H, d), 7.45-7.42 (4H, m), 7.03-7.01 (4H, m), 3.24 (3H, s), 1.62 (12H, s).

<Synthesis Example 9>
Compound 5,5 ′-(4,4 ′-(pentane-1,5-diylbis (oxy)) bis (4,1-phenylene)) bis (azanediyl) bis (methan-) represented by the following formula [21] Synthesis of 1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (16.6 g, 115 mmol) and trimethyl orthoformate [2] (111 g) were added to a 300 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [20] (15.0 g, 52.4 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 20.8 g of Compound [21] (yield 67%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.23 (2H, s), 8.45 (2H, s), 7.51-7.47 (4H, m), 7.00-6.94 (4H, m), 4.01 (4H, t), 1.82-1.72 (4H, m), 1.67 (12H, s), 1.62-1.54 (2H, m).

<Synthesis Example 10>
Synthesis of Compound 1,3-bis (4-((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenethyl) urea represented by the following formula [23]

Meldrum acid [1] (28.6 g, 147 mmol) and trimethyl orthoformate [2] (200 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [22] (20.0 g, 67.0 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 40.3 g of Compound [23] (99% yield).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.17 (2H, d), 8.48 (2H, d), 7.40 (4H, d), 7.21 (4H, d), 5.89 (2H, t), 3.18 -3.14 (4H, m), 2.62 (4H, t), 1.62 (12H, s).

<Synthesis Example 11>
Compound 5,5 ′-(6,7,9,10,17,18,20,21-octahydrodibenzo [b, k] [1,4,7,10,13,16 represented by the following formula [25] ] Synthesis of hexaoxacyclooctadecine-2,13-diyl) bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (7.38 g, 51.2 mmol) and trimethyl orthoformate [2] (100 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [24] (10.0 g, 25.6 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 17.9 g of Compound [25] (yield 96%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.16 (2H, d), 8.50 (2H, d), 7.19 (2H, d), 7.01-6.98 (2H, m), 6.93 (2H, m) , 4.09-4.08 (4H, m), 4.04-4.02 (4H, m), 3.79 (8H, m), 1.61 (12H, s).

<Synthesis Example 12>
Compound 5-((3-((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzylamino) methylene) -2,2 represented by the following formula [27] Synthesis of -dimethyl-1,3-dioxane-4,6-dione

Meldrum acid [1] (23.6 g, 164 mmol) and trimethyl orthoformate [2] (100 g) were added to a 300 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 3-aminobenzylamine [26] (10.0 g, 81.9 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain 36.2 g of Compound [27] (yield 100%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.21 (1H, s), 10.04-9.97 (1H, m), 8.55 (1H, s), 8.30 (1H, d), 7.57 (1H, s) , 7.48-7.38 (2H, m), 7.23 (1H, d), 4.65 (2H, d), 1.63 (6H, s), 1.55 (6H, s).

<Synthesis Example 13>
Compound 5,5 ′-(4,4 ′-(propane-1,3-diyl) bis (piperidine-4,1-diyl)) bis (methan-1-yl-1 represented by the following formula [29] -ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (11.7 g, 81.0 mmol) and trimethyl orthoformate [2] (128 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 1,3-di-4-piperidylpropane [28] (8.52 g, 40.5 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 20.2 g of Compound [29] (yield 99%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 8.09 (2H, s), 4.06-3.97 (4H, m), 3.56-3.49 (2H, m), 3.28-3.25 (2H, m), 1.84- 1.81 (4H, m), 1.61-1.56 (12H, m), 1.32-1.23 (12H, m).

<Synthesis Example 14>
Compound 5,5 ′-(propane-1,3-diylbis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3 represented by the following formula [31] -dioxane-4,6-dione)

Meldrum acid [1] (42.8 g, 297 mmol) and trimethyl orthoformate [2] (150 g) were added to a 500 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, 1,3-diaminopropane [30] (10.0 g, 135 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 24.8 g of Compound [31] (yield 48%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 9.57-9.54 (2H, m), 8.16 (2H, d), 3.59 (4H, q), 2.11 (2H, quin), 1.71 (12H, s).

<Synthesis Example 15>
Compound 5,5 ′-(cyclohexane-1,3-diylbis (methylene)) bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl) represented by the following formula [33] -1,3-dioxane-4,6-dione)

Meldrum acid [1] (44.6 g, 309 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 1,3-bisaminomethylcyclohexane (cis- / trans-mixture) [32] (20.0 g, 141 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 58.3 g of compound [33] (cis- / trans-mixture) (yield) 92%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 9.63-9.60 (2H, m), 8.11-7.97 (2H, m), 3.51-3.12 (4H, m), 1.87-0.54 (22H, m).

<Synthesis Example 16>
Compound 5,5 ′-(5,8-dioxa-2,11-dithiadodecane-1,12-diylidene) bis (2,2-dimethyl-1,3-dioxane-4, represented by the following formula [35] 6-dione)

Meldrum acid [1] (13.6 g, 94.2 mmol) and trimethyl orthoformate [2] (134 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 3,6-dioxa-1,8-octanedithiol [34] (7.8 g, 42.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 20.8 g of Compound [35] (99% yield).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 9.29 (2H, s), 3.72 (4H, t), 3.57 (4H, s), 3.39-3.34 (4H, m), 1.66 (12H, s) .

<Synthesis Example 17>
Synthesis of compound 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzoic acid represented by the following formula [37]

Meldrum acid [1] (10.4 g, 72.3 mmol) and trimethyl orthoformate [2] (105 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, 3,5-diaminobenzoic acid [36] (5.0 g, 32.9 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 9.0 g of Compound [37] (yield 59%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.34 (2H, d), 8.74 (2H, d), 7.92 (2H, d), 1.69 (12H, s).

<Synthesis Example 18>
Compound 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) -N- (pyridin-3-ylmethyl) represented by the following formula [39] ) Synthesis of benzamide

Meldrum acid [1] (6.5 g, 45.4 mmol) and trimethyl orthoformate [2] (66 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [38] (5.0 g, 20.6 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 11.3 g of Compound [39] (yield 98%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.35 (2H, d), 9.27 (1H, t), 8.78 (2H, d), 8.59 (1H, d), 8.49-8.47 (1H, m) , 8.16-8.15 (1H, m), 7.84 (2H, d), 7.77-7.74 (1H, m), 7.40-7.36 (1H, m), 4.55 (2H, d), 1.69 (12H, s).

<Synthesis Example 19>
A compound represented by the following formula [41] N- (3- (1H-imidazol-1-yl) propyl) -3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3- synthesis of dioxan-5-ylidene) methylamino) benzamide

Meldrum acid [1] (10.1 g, 52.1 mmol) and trimethyl orthoformate [2] (50 g) were added to a 200 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [40] (5.0 g, 23.7 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 13.4 g of Compound [41] (yield 100%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.27 (2H, s), 8.71-8.65 (3H, m), 8.01 (1H, t), 7.99 (1H, t), 7.75 (2H, d) , 7.32 (1H, t), 7.05 (1H, t), 4.07-4.03 (2H, m), 3.25-3.18 (2H, m), 1.97 (2H, t), 1.64 (12H, s).

<Synthesis Example 20>
Synthesis of compound 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzyl furan-2-carboxylate represented by the following formula [43]

Meldrum acid [1] (13.7 g, 94.7 mmol) and trimethyl orthoformate [2] (100 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, Compound [42] (10.0 g, 43.1 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 21.1 g of Compound [43] (yield 90%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.22 (2H, d), 8.67 (2H, d), 7.94-7.93 (1H, m), 7.87-7.86 (1H, m), 7.46-7.45 ( 2H, m), 7.38 (1H, dd), 6.68-6.66 (1H, m), 5.28 (2H, s), 1.63 (12H, s).

<Synthesis Example 21>
Compound 5,5 ′-(4- (dodecyloxy) -1,3-phenylene) bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2- Synthesis of dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (10.8 g, 75.2 mmol) and trimethyl orthoformate [2] (100 g) were added to a 300 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [44] (10.0 g, 34.2 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 29.7 g of Compound [45] (99% yield).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.57 (1H, d), 11.20 (1H, d), 8.90 (1H, d), 8.64 (1H, d), 8.09 (1H, d), 7.31 (1H, dd), 7.13 (1H, d), 4.06 (2H, t), 1.74-1.68 (2H, m), 1.63 (12H, s), 1.46-1.40 (2H, m), 1.25-1.16 (16H , m), 0.79 (3H, t).

<Synthesis Example 22>
Compound 5,5 ′-(4- (octadecyloxy) -1,3-phenylene) bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2- Synthesis of dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (4.2 g, 29.2 mmol) and trimethyl orthoformate [2] (42 g) were added to a 100 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [46] (5.0 g, 13.3 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 6.4 g of Compound [47] (yield 71%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.63 (1H, d), 11.26 (1H, d), 8.99 (1H, d), 8.72 (1H, d), 8.19 (1H, d), 7.40 (1H, dd), 7.20 (1H, d), 4.13 (2H, t), 1.80-1.74 (2H, m), 1.68 (12H, s), 1.49-1.45 (2H, m), 1.25-1.22 (28H , m), 0.85 (3H, t).

<Synthesis Example 23>
Compound 5,5 ′-(4- (4- (trans-4-heptylcyclohexyl) phenoxy) -1,3-phenylene) bis (azanediyl) bis (methan-1-yl-1) represented by the following formula [49] -ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (4.2 g, 28.9 mmol) and trimethyl orthoformate [2] (41 g) were added to a 100 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [48] (5.0 g, 13.1 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain 9.0 g of Compound [49] (yield 98%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.64 (1H, d), 11.30 (1H, d), 9.03 (1H, d), 8.76 (1H, d), 8.31 (1H, d), 7.40 (1H, dd), 7.28 (2H, d), 7.03 (2H, d), 6.97 (1H, d), 1.81 (2H, d), 1.69 (10H, d), 1.44-1.34 (1H, m), 1.26-1.78 (10H, m), 1.07-1.01 (1H, m), 0.86 (3H, t).

<Synthesis Example 24>
Compound 5,5 ′-(4- (trans-4- (trans-4′-pentylbi (cyclohexan) -4-yl) phenoxy) -1,3-phenylene) bis (azanediyl) represented by the following formula [51] ) Synthesis of bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (9.0 g, 62.1 mmol) and trimethyl orthoformate [2] (120 g) were added to a 300 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [50] (12.3 g, 28.2 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 20.68 g of Compound [51] (yield 98%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.64 (1H, d), 11.30 (1H, d), 9.03 (1H, d), 8.76 (1H, d), 8.31 (1H, d), 7.39 (1H, dd), 7.27 (1H, d), 7.02 (2H, d), 6.97 (2H, d), 1.88-1.03 (43H, m), 0.86 (3H, t).

<Synthesis Example 25>
Compound 5,5 ′-(5-((trans-4- (trans-4′-pentylbi (cyclohexan) -4-yl) phenoxy) methyl) -1,3-phenylene) represented by the following formula [53] Synthesis of bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (19.0 g, 98.6 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [52] (20.0 g, 44.6 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 33.4 g of Compound [53] (yield 99%).
¹ H-NMR (400MHz, DMSO-d6, δppm): 11.29 (2H, d), 8.74 (2H, d), 7.94 (1H, s), 7.53 (2H, d), 7.12 (2H, d), 6.92 (2H, d), 5.09 (2H, s), 1.81-1.68 (20H, m), 1.36-0.84 (23H, m).

<Synthesis Example 26>
The compound represented by the following formula [55] 4′-pentylbi (trans-cyclohexan) -4-yl 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5- Synthesis of (ylidene) methylamino) benzoate

Meldrum acid [1] (13.3 g, 92.0 mmol) and trimethyl orthoformate [2] (150 g) were added to a 500 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [54] (15.0 g, 41.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 28.8 g of Compound [55] (99% yield).
¹ H-NMR (400MHz, DMSO-d6, δppm): 11.28 (2H, s), 8.67 (2H, s), 8.17 (1H, t), 7.86 (2H, d), 4.79-4.73 (1H, m) , 2.02 (2H, d), 1.74-1.64 (18H, m), 1.44-1.32 (2H, m), 1.29-0.76 (20H, m).

<Synthesis Example 27>
The compound represented by the following formula [57] N- (2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenyl) -4- ( synthesis of trans-4-pentylcyclohexyl) benzamide

Meldrum acid [1] (8.2 g, 56.7 mmol) and trimethyl orthoformate [2] (80 g) were added to a 300 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [56] (10.0 g, 25.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 16.0 g of Compound [57] (yield 92%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.36-11.27 (2H, m), 10.38 (1H, s), 8.80-8.74 (2H, m), 8.09 (1H, s), 7.87 (2H, d), 7.44 (1H, dd), 7.34 (2H, d), 2.51-2.46 (3H, m), 1.77 (2H, d), 1.66 (6H, s), 1.59 (6H, s), 1.50-1.37 (3H, m), 1.29-1.14 (8H, m), 0.99 (2H, q), 0.82 (3H, t).

<Synthesis Example 28>
A compound represented by the following formula [59] N- (2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenyl) -4- ( synthesis of trans-4-Heptylcyclohexyl) benzamide

Meldrum's acid [1] (11.7 g, 81.0 mmol) and trimethyl orthoformate [2] (150 g) were added to a 300 mL four-necked flask and heated under reflux for 1 hour. Thereafter, Compound [58] (15.0 g, 36.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 26.1 g of Compound [59] (yield 99%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.36-11.27 (2H, m), 10.38 (1H, s), 8.78 (2H, t), 8.10 (1H, s), 7.88 (2H, d) , 7.44 (1H, dd), 7.35 (3H, d), 2.52 (2H, t), 1.78 (2H, d), 1.65 (6H, s), 1.60 (6H, s), 1.50-1.37 (2H, m ), 1.29-1.12 (14H, m), 0.99 (2H, q), 0.82 (3H, t).

<Synthesis Example 29>
Compound 5,5 ′-(4-((3S, 8S, 9S, 10R, 13R, 14S, 17R) -10,13-dimethyl-17-((R) -5- methylhexan-2-yl) -2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta [a] phenanthren-3-yloxy)- Synthesis of 1,3-phenylene) bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (4.1 g, 29 mmol) and trimethyl orthoformate [2] (50 g) were added to a 100 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [60] (10.0 g, 13 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 9.9 g of Compound [61] (99% yield).

<Synthesis Example 30>
(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenethyl 3- (4- Synthesis of (decyloxy) phenyl) acrylate

Meldrum acid [1] (7.3 g, 37 mmol) and trimethyl orthoformate [2] (75 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [62] (7.46 g, 17 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 12.5 g of Compound [63] (yield 99%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.57 (1H, d), 11.29 (1H, s), 8.82 (1H, dd), 8.23 (1H, dd), 8.04 (1H, s), 7.57 -7.46 (5H, m), 6.92 (2H, d), 6.35 (1H, d), 4.34 (2H, t), 3.99 (2H, t), 1.74-1.65 (15H, m), 1.43-1.21 (15H , m), 0.85 (3H, t).

<Synthesis Example 31>
(E) -3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzyl 3- (4- Synthesis of (decyloxy) phenyl) acrylate

Meldrum's acid [1] (6.3 g, 33 mmol) and trimethyl orthoformate [2] (63 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [64] (6.3 g, 15 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 10.7 g of Compound [65] (99% yield).
¹ H-NMR (400MHz, DMSO-d6, δppm): 11.25 (1H, d), 8.71 (1H, d), 7.93 (1H, s), 7.67-7.62 (3H, m), 7.48 (2H, d) , 6.91 (2H, d), 6.52 (1H, d), 5.19 (2H, s), 3.96 (2H, t), 3.62-3.60 (2H, m), 1.68-1.63 (15H, m), 1.38-1.20 (15H, m), 0.81 (3H, t).

<Synthesis Example 32>
Synthesis of compound 5- (methoxymethylene) -2,2-dimethyl-1,3-dioxane-4,6-dione represented by the following formula [66]

Meldrum acid [1] (50.0 g, 347 mmol) and trimethyl orthoformate [2] (184 g) were added to a 500 mL four-necked flask and heated under reflux for 1 hour. After completion of the reaction, the solvent was removed by an evaporator, and the crude product was recrystallized from a hexane / tetrahydrofuran mixed solvent to obtain 43.7 g of Compound [66] (yield 68%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 8.16 (1H, s), 4.29 (3H, s), 1.73 (6H, s).

<Synthesis Example 33>
Synthesis of Compound 5-((dodecylamino) methylene) -2,2-dimethyl-1,3-dioxane-4,6-dione represented by Formula [68]

Meldrum acid [1] (21.4 g, 148 mmol) and trimethyl orthoformate [2] (250 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, dodecylamine [67] (25.0 g, 135 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 45.3 g of Compound [68] (yield 99%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 9.64 (1H, s), 8.10 (1H, d), 3.35-3.37 (2H, m), 1.54-1.48 (6H, m), 1.43-1.21 ( 20H, m), 0.85 (3H, t).

<Synthesis Example 34>
Synthesis of Compound 2,2-dimethyl-5-((octadecylamino) methylene) -1,3-dioxane-4,6-dione represented by Formula [70]

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (250 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, octadecylamine [69] (25.0 g, 93 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 38.9 g of Compound [70] (yield 99%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 9.67 (1H, s), 8.10 (1H, d), 2.89-2.47 (2H, m), 1.54-0.72 (38H, m), 0.85 (3H, t).

<Synthesis Example 35>
Compound 5,5 ′-(1,4-phenylenebis (methan-1-yl-1-ylidene)) bis (2,2-dimethyl-1,3-dioxane-4,6 represented by the following formula [72] -dione)

To a 500 mL four-necked flask were added terephthalaldehyde [71] (10.0 g, 75 mmol), Meldrum acid [1] (22.6 g, 157 mmol), and pyridine (150 g), and the mixture was stirred overnight at room temperature. Thereafter, pyridine was removed by an evaporator. Thereafter, the residue was dissolved in a 1,2-dichloroethane / methanol mixed solvent and crystallized by removing the solvent again with an evaporator. The obtained solid was recrystallized from 2-propanol to obtain 18.8 g of Compound [72] (yield 65%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 8.56 (2H, s), 7.96 (4H, s), 1.74 (12H, s).

<Synthesis Example 36>
Compound 5,5 ′-(1,3-phenylenebis (methan-1-yl-1-ylidene)) bis (2,2-dimethyl-1,3-dioxane-4,6 represented by the following formula [74] -dione)

Isophthalaldehyde [73] (10.0 g, 75 mmol), Meldrum acid [1] (22.6 g, 157 mmol), and pyridine (150 g) were added to a 500 mL four-necked flask and stirred overnight at room temperature. Thereafter, pyridine was removed by an evaporator. Thereafter, the residue was dissolved in a 1,2-dichloroethane / methanol mixed solvent and crystallized by removing the solvent again with an evaporator. The obtained solid was recrystallized from 2-propanol to obtain 16.2 g of Compound [74] (yield 56%).
¹ H-NMR (400MHz, DMSO-d6, δppm): 8.55 (2H, s), 7.80-7.76 (2H, m), 7.52-7.42 (1H, m), 1.74 (6H, s), 1.72 (6H, s).

<Synthesis Example 37>
Compound represented by the following formula [78] tris (4-((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) phenyl) benzene-1,3,5- Synthesis of tricarboxylate

4-Hydroxybenzaldehyde [76] (35.7 g, 292 mmol), triethylamine (31.5 g, 311 mmol), and tetrahydrofuran (150 g) were added to a 1 L four-necked flask, and the internal temperature was cooled to 10 ° C. or lower. . Thereto was added dropwise a solution of 1,3,5-benzenetricarbonyltrichloride [75] (25.0 g, 94 mmol) in tetrahydrofuran (225 g) while paying attention to heat generation. After completion of the dropwise addition, the reaction was further performed at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into pure water (2250 g), and the precipitated solid was filtered, washed with methanol, and the solid was dried to obtain 48.0 g of Compound [77] (yield 98%).

Compound [77] (48.0 g, 92 mmol), Meldrum acid [1] (56.2 g, 289 mmol), and pyridine (720 g) were added to a 2 L four-necked flask, and the mixture was stirred overnight at room temperature. Thereafter, pyridine was removed by an evaporator. Thereafter, the residue was recrystallized from a tetrahydrofuran / hexane mixed solvent to obtain 75.6 g of Compound [78] (yield 91%).
¹ H-NMR (400MHz, DMSO-d6, δppm): 8.57-8.55 (3H, m), 8.38 (3H, s), 7.83-7.81 (6H, m), 7.42-7.39 (6H, m), 1.74 ( 18H, s).

<Synthesis Example 38>
Synthesis of compound 5- (1-hydroxypentylidene) -2,2-dimethyl-1,3-dioxane-4,6-dione represented by the following formula [80]

To a 200 L four-necked flask, valeric acid [79] (25.0 g, 245 mmol), dichloromethane 200 g) was added, N, N-dimethylaminopyridine (DMAP: 32.6 g, 267 mmol), dicyclohexylcarbidiimide (DCC: 55). 0.6 g, 270 mmol) and Meldrum's acid [1] (35.3 g, 245 mmol) were added, and the mixture was stirred at room temperature overnight. After completion of the reaction, the solid content was filtered using Celite, and the filtrate was concentrated with an evaporator. The crude product was dissolved in ethyl acetate (300 g) and washed with 1M hydrochloric acid. The organic layer was dried over magnesium sulfate, filtered and evaporated to obtain 53.6 g of Compound [80] (yield 96%).
¹ H-NMR (400MHz, CDCl3, δppm): 3.09-3.01 (2H, m), 1.70 (6H, s), 1.70-1.53 (2H, m), 1.41 (2H, q), 0.92 (3H, t) .

<Synthesis Example 39>
Synthesis of compound 5- (1-hydroxytetradecylidene) -2,2-dimethyl-1,3-dioxane-4,6-dione represented by the following formula [82]

Meldrum acid [1] (25.0 g, 173 mmol), pyridine (27.4 g, 346 mmol), and dichloromethane (250 g) were added to a 200 L four-necked flask, and the solution was cooled to 0 ° C. under a nitrogen atmosphere. Thereto was added myristic acid chloride [81] (42.7 g, 173 mmol) dropwise while paying attention to heat generation. After completion of the dropping, the reaction solution was returned to room temperature and further stirred for 1 hour. After completion of the reaction, the organic layer was washed with 1M hydrochloric acid, pure, and saturated saline in this order, and dried over magnesium sulfate. This solution was filtered, the solvent was distilled off, and the column was purified (hexane / ethyl acetate) to obtain 29.1 g of Compound [82] (yield 66%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 3.09-3.04 (2H, m), 1.72 (6H, s), 1.72-1.65 (2H, m), 1.46-1.34 (2H, m), 1.26 (18H, s), 0.88 (3H, t).

<Synthesis Example 40>
Synthesis of compound 5- (3,5-dimethoxybenzyl) -2,2-dimethyl-1,3-dioxane-4,6-dione represented by the following formula [84]

Meldrum acid [1] (5 g, 28.9 mmol), 3,5-dimethoxybenzaldehyde (4.70 g, 28.3 mmol) and ethanol (50 g) were added to a 200 L four-necked flask, and pyridinium acetate (0.42 g) was added. 2.89 mmol) was added and stirred for 30 minutes.

Thereafter, the reaction solution was cooled to 0 ° C., sodium cyanoborohydride (2.7 g, 43.4 mmol) was added little by little, and then the reaction temperature was returned to room temperature. After completion of the reaction, while quenching the generated gas, the reaction was quenched with 10% hydrochloric acid, and then ethanol was distilled off. The crude was resuspended in 10% hydrochloric acid and extracted three times with dichloromethane (80 g). The organic layers were combined, dried over magnesium sulfate, filtered, evaporated, and the resulting crude product was recrystallized from methanol to obtain 4.7 g of Compound [84] (yield 55%). .
¹ H-NMR (400MHz, CDCl3, δppm): 6.44 (2H, d), 6.29 (1H, t), 3.73 (1H, t), 3.36 (2H, d), 1.69 (3H, s), 1.51 (3H , s).

<Synthesis Example 41>
Synthesis of compound 5- (3,5-dimethoxybenzyl) -2,2-dimethyl-5- (pyridin-4-ylmethyl) -1,3-dioxane-4,6-dione represented by the following formula [86]

To a 200 L four-necked flask, compound [84] (4.70 g, 16.0 mmol), potassium carbonate (3.31 g, 24.0 mmol), dimethylformamide (DMF) (50 g) was added, and 4- (bromomethyl) pyridine was added. A solution of hydrobromide (4.45 g, 17.6 mmol) in DMF (10 g) was added dropwise. After completion of the reaction, the reaction solution was poured into pure water (600 g) and extracted three times with ethyl acetate (150 g). Next, the organic layers were combined and washed with saturated sodium hydrogen carbonate and saturated brine, and then the organic layer was dried over magnesium sulfate. Thereafter, the solution was filtered, the solvent was distilled off, and the crude product was recrystallized from methanol to obtain 4.4 g of Compound [86] (yield 72%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 8.51 (2H, d), 7.10 (2H, d), 6.72-6.66 (3H, m), 3.82 (3H, s), 3.80 (3H, s), 3.39 (2H, s), 0.73 (3H, s), 0.68 (3H, s).

<Synthesis Example 42>
Synthesis of the compound benzyl 3- (2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl) propanoate represented by the following formula [88]

Meldrum acid [1] (15.0 g, 104 mmol) and acetonitrile (150 g) were added to a 200 L four-necked flask, and potassium carbonate (14.3 g, 104 mmol) and benzyltriethylammonium chloride (23.9 g, 104 mmol) were added. And stirred at room temperature for 15 minutes. Thereafter, compound [87] (25.3 g, 156 mmol) was added, and the mixture was heated and stirred at 60 ° C. After completion of the reaction, the solvent was distilled off, the crude product was dissolved in ethyl acetate (150 g), washed 3 times with 10% potassium hydrogen sulfate, and the organic layer was dried over magnesium sulfate. The solution was filtered and the solvent was distilled off, and then the obtained crude product was subjected to column purification (SiO ₂ : hexane / ethyl acetate) to obtain 28.4 g of Compound [88] (yield 89%).
¹ H-NMR (400MHz, CDCl3, δppm): 7.38-7.29 (5H, m), 5.08 (2H, s), 3.89 (1H, t), 2.67 (2H, t), 2.44-2.34 (2H, m) , 1.73 (3H, s), 1.72 (3H, s).

<Synthesis Example 43>
Compound (S) -tert-butyl 2- (tert-butoxycarbonylamino) -5- (2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl) represented by the following formula [90] Synthesis of pentanoate

Meldrum acid [1] (15.0 g, 104 mmol), DMAP (18.4 g, 151 mmol), compound [89] (28.4 g, 94 mmol) and dichloromethane (100 g) were added to a 200 L four-necked flask, and the reaction solution was added. After cooling to 0 ° C., a solution of DCC (22.5 g, 109 mmol) in dichloromethane (50 g) was added and stirred overnight. After completion of the reaction, the solid was removed by filtration, and the filtrate was washed 3 times with 10% potassium hydrogen sulfate and saturated brine, and the organic layer was dried over magnesium sulfate. Then acetic acid (50 mL) was added to acidify the solution and cooled to 0 ° C. Sodium borohydride (9.0 g, 236 mmol) was added in portions and further stirred at 0 ° C. After completion of the reaction, the mixture was washed with saturated brine and pure water, the organic layer was dried over magnesium sulfate, the solution was filtered, and the solvent was distilled off to obtain a crude product. This crude product was subjected to column purification (SiO ₂ : hexane / ethyl acetate) to obtain 34.1 g of Compound [90] (yield 79%).
¹ H-NMR (400MHz, CDCl3, δppm): 5.04 (1H, d), 4.20-4.08 (1H, m), 3.52 (1H, t), 2.20-2.00 (2H, m), 1.89-1.40 (4H, m), 1.77 (3H, s), 1.73 (3H, s), 1.43 (9H, s), 1.41 (9H.s).

<Synthesis Example 44>
Synthesis of Compound 5- (bis (methylthio) methylene) -2,2-dimethyl-1,3-dioxane-4,6-dione represented by Formula [92]

Meldrum acid [1] (40.9 g, 284 mmol), triethylamine (57.5 g, 568 mmol) and DMSO (140 g) were added to a 200 mL four-necked flask, followed by carbon disulfide (21.6 g, 284 mmol). And stirred at room temperature for 1 hour. Thereafter, the reaction solution was ice-cooled, methyl iodide (80.6 g, 568 mmol) was gradually added, and the reaction was further performed at room temperature. After completion of the reaction, the reaction solution was poured into ice water (250 g), and the precipitated solid was filtered and washed with hexane to obtain 36.7 g of Compound [92] (yield 52%).
¹ H-NMR (400MHz, CDCl3, δppm): 2.57 (6H, s), 1.53 (6H, s).

<Synthesis Example 45>
Synthesis of a compound represented by the following formula [94] 2,2-dimethyl-5- (methylthio (neopentylamino) -methylene) -1,3-dioxane-4,6-dione

Compound [92] (18.6 g, 75 mmol), 2,2-dimethylpropylamine (6.53 g, 75 mmol) and THF (180 g) were added to a 200 mL four-necked flask, and the mixture was stirred at room temperature. After completion of the reaction, the solvent was concentrated to about half by an evaporator, diethyl ether (100 g) was added, the precipitated solid was filtered, and recrystallized from a THF / diethyl ether mixed solvent to obtain Compound [94] 16 0.9 g was obtained (yield 77%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 3.11 (2H, d), 2.58 (3H, s), 1.73 (6H, s).

<Synthesis Example 46>
Synthesis of Compound 2,2-dimethyl-5- (methylthio (neopentylamino) -methylene) -1,3-dioxane-4,6-dione represented by Formula [95]

To a 200 mL four-necked flask, compound [92] (2.42 g, 10 mmol), 2,2-dimethylpropylamine (2.62 g, 30 mmol), and ethanol (60 g) were added and heated to reflux. After completion of the reaction, the mixture was concentrated with an evaporator until the solvent was reduced to about half, diethyl ether (50 g) was added, and the mixture was cooled to 0 ° C. to precipitate a solid. Thereafter, the solid was filtered and recrystallized from a THF / diethyl ether mixed solvent to obtain 1.62 g of Compound [95] (yield 50%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 9.83 (2H, s), 3.10 (2H, d), 1.61 (6H, s), 0.96 (18H, s).

<Synthesis Example 47>
Compound 5,5 ′-(1,8-dihydroxyoctane-1,8-diylidene) -bis (2,2-dimethyl-1,3-dioxane-4,6-dione) represented by the following formula [97] Composition

Meldrum acid [1] (14.7 g, 11 mmol), pyridine (19.87 g, 0.26 mmol), and dichloromethane (200 g) were added to a 200 mL four-necked flask, and the reaction solution was cooled to 0 ° C. A solution of dichloride [96] (11.98 g, 51 mmol) in dichloromethane (50 g) was gradually added while paying attention to heat generation, and further reaction was carried out at 23 ° C. After completion of the reaction, the solution was acidified with a 10% aqueous hydrochloric acid solution, and the solvent was distilled off with an evaporator. Thereafter, the solid was filtered, washed with pure water, and recrystallized from a mixed solvent of dichloromethane / diethyl ether to obtain 16.6 g of Compound [97] (yield 78%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 15.30 (2H, s), 3.09 (4H, t), 1.73 (12H, s), 1.66 (4H, m), 1.47 (4H, m).

<Synthesis Example 48>
5,5 ′-((((6,7,9,10,17,18,20,21-octahydrodibenzo [b, k] [1,4,7,10,13, Synthesis of 16] hexaoxacyclooctadecine-2,14-diyl) bis (azanediyl)) bis (methanylylidene)) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (4.87 g, 33.8 mmol) and trimethyl orthoformate [2] (60 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, Compound [98] (6.00 g, 15.4 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain 10.4 g of Compound [99] (yield 97%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.21 (2H, d), 8.54 (2H, d), 7.26 (2H, d), 7.05 (2H, dd), 6.96 (2H, d), 4.15 -4.06 (8H, m), 3.88-3.80 (6H, m), 3.17 (2H, d), 1.67 (12H, s).

<Synthesis Example 49>
5,5 ′-((1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diyl) bis (methanylylidene)) bis (2,2-dimethyl) represented by the following formula [101] -1,3-dioxane-4,6-dione)

Meldrum acid [1] (24.17 g, 167.7 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [100] (20.00 g, 76.2 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 43.2 g of Compound [101] (yield 100%).

<Synthesis Example 50>
5,5 ′-((((((oxybis (ethane-2,1-diyl)) bis (oxy)) bis (4,1-phenylene)) bis (azanediyl)) bis represented by the following formula [103] Synthesis of (methanylylidene)) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

Meldrum acid [1] (22.00 g, 153 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [102] (20.00 g, 69.4 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 40.2 g of Compound [103] (yield 97%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.23 (2H, d), 8.44 (2H, d), 7.50-7.48 (2H, m), 7.01-6.99 (4H, m), 4.42-4.12 ( 4H, m), 3.89-3.78 (4H, m), 1.67 (12H, s).

<Synthesis Example 51>
2- (methacryloyloxy) ethyl3,5-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) benzoate represented by the following formula [105] Composition

Meldrum acid [1] (24.18 g, 168 mmol) and trimethyl orthoformate [2] (300 g) were added to a 500 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [104] (20.00 g, 76.3 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, hexane was added and filtered, followed by drying to obtain 43.7 g of Compound [105] (yield 100%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.36 (2H, d), 8.72 (2H, d), 7.80 (2H, d), 7.37 (1H, t), 6.17 (1H, t), 5.64-5.62 (1H, m), 4.67-4.65 (2H, m), 4.55-4.52 (2H, m), 3.79 (1H, s), 3.47 (1H, s), 3.34 (2H, s), 1.97-1.96 (3H , m), 1.78-1.76 (13H, m).

<Synthesis Example 52>
(E) -2,4-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- represented by the following formula [107] Synthesis of (4'-butoxy- [1,1'-biphenyl] -4-yl) acrylate

Meldrum acid [1] (4.00 g, 20.4 mmol) and trimethyl orthoformate [2] (40 g) were added to a 100 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [106] (4.00 g, 9.3 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 6.8 g of Compound [107] (99% yield).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.59 (1H, d), 11.29 (1H, d), 8.84 (1H, d), 8.78 (1H, d), 8.23 (1H, s), 8.04 (1H , s), 7.70-7.64 (7H, m), 7.62 (1H, d), 7.48 (2H, s), 7.03 (2H, d), 6.53 (1H, d), 4.41 (2H, t), 4.01 ( 2H, t), 3.66-3.63 (6H, m), 1.68-1.57 (10H, m), 1.56 (1H, s), 1.44-1.39 (1H, m), 0.94 (3H, t).

<Synthesis Example 53>
(E) -2,4-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- represented by the following formula [109] Synthesis of (4-cyclohexylphenyl) acrylate

Meldrum acid [1] (4.35 g, 30 mmol) and trimethyl orthoformate [2] (50 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [108] (5.00 g, 14 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 9.63 g of Compound [109] (yield 99%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.63 (1H, d), 11.30 (1H, d), 8.64-8.63 (2H, m), 7.60 (1H, d), 7.42-7.39 (3H, m) , 7.29-7.27 (2H, m), 7.21-7.15 (3H, m), 6.37 (1H, d), 4.49-4.46 (2H, m), 3.33-3.11 (2H, m), 2.59-2.42 (1H, m), 1.86-1.45 (2H, m), 1.76-1.70 (14H, m), 1.42-1.20 (6H, m).

<Synthesis Example 54>
(E) -2,4-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- represented by the following formula [111] Synthesis of (4-([trans-1,1'-bi (cyclohexan)]-4-yl) phenyl) acrylate

Meldrum acid [1] (2.84 g, 20 mmol) and trimethyl orthoformate [2] (40 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [110] (4.00 g, 9.0 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 6.6 g of Compound [111] (yield 99%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.63 (1H, d), 11.30 (1H, d), 8.67-8.60 (2H, m), 7.60 (1H, d), 7.41-7.39 (3H, m) , 7.26-7.14 (4H, m), 6.36 (1H, d), 4.48 (2H, t), 3.12 (2H, t), 2.52-2.45 (1H, m), 1.91-1.70 (24H, m), 1.52 -1.01 (8H, m).

<Synthesis Example 55>
(E) -4-(((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- (4- Synthesis of (cyclohexylphenyl) acrylate

Meldrum acid [1] (2.7 g, 19 mmol) and trimethyl orthoformate [2] (30 g) were added to a 200 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [112] (3.00 g, 8.6 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain 4.22 g of Compound [113] (yield 99%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.25 (1H, d), 8.62 (1H, d), 7.64 (1H, d), 7.44 (2H, d), 7.32 (2H, d), 7.24-7.19 (4H, m), 6.36 (1H, d), 4.42 (2H, t), 3.03 (2H, t), 1.87-1.38 (17H, m).

<Synthesis Example 56>
(E) -2,4-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- represented by the following formula [115] Synthesis of (4- (trans-4-pentylcyclohexyl) phenyl) acrylate

Meldrum acid [1] (13.55 g, 69.8 mmol) and trimethyl orthoformate [2] (140 g) were added to a 300 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [114] (13.79 g, 31.7 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain 22.4 g of Compound [115] (yield 95%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.63 (1H, d), 11.27 (1H, d), 8.68-8.57 (2H, m), 7.41-7.39 (3H, m), 7.26-7.14 (4H, m), 6.36 (1H, d), 4.48 (2H, t), 3.80-3.76 (3H, m), 3.48 (2H, d), 3.34 (1H, s), 3.12 (2H, d), 2.47 (2H , t), 1.86 (6H, d), 1.77-1.68 (10H, m), 1.47-1.20 (10H, m), 1.06-0.90 (5H, m).

<Synthesis Example 57>
(E) -2,4-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- represented by the following formula [117] Synthesis of (4- (trans-4-heptylcyclohexyl) phenyl) acrylate

Meldrum acid [1] (3.43 g, 23.8 mmol) and trimethyl orthoformate [2] (50 g) were added to a 100 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [116] (5.00 g, 10.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 8.3 g of Compound [117] (yield 100%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.64 (1H, d), 11.28 (1H, d), 8.70-8.63 (2H, m), 7.61 (1H, d), 7.45-7.40 (3H, m) , 7.27-7.15 (3H, m), 6.37 (1H, d), 4.46 (2H, t), 3.60 (2H, d), 3.12 (2H, t), 2.34 (1H, t), 1.87 (4H, d ), 1.85-1.75 (15H, m), 1.42-1.38 (2H, m), 1.33-1.26 (10H, m), 1.07-1.02 (2H, m), 0.89 (3H, t).

<Synthesis Example 58>
(E) -3,5-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) benzyl 3- represented by the following formula [119] Synthesis of (4- (trans-4-pentylcyclohexyl) phenyl) acrylate

Meldrum acid [1] (11.31 g, 78.5 mmol) and trimethyl orthoformate [2] (150 g) were added to a 300 mL four-necked flask, and the mixture was heated to reflux for 1 hour. Thereafter, compound [118] (15.00 g, 35.7 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 25.3 g of Compound [119] (yield 99%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.30 (2H, d), 8.66 (2H, d), 7.74 (1H, d), 7.49 (2H, d), 7.26-7.19 (4H, m), 7.08 (1H, d), 6.49 (1H, d), 5.27 (2H, s), 2.49 (1H, t), 1.93-1.77 (18H, m), 1.65-0.87 (14H, m).

<Synthesis Example 59>
(E) -3,5-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) benzyl 3- represented by the following formula [121] Synthesis of (4- (trans-4'-pentyl- [1,1'-bi (cyclohexan)]-4-yl) phenoxy) acrylate

Meldrum acid [1] (1.83 g, 12.7 mmol) and trimethyl orthoformate [2] (45 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [120] (3.00 g, 5.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 4.8 g of Compound [121] (yield 100%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.27 (2H, d), 8.64 (2H, d), 7.85 (1H, d), 7.21 (2H, d), 7.14 (2H, d), 7.10-7.09 (1H, m), 7.00-6.98 (2H, m), 5.57 (1H, d), 5.19 (2H, s), 3.81 (1H, s), 3.47-3.46 (1H, m), 3.33 (4H, s ), 1.91-1.72 (20H, m), 1.41-0.84 (13H, m).

<Synthesis Example 60>
(E) -4-(((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenyl 3- (4- Synthesis of (trans-4-pentylcyclohexyl) phenyl) acrylate

Meldrum acid [1] (3.64 g, 25 mmol) and trimethyl orthoformate [2] (90 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [122] (9.00 g, 23 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 12.1 g of Compound [123] (yield 99%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.28 (1H, d), 8.61 (1H, d), 7.85 (1H, d), 7.52 (2H, d), 7.29-7.26 (5H, m) , 6.54 (1H, d), 2.52 (1H, t), 1.89 (4H, d), 1.57-0.89 (22H, t).

<Synthesis Example 61>
(E) -4-(((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- (4- Synthesis of (trans-4-pentylcyclohexyl) phenyl) acrylate

Meldrum acid [1] (2.00 g, 14 mmol) and trimethyl orthoformate [2] (75 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [124] (4.92 g, 13 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 7.16 g of Compound [125] (yield 100%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 11.24 (1H, d), 8.62 (1H, d), 7.63 (1H, d), 7.44 (2H, d), 7.32 (2H, d), 7.24-7.19 (4H, m), 6.36 (1H, d), 4.42 (2H, t), 3.03 (2H, t), 2.48 (1H, t), 1.87 (4H, d), 1.76 (6H, s), 1.49- 1.21 (1H, m), 1.07-1.00 (2H, m), 0.97 (3H, t).

<Synthesis Example 62>
Synthesis of 5-(((4-dodecylphenyl) amino) methylene) -2,2-dimethyl-1,3-dioxane-4,6-dione represented by the following formula [127]

Meldrum acid [1] (12.13 g, 84.2 mmol) and trimethyl orthoformate [2] (100 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, compound [126] (20.00 g, 76.5 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 31.1 g of Compound [127] (yield 98%).
¹ H-NMR (400MHz, DMSO-d6, δppm): 11.24 (1H, d), 8.50 (1H, d), 7.41 (2H, d), 7.20 (2H, d), 2.53 (2H, t), 2.27 -2.46 (1H, m), 1.63 (6H, s), 1.52-1.47 (2H, m), 1.29-1.86 (17H, m), 0.83 (3H, t).

<Synthesis Example 63>
5-(((4- (1,1,2,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoroheptyl)) represented by the following formula [129] Synthesis of amino) methylene) -2,2-dimethyl-1,3-dioxane-4,6-dione

Meldrum acid [1] (3.10 g, 22 mmol) and trimethyl orthoformate [2] (20 g) were added to a 200 mL four-necked flask and heated under reflux for 1 hour. Thereafter, Compound [128] (10.00 g, 19.6 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with an evaporator and dried to obtain 12.6 g of Compound [129] (yield 100%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 11.60 (1H, d), 8.70 (1H, d), 7.68 (2H, d), 7.39 (2H, d), 1.77 (6H, s).

[Synthesis of polyamic acid or polyimide and preparation of the solution]
Abbreviations used below are as follows.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

(Diamine)
p-PDA: p-phenylenediamine DDM: 4,4′-diaminodiphenylmethane PCH7AB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

(Organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

(Measurement of molecular weight)
In this example, the molecular weight of the polymer (polyamic acid, polyimide, etc.) was determined by using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and a column manufactured by Shodex (KD-803, KD-805). ) And was measured as follows.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 ml / L)
Flow rate: 1.0 mL / minute standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratory ( Molecular weight about 12,000, 4,000, 1,000).

(Measurement of imidization rate)
In this example, the imidization ratio of polyimide was measured as follows.
About 20 mg of polyimide powder was placed in an NMR sample tube, about 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added, and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz by means of NMR measurement. The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and a peak integrated value of this proton and a proton peak integrated value derived from the NH group of the amic acid that appears near 10.0 ppm. The following formula was used. In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%). It is the number ratio of the reference proton to one.
Imidization rate (%) = (1−α · x / y) × 100

<Synthesis of polyamic acid (PAA-1) and preparation of its solution>
In a 100 mL four-necked flask, 7.93 g (40 mmol) of DDM and NMP (20 g) were added and dissolved, and then cooled to about 10 ° C., a slurry solution of 7.46 g (38 mmol) of CBDA in NMP (67 g) was added, and Then, the reaction was performed in a nitrogen atmosphere for 6 hours to obtain a 15% by mass solution of polyamic acid (PAA-1).

88 g of a 15% by weight solution of this polyamic acid (PAA-1) was transferred to a 200 mL Erlenmeyer flask, diluted by adding 87.6 g of NMP and 43.8 g of BCS, and 6% by weight of polyamic acid (PAA-1). A polyamic acid (PAA-1) solution containing 74% by mass of NMP and 20% by mass of BCS was prepared. The number average molecular weight of this polyamic acid (PAA-1) was 12,081, and the weight average molecular weight was 30,449.

<Synthesis of polyamic acid (PAA-2) and preparation of its solution>
In a 200 mL four-necked flask, 8.65 g (80 mmol) of p-PDA and NMP (49 g) were added and dissolved, then cooled to about 10 ° C., and a slurry solution of 14.1 g (72 mmol) of CBDA and NMP (80 g) was added. The solution was returned to room temperature and reacted in a nitrogen atmosphere for 6 hours to obtain a 15% by mass solution of polyamic acid (PAA-2).

125 g of a 15% by weight solution of this polyamic acid (PAA-2) was transferred to a 300 mL Erlenmeyer flask, diluted by adding 118.5 g of NMP and 60.9 g of BCS, and 6% by weight of polyamic acid (PAA-2) A polyamic acid (PAA-2) solution containing 74% by mass of NMP and 20% by mass of BCS was prepared. The number average molecular weight of this polyamic acid (PAA-2) was 7,609, and the weight average molecular weight was 15,837.

<Synthesis of polyamic acid (PAA-3) and preparation of its solution>
In a 200 mL four-necked flask, p-PDA 8.05 g (74 mmol), PCH7AB 2.13 g (5.6 mmol) and NMP (118 g) were added and dissolved, and then cooled to about 10 ° C., and CBDA 14.1 g (72 mmol). ) NMP (100 g) slurry solution was added, and the mixture was returned to room temperature and reacted in a nitrogen atmosphere for 6 hours to obtain a polyamic acid (PAA-3) solution having a concentration of 10 mass%.

234 g of this polyamic acid (PAA-3) solution having a concentration of 10% by mass was transferred to a 300 mL Erlenmeyer flask, diluted by adding 70.8 g of NMP and 76.2 g of BCS, and 6% by mass of polyamic acid (PAA-3). A polyamic acid (PAA-3) solution containing 74% by mass of NMP and 20% by mass of BCS was prepared. The number average molecular weight of this polyamic acid (PAA-3) was 6,092, and the weight average molecular weight was 12,002.

<Synthesis of Soluble Polyimide (SPI-1) and Preparation of Solution>
BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 63 mmol) and PCH7AB (10.3 g, 27 mmol) were mixed in NMP (100 g) in a 300 mL four-necked flask and reacted at 40 ° C. for 3 hours. Then, CBDA (4.1 g, 21 mmol) and NMP (52 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (130 g) and diluting to 6% by mass, acetic anhydride (16 g) and pyridine (12 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. This reaction solution was put into methanol (1.6 L), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (SPI-1). The imidation ratio of this polyimide was 54%, the number average molecular weight was 18,300, and the weight average molecular weight was 45,300. The amount of carboxyl groups in this polyimide is 0.92 with respect to the repeating unit.

NMP (98 g) and BCS (90 g) are added to the polyimide powder (SPI-1) (12.0 g) obtained above and dissolved by stirring at 80 ° C. for 40 hours to obtain a soluble polyimide (SPI-1) solution. Produced.

[Preparation of polyimide film forming coating liquid (liquid crystal aligning agent)]
<Examples 1 to 10>
To the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compounds described in the following Table 1 prepared as the modifying compound in the above synthesis example were respectively added to the solid polyamic acid (PAA-1) solution. The coating solution for forming a polyimide film of Examples 1 to 10 was added at 10% by mole (ie, polyamic acid (PAA-1)) and stirred at room temperature (25 ° C.) until a uniform solution was obtained. (Functional polymer film-forming coating solution) was prepared.

<Examples 11 to 45>
To the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compounds described in the following Table 2 prepared as the modifying compound in the above synthesis example were respectively added to the solid polyamic acid (PAA-1) solution. In order to achieve the ratio shown in Table 2 below with respect to the minute (that is, polyamic acid (PAA-1)), the mixture was stirred at room temperature until a uniform solution was obtained. A liquid was prepared.

<Examples 46 to 57>
To the polyamic acid (PAA-2) solution (10.0 g) prepared above, the compounds described in the following Table 3 prepared as the modifying compound in the above synthesis example were respectively added to the solid polyamic acid (PAA-2) solution. The coating solution for forming a polyimide film of Examples 46 to 57 was prepared by adding at 10 mol% with respect to the amount (that is, polyamic acid (PAA-2)) and stirring at room temperature until a uniform solution was obtained.

<Examples 58 to 71>
In the polyamic acid (PAA-3) solution (40.0 g) prepared above, the compounds described in the following Table 4 prepared as the modifying compound in the above synthesis example were respectively added to the solid polyamic acid (PAA-3) solution. In order to achieve the mass% described in Table 4 with respect to the fraction (that is, polyamic acid (PAA-3)), the mixture was stirred at room temperature until a uniform solution was obtained. A liquid was prepared.

<Examples 72 to 74>
In the polyamic acid (PAA-2) solution (70.0 g) prepared above, the compounds described in the following Table 5 prepared as the modifying compound in the above synthesis example were respectively added to the solid polyamic acid (PAA-2) solution. In order to achieve the ratio shown in Table 5 below with respect to the minute (that is, polyamic acid (PAA-2)), the mixture was stirred at room temperature until a uniform solution was obtained. A liquid was prepared.

<Examples 75 to 90>
In the soluble polyimide (SPI-1) solution (10.0 g) prepared above, the compounds described in the following Table 6 prepared as the modifying compound in the above synthesis example were respectively solidified in the soluble polyimide (SPI-1) solution. For the polyimide film formation of Examples 75 to 90, the mixture was added to the minute (ie soluble polyimide (SPI-1)) so as to have the ratio shown in Table 6 below, and stirred at room temperature until a uniform solution was obtained. A coating solution was prepared.

<Examples 91 to 102 and Comparative Example 1> [Confirmation test of crosslinking effect (stripping test)]
The polyimide film forming coating solutions of Examples 75 to 86 were spin coated (2500 rpm / 30 seconds) on a silicon wafer and baked on a hot plate at 230 ° C. for 30 minutes to form a coating film [a1]. The film thickness of the obtained coating film [a1] was measured using Surfcorder ET4000M manufactured by Kosaka Laboratory Ltd. Next, the silicon wafer on which the coating film [a1] is formed is set again on the spin coater, NMP is dropped until the entire surface of the silicon wafer is covered, and left for 60 seconds, and then NMP is spin-dried (1500 rpm / 30). Second) and baked on a hot plate at 100 ° C. for 30 seconds, and the remaining film was used as a coating film [a2]. The film thickness of this coating film [a2] was measured again, and the remaining film ratio was calculated based on the following calculation formula. As Comparative Example 1, the same applies to the soluble polyimide (SPI-1) solution produced above, that is, the soluble polyimide solution not containing the modifying compounds represented by the above formulas [A] to [D]. The operation was performed and the remaining film ratio was calculated. The results are shown in Table 7.
Remaining film ratio (%) = film thickness of coating film [a2] / film thickness of coating film [a1] × 100

As a result, it was confirmed that the solvent resistance of the coating film (polyimide film) can be improved by using the polyimide film forming coating liquid (liquid crystal alignment treatment agent) to which the modifying compound is added. Therefore, it can be said that the modifying compound was introduced into the soluble polyimide. In Examples 75 to 85 using the modifying compound represented by the above formula [A] having two or more Meldrum's acids, the residual film ratio was particularly high. It is estimated that it was bridge | crosslinked by the compound for a modification represented by these. Furthermore, it was confirmed that the solubility of the coating film can be controlled relatively freely by appropriately selecting the modifying compound represented by the formula [A] to be added.

In the same manner, when a coating film was formed using the polyimide film-forming coating liquids of Examples 1 to 74 and Examples 87 to 90 and a stripping test was performed, it was found that no modifier compound was added. In comparison, it was confirmed that the solvent resistance of the polyimide film can be improved by using a polyimide film-forming coating solution to which the remaining film ratio is increased and a modifying compound is added.

[Production of liquid crystal alignment film and liquid crystal cell]
Using the polyimide film forming coating solution (liquid crystal aligning agent) prepared in each of the above examples, a liquid crystal cell was prepared as follows.

A polyimide film-forming coating solution (liquid crystal aligning agent) is spin-coated on a glass substrate or a glass substrate with an ITO transparent electrode, dried on a hot plate at 80 ° C. for 70 seconds, and then subjected to a predetermined baking condition with a film thickness of 100 nm. A coating film was formed.

Then, about the liquid crystal aligning process by rubbing, this coating-film surface was rubbed on the predetermined rubbing conditions using the rayon cloth with the rubbing apparatus with a roll diameter of 120 mm, and the board | substrate with the liquid crystal aligning film V was obtained. For liquid crystal alignment treatment by light, linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm ⁻² ) was changed between 0 mJ and 1000 mJ on the coating surface, and the normal line of the plate was changed. This was performed by irradiating at an angle of 40 °. The linearly polarized light UV was prepared by passing a 313 nm band pass filter through the ultraviolet light of a high pressure mercury lamp and then passing it through a 313 nm polarizing plate.

After preparing two substrates with a liquid crystal alignment film subjected to the liquid crystal alignment treatment in this manner, a spacer of 6 μm is sprayed on the surface of the one liquid crystal alignment film, and then a sealant is printed thereon, and another sheet is obtained. The substrates are laminated so that the liquid crystal alignment film faces face each other and the rubbing directions are parallel to each other (anti-parallel liquid crystal cells, Examples 103 to 133), or are laminated so as to be perpendicular (twisted nematic liquid crystal cell, implementation) Examples 174 to 206, and Examples 322 to 343 and Examples 344 to 350), or those subjected to UV irradiation were bonded so that the directions of polarized light irradiated were parallel (anti-parallel liquid crystal cell for vertical alignment mode, Examples 207 to 209 and Examples 210 to 321) and the sealing agent were cured to produce empty cells. In this empty cell, liquid crystal MLC-2003 (manufactured by Merck) is injected in the anti-parallel liquid crystal cell, and liquid crystal MLC-2003 (manufactured by Merck) containing a chiral agent is injected in the twisted nematic liquid crystal cell, In the anti-parallel liquid crystal cell for vertical alignment mode, liquid crystal MLC-6608 (manufactured by Merck & Co., Inc.) was injected, and the injection port was sealed to obtain each liquid crystal cell.

[Liquid crystal cell evaluation]
The method of measuring the physical properties and evaluating the characteristics of each liquid crystal cell produced is as follows. In addition, the liquid crystal aligning film produced in each measurement and evaluation, the board | substrate of a liquid crystal cell, baking conditions, and rubbing conditions are shown collectively.

<Examples 103 to 133 and Comparative Examples 2 to 4><Liquid crystal orientation evaluation>
The liquid crystal cell produced using the polyimide film-forming coating solution prepared in each example shown in Table 8 was sandwiched between polarizing plates, and the liquid crystal cell was rotated in a state where the backlight was irradiated from the rear part. It was visually observed whether the liquid crystal was aligned with or without flow alignment. At that time, the following criteria were used for evaluation. In addition, the liquid crystal cell produced for liquid crystal orientation evaluation uses a glass substrate as a substrate, and baked for 30 minutes on a hot plate heated to 230 ° C. as a baking condition of a coating liquid for forming a polyimide film. Was prepared with a roll rotation speed of 300 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.15 mm. In addition, a coating liquid (Comparative Example 3 or Comparative Example 4) to which the following crosslinking agent was added as a general commercially available crosslinking agent (Comparative Example 2) without addition of a modifying compound or a crosslinking agent. Prepared and compared effects. The results are shown in Table 8.
Evaluation Criteria A: The alignment of the liquid crystal can be confirmed and there is no fluid alignment. O: The liquid crystal is aligned, but the flow alignment is slightly observed. X: The liquid crystal is aligned, but a lot of fluid alignment is observed.

As a result, when a commercially available crosslinking agent is used as in Comparative Example 3 and Comparative Example 4, the orientation of the liquid crystal generally tends to be disturbed, but the polyimide film-forming coating to which the modifying compound of the present invention is added. In the case of using the liquid, it was confirmed that even if a modifying compound having two or more Meldrum structure sites was used, the orientation could be improved in some cases without impairing the orientation of the liquid crystal. .

<Examples 134 to 173 and Comparative Examples 5 to 6><Rubbing resistance evaluation>
The surface of the liquid crystal alignment film prepared using the polyimide film forming coating solution prepared in each example shown in Table 9-1 to Table 9-2 was observed with a confocal laser microscope and evaluated according to the following criteria. went. Note that a glass substrate with an ITO transparent electrode was used as the substrate, and the baking condition of the coating film of the polyimide film forming coating solution was baking for 30 minutes on a hot plate heated to 230 ° C., and the rubbing conditions were a roll rotation speed of 1000 rpm and a roll progression. It was manufactured at a speed of 50 mm / sec and an indentation amount of 0.5 mm. Moreover, the thing which did not add the compound for a modification | combination (Comparative Example 5 and Comparative Example 6) was prepared, and the effect was compared. The results are shown in Tables 9-1 to 9-2.
○: Scraping and rubbing scratches are not observed.
Δ: Scraping and rubbing scratches are observed.
X: A film | membrane peels or a rubbing damage | wound is observed visually.

As a result, in comparison with Comparative Example 5 and Comparative Example 6 in which the modifying compound was not added, when the polyimide film forming coating solution to which the modifying compound having two or more Meldrum's acid structure sites was added was used It was confirmed that the wear resistance improved with any polymer.

<Examples 174 to 206 and Comparative Example 7><Pretilt angle measurement of twisted nematic liquid crystal cell>
About the liquid crystal cell produced using the coating liquid for polyimide film formation prepared in each Example shown in Table 10, the pretilt angle was measured after heating at 105 degreeC for 5 minute (s). The pretilt angle was measured by “Axo Scan” of AxoMetrix using the Mueller matrix method. In addition, the liquid crystal cell produced for measuring the pretilt angle of the twisted nematic liquid crystal cell uses a glass substrate with an ITO transparent electrode as the substrate, and is on a hot plate heated to 230 ° C. under the baking condition of the coating liquid for forming the polyimide film. Baked for 30 minutes, and the rubbing conditions were set at a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm. In addition, a compound with no modifier compound added (Comparative Example 7) was prepared, and the effects were compared. The results are shown in Table 10.

As a result, it was confirmed that a desired pretilt angle can be arbitrarily obtained by appropriately selecting the type and amount of the modifying compound.

<Examples 207 to 209 and Comparative Example 8><Pretilt angle measurement of anti-parallel liquid crystal cell>
About the liquid crystal cell produced using the coating liquid for polyimide film formation prepared in each Example shown in Table 11, after heating at 120 degreeC for 1 hour, the pretilt angle was measured. The pretilt angle was measured by “Axo Scan” of AxoMetrix using the Mueller matrix method. In addition, the liquid crystal cell produced for the pretilt angle measurement of the anti-parallel liquid crystal cell uses a glass substrate with an ITO transparent electrode as a substrate, and the hot air circulation type in which the baking condition of the coating film of the polyimide film forming coating liquid is heated to 200 ° C. The above-described liquid crystal cell was produced without firing the alignment treatment in an oven for 30 minutes. In addition, a compound with no modifier compound added (Comparative Example 8) was prepared, and the effects were compared. The results are shown in Table 11.

As a result, it was confirmed that the pretilt angle can be remarkably increased when the polyimide film-forming coating solution to which the modifying compound is added is used as compared with Comparative Example 8 in which the modifying compound is not added. It was. Therefore, by adding the modifying compound, the base polymer, that is, the polyimide precursor contained in the coating solution for forming the polyimide film or the side chain component that makes the liquid crystal stand up in the polyimide, can be introduced vertically It was confirmed that it can be oriented.

<Examples 210 to 321><Evaluation of liquid crystal alignment and measurement of pretilt angle of anti-parallel liquid crystal cell>
A liquid crystal cell produced using the coating liquid for forming a polyimide film prepared in each example shown in Tables 12-1 to 12-4 was sandwiched between polarizing plates, and the liquid crystal cell was rotated with the backlight irradiated from the rear part. When the liquid crystal was orientated by the presence or absence of change in brightness and the presence or absence of fluid orientation, it was observed visually. Thereafter, an AC voltage of 3 V was applied to the liquid crystal cell, and it was visually observed whether the liquid crystal was aligned. At that time, the following criteria were used for evaluation. In addition, the liquid crystal cell produced for liquid crystal orientation evaluation was obtained by baking for 30 minutes in a hot-air circulating oven heated to 200 ° C. using a glass substrate as the substrate and the coating condition of the coating liquid for forming the polyimide film was 200 ° C. It produced after performing the above-mentioned photo-alignment process to the obtained glass substrate with a coating film.
Evaluation criteria Good: The orientation of the liquid crystal can be confirmed and there is no fluid orientation. Poor: The liquid crystal is oriented, but many fluid orientations are observed.

In addition, the liquid crystal cell produced using the coating solution for forming a polyimide film prepared in each Example shown in Tables 12-1 to 12-4 was heated at 120 ° C. for 1 hour, and then the pretilt angle was measured. The pretilt angle was measured by “Axo Scan” from Axo Metrix using the Mueller matrix method.

As a result, by using a coating liquid for forming a polyimide film (liquid crystal alignment treatment agent) to which a modifying compound having a photoreactive side chain is added, a good vertical alignment can be obtained even when a photo-alignment treatment is performed. It was confirmed. It was also confirmed that the polyimide film-forming coating liquid (liquid crystal alignment treatment agent) of the present invention has the ability to align liquid crystals in a slightly tilted state by irradiating polarized ultraviolet rays. It was also confirmed that the pretilt angle can be finely adjusted by controlling the addition amount and the irradiation amount. Therefore, the coating liquid for forming a polyimide film (liquid crystal alignment treatment agent) of the present invention can be used for a liquid crystal alignment film for a vertical alignment type liquid crystal display element, and also used for a photo alignment method. It can be said that it is also useful.

<Examples 322 to 343 and Comparative Example 9><Measurement of voltage holding ratio (VHR)>
With respect to the liquid crystal cell produced using the polyimide film-forming coating solution prepared in each Example shown in Table 13, the voltage holding ratio in the initial state was measured. The voltage holding ratio was measured by applying a voltage of 4 V for 60 μs at a temperature of 90 ° C., measuring the voltage after 16.67 ms, and calculating how much the voltage could be held as the voltage holding ratio. For measuring the voltage holding ratio, a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica Co., Ltd. was used. In addition, the liquid crystal cell produced for the measurement of voltage holding ratio (VHR) uses a glass substrate with an ITO transparent electrode as a substrate, and is on a hot plate heated to 230 ° C. under the baking condition of the coating liquid for forming the polyimide film. Baked for 30 minutes, and the rubbing conditions were set at a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm. In addition, a compound with no modifier compound added (Comparative Example 9) was prepared, and the effects were compared. The results are shown in Table 13.

As a result, it was confirmed that by using the polyimide film-forming coating solution to which the modifying compound was added, better voltage holding ratio characteristics can be obtained than when not added.

<Examples 344 to 350 and Comparative Example 10><Estimation of Accumulated Charge (RDC)>
A DC voltage was applied from 0 V to 1.0 V at a 0.1 V interval at a temperature of 23 ° C. to a twisted nematic liquid crystal cell prepared using the polyimide film forming coating solution prepared in each example shown in Table 14. A calibration curve was prepared by measuring the flicker amplitude level at each voltage. After grounding for 5 minutes, an AC voltage of 3.0 V and a DC voltage of 5.0 V were applied, the flicker amplitude level after 1 hour was measured, and the RDC was estimated by comparing it with a calibration curve prepared in advance (Flicker reference method) ). In addition, the liquid crystal cell produced for the estimation measurement of the accumulated charge (RDC) uses a glass substrate with an ITO transparent electrode as a substrate, and is on a hot plate heated to 230 ° C. for the baking condition of the coating liquid for forming the polyimide film. Baked for 30 minutes, and the rubbing conditions were set at a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm. In addition, a compound with no modifier compound added (Comparative Example 10) was prepared, and the effects were compared. The results are shown in Table 14.

As a result, it was confirmed that a liquid crystal cell having a small RDC can be obtained by using a coating solution for forming a polyimide film to which a modifying compound is added.

<Examples 351 to 358 and Comparative Example 11> Measurement of ion density before and after aging test Each of the compounds shown in Table 15 prepared in Synthesis Example as a modifying compound in the above polyamic acid (PAA-1) solution (10.0 g) was used. Add to the solid content of the polyamic acid (PAA-1) solution (ie, polyamic acid (PAA-1)) so that the ratio is as shown in Table 15 below, and stir at room temperature until a uniform solution is obtained. A coating solution for film formation was prepared.

And about the twist nematic liquid crystal cell produced using each of these coating liquids (liquid crystal aligning agent) for polymer film formation, the ion density of an initial state (23 degreeC) is measured, and it hold | maintains at 60 degreeC for 30 hours (aging) After the ion density measurement was performed. In the ion density measurement, the ion density was measured when a triangular wave having a voltage of ± 10 V and a frequency of 0.01 Hz was applied to the liquid crystal cell. The measurement temperature was 80 ° C. As the measuring apparatus, a 6245 type liquid crystal property evaluation apparatus manufactured by Toyo Technica Co., Ltd. was used for all measurements. The results are shown in Table 15.

The twisted nematic liquid crystal cell is the same as that of the above twisted nematic liquid crystal cell (Examples 174 to 206) except that the firing condition of the coating film of the polyimide film forming coating solution was fired for 30 minutes on a hot plate heated to 200 ° C. The same operation was performed. In addition, the same operation was performed for those to which no modifier compound was added, and the effects were compared.

As a result, it was confirmed that the ionic impurities in the liquid crystal cell can be significantly reduced by appropriately selecting the type and amount of the modifying compound as compared with the case where it is not added.

[Synthesis of polymer and preparation of its solution]
Abbreviations used below are as follows.
(monomer)
HEMA: Methacrylic acid 2-hydroxyethyl MAA: Methacrylic acid MMA: Methyl methacrylate CHMI: N-cyclohexylmaleimide TEOS: Tetraethoxysilane

(Polymerization initiator)
AIBN: α, α'-azobisisobutyronitrile

(solvent)
PGMEA: Propylene glycol monoethyl ether CHN: Cyclohexane HG: Hexylene glycol BCS: Butyl cellosolve 1,3-BDO: 1,3-butanediol

The number average molecular weight Mn and the weight average molecular weight Mw of the acrylic polymer and polysiloxane obtained according to the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran. Was flowed through the column at a flow rate of 1 ml / min (column temperature 40 ° C.) for elution. Note that both the number average molecular weight Mn and the weight average molecular weight Mw are expressed in terms of polystyrene.

(Commercially available polymer)
Regarding the following commercially available polymer, it was used as a polymer solution prepared so as to have a solid content concentration of 6% by mass with a mixed solution of NMP / BCS (weight ratio 80:20). PSM-4326 used was purchased from Gunei Chemical Co., Ltd., and other polymers purchased from Aldrich. MEK means methyl ethyl ketone.
Polymer-1: Poly [(o-cresyl glycidyl ether) -co-formaldehyde]
Polymer-2: Poly [N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3, 5-triazine]
Polymer-3: Poly (Bisphenol A-co-epichlorohydrin)
Polymer-4: Poly (melamine-co-formaldehyde) acrylated, 80 wt% MEK Solution.
Polymer-5: Novolak resin, PSM-4326, manufactured by Gunei Chemical Industry Co., Ltd.

<Synthesis of Polymer-6 and preparation of its solution>
A solution containing MMA, MAA, HEMA, and CHMI at a molar ratio of MMA: MAA: HEMA: CHMI = 13: 26: 25: 36 and a solid content concentration of 40 wt%, and using PGMEA as a solvent. Then, AIBN was added as a polymerization catalyst to this solution and reacted at 80 ° C. for 20 hours to obtain a copolymer (acrylic polymer) solution. The number average molecular weight Mn of the obtained copolymer was 4000, and the weight average molecular weight Mw was 7500. Next, the obtained solution was diluted with NMP so that the solid content concentration became 5 wt% to obtain an acrylic polymer (Polymer-6) solution.

<Synthesis of Polymer-7 and preparation of its solution>
TEOS was added to a 100 mL four-necked flask equipped with a thermometer and a reflux tube together with a mixed solvent (HG: BCS: 1,3-BDO = 65: 30: 5 by weight) to prepare an alkoxysilane monomer solution. . A solution prepared by mixing oxalic acid as a mixed solvent, water and a catalyst in advance was added dropwise to the solution at room temperature over 30 minutes. The solution was stirred for 30 minutes and then heated to reflux for 1 hour and allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12 wt%. Next, the obtained polysiloxane solution having a SiO ₂ equivalent concentration of 12 wt% was further diluted with the above mixed solvent to obtain a 5 wt% polysiloxane (Polymer-7) solution.

[Production of liquid crystal alignment film and liquid crystal cell]
The compounds shown in Table 16 prepared in the synthesis examples as modifier compounds in the respective polymer (Polymer-1 to Polymer-5) solutions, acrylic polymer (Polymer-6) solutions, or polysiloxane (Polymer-7) solutions, respectively, Add to the solid content of the polymer solution (that is, Polymer-1 to Polymer-7) so as to have the ratio described in Table 16 below, and stir at room temperature until a uniform solution is obtained. Prepared.

And about the anti-parallel liquid crystal cell produced using each of these coating liquids (liquid crystal aligning agent) for polymer film formation, after heating at 120 degreeC for 1 hour, a liquid crystal cell is mounted on a backlight, and vertical alignment property is passed through a polarizing plate. Was visually observed. The results are shown in Table 16, assuming that the vertical alignment was “vertical” and the non-vertical alignment was “non-vertical”.

The anti-parallel liquid crystal cell uses a glass substrate with an ITO transparent electrode as a substrate, and is fired for 30 minutes in a hot-air circulating oven heated to 200 ° C. for the coating conditions of various polymer film forming coating solutions. It was manufactured by performing the same operation as that of the anti-parallel liquid crystal cell for vertical alignment mode (Examples 210 to 321) except that the treatment was not performed. In addition, the same operation was performed for those to which no modifier compound was added, and the effects were compared.

As a result, in Comparative Examples 12 to 18 in which no modifier compound was added to any polymer of Polymer-1 to Polymer-6, no vertical alignment was shown, but a polymer film-forming coating to which a modifier compound was added. In the case of the liquid, it was confirmed that the vertical orientation was exhibited by adding an appropriate amount depending on each polymer. That is, it was confirmed that by appropriately selecting the type and amount of the additive, a vertically aligned cell can be easily produced regardless of the type of the base polymer.

Regarding Polymer-7, since the vertical alignment is exhibited even when no additive is added, the additive is not essential for producing a vertical cell, but the addition of the additive has a higher vertical alignment. It was confirmed to improve.

<Examples 383 to 401>
In the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compounds described in the following Table 17 prepared in the above synthesis example as the modifying compound were respectively added to the solid polyamic acid (PAA-1) solution. In order to achieve the ratio described in Table 17 below with respect to the fraction (that is, polyamic acid (PAA-1)), the mixture was stirred at room temperature until a uniform solution was obtained. A liquid was prepared.

<Examples 402 to 403>
In the polyamic acid (PAA-3) solution (40.0 g) prepared above, the compounds described in the following Table 18 prepared as the modifying compound in the above Synthesis Example were respectively added to the solid polyamic acid (PAA-3) solution. Added to the mass (that is, polyamic acid (PAA-3)) so as to be the mass% described in Table 18, and stirred at room temperature until a uniform solution is obtained. A liquid was prepared.

Examples 404 to 536 <Evaluation of liquid crystal alignment and measurement of pretilt angle of antiparallel liquid crystal cell for vertical alignment mode>
[Production of liquid crystal alignment film and liquid crystal cell]
Using the polyimide film-forming coating solution (liquid crystal aligning agent) prepared in each of Examples 383 to 403, a liquid crystal cell was produced as follows.

A coating solution for forming a polyimide film (liquid crystal aligning agent) is spin-coated on a glass substrate, dried on a hot plate at 80 ° C. for 70 seconds, and then baked for 30 minutes in a hot air circulating oven heated to 200 ° C. A coating film having a thickness of 100 nm was formed.

After that, linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm ⁻² ) was changed between the exposure amount of 0 mJ and 1000 mJ on the surface of the coating film, and irradiated at a tilt of 40 ° with respect to the normal line of the plate. . The linearly polarized light UV was prepared by passing a 313 nm band pass filter through the ultraviolet light of a high pressure mercury lamp and then passing it through a 313 nm polarizing plate.

After preparing two substrates with a liquid crystal alignment film subjected to the liquid crystal alignment treatment in this manner, a spacer of 6 μm is sprayed on the surface of the one liquid crystal alignment film, and then a sealant is printed thereon, and another sheet is obtained. The substrates were laminated so that the surfaces of the liquid crystal alignment film faced each other and irradiated, and the directions of polarized light were parallel to each other, and the sealing agent was cured to produce an empty cell. Liquid crystal MLC-6608 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain each antiparallel liquid crystal cell for vertical alignment mode.

Then, the prepared liquid crystal cell is sandwiched between polarizing plates, and the liquid crystal cell is rotated in a state where the backlight is irradiated from the rear, and it is visually observed whether the liquid crystal is aligned with the presence or absence of change in light and darkness or flow alignment. As a result, good orientation was exhibited. Thereafter, an AC voltage of 3 V was applied to the liquid crystal cell, and it was visually observed whether the liquid crystal was aligned. At that time, the following criteria were used for evaluation. The results are shown in Tables 19-1 to 19-5.
Evaluation criteria Good: The orientation of the liquid crystal can be confirmed and there is no fluid orientation. Poor: The liquid crystal is oriented, but many fluid orientations are observed.

The prepared liquid crystal cell was heated at 120 ° C. for 1 hour, and then the pretilt angle was measured. The pretilt angle was measured by “Axo Scan” from Axo Metrix using the Mueller matrix method. The results are shown in Tables 19-1 to 19-5.

As a result, as shown in Tables 19-1 to 19-5, the photo-alignment treatment was performed by using a polyimide film-forming coating liquid (liquid crystal alignment treatment agent) to which a modifying compound having a photoreactive side chain was added. It was confirmed that good vertical alignment could be obtained even in the case of carrying out. It was also confirmed that the polyimide film-forming coating liquid (liquid crystal alignment treatment agent) of the present invention has the ability to align liquid crystals in a slightly tilted state by irradiating polarized ultraviolet rays. It was also confirmed that the pretilt angle can be finely adjusted by controlling the addition amount and the irradiation amount. Therefore, the coating liquid for forming a polyimide film (liquid crystal alignment treatment agent) of the present invention can be used for a liquid crystal alignment film for a vertical alignment type liquid crystal display element, and also used for a photo alignment method. It can be said that it is also useful.

<Examples 537 to 578>
In the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compounds described in the following Tables 20-1 to 20-2 prepared in the above synthesis examples as modifying compounds were respectively added to the polyamic acid (PAA). -1) Add to the solid content of the solution (ie, polyamic acid (PAA-1)) so that the ratio is as described in Tables 20-1 to 20-2 below, and stir at room temperature until a uniform solution is obtained. The coating solutions for forming a polyimide film of Examples 537 to 578 were prepared.

<Examples 579 to 620><Evaluation of liquid crystal alignment of antiparallel cell for horizontal alignment mode>
[Production of liquid crystal alignment film and liquid crystal cell]
Using the polyimide film forming coating solution (liquid crystal aligning agent) prepared in each of Examples 537 to 578, a liquid crystal cell was produced as follows.

Thereafter, linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm ⁻² ) was changed from 0 mJ to 1000 mJ on the coating surface, and the substrate was irradiated from directly above. The linearly polarized light UV was prepared by passing a 313 nm band pass filter through the ultraviolet light of a high pressure mercury lamp and then passing it through a 313 nm polarizing plate.

After preparing two substrates with a liquid crystal alignment film subjected to the liquid crystal alignment treatment in this manner, a spacer of 6 μm is sprayed on the surface of the one liquid crystal alignment film, and then a sealant is printed thereon, and another sheet is obtained. The substrates were laminated so that the surfaces of the liquid crystal alignment film faced each other and irradiated, and the directions of polarized light were parallel to each other, and the sealing agent was cured to produce an empty cell. Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an antiparallel liquid crystal cell for horizontal alignment mode.

Then, the prepared anti-parallel liquid crystal cell for horizontal alignment mode is sandwiched between polarizing plates, and the liquid crystal cell is rotated in a state where a backlight is irradiated from the rear portion, and the liquid crystal is aligned with the presence or absence of light / dark change or fluid alignment. It was observed visually. At that time, the following criteria were used for evaluation. The results are shown in Tables 21-1 to 21-2.
Evaluation Criteria A: The orientation of the liquid crystal can be confirmed and there is no fluid orientation. ○: The liquid crystal is oriented, but the fluid orientation is slightly observed. Δ: The liquid crystal is oriented, but a lot of fluid orientation is observed. ×: Liquid crystal is not aligned at all

As a result, in any liquid crystal cell, the liquid crystal cell that has not been irradiated with light does not exhibit orientation at all, but in the liquid crystal cell that has been irradiated with light, depending on the amount of the modifying compound added and the amount of light irradiated, It was confirmed that the liquid crystal was aligned. In addition, even when each liquid crystal cell in which alignment was recognized was subjected to an isotropic treatment at 130 ° C. for 30 minutes, no significant change was observed in the alignment. That is, it was confirmed that the horizontal alignment cell can be easily produced by appropriately selecting the type and amount of the additive.

Claims

For at least one modification selected from the group represented by the following formulas [A] to [D], which comprises a functional structural portion imparting functionality and at least one meldrum acid structural portion linked thereto A functional polymer film-forming coating solution comprising a compound and a polymer for modification or a monomer for synthesizing the polymer for modification.

(Wherein, W 1 is .V 1 representing the k 1 monovalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -OR, an -SR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k 1 a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.)

(Wherein, W 2 is .V 2 representing the k 2 divalent organic group which is a functional structural part that imparts functionality represents -H, -OH, -SR, an -OR or -NHR, R a benzene ring, a cyclohexane ring, a hetero ring, fluorine, an ether bond, an ester bond, .k 2 a good number of carbon atoms an amide bond anywhere represents a monovalent organic group having 1 to 35 1 represents an integer of 1 to 8.)

(Wherein, W 3 and W 4 represents a k 3 monovalent organic group is a functional structural part that imparts respective functional, W 3 and W 4 are .k 3 may be the same or different are Represents an integer of 1 to 8.)

(Wherein, W 5 is .k 4 representing the 2k 4-valent organic group that is functional structural moiety which imparts functionality is an integer of 1-8.)
A functional polymer film, wherein the functional polymer film-forming coating solution according to claim 1 is applied to a substrate, baked, and the functional structure portion is bonded to the modified polymer via the Meldrum's acid structure portion. A method for forming a functional polymer film.