KR101916976B1 - Coating solution for forming functional polymer film, and method for forming functional polymer film - Google Patents

Abstract

At least one hydrolyzable compound selected from the group consisting of the following formulas [A] to [D] and having at least one functional group for imparting functionalities and at least one marmer acid structural unit connected thereto, Or a functional polymer film for forming a functional polymer film containing a monomer for synthesizing the above-mentioned water-soluble polymer, and a functional polymer film obtained by applying the coating liquid to a substrate and firing. (The symbol in each formula is the same as defined in Paragraph 1)

Description

TECHNICAL FIELD [0001] The present invention relates to a coating liquid for forming a functional polymer film and a method for forming a functional polymer film,

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

In the liquid crystal display element, the liquid crystal alignment film plays a role of orienting the liquid crystal in a certain direction. Presently, the main liquid crystal alignment film that is industrially used is a polyimide-based liquid crystal aligning agent comprising a solution of polyamic acid (also referred to as polyamic acid), polyamic acid ester, or polyimide, which is a polyimide precursor, Followed by coating to form a film. When the liquid crystal is oriented parallel or obliquely with respect to the substrate surface, the film is further subjected to surface stretching treatment by rubbing. A method of using an anisotropic photochemical reaction by polarized ultraviolet irradiation or the like has also been proposed as an alternative to the rubbing treatment, and studies for industrialization have been conducted recently.

In order to improve the display characteristics of such a liquid crystal display device, a method of changing the structure of a polyamic acid, a polyamic acid ester or a polyimide, a blend of a polyamic acid, a polyamic acid ester or a polyimide having different characteristics, , Improvements in liquid crystal alignment properties and electrical characteristics, and control of the pre-tilt angle are performed.

Among techniques for controlling the pretilt angle by the structure of polyimide, a method of using a diamine having a side chain as a part of a polyimide raw material can control the pretilt angle according to the use ratio of the diamine, Is relatively easy and is useful as means for increasing the pre-tilt angle. Examples of the side chain structure of diamines that increase the pretilt angle of the liquid crystal include long chain alkyl or fluoroalkyl groups (for example, see Patent Document 1), combinations of cyclic groups or cyclic groups and alkyl groups (for example, in Patent Document 2 , A steroid skeleton (see, for example, Patent Document 3), and the like.

The diamine for increasing the pretilt angle of the liquid crystal as described above has also been studied for the structure to improve the stability of the pretilt angle and process dependency. As the side chain structure used here, a ring such as a phenyl group or a cyclohexyl group Structure (see, for example, Patent Documents 4 and 5). Furthermore, diamines having such a ring structure in three to four side chains have been proposed (see, for example, Patent Document 6).

2. Description of the Related Art Recently, liquid crystal display devices have been widely used as liquid crystal televisions for large screens and high-precision mobile applications (display portions of digital cameras and cellular phones). Even in such a situation, it has been demanded that a liquid crystal alignment film is uniformly applied to a large substrate or a step in terms of display characteristics.

When a solution of a polyamic acid or a solution of a solvent-soluble polyimide is applied to a substrate in a production process of a liquid crystal alignment film, it is generally industrially carried out by flexography or the like. As the solvent of the coating liquid, in order to improve the uniformity of the coating film, it is preferable that the solubility of the resin (hereinafter also referred to as " good solvent ") in addition to N-methyl-2-pyrrolidone, Butylcellosolve which is a low solvent (hereinafter also referred to as a poor solvent), and the like are mixed. However, since the poor solvent has a poor ability to dissolve polyamic acid or polyimide, precipitation occurs when mixed in a large amount (see, for example, Patent Document 7). Particularly, in the solution of the solvent-soluble polyimide, this problem is conspicuous. In addition, the polyimide obtained by using the diamine having the side chain as described above tends to lower the coating uniformity of the solution. Therefore, it is necessary to increase the mixing amount of the poor solvent, It becomes an important characteristic of polyimide.

In addition, the performance of the liquid crystal display device has been improved, the size of the liquid crystal display device has been increased, the power saving of the display device has been promoted, and furthermore, the liquid crystal display has been used under various circumstances. Particularly, when a liquid crystal aligning agent is applied to a substrate, problems such as occurrence of printing failure due to precipitation or separation due to prolongation of the tact time and exposure due to accumulated charge (RDC) become a problem. It is difficult to solve both at the same time.

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 properties. However, in the relationship with other properties, the desired diamine component can not be freely used have.

In addition, polyimide is widely used as a protective material and an insulating material in electrical and electronic fields in addition to a liquid crystal alignment film for its high mechanical strength, heat resistance and solvent resistance. It is practiced to improve the diamine component which is a raw material of the polyimide, but it is also the same that the desired diamine component can not be used freely.

The demand for improving such desired characteristics is not limited to the polyimide-based liquid crystal alignment film but also exists in the polymer film formed by applying a solution of another polymer or the like onto the substrate to form a film.

Japanese Patent Application Laid-Open No. 2-282726 Japanese Unexamined Patent Application Publication No. 3-179323 Japanese Patent Application Laid-Open No. 4-281427 Japanese Patent Application Laid-Open No. 9-278724 International Publication No. 2004/52962 pamphlet Japanese Patent Application Laid-Open No. 2004-67589 Japanese Unexamined Patent Application Publication No. 2-37324

It is an object of the present invention to solve the above-described problems of the prior art and to provide a coating solution for forming a functional polymer film which can obtain a functional polymer film in which various characteristics are relatively freely improved and a functional polymer film forming And to provide a method.

The coating liquid for forming a polyimide film of the present invention which solves the above problems is a coating liquid for forming a polyimide film having a functional structure portion for imparting functionality and at least one mulsion acid structure portion connected thereto, , And a monomer for synthesizing the water-soluble polymer or the water-soluble polymer for use in the present invention.

[Chemical Formula 1]

(Wherein W < _{1 >} Lt; RTI ID = 0.0 &_gt; k1 &_lt; / RTI _> ≪ / RTI > V ₁ R represents a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond, or an amide bond at any arbitrary position Represents a monovalent organic group having 1 to 35 carbon atoms. and k ₁ represents an integer of 1 to 8.)

(2)

(Wherein W < _{2 >} Represents a k ₂ -valent organic group which is a functional structural moiety for imparting functionality. V ₂ R represents a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond or an amide bond at any arbitrary position, Represents a monovalent organic group having 1 to 35 carbon atoms. k ₂ Represents an integer of 1 to 8).

(3)

(Wherein W ₃ and W ₄ Is a functional structural moiety that imparts functionality, k ₃ And W < ₃ > and W < ₄ > May be the same or different. k ₃ Represents an integer of 1 to 8.)

[Chemical Formula 4]

(Wherein W < ₅ > 2k < / _RTI > _{4 < RTI ID = 0.0} > ≪ / RTI > k ₄ Represents an integer of 1 to 8).

The method for forming a functional polymer film according to the present invention is a method for forming a functional polymer film by applying a coating liquid for forming a functional polymer film to a substrate and firing the functional polymer film, Thereby obtaining a film.

According to the present invention, there is provided a water-soluble, water-soluble, water-dispersible, water-dispersible, water-dispersible, water- By using the coating liquid for forming a functional polymer film containing a compound, it is possible to obtain a functional polymer film in which various characteristics are relatively freely improved.

Hereinafter, the present invention will be described in detail.

The coating liquid for forming a functional polymer film of the present invention is selected from a group represented by the following formulas [A] to [D] having functional structural moieties for imparting functionality and at least one meld acid structural moiety connected thereto And at least one hydratable compound.

[Chemical Formula 5]

(Wherein, W ₁ represents a functional structure portion is an organic divalent k ₁ for imparting functionality. V ₁ represents -H, -OH, -SR, -OR or -NHR, R is a benzene ring, a cyclohexane Represents a monovalent organic group having 1 to 35 carbon atoms which may contain a ring, a heterocyclic group, a fluorine atom, an ether bond, an ester bond or an amide bond at an arbitrary position, and k ₁ represents an integer of 1 to 8.

[Chemical Formula 6]

(Wherein W < _{2 >} Represents a k ₂ -valent organic group which is a functional structural moiety for imparting functionality. V ₂ R represents a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond, or an amide bond at any arbitrary position Represents a monovalent organic group having 1 to 35 carbon atoms. k ₂ Represents an integer of 1 to 8).

(7)

(Wherein W ₃ and W ₄ Is a functional structural moiety that imparts functionality, k ₃ And W < ₃ > and W < ₄ > May be the same or different. k ₃ Represents an integer of 1 to 8.)

[Chemical Formula 8]

(Wherein W < ₅ > 2k < / _RTI > _{4 < RTI ID = 0.0} > ≪ / RTI > k ₄ Represents an integer of 1 to 8).

Specific examples of the hydrating compound represented by the above formula [A] include the hydrating compounds represented by the following formulas [i] to [iii]. When the hydrazine compound or the hydrazine compound having a terminal amino group of a primary or secondary group is used as a raw material and the hydrazine compound represented by the above formula [A] is synthesized, the hydrazine compound becomes a hydrazine compound represented by the following formula [i] When a hydrazine compound or a disulfide carbon is used as a raw material and the hydrazine compound represented by the above formula [A] is synthesized, the hydrazine compound becomes a hydrazine compound represented by the following formula [ii], and an aldehyde or ketone compound, When the hydrazine compound represented by the above formula [A] is synthesized from an acid derivative as a raw material, the hydrazine compound is represented by the following formula [iii]. When a carbodiimide compound is used as a raw material, the compound represented by the following formula [i] is obtained. In this case, R _j Is -H.

[Chemical Formula 9]

(Wherein Y ₁ represents an amine compound, hydrazine compound, or carbodiimide compound-derived k ₁ , which is a primary amino group or a secondary amino group, which is a raw material of the hydratable compound represented by the above formula [A] And is, for example, a single bond or a linear or branched organic group having 1 to 60 carbon atoms, which may have a hetero atom or ring structure, and is a k ₁ -valent organic group. k ₁ and V ₁ is, k _1, and V ₁ in the formula [A] . p is 1 when an amine compound or carbodiimide compound is used as a raw material, and 2 when a hydrazine compound is used as a raw material. R _j Is a group represented by R ₁ to R ₈ , which may contain -H or a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond or an amide bond at an arbitrary position, Monovalent organic group, and R ₁ to R ₈ May be the same or different. In addition, R _j May be connected to a part of Y < ₁ > to form a ring.)

[Chemical formula 10]

(Wherein Y < _{2 >} Is a thiol compound, which is a raw material of the hydrating compound represented by the above formula [A], or k ₁ Monovalent organic group is, for example, a single bond or a carbon atom of the hetero atoms or linear or branched which may have a ring structure of ₁ ~ 60 k 1 And the like. k ₁ and k ₁ and V ₁ is V ₁ in the formula [A] .

(11)

(Wherein Y ₃ Is an aldehyde, a ketone compound or a carboxylic acid derivative which is a raw material of the hydrolysis compound represented by the above formula [A], or k ₁ from an orthoformate ester Monovalent organic group is, for example, a single bond or a carbon atom of the hetero atoms or linear or branched which may have a ring structure of ₁ ~ 60 k 1 And the like. k ₁ and k ₁ and V ₁ is V ₁ in the formula [A] .

In the hydrolytic compounds represented by the above formulas [i] to [iii], k ₁ Specific examples of Y ₁ to Y _{4 in} the case of 2 include divalent organic groups represented by the following formulas (Y-1) to (Y-120). Among them, when a functional polymer film to be obtained is used as a liquid crystal alignment film, it is preferable to use a structure in which a diamine compound having a high linearity is used as a raw material in order to obtain a good liquid crystal alignability. Examples of such Y include (Y-7) Y-22, Y-23, Y-25, Y-26, and Y- ), Y-27, Y-41, Y-42, Y-44, Y-45, (Y-67), (Y-69), (Y-64), (Y-63), Y-79, Y-80, Y-81, Y-82, Y-109, etc. . When the obtained functional polymer film is used as a liquid crystal alignment film for increasing the pretilt angle of the liquid crystal, it is possible to use a long chain alkyl group (for example, an alkyl group having 10 or more carbon atoms), an aromatic ring, an aliphatic ring, a steroid skeleton, (Y-84), (Y-85), (Y-86), and (Y-87) Y-91, Y-92, Y-93, Y-94, Y-95, and Y- (Y-101), (Y-102), (Y-103), (Y-103) -104), (Y-105), (Y-106), (Y-107), or (Y-108). (Y-31), (Y-40), (Y-64), (Y-65) ), (Y-109), (Y-110) and the like. (Y-18), (Y-111), (Y-112), (Y-113), (Y-114) , Y-115, Y-116, Y-117, Y-118 and Y-119.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

In the hydrolytic compounds represented by the above formulas [i] to [iii], k ₁ Specific examples of Y ₁ to Y ₃ in this case include a monovalent organic group represented by the following formula and a structure in which one bond of [Y-1] to [Y-120] is bonded to a hydrogen atom , But is not limited thereto.

(27)

In the hydrolysis compounds represented by the above formulas [i] to [iii], k ₁ Specific examples of Y ₁ to Y _{4 in} the case of 3 or more include a trivalent or higher organic group represented by the following formula or a structure in which hydrogen atoms of [Y-1] to [Y-120] are eliminated, It is not. In the present specification, Me is a methyl group.

(28)

The method for producing the hydrolytic compound represented by the above formula [A] is not particularly limited. For example, the hydrolytic compound represented by the above formulas [i] and [ii] may be prepared by reacting trimethyl orthoformate or triethyl orthoformate (For example, ethyl acetate, hexane, toluene, tetrahydrofuran, acetonitrile, methanol, chloroform, 1,4-dioxane, N, N-dimethylformamide, N-methyl-2-pyrrolidone) is reacted with trimethyl orthoformate or triethyl orthoformate to react an amine compound represented by the following formula [E1] or a thiol compound represented by the following formula [E2] can do. The reaction temperature and the reaction time of the reaction are not particularly limited. For example, the reaction may be carried out at 60 to 120 ° C for 30 minutes to 2 hours.

[Chemical Formula 29]

(Wherein, Y _1, R _j, and k ₁ is Y _1, R _j and k ₁ in the formula [i] .

(30)

(Wherein, Y ₂ and k ₁ and k ₂ are Y ₁ in the formula [ii] .

The hydriding compound represented by the above formula (iii) may be used in an organic base compound (for example, triethylamine, tributylamine, diisopropylethylamine) in pyridine or other organic base compounds, Can be produced by reacting an aldehyde compound represented by the following formula [E3] with a melamine acid in an organic solvent used in the general organic synthesis in which a phosphine compound such as triphenylphosphine coexists. The reaction temperature and the reaction time of the reaction are not particularly limited. For example, the reaction may be carried out at 0 ° C to 100 ° C for 1 to 24 hours.

(31)

(In the formula, Y ₃ and Y ₃ is k ₁ and k ₁ in the formula [iii] .

Examples of the other method for producing the hydroscopic compound represented by the above formula [A] include an amino compound such as the above-mentioned [E1], a thiol compound such as the above-mentioned [E2], an amino group, The aldehyde group is chemically modified according to various organic synthesis methods generally known, and a compound having an amino group, a thiol group, or an aldehyde group through a spacer is reacted with Meldrum acid as a raw material. Of course, this chemical modification may be carried out plural times.

Specifically, for example, the amino group of the amine compound [E1] is chemically modified according to various organic synthesis methods generally known and is represented by the following formulas [E4] to [E6] Can also be produced by reacting the compound with melamine acid by the same synthetic method as the hydrating compound represented by the formula [i] to [iii]. When the compound represented by the following formula [E4] to [E6] is used as a raw material and reacted with melamine acid, the compound is represented by the formula [A] of the following formulas [i '] to [iii'].

(32)

(Wherein, Y _1, R _j, and k ₁ is Y _1, R _j and k ₁ in the formula [i] . Q ₁ represents a single bond or a divalent organic group having 1 to 15 carbon atoms in the form of a linear or branched chain which may have a hetero atom or a cyclic structure. R _i , R ₁ to R ₈ Or a monovalent organic group having 1 to 35 carbon atoms which may contain a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond or an amide bond at an arbitrary position, and R ₁ to R ₈ May be the same or different. R _i may be connected to a part of Q ₁ to form a ring.)

(33)

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

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

(34)

(Wherein Y ₄ Is the formula [B] the aldehydes of the raw edible compound represented by the ketone compound, alkyl halide compound or a compound having an electron lack unsaturated bond (e.g., a compound having an acryloyl group) of the resulting k ₂ Monovalent organic group is, for example, a single bond or a hetero atom or carbon atom of the linear or branched which may have a ring structure 1 ~ 60 k ₂ And the like. k ₂ and V ₂ K is _2, and V ₂ in the formula [B] .

(35)

(Wherein Y < ₅ > It is of the formula [B] compounds of the drinking water in the raw material carboxylic acid derivative represented by the origin k ₂ Monovalent organic group is, for example, a single bond or a hetero atom or carbon atom of the linear or branched which may have a ring structure 1 ~ 60 k ₂ And the like. k ₂ and V ₂ K is _2, and V ₂ in the formula [B] .

Specific examples of Y ₄ and Y _{5 in} the formula compounds represented by the above formulas [iv] and [v] are the same as Y ₁ to Y ₃ .

The method for producing the water-soluble compound represented by the formula [B] is not particularly limited. For example, the water-soluble compound represented by the formula [iv] A ketone compound, a halogenated alkyl compound (for example, an aldehyde, a ketone compound, or a halogenated alkyl compound (for example, triethylamine, tributylamine or diisopropylethylamine) together with an inorganic base such as potassium carbonate, sodium hydrogencarbonate, The halogen can be produced by reacting a compound having an electron-poor unsaturated bond (for example, a compound having an acryloyl group) with Meldrum's acid, either of -Cl, -Br or -I. The reaction temperature and the reaction time of the reaction are not particularly limited. For example, the reaction may be carried out at 0 ° C to 120 ° C for 30 minutes to 2 hours. Further, by using a compound having an unsaturated bond such as an aldehyde, a ketone compound, a halogenated alkyl compound, or an electron-deficient unsaturated bond (for example, a compound having an acryloyl group) as a raw material and synthesizing the hydratable compound represented by the above formula [B] , Or directly via a compound represented by the above formula [iii], and thereafter, the carbon-carbon double bond is reduced to obtain the hydrating compound represented by the above formula [iv].

The water-soluble compound represented by the above formula [v] can be obtained by reacting pyridine or other organic base compound (for example, triethylamine, tributylamine, diisopropylethyl Amine) or a carboxylic acid derivative such as a carboxylic acid chloride or the like and a mordaric acid together with an inorganic base such as potassium carbonate, sodium hydrogencarbonate or sodium hydroxide. The reaction temperature and the reaction time of the reaction are not particularly limited. For example, the reaction may be carried out at -20 to 120 ° C for 30 minutes to 2 hours.

Other methods for producing the hydroscopic compound represented by the above formula [B] include the steps of reacting the compound represented by the formula [A] with an aldehyde, a ketone compound, a halogenated alkyl compound, a compound having an electron deficient unsaturated bond, An acid or a carboxylic acid derivative is chemically modified according to various generally known organic synthesis methods and a group having an aldehyde group, a ketone group, a halogenated alkyl group, an electron-poor unsaturated bond (for example, ), A method of reacting a compound having a carboxyl group with meldrum acid using the compound as a raw material. Of course, this chemical modification may be carried out plural times. Also, this way, by carrying out chemical modification when manufacturing a drinking water a compound represented by the formula [B], for example, the formula [iv] number Y of the edible compound represented by the ₄ (For example, 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 cyclic structure), which is chemically modified, Y ₅ is the number represented by the formula [B] of the insert structure can be represented by the edible compound or, the formula [v] edible compound (For example, 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 between the carbonyl group and the carbonyl group Of the formula [B].

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

(36)

(Wherein Y ₆ and Y ₇ Are each a halogenated alkyl compound which is a raw material of the hydrolyzing compound represented by the above formula [C], or k ₃ Represents a monovalent organic, for example, a single bond or a hetero atom or carbon atom of the linear or branched which may have a ring structure 1 ~ 60 k ₃ And the like. Y ₆ and Y ₇ May be the same or different. k ₃ In the formula [C], k < ₃ > .

Specific examples of Y ₆ and Y _{7 in} the hydriding compound represented by the formula [vi] include Y ₁ to Y ₃ .

The method for producing the water-soluble compound represented by the above formula [C] is not particularly limited. For example, the water-soluble compound represented by the formula [vi] Or an organic base compound (e.g., triethylamine, tributylamine, diisopropylethylamine) or an inorganic base such as potassium carbonate, sodium hydrogencarbonate or sodium hydroxide, Or a compound having a terminal hydroxyl group by allowing a compound and a halogenated alkyl compound or a palladium catalyst to coexist. Alternatively, it is possible to use pyridine or other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine) or potassium carbonate, sodium hydrogen carbonate, Can be produced by reacting a halogenated alkyl compound or an additional palladium catalyst together with an inorganic base such as sodium to give a compound having a hydroxyl group at the terminal. In this case, Y ₆ and Y ₇ May be the same or different. Y ₆ and Y ₇ , They can be produced by coexisting or stepwise addition of two or more kinds of halogenated alkyl compounds or compounds having hydroxyl groups at the terminals in the above production method. The reaction temperature and the reaction time of the reaction are not particularly limited. For example, the reaction may be carried out at 60 to 120 ° C for 30 minutes to 2 hours.

As another method for producing the hydrolysis compound represented by the above formula [C], the halogenated alkyl compound or the alcohol derivative may be synthesized by various organic synthesis methods generally known in the same manner as the method for producing the compound represented by the above formula [A] , A method of chemically modifying a compound having a halogenated alkyl group, an alkoxy group or a hydroxy group through a spacer, and reacting the resulting compound with a melamine acid as a raw material. Of course, this chemical modification may be carried out plural times. Also, this way, when subjected to a chemical modification preparing the drinking water a compound represented by the formula [C] include, for example, Y ₆ of the drinking water a compound represented by the general formula [vi] And the structure of the Meldrum acid structure, Y ₇ (For example, 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 cyclic structure) between the mordenic acid structural unit and the chemical modification moiety, Is a hydrolyzable compound represented by the formula [C] of the inserted structure.

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

(37)

(Wherein Y ₈ Is the formula [D] to be the raw material for the cyclic ketone compound represented edible compound, cyclic alkoxy imine compound, or, the number of carbon atoms from 1 to 15 derived from a cyclic carbodiimide compound 2k ₄ ≪ / RTI > k ₄ In the formula [D], k ₄ .

Specific examples of Y _{8 in} the hydriding compound represented by the above formula (vii) include cyclic structures derived from cyclic ketones such as cyclopentane ring, cyclohexane ring, cyclooctane ring, and γ-pyrone.

The method for producing the water-soluble compound represented by the formula [D] is not particularly limited. For example, the water-soluble compound represented by the formula [vii] (E.g., triethylamine, tributylamine, diisopropylethylamine) or an inorganic base such as potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, (E.g., a cyclohexanone derivative or a? -Pyrone derivative), a cyclic alkoxyimine compound (e.g., 6-position alkoxy substituted tetrahydropyridine), or a cyclic carbodiimide compound (e.g., 3-diazacyclo -1,2-diene derivative) with Meldrum's acid. The reaction temperature and the reaction time of the reaction are not particularly limited. For example, the reaction may be carried out at 60 to 120 ° C for 30 minutes to 2 hours.

Of course, the hydrating compounds represented by the above formulas [A] to [D] may be one kind or two or more kinds may be used in combination.

In addition, the coating liquid for forming a functional polymer film of the present invention contains a monomer for synthesizing a subject-use polymer or a subject-use polymer. The fishmeal edible polymer is not particularly limited as long as it has a moiety reactive with the myristic acid structure. For example, it is possible to polymerize at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component A polyimide precursor obtained by imidizing the polyimide precursor, an acrylic polymer, a methacrylic polymer, an acrylamide polymer, a methacrylamide polymer, a polystyrene, a polyvinyl, a polysiloxane or a polyamide, a polyester, a polyurethane, Polycarbonate, polyurea, polyphenol (novolac resin), maleimide polymer, or a polymer having a compound having an isocyanuric acid skeleton or a triazine skeleton. The polymer may be in the form of a branched polymer such as a dendrimer or a hyperbranched polymer or a starch polymer, or a non-covalent polymer such as polycarbonate or polyrotaxane. As the monomers for synthesizing the above-mentioned subject matter-containing polymers, it is preferable to use at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof in the case of a polyimide precursor or polyimide, a diamine component, In the case of the acrylic polymer, the acrylic acid and derivatives thereof, the acrylic acid ester and the derivatives thereof in the case of the acrylic polymer, the methacrylic acid and the derivatives thereof, the methacrylic acid ester and the derivatives thereof in the case of the methacrylic polymer, Acrylamide and its derivatives in the case of the acrylamide polymer as the edible polymer, methacrylamide and derivatives thereof as the methacrylamide polymer in the case of the acrylamide polymer as the acrylamide polymer, styrene and derivatives thereof as the polystyrene in the case of polystyrene, When the edible polymer is polyvinyl, it is a derivative having a vinyl group, A silane compound having a methoxy group or an ethoxy group in the case where the polymer is a polysiloxane and a silane compound having at least one dicarboxylic acid component and diamine component selected from a dicarboxylic acid and a derivative thereof in the case of a polyamide, In the case where the polymer is polyester, at least one kind of dicarboxylic acid component selected from dicarboxylic acid and its derivatives, diol component, and polymer for processing are polyurethane, compounds having isocyanate, compound and hydroxyl group, In the case where the polymer is a polycarbonate, in the case of a bisphenol derivative and a phosgene, or a phosgene equivalent (for example, trichlorophosgene) or diphenyl carbonate, and a polymer for use in processing is a polyurea, a bisisocyanate derivative and a diamine component, In the case of the maleimide polymer, the maleimide derivative alone or the styrene In the case of copolymerization, a grantee edible polymer is introduced into the compound having the isocyanuric acid skeleton or a triazine skeleton polymer, there may be mentioned compounds having the isocyanuric acid skeleton or a triazine skeleton. Of course, the monomers for synthesizing the fishmeal edible polymers or the processing-use polymers thereof may be of one kind or two or more kinds thereof may be used in combination. The polyimide precursor refers to polyamic acid and polyamic acid ester.

The water-soluble polymer contained in the coating liquid for forming a functional polymer film of the present invention can be produced by a commonly practiced method. For example, the polyimide precursor or polyimide is obtained by polymerizing at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component as described above.

As the diamine component, for example, k ₁ And the diamine compound represented by the above formula [E1]. In addition, a diamine component that is used when a polyimide precursor is obtained by reacting a conventional diamine component with a tetracarboxylic acid component can be used. The diamine component as the raw material of the polyimide precursor may be the same as the raw material of the hydrolyzing compound represented by the above formula [A], and the diamine component may be mixed with the hydrolyzable group represented by the formula [A] The raw material of the compound may be a different compound.

As the at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof, a tetracarboxylic acid component used when a polyimide precursor is obtained by reacting a diamine component with a tetracarboxylic acid component is used . Examples of the tetracarboxylic acid derivative include a tetracarboxylic acid dihalide, a tetracarboxylic acid dianhydride represented by the following formula [F], a tetracarboxylic acid diester dichloride, and a tetracarboxylic acid diester. For example, a polyamic acid can be obtained by reacting a tetracarboxylic acid or a derivative thereof with a diamine component such as a tetracarboxylic acid dihalide or a tetracarboxylic acid dianhydride. The polyamic acid ester can be obtained by reacting the tetracarboxylic acid diester dichloride with the diamine component or by reacting the tetracarboxylic acid diester and the diamine component in the presence of a suitable condensing agent or a base.

(38)

(X is a tetravalent organic group).

Specific examples of X in the formula [F] include quaternary organic groups represented by the following formulas (X-1) to (X-46). (X-1), (X-2), (X-3), (X-4) , X-16, X-17, X-19, X-21, X-25, X-26, X- X-32) or (X-46). When it is desired to improve the transparency of the functional polymer film (polyimide film) to be obtained, it is preferable to use tetracarboxylic acid dianhydride having an aliphatic and alicyclic structure, and examples of X include (X-1), (X -2) and (X-25) are more preferable, and (X-1) is more preferable from the viewpoint of reactivity with the diamine component.

[Chemical Formula 39]

(40)

Specific examples of the tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1 , 3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, Ester, 3,4-dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, Butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-dicyclohexyltetra Carboxylic 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- di-alkyl ester, 4- (2,5-dioxo-tetrahydro-furan -3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarbondioxy ester, and aliphatic tetracarboxylic acid diesters such as 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'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3', 4-benzophenonetetracarboxylic acid dialkyl ester, bis (3,4-dicar Bis (phenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfonyl alkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalenetetracar And an aromatic tetracarboxylic acid dialkyl ester such as a dialkyldicarboxylate.

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

A method of synthesizing a polyimide precursor by polymerization reaction of a tetracarboxylic acid component and a diamine component is not particularly limited, and a known synthetic method may be used.

For example, the reaction between the diamine component and the tetracarboxylic acid dianhydride may be performed by reacting the diamine component and the tetracarboxylic acid dianhydride in an organic solvent. The organic solvent used at this time is not particularly limited as long as the resulting polyimide precursor dissolves. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, , Ethyl 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 mono 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, An organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, isopropanol, butanol, isobutanol, isobutanol, isobutanol, , Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, Propyl propionate, butyl 3-methoxypropionate, diglyme or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Further, a solvent that does not dissolve the polyimide precursor may be used in combination with the solvent insofar as the resulting polyimide precursor does not precipitate. In addition, water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid dianhydride are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred to disperse or dissolve the tetracarboxylic acid dianhydride as it is or in an organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride and a diamine component, and the like, Either of these methods may be used. When a plurality of diamine components or tetracarboxylic acid dianhydrides are used in the reaction, they may be reacted in advance in a mixed state, or they may be sequentially reacted individually, or the low molecular weight compounds reacted individually may be mixed and reacted, . The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, preferably between -5 DEG C and 100 DEG C. The reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The initial reaction may be carried out at a high concentration, and then an organic solvent may be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid dianhydride is preferably 0.8 to 1.2. As in the case of a typical polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyamic acid ester can be obtained by reacting the tetracarboxylic acid diester dichloride with the diamine component as described above, or by reacting the tetracarboxylic acid diester and the diamine component in the presence of a suitable condensing agent and a base. Alternatively, it is also possible to synthesize polyamic acid in advance by the above-mentioned method and esterify the carboxyl group of the polyamic acid by using a polymer reaction.

Specifically, for example, the tetracarboxylic acid diester dichloride and the diamine component are reacted 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 hour to 4 hours, to obtain a polyamic acid ester.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable for the reaction to proceed mildly. The added amount of the base is an amount that is easy to remove and is preferably 2 to 4 times the tetracarboxylic acid diester dichloride from the viewpoint of easily obtaining a high molecular weight material.

When the tetracarboxylic acid diester and the diamine component are polycondensed in the presence of a condensing agent, the base is preferably a compound selected from the group consisting of triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride , N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorphuronium, O- (benzotriazol- Tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro- -Thioxo-3-benzoxazolyl) phosphinate, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4- methoxymorpholinium chloride n- Can be used.

Further, 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 to be used in the above reaction may be the same solvent as the solvent used in the synthesis of the polyamic acid shown above, but the solubility of the monomer and the polymer is preferably selected from the group consisting of N-methyl-2-pyrrolidone, Lactones are preferable, and they may be used alone or in combination of two or more. From the viewpoint that precipitation of the polymer is difficult to occur and that a high molecular weight material can be easily obtained, the concentration at the time of the synthesis is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the tetracarboxylic acid derivative in the reaction solution of the tetracarboxylic acid derivative such as the tetracarboxylic acid diester dichloride or the tetracarboxylic acid diester and the diamine component The total concentration is preferably 1 to 30 mass%, more preferably 5 to 20 mass%. In order to prevent the hydrolysis of the 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 the introduction of outside air in a nitrogen atmosphere.

The polyimide contained in the coating liquid for forming a functional polymer film of the present invention is obtained by subjecting the polyimide precursor to dehydration ring closure. In the polyimide, the degree of dehydration and closure of the amidic acid group (imidization ratio) does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose.

Examples of the method of imidizing the polyimide precursor include heat imidization for directly heating the solution of the polyimide precursor or catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

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 the removal while removing the water generated by the imidation reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Of these, pyridine is preferred because it has a suitable basicity for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When the polyimide precursor or polyimide is recovered from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, by repeating the operation of re-dissolving the polymer recovered and precipitated in the organic solvent and re-precipitating and recovering the polymer 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones or hydrocarbons can be exemplified, and when three or more solvents selected from these solvents are used, the purification efficiency is further improved, which is preferable.

As the polymer other than the polyimide precursor and the polyimide usable as the processing-use polymer, an acrylic polymer, a methacrylic polymer, an acrylamide polymer, a methacrylamide polymer, a polystyrene, a polyvinyl, a polysiloxane, a polyamide, A polyurethane, a polycarbonate, a polyurea, a polyphenol (novolac resin), a maleimide polymer, or a polymer introduced with an isocyanuric acid skeleton or a triazine skeleton, a dendrimer, a hyperbranched polymer, And a noncovalent bonding polymer such as polycarbonate or polyrotaxane. In these polymers, a functional group capable of reacting with a ketene intermediate formed by thermal decomposition of a marmer acid compound (for example, a carboxyl group, a hydroxyl group A thiol, an amino group, an imino group, a carbon-carbon double bond (alkene) or a carbon- Bond (alkyne) unsaturation, nitriles such as, and if there is a ketone or aldehyde, ester, amide, imide), these polymers would be available, it does not matter even if applied to those that are known.

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

The functional structure portions W ₁ to W ₅ And at least one hydriding compound selected from the group consisting of the compounds represented by the above formulas [A] to [D] and at least one melding acid structural moiety connected thereto, That is, for example, in addition to the coating liquid for forming a polymer film for forming a conventional polymer film or the like, at least one kind of water selected from the group represented by the above formulas [A] to [D] By containing an edible compound, it becomes a coating liquid for forming a functional polymer film which is capable of obtaining a functional polymer film in which various properties are relatively freely improved.

More specifically, the hydrolytic compounds represented by the above formulas [A] to [D] have at least one structure having a meldrum acid structure, that is, a structure derived from meldrum acid at the terminal, (I.e., a carbonyl compound having a bivalent group > C = C = O) accompanied by the elimination of carbon dioxide and acetone by heating the polyimide precursor (for example, 180 to 250 DEG C or higher) , Polyimide, acrylic polymer, methacrylic polymer, acrylamide polymer, methacrylamide polymer, polystyrene, polyvinyl, polysiloxane, polyamide, polyester, polyurethane, polycarbonate, polyurea, polyphenol (novolak resin) , A maleimide polymer, or a polymer introduced with an isocyanuric acid skeleton or a triazine skeleton, a branched polymer such as a dendrimer or hyperbranched polymer or a starch polymer, (For example, a carboxyl group, a hydroxyl group, a thiol, an amino group, an imino group, a carbon-carbon double bond (alkene) or a carbon-carbon triple bond (alkyne)) present in a noncovalent bonding polymer , An unsaturated bond, a nitrile group, a ketone group, an aldehyde group, an ester group, an amide group, an imide group), or by ketone itself. Therefore, in the case of the coating liquid for forming a functional polymer film which is not heated to a high temperature (for example, 100 ° C or less), the water-soluble polymer represented by the above formulas [A] to [D] Does not react with the monomer for synthesis, but is heated and introduced into the polymer for processing via the myristic acid structure. Further, k ₁ to k ₄ [A] to [D] in the formula [A] to [D] have two or more meldrum structures. Therefore, after heating, It is presumed that the structure is crosslinked by the water-soluble compound.

Therefore, the functional polymer film obtained by applying the coating liquid for forming a functional polymer film of the present invention to a substrate and firing is characterized in that the structure of W ₁ to W ₅ of the hydrolytic compound represented by the above formulas [A] to [D] Which is introduced into the polymer.

Here, the polyimide film, which is one example of the conventional functional polymer film, is widely used as a liquid crystal alignment film, a protective material and an insulating material in the electric and electronic fields due to its high mechanical strength, heat resistance and solvent resistance. A variety of diamine components are used as a part of raw materials, but there are cases where desired diamine components can not be freely used. For example, in a liquid crystal alignment film, various diamine components are used as a part of raw materials in order to improve desired properties such as liquid crystal orientation and pretilt angle improvement. However, diamines Depending on the kind, combination, and amount of the components, the polymerization reactivity between the diamine component and the tetracarboxylic acid component deteriorates, so that the types, combinations, and amounts of the diamine components for obtaining desired characteristics may be limited. It is also necessary to study the polymerization reaction conditions of the diamine component and the tetracarboxylic acid component for each type and combination of diamine components used to obtain desired properties. In order to form a coating liquid for forming a polyimide film (coating liquid for forming a functional polymer film) capable of forming a uniform polyimide film, it is necessary to prepare a solution state in which the contained component is dissolved in a solvent. However, There is a problem that the solubility of the polyimide precursor and polyimide contained in the coating solution for forming a polyimide film deteriorates depending on the kind, combination, or amount of the diamine component used for the polyimide film forming solution. In addition, when various monomers are used as a part of raw materials in order to improve desired characteristics in various polymer films, not only the polyimide film, but also the problem that polymerization reactivity is deteriorated, There is a problem in that it is necessary to examine the polymerization reaction conditions for each type and combination of monomers to be used and the problem that the solubility of the polymer contained in the functional polymer film forming coating liquid deteriorates.

In the present invention, at the stage of the coating liquid for forming a functional polymer film, a monomer for synthesizing a subject-use polymer or a subject-use polymer is mixed with a monomer for obtaining a desired property, (A) to (D), which is a compound for obtaining desired properties, in the step of heating (firing) the coating solution for forming a functional polymer film, Polymer. Therefore, the water-useable polymer contained in the coating liquid for forming a functional polymer film does not need to have a monomer as a raw material for obtaining a desired property, so that the polymerization reactivity of the monomer is deteriorated, the type of the monomer There is no problem that the polymerization reaction conditions need to be examined for each combination or the problem that the solubility of the polymer contained in the coating liquid for forming a functional polymer film deteriorates. Therefore, the coating liquid for forming a functional polymer film of the present invention can be used for the purpose of obtaining a desired property (function) without considering the polymerization reactivity of the monomer, the necessity of examination of polymerization reaction conditions, and the solubility of the polymer It is possible to comparatively freely improve various properties of the obtained functional polymer film as compared with the conventional coating liquid for forming a polymer film.

When the coating liquid for forming a functional polymer film of the present invention contains the hydrolyzable compound represented by the above formulas [A] to [D] having two or more melamine structures, the water-soluble polymer is heated The functional polymer film obtained is crosslinked with the water-soluble compounds represented by the above-mentioned formulas [A] to [D], so that the resulting functional polymer film is resistant to organic solvents and becomes a hard film.

It is also possible to use a polyimide precursor obtained by polymerizing at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component and a polyimide obtained by imidizing the polyimide precursor , And a coating solution for forming a functional polymer film containing the hydrolyzable compound represented by the formula [i] and having two melamine acid structures, is used, the hydrolyzing compound represented by the formula [i] A diamine compound is introduced into each of the two amino groups of the diamine compound, and a diamine component, that is, a tetracarboxylic acid component is reacted with the diamine component to obtain desired properties, which have been conventionally studied as the diamine compound, As a diamine component for producing a midium, a diamine component for obtaining desired properties It can be used. Therefore, various characteristics of the obtained polyimide film can be easily improved.

In the case of a coating liquid for forming a functional polymer film containing a water-soluble polymer, the water-soluble compounds represented by the above formulas [A] to [D] are introduced as side chains in the water- When the hydrolytic compound represented by [A] to [D] has two or more hydrolyzate structures, the hydrolyzable polymer is a structure crosslinked by the hydrolytic compounds represented by the above formulas [A] to [D] . In the case of a coating liquid for forming a functional polymer film containing a monomer for synthesizing a fishmealable polymer, the melamine acid structure of the water-soluble compound represented by the above formulas [A] to [D] The polymer for processing is first polymerized at a low temperature to synthesize a polymer to be used for the synthesis of a carbohydrate polymer and then heated so that the carbohydrate compound represented by the formula [A] to [D] In the case where the hydrolyzable polymer represented by the above formulas [A] to [D] has two or more melamine structures, it is preferable that the hydrogenated polymer is represented by the formula [A] to [D Is a structure bridged by a hydrotreating compound represented by the following formula. However, in the case of the coating liquid for forming a functional polymer film containing the monomer for synthesizing the water-soluble polymer and the water-soluble compound represented by the above formulas [A] to [D] having two or more melamine structures, A to D are added to the main chain of the polymer to be processed so as to generate a reaction with the mordaric acid structure simultaneously with the polymerization of the monomers by setting the temperature at which both of the polymerization reaction and the reaction of the melamine acid structure occurs May also be introduced.

The method of producing the coating liquid for forming a functional polymer film of the present invention is not particularly limited and may be any one of the above-mentioned formulas [A] to [D] having functional structural moieties for imparting functionality and at least one meld acid structural moiety connected thereto And a monomer for synthesizing a polymer to be used for processing or a polymer to be used for processing can be dissolved in a solvent.

The solvent of the coating liquid for forming a functional polymer film of the present invention contains a monomer for synthesizing the above-mentioned subject matter-containing polymer or subject matter-containing polymer, a functional structure region for imparting functionality and at least one mulsion acid structure region connected thereto As long as it is capable of dissolving the water-soluble compounds represented by the above formulas [A] to [D], for example, N, N-dimethylformamide, N, N-dimethylacetamide, But are not limited to, pyrrolidone, pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, isobutyl ketone, Diglyme and 4-hydroxy-4-methyl-2 - pentanone, and the like. These may be used alone or in combination.

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

It is preferable that the content of the monomer for synthesizing the subject-use polymer or the subject-use polymer in the coating liquid for forming a functional polymer film of the present invention is 3 to 30% by mass. This content can also be appropriately changed depending on the intended thickness of the functional polymer film.

The content of the water-soluble compound represented by the above formulas [A] to [D] in the coating liquid for forming a functional polymer film of the present invention is not particularly limited as long as it dissolves. However, It is preferably 1 to 200 parts by mass based on 100 parts by mass of the total amount of the monomers to be used, more preferably 1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass in order not to lower the alignment property of the liquid crystal.

The coating liquid for forming a functional polymer film of the present invention can improve the uniformity of the thickness of the functional polymer film and the surface smoothness when the coating liquid for forming a functional polymer film of the present invention is applied as long as the effect of the present invention is not impaired An organic solvent (also referred to as a poor solvent) or a compound can be used. Further, a compound or the like which improves the adhesion between the functional polymer film and the substrate may be used.

Specific examples of the poor solvent for improving the uniformity of the film thickness or the surface smoothness include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve, Propylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, ethylene glycol monoacetate, ethylene 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, dipropyl ether Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol Diisobutyl ether, diisobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, ethyl acetate, isopropyl acetate, n-butyl acetate, propyleneglycol monoethyl ether acetate, methyl pyruvate, methyl pyruvate, methyl 3-methoxypropionate, 3-ethoxypropionate Methyl ethyl, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol- Acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n- Butyl ester of lactic acid, or an organic solvent having low surface tension such as lactic acid diisobutyl ester. These poor solvents may be used alone or in combination. When such a poor solvent is used, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total amount of the organic solvent contained in the coating liquid for forming a functional polymer film.

Examples of the compound that improves film thickness uniformity and surface smoothness include fluorinated surfactants, silicone surfactants, and nonionic surfactants. Specific examples thereof include Fulfone EF301, EF303, EF352 SC101, SC102, SC103, SC104, SC105 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, R-30 (manufactured by Dainippon Ink), Florad FC430 and FC431 , SC106 (manufactured by Asahi Glass Co., Ltd.), and the like. The ratio of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, relative to 100 parts by mass of the total amount of the monomers for synthesizing the water-extractable polymer or the water-soluble polymer contained in the coating liquid for forming a functional polymer film Is 0.01 to 1 part by mass.

Specific examples of the compound improving the adhesion between the functional polymer film and the substrate include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3- Aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl triethylenetriamine , N-trimethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-tri Methoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2, N, N ', N', N'-tetraglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, 2-dibromoneopentyl glycol diglycidyl ether, (N, N-diglycidylaminomethyl) cyclohexane or N, N, N ', N', -tetraglycidyl-4,4'-diamino di Phenylmethane Functional silane-containing compounds and epoxy group-containing compounds.

When a compound which adheres to these substrates is used, it is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total amount of the monomer for synthesizing the water-soluble polymer or the water-soluble polymer contained in the coating liquid for forming a functional polymer film of the present invention And 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 can not be expected. If the amount is more than 30 parts by mass, the alignment property of the liquid crystal may deteriorate when the functional polymer film is used as the liquid crystal alignment film.

The coating liquid for forming a functional polymer film of the present invention may contain a dielectric material or a conductive material for the purpose of changing electric characteristics such as dielectric constant and conductivity of the functional polymer film as long as the effect of the present invention is not impaired.

In the coating liquid for forming a functional polymer film of the present invention, a crosslinking compound having an epoxy group, an isocyanate group or an oxetane group, and further, a hydroxyl group or an alkoxyl group, A crosslinkable compound having at least one substituent selected 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 alignment film. The liquid crystal alignment film is a film for aligning the liquid crystal in a predetermined direction.

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

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

The method of applying the coating liquid for forming a functional polymer film to the substrate is not particularly limited, but is generally industrially carried out by screen printing, offset printing, flexographic printing, inkjet or the like. As other coating methods, there are dips, roll coaters, slit coaters, spinners and the like, and they may be used depending on the purpose.

A coating liquid for forming a functional polymer film is applied on a substrate, and if necessary, a part or all of the solvent is dried. In the case where the coating liquid for forming a functional polymer film contains a monomer for synthesizing a polymer to be processed, it is preferable that the monomer is polymerized in the step of applying the coating liquid for forming a functional polymer film on the substrate or in the step of drying .

Then, a coating solution for forming a functional polymer film is coated on a substrate, and if necessary, a part or the whole of the solvent is dried and then fired. This firing is carried out in such a manner that the molar acid structure of the hydrolytic compound represented by the above formulas [A] to [D] becomes ketene or the like and the carboxyl group, hydroxyl group, thiol group, amino group, imino group, It may be heated to a temperature capable of reacting with a reactive site such as an unsaturated bond such as carbon double bond (alkene) or carbon-carbon triple bond (alkyne), nitrile group, ketone group, aldehyde group, ester bond, amide bond, . For example, by heating at 180 to 250 DEG C by a heating means such as a hot plate, a hot air circulation path or an infrared ray furnace, allowing the solvent to evaporate and reacting the melamine acid structure with the water-soluble polymer, The functional group represented by [A] to [D] is introduced to form the functional polymer film of the present invention.

The thickness of the functional polymer film formed after firing is deteriorated in view of the power consumption of the liquid crystal display element if it is made too large when the liquid crystal alignment film is used and the reliability of the liquid crystal display element is deteriorated when it is too thin. 300 nm, more preferably 10 to 200 nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a liquid crystal cell is produced by a known method after obtaining a substrate having a liquid crystal alignment film attached thereto by the above-mentioned technique, thereby forming a liquid crystal display element. A liquid crystal layer formed between the substrate and the liquid crystal layer and formed by a liquid crystal aligning agent composed of a coating liquid for forming a functional polymer film of the present invention, A liquid crystal display device comprising a liquid crystal cell having a liquid crystal alignment film. Examples of the liquid crystal display of the present invention include various types of liquid crystal display devices such as twisted nematic (TN), vertical alignment (VA), and in-plane switching (IPS) have.

The substrate used in the liquid crystal display of the present invention is not particularly limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrates as those described in the above-mentioned functional polymer film.

The liquid crystal alignment film is formed by applying a liquid crystal aligning agent comprising the coating liquid for forming a functional polymer film of the present invention onto the substrate and then firing the liquid crystal alignment film. 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 and MLC-6609 manufactured by Merck can be used.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads are dispersed on a liquid crystal alignment film of one of the substrates to make the liquid crystal alignment film face inward, A method in which a substrate is bonded and a liquid crystal is injected under reduced pressure and a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed and a substrate is bonded and sealed is exemplified. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

The liquid crystal display device manufactured as described above can be used as a liquid crystal display device which is capable of introducing desired characteristics, a liquid crystal compound containing a monomer for synthesizing a water-soluble polymer or a water-soluble polymer, And since it is produced by using an aligning agent, various properties can be improved.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the interpretation of the present invention is not limited to these examples.

[Synthesis of hydrolyzable compounds represented by the above formulas [A] to [D]

≪ Synthesis Example 1 &

The compound represented by the following formula [4]

Synthesis of bis (methane-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(41)

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 ml four-necked flask and refluxed for 1 hour. Thereafter, paraphenylenediamine [3] (5.0 g, 46 mmol) was added, and the mixture was 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 15.8 g (yield: 82%) of compound [4].

≪ Synthesis Example 2 &

The compound represented by the following formula [6]

Synthesis of 5,5 '- (1,3-phenylenebis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(42)

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, metaphenylenediamine [5] (5.0 g, 46 mmol) was added, and the mixture was refluxed with heating 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 14.1 g (yield: 72%) of compound [6].

≪ Synthesis Example 3 &

The compound represented by the following formula [8]

5,5'- (pyridine-2,6-diylbis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione) synthesis

(43)

Meldrum acid [1] (16.0 g, 111 mmol) and trimethyl orthoformate [2] (160 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, 2,6-diaminopyridine [7] (5.5 g, 50 mmol) was added, and the mixture was 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 16.7 g (yield: 80%) of compound [8].

≪ Synthesis Example 4 &

The compound represented by the following formula [11]

(Benzene-1,3,5-triyltris (azanediyl)) tris (methan-1-yl-1-ylidene) tris (2,2- dimethyl- 1,3-dioxane-4 , 6-dione)

(44)

(32.6 g, 178 mmol), 5% palladium carbon (3.75 g, 10 wt%) and 1,4-dioxane (375 g) in a 1 L four- Was stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, the palladium carbon was filtered through a celite, and the filtrate was concentrated by using an effervescent device to obtain 21.7 g (yield: 99%) of the compound [10].

Meldrum acid [1] (83.8 g, 582 mmol) and trimethyl orthoformate [6] (660 g) were added to a 1 L four-necked flask and refluxed for 1 hour. Thereafter, the compound [10] (21.7 g, 176 mmol) was added, and the mixture was 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 73.0 g (yield: 71%) of the compound [11].

≪ Synthesis Example 5 &

The compound represented by the following formula [13]

1-ylidene) bis (2,2-dimethyl-1,3-dioxane-1-ylidene) bis- (4,4'- methylenebis (4,1- phenylene) bis (azanediyl) 4,6-dione)

[Chemical Formula 45]

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, 4,4'-diaminodiphenylmethane [12] (5.0 g, 46 mmol) was added, and the mixture was 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 14.1 g (yield: 72%) of the compound [13].

≪ Synthesis Example 6 &

The compound represented by the following formula [15]

Bis (2,2-dimethyl-1,3-dioxane-1-ylidene) bis (4,4'-oxybis (4,1-phenylene) bis (azanediyl) 4,6-dione)

(46)

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 under reflux for 1 hour. Thereafter, 4,4'-diaminodiphenyl ether [14] (5.0 g, 25.0 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtrated and washed with hexane. Thereafter, the solid was dried to obtain 11.7 g (yield 92%) of compound [15].

≪ Synthesis Example 7 &

The compound represented by the following formula [17]

1-ylidene) bis (2,2-dimethyl-1,3-dioxane-bis- (4,4'-azinediylbis (4,1- 4,6-dione)

(47)

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 refluxed for 1 hour. Thereafter, 4,4'-diaminodiphenylamine [16] (5.0 g, 25.1 mmol) was added, and the mixture was refluxed 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 10.1 g (yield: 79%) of the compound [17].

≪ Synthesis Example 8 &

The compound represented by the following formula [19]

1-ylidene) bis (2,2-dimethyl-1,3,5-bis (4,1'-phenylene) bis (azanediyl) bis (methan- -dioxane-4,6-dione < / RTI >

(48)

Meldrum acid [1] (14.9 g, 103 mmol) and trimethyl orthoformate [2] (100 g) were added to a 500 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, 4,4'-diaminodiphenylmethylamine [18] (10.0 g, 46.9 mmol) was added and the mixture was refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtrated and washed with hexane. Thereafter, the solid was dried to obtain 21.7 g (yield: 86%) of the compound [19].

≪ Synthesis Example 9 &

The compound represented by the following formula [21]

Bis (4-phenylene)) bis (azanediyl) bis (methan-1-yl-1-ylidene) bis 2,2-dimethyl-1,3-dioxane-4,6-dione)

(49)

Meldrum acid [1] (16.6 g, 115 mmol) and trimethyl orthoformate [2] (111 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [20] (15.0 g, 52.4 mmol) was added, and the mixture was heated under reflux for 2 hours. After the 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 (yield 67%) of the compound [21].

≪ Synthesis Example 10 &

The compound represented by the following formula [23]

1,3-bis (4 - ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino)

phenethyl) urea

(50)

Meldrum acid [1] (28.6 g, 147 mmol) and trimethyl orthoformate [2] (200 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [22] (20.0 g, 67.0 mmol) was added, and the mixture was 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 40.3 g (yield: 99%) of compound [23].

≪ Synthesis Example 11 &

The compound represented by the following formula [25]

5,5 '- (6,7,9,10,17,18,20,21-octahydrodibenzo [b, k] [1,4,7,10,13,16] hexaoxa cyclooctadecine-2,13- Synthesis of bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(51)

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 the mixture was heated under reflux for 1 hour. Thereafter, the compound [24] (10.0 g, 25.6 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 17.9 g (yield: 96%) of the compound [25].

≪ Synthesis Example 12 &

The compound represented by the following formula [27]

5 - ((3 - ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino)

benzylamino) methylene) -2,2-dimethyl-1,3-dioxane-4,6-dione

(52)

Meldrum acid [1] (23.6 g, 164 mmol) and trimethyl orthoformate [2] (100 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Then, 3-aminobenzylamine [26] (10.0 g, 81.9 mmol) was added, and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 36.2 g (yield: 100%) of the compound [27].

≪ Synthesis Example 13 &

The compound represented by the following formula [29]

1-ylidene) bis (2,2-dimethyl-1,3,4-triazolo [4,5-b] -1,3-dioxane-4,6-dione)

(53)

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 refluxed for 1 hour. Thereafter, 1,3-di-4-piperidyl propane [28] (8.52 g, 40.5 mmol) was added and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 20.2 g (yield: 99%) of the compound [29].

≪ Synthesis Example 14 &

The compound represented by the following formula [31]

5,5'- (propane-1,3-diylbis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione) synthesis

(54)

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 under reflux for 1 hour. Thereafter, 1,3-diaminopropane [30] (10.0 g, 135 mmol) was added, and the mixture was refluxed for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane. Thereafter, the solid was dried to obtain 24.8 g (yield: 48%) of the compound [31].

≪ Synthesis Example 15 &

The compound represented by the following formula [33]

Bis (2,2-dimethyl-1,3-dioxane-4,6 (cyclohexane-1,3-diylbis (methylene) -dione < / RTI >

(55)

Meldrum acid [1] (44.6 g, 309 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 ml four-necked flask, and the mixture was 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 refluxed 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 a compound [33] (cis- / trans- mixture) ).

≪ Synthesis Example 16 &

The compound represented by the following formula [35]

Synthesis of 5,5 '- (5,8-dioxa-2,11-dithiadodecane-1,12-diylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(56)

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 refluxed for 1 hour. Thereafter, 3,6-dioxa-1,8-octanedithiol [34] (7.8 g, 42.8 mmol) was added and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 20.8 g (yield: 99%) of the compound [35].

≪ Synthesis Example 17 &

The compound represented by the following formula [37]

3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino)

Synthesis of benzoic acid

(57)

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 refluxed for 1 hour. Thereafter, 3,5-diaminobenzoic acid [36] (5.0 g, 32.9 mmol) was added, and the mixture was refluxed 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 9.0 g (yield: 59%) of compound [37].

≪ Synthesis Example 18 &

The compound represented by the following formula [39]

Synthesis of 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) -N- (pyridin-3-ylmethyl)

(58)

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 the mixture was heated under reflux for 1 hour. Thereafter, Compound [38] (5.0 g, 20.6 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 11.3 g (yield: 98%) of the compound [39].

≪ Synthesis Example 19 &

The compound represented by the following formula [41]

Synthesis of N- (3- (1H-imidazol-1-yl) propyl) -3,5-bis (2,2-dimethyl-4,6-dioxo-1,3-dioxan- synthesis

[Chemical Formula 59]

Meldrum acid [1] (10.1 g, 52.1 mmol) and trimethylorthoformate [2] (50 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [40] (5.0 g, 23.7 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 13.4 g (yield: 100%) of the compound [41].

≪ Synthesis Example 20 &

The compound represented by the following formula [43]

Synthesis of 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzyl furan-2-carboxylate

(60)

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 the mixture was heated under reflux for 1 hour. Thereafter, the compound [42] (10.0 g, 43.1 mmol) was added and the mixture was 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 21.1 g (yield: 90%) of the compound [43].

≪ Synthesis Example 21 &

The compound represented by the following formula [45]

Bis (2,2-dimethyl-1,3-dioxane-4, 4-dodecyloxy) -1,3-phenylene) bis (azanediyl) bis (methan- 6-dione < / RTI >

(61)

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 under reflux for 1 hour. Thereafter, the compound [44] (10.0 g, 34.2 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 29.7 g (yield: 99%) of the compound [45].

≪ Synthesis Example 22 >

The compound represented by the following formula [47]

1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,4-dicarboxylate) 6-dione < / RTI >

(62)

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 the mixture was heated under reflux for 1 hour. Thereafter, the compound [46] (5.0 g, 13.3 mmol) was added, and the mixture was 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 (yield: 71%) of the compound [47].

≪ Synthesis Example 23 >

The compound represented by the following formula [49]

Bis (2,2-dimethyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethylphenyl) -1,3-dioxane-4,6-dione)

(63)

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 the mixture was heated under reflux for 1 hour. Thereafter, the compound [48] (5.0 g, 13.1 mmol) was added and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 9.0 g (yield: 98%) of the compound [49].

≪ Synthesis Example 24 &

The compound represented by the following formula [51]

Bis (methan-1-yl) -1,2,3,4-tetrahydronaphthalen-1-yl] -ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

≪ EMI ID =

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 under reflux for 1 hour. Thereafter, the compound [50] (12.3 g, 28.2 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 20.68 g (yield: 98%) of the compound [51].

≪ Synthesis Example 25 >

The compound represented by the following formula [53]

Bis (methan-1-yl) phenoxy) methyl) -1,3-phenylene) bis (azanediyl) bis- (trans- 4- yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(65)

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 refluxed for 1 hour. Thereafter, the compound [52] (20.0 g, 44.6 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 33.4 g (yield: 99%) of the compound [53].

≪ Synthesis Example 26 &

The compound represented by the following formula [55]

Synthesis of 4'-pentylbi (trans-cyclohexan) -4-yl 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzoate

(66)

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 refluxed for 1 hour. Thereafter, the compound [54] (15.0 g, 41.8 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 28.8 g (yield: 99%) of compound [55].

≪ 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- (trans-4-pentylcyclohexyl) benzamide

(67)

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 under reflux for 1 hour. Thereafter, Compound [56] (10.0 g, 25.8 mmol) was added, and the mixture was 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 16.0 g (yield: 92%) of the compound [57].

≪ Synthesis Example 28 >

The compound represented by the following formula [59]

Synthesis of N- (2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenyl) -4- (trans-4-heptylcyclohexyl)

(68)

Meldrum acid [1] (11.7 g, 81.0 mmol) and trimethyl orthoformate [2] (150 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [58] (15.0 g, 36.8 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtrated and washed with hexane. Thereafter, the solid was dried to obtain 26.1 g (yield: 99%) of Compound [59].

≪ Synthesis Example 29 &

The compound represented by the following formula [61]

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

(69)

Meldrum acid [1] (4.1 g, 29 mmol) and trimethyl orthoformate [2] (50 g) were added to a 100 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [60] (10.0 g, 13 mmol) was added, and the mixture was 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 9.9 g (yield: 99%) of Compound [61].

≪ Synthesis Example 30 &

And is represented by the following formula [63]

Synthesis of (E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenethyl 3-

(70)

Meldrum acid [1] (7.3 g, 37 mmol) and trimethyl orthoformate [2] (75 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [62] (7.46 g, 17 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 12.5 g (yield: 99%) of the compound [63].

≪ Synthesis Example 31 &

And is represented by the following formula [65]

Synthesis of (E) -3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino)

(71)

Meldrum acid [1] (6.3 g, 33 mmol) and trimethyl orthoformate [2] (63 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [64] (6.3 g, 15 mmol) was added and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 10.7 g (yield: 99%) of the compound [65].

≪ Synthesis Example 32 >

The compound represented by the following formula [66]

Synthesis of 5- (methoxymethylene) -2,2-dimethyl-1,3-dioxane-4,6-dione

(72)

Meldrum acid [1] (50.0 g, 347 mmol) and trimethyl orthoformate [184 g) were added to a 500 ml four-necked flask, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was removed with a separator, and the crude product was recrystallized from a hexane / tetrahydrofuran mixed solvent to obtain 43.7 g (yield: 68%) of Compound [66].

≪ Synthesis Example 33 >

The compound represented by the following formula [68]

Synthesis of 5 - ((dodecylamino) methylene) -2,2-dimethyl-1,3-dioxane-4,6-dione

(73)

Meldrum acid [1] (21.4 g, 148 mmol) and trimethyl orthoformate [2] (250 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, dodecylamine [67] (25.0 g, 135 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 45.3 g (yield: 99%) of the compound [68].

≪ Synthesis Example 34 &

The compound represented by the following formula [70]

Synthesis of 2,2-dimethyl-5 - ((octadecylamino) methylene) -1,3-dioxane-4,6-dione

≪ EMI ID =

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (250 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, octadecylamine [69] (25.0 g, 93 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 38.9 g (yield: 99%) of the compound [70].

≪ Synthesis Example 35 >

The compound represented by the following formula [72]

Synthesis of 5,5 '- (1,4-phenylenebis (methan-1-yl-1-ylidene)) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(75)

Terephthalaldehyde [10] (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 the mixture was stirred at room temperature overnight . Thereafter, the pyridine was removed by means of this distributor. Thereafter, the residue was dissolved in a mixed solvent of 1,2-dichloroethane / methanol, and the solvent was again removed by using a diverterator to cause crystallization. The obtained solid was recrystallized from 2-propanol to obtain 18.8 g (yield: 65%) of the compound [72].

≪ Synthesis Example 36 >

The compound represented by the following formula [74]

Synthesis of 5,5 '- (1,3-phenylenebis (methan-1-yl-1-ylidene)) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

[Formula 76]

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 did. Thereafter, the pyridine was removed by means of this distributor. Thereafter, the residue was dissolved in a mixed solvent of 1,2-dichloroethane / methanol, and the solvent was again removed by using a diverterator to cause crystallization. The resulting solid was recrystallized from 2-propanol to obtain 16.2 g (yield: 56%) of the compound [74].

≪ Synthesis Example 37 &

The compound represented by the following formula [78]

Synthesis of tris (4 - ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) phenyl) benzene-1,3,5-tricarboxylate

[Formula 77]

4-hydroxybenzaldehyde (35.7 g, 292 mmol), triethylamine (31.5 g, 311 mmol) and tetrahydrofuran (150 g) were added to a 1 L four-necked flask, Lt; / RTI > Thereto was added dropwise a solution of 1,3,5-benzenetricarbonyl trichloride [75] (25.0 g, 94 mmol) in tetrahydrofuran (225 g) while paying attention to heat generation. After completion of dropwise addition, the reaction was further carried out 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 and washed with methanol, and the solid was dried to obtain 48.0 g (yield: 98%) of Compound [77].

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 stirred overnight at room temperature. Thereafter, the pyridine was removed by means of this distributor. Thereafter, the residue was recrystallized from a tetrahydrofuran / hexane mixed solvent to obtain 75.6 g (yield: 91%) of the compound [78].

≪ Synthesis Example 38 &

The compound represented by the following formula [80]

Synthesis of 5- (1-hydroxypentylidene) -2,2-dimethyl-1,3-dioxane-4,6-dione

(78)

N, N-dimethylaminopyridine (DMAP: 32.6 g, 267 mmol), dicyclohexylcarbamate (25.0 g, 245 mmol) and dicyclohexylcarbodiimide (DCC: 55.6 g, 270 mmol) and Meldrum 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 this separator. The crude product was dissolved in ethyl acetate (300 g) and washed with 1 M hydrochloric acid. The organic layer was dried over magnesium sulfate, filtered and the solvent was distilled off to obtain 53.6 g (yield: 96%) of the compound [80].

≪ Synthesis Example 39 &

The compound represented by the following formula [82]

Synthesis of 5- (1-hydroxytetradecylidene) -2,2-dimethyl-1,3-dioxane-4,6-dione

(79)

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 . In addition, myristic acid chloride (42.7 g, 173 mmol) was added dropwise while paying attention to heat generation. After completion of dropwise addition, 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 water and saturated brine in this order, and dried with magnesium sulfate. This solution was filtrated and the solvent was distilled off, and the obtained product was purified by column (hexane / ethyl acetate) to obtain 29.1 g of the compound [82] (yield: 66%).

≪ Synthesis Example 40 &

The compound represented by the following formula [84]

Synthesis of 5- (3,5-dimethoxybenzyl) -2,2-dimethyl-1,3-dioxane-4,6-dione

(80)

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. Pyridinium acetate g, 2.89 mmol), and the mixture was stirred for 30 minutes.

Thereafter, the reaction solution was cooled to 0 占 폚, sodium cyanoborohydride (2.7 g, 43.4 mmol) was added little by little, and then the reaction temperature was returned to room temperature. After the completion of the reaction, the gas generated was quenched with 10% hydrochloric acid while care was taken, and then ethanol was distilled off. The crude product was suspended again in 10% hydrochloric acid and extracted three times with dichloromethane (80 g). The organic layer was combined, dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained crude product was recrystallized from methanol to obtain 4.7 g (yield: 55%) of the compound [84].

≪ Synthesis Example 41 &

The compound represented by the following formula [86]

Synthesis of 5- (3,5-dimethoxybenzyl) -2,2-dimethyl-5- (pyridin-4-ylmethyl) -1,3-dioxane-4,6-dione

[Formula 81]

Compound (84) (4.70 g, 16.0 mmol), potassium carbonate (3.31 g, 24.0 mmol) and dimethylformamide (DMF) (50 g) were added to a 200 L four- Pyridine 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, washed with saturated sodium hydrogencarbonate and saturated brine, and then the organic layer was dried with 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 (yield: 72%) of the compound [86].

≪ Synthesis Example 42 &

The compound represented by the following formula [88]

Synthesis of benzyl 3- (2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl) propanoate

(82)

(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), benzyltriethylammonium chloride (23.9 g, 104 mmol), which was stirred for 15 minutes at room temperature. Thereafter, Compound [87] (25.3 g, 156 mmol) was added and the mixture was heated and stirred at 60 占 폚. After completion of the reaction, the solvent was distilled off, and the resulting crude product was dissolved in ethyl acetate (150 g), washed with 10% potassium hydrogen sulfate three times, and then the organic layer was dried with magnesium sulfate. The solution was filtered and the solvent was distilled off. The obtained crude product was purified by column (SiO ₂ : hexane / ethyl acetate) to obtain 28.4 g (yield: 89%) of the compound [88].

≪ Synthesis Example 43 >

The compound represented by the following formula [90]

Synthesis of (S) -tert-butyl 2- (tert-butoxycarbonylamino) -5- (2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl) pentanoate

(83)

(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 equipped with a stirrer, After the reaction solution was cooled to 0 占 폚, 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 with 10% potassium hydrogen sulfate three times with saturated brine, and the organic layer was dried with magnesium sulfate. Acetic acid (50 mL) was then added to make the solution acidic and cooled to 0 < 0 > C. Sodium borohydride (9.0 g, 236 mmol) was added little by little and the mixture was stirred at 0 캜 again. After completion of the reaction, the reaction mixture was washed with saturated brine and pure water, and the organic layer was dried over magnesium sulfate. The solution was filtered and the solvent was distilled off to obtain an amorphous product. This non offerings column purification (SiO ₂ : Hexane / ethyl acetate) to obtain 34.1 g (yield: 79%) of the compound [90].

≪ Synthesis Example 44 >

The compound represented by the following formula [92]

Synthesis of 5- (bis (methylthio) methylene) -2,2-dimethyl-1,3-dioxane-4,6-dione

(84)

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 and carbon disulfide (21.6 g, 284 mmol ), Which was stirred for 1 hour at room temperature. Thereafter, the reaction solution was ice-cooled, and methyl iodide (80.6 g, 568 mmol) was slowly added thereto and the reaction was carried out again 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 (yield: 52%) of the compound [92].

≪ Synthesis Example 45 >

The compound represented by the following formula [94]

Synthesis of 2,2-dimethyl-5- (methylthio (neopentylamino) -methylene) -1,3-dioxane-4,6-dione

(85)

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 stirred at room temperature. After completion of the reaction, the solvent was concentrated to about half with a separator, and diethyl ether (100 g) was added thereto. The precipitated solid was filtered and recrystallized from a THF / diethyl ether mixed solvent to obtain Compound [94 ] To obtain 16.9 g (yield: 77%).

≪ Synthesis Example 46 >

The compound represented by the following formula [95]

Synthesis of 2,2-dimethyl-5- (methylthio (neopentylamino) -methylene) -1,3-dioxane-4,6-dione

≪ EMI ID =

Compound [92] (2.42 g, 10 mmol), 2,2-dimethylpropylamine (2.62 g, 30 mmol) and ethanol (60 g) were added to a 200 ml four-necked flask and heated under reflux. After completion of the reaction, the solvent was concentrated to about half with a diverter, diethyl ether (50 g) was added, and the mixture was cooled to 0 캜 to precipitate a solid. Thereafter, the solid was filtered and recrystallized from a THF / diethyl ether mixed solvent to obtain 1.62 g (yield: 50%) of the compound [95].

≪ Synthesis Example 47 >

Synthesis of 5,5 '- (1,8-dihydroxyoctane-1,8-diylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione) represented by the following formula [97]

[Chemical Formula 87]

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. The reaction solution was cooled to 0 ° C, A solution of dicarbonyl dichloride [96] (11.98 g, 51 mmol) in dichloromethane (50 g) was slowly added with caution to exothermicity, and then the reaction was carried out again at 23 ° C. After completion of the reaction, the solution was acidified with a 10% hydrochloric acid aqueous solution, and the solvent was distilled off using this separator. Thereafter, the solid was filtered, washed with pure water, and recrystallized from a mixed solvent of dichloromethane / diethyl ether to obtain 16.6 g (yield: 78%) of the compound [97].

≪ Synthesis Example 48 >

Represented by the following formula [99]

5,5 '- (((6,7,9,10,17,18,20,21-octahydrodibenzo [b, k] [1,4,7,10,13,16] hexa oxacyclooctadecine- bis (azanediyl) bis (methanylylene)) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

[Formula 88]

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 refluxed for 1 hour. Thereafter, the compound [98] (6.00 g, 15.4 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 10.4 g (yield: 97%) of the compound [99].

≪ Synthesis Example 49 >

Represented by the following formula [101]

Bis (2,2-dimethyl-1,3-dioxane-4,6-diazacyclooctadecane-7,16-diyl) bis (methanylidene) 6-dione < / RTI >

(89)

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 refluxed for 1 hour. Thereafter, the compound [100] (20.00 g, 76.2 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 43.2 g (yield: 100%) of the compound [101].

≪ Synthesis Example 50 &

[0092]

Bis (oxy) bis (4,1-phenylene)) - bis

bis (azanediyl) bis (methanylylene)) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(90)

Meldrum acid [1] (22.00 g, 153 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 ml four-necked flask and refluxed for 1 hour. Thereafter, Compound [102] (20.00 g, 69.4 mmol) was added, and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 40.2 g (yield: 97%) of the compound [103].

≪ Synthesis Example 51 &

The following formula [105]

Synthesis of 2- (methacryloyloxy) ethyl3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) benzoate

[Formula 91]

Meldrum acid [1] (24.18 g, 168 mmol) and trimethyl orthoformate [2] (300 g) were added to a 500 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [104] (20.00 g, 76.3 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, hexane was added thereto, followed by filtration, followed by drying to obtain 43.7 g (yield: 100%) of the compound [105].

≪ Synthesis Example 52 &

Represented by the following formula [107]

(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- (4'- 1'-biphenyl] -4-yl) acrylate

≪ EMI ID =

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 the mixture was heated under reflux for 1 hour. Thereafter, Compound [106] (4.00 g, 9.3 mmol) was added, and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 6.8 g (yield: 99%) of the compound [107].

≪ Synthesis Example 53 >

The following formula [109]

Synthesis of (E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- (4-cyclohexylphenyl)

≪ EMI ID =

Meldrum acid [1] (4.35 g, 30 mmol) and trimethyl orthoformate [2] (50 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Thereafter, the compound [108] (5.00 g, 14 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 9.63 g (yield: 99%) of the compound [109].

<Synthesis Example 54>

Represented by the following formula [111]

(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino] phenethyl 3- (4- Synthesis of 1'-bi (cyclohexan)] -4-yl) phenyl) acrylate

(94)

Meldrum acid [1] (2.84 g, 20 mmol) and trimethyl orthoformate [2] (40 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [110] (4.00 g, 9.0 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 6.6 g of a compound [111] (yield: 99%).

&Lt; Synthesis Example 55 &

Represented by the following formula [113]

Synthesis of (E) -4 - ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenethyl 3- (4-cyclohexylphenyl)

&Lt; EMI ID =

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 under reflux for 1 hour. Then, Compound [112] (3.00 g, 8.6 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 4.22 g (yield: 99%) of the compound [113].

&Lt; Synthesis Example 56 &gt;

The following formula [115]

(E) -2,4-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- (4- (trans -4-pentylcyclohexyl ) phenyl) acrylate

&Lt; EMI ID =

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 under reflux for 1 hour. Thereafter, the compound [114] (13.79 g, 31.7 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 22.4 g (95% yield) of the compound [115].

&Lt; Synthesis Example 57 &gt;

Represented by the following formula [117]

(E) -2,4-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- (4- (trans-4-heptylcyclohexyl ) phenyl) acrylate

[Formula 97]

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 under reflux for 1 hour. Thereafter, the compound [116] (5.00 g, 10.8 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 8.3 g (yield: 100%) of the compound [117].

&Lt; Synthesis Example 58 &

Represented by the following formula [119]

(E) -3,5-bis (((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) benzyl 3- (4- (trans-4-pentylcyclohexyl ) phenyl) acrylate

(98)

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 under reflux for 1 hour. Thereafter, the compound [118] (15.00 g, 35.7 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 25.3 g (yield: 99%) of the compound [119].

&Lt; Synthesis Example 59 &gt;

Represented by the following formula [121]

(E) -3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzyl 3- (4- (trans- - [1,1'-bi (cyclohexan)] -4-yl) phenoxy) acrylate

[Formula 99]

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 the mixture was heated under reflux for 1 hour. Then, Compound [120] (3.00 g, 5.8 mmol) was added, and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 4.8 g (yield: 100%) of the compound [121].

&Lt; Synthesis Example 60 &

The following formula [123]

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

(100)

Meldrum acid [1] (3.64 g, 25 mmol) and trimethyl orthoformate [2] (90 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Thereafter, the compound [122] (9.00 g, 23 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 12.1 g (yield: 99%) of the compound [123].

&Lt; Synthesis Example 61 &

Represented by the following formula [125]

((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- (4- (trans- Synthesis of acrylate

(101)

Meldrum acid [1] (2.00 g, 14 mmol) and trimethyl orthoformate [2] (75 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [124] (4.92 g, 13 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 7.16 g (yield: 100%) of the compound [125].

&Lt; Synthesis Example 62 &

The following formula [127]

Synthesis of 5 - (((4-dodecylphenyl) amino) methylene) -2,2-dimethyl-1,3-dioxane-4,6-dione

&Lt; EMI ID =

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 the mixture was heated under reflux for 1 hour. Thereafter, the compound [126] (20.00 g, 76.5 mmol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 31.1 g (yield: 98%) of the compound [127].

&Lt; Synthesis Example 63 &

Represented by the following formula [129]

5 - (((4- (1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoroheptyl) amino) methylene) -2,2- dimethyl-1,3-dioxane-4,6-dione

&Lt; EMI ID =

Meldrum acid [1] (3.10 g, 22 mmol) and trimethyl orthoformate [2] (20 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [128] (10.00 g, 19.6 mmol) was added, and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 12.6 g (yield: 100%) of the compound [129].

[Synthesis of polyamic acid or polyimide and preparation of solution thereof]

The abbreviations used in the following are as follows.

(Tetracarboxylic acid dianhydride)

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

&Lt; EMI ID =

(Diamine)

p-PDA: p-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

PCH7AB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

&Lt; EMI ID =

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Measurement of molecular weight)

The molecular weight of the polymer (polyamic acid, polyimide and the like) in the present example was measured using a gel permeation chromatography (GPC-101) at room temperature by Shodex Co., Ltd. (GPC-101) -805) manufactured by Mitsui Chemicals, Inc. was used as follows.

Column temperature: 50 ° C

30 mmol / l of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid), 30 ml of tetrahydrofuran (THF) 10 ml / l)

Flow rate: 1.0 ml / min

Sample for Standard Calibration Standard: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Torosaka and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

(Measurement of imidization rate)

In the present embodiment, the imidation rate of polyimide was measured as follows.

About 20 mg of the polyimide powder was placed in an NMR sample tube, and about 0.53 ml of deuterated dimethylsulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added and completely dissolved by ultrasonic wave. This solution was measured by proton NMR at 500 MHz with an NMR measuring device. The proton derived from the structure in which the imidation rate does not change before and after the imidization is determined as the reference proton and the peak integrated value of the proton and the proton peak cumulative value derived from the NH group of the amic acid appearing around 10.0 ppm . 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? Is the sum of the amounts of the amikic acid in the case of the polyamic acid (the imidization rate is 0% Is the number of reference protons for one NH group proton.

Imidization ratio (%) = (1 -? X / y) x 100

<Synthesis of polyamic acid (PAA-1) and preparation of the solution>

7.93 g (40 mmol) of DDM and 20 g of NMP were added and dissolved in a 100 ml four-necked flask. The solution was cooled to about 10 캜, and 7.46 g (38 mmol) of CBDA in NMP (67 g) And the mixture was returned to room temperature and reacted under a nitrogen atmosphere for 6 hours to obtain a solution having a concentration of polyamic acid (PAA-1) of 15 mass%.

88 g of a solution having a concentration of 15 mass% of the polyamic acid (PAA-1) was transferred to a 200 ml Erlenmeyer flask, and 87.6 g of NMP and 43.8 g of BCS were added and diluted to obtain a polyamic acid (PAA- , Polyamic acid (PAA-1) solution having 74 mass% of NMP and 20 mass% of BCS. This polyamic acid (PAA-1) had a number average molecular weight of 12,081 and a weight average molecular weight of 30,449.

<Synthesis of polyamic acid (PAA-2) and preparation of its solution>

8.65 g (80 mmol) of p-PDA and 49 g of NMP were added and dissolved in a 200 ml four-necked flask, and the solution was cooled to about 10 ° C and NMP (80 g) slurry of CBDA 14.1 g (72 mmol) Solution was added, and the mixture was returned to room temperature and reacted under a nitrogen atmosphere for 6 hours to obtain a solution having a concentration of polyamic acid (PAA-2) of 15 mass%.

125 g of a solution having a concentration of 15 mass% of the polyamic acid (PAA-2) was transferred to a 300 ml Erlenmeyer flask, and 118.5 g of NMP and 60.9 g of BCS were added to dilute the polyamic acid (PAA- , Polyamic acid (PAA-2) solution having 74 mass% of NMP and 20 mass% of BCS. This polyamic acid (PAA-2) had a number average molecular weight of 7,609 and a weight average molecular weight of 15,837.

<Synthesis of polyamic acid (PAA-3) and preparation of its solution>

8.05 g (74 mmol) of p-PDA, 2.13 g (5.6 mmol) of PCH7AB and 118 g of NMP were added to and dissolved in a 200 ml four-necked flask, followed by cooling to about 10 캜. ) NMP (100 g) was added thereto, and the mixture was returned to room temperature and reacted under a nitrogen atmosphere for 6 hours to obtain a solution having a concentration of 10 mass% of polyamic acid (PAA-3).

234 g of the solution having a concentration of 10 mass% of the polyamic acid (PAA-3) was transferred to a 300 ml Erlenmeyer flask, and 70.8 g of NMP and 76.2 g of BCS were added to dilute the solution. Polyamic acid (PAA- , Polyamic acid (PAA-3) solution having 74 mass% of NMP and 20 mass% of BCS. This polyamic acid (PAA-3) had a number average molecular weight of 6,092 and a weight average molecular weight of 12,002.

<Synthesis of Soluble Polyimide (SPI-1) and Preparation of Its 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) After the reaction, 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. NMP was added to the polyamic acid solution (130 g) to dilute it to 6 mass%, acetic anhydride (16 g) and pyridine (12 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (1.6 L), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (SPI-1). The imidization ratio of the polyimide was 54%, the number average molecular weight was 18,300, and the weight average molecular weight was 45,300. The amount of the carboxyl group in the polyimide is 0.92 relative to the repeating unit.

NMP (98 g) and BCS (90 g) were added to the polyimide powder (SPI-1) (12.0 g) obtained above and stirred at 80 ° C for 40 hours to dissolve the polyimide powder (SPI- .

[Preparation of coating liquid (liquid crystal aligning agent) for forming polyimide film]

&Lt; Examples 1-10 &gt;

To the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compound described in the following Table 1 as the hydrating compound in the above Synthesis Example was added to the solid content of the polyamic acid (PAA-1) (PAA-1)) was added in an amount of 10 mol%, and the mixture was stirred at room temperature (25 DEG C) until a homogeneous solution was obtained to obtain a coating liquid for forming a polyimide film of Examples 1 to 10 A coating solution for forming a functional polymer film) was prepared.

[Table 1]

&Lt; Examples 11 to 45 &gt;

To the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compound shown in the following Table 2 prepared in the above Synthesis Example as the water-soluble compound was added to each of the solid components of the polyamic acid (PAA- (PAA-1)) was added so as to be the ratio shown in the following Table 2, and stirring was performed at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 11 to 45 was prepared did.

[Table 2]

&Lt; Examples 46 to 57 &gt;

To the polyamic acid (PAA-2) solution (10.0 g) prepared above, the compound shown in the following Table 3 as the hydrating compound in the above Synthesis Example was added to the solid content of the polyamic acid (PAA-2) Polyamic acid (PAA-2)) in an amount of 10 mol%, and stirring was carried out at room temperature until a homogeneous solution was obtained to prepare coating liquids for forming polyimide films of Examples 46 to 57.

[Table 3]

&Lt; Examples 58 to 71 &gt;

(40.0 g) of the polyamic acid (PAA-3) solution prepared in the above-mentioned Synthesis Example as the hydrating compound were added to the polyamic acid solution (PAA-3) (PAA-3)) as shown in Table 4, and the mixture was stirred at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 58 to 71 was prepared did.

[Table 4]

&Lt; Examples 72 to 74 &gt;

(PAA-2) solution (70.0 g) prepared above was added to a solution of polyamic acid (PAA-2) solution prepared in Synthesis Example Polyamic acid (PAA-2)) was added so as to be a ratio shown in Table 5 below, and stirring was performed at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 72 to 74 was prepared did.

[Table 5]

&Lt; Examples 75 to 90 &gt;

To the soluble polyimide (SPI-1) solution (10.0 g) prepared above, the compound described in the following Table 6, which was prepared in the above Synthesis Example as a water-soluble compound, was added to the solubilized polyimide (SPI- (I.e., soluble polyimide (SPI-1)) was added so as to have the ratios shown in Table 6 below, and the mixture was stirred at room temperature until a homogeneous solution was obtained. Thus, the polyimide films of Examples 75 to 90 To prepare a coating liquid.

[Table 6]

&Lt; Examples 91 to 102 and Comparative Example 1 &gt; [Confirmation test of crosslinking effect (stripping test)] [

The coating liquid for forming a polyimide film of Examples 75 to 86 was spin-coated on a silicon wafer (2500 rpm / 30 seconds) and fired on a hot plate at 230 캜 for 30 minutes to form a coating film [a1] . The film thickness of the obtained coating film [a1] was measured using a Surfcoder ET4000M manufactured by Kosaka Laboratory Co., Ltd. Next, the silicon wafer on which the coating film [a1] was formed was set again on the spin coater, and NMP was dropped until the entire surface of the silicon wafer was covered. After 60 seconds of stoppage, the NMP was spin-dried (1500 rpm / ) And baked on a hot plate at 100 DEG C for 30 seconds to obtain a coating film [a2]. The film thickness of the coating film [a2] was measured again, and the residual film ratio was calculated based on the following calculation formula. As the comparative example 1, the soluble polyimide solution (SPI-1) prepared as described above, that is, the soluble polyimide solution not containing the hydrolyzing compound represented by the above formulas [A] to [D] Was carried out to calculate the residual film ratio. The results are shown in Table 7.

(%) = Film thickness of coating film [a2] / film thickness of coating film [a1] x 100

As a result, it was confirmed that the solvent resistance of the coating film (polyimide film) can be improved by using the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film to which the water-soluble compound is added. Therefore, it can be said that the soluble compound is introduced into the soluble polyimide. Further, in Examples 75 to 85 using the hydrolyzable compound represented by the above formula [A] having two or more Meldrum acids, the residual film ratio was particularly high, so that the soluble polyimide was found to have a water solubility It is presumed to be crosslinked by the compound. Further, it has been confirmed that the solubility of the coating film can be relatively freely controlled by appropriately selecting the water-soluble compound represented by the above formula [A] to be added.

In the same manner, coating films were formed using the coating liquids for forming polyimide films of Examples 1 to 74 and 87 to 90, and stripping tests were carried out. As a result, compared with the case where no treating compound was added, It was confirmed that the solvent resistance of the polyimide membrane can be improved by using the coating liquid for forming a polyimide film to which the water-soluble compound is added.

[Table 7]

[Production of liquid crystal alignment film and liquid crystal cell]

Using the coating liquid (liquid crystal aligning agent) for forming a polyimide film prepared in each of the above Examples, a liquid crystal cell was produced as follows.

A coating liquid for forming a polyimide film (liquid crystal aligning agent) was spin-coated on a glass substrate or a glass substrate on which an ITO transparent electrode was formed, dried on a hot plate at 80 DEG C for 70 seconds, To form a coating film.

Thereafter, for the liquid crystal alignment treatment by rubbing, the coated film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under a predetermined rubbing condition to obtain a substrate on which the liquid crystal alignment film V was formed. As for the 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 coated film surface, 40 DEG. The linearly polarized UV was prepared by passing a 313 nm band-pass filter through ultraviolet light of a high-pressure mercury lamp, and then passing through a polarizer of 313 nm.

Two substrates on which the liquid crystal alignment film subjected to the liquid crystal alignment treatment was formed were prepared, a spacer of 6 占 퐉 was dispersed on the liquid crystal alignment film side of the substrate, the sealant was printed thereon, (Anti-parallel liquid crystal cell, Examples 103 to 133) or directly (anti-parallel liquid crystal cell, Examples 174 to 176) so that the liquid crystal alignment film faces the liquid crystal alignment film and the rubbing directions are parallel to each other 206, and Examples 322 to 343, and Examples 344 to 350), or with respect to UV irradiation, the direction of the polarized light irradiated was made parallel so that the anti-parallel liquid crystal cell for vertical alignment mode, Examples 207 to 209, Examples 210 to 321), and the sealant was cured to prepare empty cells. The liquid crystal MLC-2003 (manufactured by Merck) was injected into the empty cell by a vacuum injection method, the liquid crystal MLC-2003 (manufactured by Merck Co.) containing a chiral agent in the twisted nematic liquid crystal cell was injected into the anti-parallel liquid crystal cell And liquid crystal MLC-6608 (manufactured by Merck Co.) was injected in the anti-parallel liquid crystal cell for the vertical alignment mode, and the injection port was sealed to obtain each liquid crystal cell.

[Evaluation of liquid crystal cell]

Methods of measuring physical properties and evaluating properties of each liquid crystal cell thus manufactured are as follows. The liquid crystal alignment film and the substrate of the liquid crystal cell, firing condition and rubbing condition produced in each measurement and evaluation are also shown.

&Lt; Examples 103 to 133 and Comparative Examples 2 to 4 &gt; &lt; Evaluation of liquid crystal alignment property &

The liquid crystal cell prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 8 was sandwiched by a polarizing plate and the liquid crystal cell was rotated in a state in which the backlight was irradiated from the rear portion, And whether or not the liquid crystal was aligned was visually observed. At that time, evaluation was made based on the following criteria. The liquid crystal cell prepared for evaluating the liquid crystal alignability had a glass substrate as a substrate and fired on a hot plate heated at 230 캜 for 30 minutes under a firing condition of a coating film of a coating solution for forming a polyimide film, At a roll revolution speed of 300 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.15 mm. Further, a coating liquid (Comparative Example 3 or Comparative Example 4) to which the following crosslinking agent was added (Comparative Example 3 or Comparative Example 4) was prepared as Comparative Example 2 in which a hydrating compound or a crosslinking agent was not added and a commercially available crosslinking agent, did. The results are shown in Table 8.

Evaluation standard

?: Alignment of liquid crystal can be confirmed, and there is no flow alignment

&Amp; cir &amp;: The liquid crystal was oriented, but the flow orientation was slightly observed

X: The liquid crystal was aligned, but a large amount of flow orientation was observed

&Lt; EMI ID =

As a result, as in Comparative Example 3 and Comparative Example 4, when a commercially available crosslinking agent was used, the alignment properties of the liquid crystal were generally liable to be inhibited. However, the coating liquid for forming a polyimide film , It has been confirmed that even if a hydrolytic compound having two or more melamine structure sites is used, orientation can be improved in some cases without inhibiting the orientation of the liquid crystal.

[Table 8]

&Lt; Examples 134 to 173 and Comparative Examples 5 to 6 &gt; &lt; Evaluation of rub resistance &

The surface of the liquid crystal alignment film prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Tables 9-1 to 9-2 was observed with a confocal laser microscope and evaluated according to the following criteria . The glass substrate on which the ITO transparent electrode was formed was used as the substrate. The firing condition of the coating film of the coating liquid for forming a polyimide film was baked for 30 minutes on a hot plate heated at 230 DEG C, , A roll advancing speed of 50 mm / sec, and an indentation amount of 0.5 mm. In addition, the compounds (Comparative Example 5 and Comparative Example 6) to which the compounds for hydration were not added were prepared, and the effects were compared. The results are shown in Tables 9-1 to 9-2.

○: No scratches or rubbing scratches were observed.

?: Cutting residue or rubbing scratches were observed.

X: The film was peeled off or rubbing scratches were visually observed.

As a result, in the case of using a coating solution for forming a polyimide film to which a hydrolyzing compound having two or more melamine acid structural sites was added as compared with Comparative Example 5 and Comparative Example 6 to which no hydrolytic compound was added, It was confirmed that the use of the polymer improves the cutting resistance.

[Table 9-1]

[Table 9-2]

&Lt; Examples 174 to 206 and Comparative Example 7 &gt; &lt; Pretilt angle measurement of twisted nematic liquid crystal cell &gt;

The liquid crystal cell prepared by using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 10 was heated at 105 캜 for 5 minutes, and the pretilt angle was measured. The pretilt angle was measured by Axo Metrix &quot; Axo Scan &quot; using the Mueller matrix method. The liquid crystal cell prepared for measuring the pretilt angle of the twisted nematic liquid crystal cell was a glass substrate on which an ITO transparent electrode was formed as a substrate and the firing condition of the coating film of the coating liquid for forming a polyimide film was heated to 230 캜 Firing was carried out on one hot plate for 30 minutes, and rubbing conditions were set at a roll revolution of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.3 mm. In addition, a compound having no hydrating compound (Comparative Example 7) was prepared, and the effect was compared. The results are shown in Table 10.

As a result, it was confirmed that a desired pretilt angle could be arbitrarily obtained by appropriately selecting the kind and amount of the compound to be added.

[Table 10]

&Lt; Examples 207 to 209 and Comparative Example 8 &gt; &lt; Pretilt angle measurement of antiparallel liquid crystal cell &gt;

The liquid crystal cell prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 11 was heated at 120 占 폚 for 1 hour, and then the pretilt angle was measured. The pretilt angle was measured by Axo Metrix &quot; Axo Scan &quot; using the Mueller matrix method. The liquid crystal cell prepared for measuring the pretilt angle of the anti-parallel liquid crystal cell was a glass substrate on which an ITO transparent electrode was formed as a substrate, and the firing conditions of the coating film of the coating liquid for forming a polyimide film were heated to 200 DEG C Firing was carried out in a hot-air circulating oven for 30 minutes, and the aforementioned liquid crystal cell was produced without performing orientation treatment. In addition, a compound having no hydrating compound (Comparative Example 8) was prepared, and the effect was compared. The results are shown in Table 11.

As a result, it was confirmed that the pretilt angle could be remarkably increased in the case of using the coating liquid for forming a polyimide film to which the water-soluble compound was added as compared with Comparative Example 8 in which the water-soluble compound was not added. Therefore, even when the base polymer, that is, the polyimide precursor contained in the coating solution for forming a polyimide or the polyimide is not introduced with the side chain component for causing the liquid crystal to be oriented, the liquid crystal can be vertically aligned It was confirmed that it could.

[Table 11]

&Lt; Examples 210 to 321 &gt; &lt; Evaluation of liquid crystal alignability and pretilt angle measurement of anti-parallel liquid crystal cell &

The liquid crystal cell prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Tables 12-1 to 12-4 was sandwiched by a polarizing plate and the liquid crystal cell was rotated in a state in which the backlight was irradiated from the rear portion, As a result of visually observing whether or not the liquid crystal was aligned due to the change of the contrast or the presence of the flow orientation, the liquid crystal showed good alignment. Thereafter, an AC voltage of 3 V was applied to the liquid crystal cell to visually observe whether or not the liquid crystal was aligned. At that time, evaluation was made based on the following criteria. The liquid crystal cell prepared for the evaluation of liquid crystal alignability had a glass substrate used as a substrate and fired in a hot-air circulating oven heated at 200 DEG C for firing conditions of the coating film of the coating liquid for forming a polyimide film for 30 minutes, The glass substrate on which the obtained coating film was formed was produced after the above-described photo-alignment treatment.

Evaluation standard

Good: The alignment of the liquid crystal can be confirmed, and there is no flow alignment

Bad: The liquid crystal is oriented, but the flow orientation is observed a lot

The liquid crystal cell prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Tables 12-1 to 12-4 was heated at 120 占 폚 for 1 hour and then the pretilt angle was measured did. The pretilt angle was measured by Axo Metrix &quot; Axo Scan &quot; using the Mueller matrix method.

As a result, it was confirmed that a good vertical alignment property was obtained even when a photo alignment treatment was performed by using a coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film to which a hydriding compound having a photoreactive side chain was added. Further, it was confirmed that the application liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention was capable of aligning the liquid crystal in a slightly inclined state from the vertical direction by irradiating ultraviolet rays of polarized light. It was also confirmed that the pretilt angle could be finely adjusted by controlling the addition amount and the irradiation amount. In view of these points, the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention is useful as a liquid crystal alignment film for a liquid crystal display device of a vertical alignment type and as a liquid crystal alignment film for use in a photo alignment method can do.

[Table 12-1]

[Table 12-2]

[Table 12-3]

[Table 12-4]

&Lt; Examples 322 to 343 and Comparative Example 9 &gt; &lt; Measurement of voltage holding ratio (VHR)

In the liquid crystal cells produced by using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 13, the initial voltage holding ratio was measured. To measure the voltage holding ratio, a voltage of 4 V was applied for 60 μs under a temperature of 90 ° C., and a voltage after 16.67 ms was measured. The voltage holding ratio was calculated as a voltage holding ratio. For the measurement of the voltage holding ratio, a VHR-1 voltage holding ratio measuring apparatus manufactured by Toyota Technica was used. The liquid crystal cell prepared for the measurement of the voltage holding ratio (VHR) was a glass substrate on which an ITO transparent electrode was formed as a substrate, and a fired condition of the coating film of the coating liquid for forming a polyimide film was heated to 230 DEG C, And the rubbing conditions were set at a roll revolution of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.3 mm. In addition, a compound (Comparative Example 9) to which no compound for hydrolysis was added was prepared, and the effect was compared. The results are shown in Table 13.

As a result, it was confirmed that by using the coating liquid for forming a polyimide film to which the water-soluble compound was added, better voltage holding ratio characteristics could be obtained than when the water-insoluble compound was added.

[Table 13]

&Lt; Examples 344 to 350 and Comparative Example 10 &gt; &lt; Estimation of accumulated charge (RDC) &gt;

A DC voltage was applied from 0 V to 1.0 V at 0.1 V intervals at a temperature of 23 캜 to a twisted nematic liquid crystal cell manufactured using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 14, The flicker amplitude level at the voltage was measured to produce a calibration curve. After grounding for 5 minutes, an AC voltage of 3.0 V and a DC voltage of 5.0 V were applied, and the flicker amplitude level after 1 hour was measured. The RDC was estimated by comparing with the previously prepared calibration curve (Flicker-Reference method). The liquid crystal cell produced for the estimation measurement of the accumulated charge (RDC) was a glass substrate on which an ITO transparent electrode was formed as a substrate, and the firing condition of the coating film of the coating liquid for forming a polyimide film was heated to 230 DEG C The plate was baked on the plate for 30 minutes, and rubbing conditions were set at a roll revolution of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.3 mm. In addition, a compound (Comparative Example 10) in which the compound for hydrolization was not added was prepared, and the effect was compared. The results are shown in Table 14.

As a result, it was confirmed that a liquid crystal cell with a small RDC could be obtained by using a coating liquid for forming a polyimide film to which a water-soluble compound was added.

[Table 14]

&Lt; Examples 351 to 358 and Comparative Example 11 &gt; Measurement of ion density before and after aging test

(Polyamic acid (PAA-1)) of the polyamic acid (PAA-1) solution was added to the polyamic acid (PAA-1) solution (10.0 g) Was added so as to have the ratios shown in Table 15 below and stirred at room temperature until a homogeneous solution was obtained to prepare a coating liquid for forming a polyimide film.

Then, the ion density of the twisted nematic liquid crystal cell prepared by using each of these polymer film forming liquids (liquid crystal aligning agent) was measured at an initial state (23 ° C), and the ion density at 60 ° C was maintained for 30 hours Aging), and the ion density was measured. In the ion density measurement, the ion density when a triangular wave voltage of ± 10 V and a frequency of 0.01 Hz was applied to the liquid crystal cell was measured. The measurement temperature was 80 占 폚. As the measuring apparatus, any measurement or a liquid crystal property evaluation apparatus of Model 6245 manufactured by Toyotec Corporation was used. The results are shown in Table 15.

The twisted nematic liquid crystal cell (Examples 174 to 206) was produced in the same manner as in the twisted nematic liquid crystal cell except that the firing conditions of the coating film of the coating liquid for forming a polyimide film were fired on a hot plate heated to 200 占 폚 for 30 minutes. . In addition, the same operation was carried out for the animals to which no animal compound was added, and the effects were compared.

As a result, it was confirmed that the ionic impurities in the liquid crystal cell were significantly reduced as compared with the case where the compound was not added, by appropriately selecting the kind and amount of the water-soluble compound.

[Table 15]

[Synthesis of polymer and preparation of solution thereof]

The following abbreviations are used in the following.

(Monomer)

HEMA: 2-hydroxyethyl methacrylate

MAA: methacrylic acid

MMA: methyl methacrylate

CHMI: N-cyclohexylmaleimide

TEOS: tetraethoxysilane

(Polymerization initiator)

AIBN: α, α'-azobisisobutyronitrile

(menstruum)

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 Nippon Bunko K.K.) Furan was eluted at a flow rate of 1 ml / min in a column (column temperature: 40 占 폚). The number-average molecular weight Mn and the weight-average molecular weight Mw are both expressed in terms of polystyrene.

(Commercially available polymer)

The commercially available polymer was used as a polymer solution prepared so as to have a solid content concentration of 6 mass% in a mixed solution of NMP / BCS (weight ratio 80: 20). In addition, PSM-4326 was purchased from Guyi Chemical Co., Ltd., and other polymers were 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-c2,4-dichloro-6-morpholino- 5-triazine]

Polymer-3: Poly (bisphenol A-co-epichlorohydrin)

Polymer-4: Poly (melamine-co-formaldehyde) acrylated, 80 wt% MEK Solution.

Polymer-5: Novolac resin, PSM-4326

<Synthesis of Polymer-6 and Preparation of its Solution>

A solution containing MMA, MAA, HEMA and CHMI in a molar ratio of MMA: MAA: HEMA: CHMI = 13: 26: 25: 36 and having a solid concentration of 40 wt% and PGMEA as a solvent was prepared, AIBN was added as a polymerization catalyst to the solution and reacted at 80 DEG C for 20 hours to obtain a solution of the copolymer (acrylic polymer). The number-average molecular weight Mn and the weight-average molecular weight Mw of the obtained copolymer were 4000 and 7500, respectively. Next, the obtained solution was diluted with NMP to a solid concentration of 5 wt% to obtain an acrylic polymer (Polymer-6) solution.

&Lt; Synthesis of Polymer-7 &

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 a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing the above mixed solvent, water and oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes. This solution was stirred for 30 minutes and then heated and refluxed for 1 hour and then cooled to obtain a solution of polysiloxane having a concentration of 12 wt% in terms of SiO ₂ . Next, the resulting polysiloxane solution having a concentration of 12 wt% in terms of SiO ₂ was further diluted with the 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 Example as a water-soluble compound were dissolved in a solution of each polymer (Polymer-1 to Polymer-5), acrylic polymer solution or polysiloxane The solid components (i.e., Polymer-1 to Polymer-7) of the solution were added in such proportions as shown in Table 16 below and stirred at room temperature until a uniform solution was obtained to prepare a coating solution for forming a polymer film.

Then, the anti-parallel liquid crystal cell prepared by using each of these coating liquids for forming a polymer film (liquid crystal aligning agent) was heated at 120 占 폚 for 1 hour, then the liquid crystal cell was placed on the backlight, Was visually observed. The case where the liquid crystal molecules were vertically aligned was defined as &quot; vertical &quot;, and the case where the liquid crystal molecules were not aligned vertically was defined as &quot; non-vertical &quot;.

In the antiparallel liquid crystal cell, a glass substrate on which an ITO transparent electrode was formed as a substrate was subjected to firing in a hot-air circulating oven heated at 200 캜 for 30 minutes under a firing condition of a coating film of various polymer film forming coating liquids (Examples 210 to 321) for vertical alignment mode, except that the liquid crystal cell was subjected to the alignment treatment without the alignment treatment. In addition, the same operation was carried out for the animals to which no animal compound was added, and the effects were compared.

[Table 16]

As a result, in any polymer of Polymer-1 to Polymer-6, Comparative Example 12 to 18 in which the hydrogenation compound was not added showed no vertical orientation at all. In the case of the coating solution for forming a polymer film to which the hydrogenation compound was added , And it was confirmed that vertical orientation was exhibited by adding an appropriate amount depending on each polymer. That is, it was confirmed that, by appropriately selecting the kind of the additive and the amount of the additive, it is possible to easily manufacture the vertically aligning cell regardless of the kind of the base polymer.

In addition, as for Polymer-7, since it shows vertical orientation even with no additive added, it is confirmed that the additive is not essential for producing a vertical cell, but the addition of the additive improves the vertical alignment property.

&Lt; Examples 383 to 401 &gt;

To the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compounds described in the following Table 17, which were prepared in the above Synthesis Example as a water-soluble compound, were added to the solid content of the polyamic acid (PAA- Polyamic acid (PAA-1)) was added so as to have the ratios shown in Table 17 below, and the mixture was stirred at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 383 to 401 was prepared did.

[Table 17]

&Lt; Examples 402 to 403 &gt;

To the polyamic acid (PAA-3) solution (40.0 g) prepared above, the compound described in the following Table 18 as the hydrating compound in the above Synthesis Example was added to the solid content of the polyamic acid (PAA-3) (PAA-3)) as shown in Table 18, and the mixture was stirred at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 402 to 403 was prepared did.

[Table 18]

&Lt; Examples 404 to 536 &gt; &lt; Evaluation of liquid crystal alignability and pretilt angle measurement of anti-parallel liquid crystal cell for vertical alignment mode &gt;

[Production of liquid crystal alignment film and liquid crystal cell]

Using the coating liquid (liquid crystal aligning agent) for forming a polyimide film prepared in each of Examples 383 to 403, a liquid crystal cell was produced as follows.

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

Thereafter, linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm ^-2 ) was changed between 0 mJ and 1000 mJ in the coating film surface, and the film was irradiated while being inclined at 40 ° with respect to the normal to the plate. The linearly polarized UV was prepared by passing a 313 nm band-pass filter through ultraviolet light of a high-pressure mercury lamp, and then passing through a polarizer of 313 nm.

Two substrates on which the liquid crystal alignment film subjected to the liquid crystal alignment treatment was formed were prepared, a spacer of 6 占 퐉 was dispersed on the liquid crystal alignment film side of the substrate, the sealant was printed thereon, Was adhered in such a manner that the direction of the polarized light irradiated with the liquid crystal alignment film faced to be parallel and the sealant was cured to prepare empty cells. A liquid crystal MLC-6608 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a low pressure injection method and the injection port was sealed to obtain an anti-parallel liquid crystal cell for each vertical alignment mode.

The obtained liquid crystal cell was sandwiched with a polarizing plate and the backlight was irradiated from the rear part. The liquid crystal cell was rotated to visually observe whether or not the liquid crystal was aligned with the change of lightness or flow direction or not, Orientation. Thereafter, an AC voltage of 3 V was applied to the liquid crystal cell to visually observe whether or not the liquid crystal was aligned. At that time, evaluation was made based on the following criteria. The results are shown in Tables 19-1 to 19-5.

Evaluation standard

Good: The alignment of the liquid crystal can be confirmed, and there is no flow alignment

Bad: The liquid crystal is oriented, but the flow orientation is observed a lot

The prepared liquid crystal cell was heated at 120 占 폚 for 1 hour, and the pretilt angle was measured. The pretilt angle was measured by Axo Metrix &quot; Axo Scan &quot; 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, when a photo-alignment treatment was carried out by using a coating solution (liquid crystal alignment treatment agent) for forming a polyimide film to which a hydriding compound having a photoreactive side chain was added It was confirmed that a good vertical alignment property can be obtained. Further, it was confirmed that the application liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention was capable of aligning the liquid crystal in a slightly inclined state from the vertical direction by irradiating ultraviolet rays of polarized light. It was also confirmed that the pretilt angle could be finely adjusted by controlling the addition amount and the irradiation amount. In view of these points, the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention is useful as a liquid crystal alignment film for a liquid crystal display device of a vertical alignment type and as a liquid crystal alignment film for use in a photo alignment method can do.

[Table 19-1]

[Table 19-2]

[Table 19-3]

[Table 19-4]

[Table 19-5]

&Lt; Examples 537 to 578 &gt;

To a 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 Example as a water-soluble compound were added to a polyamic acid (PAA-1 ) (PAA-1) was added so that the ratio was as shown in Tables 20-1 to 20-2 below, and stirring was carried out at room temperature until a homogeneous solution was obtained. To 578 of a coating liquid for forming a polyimide film was prepared.

[Table 20-1]

[Table 20-2]

&Lt; Examples 579 to 620 &gt; &lt; Evaluation of liquid crystal orientation of anti-parallel cell for horizontal alignment mode &

[Production of liquid crystal alignment film and liquid crystal cell]

Using the coating liquid (liquid crystal aligning agent) for forming a polyimide film prepared in each of Examples 537 to 578, a liquid crystal cell was produced as follows.

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

Thereafter, 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 coated film surface, and the substrate was irradiated directly from above. The linearly polarized UV was prepared by passing a 313 nm band-pass filter through ultraviolet light of a high-pressure mercury lamp, and then passing through a polarizer of 313 nm.

Two substrates on which the liquid crystal alignment film subjected to the liquid crystal alignment treatment was formed were prepared, a spacer of 6 占 퐉 was dispersed on the liquid crystal alignment film side of the substrate, the sealant was printed thereon, Was adhered in such a manner that the direction of the polarized light irradiated with the liquid crystal alignment film faced to be parallel and the sealant was cured to prepare empty cells. A liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an anti-parallel liquid crystal cell for a horizontal alignment mode.

Then, the prepared anti-parallel liquid crystal cell for horizontal alignment mode was sandwiched by a polarizing plate, and the liquid crystal cell was rotated in a state in which the backlight was irradiated from the rear portion to determine whether the liquid crystal was aligned due to the change in lightness or flow direction, Respectively. At that time, evaluation was made based on the following criteria. The results are shown in Tables 21-1 to 21-2.

Evaluation standard

?: Alignment of liquid crystal can be confirmed, and there is no flow alignment

&Amp; cir &amp;: The liquid crystal was oriented, but the flow orientation was slightly observed

?: The liquid crystal is oriented, but a large amount of flow orientation is observed

X: The liquid crystal is not aligned at all

As a result, in any of the liquid crystal cells, the liquid crystal cell not irradiated with light did not exhibit any orientation at all, but in the liquid crystal cell subjected to light irradiation, it was confirmed that the liquid crystal was oriented in accordance with the amount of the compound to be added and the light irradiation amount . Further, even when each liquid crystal cell whose orientation was confirmed was subjected to isotropic treatment at 130 占 폚 for 30 minutes, no significant change in orientation was observed. That is, it was confirmed that the horizontally oriented cell can be easily produced by appropriately selecting the kind and amount of the additive.

[Table 21-1]

[Table 21-2]

Claims (2)

At least one hydrolyzable compound selected from the group consisting of the following formulas [A] to [D] and having at least one functional group for imparting functionalities and at least one marmer acid structural unit connected thereto, Or a monomer for synthesizing the water-soluble polymer,
[Chemical Formula 1]

(Wherein, W ₁ is a functional structural part that imparts the functionality represents an organic divalent k _1. V ₁ represents -H, -OH, -OR, -SR, or -NHR, R is a benzene ring, a cyclohexane ring , A monovalent organic group having 1 to 35 carbon atoms which may contain a hetero ring, a fluorine atom, an ether bond, an ester bond or an amide bond at an arbitrary position, and k ₁ represents an integer of 1 to 8.
(2)

(In the formula, W ₂ represents a functional structural moiety of ₂ k-valent organic granting functionality. V ₂ represents -H, -OH, -SR, -OR or -NHR, R is a benzene ring, a cyclohexane Represents a monovalent organic group having 1 to 35 carbon atoms which may contain a ring, a heterocyclic group, a fluorine atom, an ether bond, an ester bond or an amide bond at an arbitrary position, and k ₂ represents an integer of 1 to 8.
(3)

W ₃ and W ₄ may be the same or different from each other, and k ₃ represents an integer of 1 to 8, provided that W ₃ and W ₄ each represent an organic group of k ₃ valency, )
[Chemical Formula 4]

(Wherein W ₅ represents a 2 k ₄ -valent organic group which is a functional structural moiety for imparting functionality, and k ₄ represents an integer of 1 to 8)
The hydrating compound represented by the formula [A] is selected from the hydrating compounds represented by the formulas [i] to [iii] or selected from the hydrating compounds represented by the formulas [i '] to [iii'

(Wherein Y ₁ is an organic group having k _{1 value} derived from an amine compound, a hydrazine compound or a carbodiimide compound having a terminal amino group of a primary or secondary amino group as a raw material of the hydrolyzing compound represented by the above formula [A] a single bond or a hetero atom or ring structure linear or carbon atom number of a valence k ₁ of 1-60 organic group of branched which may have a. k ₁ and V ₁ is, k in the formula [a] ₁ and V _1. p is 1 when the amine compound or carbodiimide compound is used as a raw material and is 2 when the hydrazine compound is used as a raw material R _j is a group represented by R ₁ to R ₈ , Or a monovalent organic group having 1 to 35 carbon atoms which may optionally contain a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond or an amide bond, and R ₁ to R ₈ Are the same or different It is. In addition, R _j is, in connection with a part of Y ₁ may form a ring.)

(Wherein Y ₂ is an organic group having a k _{1 value} derived from a thiol compound or a carbon disulfide, which is a raw material of the hydriding compound represented by the above formula [A], may be a single bond or a straight chain having a hetero atom or a cyclic structure or type ₁ is a k-valent organic group of carbon number of the branched ₁ ~ 60. k 1 and V ₁ is equal to the k ₁ and V ₁ in the formula [a].)

(Wherein Y ₃ represents an aldehyde, a ketone compound or a carboxylic acid derivative, which is a raw material of the hydrotreating compound represented by the above formula [A], or an organic group of k ₁ derived from an orthoformate ester, or a linear or branched carbon atoms and a valence k ₁ of 1 to 60 of the organic group which may have a ring structure. k ₁ and V ₁ is equal to the k ₁ and V ₁ in the formula [a] .)

(Wherein, Y _1, R _j, and k ₁ is the same as Y _1, R _j and k ₁ in the formula [i]. Q ₁ is a straight-which may have a single bond or a hetero atom or ring structure Or a branched or branched divalent organic group having 1 to 15 carbon atoms, R _i represents -H represented by R ₁ to R ₈ , or a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond, and contains an amide bond in an arbitrary position, and a monovalent organic group of carbon number 1 to 35 which may, R ₁ ~ R ₈ are may be the same or different. also, R _i is associated with a portion of Q ₁ and it may form a ring. V ₁ is equal to V ₁ in the formula [a].)
The hydriding compound represented by the formula [B] is selected from the hydrating compounds represented by the formula [iv] and [v]

(Wherein Y ₄ represents k ₂ -valent organic group derived from an aldehyde, a ketone compound, a halogenated alkyl compound or a compound having an electron-poor unsaturated bond, which is a raw material of the hydrating compound represented by the above formula [B] a hetero atom or a linear or carbon atoms of the branched 1 ~ 60 k ₂ a valence of the organic group which may have a ring structure. k ₂ and V ₂ is the k ₂ and V ₂ in the formula [B] same.)

(Wherein Y ₅ represents k ₂ -valent organic group derived from a carboxylic acid derivative which is a raw material of the hydrolyzable compound represented by the above formula [B], which may have a single bond or a linear chain structure which may have a hetero atom or a cyclic structure or the carbon atoms of the branched k ₂ is a monovalent organic group of 1 ~ 60. k ₂ and V ₂ are the same as k ₂ and V ₂ in the formula [B].)
The water-soluble compound represented by the formula [C] is selected from the water-soluble compounds represented by the formula [vi]

(Wherein Y ₆ and Y ₇ each represent a k ₃ -valent organic group derived from an alkyl halide compound or an alcohol derivative which is a raw material of the hydrolyzing compound represented by the above formula [C], or a single bond or a hetero atom or a ring carbon atoms in a linear or branched number of which may have the structure is k ₃ monovalent organic group of 1 ~ 60. Y ₆ and Y ₇ will be the same or different. k ₃ is, in the formula [C] k ₃ ).
The water-soluble compound represented by the formula [D] is selected from the water-soluble compounds represented by the formula [vii]

(Wherein Y ₈ represents a cyclic ketone compound, a cyclic alkoxyimine compound, or a cyclic carbodiimide compound as a raw material of the hydrotreating compound represented by the above formula [D], or a 2k _And k ₄ is the same as k ₄ in the formula [D]).
Wherein the water-soluble polymer has a moiety reacting with the mulsion acid structure and is selected from the group consisting of polyimide, acrylic polymer, methacrylic polymer, acrylamide polymer, methacrylamide polymer, polystyrene, polyvinyl, polysiloxane or polyamide, polyester , A polyurethane, a polycarbonate, a polyurea, a polyphenol (novolak resin), a maleimide polymer, or a polymer having an isocyanuric acid skeleton or a triazine skeleton introduced thereinto. Coating liquid. A functional polymer film obtained by applying the coating liquid for forming a functional polymer film according to any one of claims 1 to a substrate and firing the polymer coating film to bond the functional structural moiety to the water- A method of forming a functional polymer film.