KR20230001533A - Novel functional diamine and polyimide prepared using the same - Google Patents

Abstract

The present invention provides a novel benzimidazole-based diamine, a polyamic acid and a polyimide polymer manufactured by using the diamine, and polymer coating materials, films, and substrates for electronic devices containing these polymers. According to one embodiment of the present invention, compared to conventional diamine, chemical stability is high and light transmittance, processability, and solubility characteristics can be improved.

Description

Novel functional diamine compound and polyimide prepared using the same {NOVEL FUNCTIONAL DIAMINE AND POLYIMIDE PREPARED USING THE SAME}

The present invention relates to a novel benzimidazole-based diamine, a polyamic acid and a polyimide polymer prepared using the diamine, and a polymer coating material for electronic devices containing the polymer, a film, and a substrate.

Polyimide resin (polyimide, PI) is obtained by polymerizing a diamine monomer and a tetracarboxylic dianhydride monomer, and has excellent heat resistance, mechanical strength, dimensional stability, flame retardancy and electrical insulation. Due to these excellent physical properties, polyimide has been used in various application fields such as electrical and electronic devices, aerospace devices, and transportation devices, and various forms of research are being conducted depending on the intended use. In particular, aromatic polyimide has excellent physical properties such as thermal stability, mechanical properties, electrical insulation, and chemical resistance, so it is used in the electronics industry as an interlayer insulating material, a support for polymer composites, a separator for separating mixed gases, high-temperature adhesives, and coatings. It is a representative high-performance polymer used for such purposes.

In general, aromatic polyimide is completely insoluble in an organic solvent in the final stage of complete imidization and decomposes before melting, making it impossible to process. Accordingly, a final finished product is manufactured through a two-step process in which imidization is terminated through a heat treatment process after processing in the form of an intermediate polyamic acid. However, the method of manufacturing a final molded article through the above-described two-step process fundamentally has a problem of causing deformation and defects of the molded article due to the instability of the intermediate polyamic acid and the formation of by-products such as water generated during curing.

Research has been actively conducted to develop a soluble polyimide that can be easily processed even in the final stage with sufficient solubility in organic solvents even after complete imidization while minimizing the degradation of the physical properties of the aforementioned aromatic polyimide. . For example, as a method for producing soluble polyimide, a method of introducing a flexible functional group or a bulky substituent into a polymer main chain, a method of distorting the flat shape of a polymer chain, and a monomer having an aliphatic ring structure (alicyclic) are used. method, a method of reducing the regularity of the molecular structure by introducing an asymmetric structure, a method of copolymerizing components having good solubility in an organic solvent together, and the like. Another method for preparing the soluble polyimide is a method of introducing a perfluoroalkyl group including a fluoro group and a trifluoromethyl group into the main chain of the polyimide. In this method, the solubility of polyimide is greatly increased by suppressing various interactions of the conventional polyimide without greatly reducing the heat resistance of the polyimide due to the stronger carbon-fluorine bond than the carbon-hydrogen bond. can make it However, due to the low polarization of fluorine atoms, significant deterioration in physical properties such as water absorption, dielectric constant, and refractive index is caused.

The present invention has been made to solve the above problems, and is a monomer for suppressing various interactions of polyimide and imparting toughness and adhesiveness to polyimide itself, having a benzimidazole skeleton, and having a flexible linking group. , A technical problem is to provide a novel diamine compound having an asymmetric structure including a functional moiety such as a fluoro group or a trifluoromethyl group.

In addition, another technical problem of the present invention is to provide a polyamic acid and a polyimide polymer capable of securing excellent solubility, toughness and adhesiveness at the same time after imidation is completely performed by using the novel diamine described above, and a polymer film including the same. do.

Other objects and advantages of the present invention can be more clearly described by the following detailed description and claims.

In order to achieve the above technical problem, the present invention provides a compound selected from the group consisting of Formulas 1 to 3 below, specifically a benzimidazole-based asymmetric diamine monomer.

[Formula 1]

[Formula 2]

[Formula 3]

In the above formula,

A plurality of X's are the same as or different from each other, and are each independently selected from the group consisting of -O-, -S-, - and S(=O) ₂ -,

R ₁ to R ₆ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, fluoro, an alkyl group having 1 to 30 carbon atoms, and trifluoromethyl (CF ₃ );

Ar is a moiety selected from the group consisting of Formulas Ar-1 to Ar-12,

In the above formula,

* denotes a portion bonded to Formula 1,

R ₇ to R ₁₆ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, fluoro, an alkyl group having 1 to 30 carbon atoms, and trifluoromethyl (CF ₃ );

Any hydrogen included in the alkyl group of R ₁ to R ₁₆ may be independently substituted with one or more substituents selected from the group consisting of halogen and -CF ₃ .

In addition, the present invention is a diamine containing the compound of the above formula (1); And it provides a composition for preparing a polyamic acid containing an acid dianhydride.

In addition, the present invention provides a polyamic acid formed from the above-described composition for producing a polyamic acid and a polyimide polymer formed by imidizing the polyamic acid.

According to one embodiment of the present invention, by using an asymmetric diamine monomer having a benzimidazole skeleton in the molecule and a linking group such as ether or sulfone, chemical stability is higher than that of conventional diamines, and light transmittance, processability, and solubility characteristics are improved. can improve

The polyamic acid and/or polyimide polymer obtained by using the diamine described above has excellent heat resistance and mechanical properties, and at the same time can exhibit excellent processability. Accordingly, the polyimide film of the present invention is not only usefully used as a substrate for electronic devices and a coating material for electric and electronic parts, but can also be applied to various other fields.

Effects according to the present invention are not limited by the contents exemplified above, and more diverse effects are included in the present specification.

Hereinafter, the present invention will be described in detail.

All terms (including technical and scientific terms) used in this specification, unless otherwise defined, may be used in a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless explicitly specifically defined.

In addition, throughout this specification, when a certain component is said to "include", this is an open term that implies the possibility of further including other components, not excluding other components, unless otherwise stated. (open-ended terms). In addition, throughout the specification, "above" or "on" means not only the case of being located above or below the target part, but also the case of another part in the middle thereof, and must necessarily specify the direction of gravity It does not mean that it is located above the standard.

As used herein, “preferred” and “preferably” refer to embodiments of the invention that may provide certain advantages under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Additionally, the recitation of one or more preferred embodiments does not imply that the other embodiments are not useful, nor is it intended to exclude the other embodiments from the scope of the present invention.

In addition, in this specification, "monomer" and "monomer" have the same meaning. Monomers in the present invention are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight (Mw) of 1,000 g/mol or less. Also, the term polymer includes all homopolymers, copolymers, and resins.

<Diamine monomer>

One embodiment of the present invention is a diamine monomer for producing polyamic acid and/or polyimide polymer. These diamine monomers are differentiated from conventional diamines in that they have an asymmetric structure having a benzimidazole-based skeleton and a flexible linking group (eg, X, linker) such as an ether group or a sulfone group.

For one specific example, the diamine monomer may be represented by any one of Formulas 1 to 3 below.

[Formula 1]

[Formula 2]

[Formula 3]

In the above formula,

A plurality of X's are the same as or different from each other, and are each independently selected from the group consisting of -O-, -S-, - and S(=O) ₂ -,

R ₁ to R ₆ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, fluoro, an alkyl group having 1 to 30 carbon atoms, and trifluoromethyl (CF ₃ );

Ar is a moiety selected from the group consisting of Formulas Ar-1 to Ar-12,

In the above formula,

* denotes a portion bonded to Formula 1,

R ₇ to R ₁₆ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, fluoro, an alkyl group having 1 to 30 carbon atoms, and trifluoromethyl (CF ₃ );

Any hydrogen included in the alkyl group of R ₁ to R ₁₆ may be independently substituted with one or more substituents selected from the group consisting of halogen and -CF ₃ .

The diamine compounds represented by Chemical Formulas 1 to 3 include a benzimidazole ring for imparting heat resistance, adhesive strength and toughness. When such diamine is used, it is possible to increase the strength of the polymer material by including a heterocyclic ring (eg, benzimidazole) in the chain of the polymer to increase the attractive force between molecules while maintaining the existing rigid structure, as well as to increase the toughness of the polymer material, such as copper. Adhesion to various substrates including metals can be greatly improved.

In addition, by including at least one flexible linking group (eg, X) such as an ether group or a sulfone group in the molecule, chemical stability is very high, and structural rigidity and flexibility can be exhibited at the same time.

In addition, when the compounds represented by Formulas 1 to 3 have at least one fluoro or trifluoromethyl group, they serve to lower the dielectric constant of polyamic acid and polyimide obtained from diamine, and improve light transmittance and processability and the solubility can be greatly improved. In addition, by introducing a fluoro group and a trifluoromethyl group (CF ₃ ), the degree of polymerization and molecular weight of the prepared polyimide can be controlled according to the position of the trifluoromethyl group and the degree of nucleophilicity of the amine group. In addition, it has a structure in which a fluoro group and a trifluoromethyl group are bonded to a phenyl group, thereby preventing π-stacking between polymers and improving the solubility of the polymer, which lowers the crystallinity of the polymer and increases the low permittivity and light transmittance. will bring

Furthermore, since the compounds of Formulas 1 to 3 have an asymmetric structure including a benzoamidazole ring and a linking group on one side of the molecule, the crystallinity of polymers such as polyamic acid and polyimide prepared using the same is lowered. . As such, when the crystallinity of the polymer is lowered, the solubility characteristics of the polymer may be improved, and the dielectric constant, refractive index, birefringence, and light transmittance of the polymer may be affected.

Accordingly, the polyamic acid and/or polyimide polymer obtained by using the novel diamine represented by any one of Chemical Formulas 1 to 3 may have a low thermal expansion coefficient by minimizing structural deformation of the polymer main chain due to heat, and have excellent heat resistance. , with chemical and mechanical properties. In addition, characteristics such as low water absorption, low dielectric constant, excellent solubility and processability can be secured through the introduction of a fluoro or trifluoromethyl group.

The compound represented by Formula 1 of the present invention described above may be further exemplified by the compounds exemplified below. However, the compound represented by Formula 1 of the present invention is not limited to those exemplified below.

A method for preparing the novel diamine compound according to the present invention is not particularly limited, and may be prepared according to a conventional method known in the art. For example, synthesizing nitrophenoxy benzoic acid substituted with fluorine; synthesizing a dinitro compound having a benzimidazole ring; and reducing the dinitro group. For example, the diamine compounds represented by Chemical Formulas 1 to 3 may be prepared by the following Reaction Schemes 1 to 3.

At this time, the step of reducing the nitro group is not particularly limited, and a conventional method known in the art may be used. For example, it may include injecting hydrogen gas into a solvent using palladium/carbon, platinum, nickel, or the like as a catalyst, or reacting hydrogen chloride with a metal such as iron or tin.

[Scheme 1]

[Scheme 2]

[Scheme 3]

The term "alkyl group" used herein refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 20 carbon atoms (specifically, 1 to 10 carbon atoms). In one embodiment, the alkyl may be selected from the group consisting of methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc., but is not limited thereto.

As used herein, the term "alkenyl group" refers to a monovalent substituent derived from a linear or branched chain unsaturated hydrocarbon having 2 to 20 carbon atoms (specifically, 2 to 10 carbon atoms) having at least one carbon-carbon double bond. . In one embodiment, the alkenyl may be selected from the group consisting of vinyl, allyl, isopropenyl, 2-butenyl, and the like, but is not limited thereto.

As used herein, the term "aryl group" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 20 carbon atoms (specifically, 6 to 10 carbon atoms) in a single ring or a combination of two or more rings. In addition, a form in which two or more rings are simply attached to each other or condensed may be included. In one embodiment, the aryl may be selected from the group consisting of phenyl, naphthyl, phenanthryl, anthryl, and the like, but is not limited thereto.

As used herein, the term "heterocyclic group" means a cyclic monovalent substituent having one or more heteroatoms selected from the group consisting of N, O, S, and Se, and the rest consisting of C atom(s). In this case, the 'heterocyclic group' may be a single ring or a polycyclic ring. When the heterocyclic group is an aromatic ring, it is referred to as a heteroaryl group, and when the heterocyclic group is an alicyclic ring, it is referred to as a heterocycloalkyl group. The heterocyclic group may be a cyclic group comprising a 4-, 5-, 6-, 7- or 8-membered ring, wherein the ring contains at least one ring atom selected from the group consisting of N, O, Se and S, It has C as the remaining ring atoms. In one embodiment, the heterocyclic group is a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a morpholino group, a thiomorpholino group, a homopiperidinyl group, a chromanyl group, an isochromanyl group, a chromenyl group, and a pyrrolyl group. , Furanyl group, thienyl group, pyrazolyl group, imidazolyl group, furazanyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, Pyrazinyl group, pyranyl group, indolyl group, isoindolyl group, indazolyl group, purinyl group, indolizinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, pteridinyl group, quinolizinyl group, It may be selected from the group consisting of a benzoxazinyl group, a carbazolyl group, a phenazinyl group, a phenothiazinyl group, and a phenanthridinyl group, but is not limited thereto.

As used herein, the term "alkyloxy group" is a monovalent substituent represented by R'O-, wherein R' means an alkyl having 1 to 20 carbon atoms (specifically, 1 to 10 carbon atoms), straight-chain or branched-chain. or a cyclic structure. In one embodiment, the alkyloxy may be selected from the group consisting of methoxy, ethoxy, n-propoxy, 1-propoxy, t -butoxy, n-butoxy, pentoxy, etc., but is not limited thereto don't

As used herein, the term "aryloxy group" is a monovalent substituent represented by RO-, wherein R means an aryl having 5 to 20 carbon atoms (specifically, 6 to 10 carbon atoms). In one embodiment, the aryloxy may be selected from the group consisting of phenyloxy, naphthyloxy, diphenyloxy, etc., but is not limited thereto.

<Composition for producing polyamic acid>

Another embodiment of the present invention is a composition for producing polyamic acid containing the novel diamine compound described above, which corresponds to a precursor solution for forming polyamic acid and/or polyimide (co)polymer.

Specifically, the composition for producing polyamic acid includes at least one diamine compound and at least one acid dianhydride, and the diamine compound includes the benzimidazole-based diamine compound represented by Formula 1 above. If necessary, a latent curing agent and/or at least one conventional additive known in the art may be further included.

Hereinafter, the composition of the composition for preparing the polyamic acid will be described in detail.

Diamine

The composition for producing a polyamic acid according to the present invention includes at least one of the compounds represented by the above-described Chemical Formulas 1 to 3.

Here, since the diamine compounds represented by Chemical Formulas 1 to 3 are the same as those described above, a separate description thereof will be omitted.

In the composition for producing polyamic acid according to the present invention, the content of the compounds represented by Chemical Formulas 1 to 3 is not particularly limited and may be appropriately adjusted within a content range known in the art. For example, the compound represented by Chemical Formulas 1 to 3 may be included in an amount of 1 to 100 mol%, specifically 10 to 100 mol%, based on 100 mol% of the total diamine.

The present invention may further include conventional diamine compounds known in the art.

Such a diamine compound may be used without particular limitation as long as it is a non-benzimidazole-based diamine compound different from the above-mentioned Formula 1, and examples thereof include aromatic, alicyclic, or aliphatic compounds having a diamine structure. Specifically, the diamine compound is a non-fluorinated aromatic diamine known in the art, a fluorinated aromatic diamine having a fluorine substituent introduced therein, a sulfone-based aromatic diamine, a hydroxy-based aromatic diamine, an ether-based aromatic diamine, an alicyclic diamine, an aminosiloxane, a poly- Diaminosiloxane and the like may be used alone or in combination of two or more, respectively.

Non-limiting examples of usable diamine compounds include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenyl Rendiamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5 -Diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3 '-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-dia Minobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4' -Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether , 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldi Aniline, bis(4-aminophenyl)silane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis (3-aminophenyl)silane, aminopropyl terminated polydimethylsiloxane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3' -Diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-dia Minodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodi Phenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2' -Diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2, 5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3 -Aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) Benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-amino Phenoxy) benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'- [1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene) )] dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis [(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4 -Phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis( 3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N '-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4 -phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide; N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'- Bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino- 4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4- Methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4- Bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy) Hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4 -aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1 ,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy) Undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane. Bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, 12-diamino dodecane etc. are mentioned. Moreover, as a diamine side chain, the diamine compound which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and the cyclic substituent which consists of them is mentioned.

Each of the aforementioned diamines may be used alone or two or more of them may be used in a mixed form.

Specifically, as the fluorinated diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFDB) capable of inducing linear polymerization may be used. In addition, bis(4-aminophenyl)sulfone (DDS) may be used as the sulfone-based diamine, and 2,2-bis(3-amino-4-methylphenyl)-hexafluoropropane (BISATAF) may be used as the hydroxy-based diamine. can be used In addition, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6-FODA) or oxydianiline (ODA) may be used as the ether-based diamine. As the aminosiloxane and/or poly-diaminosiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, aminopropyl terminated polydimethylsiloxane, and the like can be used. When mixed with the above-mentioned conventional diamine, diamines represented by Chemical Formulas 1 to 3 may be included in an amount of 50 to 95 mol%, specifically 70 to 90 mol%, based on 100 mol% of the total diamine.

acid dianhydride

The composition for producing a polyamic acid according to the present invention includes at least one acid dianhydride compound known in the art.

As the acid dianhydride monomer, tetracarboxylic dianhydride compounds known in the art having a dianhydride structure in a molecule may be used without limitation. Specifically, common fluorinated aromatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and non-fluorinated aromatic tetracarboxylic acid dianhydrides known in the art may be used alone or in combination of two or more.

The fluorinated aromatic tetracarboxylic dianhydride monomer is not particularly limited as long as it is an aromatic dianhydride having a fluorine substituent introduced therein. Examples of usable fluorinated aromatic acid dianhydrides include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, (2,2-bis(3,4-dicarboxyphenyl)hexafluoro Lopropane tetracarboxylic dianhydride (6FDA), 4-(trifluoromethyl)pyromellitic tetracarboxylic dianhydride (TFPMDA), norborene-2-spiro-α-cyclopentanone-α'— spiro-2"-norborene-5,5",6,6"-tetracarboxylic dianhydride (CpODA), etc. These may be used alone or in combination of two or more.

In addition, the alicyclic tetracarboxylic acid dianhydride is not particularly limited as long as it has an alicyclic ring other than an aromatic ring in the compound and has a tetracarboxylic acid dianhydride structure. Examples of usable alicyclic tetracarboxylic acid dianhydrides include cyclobutane tetracarboxylic acid dianhydride (CBDA), 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride (CPDA), bicyclo[2,2 ,2]-7-octene-2,3,5,6-tetracarboxylic dianhydride (BCDA); and the like, but are not particularly limited thereto. The aforementioned tetracarboxylic dianhydride may be used alone or in a mixed form of two or more thereof.

In addition, the non-fluorinated aromatic tetracarboxylic dianhydride monomer is not particularly limited as long as it is a non-fluorinated aromatic tetracarboxylic dianhydride in which no fluorine substituent is introduced. Non-limiting examples of non-fluorinated aromatic tetracarboxylic acid dianhydride monomers that can be used include pyromellitic tetracarboxylic acid dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic tetracarboxylic acid dianhydride (BPDA), benzophenone tetracarboxylic tetracarboxylic dianhydride (BTDA), oxydiphthalic tetracarboxylic dianhydride (ODPA), and the like. These may be used alone or in combination of two or more thereof.

Non-limiting examples of usable acid dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracentetracarboxylic dianhydride, 1,2,5,6-anthracentetracarboxylic dianhydride, 3, 3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether, 3,3 ',4,4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4- Dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane , bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3 ',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,3-diphenyl-1,2,3,4-cyclo Butanetetracarboxylic dianhydride, oxydiphthaltetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 -Cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxy Cyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3,3,0]octane-2,4,6,8- tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2, 4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane- 2,4,8,10-tetracarboxylic dianhydride, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic dianhydride, 1,2,3 ,4-Butanetetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydrinaphthalene-1,2-dicarboxylic acid dianhydride, bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride,5-(2,5-dioxotetrahydrofuryl)-3-methyl -3-cyclohexane-1,2-dicarboxylic dianhydride, tetracyclo[6,2,1,1,0,2,7]dodeca-4,5,9,10-tetracarboxylic dianhydride , 3,5,6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, and the like.

Each of the aforementioned acid dianhydrides may be used alone or in a mixed form of two or more thereof.

In the composition for preparing polyamic acid of the present invention, the ratio (a/b) of the number of moles of the diamine (a) to the number of moles of the dianhydride component (b) may be 0.7 to 1.3, preferably 0.8 to 1.2, and , more preferably in the range of 0.9 to 1.1. However, it is not particularly limited thereto.

menstruum

In the composition for preparing polyamic acid of the present invention, organic solvents known in the art may be used without limitation as a solvent for solution polymerization of the above-described diamine monomer and acid dianhydride monomer.

Non-limiting examples of usable organic solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethyl Urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl Isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, ethylene glycol monoacetate, diethylene glycol dimethyl ether, di Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl -3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butylate, butyl ether, di Isobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy methyl ethyl propionate, 3-methoxy ethyl propionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, etc. are mentioned. These may be used independently or may be used in mixture. However, it is not limited thereto and may include all organic solvents in which the polymer of the polymerization reaction is dissolved. For example, m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate, and One or more polar solvents selected from dimethyl phthalate (DMP) may be used. In addition, a low boiling point solution such as tetrahydrofuran (THF) or chloroform or a solvent such as γ-butyrolactone may be used. The content of the solvent is not particularly limited as long as the remaining amount is such that the total amount of the composition is 100 parts by weight. In order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, it may be 50 to 95 parts by weight, specifically 70 to 90 parts by weight based on the total weight of the composition for preparing the polyamic acid.

additive

In addition to the above components, the composition for preparing polyamic acid of the present invention may include at least one or more conventional additives known in the art within a range that does not impair the effects of the present invention.

Examples of usable additives may include a curing agent, a latent curing agent, a plasticizer, an antioxidant, a flame retardant, a dispersing agent, a viscosity modifier, a leveling agent, an inorganic filler, and a curing accelerator. These may be used alone or in combination of two or more. The content of the additive is not particularly limited, and may be appropriately adjusted within a range of usage known in the art. For example, the at least one additive may be included in an amount of 0.01 to 10 parts by weight, specifically 0.1 to 5 parts by weight based on the total weight of the composition for preparing the polyamic acid.

The composition for preparing polyamic acid according to the present invention may be prepared according to a conventional method known in the art, and for example, diamine represented by Formula 1 and an acid dianhydride may be added to a solvent and then reacted. Specifically, a diamine containing the compound of Formula 1, at least one dianhydride, a solvent, and, if necessary, a conventional additive, but preferably, the equivalent ratio of diamine (a) and dianhydride (b) is approximately 1: 1 can form a composition for preparing a polyamic acid.

The composition of the composition for preparing polyamic acid is not particularly limited, and for example, 2.5 to 25.0 parts by weight of acid dianhydride, 2.5 to 25.0 parts by weight of diamine, and 100 parts by weight of the composition based on 100 parts by weight of the total weight of composition for preparing polyamic acid It may be constituted by including a residual amount of solvent.

The composition for preparing a polyamic acid configured as described above may have a viscosity (at 25° C.) in the range of about 1,000 to 400,000 cps, specifically about 5,000 to 100,000 cps. When the viscosity of the polyamic acid solution falls within the above range, the thickness can be easily controlled during coating of the polyamic acid solution, and the coating surface can be exhibited uniformly.

<Polyamic acid>

Another embodiment of the present invention is a polyimide precursor [poly(amic acid), PAA] polymer for preparing a polyimide polymer as a polyamic acid formed using the above-described composition for preparing a polyamic acid.

For one specific example, the polyamic acid includes a repeating unit represented by any one of Formulas 4 to 6 below.

[Formula 4]

[Formula 5]

[Formula 6]

In the above formula,

B ₁ and B ₂ of Formula 5 and B ₁ to B ₃ of Formula 6 are _the same as or different from each other,

However, B in Formula 4; At least one of B ₁ and B ₂ in Formula 5; At least one of B ₁ to B ₃ in Formula 6 is a group derived from a diamine selected from the group consisting of compounds of Formulas 1 to 3,

A is a group derived from an acid dianhydride,

In Formula 5, x and y are rational numbers satisfying x + y = 1,

In Formula 6, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1.

In Chemical Formulas 5 and 6, B ₁ to B ₃ may include a group derived from another diamine different from the diamine represented by Chemical Formulas 1 to 3 described above. Since this diamine is the same as the additional diamine component described in the above-described composition for preparing a polyamic acid, a separate description thereof will be omitted.

In Formulas 4 to 6, A is a group derived from acid dianhydride, and since the component of the acid dianhydride is the same as the specific acid dianhydride component described in the composition for preparing polyamic acid, a separate description thereof will be omitted.

For one specific example, the A may be further embodied in the structural formula exemplified below. However, it is not limited by those exemplified below.

And in Formula 6, B ₁ to B ₃ may be the same as or different from each other, and specifically, B ₂ or B ₃ may be the same as or different from B ₁ .

The polyamic acid polymer according to the present invention may be prepared according to a conventional method known in the art. For example, a polyamic acid is prepared by mixing diamine including a compound represented by Formulas 1 to 3 with an acid dianhydride or a derivative thereof with a solvent, and then polymerizing the mixture under an inert gas atmosphere. As the solvent, for example, N-methylpyrrolidone, metacresol, dimethylacetamide and the like are used. As the inert gas atmosphere, argon, nitrogen, or the like can be used. In the polymerization reaction described above, reaction conditions such as temperature may vary depending on the type of diamine compound and acid dihydride used.

<Polyimide polymer and film>

In addition, another embodiment of the present invention is a polyimide polymer formed by imidizing the above-described polyamic acid.

In general, a polyimide resin is prepared by condensation polymerization of aromatic tetracarboxylic dianhydride or a derivative thereof and aromatic diamine or aromatic diisocyanate to prepare a polyamic acid derivative, followed by cyclization at high temperature or under catalytic conditions to prepare polyimide. In contrast, the polyimide polymer according to the present invention is a polyamic acid-containing solution (eg, polyamic acid solution) obtained by solution polymerization of a composition for preparing a polyamic acid containing a novel diamine compound represented by Chemical Formulas 1 to 3 and an acid dianhydride. and a polyimide resin obtained by dehydration ring closure thereof. Both of these polyamic acids and polyimides can be usefully applied as materials for electric and electronic parts, such as coating materials, substrates, compositions, or films, by securing improved processability while maintaining excellent heat resistance and chemical/mechanical properties.

The polyimide polymer may be a conventional polymer or copolymer, and is not particularly limited. For example, it may be in the form of a conventional random copolymer or block copolymer known in the art.

For example, the polyimide polymer includes a repeating unit represented by any one of Formulas 7 to 9 below.

[Formula 7]

[Formula 8]

[Formula 9]

In the above formula,

B ₁ and B ₂ of Formula 8 and B ₁ to B ₃ of Formula 9 are _the same as or different from each other;

However, B in Formula 7; at least one of B ₁ and B ₂ in Formula 8; At least one of B ₁ to B ₃ in Formula 9 is a group derived from a diamine selected from the group consisting of compounds of Formulas 1 to 3,

A is a group derived from an acid dianhydride,

In Formula 8, x and y are rational numbers satisfying x + y = 1,

In Formula 9, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1.

In Chemical Formulas 8 and 9, B ₁ to B ₃ may include a group derived from another diamine different from the diamines of Chemical Formulas 1 to 3 described above. Since this diamine is the same as the additional diamine component described in the above-described composition for preparing a polyamic acid, a separate description thereof will be omitted.

In Formulas 7 to 9, A is a group derived from acid dianhydride, and since the component of the acid dianhydride is the same as the specific acid dianhydride component described in the above-described composition for preparing polyamic acid, a separate description thereof will be omitted. And in Formula 9, B ₁ to B ₃ may be the same as or different from each other, and specifically, B ₂ or B ₃ may be the same as or different from B ₁ .

The polyimide polymer according to the present invention can be prepared according to conventional methods known in the art. For example, preparing a polyamic acid by reacting a diamine containing a compound represented by Formulas 1 to 3, and an acid dianhydride or a derivative thereof; and obtaining a polyimide polymer by subjecting the polyamic acid to cyclization dehydration.

The preparing of the polyamic acid may include polymerization of an acid dianhydride or a derivative thereof and a diamine compound, and an organic solvent may be used for the polymerization reaction. Since this organic solvent is the same as the specific organic solvent component described in the above-described composition for preparing polyamic acid, a separate description thereof will be omitted.

In addition, in the step of preparing a polyamic acid by reacting an acid dianhydride or a derivative thereof and a diamine compound in an organic solvent, a solution in which the diamine compound is dispersed or dissolved in an organic solvent is stirred, and the acid dianhydride is either dispersed or dissolved in an organic solvent. It may be carried out by a method selected from the group consisting of a method of adding by dissolving, a method of adding a diamine compound to a solution obtained by dispersing or dissolving acid dianhydride in an organic solvent, and a method of adding acid dianhydride and diamine compound alternately. there is. In addition, when the acid dianhydride or diamine compound is composed of plural types of compounds, in the group consisting of a method of reacting in a premixed state, a method of sequentially reacting individually, and a method of mixing and reacting individually reacted low molecular weight substances, etc. This can be done in any way you choose.

The temperature of the polymerization reaction is not particularly limited, and may be, for example, -20 °C to 150 °C, and preferably -5 °C to 100 °C. In addition, the polymerization reaction can be carried out at any concentration of the acid dianhydride and the diamine compound. However, if the concentration is too low, it may be difficult to obtain a polymer with a high molecular weight. If the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult It can get difficult. Accordingly, the concentration of the acid dianhydride and diamine compound in the reaction solution of the acid dianhydride and diamine may be 1 to 50% by mass, preferably 5 to 30% by mass.

Obtaining a polyimide polymer by subjecting the polyamic acid to cyclization dehydration includes imidizing the polyamic acid. In one embodiment, the polyamic acid may be thermally imidized. Thermal imidation may be performed at 100 °C to 400 °C, preferably at 120 °C to 250 °C. At this time, the thermal imidation process is preferably performed while removing water generated by the imidation reaction.

In another embodiment, the polyamic acid may be catalytically imidated. Specifically, catalyst imidation may be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring at -20°C to 250°C, preferably 0°C to 180°C.

At this time, the amount of the basic catalyst may be 0.5 to 30 mole times, preferably 2 to 20 mole times the amount of the amide acid group. In addition, the amount of the acid anhydride may be 1 to 50 mole times the amount of the amide acid group, preferably 3 to 30 mole times. Examples of usable basic catalysts may be selected from the group consisting of pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Do. Examples of usable acid anhydrides may be selected from the group consisting of acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Acetic anhydride is preferred in view of the ease of purification after completion of the reaction. The imidation rate by catalyst imidation can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

The imidization ratio of the polyimide subjected to the imidization process does not necessarily have to be 100%, and can be arbitrarily adjusted according to the use or purpose. For example, it may be 1 to 100%.

The polyamic acid or polyimide polymer may be recovered by precipitating a reaction solution of polyamic acid or polyimide in a poor solvent. In this case, the poor solvent may be selected from the group consisting of methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. In addition, the precipitate precipitated by inputting into the poor solvent may be dried under normal pressure or reduced pressure, at room temperature or under heating conditions.

The molecular weight of the polyamic acid and polyimide polymer prepared as described above is not particularly limited and may be appropriately adjusted within a common range known in the art. For example, when measured by gel permeation chromatography, the weight average molecular weight (Mw) may be 1,000 to 400,000 g/mol, preferably, 5,000 to 100,000 g/mol.

The polyimide polymer according to the present invention can be applied to all fields where conventional polyimide is used, and may be, for example, a film, a substrate, a composition, and/or a polymer coating material for electronic devices. In this case, the components constituting the composition, content, composition and / or use thereof are not particularly limited.

Specifically, the present invention provides a polyimide film comprising the polyimide polymer described above.

Such a polyimide film may be manufactured according to a conventional method known in the art, and may be obtained by applying, for example, a composition containing a polyimide polymer onto a substrate and then curing it.

As the coating method, conventional methods known in the art may be used without limitation, and examples thereof include spin coating, bar coating, dip coating, solvent casting, and slot die coating. coating) and at least one method selected from the group consisting of spray coating. The polyamic acid composition may be coated at least once or more so that the polyimide layer has a thickness of several hundred nm to several tens of μm.

On the other hand, the existing polyimide film is manufactured through a two-step thermal curing process of pre-curing and main-curing after applying a polyamic acid composition in a relatively unstable state to a substrate due to the insoluble and insoluble characteristics of polyimide. At this time, the pre-curing is a process for volatilizing the solvent at a temperature range of 100 to 150 ° C, and the main curing is a process for polymerizing polyimide through a ring-closure dehydration reaction of polyamic acid at a temperature range of 300 to 550 ° C. In contrast, in the present invention, as a polyimide polymer with improved solubility and processability is proposed, a composition in a polyimide state can be provided. Accordingly, there may be a difference in that film formation is possible only through a solvent volatilization process after coating a polyimide composition in a stable polyimide state on a substrate without going through the film formation process in the above-described polyamic acid state.

In particular, when a polyimide coating or film is prepared using the novel diamine of the present invention, the benzimidazole ring having a rigid rod-shaped structure functions to exhibit excellent thermal stability and excellent chemical and mechanical properties, and fluoro group or trifluoromethyl group leads to excellent solubility in organic solvents and improved fluidity, and thus can exhibit excellent processability and optical transparency. In addition, the polyimide film has high heat resistance, low thermal expansion, and chemical resistance, and thus can be suitably used as a conventional display substrate known in the art.

For one specific example, the film including the polyimide polymer may satisfy at least four or more physical properties of the following (i) to (vi), preferably all of them. (i) The 5% weight loss temperature (Td _5% ) of the film measured by thermogravimetric analysis (TGA) may be greater than 300°C, preferably greater than 500°C. (ii) The average value of the coefficient of thermal expansion (CTE) of 50 to 200 ° C according to the ASTM E831 standard may be less than 65 ppm / ° C, preferably 40 ppm / ° C or less, and more preferably 35 ppm / ° C or less. (iii) The permittivity (@10 GHz) may be less than 3.5, preferably 3.0 or less. (iv) The adhesive force according to KS M ISO1514 standard may exceed 0.5 kg/cm, preferably 0.8 kg/cm or more. (v) a moisture absorption rate of less than 1.0%, preferably 0.8% or less. (vi) The number of repeated bendings according to the ASTM D2176 standard may exceed 50,000 times, preferably 100,000 times or more. Furthermore, (vii) may have a solubility of 50% or less, for example, greater than 0% or less than 50% in the solvent of at least one of MC and Cyclohexanon, preferably at least one polarity among NMP, DMF, and THF It may be 50% or more solubility in the solvent.

The thickness of the polyimide film of the present invention thus formed is not particularly limited and may be appropriately adjusted depending on the applied field. For example, it may be in the range of 1 to 150 μm, specifically in the range of 3 to 80 μm, and preferably in the range of 3 to 50 μm.

The polyimide film according to the present invention can be applied to various fields, and specifically, it can be usefully applied to various technical fields requiring heat resistance, excellent mechanical properties, and low permittivity. For example, a display for an organic EL device (OLED), a display for a liquid crystal device, a TFT substrate, a flexible printed circuit board, a flexible OLED surface lighting substrate, a flexible display substrate such as a substrate material for electronic paper and / Alternatively, it can be used as a protective film. However, it is not limited thereto.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example: Synthesis of Diamine Monomer]

Synthesis Example 1a: Synthesis of 4-(4-nitrophenoxy)benzoic acid

Put p -chloronitrobenzene (78.8g, 0.50 mol) and 4-hydroxybenzoic acid (69.4g, 0.50 mol) and 400ml of dimethyl sulfoxide in a 1L 3neck flask and stir under nitrogen. Sodium hydroxide (40g, 1.0 mol) was added by dissolving 50ml of distilled water. The temperature was raised to 130° C. and stirred for 12 hours. Upon completion of the reaction, the reaction water was poured into 3L distilled water and acidified to pH 2 while stirring. The resulting white solid was filtered, washed several times with water to remove acid, and washed twice with methanol. The filtrate was recrystallized from methanol. The resulting crystals were filtered, washed twice with methanol, and vacuum dried at 60° C. for 24 hours to obtain 105 g of the target compound, 4-(4-nitrophenoxy)benzoic acid, in a yield of 81%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): ¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 12.71 (COOH), 8.27 (2H, d, Ar-H), 8.06 (2H, d, Ar-H), 7.25 (2H, d, Ar-H), 7.21 (2H, d, Ar-H).

Synthesis Example 1b: Synthesis of 5-nitro-2-(4-(4-nitrophenoxy)phenyl)-7-(trifluoromethyl)-1H-benzo[d]imidazole

In a 1L 3neck flask, 4-(4-nitrophenoxy)benzoic acid (55.0g, 0.21 mol) and 5-nitro-3-(trifluoromethyl)benzene-1,2-diamine (46.92g, 0.21 mol) 450 g of polyphosphoric acid was added thereto and stirred at 120° C. under nitrogen for 12 hours. When the reaction was completed, it was cooled to 40° C., and distilled water was added little by little until the polyphosphoric acid was dissolved. The reactant was poured into 3L distilled water and then slowly neutralized with 3N aqueous sodium hydroxide solution. The resulting crystals were filtered, washed with distilled water several times, dried under vacuum at 80° C. for 12 hours, and then recrystallized with dimethylformaldehyde to obtain 65 g of the target compound in a yield of 70%.

1H NMR (400 MHz, DMSO-d6) δ (ppm): 12.8 (1H, s, -NH), 8.39 (1H, s, Ar-H), 8.38-8.22 (5H, m, Ar-H), 7.21 (2H, d, ArH), 6.93 (2H, d, Ar-H).

Synthesis Example 1c: Synthesis of 2-(4-(4-aminophenoxy))phenyl-7-(trifluoromethyl)-1H-benzo[d]imidazol-5-amine

5-nitro-2-(4-(4-nitrophenoxy)phenyl)-7-(trifluoromethyl)-1H-benzo[d]imidazole (20g, 0.04 mol), 5% palladium in a 1L 3neck flask / After adding 3 g of carbon, 100 ml of 2-methoxyethanol was added, stirred for 6 hours in a hydrogen atmosphere, and when the reaction was completed, the catalyst was removed, and the filtrate was concentrated under reduced pressure and recrystallized with dimethylformaldehyde to obtain 8.9 g of the target compound, 58%. obtained in yield.

1H NMR (400 MHz, DMSO-d6) δ (ppm): 12.8 (1H, s, NH-), 8.22 (2H, d, Ar-

H), 7.10 (1H, d, Ar-H), 6.93 (2H, d, Ar-H), 6.85 (1H, s, Ar-H), 6.74 (4H, s, Ar-H), 5.28 (2H , br, -NH2), 6.50 (1H, d, Ar-H), 5.50 (2H, br, -NH2).

Synthesis Example 2a: Synthesis of 2,3,4,5-tetraphylluoro-4-(4-nitrophenoxy)benzoic acid

In a 1L 3neck flask, p-chloronitrobenzene (50.0g, 0.31 mol) and 2,3,5,6-tetrafluorohydroxybenzoic acid (66.6g, 0.31 mol) and 400ml of dimethyl sulfoxide were put and stirred under nitrogen. . After dissolving sodium hydroxide (40g, 1.0 mol) in 50ml of distilled water, the mixture was heated to 130°C and stirred for 12 hours. Upon completion of the reaction, the reaction water was poured into 3L distilled water and acidified to pH 2 while stirring. The resulting white solid was filtered, washed several times with water to remove acid, and recrystallized from methanol. The resulting crystals were filtered and vacuum dried at 60° C. for 24 hours to obtain 82 g of the target compound in a yield of 80%.

1H NMR (400 MHz, DMSO-d6) δ (ppm): 1H NMR (400 MHz, DMSO-d6) δ (ppm): 12.71 (COOH), 8.27 (2H, d, Ar-H), 7.21 (2H, d, Ar-H).

Synthesis Example 2b: 5-nitro-2-(2,3,5,6-tetrafluoro-4-(4-nitrophenoxy)phenyl)-1 H -benzo[ d ]Synthesis of imidazole

In a 1L 3neck flask, 2,3,4,5-tetrafiluoro-4-(4-nitrophenoxy)benzoic acid (55.0 g, 0.15 mol) and 4-nitro-benzene-1,2-diamine (23.1 g, 0.15 mol) and 230 g of polyphosphoric acid were added and stirred at 120° C. under nitrogen for 12 hours. When the reaction was completed, it was cooled to 40° C., and distilled water was added little by little until the polyphosphoric acid was dissolved. The reactant was poured into 3L distilled water and then slowly neutralized with 3N aqueous sodium hydroxide solution. The resulting crystals were filtered, washed several times with distilled water, dried under vacuum at 80° C. for 12 hours, and recrystallized from dimethylformaldehyde/tetrahydrofuran to obtain 53 g of the target compound in a yield of 80%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 12.6 (1H, s, -NH-), 8.27 (2H, o, Ar-H), 8.09- (1H, d, Ar-H) , 7.91 (1H, s, ArH), 7.66 (1H, d, Ar-H), 7.21 (2H, d, Ar-H).

Synthesis Example 2c: 2-(4-(4-aminophenoxy)-2,3,5,6-tetrafluorophenyl)-1 H -benzo[ d ] Synthesis of imidazol-5-amine

In a 1 L 3neck flask, add 5-nitro-2-(2,3,5,6-tetrafluoro-4-(4-nitrophenoxy)phenyl) -1H -benzo[ d ]imidazole (30g, 0.06 mol) , After adding 5g of 5% palladium / carbon, 100ml of 2-methoxyethanol was added, stirred for 6 hours in a hydrogen atmosphere, and when the reaction was completed, the catalyst was removed, the filtrate was concentrated under reduced pressure, and the target compound was recrystallized with dimethylformaldehyde. 15 g, yield 65%.

¹ H NMR (400 MHz, DMSOd ₆ ) δ (ppm): 12.6 (1H, s, NH-), 7.43 (1H, d, ArH), 7.10 (1H, d, ArH), 6.74 (4H, s, ArH ), 6.66 (1H, d, ArH), 5.50 (2H, br, NH ₂ ), 5.28 (2H, br, -NH ₂ ).

Synthesis Example 3a: Synthesis of 5-nitro-2-(4-(4-nitrophenoxy)phenyl)-1H-benzo[d]imidazole

4-(4-nitrophenoxy)benzoic acid (3.4 g, 0.013 mol), 4-nitro-1,2-phenylenediamine (2.0 g, 0.0131 mol) and polyphosphoric acid 18 g in a 100 ml flask put in The temperature was raised to 125°C, stirred for 7 hours, and then cooled to 40°C. Distilled water was slowly added to the mixture to dissolve it, and then it was slowly poured into 60 ml of ice water. The resulting crystals were filtered, washed with distilled water, and vacuum dried at 80°C. After recrystallization from DMF/MeOH twice, the resulting crystals were filtered, washed with methanol several times, and vacuum dried at 80° C. to obtain a target compound in a yield of 62%.

1HNMR (400MHz, DMSO-d6)δ (ppm): 13.6 (1H, s, -NH-), 8.51 (1H, s, Ar-H), 8.11 (1H, d, Ar-H), 7.27 (2H, d, Ar-H).

Synthesis Example 3b: Synthesis of 2-(4-(4-aminophenoxy)phenyl)-1H-benzo[d]imidazol-5-amine

5-nitro-2-(4-(4-nitrophenoxy)phenyl)-1H-benzo[d]imidazole (20 g, 0.053 mol), 5% palladium/carbon (2.26 g, 0.001 mol) in a 500 ml flask ) was added, 160 ml of 2-methoxyethanol was added, and the inside of the reactor was substituted with hydrogen using a hydrogen balloon. After stirring at 25°C for 4 hours, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure to remove half of the solvent, and crystallized with distilled water. The resulting crystals were filtered, washed twice with ethanol, and vacuum dried at 60° C. for 24 hours to obtain a target compound in a yield of 59%.

1HNMR (400 MHz, DMSO-d6)δ (ppm): 1H NMR (400 MHz, DMSO-d6)δ (ppm): 12.1 (1H, s, -NH-), 7.99 (2H, d, Ar-H), 7.25 (1H, d, Ar-H), 6.95 (2H, d, Ar-H), 6.83 (2H, d, Ar-H), 6.63 (3H, m, Ar-H), 6.51 (1H, d, Ar-H), 5.03 (4H, s, Ar-NH2).

[Example 1: Preparation of polyamic acid composition and polyimide film]

24.21 g (0.063 mol) of the diamine monomer and 19.61 g (0.063 mol) of 4,4'-oxydiphthalic anhydride (ODPA) prepared in Synthesis Example 1c were dissolved in 250 g of N-methyl-2-pyrrolidone and nitrogen The mixture was stirred for 12 hours at 25°C in the atmosphere. After the reaction was completed, polyamic acid in the form of a viscous solution was obtained.

After applying the polyamic acid solution to a constant thickness of 500 μm on a glass substrate using a blade, the polyimide film of Example 1 was obtained by heat treatment up to 400° C. at a heating rate of 50° C./30 min in a vacuum oven.

[Example 2: Preparation of polyamic acid composition and polyimide film]

24.21 g (0.063 mol) of the diamine monomer and 13.74 g (0.063 mol) of pyromellitic dianhydride (PMDA) prepared in Synthesis Example 1c were used, and then the polyimide of Example 2 was prepared in the same manner as in Example 1. got the film

[Example 3: Preparation of polyamic acid composition and polyimide film]

16.14 g (0.042 mol) of the diamine monomer prepared in Synthesis Example 1c, 9.50 g (0.010 mol) of aminopropyl terminated polydimethylsiloxane, and 16.13 g (0.052 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was used, and then the polyimide film of Example 3 was obtained in the same manner as in Example 1.

[Example 4: Preparation of polyamic acid composition and polyimide film]

Using 9.22 g (0.024 mol) of the diamine monomer prepared in Synthesis Example 1c, 5.7 g (0.006 mol) of aminopropyl terminated polydimethylsiloxane, and 6.54 g (0.030 mol) of pyromellitic dianhydride (PMDA), Thereafter, the polyimide film of Example 4 was obtained in the same manner as in Example 3.

[Example 5: Preparation of polyamic acid composition and polyimide film]

8.07 g (0.021 mol) of the diamine monomer prepared in Synthesis Example 1c and 1.29 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 4,4'-oxydiphthalic anhydride (ODPA) 8.07 g (0.026 mol) was used, and then the polyimide film of Example 5 was obtained in the same manner as in Example 1.

[Example 6: Preparation of polyamic acid composition and polyimide film]

7.99 g (0.021 mol) of the diamine monomer prepared in Synthesis Example 1c, 1.29 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 13.74 g (0.063 g) of pyromellitic dianhydride (PMDA) mol) was used, and then the polyimide film of Example 6 was obtained in the same manner as in Example 1.

[Example 7: Preparation of polyamic acid composition and polyimide film]

Using 19.93 g (0.063 mol) of diamine monomer and 19.54 g (0.063 mol) of 4,4'-oxydiphthalic anhydride (ODPA) prepared in Synthesis Example 3b, and then carried out in the same manner as in Example 1 to obtain Example The polyimide film of 7 was obtained.

[Example 8: Preparation of polyamic acid composition and polyimide film]

19.93 g (0.063 mol) of the diamine monomer and 13.74 g (0.063 mol) of pyromellitic dianhydride (PMDA) prepared in Synthesis Example 3b were used, and then the polyimide of Example 8 was prepared in the same manner as in Example 1. got the film

[Example 9: Preparation of polyamic acid composition and polyimide film]

15.81 g (0.050 mol) of the diamine monomer prepared in Synthesis Example 3b and 11.97 g (0.013 mol) of aminopropyl terminated polydimethylsiloxane were dissolved in 250 g of N-methyl-2-pyrrolidone and 4,4' -Oxydiphthalic anhydride (ODPA) 19.54 g (0.063 mol) was used, and then the polyimide film of Example 9 was obtained in the same manner as in Example 1.

[Example 10: Preparation of polyamic acid composition and polyimide film]

Using 15.81 g (0.050 mol) of the diamine monomer prepared in Synthesis Example 3b and 11.97 g (0.013 mol) of aminopropyl terminated polydimethylsiloxane, 13.74 g (0.063 mol) of pyromellitic dianhydride (PMDA) , In the same manner as in Example 1, a polyimide film of Example 10 was obtained.

[Example 11: Preparation of polyamic acid composition and polyimide film]

15.81 g (0.05 mol) of the diamine monomer prepared in Synthesis Example 3b, 3.13 g (0.013 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 4,4'-oxydiphthalic anhydride (ODPA) A polyimide film of Example 11 was obtained in the same manner as in Example 1 using 19.54 g (0.063 mol).

[Example 12: Preparation of polyamic acid composition and polyimide film]

15.81 g (0.05 mol) of the diamine monomer prepared in Synthesis Example 3b, 3.13 g (0.013 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 13.74 g (0.063 g) of pyromellitic dianhydride (PMDA) mol) was used, and the polyimide film of Example 12 was obtained in the same manner as in Example 1.

[Example 13: Production of polyimide and film]

9.70 g (0.025 mol) of the diamine monomer prepared in Synthesis Example 2c, 7.94 g (0.026 mol) of 4,4'-oxydiphthalic anhydride (ODPA), and 7.94 g of isoquinoline were mixed with 230 g of N-methyl-2-p It was dissolved in Rolidone and stirred at 70 °C for 2 hours and 150 °C for 3 hours in a nitrogen atmosphere. After the reaction was completed, the reactor was cooled to room temperature, and the polyimide solution was slowly dropped into methanol to precipitate, and the precipitate was filtered. The precipitate was washed twice each with water and methanol, and then dried in a vacuum oven at 80 °C for 15 hours to obtain a target polyimide polymer.

The synthesized polyimide was dissolved in N-methyl-2-pyrrolidone (NMP) at a concentration of 10 wt% to prepare a solution, and it was coated on a glass plate with an initial film interval of 500 μm using a blade coater, and then in a vacuum oven at 50 ° C. The polyimide film of Example 13 was prepared by heat treatment up to 400 ° C. at a heating rate of / 30 min.

[Example 14: Preparation of polyamic acid composition and polyimide film]

Except for using 9.70 g (0.025 mol) of the diamine monomer prepared in Synthesis Example 2c, 5.62 g (0.025 mol) of pyromellitic dianhydride (PMDA), and 7.75 g of isoquinoline, the same procedure as in Example 13 was performed. Thus, the polyimide film of Example 14 was obtained.

[Example 15: Preparation of polyamic acid composition and polyimide film]

8.15 g (0.021 mol) of the diamine monomer prepared in Synthesis Example 2c and 4.94 g (0.005 mol) of aminopropyl terminated polydimethylsiloxane were dissolved in 250 g of N-methyl-2-pyrrolidone and 4,4' -Oxydiphthalic anhydride (ODPA) 7.94 g (0.026 mol) and isoquinoline 7.94 g were used, and then the polyimide film of Example 15 was obtained in the same manner as in Example 13.

[Example 16: Preparation of polyamic acid composition and polyimide film]

8.15 g (0.021 mol) of the diamine monomer prepared in Synthesis Example 2c and 4.75 g (0.005 mol) of aminopropyl terminated polydimethylsiloxane, 5.62 g (0.025 mol) of pyromellitic dianhydride (PMDA) and isoquinoline Using 7.75 g, the polyimide film of Example 16 was obtained in the same manner as in Example 13.

[Example 17: Preparation of polyamic acid composition and polyimide film]

8.15 g (0.021 mol) of the diamine monomer prepared in Synthesis Example 2c, 1.29 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 4,4'-oxydiphthalic anhydride (ODPA) A polyimide film of Example 17 was obtained in the same manner as in Example 13, using 7.94 g (0.026 mol) and 7.75 g of isoquinoline.

[Example 18: Preparation of polyamic acid composition and polyimide film]

8.15 g (0.021 mol) of the diamine monomer prepared in Synthesis Example 2c, 1.29 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 5.62 g (0.025 g) of pyromellitic dianhydride (PMDA) mol) and 7.75 g of isoquinoline, and the same procedure as in Example 13 was performed to obtain a polyimide film of Example 18.

[Comparative Example 1: Preparation of polyamic acid composition and polyimide film]

20 g (0.09 mol) of commercially available 5-amino-2-(4-aminophenyl)benzimidazole diamine monomer (5APBA) and 27.66 g (0.089 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) It was dissolved in N-methyl-2-pyrrolidone and stirred at 25 °C for 12 hours in a nitrogen atmosphere. After the reaction was completed, the temperature was cooled to room temperature, and a polyamic acid composition in the form of a viscous solution was obtained.

After applying the polyamic acid solution to a constant thickness of 500 μm on a glass substrate using a blade, the polyimide film of Comparative Example 1 was obtained by heat treatment up to 400° C. at an interval of 50° C./30 min at a heating rate in a vacuum oven.

[Comparative Example 2: Preparation of polyamic acid composition and polyimide film]

20 g (0.09 mmol) of the diamine monomer (5APBA) and 19.41 g (0.09 mol) of pyromellitic dianhydride (PMDA) used in Comparative Example 1 were dissolved in 250 g of N-methyl-2-pyrrolidone, and then A polyimide film of Comparative Example 2 was obtained in the same manner as in Comparative Example 1.

[Comparative Example 3: Preparation of polyamic acid composition and polyimide film]

15.92 g (0.07 mmol) of the diamine monomer (5APBA) used in Comparative Example 1, 16.91 g (0.018 mol) of aminopropyl terminated polydimethylsiloxane, and 27.66 g of 4,4'-oxydiphthalic anhydride (ODPA) ( 0.089 mmol) was used, and then the polyimide film of Comparative Example 3 was obtained in the same manner as in Comparative Example 1.

[Comparative Example 4: Preparation of polyamic acid composition and polyimide film]

16.14 g (0.07 mmol) of the diamine monomer (5APBA) used in Comparative Example 1 and 17.10 g (0.018 mol) of aminopropyl terminated polydimethylsiloxane, 19.41 g (0.09 mol) of pyromellitic dianhydride (PMDA) was used, and the polyimide film of Comparative Example 4 was obtained in the same manner as in Comparative Example 1.

[Comparative Example 5: Preparation of polyamic acid composition and polyimide film]

15.92 g (0.07 mmol) of the diamine monomer (5APBA) used in Comparative Example 1 and 4.42 g (0.018 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 4,4'-oxydiphthalic anhydride A polyimide film of Comparative Example 5 was obtained in the same manner as in Comparative Example 1 using 27.66 g (0.089 mmol) of (ODPA).

[Comparative Example 6: Preparation of polyamic acid composition and polyimide film]

15.92 g (0.07 mmol) of the diamine monomer (5APBA) used in Comparative Example 1 and 3.13 g (0.013 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, pyromellitic dianhydride (PMDA) 19.41 A polyimide film of Comparative Example 6 was obtained in the same manner as in Comparative Example 1 using g (0.09 mol).

For reference, the compositions of the polyimide films prepared in Examples 1 to 16 and Comparative Examples 1 to 6 of the present application are shown in Table 1 below.

Diamine (mol %) Acid dianhydride (mol%) primary diamine secondary diamine Example 1 Synthesis Example 1c (100) - OPDA Example 2 Synthesis Example 1c (100) - PMDA Example 3 Synthesis Example 1c (80) Siloxane A (20) OPDA Example 4 Synthesis Example 1c (80) Siloxane A (20) PMDA Example 5 Synthesis Example 1c (80) Siloxane B (20) OPDA Example 6 Synthesis Example 1c (80) Siloxane B (20) PMDA Example 7 Synthesis Example 3b (100) - OPDA Example 8 Synthesis Example 3b (100) - PMDA Example 9 Synthesis Example 3b (80) Siloxane A (20) OPDA Example 10 Synthesis Example 3b (80) Siloxane A (20) PMDA Example 11 Synthesis Example 3b (80) Siloxane B (20) OPDA Example 12 Synthesis Example 3b (80) Siloxane B (20) PMDA Example 13 Synthesis Example 2c (100) - OPDA Example 14 Synthesis Example 2c (100) - PMDA Example 15 Synthesis Example 2c (80) Siloxane A (20) OPDA Example 16 Synthesis Example 2c (80) Siloxane A (20) PMDA Example 17 Synthesis Example 2c (80) Siloxane B (20) OPDA Example 18 Synthesis Example 2c (80) Siloxane B (20) PMDA Comparative Example 1 5APBA (100) - OPDA Comparative Example 2 5APBA (100) - PMDA Comparative Example 3 5APBA (80) Siloxane A (20) OPDA Comparative Example 4 5APBA (80) Siloxane A (20) PMDA Comparative Example 5 5APBA (80) Siloxane B (20) OPDA Comparative Example 6 5APBA (80) Siloxane B (20) PMDA

[Experimental example. Evaluation of physical properties]

For the polyimide films prepared in Examples 1 to 16 and Comparative Examples 1 to 6, the film forming properties and the thickness of the finally obtained film were measured, and mechanical properties, thermal properties, permittivity, cyclic bending and solubility properties were evaluated to determine the The results are shown in Table 2 below. At this time, the specific measurement method for each physical property is as follows, and the judgment standard is shown in Table 3 below.

(1) Solubility (polyimide)

While maintaining the temperature at 20 ° C., the sample was added dropwise in small portions to 100 g of the solvent under stirring until it was no longer dissolved, and left for 23 hours. Solubility was measured according to Equation 1 below.

[Equation 1]

Solubility (%) = amount of dissolved sample (g) / solvent (100 g) × 100

(2) film thickness

The thickness of the film was measured using a thickness measuring device (KG601B Electric Micrometer (Anritsu)).

(3) heat resistance

It was measured using a thermogravimetric analyzer (TGA) under a nitrogen atmosphere. At this time, the heat resistance measurement range was 25 to 700 ° C, and the temperature increase rate was 10 ° C / min. In order to remove moisture absorbed in the air, after incubating at 105 ° C. for 30 minutes, the weight was calculated as 100%, and the temperature at which a 5% weight loss compared to the weight (Td _5% ) was measured.

(4) Permittivity

The size of the specimen was 5 × 5 cm or more, and the thickness of the specimen was prepared at 80 μm. Each specimen was put into the resonator and measured at room temperature/pressure.

(5) Coefficient of Thermal Expansion (CTE)

The probe position was measured while raising the temperature to 20℃-350℃. After solving the thermal history through the first temperature increase, the TMA result obtained at the second temperature increase was secured, and the polymer film specimen was prepared as 40x40 mm, and the change slope of the probe position obtained in the temperature range of 50 ℃ to 250 ℃ was measured. The thermal expansion coefficient was calculated.

(7) Adhesion

A glass substrate and a copper film were used as the test plate, and each substrate was manufactured according to KS M ISO1514 and used after drying. The test was performed at (23±2)° C. and relative humidity (50±5)%, and the number of cuts was measured by cutting six times in each direction of the grid shape.

(8) Moisture absorption rate

After making the prepared polyimide film into a specimen having a size of 10 x 10 mm, the initial weight (W1) was measured. Then, each specimen was left in a purified water bath for 24 hours at a temperature of 25 ± 2 ° C and a relative humidity of 30% to treat moisture, and then the specimen was taken out, wiped with a cloth, and the weight (W2) was measured after the moisture absorption treatment. The measured value was substituted into Equation 2 below to calculate the moisture absorption.

[Equation 2]

Moisture absorption rate (%) = [(W2-W1)/W1] × 100

(9) repeated bending test

In accordance with KS M ISO5626 and ASTM D2176, a film specimen of appropriate size is applied with a load at a speed of 175 times per minute using an MIT theft resistance tester, and the bending grip repeats folding and unfolding while performing left and right reciprocating rotational movements of 90 to 135 ° The number of times until the specimen split was measured.

thickness
(μm) Properties Td _5% (℃) permittivity thermal expansion
Coefficient adhesion solubility moisture absorption rate repeat
flex powder film Example 1 60 ++ ++ + ++ + ++ ++ ++ Example 2 60 ++ ++ ++ ++ + + ++ ++ Example 3 60 ++ + ++ ++ ++ + + ++ Example 4 60 ++ + ++ ++ ++ + ++ ++ Example 5 60 + ++ ++ ++ ++ ++ + ++ Example 6 60 + ++ ++ + ++ ++ ++ ++ Example 7 60 ++ ++ ++ ++ + ++ ++ ++ Example 8 60 ++ ++ ++ + ++ ++ ++ + Example 9 60 ++ ++ ++ + ++ ++ + + Example 10 60 ++ + ++ ++ ++ + ++ ++ Example 11 60 ++ ++ + + ++ + + ++ Example 12 60 ++ + ++ ++ + + ++ ++ Example 13 60 ++ ++ ++ + + ++ ++ ++ Example 14 60 ++ ++ ++ ++ + + ++ ++ Example 15 60 ++ + ++ + + ++ ++ ++ Example 16 60 ++ + ++ ++ + ++ ++ ++ Example 17 60 + ++ ++ ++ + ++ ++ + Example 18 60 + ++ ++ + + ++ ++ + Comparative Example 1 60 + + + + + + + + Comparative Example 2 60 + + + + + + + + Comparative Example 3 60 + + + + + + + + Comparative Example 4 60 + + + + ++ + + + Comparative Example 5 60 + + + + + + + + Comparative Example 6 60 + + + + + + + +

Properties judging criteria Heat resistance (Td _5%) powder + (>300℃), ++ (≥ 500℃) Film (@150 ㎛) + (> 300℃), ++ (≥ 500℃) Permittivity (@10 GHz) + (< 3.5), ++ (≤3.0) Coefficient of thermal expansion (ppm/℃,2 ^nd ) + (< 65), ++ (≤ 40) Moisture absorption rate (%) + (< 1.0), ++ (≤ 0.8) Adhesion (kg/cm) + (> 0.5), ++ (≥ 0.8) Solubility (%) + 50% or less solubility in at least one solvent of MC, and cyclohexanone
++ 50% or more solubility in at least one solvent of NMP, DMF, and THF Repeated bending test (times) + ( > 50,000), ++ (≥ 100,000)

As shown in Table 2, the polyimide film containing the novel diamine monomer according to the present invention exhibits high solubility, low dielectric constant, low moisture absorption, high adhesive strength, and repeated bending properties, thereby preparing a film with excellent processability and heat resistance. knew that it could be done.

In the above, preferred embodiments of the present invention have been illustrated, but the present invention is not limited to the specific preferred embodiments described above, and common knowledge in the technical field to which the invention belongs without departing from the gist of the present invention claimed in the claims. Any person who has, of course, various modifications can be implemented, and such changes are within the scope of the claims.

Claims (13)

A compound selected from the group consisting of the following formulas 1 to 3:
[Formula 1]

[Formula 2]

[Formula 3]

In the above formula,
A plurality of X's are the same as or different from each other, and are each independently selected from the group consisting of -O-, -S-, - and S(=O) ₂ -,
R ₁ to R ₆ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, fluoro, an alkyl group having 1 to 30 carbon atoms, and trifluoromethyl (CF ₃ );
Ar is a moiety selected from the group consisting of Formulas Ar-1 to Ar-12,

In the above formula,
* denotes a portion bonded to Formula 1,
R ₇ to R ₁₆ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, fluoro, an alkyl group having 1 to 30 carbon atoms, and trifluoromethyl (CF ₃ );
Any hydrogen included in the alkyl group of R ₁ to R ₁₆ may be independently substituted with one or more substituents selected from the group consisting of halogen and -CF ₃ . According to claim 1,
The compound represented by Formula 1 is a compound selected from the group of compounds represented by the following formula.

diamine containing the compound according to claim 1 or 2; and
acid dianhydride;
A composition for producing a polyamic acid comprising a. According to claim 3,
The compound of Formula 1 is included in the range of 1 to 100 mol% based on 100 mol% of the total diamine, a composition for producing a polyamic acid. According to claim 3,
The diamine is different from the compound of Formula 1, and may include fluorinated aromatic diamine; A composition for preparing a polyamic acid further comprising at least one selected from the group consisting of sulfone-based aromatic diamines, hydroxy-based aromatic diamines, ether-based aromatic diamines, alicyclic diamines, aminosiloxanes, and poly-diaminosiloxanes. According to claim 3,
The acid dianhydride includes at least one selected from the group consisting of fluorinated aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and non-fluorinated aromatic tetracarboxylic acid dianhydride, polyamic acid production composition. According to claim 3,
The acid dianhydride is pyromellitic tetracarboxylic dianhydride (PMDA), 4,4'-oxydiphthal tetracarboxylic dianhydride (OPDA), 4,4'-hexafluoroisopropyldendiphthal tetra Carboxylic dianhydride (6FDA), cyclohexane 1,2,4,5-tetracarboxylic dianhydride (HPMDA), bicyclo[2,2,2]-7-octene-2,3,5,6- Tetracarboxylic dianhydride (BCDA), norborene-2-spiro-α-cyclopentanone-α'-spiro-2"-norborene-5,5",6,6"-tetracarboxylic dianhydride A composition for preparing a polyamic acid comprising at least one of water (CpODA) and cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA). A polyamic acid formed from the composition for preparing a polyamic acid according to claim 3. According to claim 8,
The polyamic acid includes a repeating unit represented by any one of Formulas 4 to 6 below:
[Formula 4]

[Formula 5]

[Formula 6]

In the above formula,
B ₁ and B ₂ of Formula 5 and B ₁ to B ₃ of Formula 6 are _the same as or different from each other,
However, B in Formula 4; at least one of B ₁ and B ₂ in Formula 5; At least one of B ₁ to B ₃ in Formula 6 is a group derived from a diamine selected from the group consisting of compounds of Formulas 1 to 3,
A is a group derived from an acid dianhydride,
In Formula 5, x and y are rational numbers satisfying x + y = 1,
In Formula 6, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1. A polyimide polymer formed by imidizing the polyamic acid of claim 8. According to claim 10,
The polyimide polymer includes a repeating unit represented by any one of Formulas 7 to 9 below.
[Formula 7]

[Formula 8]

[Formula 9]

In the above formula,
B ₁ and B ₂ of Formula 8 and B ₁ to B ₃ of Formula 9 are _the same as or different from each other;
However, B in Formula 7; at least one of B ₁ and B ₂ in Formula 8; At least one of B ₁ to B ₃ in Formula 9 is a group derived from a diamine selected from the group consisting of compounds of Formulas 1 to 3,
A is a group derived from an acid dianhydride,
In Formula 8, x and y are rational numbers satisfying x + y = 1,
In Formula 9, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1. According to claim 10,
A polyimide polymer that satisfies at least four or more physical properties of the following (i) to (vi):
(i) a 5% weight loss temperature (Td _5% ) measured by thermogravimetric analysis (TGA) is 500 ° C or higher;
(ii) the coefficient of thermal expansion (CTE) according to ASTM E831 standard is 40 ppm/℃ or less;
(iii) the permittivity (@10 GHz) is less than 3.0;
(iv) The adhesive strength according to KS M ISO1514 exceeds 0.5 kg/cm,
(v) the moisture absorption is less than 1.0%;
(vi) The number of repeated bendings according to ASTM D2176 standard is 100,000 times or more. A polyimide film comprising the polyimide polymer of claim 10.